You are on page 1of 34

View Article Online / Journal Homepage / Table of Contents for this issue

Dynamic Article Links

RSC Advances
Cite this: RSC Advances, 2012, 2, 93259358

REVIEW

www.rsc.org/advances

Iron-containing nanomaterials: synthesis, properties, and environmental


applications

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

Boris I. Kharisov,a H. V. Rasika Dias,b Oxana V. Kharissova,*a Victor Manuel Jimenez-Perez,a


Betsabee Olvera Pereza and Blanca Munoz Floresa
Received 30th April 2012, Accepted 23rd July 2012
DOI: 10.1039/c2ra20812a
Available data on the iron-containing nanomaterials are reviewed. Main attention is paid to the
following themes: synthetic methods, structures, composition and properties of the nano zerovalent
iron (NZVI), and polymorphic forms of iron oxides and FeOOH. Synthetic methods summarized
here include a series of physico-chemical methods such as microwave heating, electrodeposition, laser
ablation, radiolytical techniques, arc discharge, metal-membrane incorporation, pyrolysis,
combustion, reverse micelle and co-deposition routes. We have also included a few greener
methods. Coated, doped, supported with polymers or inert inorganic materials, coreshell
nanostructures, in particular those of iron and its oxides with gold, are discussed. Studies of
remediation involving iron-containing nanomaterials are discussed and special attention is paid to the
processes of remediation of organic contaminants (chlorine-containing pollutants, benzoic and formic
acids, dyes) and inorganic cations (Zn(II), Cu(II), Cd(II) and Pb(II)) and anions (nitrates, bromates,
arsenates). Water disinfection (against viruses and bacteria), toxicity and risks of iron nanomaterials
application are also examined.

Universidad Autonoma de Nuevo Leon, Monterrey, Mexico.


E-mail: bkhariss@mail.ru
Department of Chemistry and Biochemistry, The University of Texas at
Arlington, Arlington, Texas, 76019, USA

nano-objects they contain. Nanomaterials are classified into


compact materials and nanodispersions. The first type includes
so-called nanostructured materials, i.e., materials isotropic in
the macroscopic composition and consisting of closely packed
nanometer-sized units as repeating structural elements. Among
nanomaterials, the iron-containing nanomaterials have attracted
a great deal of interest due to their magnetic properties, allowing
such applications as targeted drug delivery1 and other areas of

Dr Boris I. Kharisov (born in


Russia in 1964) is currently a
Professor and Researcher at the
Universidad Autonoma de Nuevo
Leon (UANL). Degrees: An MS in
1986, in radiochemistry and a PhD
in inorganic chemistry in 1993, from
the Moscow State University,
Russia; Dr Hab. in physical chemistry in 2006 from Rostov State
University, Russia. He is the coauthor of six books, 122 articles,
five book chapters, and has two
patents. Co-editor: Three invited
special issues of international journals. He is the member of the
Editorial board of four journals.
Specialties: Coordination and inorganic chemistry, phthalocyanines,
ultrasound, and nanotechnology.

Dr Rasika Dias is a Professor of


Chemistry at the University of
Texas at Arlington. Born in
Colombo, Sri Lanka, he received
his BSc Degree from University of
Peradeniya (Sri Lanka) and PhD
from University of California, Davis
(USA). Dr Dias was a Visiting
Research Scientist at the DuPont
Central Research & Development,
Delaware before joining the
University of Texas at Arlington
faculty in 1992. Professor Dias
specializes in inorganic and organometallic chemistry, and has been the
author or co-author of several
patents and over 160 publications.
He has won several awards including
the 2009 Southwest Regional
American Chemical Society Award.

Introduction
According to the classic definition, nanomaterials are those
materials whose key physical characteristics are dictated by the
a
b

Boris I. Kharisov

This journal is The Royal Society of Chemistry 2012

H. V. Rasika Dias

RSC Adv., 2012, 2, 93259358 | 9325

View Article Online

nanomedicine. Coreshell iron (iron oxide)/gold nanoparticles


are of special interest due to possibility to be controlled by
magnetic fields (iron core) and functionalization (gold shell).2
Some applications of iron-containing nanomaterials have been
recently reviewed,3,4 including their usefulness in water treatment
(remediation of pollutants and bacteria).57 In this review, we
pay main attention to the synthetic methods for obtaining Fe0
and FexOy based nanomaterials and their application in water
treatment8 (remediation of (in)organic contaminants and disinfection of groundwater).

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

General data on the iron-containing nanostructures


Iron-containing nanomaterials (Table 1) are mainly consisted of
zerovalent iron (ZVI is currently a classic term, as well as NZVI
(nano zerovalent iron)), iron nanoalloys or coreshell nanoparticles, and oxides, among others, such as, for example, ferrites.
Iron typically exists in the environment as iron(II) and iron(III)

Oxana V. Kharissova

oxides.9 Iron oxides (iron oxide nanoparticles are also referred in


several reports to as superparamagnetic iron-oxide nanoparticles
(SPIONs) although SPIONS have inducible magnetic properties),10,11 are one of the most important transition metal oxides
of technological importance. Iron oxides is also a collective term
for oxides, hydroxides and oxy-hydroxides composed of Fe(II)
and/or Fe(III) cations and O22 and/or OH2 anions. Sixteen pure
phases of iron oxides, i.e., oxides, hydroxides or oxy-hydroxides
are known to date. These are Fe(OH)3, Fe(OH)2, Fe5HO8?4H2O,
Fe3O4, FeO, five polymorphs of FeOOH and four of Fe2O3.
Characteristics of these oxide compounds include mostly the
trivalent state of the iron, low solubility and brilliant colors. The
main advantages of nano-iron among other nanomaterials are
relatively low toxicity and biodegradability. In addition, iron is a
relatively cheap and a widespread material.12
Metallic or zerovalent iron (Fe0) is a moderate reducing
reagent, which can react with dissolved oxygen and to some
extent with water (eqn (1) and (2)):

Dr Oxana V. Kharissova (born in


1969 in Ucrania, former USSR) is
currently a Professor and Researcher
at the UANL. Degrees: An MS in
1994, in crystallography from
Moscow State University, Russia,
and a Ph.D. in Materials from the
Universidad Autonoma de Nuevo
Leon, 2001, Mexico. Memberships:
National Researchers System (Level
I), Materials Research Society. She
is the co-author of three books, four
book chapters, 60 articles, and has
two patents. Specialties: Nanotechnology (carbon nanotubes, nanometals, fullerenes), microwave irradiation and crystallography.

Dr Victor Manuel Jimenez-Perez


was born in Tlaxcala (Mexico,
1974). He received his BSc (1998)
in Chemistry at the Universidad
Autonoma de Tlaxcala. In 2005, he
received his PhD in Chemistry at the
CINVESTAV under the supervision
of Prof. Rosalinda Contreras in the
field of tin chemistry. After postdoctoral work in the Prof. Herbert
Roeskys group at Universitat
Gottingen (2007), he jointed as a
full-professor in Chemistry Faculty
at the Universidad Autonoma de
Nuevo
Leon. So far, he is the author
Victor Manuel Jimenez-Perez
of more than 20 publications. His
research is mainly focused on the
design and synthesis of luminescent
and sensor organometallic compounds and green chemistry.

Betsabee Olvera Perez studied


Industrial Chemistry at the
Universidad Autonoma de Nuevo
Leon (2011). After working for a
short time in a private chemical
company in Monterrey, Mexico,
she is currently an active MSc
student at the same University,
working in the area of fabrication
of iron nanoparticles by green
chemical and biological methods.
She is co-author of two submitted
manuscripts.

Dr Blanca Munoz Flores (born in


Tlaxcala, Mexico, 1976) studied
Industrial Chemistry at the Universidad Autonoma de Tlaxcala
(1999). She received her PhD in
Organic Chemistry (2008) at the
CINVESTAV-IPN under direction
of Prof. Norberto Farfan Garca.
She moved to the Chemistry Faculty
of the Universidad Autonoma de
Nuevo Leon (2009) as a full professor. Presently, her research group
is working on the design, synthesis,
characterization and determination
nonlinear optical (NLO) properties
of organic and organometallic compounds, as well as on nanoalloys. So
far, she is the author of more than 10
research publications in leading
scientific journals.

Betsabee Olvera Perez

9326 | RSC Adv., 2012, 2, 93259358

Blanca Munoz Flores

This journal is The Royal Society of Chemistry 2012

View Article Online

Table 1 Main iron-containing nanostructures

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

Composition
Fe

Description
The preparation of nanoparticles consisting of pure iron is a complicated task, because they always contain oxides,
carbides and other impurities.
BCC-Fe (a-Fe)
a-Fe nanoparticles with a body-centered cubic (BCC) lattice can be prepared by (a) grinding a high-purity (99.999%) Fe
powder, (b) evaporation of the metal in an Ar or He atmosphere followed by deposition on a substrate, (c) laser
vaporization of pure iron.
FCC-Fe (c-Fe)
In the phase diagram of a bulk Fe sample, this phase exists at the ambient pressure in the temperature range of 1183
1663 K, i.e., above the Curie point (1096 K). In some special alloys, this phase, which exhibits antiferromagnetic properties
(the Neel temperature is in the 4067 K range), was observed at room temperature. These nanoparticles, in several syntheses,
can contain substantial amounts of carbon (up to 14 mass%). c-Fe nanoparticles, synthesized by treatment of Fe(CO)5 with a
CO2 laser radiation, may contain, for example, c-Fe (30 atom%), a-Fe (25 atom%) and iron oxides (45 atom%).
Amorphous
Synthesis by: (a) the ultrasonic treatment of Fe(CO)5 in the gas phase or of a solution of Fe(CO)5 in decane under an inert
Fe (metallic glass) atmosphere; (b) thermal decomposition of Fe(CO)5 in decalin (460 K) in the presence of surfactants.
Among several crystalline modifications of Fe2O3, there are two magnetic phases, namely, rhombohedral a-Fe2O3 (hematite)
Fe2O3
and cubic c-Fe2O3 (maghemite) phases. The a-Fe2O3 and FeOOH (goethite) nanoparticles are obtained by controlled
hydrolysis of Fe3+ salts. The c-Fe2O3 nanoparticles are obtained by (a) mild oxidation (on treatment with Me3NO) of
pre-formed metallic nanoparticles, (b) by direct introduction of Fe(CO)5 into a heated solution of Me3NO, (c) thermal
decomposition of Fe3+ salts in various media, (d) vaporization of iron(III) oxide in a solar furnace with subsequent
condensation, (e) mechanochemical synthesis milling iron powder in a planetary mill with water.
Fe3O4 (magnetite) The cubic spinel Fe3O4 is ferrimagnetic at temperatures below 858 K. The route to these particles most often involves
treatment of a solution of a mixture of iron salts (Fe2+ and Fe3+) with a base under an inert atmosphere.
In some cases, thermal decomposition of compounds containing Fe3+ ions under oxygen-deficient conditions is
accompanied by partial reduction of Fe3+ to Fe2+. Fe3O4 nanoparticles can be also prepared by thermal decomposition
of Fe2(C2O4)3?5H2O or by the controlled reduction of ultradispersed a-Fe2O3 in a hydrogen stream.
FeO (wustite)
Cubic Fe2+ oxide is antiferromagnetic (Tc = 185 K) in the bulk state. Synthesis technique: joint milling of Fe and Fe2O3
powders taken in a definite ratio gives nanoparticles consisting of FeO and Fe. On heating of these particles at temperatures
of 250-400 uC, the metastable FeO phase disproportionates to Fe3O4 and Fe, while above 550 uC it is again converted into
nanocrystalline FeO.
a-FeOOH
The orthorhombic a-FeOOH (goethite) is antiferromagnetic in the bulk state and has Tc = 393 K, b-FeOOH (akagenite) is
paramagnetic at 300 K, c-FeOOH (lipidocrokite) is paramagnetic at 300 K and d-FeOOH (ferroxyhite) is ferrimagnetic. As a
(goethite)
rule, a-FeOOH is present in iron nanoparticles as an admixture phase.
Iron carbide is often present in Fe-containing nanoparticles. It is formed either upon decomposition of organic ligands present
FexCy
in the starting MCC or upon the reaction of Fe with the organic medium. Thermal decomposition of Fe(CO)5 on a carbon
support forms Fe78C22 nanoparticles.
Ferrofluids
Ferrofluids or so-called magnetic liquids are suspensions of colloid magnetic particles stabilized by surfactants in liquid media.
The magnetic phase in ferrofluids can be represented by magnetite, ferrites (group of nonmetallic, ceramic like, usually
ferromagnetic compounds of ferric oxide with other oxides) and FexCy particles resulting from the thermal decomposition
of Fe(CO)5.
FeCo alloys
The saturation magnetization of FeCo alloys reaches a maximum at a Co content of 35 atom%. Fe, Co and FeCo (20, 40,
60, 80 atom%) nanoparticles with a structure similar to the corresponding bulk phases can be prepared in a stream of hydrogen
plasma.
FeNi
Bulk samples of ironnickel alloys are either nonmagnetic or are magnetically soft ferromagnets (for example, permalloys
containing .30% of Ni and various doping additives).
FePt
FePt nanoparticles can be prepared by joint thermolysis of Fe(CO)5 and Pt(acac)2 in the presence of oleic acid and oleylamine.
The reaction of FePt nanoparticles with Fe3O4 followed by heating of the samples at 650 uC in an Ar + 5% H2 stream resulted
in a FePtFe3Pt nanocomposite with unusual magnetic characteristics.

2Fe0(s) + 4H+(aq) + O2(aq) A 2Fe2+(aq) + 2H2O(l)

(1)

Fe0(s) + 2H2O(aq) A Fe2+(aq) + H2(g) + 2OH2(aq)

(2)

The above equations are the classical electrochemical/corrosion reactions by which iron is oxidized from exposure to oxygen
and water. The corrosion reactions can be accelerated or
inhibited by manipulating the solution chemistry and/or solid
(metal) composition.
NZVI particles range from 10 to 100 nm in diameter.13 They
exhibit a typical coreshell structure. The core consists primarily
of zerovalent or metallic iron whereas the mixed valent [i.e.,
Fe(II) and Fe(III)] oxide shell is formed as a result of oxidation of
the metallic iron (Fig. 1). The presence of excess stabilizers was
shown to stabilize the core/shell nanoparticles from further
oxidation.14 Various organic molecules can be used for
functionalization of NZVI to improve the stability of their
aqueous dispersions (strong inhibition of the agglomeration of
the iron nanoparticles), for instance PEG, methoxyethoxyethoxyacetic acid (MEEA), polyacrylic acid and 1,4-butanediphosphonic acid (Fig. 2) have been used for this purpose.15
This journal is The Royal Society of Chemistry 2012

Fig. 1 Schematic diagram of zerovalent iron nanoparticle. Reproduced


with permission.

RSC Adv., 2012, 2, 93259358 | 9327

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online

Fig. 2 Scheme of a nanoscale iron particle covered by MEEA.

Among iron oxides (SPIONs), magnetite (Fe3O4) and maghemite (c-Fe2O3) are of a particular interest. Magnetite is an
inverse spinel ferrite. The oxygen ions form a close-packed cubic
lattice with the iron ions located at two different interstices
between them, tetrahedral (A) sites and octahedral (B) sites.
Chemically, magnetite/maghemite can be represented by the
formula: Fe3+ [Fe2+12yFe3+12yFe3+1.67y%0.33y]O4, where y = 0
for pure magnetite and y = 1 for pure maghemite (fully oxidized
magnetite). In the temperature range from room to Curie
temperature (Tc = 860 K) the A sites are populated by Fe3+ ions
and the B sites are populated equally by Fe3+ and Fe2+ ions.
That way, twice as many sites are populated with Fe3+ than with
Fe2+ ions. Although a simple dehydration of lepidocrocite
(c-FeOOH) topotactically transforms into c-Fe2O3, commercial
manufacturing of maghemite follows the multistep process (3):
(a and/or c)-FeOOH (oxidation) A a-Fe2O3 (reduction) A
Fe3O4 (controlled oxidation) A c-Fe2O3
(3)
SPIONs typically consist of two components, an iron oxide
core of one or more magnetic crystallites embedded in a coating.
The SPIONs core can be composed of magnetite (Fe3O4) and/or
maghemite (c-Fe2O3). The size of SPIONs makes important
contribution to their fate in organism. Categories of SPIONs,
based on their overall diameter (including iron oxide core and
hydrated coating), are noted in the literature as oral or micronsized SPIONs between 300 nm and 3.5 mm; standard or small
SPIONs (SSPIONs) at approximately 60150 nm; ultrasmall
SPIONs (USPIONs) of approximately 1050 nm; and monocrystalline iron oxide nanoparticles (MIONa subset of
USPIONs) of approximately 1030 nm. MION are so named
to underline the single crystal nature of their core. This is in
contrast to SPIONs greater than 50 nm that are comprised of
multiple iron oxide crystals.16 SPIONs have much larger
magnetic susceptibilities (compared with strictly paramagnetic
materials) as the entire crystal aligns with the applied field due to
its single crystal nature. Hence SPIONs are useful as contrast
agents or for hyperthermic treatment of malignant tumors.17
Magnetic nanoparticles offer advantages over non-magnetic
nanoparticles because they can easily be separated from water
9328 | RSC Adv., 2012, 2, 93259358

using an external magnetic field. Separation using magnetic


gradients, the so-called high magnetic gradient separation
(HGMS), is a process widely used in medicine and ore
processing.18 This technique allows one to design processes
where the particles can not only be used to remove compounds
from water but also be separated and then be recycled or
regenerated. This approach has been proposed with magnetite
(Fe3O4), maghemite (c-Fe2O3) and jacobsite (MnFe2O4) nanoparticles for removal of chromium(VI) from wastewater. In
addition, the following iron-based compositions are usually
considered in the literature as media for magnetic information
recording: a-Fe, c-Fe2O3, Fe2O3Fe3O4, Coc-Fe2O3, CrO2,
BaFe12O19. In recent years, nanocrystalline (510 nm) CoPr,
FePt, CoPt, CoSm, SmFeSiC and SmFeAlC films are regarded
as the most promising candidates for magnetic materials.
Types of materials containing iron-based magnetic nanoparticles are, in general, as follows: (1) nanoparticles on a substrate
surface (for instance, a-Fe or Fe3O4 on ZrO2), (2) ironcontaining nanoparticles in matrices, including (a) inorganic
matrices (such as zeolites, molecular sieves, glass, xerogels and
silica gel, dispersed carbon, highly dispersed SiO2 and Al2O3,
magnetic nanoparticles in non-magnetic metals (for example,
FeAg or FeHg samples) and organic polymer matrices (ion
exchange resins, soluble polymers (such as PVA), polybutadiene,
polystyrene and styrene copolymers with butadiene, 4-vinylpyridine, N-vinylpyrrolidone, phenylvinylketoxime, carbochain
polymers without heteroatoms and functional groups, polymers
containing heteroatoms (such as polyimines or polyvinylpyrrolidone) or block copolymers (for example, [NORCOOH]30
[MTD]300 block copolymers (NORCOOH is 2-norbornerne5,6-dicarboxylic acid, MTD is methyltetracyclododecene)).
In addition to the NZVI and SPIONs, a variety of composite
inorganic iron-based nanomaterials have been discovered, in
particular coreshell Fe (or FexOy)/Au (see section below) or
more complex trimetallic nanoparticles such as (Fe60Co49)core/
Au.19 Figuerola et al.20 classified them based on their levels of
compositional and/or structural complexity: (1) nanostructures
made of an iron-based magnetic material different from iron
oxide; (2) nanostructures whose morphology is not a sphere (e.g.
hollow structure); (3) multi-material nanostructures, i.e. each of
them is made of two or more domains of different inorganic
materials joined together. Some examples of these approaches
are as follows. Thus, the strategy for functionalization of
CoFe2O4 superparamagnetic Nps (nanoparticles) with a mixture
of amino and thiol groups that facilitate the electrostatic
attraction and further chemisorption of gold Nps, respectively,
is shown in Fig. 3.21 Related MnFe2O4 nanoparticles have
surpassed SPIONs as contrast agents for MRI in vivo.22 The
enhanced sensitivity of MnFe2O4 nanoparticles has been proven
in vivo, enabling detection of a tumor mass as small as 50 mg.
The composite iron-based nanocrystals can be used for treatment
of malignant tumors. Thus, FePt nanoparticles functionalized
with luteinizing hormone-releasing hormone (LHRH) peptide
have enhanced cytotoxicity against ovarian cancer cells that
express LHRH-receptors.23 In the acidic environment of
lysosomes, these nanoparticles release toxic iron species, which
catalyze the formation of reactive oxygen. The latter is toxic for
cells as it can damage lipid membranes, DNAs and proteins.
This journal is The Royal Society of Chemistry 2012

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online

Fig. 3 Reaction strategy showing the successive steps for gold covering
process onto 4 : 1 amino : mercapto functionalized cobalt ferrite Nps.
Reproduced with permission from Elsevier Science.

Nanoshells CoS2@FePt also possess better antitumor activity


than that of cis-platin.24
Several groups revealed that ZVI nanoparticles exhibit
antimicrobial properties (see section below) against Gramnegative E. coli, Pseudomonas fluorescens and Gram-positive
Bacillus subtilis var. niger microorganisms.25,26 The inactivation
of E. coli by ZVI nanoparticles could be because of the
penetration of the small particles (size ranging from 1080 nm)
into E. coli membranes. ZVI nanoparticles could then react with
intracellular oxygen, leading to oxidative stress and causing
disruption of the cell membrane. In addition, iron oxide
nanoparticles also possess antimicrobial properties (see the
section on water disinfection below). In general, iron-based
nanomaterials are thoroughly investigated according to their
relatively low toxicity integrated with unique properties in order
to exploit them in such biomedical applications as remediation of
environment, development of novel diagnostic tools and
methods for individualized treatment.

Synthesis techniques for NZVI and nano-iron oxides


There is a series of special techniques for preparation of iron and
other nanomaterials, which could be artificially divided into
physical, physico-chemical, chemical and biological
methods. Of course, such a separation is conditional; almost any
physical process in these transformations is accompanied in these
reactions by a chemical transformation. We consider as
physical methods those requiring special equipment, for
example a 60Co source for c-irradiation of samples or sputtering
equipment. Application of different methods has led to formation of iron-containing nanostructures having distinct compositions, iron oxidation states and structures. It is worth mentioning
that the use of Mossbauer spectroscopy is almost a strict
requirement in working with Fe-nanostructures in order to
determine exact iron oxidation number. Tables 2 and 3 contain
examples of methods used and the corresponding products.
A host of modern techniques, as described below, are being
currently used for obtaining nanoparticles of Fe-containing
nanomaterials, although well-known classic wet chemical routes
are not forgotten and continue to be applied for production of
NZVI27 (in particular, by classic borohydride reduction),28
Fe2O3 (solgel method29 or electrochemical deposition from
This journal is The Royal Society of Chemistry 2012

solution30), or Fe3O4 (hydrolysis of Fe3+ and Fe2+ salts in the


presence of urea and NaOH with the following ultrasonic
treatment of FeO(OH)/Fe(OH)2). Morphology and sizes of the
resulting products, produced by various methods, can vary
depending on the synthetic method used and conditions. For
instance, it was shown that the Fe3O4 nanoparticles31 produced
by radiofrequency nitrogen plasma had regular spherical form
while the particles produced by wet chemical synthesis had well
shaped cubic form. The size distribution of the plasma prepared
oxides was wider, producing small particles with size in the range
of 2580 nm, and larger particles with size above 100 nm. The
wider particle size distribution is characteristic of plasma
prepared powders and it was explained by the authors by
different growth conditions of particles due to temperature and
velocity gradients of the plasma flow. This does not take place in
the wet chemical route: the liquid phase synthesis provides
preparation of Fe3O4 nanoparticles with average particles size in
the range of 1626 nm. Similarly, the shape, size and production
rate of Fe2O3 nanoparticles, obtained by electrodeposition, were
strongly influenced by the electrochemical conditions (e.g. FeCl3
precursor concentration and current density).

NZVI and FeM nanoalloys or coreshell


nanostructures
Among physical methods, the method of electrical explosion of
wires for production of nanopowders was reported.32,33
Intermetallic species can be also prepared by the arc discharge
method, for instance FeSn nanoparticles.34 The synthesized
nanoparticles have a shell/core structure with a SnO2 shell of 5
10 nm in thickness and a core of polycrystalline intermetallic
compounds. It was found that the intermetallic compounds
FeSn2 and Fe3Sn2 were generated and coexist with the Sn phase
as a single nanoparticle. Microwave treatment (used to produce
mainly inorganic compounds/composites/materials, and to a
lesser extent, organic/organometallic compounds), is an alternative method to common heating of mixtures/precursors. The
transformations of metals in MW field are generalized in a
comprehensive recent book.35 Metallic nanoparticles in distinct
forms can also be produced using MW. For instance, Fe based
nanoparticles have been produced using the microwavepolyol
process in ethylene glycol at 100 and 150 uC in the presence of
poly(vinyl pyrrolidone) and dodecyl amine.36 In addition, pulsed
excimer laser radiation at 248 nm wavelength was used to ablate
~2 mm feedstock of permalloy (Ni 81% : Fe 19%) under both
normal atmospheric conditions and in other gases and pressures.37 a-Fe particles were also prepared using a modified
metalmembrane incorporation technique based on diffusing
metal ions through a dialysis membrane.38 The diffusion-time
varied up to 15 min.
For ZVI,39 the easiest, standard and most popular synthetic
method is through the reduction of ferric Fe(III) or ferrous Fe(II)
salts with NaBH4, NaAlH4 or LiAlH4 as reducing agents. Thus,
NZVI was synthesized (Fig. 4, reaction (4))40 in ethanol medium
by the method of reduction of FeXn (X = Cl, OH, OR, CN,
OCN, SCN) using sodium borohydride under atmospheric
conditions.41 The resulting iron nanoparticles were found to be
mainly in zerovalent oxidation state and remained without
significant oxidation for weeks. Among other reductants used for
RSC Adv., 2012, 2, 93259358 | 9329

View Article Online

Table 2 Physical, chemical and biological methods for preparation of iron-containing nanoparticles148150

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

Method
Physical methods
Condensation methods

Nanodispersion of
a compact material

Description

Examples of products

The method of nanoparticle synthesis from supersaturated metal vapors


is based on the classical nucleation theory in which the nascent phase
clusters are described by the spherical liquid drop model. Nanoparticles
(clusters) are prepared using various means of metal evaporation: laser
vaporization, thermal vaporization, arc discharge, plasma vaporization
and solar energy-induced evaporation. Special installations are needed.
In the classical thermal vaporization method, a metal or alloy sample
is heated in a tungsten boat in an argon or helium stream. The atoms
of the vaporized metal lose kinetic energy upon collisions with inert
gas atoms, gather in clusters and condense on a cooled substrate as
a nanodispersed powder.
The mechanochemical dispersion of a compact material in mills of
various designs is applied, as well as electrolytic erosion and
electrochemical generation.

Heterometallic nanoparticles
(y30 nm) with the composition
FeM (M = Ni, Mn, Pt, Cr).

Chemical synthesis of magnetic nanoparticles


Thermolysis of ironMetal organic chemical vapor deposition (MOCVD) technique.
containing compounds
Cold-plasma chemical
vapor deposition

Aerosol/vapor methods

Combustion synthesis

Chemical precipitation
Coprecipitation

Precipitation by
anhydrous solution

The growth occurs on an Fe catalyst supported by kanthal (iron


chromiumaluminium (FeCrAl) alloys) wires while heating under
a hydrocarbon precursor gas and plasma created by a bias. A
possible application for such nanotubes on metallic wires is in
luminescent tubes.
In spray pyrolysis, a solution of ferric salts and a reducing
agent in organic solvent is sprayed into a series of reactors,
where the aerosol solute condenses and the solvent evaporates.
The resulting dried product consists of particles whose size
depends upon the initial size of the original droplets.
Reaction process is completed within a few minutes. The method
uses no additional fuel and nitrate, which is present in the
precursor itself, to drive the reaction.
Addition of alkali to iron salt solutions and keeping the suspensions
for ageing. A large amount of nanoparticles can be synthesized.
Alkaline coprecipitation of Fe(III) and Fe(II) salts in aqueous media:
2Fe3+ + Fe2+ + 8OH2 A Fe3O4 + 4H2O
It is essential to adjust the stoichiometric ratio of Fe(II)/2Fe(III) at
the initial stage because it is difficult to control the oxidation
kinetics of Fe(II) afterward. Oxygen also plays an important role in
the formation of single phase magnetite; usually bubbling nitrogen
gas directly into the media prior to reaction is efficient enough for
removal of oxygen.
Anhydrous solution approaches for the production of metal oxide
nanoparticles and in particular iron oxide.

Decomposition of ironcontaining compounds


by ultrasonic treatment
The reduction of ironcontaining compounds

Use of strong sources of ultrasound. At very high temperatures,


hot spots generated by the rapid collapse of sonically generated
cavities, allows for the conversion of salts into nanoparticles.
Magnetic metallic nanoparticles can be prepared from metal salts
using strong reducing agents, namely, alkali metal dispersions in
ethers or hydrocarbons, alkali metal complexes with organic electron
acceptors (e.g., naphthalene), NaBH4 and other complex hydrides.

Biomimetic
mineralization

Bio-mimetic mineralization within protein cages provides an attractive


alternative approach for synthesizing monodisperse nanosized particles.
Since maximum particle sizes are limited by the cage inner diameter,
reactions carried out in cages can lead to highly monodisperse size
distributions, particularly if nucleation rather than growth is the
rate-limiting stage of the synthesis.
A microemulsion is defined as the thermodynamically stable
isotropic dispersion of two immiscible liquids, stabilized by a
monolayer of surfactant at the interface of the two liquids.
Synthesis of nanoparticles in nanosized reactors as the size
of nanoreactors can be controlled within certain limits. A
micelle is an example of these nanoreactors. Reverse micelles
are tiny drops of water stabilized in a hydrophobic liquid phase
due to the formation of a surfactant monolayer on their surface.

Synthesis in
reverse micelles

9330 | RSC Adv., 2012, 2, 93259358

c-Fe2O3 nanoparticles.

Nanodispersed Fe oxides from


[Fe(OtBu)3]2 precursor.
a-Fe nanoparticles from Fe(CO)5
as a precursor.
Growth of CNTs on Fe wires
from hydrocarbon precursor.

Maghemite c-Fe2O3 nanoparticles.

Iron oxide/iron (c-Fe2O3, a-Fe2O3,


Fe3O4 and Fe) coated carbons
(activated carbon, anthracite,
cellulose fiber) or silica.
FeOOH, Fe3O4 or c-Fe2O3.
Fe3O4

c-Fe2O3 nanoparticles (direct


oxidation of iron pentacarbonyl
in the presence of oleic acid with
trimethylamine oxide as an oxidant).
Iron nanoparticles from Fe(CO)5
as a precursor, Fe2O3 and Fe3O4
nanoparticles.
Using NaBH4 as a reductant, both
homo- (Fe, Co, Ni) and heterometallic
(FeCo, FeCu, CoCu) nanoparticles
are obtained as amorphous powders
containing substantial amounts of
boron (20 mass% or more).
Fe2O3 nanoparticles.

This journal is The Royal Society of Chemistry 2012

View Article Online


Table 2

(continued)

Microemulsion
technique

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

Solgel method and


forced hydrolysis
technique

Microemulsions may consist of oil-in-water or water-in-oil,


depending on the concentration of the different components.
By varying the concentration of the dispersed phase and the
surfactant, it is possible to tailor the size of the droplets in
the approximate range of 1100 nm.
Extremely versatile method since it allows the formation of
a large variety of metal oxides at relatively low temperatures
via the processing of metal salt or metal alkoxide precursors.

Surfactant mediated/
template synthesis

This technique uses neutral or charged template molecules.

Synthesis of magnetic
nanoparticles at a
gasliquid interface

Nanoparticles can also be synthesized in the absence of solid


substrates or matrices by redox reactions at an interface between
two phases, one containing a metal compound (precursor) and
the other, the reducing agent.
Iron pentacarbonyl is exposed to an UV-irradiation.

UV-irradiation
Hydrothermal
technique
Flow injection
Electrochemical
methods
Biosynthesis

Hydrothermal treatment of iron salt could generate iron oxides


when the applied conditions are appropriate.
The technique consists of continuous or segmented mixing of
reagents under laminar flow regime in a capillary reactor.
Electrons act as reactant. It is an environmental friendly
process with no pollution. However, the costly platinum is
used as an electrode and not for reuse in aqueous solution.
Biosynthesis of iron oxide nanoparticles with the help of
Fe(III)-reducing bacteria (Shewanella sps., Geobacter sps.,
Thermoanaerobacter ethanolicus etc.), SRB (Archaeoglobus
fulgidus, Desulfuromonas acetoxidans) and MTB
(Magnetospirillum magnetotacticum, M. gryphiswaldense),
are reliable, ecofriendly and economic at ambient
temperatures, pressures and neutral pH, that can be
used in environmental remediation.

a-FeOOH, magnetite nanoparticles.

a-FeOOH, c-FeOOH and Fe3O4


(prepared by forced hydrolysis technique).
Reduction of Ni2+ and Fe2+ ions
inserted in silica gel in 3 : 1 ratio
with hydrogen at 733923 K results
in Ni3Fe nanoparticles (419 nm)
within the SiO2 matrix.
a-Fe2O3 nanorods and nanotubes
(polyisobutylene bissuccinimide or
Span80 as surfactants).
c-Fe2O3 nanoparticles from Fe(CO)5
as a precursor.
c-Fe2O3 nanoparticles Fe(CO)5 as a
precursor.
Decomposition of a-FeOOH to a-Fe2O3.
Magnetite nanoparticles.
Maghemite or c-Fe2O3 nanoparticles.
Iron oxides.

Table 3 Methods for preparation of specific types of iron-containing nanoparticles151


Method
Description
Specific methods for the preparation of particular types of iron-containing nanoparticles
Heterometallic
As a rule, these particles are prepared by simultaneous thermal decomposition
nanoparticles
of two metal complexes of different compositions (hydrogen is used most
often as the reducing agent).
Ferrites
Magnetic
nanoparticles
with anisotropic
shapes

The key method for the preparation of powders of magnetic hexagonal ferrites
with a grain size of more than 1 mm includes heating of a mixture of the
starting compounds at temperature above 1000 uC (so-called ceramic method).
(1) Decomposition of metalloorganic compounds, in particular by ultrasound
in magnetic fields.
(2) The standard way of synthesis of nanothreads and nanowires composed
of anisotropic Fe and Co nanoparticles includes the electrolysis of solutions
of the metal salts at an aluminium cathode, which is pre-coated by an Al2O3
layer containing channels with a diameter of 1835 nm and a depth of up to
500 nm. During the electrolysis, these channels are filled by the reduced metal.
After completion of the process, the matrix is dissolved in a mixture of acids
to separate the nanoparticles.
3) Electric arc decomposition of Fe(CO)5 resulted in thread-like (10 to 100 nm
in diameter) compounds also consisting of a-Fe and Fe3C nanoparticles.

Methods for the synthesis of stoichiometrically inhomogeneous magnetic nanoparticles


Oxidation of
Oxidation of formed nanoparticles by oxygen-containing gas mixtures.
nanoparticles

Examples of products
Heterometallic nanoparticles, Fe48Pt52 and
Fe70Pt30, from Pt(acac)2 and Fe(CO)5.
FeCo nanoparticles from cobalt ferrite
CoFe2O4 nanoparticles or (g5-C5H5)
CoFe2(CO)9.
MnFe2O4 (40 nm), MgFe2O4 (618 nm),
Co0.2Zn0.8Fe2O4 (245 nm), BaFe1222xSnx
ZnxO19 (45 nm), SrFe12O19 (3080 nm).
Fe nanoparticles from Fe(CO)5 as a
precursor.

Iron oxide nanoparticles from Fe


nanoparticles (contact with air). Iron
passivation is possible. a- and c-Fe2O3
by oxidation of Fe12xCx nanoparticles.
Chemisorption of N2 on a-Fe surface.

The interaction of a-Fe nanoparticles with small CO, H2 and O2 molecules.


Chemisorption of these molecules on a nanoparticle surface induces only minor
changes in the parameters of the Mossbauer spectra. Studies of the reaction of
a-Fe nanoparticles with nitrogen showed that only the Fe atoms of the surface
layer participate in the chemical binding of nitrogen (the process starts at 300 K).
Targeted modification The immobilisation of biological molecules (amino acids, DNA, simple peptides, c-Fe2O3 nanoparticles containing
enzymes on the surface.
of the surface of
polysaccharides, lipids) on the surface of magnetic nanoparticles.
magnetic nanoparticles

Chemisorption of
small molecules
on a nanoparticle
surface

This journal is The Royal Society of Chemistry 2012

RSC Adv., 2012, 2, 93259358 | 9331

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online

Fig. 4 Schematic diagram for synthesis of iron


Reproduced with permission.

nanoparticles.

obtaining iron nanoparticles, poly(vinyl alcohol-co-vinyl acetatecoitaconic acid) is an example.42


2FeCl3+6NaBH4+18H2OA2Fe0+6NaCl+6B(OH)3+21H2 (4)
A patent43 describes a route to metal nanoparticles by thermal
decomposition of iron acetate Fe(OOCCH3)2, placed in a
reaction vessel with a passivating solvent such as a glycol ether.
The contents of the reaction vessel were mixed for a period of
time to form a substantially homogenous mixture. The contents
of the reaction vessel were then refluxed at a temperature above
the melting point of the iron acetate. The desired particle size was
achieved by controlling the concentration of metal salt in the
passivating solvent and by varying the amount of reflux time. As
an application of the pyrolysis technique, we would like to
mention obtaining iron nanoparticles embedded in a carbon
matrix from metal phthalocyanine,44 and carbon-encapsulated
Fe nanoparticles (size between 5 and 20 nm) via a picric aciddetonation-induced pyrolysis of ferrocene, which is characterized
by a self-heating and extremely fast process.45
There are also green techniques4650 for nanoparticle
synthesis. Among these methods, use of plant extracts and other
natural products as reductants and capping agents for NZVI and
various other Fe-containing nanoparticle preparation is interesting51 as well. For example, the use of herbal tea extracts to
reduce iron(III) chloride to iron nanoparticles (50 nm) has been
reported.52 This process as well as several others involving Ag
and Au salts employs the principle that the tea extracts (green
tea, chamomile tea, hibiscus tea and the normal table tea)
contain phenolic compounds that can act as reducing and
capping agents in their application. A similar green single-step
preparation of Fe nanoparticles using tea (Camellia sinensis)
polyphenols has been described.53 The expedient reaction
between polyphenols and ferric nitrate occurs within a few
minutes at room temperature and is indicated by color changes
from pale yellow to dark greenish/black in the formation of Fe
nanoparticles. The nanoparticles were utilized to catalyze H2O2
for treatment of organic contamination. In addition, nanoscale
zerovalent iron (NZVI) particles, prepared using tea polyphenols,54 were assessed with methyl tetrazolium (MTS, (3-(4,
5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium)) and lactate dehydrogenase (LDH)
toxicological assays, and some of them were found to be
nontoxic when compared with control samples prepared using
9332 | RSC Adv., 2012, 2, 93259358

the conventional borohydride reduction protocols. The authors


anticipated the development of various technological and
environmental remediation applications for these stable particles including dechlorination of dibenzo-P-dioxins, reduction of
chlorinated ethanes, arsenic and hexavalent chromium removal.
A variety of mainly physico-chemical methods have been used
for the synthesis of Fe-containing bi- and polymetallic alloys and
coreshell nanostructures. For example, high-entropy NdFe
CoNiMn alloy nanostructure films were synthesized55 by
electrodeposition at room temperature. It was shown that the
surfaces of the films, prepared at 22.2 V on Ti substrates for
5 min, were composed of great deal of close-grained and
homogeneous nanoparticles with size about 200 nm. The film
becomes more compact with a longer deposition time. The EDS
indicated that the five elements were co-deposited. Monodisperse
crystalline zerovalent Fe, FeNi, FePd nanowires were synthesized similarly.56 Prior to nanowire fabrication, alumina
nanotemplates with controlled pore structure (e.g. pore diameter
and porosity) were fabricated by anodizing high purity Al foil in
H2SO4. After fabrication of alumina nanotemplates, Fe, FeNi
and FePd nanowires were electrodeposited within the pore
structure. 200 nm-thick FePt nanocrystalline magnetic films
having planar texture were prepared using magnetron sputtering
and crystalline annealing in a magnetic field.57 The prepared
films were used to manufacture trial samples of magnetic
memory devices having open Kittel domain structure for
super-high density recording heads. For Fe3Pt, FePt and
FePt3, heat formation was determined.58 X-Ray diffraction,
magnetic measurements and Mossbauer spectroscopy were used
to study magnetic properties and hyperfine interaction parameters of nanocrystalline (,10 nm) and bulk bcc Fe, Fe90Ge10
and Fe77Al23 alloys.59 It was established that the nanocrystalline
state does not influence the formation of specific saturation
magnetization, Curie temperature, isomer shift and hyperfine
magnetic field. A slight increase (y20%) of the width of the
nanocrystalline iron Mossbauer spectral lines was observed.
Irongold alloys and coreshell nanoparticles
A special case, which should be discussed apart, corresponds to
coreshell nanoparticles on the basis of iron and its oxides with
gold due to the following justification. Finely divided iron has
long been known to be pyrophoric, which is major reason that
Fe nanoparticles have not been more fully studied.60 This
extreme reactivity has traditionally made Fe Nps difficult to
study and problematic for practical applications. However, iron
has a great deal to offer at the nanoscale, including very potent
magnetic, catalytic and medical applications, so methods for
reducing its reactivity with simultaneous retention of magnetic
and catalytic properties have been developed. Although pure
metal iron Nps are unstable in air, by coating the Nps surface
with a noble metal, the formed air-stable Nps are protected from
oxidation and retain most of the favorable magnetic properties,
which possess the potential for applications mentioned above, as
well as in high density memory devices by forming selfassembling nanoarrays.61
Gold is very promising coating for magnetic and other
particles to be functionalized for targeted drug delivery. This
metal (Au) as well as iron oxides Fe2O3 and Fe3O4, are
This journal is The Royal Society of Chemistry 2012

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online

biocompatible and suitable for human use. It is also possible to


track within human body, and can be functionalized with
organic and bioorganic molecules, such as proteins or enzymes.
At the same time, Nps of iron and its oxides possessing magnetic
properties can be delivered to an organ, tissue, or cancer tumor
by using an external magnetic field. So, the unique combination
of the nanoscale magnetic core and the functional shell makes
Fe-doped Au Nps ideal for biological and biomedical applications due to their conjugation chemistry, optical properties, and
surface chemistry.
During the last decade, considerable experimental efforts have
been dedicated to biomedical applications of coated magnetic
Nps, such as in magnetic resonance imaging contrast enhancement, tissue repair, immunoassay, detoxification of biological
fluids, hyperthermia, targeted drug delivery, and cell separation.
Results of the investigations in the area of gold-coated iron (iron
oxides) core Nps are detailed in a series of monographs,6268 as
well as in reviews69,70 and patents71,72 describing strategies for
the synthesis of these Nps, characterization of the core/shell
nanostructures, and exploration of potential applications of the
core/shell nanomaterials in terms of biological and catalytic
interfacial reactivities.
Types of Fe/Au Nps
Water-soluble Fe/Au alloy Nps (Fe/Au alloy Nps are solid
solutions where iron atoms substitute gold sites in the face center
cubic lattice) have been reported.73 The diameter of these alloy
Nps was 4.9 1.0 and 3.8 1.0 nm for two different precursors
of iron, ferrous sulfate heptahydrate and iron pentacarbonyl;74
while the estimated particle iron content was 14.8 4.7 mol%.
Formation of alloy nanostructure with a narrow distribution of
particle sizes and three compositions Au0.25Fe0.75, Au0.5Fe0.5 and
Au0.75Fe0.25 by a polyol process while retaining the optical and
magnetic properties of the individual components has been
discussed.75 Fe/Au Nps of L10 type (mean composition Fe-22
atom% Au) were fabricated by annealing Fe/Au particles.76 Aurich (.32 atom%) and Au-poor (,16 atom%) regions were
formed in most of particles.
The major part of publications has been devoted to Fe cores
coated with Au shells.7780 For instance, nanosized irongold
magnetic Nps with an average particle size 525 nm were
prepared by a reverse micelle method, which is the principal
technique in obtaining coreshell Nps, together with the polylol
technique and homogenous solution reduction, efficiently used in
many reports. The magnetic properties measurements confirmed
behavior typical of a superparamagnetic system.81,82 The XPS
studies of the coreshell Fe/Au Nps indicate that besides Fe0
inside the cores, small amounts of Fe(II,III), located onto the gold
surface, were also formed during the sample preparation. A
certain number of reports have mentioned pure iron core, for
instance Fe core/Au shell (11 nm Fe core, 2.5 nm Au shell)
without iron oxides.83
The general method for obtaining Fe core/Au shell Nps
consists of subsequent reduction of iron and Au salts by NaBH4
and other reductants in aqueous or organic media in the presence
of surfactants for preventing agglomeration of the resulting Nps.
In a series of reports, the characterized Nps were considered as
containing pure metallic iron as a core. However, it should be
This journal is The Royal Society of Chemistry 2012

especially emphasized that the authors of the communications


who applied Mossbauer and X-ray absorption (XAS) spectroscopy, together with SEM, TEM and other techniques, noted
that only the use of two additional methods mentioned above
can give complete information on the state of iron in the core.
Thus, gold passivated Fe Nps were prepared in a reverse micelle
of cetyltrimethylammonium bromide,84 and their studies by a
series of methods above, including Mossbauer spectral study
(57Fe), showed the presence of iron in the forms of a-Fe (major
part), unexpected Fe1-xBx alloy and several poorly crystallized
ordered Fe2O3 components, as well as residual paramagnetic
Fe(II) and Fe(III), indicating a more complex structure than had
been believed, although the powder X-ray diffraction of Fe/Au
Nps-containing samples revealed both the presence of crystalline
a-Fe and gold and the absence of any crystalline iron oxides or
other crystalline products. In another report,85 the oxidation
state of Fe in Fe/Au coreshell Nps was analyzed showing that,
in contrast to many previous reports assuming the metallic state
of iron in Fe/Au Nps obtained from reverse micelles, the iron
component was found to be fully oxidized, according to X-ray
absorption spectroscopy data (this method was considered as
an ideal tool for characterizing iron Nps).
Additionally to the above mentioned reverse micelle technique, other methods have also been well-developed for obtaining
Fe/Au Nps. Thus, Fe/Au Nps (8 nm) were prepared by
sequential high temperature decomposition of organometallic
compounds in a coordinating solvent and functionalized with
alkanethiolate ligands preventing aggregation, enabling solubility in a series of both hydrophilic and hydrophobic solvents and
allowing further derivatization via ligand exchange reactions.86
Fe/Au Nps, confirmed to be solid solutions, were electrodeposited on an amorphous carbon electrode in a three-compartment
glass-made electrochemical cell from aqueous electrolytes at
room temperature using 1 mM FeSO4 and HAuCl4 solutions as
precursors and CsClO4 as supporting electrolyte in Ar atmosphere.87 It has been reported that these Nps were homogeneously alloyed and the composition of the alloyed Nps was
dependent on the electrodepositing potential. In comparison
with similarly prepared Au/Ni and Au/Co Nps, the chain length
for Fe/Au Nps is lower: Fe/Au , Ni/Au , Co/Au (the largest
length was observed for pure Au Nps); this suggests that the
transition metals in the alloyed Nps may prohibit the agglomeration of the alloyed particles. Radiolytical reduction of mixed
AuIII/FeII ethylene glycol solutions led to two kinds of particles:
2 nm Fe rich Nps as well as large rods (a few tens of nm) and
faceted particles rich in gold and containing a small amount of
iron.88 The adjunction of iron to gold enhances remarkably its
electro-catalytic properties toward oxygen and proton reduction.
The authors noted that AuFe system is very promising for
application in fuel cells. Pulsed laser deposition of the FeAu
alloy (35% Fe) in a mesoporous alumina membrane template
allowed formation of strongly paramagnetic Fe/Au Nps (17%
Fe, 46 13 nm), which can be easily functionalized with
biological macromolecules.89
Current and proposed uses
Fe/Au Nps, in particular those supported onto HY- and NaYtype zeolites have been investigated for use as catalysts or
RSC Adv., 2012, 2, 93259358 | 9333

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online

cleaning surfaces.90 Thus, interactions of Au with Fe species,


introduced into the NaY zeolite by two methods (wet-impregnation and ion exchange), in Fe/Au-imp/NaY zeolite system
were studied.91 1%Au-0.5%Fe/HY sample, possessing high
activity in the CO oxidation, was prepared by coexchange in
HY zeolite using Fe(II) ethylenediamine and Au(III) ethylenediamine complex ions.92 Photoinduced sulfur desorption from
the surfaces of Au Nps loaded on a series on metal oxides, in
particular Fe2O3, was studied.93 Elemental sulfur S8 was
selectively adsorbed on the Au Nps surfaces of Au/metal oxides
in an atomic state. This phenomenon is applicable to the lowtemperature cleaning of sulfur-poisoned metal catalysts.
In addition to coreshell FexOy/Au Nps, Fe/Au Nps have also
been used in biomedicine. Thus, the method for synthesizing
antibody-magnetic Nps with gold shell and iron core for
recognition and separation of tumor cells was elaborated.94 Also,
their utility as T1 contrast agents in the unoxidized form,95
capturers for pathogens,96 carriers of streptavidin,97 etc, have been
reported. The 7 nm Fe/Au Nps (1.5% of Fe), obtained98 by
simultaneous reduction of Fe3+ and Au3+, can be easily conjugated
to thiolated DNA; moreover, and heated in solution to
temperatures above 40 uC, indicating suitability for hyperthermia.
Fe/Au Nps can serve as precursors for other Nps or
functionalized derivatives. Thus, 200350 nm C-encapsulated
magnetic Nps possessing surfaces with functional groups such as
OH were prepared by hydrothermal heating an aqueous glucose
solution of FeAu Nps at 160180 uC for 2 h.99,100 An
organometallic approach to the synthesis of CO-protected Fe/
Au Nps led to colloids with hydrodynamic diameters between 4
and 300 nm, from which [Au21{Fe(CO)4}10]52, [Au22
{Fe(CO)4}12]62, [Au28{Fe(CO)3}4{Fe(CO)4}10]82 and [Au34
{Fe(CO)3}6{Fe(CO)4}8]82 were isolated.101 Chemical oxidation
in solution of Au Nps, protected by octanethiol and 12(N-pyrrolyl)dodecanethiol, with FeCl3 leads to cross-linked Au
Nps with chainlike structures.102 The authors proposed that this
approach may also be applied for Fe/Au.

Coated and supported iron nanoparticles


Fe0 composite nanoparticles, coated with inorganic compounds
and minerals, are common and prepared by distinct techniques.
Thus, iron nanoparticles coated with boron nitride (BN)
nanomaterials were synthesized by using Fe4N and B powders
as raw materials.103 The Fe4N was reduced to a-Fe during
annealing at 1000 uC for several hours with flowing N2 gas.
NZVI/montmorillonite heterostructures were synthesized and
their textural evolution under different Fe loadings was
investigated.104 The hybridized Fe nanoparticles were well
dispersed on the montmorillonite surface, size adjustable, and
resistant to oxidation under the protection of native Fe-oxide
shells. It was revealed that as the Fe loadings increased, the total
pore and mesopore volumes remained almost unchanged but the
total, micropore and external surface areas as well as the
micropore volume decreased and the average pore diameter
increased. With increasing Fe loadings, the mesoporous character was enhanced for these heterostructures. Nanosized
composite magnetic particles MgO/Fe were in situ combustionsynthesized at 620 uC for the Mg-70.9 wt% Fe3O4 system.105 It
was identified that Mg (29.1 wt%) was the suitable reactant ratio,
9334 | RSC Adv., 2012, 2, 93259358

the sintered composite spherical particles with mean diameter


40 nm were distributed evenly, the particles had good soft
magnetic properties, and could serve in the future as drug carrier
materials. In addition, well-protected, isolated bcc-iron nanoparticles embedded in silicon dioxide were prepared by e-beam
evaporation and post-annealing of multilayers in an ultrahigh
vacuum system. The spherical shape and isolation of the particles
were confirmed by plan-view and cross-sectional transmission
electron microscopy.106 Similarly, an approach using a lowenergy electron beam radiation system was investigated to
synthesize carbon hybrid structures in amorphous carbon thin
films.107
Large-size 2D nano-TiO2 and iron-doped nano-TiO2 thin
films were prepared108 in a low-temperature aqueous system by
using a molecular self-assembly method. The photocatalytic
activity was evaluated with the degradation of methyl orange
solution under UV and visible light radiation. The doped iron
could obviously improve photocatalytic activity of TiO2. The
degradation data of methyl orange were respectively 98.62% and
89.24% under illumination by using UV lamp and visible light.
Fe-nano ZrO2 composite coating was prepared109 by adopting
iron electroplating technology, choosing nano ZrO2 as second
phase particle, and using asymmetrical ACDC electroplating. It
was indicated that this method can lead to compact coatings
(body-centered cubic a-Fe crystal structure) with small inner
stress. Al2O3 coated polyhedral Fe nanocapsules were prepared
by arc-discharging a FeAl (8 atom% Al) alloy.110 In addition,
mobilization and deposition of iron nano and sub-micrometer
particles (INSMP) in a porous medium were investigated using a
water-saturated glass micromodel.111 It was shown that there
were dense aggregations at the pores as the concentration of
INSMP increased. The presence of dissolved humic substances
(.1 ppm) significantly reduced deposition of suspended particles
and enhanced detachment of the deposited particles.
A host of reports are dedicated to carbon-supported ZVI
nanomaterials.112 Such encapsulation of iron nanoparticles in
protective carbon cages can lead to unique hybrid coreshell
nanomaterials.113 Thus, special carbon encapsulated Fe core
shell nanoparticles (1540 nm) with a size range of 1540 nm
were prepared via a confined arc plasma method.114 It was
shown that the carbon encapsulated Fe nanoparticles had clear
coreshell structure, the core (16 nm diameter) of the particles is
bcc-structure Fe, and the shell (thickness 68 nm) of the particles
is disordered carbon. The related arc discharge technique115 is
also common for production of nanomaterials, in particular for
iron. Thus, a simple, inexpensive and one-step synthesis method
of metal-containing carbon nanocapsules using an arc discharge
in aqueous solution is reported.116 It was found that Fe
nanoparticles could be in situ encapsulated in carbon shells
when the arc was performed respectively in aqueous solutions of
FeSO4. To explain the formation mechanism of metal-containing
carbon nanocapsules, a model of discharge in solution was
proposed. Iron nanoparticles, coated with graphite nanolayers,
were synthesized by annealing mixtures of hematite and carbon
under nitrogen atmosphere.117 Hematite was reduced to Fe3O4,
FeO, and finally to Fe completely at 1200 uC. High-resolution
electron micrographs reveal that the Fe particles are ~200 nm in
diameter and coated with graphite nanolayers of ~30 nm.
Combustion synthesis of iron oxide/iron coated carbons such as
This journal is The Royal Society of Chemistry 2012

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online

activated carbon, anthracite, cellulose fiber and silica using a


Panasonic kitchen microwave with inverter technology was
described.118 The size of the iron oxide/iron nanoparticle-coated
activated carbon, anthracite, cellulose fiber and silica samples
were found to be in the nano range (50400 nm). Iron oxide/iron
nano particles existed in four major phases: c-Fe2O3, a-Fe2O3,
Fe3O4 and Fe, some of which showed significant arsenic
adsorption. In addition, carbon-coated iron nanoparticles with
well-developed quasi-spherical shape were prepared with
Fe(NO3)3?9H2O and starch as carbon source (Fig. 5).119,120
This is an efficient approach for the mass production of
nanocage structures under mild conditions, which needs to be
further explored for preparing various carbon coated metal
nanomaterials. Radiation methods are being applied more
widely in the last decade, in particular for iron carbon-supported
nanostructures fabrication. Thus, two types of amorphous
carbon films, a 15 atom% iron containing film and with
column/inter-column structures, were deposited onto Si substrates by a sputtering technique and subsequently exposed to an
electron shower of which the energy and dose rate were much
smaller compared to an intense electron beam used in transmission electron microscopy. Graphitic structures were formed in an
amorphous matrix at a relatively low temperature up to 450 K. It
was found that the graphitization progressed more in the
electron irradiation than in annealing at 773 K, and it was
attributed to thermal and catalytic effects which are strongly
related to grain growth of metal clusters.
Significant attention is paid to ferrocene as a metal precursor
for carbon-supported nanoparticle synthesis121 and the resulting
carbon support can exist in distinct forms. For example, carbon
nanotubes containing iron nanoparticles were fabricated using
microwave heating.122,123 Carbon-encapsulated iron nanoparticles with uniform diameters were synthesized on a large scale by
co-carbonization of an aromatic heavy oil and ferrocene at
480 uC under autogenous pressure (Fig. 6).124 It was found that,
by increasing the amount of ferrocene added from 2 to 45 wt%,
the size of the nanoparticles increased from 15 to 50 nm and the
morphologies of the resulting products changed from sphericaltype to iron-filled carbon nanorods when the ferrocene loading

Fig. 6 HREM images of carbon-encapsulated iron nanomaterials


obtained at 480 uC in the presence of ferrocene contents of 13.0 wt%
[(a) and (b)] and 40.0 wt% (c). Reproduced with permission.

was higher than 30 wt%. The iron particles pyrolyzed from


ferrocene existed mainly in the form of a-Fe and small amounts
of Fe3C were also formed when the ferrocene content was higher
than 20 wt%.
Ferric alginate fibers were prepared by wet spinning of sodium
alginate into a coagulating bath containing ferric chloride.125
Carbon-supported nanoscale zerovalent iron fibers (CSNZVIF,
with high surface areas of 352 m2 g21) were obtained through
thermal degradation of ferric alginate fibers at 900 uC under an
N2 atmosphere. It was found that zerovalent iron particles were
well dispersed in the amorphous carbon fibers. The authors
stated that the existence of carboxylic and hydroxyl groups in the
ferric alginate structure unit play a key role in the formation of
carbon-supported nanoscale zerovalent iron fibers. Fe3+ was
reduced to Fe0 by hydroxyl group and as-formed amorphous
carbon during heating under N2.
Polymer-supported Fe nanoparticles are also widespread.
Thus, the procedure developed to produce polymer-supported
nano Fe metal particles involved thermal decomposition of
Fe(CO)5 in the presence of a monomer (styrene) (reaction (5),
which can be better described as a combination of reactions (6)
and (7)) that was allowed to concurrently polymerize.126
nH2C=C(H)Ph+Fe(CO)5 A(CH2CH(Ph))n+5CO+Fe0 (5)

Fig. 5 HRTEM of carbon-encapsulated iron nanoparticles from starch


(scale bar 10 nm) and inset corresponding electron diffraction pattern
taken from iron core regions. Reproduced with permission.

This journal is The Royal Society of Chemistry 2012

Fe(CO)5 A Fe + 5CO

(6)

nH2C=C(H)Ph + Fe A Fe(CH2CH(Ph))n

(7)

RSC Adv., 2012, 2, 93259358 | 9335

View Article Online

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

The effect of pH on the aggregation of polymer-coated NZVI


and its deposition onto sand and clay (kaolinite) surfaces was
studied.127 NZVI coatings included a high molecular weight
(90 kg mol21) strong polyanion, poly(methylacrylic acid)-b(methyl methacrylate)-b-(styrenesulfonate) (PMAA-PMMAPSS) and a low molecular weight (2.5 kg mol21) weak polyanion,
polyaspartate. Enhanced deposition at lower pH was indicated
because the elutability of polyaspartate-modified hematite
(which did not aggregate) also decreased at lower pH. The
greater deposition onto clay minerals compared to similar sized
fine silica is attributed to charge heterogeneity on clay mineral
surfaces, which is sensitive to pH.

Nano-Fe2O3 phases and their composites


Distinct iron oxide nanostructures and composites based upon
them have been prepared by a variety of conventional
techniques. Thus, iron oxide nanowires were grown by resistive
heating of iron wire (with a diameter of 0.25 mm) under ambient
laboratory conditions.128 The synthesis can be easily controlled
by observing the color of the wire and by varying the applied
heating power. The wire was completely covered by nanowires,
having a sword-like shape, i.e., they are belt-like structures,
which are thicker at the base and thinner at the end. Maghemite
(c-Fe2O3) nanoparticles were fabricated by microwave heating of
(acetylacetonato)iron(III) precursor.129 This precursor is very
easy to make, and there is no need for controlling the reaction
conditions and heat treatments. Upon irradiation by microwaves
it decomposes to maghemite nanoparticles. The b-Fe2O3 cubic
phase, one of the least studied FeO systems, was obtained by
CVD method using a Fe(II) b-diketonate diamine complex,
Fe(hfa)2TMEDA, as the molecular source (hfa = 1,1,1,5,5,5hexafluoro-2,4-pentanedionate,
TMEDA
=
N,N,N9,N9tetramethylethylenediamine).130 Also, a Fe(II) 1D coordination
polymer, [Fe(pyterpy)2](SCN)2?MeOH (pyterpy = 49-(4-pyridyl)2,29:69,29-terpyridine), was synthesized by using a branched tube
and used as a precursor to fabricate Fe(III) oxide nanoparticles131 by its thermolysis in oleic acid (surfactant) at 286 uC in
air. Magnetic iron oxide nanopowders were synthesized electrochemically,132 using a low-carbon steel electrode immersed in a
NaCl aqueous solution, at constant temperature of the electrolyte, pH and current density. In the second step, portions of the
starting admixture were boiled at y360 K during 2 h and
autoclaved at various temperatures. In addition, nanostructured
iron oxide/hydroxide materials were synthesized by solgel
technology, starting from the ternary system Fe(NO3)3?9H2O
ethanolpropylene oxide.133 The produced materials were
composed by aggregates of nanometric crystallites: y1 nm for
xerogels and y5 nm for aerogels. Their high porosity and
surface area (xerogels y50% and 150 m2 g21; aerogels y90%
and 400 m2 g21) make them suitable for surface-dependent
processes, with the aerogels far superior. It was shown that the
2-line ferrihydrite is their most probable constituent phase.
As well as in case of Fe0-containing nanomaterials (see above),
radiation methods have been applied for the generation of oxides
and composites. Thus, to prepare nanocrystalline iron(III) oxide
at room temperature and ambient pressure without using any
kind of catalysts, a 2 MeV 10 mA GJ-2-11 electronic accelerator
was used as the radiation source.134 The optimal conditions were
9336 | RSC Adv., 2012, 2, 93259358

pH of the solution = 6.54 and a 300 kGy radiation dose. It was


shown that the a-Fe2O3 particles had hexagonal structures,
spherical shape morphology and good dispersity, and average
diameter of y3060 nm. Alternatively, Fe2O3 was fabricated135
from metallic iron under electron beam irradiation and further
reaction with oxygen. Iron oxide nanowires were rapidly
synthesized in large quantities at room temperature by pulsedlaser ablation (248 nm) of iron powder under methanol.136 At
high collection rates, a lamellate nanobelt morphology was
observed, whereas at low collection rates nanowires dominated.
The as-synthesized products had the stoichiometry of the
goethite [FeO(OH)] phase (proposal formation reactions are
shown by reactions (8) and (9)) which after annealing at
temperatures above 400 uC crystallizes into hematite (a-Fe2O3).
2Fe + 12CH3OHA 6C2H5OH + 2Fe(OH)3 + 3H2

(8)

Fe(OH)3 AFeO(OH) + H2O

(9)

Composite nanoparticles consisting of gold and iron oxide were


synthesized in aqueous solution systems by using a high-energy
electron beam.137 The electron irradiation induced radiationchemical reaction to form metallic gold nanoparticles (reaction
mechanism is shown by eqns (10)(14)), which were firmly
immobilized on the surface of the support iron oxide nanoparticles. The size of these gold nanoparticles depended on the
concentrations of gold ions, polymers and iron oxide nanoparticles in the solutions before the irradiation. Many other examples
of coreshell iron oxide/gold nanoparticles were reviewed,138
where many possible synthetic techniques for coreshell structures
on the basis of iron or its oxides with gold have been discussed.
Among them, we emphasize that, additionally to the mostly
represented standard iron oxide core/gold shell Nps, some
reports concerned interesting unexpected nanostructures. Thus,
iron oxide coated gold nanorods were prepared (Fig. 7) starting
from gold nanorods, synthesized by a three-step seed mediated
protocol and coated with a layer of poly(sodium 4-styrenesulfonate).139 Here, on the contrary, the gold metal acts as a core and
the iron oxide as a shell. The negatively charged polymer on the
nanorod surface electrostatically attracted a mixture of aqueous
Fe(II) and Fe(III) ions. Coprecipitation of these iron salts was used
to form uniform coatings of iron oxide Nps on the surface of the
gold nanorods. The oxidation state of iron in the iron oxide
coatings was determined and was consistent with Fe2O3 rather
than Fe3O4. Multifunctional Fe3O4/polymer/Au shell Nps140 with
preserved strong magnetization and good NIR absorption display
good dispersibility and stability in aqueous solution. The authors
supposed that these features should facilitate biomedical applications, combining the benefits of MRI diagnosis, magnetically
targeted delivery and photothermal ablation.
H2O (c-rays or e-beam) A e2aq, H?, OH?, etc.

(10)

(CH3)2CHOH + OH? A (CH3)2?COH + H2O

(11)

(CH3)2?CHOH + H? A (CH3)2?COH + H2

(12)

e2aq + Mn+ A M(n21)+

(13)

(CH3)2?COH + Mn+ A (CH3)2CO + M(n21)+ + H+ (14)


This journal is The Royal Society of Chemistry 2012

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online

Fig. 7 General protocol used to prepare in situ iron oxide coated gold nanorods. Reproduced with permission from ACS (Journal of Electron
Microscopy; jmicro.oxfordjournals.org).

Zeolite and related supporting materials serve as an ideal basis


for iron oxide composites. Thus, the loading of zeolite with
nano-iron oxide (Fig. 8) by a simple chemical route has been
described.141 The average crystallite sizes of the doped nanomaterials were 46 nm. It was revealed that zeolite acquire magnetic
properties after doping with nano-iron oxide. Mesoporous iron
oxide silicate nanocomposites Fe2O3-SBA-15 (SBA-15 is hexagonally ordered mesoporous silica) with iron loadings in the
range of 1.235.8 wt% were synthesized by a direct hydrothermal
method.142 It was shown that these mesoporous nanocomposites
with well-dispersed nanoclusters of iron oxide in the walls of
ordered mesoporous silica structures and high surface area were
attained under the condition of adjustment of Fe/Si molar ratios
and appropriate Fe loadings.

Fe3O4 and other iron-containing nanomaterials


A certain number of composite nanomaterials based on Fe3O4
is known, for instance core/shell Fe3O4 coated gold nanoparticles (diameter 50100 nm).143 Their possible formation

Fig. 8 Loading of iron oxide nanoparticles by zeolite. Reproduced with


permission.

This journal is The Royal Society of Chemistry 2012

mechanism was proposed as follows: pH-sensitive polymer


owing to a shrunken or stretched structure of polyethyleneimine
(PEI), led to the aggregation of Fe3O4gold seed nanoparticles,
then gold reduces onto the surface of Fe3O4gold seed
nanoparticles. It was concluded that these core/shell multifunction nanomaterials will not only have external magnetic
separation by the core of Fe3O4, but also detect large biological
molecules using the shell of gold. In addition, iron phthalocyanine prepolymer/Fe3O4 nano hybrid magnetic material144 can
be applied as high temperature-resistant polymer magnetic
composite material.
Use of Greener methods superparamagnetic Fe3O4 nanoparticles (blocking temperature (TB) of 150 K and saturation
magnetization of 37.1 emu g21) have been synthesized via soya
bean sprouts (SBS) templates at room temperature and at
normal atmospheric pressure.145 Spherical Fe3O4 nanoparticles
with an average diameter of 8 nm simultaneously formed on the
epidermal surface and the interior stem wall of SBS, which were
responsible for size and morphological control during the whole
formation of nanoparticles. In a related report,146 similar Fe3O4
superparamagnetic nanoparticles (12.5 nm, inverse spinel structure) were prepared using a-D-glucose as the reducing agent and
gluconic acid (a product of glucose oxidation) as the stabilizer
and dispersant. In this case, the TB was found to be higher
(190 K) and the magnetic hysteresis loop at 300 K showed a
saturation magnetization of 60.5 emu g21.
Among other iron-containing nanomaterials, we note carbon
encapsulated iron carbide nanoparticles (540 nm) were synthesized from ferrocene in a quite narrow temperature range (about
600800 uC) under high (4 GPa) static pressure.147 The material
produced under optimum parameters consists of round carbide
particles covered with onion-like carbon shells that are
embedded into the carbon matrix. In the presence of an excess
of carbon a solid-state Fe3C A Fe7C3 transformation is possible
in nanoparticles under high (13 GPa) pressure and temperature
(1200 uC). Other examples of Fe-containing nanomaterials are
shown in Table 2.
RSC Adv., 2012, 2, 93259358 | 9337

View Article Online

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

Remediation of groundwater using iron-based


nanomaterials
Research over the past two decades has demonstrated the
efficiency of Fe for the removal of a wide range of chemical and
microbial contaminants (e.g. bacteria, chlorinated organics,
dyes, emerging contaminants, heavy metals, radionuclides,
viruses) from water.152 The prevailing concept considers that
the mechanism of Fe0 remediation varies depending on the
contaminant of interest. This concept was recently revisited and
Fe was proven as a universal material for water treatment.
The following methods are currently considered as conventional treatment technologies for water treatment:153 (a) filtration (using ceramic or biosand filters, charcoal and activated
carbon filters, granular media and rapid rate filters, fiber and
fabric filters), (b) heat and UV-radiation, (c) chemical treatment
(coagulationflocculation, chemical disinfection and flocculant
disinfection), desalination and arsenic removal (reverse osmosis,
distillation, adsorptive filter media for arsenic removal). The
nanotechnology-based water treatment technologies include: (a)
carbon nanotube-based technologies (CNTs membranes, nanomesh), (b) other nanofiltration approaches (nanofiltration
membranes and devices, nanofibrous alumina filters and
nanofiber gravity-flow devices), (c) nanoporous ceramics, clays
and other adsorbents, (d) zeolites, (e) nanocatalyst-based
technologies (nanostructured ZVI, TiO2 and iron oxide adsorbents) and (f) magnetic nanoparticles (magnetoferritin and ZVI).
Starting from the 1990s, inorganic nanoparticles,154 in
particular NZVI and iron oxides have been used for elimination
of certain inorganic and organic substances from groundwater,155 sediments and soils, despite that the NZVI utility in
full-scale remediation projects is limited by material costs. ZVI
nanoparticles react with a wide range of contaminants, and the
effect of particle size on the reactivity of NZVI is as important as
other effects such as particle composition, contaminant structure
and solution chemistry. It has been established that NZVI is very
effective, covering the broadest range of environmental contaminants. Common environmental contaminants (Tables 46)
that can be transformed by nanoscale iron particles are as
follows:156 (a) chlorinated methanes (CHnCl42n), (b) chlorinated
benzenes (C6HnCl62n), (c) pesticides (DDT, lindane), (d) organic
dyes (Orange II, Chrysoidine, Tropaeolin O, Acid Orange, Acid
Red), (e) heavy metal ions (Hg2+, Ni2+, Ag+, Cd2+), (f)
trihalomethanes (CHBr3, CHBr2Cl, CHBrCl2), (g) chlorinated
ethenes (C2Cl4), C2HCl3, cis- or trans-C2H2Cl2, 1,1-dichloroethene C2H2Cl2, vinyl chloride), (h) other polychlorinated
hydrocarbons (PCBs, for example hexachlorocyclohexanes157),
dioxines, pentachlorophenol (C6HCl5O), (i) other organic contaminants (N-nitrosodimethylamine (NDMA) (C4H10N2O),
TNT (C7H5N3O6) and dinitrotoluene,158 (j) inorganic anions
(Cr2O722, AsO432, ClO42, NO32, SeO422), (k) also removing
dissolved metals from solution, e.g. Pb,2+ Ag+ and Ni2+. It may
also be able to reduce radionuclides.
Nanoscale zerovalent iron (NZVI) is used for both in situ and
ex situ treatment of contaminated groundwater. It functions
simultaneously as an adsorbent and a reducing agent, causing
organic contaminants to break down into less toxic simple
carbon compounds and heavy metals to agglomerate and stick to
the soil surface. NZVI can be injected directly into the source of
9338 | RSC Adv., 2012, 2, 93259358

contaminated groundwater as slurry for in situ treatment, or it


can be used in membranes for ex situ applications. Bimetallic
NZVI, in which the iron nanoparticles are coated with a second
metal such as palladium to further increase the reactivity of the
iron, is also available. NZVI is more reactive and has a large
surface area than granular ZVI.
Among many important investigations in this area, we note
recent contributions of Tratnyek et al.159168 In relation to
chlorohydrocarbons, the mechanism of reactivity for ZVI is
similar to the mechanism of corrosion (i.e., oxidation of iron)
and involves the generation of electrons which in turn reduces
the organic species through dechlorination (reaction (15)):
Fe0 + RCl + H+ A Fe2+ + RH + Cl2

(15)

Similarly, ZVI acts as a reducing agent for sequestration of


metal ions having reduction potential higher than Fe. The
chemistry can be understood by an example of interaction of
Ni2+ with ZVI (Fig. 9). In the beginning of the reaction, Ni2+ is
physically adsorbed (outer sphere interaction) and then is
chemisorbed (inner sphere interaction) and finally reduced to
metallic nickel. Similar chemistry has been applied for sequestration of many metal ions and metalloids: Pb, Cd, Cr, Co, Cu,
Hg, Ni and Se.
There is an ambiguity regarding the relationship between
NZVI and conventional (micron- to millimeter-sized) ZVI.169
NZVI exhibits unique properties like those of some other
nanostructured materials, when the behavior of NZVI under
environmental remediation conditions is, in fact, not very much
different than conventional ZVI. It was shown that: (a) the
NZVI used in groundwater remediation that are much larger
than particles that exhibit true nanosize effects, (b) the higher
reactivity of this NZVI is mainly due to its high specific surface
area, (c) one factor that limits the intrinsic reactivity of NZVI is
the high degree of passivation by enveloping oxides, and (d) the
mobility of NZVI is less than a few meters under almost all
relevant conditions.
NZVI and iron oxide magnetic nanoparticles have also been
chosen171 as promising adsorbents for the removal of (in)organic
contaminants from polluted water, because: (a) they can be
produced in large quantities using physicochemical methods, (b)
it is expected that their adsorption capacity and affinity for
pollutants is higher considering the larger surface area and
possibly highly active surface sites, (c) the separation of metalloaded magnetic nano-adsorbent from treated water can be
achieved via an external magnetic field, and (d) nanoparticles
might be regenerated and reused. Also, iron oxide nanoparticles
can be surface-coated with organic compounds to increase their
sorption efficiency and specificity for pollutants. In this case, it is
worth noting that the covalent attachment of molecules to the
surface of nanoparticles and the stability of the coating are
important. Some adsorption processes for wastewater treatment
have utilized ferrites and a variety of iron containing minerals,
such as akaganeite, feroxyhyte, ferrihydrite, goethite, hematite,
lepidocrocite, maghemite and magnetite.172 Adsorption of
organics to the nanoparticle media was extremely rapid. More
than 90% of the organics were adsorbed within 30 min. The
isotherm studies indicated that, on a surface area basis,
the adsorption capacities of the nanoparticle media were
This journal is The Royal Society of Chemistry 2012

View Article Online

Table 4 Examples of pollutant remediation using NZVI

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

System
NZVI

Ion/substance to
be eliminated
Cr(VI)

NZVI (size
30400 nm)
NZVI

Heavy metals
(Cd, Cr, Hg)
Cd(II)

NZVI

Chlorinated organic
contaminants (e.g.,
solvents, pesticides)
and inorganic anions
or metals.
Orange 6

NZVI (10 mm
particles)
NZVI
NZVI

Pyrene

NZVI

Lindane (classified by
the United States
Environment Protection
Agency as a potent
carcinogen and teratogen).
Malodorous sulfides

NZVI

Xanthan

NZVI (40 nm)

Arsenite [As(III)]

NZVI

Chlorinated ethenes

NZVI

Hexahydro-1,3,
5-trinitro-1,3,
5-triazine (RDX)

NZVI

Anions (NO32, Cl2,


SO422, HCO32)
and natural organic
matter (NOM).

NZVI, Fe/Ni
or Fe3O4

Uranium ions.

NZVI

Vinyl chloride (VC)

Description

Ref.

0.10 g L21 NZVI completely reduces Cr(VI) within 120 min following pseudo-first order
kinetics. NZVI showed significant Cr(VI) reduction at field also, indicating it an effective
tool for managing sites contaminated with Cr(VI).
Reduction of heavy metals in the heavy metal-polluted soil into lower valent fixed heavy
metals.
The adsorption of Cd2+ on NZVI increased significantly with increasing pH. Zn2+, Co2+
and Mg2+ are potential inhibitors to Cd2+ adsorption by NZVI.
Use of NZVI for remediation of a series of substances.

219

222

98% of the dye can be degraded within 30 min of contact.

223

NZVI particles were found to be more efficient in removing pyrene than commercially
available microscale ZVI (MZVI, ,10 mm) particles.
Lindane (10 m/g) completely disappeared from spiked soil within 24 h at nZVI
concentration of 1.6 g L21, indicating its possible use in environmental cleanup.

224

NZVI has high capacity for the removal and sequestration of malodorous sulfides
such as hydrogen sulfide and dimethyl disulfide. The coreshell structure of iron
nanoparticles plays a key role during the reactions. Both iron in the core and
FeOOH in the shell provide rich surface sites for the sorption of sulfides, while
the surface associated sulfide can further react with hydrogen sulfide and evolve
to iron polysulfide.
The rheological properties of NZVI-xanthan suspensions were extensively tested
under two different flow conditions (simple shear flow and flow through a porous
medium), showing a shear thinning behavior that is dependent on iron concentration.
NZVI demonstrated very rapid adsorption and large capacity for the removal of
As(III). The maximum As(III) adsorption capacity in batch experiments calculated
by Langmuir adsorption isotherm was 76.3 mg L21 of As(III)/g of NZVI.
The concentration of chlorinated ethenes decreased by 3050%. The oxidizing iron
reduces chlorinated hydrocarbons and forms non-chlorinated hydrocarbons. Organic
matter in water is thus reduced and treated water is safe for living organisms without
health danger.
RDX is a common contaminant of soil and water at military facilities. Its degradation
with NZVI nanoparticles in water in the presence or absence of a stabilizer additive
such as CM-cellulose (CMC) or poly(acrylic acid) (PAA) was studied, showing that
the degraded RDX to the corresponding nitroso derivatives prior to completed
decomposition.
More than 95% of 1.8 mM TCE was removed within 20 h with a NZVI dosage of
25 g L21 (k = 0.15 h21). TCE degradation reactions were not substantially affected by
the presence of each anion with concentrations as high as 100 times the average field
concentrations. However, when four anions (NO32, Cl2, SO422, HCO32) were present
simultaneously, the degradation reactivity was decreased by 60% (k = 0.069 h21).
The Fe nanoparticles removed 98% of the total uranium from solution, resulting in a
final U-concentration of ,4 mg L21. In all the systems, uranium was reduced to U(IV)
and retained on the surfaces of the nanoparticulate solids for up to 48 h; the U-stability
was not affected by annealing the Fe or the FeNi nanoparticles before use.
The degradation efficiency of vinyl chloride (VC) detected at most of monitoring
wells was 5099%.

226

significantly (.2 fold) higher than the ferric oxide media


typically used in water treatment.
Remediation of metal ions
NZVI (2080 nm), obtained using the borohydride reduction
method, was examined for aqueous Co2+ removal over a wide
concentration range, 11000 mg L21.173 Fe nanoparticles
demonstrated very rapid uptake and large removal capacity for
Co2+. It was indicated that Co2+ fixation occurred by the
interaction of cobalt ions with oxohydroxyl groups on Fe
nanoparticle surfaces as well as spontaneous precipitation
formation at high loads. The sorption properties of Zn(II),
This journal is The Royal Society of Chemistry 2012

220
221

225

227
228
229

230

231

232, 233

234

Cu(II), Cd(II) and Pb(II) to nanohematite in single- and binaryadsorbate systems were investigated.174 It was indicated that the
presence of a secondary metal can affect the sorption process
depending upon the molar ratios, such as increased or reduced
adsorption. Also, Pb and Cu adsorption to nanohematite is an
endothermic, and a physical adsorption process; however, it is
only spontaneous at higher temperatures.
Remediation of inorganic anions
The elimination of nitrates175 and arsenic-containing anions is
the main application of the NZVI in respect to inorganic matter;
a host of reports are dedicated to this area. Thus, the NZVI in
RSC Adv., 2012, 2, 93259358 | 9339

View Article Online

Table 5 Examples of pollutant remediation using supported and alloyed NZVI

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

System
Ion/substance to be eliminated
Fe0/M nanoparticles and their composites with supports
Pd/Fe and Fe (NZVI
Water disinfection byproducts;
and MZVI
trihalomethanes (THMs) including
(microscale ZVI))
chloroform, bromoform,
dichlorobromomethane,
dibromomethane and
dibromochloromethane
Pd/Fe
Pentachlorophenol (PCP)

FePd nanoparticle
suspensions in water
the presence of various
stabilizers (i.e., CMcellulose (CMC),
polyvinylpyrrolidone
(PVP) and guar gum).
NZVI, bimetallic
nanoparticles (NZVI/Pd),
and NZVI/Pd impregnated
activated carbon
(NZVI/Pd-AC)
composite particles

Trichloroethylene

Fe/Cu (Cu amended


zerovalent iron
bimetallic nanoparticles),
supported in activated
carbon (AC).

c-HCH
(c-hexachlorocyclohexane)

FexNi12x nanostructures
(0 , x , 1.0)

1,1,1,2-Tetrachloroethane

Na CM-cellulose
(CMC)-stabilized
Pd/Fe nanoparticles

2,4-Dichlorophenoxyacetic
acid (2,4-D),
2-chlorophenoxyacetic
acid (2-CPA)

Fecarbon composites
FeC nanocomposites,
in particular Fe NPs
on the external surface
of carbon microspheres
(synthesis see Fig. 10)

Polybrominated
di-Ph ethers
(PBDEs) and/or
polychlorinated
biphenyls (PCBs).

Chlorinated hydrocarbons

9340 | RSC Adv., 2012, 2, 93259358

Description

Ref.

Complete dehalogenation of THMs by nanoscale Pd/Fe particles


was achieved in less than one hour. Methane, accounting for
6090% of the THMs lost, was the major product. Nanoscale
Pd/Fe particles lasted over 700 h without exhausting their
ability to dehalogenate THMs in a closed batch system.

235

Degradation of PCP by Pd/Fe nanoparticles was carried out in


aqueous solutions containing different cations in sulfate form,
Na2SO4, CuSO4, NiSO4 and Fe2(SO4)3, respectively. The
observed inhibitory effect of Na2SO4 on degradation of PCP
was contributed to the existence of SO422. Overcoming the
inhibitory effect of SO422, Cu2+, Ni2+ and Fe3+ could facilitate
the degradation kinetics and efficiencies of PCP by Pd/Fe
nanoparticles. The enhancement effect of Cu2+ and Ni2+
result from the presence of reduced forms of Cu and Ni
on Pd/Fe surfaces.
A dramatic improvement in FePd suspension stability
was observed when the stabilizer is present in the matrix
during the nanoparticle synthesis step. In case of guar gum,
gelation during synthesis significantly increased suspension
viscosity, enhancing suspension stability.

236

Compared to NZVI, the Fe-normalized rate constants for


NZVI/Pd were about 2-, 3- and 4-orders of magnitude
greater for tri-, di- and mono-BDEs, respectively, with
di-Ph ether as a main reaction product. Pd mainly deposits
on the outer part of particles, while Fe was present
throughout the AC particles. It was suggested that y7%
of the total Fe within the AC was zerovalent, which shows
the difficulty with in situ synthesis of a significant fraction
of zerovalent Fe in the microporous material.
Cu amended zerovalent iron bimetallic nanoparticles were
synthesized by doping Cu on the surface of iron and
incorporated with granular activated carbon to prepare
supported particles (ACFe0Cu), which were used to
remove c-HCH. Cu on the surface of iron enhanced the
dechlorination activity of Fe0. The dechlorination rate
constant increased with the Cu loading on the surface of
iron and the maximum was achieved with 6.073% Cu.
AC could adsorb the degradation products.
Fe1.0, Fe0.71Ni0.29 and Fe0.55Ni0.45 exhibited reactivity
toward 1,1,1,2-tetrachloroethane, with Fe1.0 yielding
the greatest rate of reductive dechlorination.
Considerable enhancements in particle stability and
chemical reactivity with the addition of CMC to Pd/Fe
nanoparticles were established. CMC-stabilized Pd/Fe
nanoparticles (0.6 g Fe L21) were able to remove much
higher levels of 2,4-D with only one intermediate
2-chlorophenoxyacetic acid (2-CPA) and the final
organic product phenoxyacetic acid (PA), than
non-stabilized Pd/Fe nanoparticles or microsized
Pd/Fe particles.

238

Spherical FeC nanocomposites were synthesized through


a facile aerosol-based process and a subsequent
carbothermal reduction. The distribution and
immobilization of Fe particles throughout the C
microspheres prevents nano-Fe aggregation, allowing
the maintenance of particle reactivity. The carbon
microspheres allow adsorption of trichloroethylene
(TCE), thus removing dissolved TCE rapidly and
facilitating reaction by increasing the local
concentration of TCE in the vicinity of Fe
particles (Fig. 11).

237

239

240
241

242244

This journal is The Royal Society of Chemistry 2012

View Article Online

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

Table 5

(continued)

Carbon-coated Fe
nanoparticles

Cr(VI)

Poly(acrylic acid)/poly
(vinyl alcohol)/multiwalled
carbon nanotube
(MWCNT) composite

Dyes of acid fuchsine,


acridine orange, and
methyl blue.

Encapsulated and supported NZVI


NZVI particles
Trichloroethylene
(1090 nm) were
encapsulated in
biodegradable
calcium-alginate
capsules
NZVI/chitosan
Cr(VI)
(CS) composite

NZVI/CTMABent composite
(CTMA-Bent =
organobentonite)

Atrazine

NZVI supported
on montmorillonite
(Mont) and hexadecyl
trimethylammonium
modified
montmorillonite
(HDTMA-Mont)

Cr(VI)

NZVI-kaolinite
composite (K-NZVI)

Pb2+

ZVI/TiO2 nanocomposite
(+UV light)

Phenol and CCl4

Fe0silica composites
Fe0 nanoparticles
(20110 nm diameter)
supported on silica
fume (SFFe0)

Nanoscale zerovalent
iron entrapped in
porous silica particles.

Cr(VI)

Trichloroethylene
(TCE).

This journal is The Royal Society of Chemistry 2012

Ferromagnetic carbon-coated Fe nanoparticles


(core size of 15 nm) demonstrate strong ability to
effectively remove more than 95 wt% of Cr(VI) in
wastewater via carbon shell physical adsorption,
which is much higher than the commercial available
Fe NPs.
The produced composite nanofibrous mats exhibited
a superior capability to decolorize the dyes of acid
fuchsine, acridine orange and methyl blue, which are
model dyes in wastewater of the printing and dyeing
industry.

245

Trichloroethylene (TCE) degradation was 8991% in 2 h.


TCE degradation reaction rates for encapsulated and
bare NZVI were similar indicating no adverse affects of
encapsulation on degradation kinetics. The shelf-life of
encapsulated NZVI was found to be four months with
little decrease in TCE removal efficiency.
There is no significant difference between the reaction
rates of bare NZVI and entrapped NZVI. The reduction
capacity for Cr(VI) increases with increasing temperature
and NZVI dosage but decreases with the increase in
initial concentration of Cr(VI) and pH.
The removal efficiency of atrazine by the composite was
compared with that by commercial Fe powder and NZVI
itself. For both treatments by NZVI and NZVI/CTMABent, the removal efficiency increased as the pH of the
solution decreased, and the removal percentage of atrazine
by NZVI/CTMA-Bent reached 63.5% at initial pH 5.0
after 120 min.
The presence of organo-montmorillonite apparently
decreased the extent of aggregation and the size of
the iron particles. Iron nanoparticles had a coreshell
structure with the core being iron, and the shell
consisting of iron (hydr)oxides. In contact with
Cr(VI), the reduction of Cr(VI) was highest with
HDTMA-Mont/iron particles, followed by
Mont/iron particles and free iron nanoparticles.
More than 96% of Pb2+ was removed from aqueous
solution using K-NZVI at an initial condition of
500 mg L21 Pb2+ within 30 min under the conditions
of 10 g L21 of K-NZVI, pH 5.10 and a temperature
of 30 uC.
Nanosized ZVI was synthesized and immobilized
on the surface of a TiO2 nanotube, with carbon
tetrachloride (CT) and phenol as the target
compounds. The coupled degradation of CT
and phenol by the NZVI combined with the
titanate nanotube under illumination with UV light
could be used for the simultaneous degradation
of mixed priority pollutants.

247

Attachment of Fe0 nanoparticles on the commercially


available sub-micrometer silica fume prevented them
from aggregation while maintaining the particle
reactivity. When the Fe0 concentration was
0.4 g L21, 88.00% of 40 mg L21 Cr(VI) was
removed in 120 min, 22.55% higher than unsupported
Fe0. Almost all unsupported Fe0 was retained, whereas
51.50% and 38.29% of SFFe0 were eluted from the
vertical and horizontal sand column, respectively.
Nanoscale zerovalent iron entrapped in porous silica
particles and prepared through an aerosol-assisted
process were used for TCE remediation. The
entrapment of iron nanoparticles into the silica
matrix prevents their aggregation while maintaining
the particles reactivity. Furthermore, the silica
particles are functionalized with alkyl groups and
are extremely efficient in adsorbing dissolved TCE.

246

248

249

250

251

252

253

254

RSC Adv., 2012, 2, 93259358 | 9341

View Article Online

Table 6 Examples of pollutant remediation using iron oxides and FeOOH


System

Ion/substance to
be eliminated

Description

Ref.

Disinfection byproduct
precursors (in particular,
ozonation byproducts:
aldehydes, ketones and
ketoacids)

Commercial available ceramic membranes (sintered in air at 900 uC for 30 min)


with a nominal molecular weight cut-off of 5 kDa were coated 20, 30, 40 or
45 times with sol suspension-processed Fe2O3 nanoparticles (average diameter
of 46 nm). Optimum water quality was achieved at 40 layers, which
corresponds to a surface coating morphology consisting of a uniform,
coarse-grained structure with open, nanosized interconnected pores.
Strong adsorption of arsenic to the magnetite nanoparticles in the column.
Arsenic and 12 other metals (V, Cr, Co, Mn, Se, Mo, Cd, Pb, Sb, Tl, Th, U)
could be simultaneously removed by the iron oxide nanoparticles in soil.
Irreversible sorption of arsenic to the iron oxide nanoparticle surface.

255, 256

Schwertmannite-derived biomagnetite proved capable of retaining more


(y20%) 99mTc(VII) than ferrihydrite-derived biomagnetite.

258

Nitrates

Residual NO32 concentration of 1.35 mg L21 is lower than international


standards.

259

FeOOH
Iron (oxyhydr)oxide
nanocrystallines

As(III) and
heavy metals

260

a-FeOOH

Fluorides

Various phases of iron (oxyhydr)oxide nanocrystallites were synthesized from


the phase-controlled transformation of amorphous hydrous ferric- or ferrousoxide in thermal solution with a certain ethanolwater ratio and with the
presence of oleic acid (goethite nanorods, hematite nanocubes and magnetite
nanoparticles). The as-synthesized goethite nanorods and magnetite
nanoparticles demonstrated extremely strong As(III) affinity, with 5.8 and
54 times of As(III) adsorption, respectively, higher than the micron-sized
relatives.
Fluoride from contaminated H2O sample could be successfully brought
down from 10.25 to 0.5 mg L21.

Fe2O3 and Fe3O4


Alumina
zirconiatitania
ceramic membranes
coated with iron
oxide nanoparticles

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

Iron oxide nanoparticles


(19.3 nm magnetite and
37.0 nm hematite)
Nanomagnetites
produced by the
bacterial reduction
of schwertmannite
powder.
Fe3O4

Arsenic (arsenate
and arsenite) and
metals (V, Cr, Co,
Mn, Se, Mo, Cd,
Pb, Sb, Tl, Th, U)
Tc(VII) and Cr(VI)

different forms (freshly synthesized, dried, and dried-sonicated)


was studied as an effective nitrate reduction material.176 As a
result, different types of NZVIs were found to be able effectively
reduce highly concentrated nitrate without requiring pH control.
The authors suggested that the aggregate size and catalyst
prominently affect the nitrate reduction rate and that the
aggregation effect is more important than the catalyst effect as
the aggregate size becomes smaller. The final product of the
reaction was ammonium, with nitrite being produced as a
byproduct; NZVI changed into different shapes of magnetite
(Fe3O4) after the reaction, depending on the reaction conditions.
The mechanism for nitrate reduction by nano-zerovalent iron
was also studied in ref. 177. Bimetallic iron-containing nanoparticles react similarly; thus, improved N2 selectivity of NZVI
via NO32 denitrification using bimetallic Ni/Fe nanoparticles
was discussed.178 NO32 was first adsorbed on the nano-Ni/Fe

257

261

surface and reduced to NO22. With the rapid reduction of NO22


to NH4+, this NH4+ was desorbed into solution due to its smaller
affinity for the particle surface. In addition, microbial reduction
of nitrate in the presence of NZVI was evaluated to assess the
feasibility of using NZVI in the biological nitrate treatment.179
Nitrate was completely reduced within 3 days in a nanoscale
Fe(0)-cell reactor, while only 50% of the nitrate was abiotically
reduced over 7 days at 25 uC. Efficient removal of nitrate by
Fe(II)-supported anaerobic culture in 14 days indicated that
Fe(II), which was produced during anaerobic Fe corrosion in the
Fe0-cell system, might act as an electron donor for nitrate. In
addition, microbial reduction of nitrate was not significantly
affected by low temperature conditions.
For arsenic elimination (this is a very important problem in
many countries180), nanophase Fe3O4 (magnetite, 17 nm) and
Fe2O3 (hematite, 12 nm) were synthesized through a precipitation

Fig. 9 (a) TEM images of iron nanoparticles, (b) HR-XPS survey on the Ni 2p3/2 of iron nanoparticles and (c) a conceptual model for nickel
deposition on iron nanoparticles.170

9342 | RSC Adv., 2012, 2, 93259358

This journal is The Royal Society of Chemistry 2012

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online

Fig. 10 (a) Schematic of aerosol-based process and (b) schematic of


synthesis route to synthesize ironcarbon composites. Reproduced with
permission.

method181 and were utilized for the removal of either arsenic(III) or


(V) from aqueous solution as a possible method for drinking water
treatment. The binding was observed to be pH independent from
pH 6 through pH 9 and a significant drop in the binding was
observed at pH 10. Batch isotherm studies were performed using the
Fe2O3 and Fe3O4 to detect the binding capacity of As(III) and As(V)
to the iron oxide nanomaterials. Among other studies, XPS and
X-ray absorption spectroscopy were used for NZVI treated with
Cr(III) and Cr(VI).182 It was shown that (a) the crystalline Fe(III)
phase is composed of lepidocrocite (c-FeOOH), (b) Cr(VI) was
entirely reduced to Cr(III) by nano Fe0 with no residual Cr(VI) after
reaction. Cr(III) precipitated as Cr(OH)3 in the presence of
corroding nano Fe0 was nearly identical to the Cr(VI)-nano Fe0
reaction product and both Cr(III)- and Cr(VI)-treated nano Fe0
yielded a predominantly hydroxylated Cr(OH)3 and/or a mixed
phase CrxFe12x(OH)3 product, both of which are highly insoluble
under environmental conditions. In addition, NNZVI was also
evaluated for the reduction of bromate that is a highly persistent and
carcinogenic oxyhalide formed as an ozonization byproduct during
oxidative disinfection in drinking water treatment.183 It was revealed
that in a 20 min bromate reduction NZVI mostly converted to
Fe2O3 and Fe3O4 corrosion products mixed with Fe hydroxides.
Humic acid was the most influencing factor to decrease NZVI
reactivity in bromate reduction. In addition, the effect of sonication
pretreatment showed that the bromate reduction efficiency could be
enhanced by increasing the actual reactive surface area.
Remediation of organic pollutants
A large variety of organic pollutants, especially chlorinated
hydrocarbons, have been used in remediation experiments using
This journal is The Royal Society of Chemistry 2012

Fig. 11 Conceptual schematic showing potential applicability of FeC


composites for the adsorption and simultaneous dechlorination of
chlorinated hydrocarbon contaminants. Reproduced with permission.

NZVI, Fe/M nanoparticles and iron oxides. Thus, the oxidative


capability of NZVI was analytically compared via experiments
using the model compounds benzoic acid and formic acid.184
Rapid production of H2O2 with concomitant loss of the model
compound was observed upon addition of NZVI and bimetallic
nanoparticles to oxygenated solutions with eventual loss of
formic acid. On the other hand, functionalization of NZVI with
polymeric stabilizers starch, carboxylmethylcellulose and alginate slowed down the rate of H2O2 production and the
consumption of formic acid. Fe nanoparticles were used to
remediate PCB-contaminated soil and an attempt was made to
maximize PCB destruction in each treatment step.185 The
destruction efficiency during the preliminary treatment (mixing
of soil and Fe nanoparticles in water) can be increased by
increasing the water temperature. A minimum total PCB
destruction efficiency of 95% can be achieved. At 300 uC in
air, Fe2O3 is also a good catalyst for remediating PCBcontaminated soils. Nanoscale palladized iron (Pd/Fe) bimetallic
particles (spherical granules with diameter of 47 11.5 nm
connected with one another to form chains and the chains
composed nanoscale Pd/Fe bimetallic particles), prepared by
reductive deposition method186 and containing a-Fe0, revealed
the best dechlorination effect in elimination of monochloroacetic
acid by different reductants followed the trend: nanoscale Pd/Fe
RSC Adv., 2012, 2, 93259358 | 9343

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online

bimetallic particles of 0.182% Pd/Fe . nanoscale Fe . reductive


Fe. The effectiveness of NZVI to dechlorinate atrazine (1-chloro3-ethylamino-5-isopropylamino-2,4,6-triazine) in contaminated
water and soil was studied, analyzing the influence of iron
sources, solution pH, Pd catalyst and presence of Fe or Al sulfate
salts.187 The results indicated nano ZVI can be successfully used
to remediate atrazine in water and soil. Atrazine destruction
kinetic rates were greatly enhanced in both contaminated water
and soil treatments by NZVI when sulfate salts of Fe(II), Fe(III)
or Al(III) was added with the following order of removal rates:
Al(III) 2.23 . Fe(III) 2.04 . Fe(II). Another example of higher
activity of composite Fe nanoparticles in comparison to free Fe0
samples is a one-pot method,188 developed to prepare Fe/FeS
nanoparticles using dithionite at r.t. The FeS precipitations on
the Fe surface were formed by the interaction between dissolved
Fe species and H2S, one of the decomposition products of
dithionite in solution. The resulting Fe/FeS nanoparticles
showed a much higher reactivity toward contaminants than the
pure Fe nanoparticles and were applied for the rapid removal of
TCE from water.
Supporting NZVI or iron oxides on natural materials or
compounds having high surface area leads to their longer
activity. Thus, NZVI was reported as an effective material for
azo dye removal, however, similar to other nanomaterials, ultrafine powder has a strong tendency to agglomerate into larger
particles, resulting in an adverse effect on both effective surface
area and catalyst performance. Nanosized Fe0 particles dispersed
onto the surface of natural bentonites were fabricated189 and
their ability to decolorize Orange II (OII) was evaluated.
Spherical individual Fe0 particles were observed after dispersion
onto bentonites, and these samples were used for Orange II
decolorization over a wide pH range. Higher reactivity was
attributed to the good dispersion of Fe0 particles on clay mineral
surface. The same pollutant (Orange II) was also removed by use
of non-supported self-assembled Fe3O4 hierarchical nanostructures (obtained by hydrothermal approach),190 which could be
easily transformed to c-Fe2O3 and a-Fe2O3 without changing its
original morphology by calcination in air. Another example is
the study of the kinetics of nitrobenzene reduction by Fe(II)
sorbed on a-Al2O3, measured while simultaneously characterizing the Fe oxidation product with Mossbauer spectroscopy and
electron microscopy.191 The onset of nitrobenzene reduction
coincided with a change in particle suspension color from white
to yellowochre due to formation of nanogoethite rods
(a-FeOOH) from oxidation of sorbed Fe(II). Formation of
nanogoethite on the a-Al2O3 particles appears to promote the
rapid reduction of nitrobenzene. In addition, an encapsulation
approach that relies upon Gum Arabic to stabilize high
quantities of NZVI (y12 g L21) in the dispersed phase of a
soybean oil-in-water emulsion was offered.192 The formed
emulsion is kinetically stable due to substantial repulsive barriers
to dropletdroplet induced deformation and subsequent coalescence. Sedimentation time scales were found to be on the order
of hours (t = 4.77 0.02 h). NZVI within the emulsion was
shown to be reactive with both trichloroethane degradation and
H2 production observed. A special case is the use of iron oxide/
TiO2 nanoparticles.193 Thus, photocatalytic oxidation with TiO2
nanoparticles (620 nm) was investigated as a promising watertreatment process.194 195 When irradiated with UV light, TiO2
9344 | RSC Adv., 2012, 2, 93259358

nanoparticles can adsorb and degrade a wide variety of


environmental organic pollutants. For instance, the strong
affinity between the surface of TiO2 nanoparticles for organic
arsenic species (monomethylarsonic [MMA] and dimethylarsinic
[DMA] acids) leads to covalent bonding between MMA or
DMA and the surface of nanoparticles through bidentate
) and monodentate (AsDMA-Ti 3.37 A
)
(AsMMA-Ti 3.32 A
inner-sphere complexes, respectively. Doping TiO2 nanoparticles
with Fe3+ ions at 0.10.5% may significantly increase the
photocatalytic activity. The doped ions act as charge separators
of the photoinduced electronhole pair and enhanced interfacial
charge transfers. In a related work, iron-doped-TiO2 was
prepared by the hydrothermal method.196 Titanium(IV) tetratert-butoxide and FeCl3 or FeCl2 dissolved in n-octanol was
heated at 230 uC for 2 h in the presence of water. The resulting
powders were rinsed, dried and calcined at 560 uC. Photocatalyst
doped with FeCl3 had better photoactivity for degradation of
dye in aqueous solution under UV and visible light. It was found
that the amount of doped iron ions plays a significant role in
affecting its photocatalytic activity.
Special studies of remediation applying iron-containing
nanomaterials
Radiotracer studies of remediation. NZVI synthesized under
atmosphere conditions were used for the removal of Ba2+ at
concentrations 10231026 M.133,197 Ba was used as a tracer to
study the effects of time, concentration and temperature.
Observed thermodynamic parameters showed that the process
is exothermic and hence enthalpy driven. Carbon isotope
fractionation is of great interest in assessing chlorinated ethene
transformation by nanoscale Fe0 at contaminated sites, particularly in distinguishing the effectiveness of an implemented abiotic
degradation remediation scheme from intrinsic biotic degradation.198 Thus, transformation of trichloroethylene (TCE), cisdichloroethylene (cis-DCE), and vinyl chloride (VC) with two
types of nanoscale Fe materials showed different reactivity
trends, but relatively consistent carbon isotope enrichment
factors of 219.4 1.8% (VC), 221.7 1.8% (cis-DCE) and
223.5 2.8% (TCE) with one type of iron (FeBH), and from
220.9% 1.1% to 226.5 1.5% (TCE) with the other (FeH2,
manufactured by a reduction of goethite and hematite particles
with H2 gas at 200600 uC) (distinct types of iron were purchased
with different companies). Related monitoring of the effectiveness of ZVI injection by assessing TCE and 1,1,1-TCA (1,1,1trichloroethane) degradation was carried out by the same
research group.199 Prior to ZVI injection, carbon isotope
measurements demonstrated biodegradation of TCE by native
microorganisms, which was quantified by measuring the enrichment of 13C in TCE samples downstream of the suspected
source. When ZVI was injected through only two injection wells,
no changes in TCE and 1,1,1-TCA isotope signatures were
detected compared to preinjection values.
NZVI oxidative capacity studies. The addition of electron
shuttling molecules was shown to enhance the oxidative capacity
of NZVI. It was established that the addition of the polyoxometallates (POM), sodium polyoxotungstate (Na3PW12O40),
enhances the oxidative capacity of NZVI in oxidation of
This journal is The Royal Society of Chemistry 2012

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online

HCOOH and production of H2O2.200 Based on these results, the


mechanism for the enhancement in oxidative capacity of NZVI
was offered as is through two separate processes: (a) the POM
out-competes H2O2 for electrons from Fe0 thereby increasing the
H2O2 concentration, and (b) the reduced form of the POM,
PW12O4042, facilitates the cycling of Fe(III) to Fe(II) which
enhances the homogeneous Fenton reaction. Elucidating the
factors which affect the yield of oxidants, it was established that
HCHO production by NZVI was low under acidic conditions,
increased with increasing pH until pH 7 and then decreased at
higher pH.201 The addition of Fe(II) resulted in negligible HCHO
generation at pH , 5, as expected based on the pH-dependent
rate of Fe(II) oxidation. It was indicated that Fe(s)0 oxidation
was responsible for H2O2 production at pH , 5 and that Fe(II)
oxidation produces almost all of the H2O2 at pH . 6.5. The
decrease in yields above pH 7 may be attributable to limited Fe
solubility at elevated pHs.
Stability, air contact, decrease of activity and movility of NZVI.
Nanosized particles of pure ZVI are pyrophoric and react
spontaneously with atmosphere oxygen. So, a series of methods
to stabilize the particles against aerial oxidation were presented.202 Thus, using different chelating agents, an attempt to
synthesize air-stable NZVI in the presence of EDTA, diethylenetriamine pentacetic acid (DTPA), nitriloacetic acid (NTA),
trans-1,2-diaminocyclohexane-N,N,N9,N9-tetraacetic acid (CDTA),
hydroxyethylenediaminetetraacetic acid (HEDTA), triethylene
tetraamine (TRTA) and N-cetyl-N,N,N-trimethyl ammonium
bromide (CTAB) chelating agents, was carried out.203 The
chelating effect was the best for EDTA, NTA and HEDTA, but
the least for CDTA and CTAB. Hydroxyl groups, lone pair
electrons on nitrogen atom and steric effects of the cyclohexane
ring and bulky surroundings played the main role to provide air
stability towards synthesized NZVI. Trying to stabilize NZVI
by another route, nanosized air-stable ZVI particles were
produced204 by applying ultrasound to a solution of Fe(CO)5
in edible oil. The resulting iron nanoparticles were dispersed in
a carbon matrix, and coated with a non-crystalline carbon layer
of ~2.5 nm. Although these nanoparticles are non-pyrophoric
and stable in air, dechlorination of tetrachloroethene was
demonstrated in synthetic aqueous medium and in polluted
groundwater. Dechlorination reaction products of this NZVI
were trichloroethene, cis-dichloroethene, vinyl chloride, ethene
and ethane. The effect of anions on the reactivity of final NZVI
was also studied, Thus, solutions containing chloride, phosphate, sulfate and nitrate anions and ferric ions were used to
generate iron oxide nanoparticles.205 The reactivity of the
resulting zerovalent iron nanoparticles was quantified by
monitoring the kinetics as well as products of carbon
tetrachloride reduction. The reactivity of nanoparticles prepared in the presence of sulfate and phosphate demonstrated
the highest reactivity and chloroform yield.
Generally, in soils the NZVI particles remain active towards
the contaminants for a period of 68 weeks. During this time, the
NZVI particles can aggregate and attach to soil grains in the
subsurface leading to reduced mobility, thereby limiting their
remediation potential. NZVI has been shown to be effective
across a broad range of soil pHs, temperatures, and nutrient
levels. Competing anions, however, may reduce its effectiveness.
This journal is The Royal Society of Chemistry 2012

The amount of groundwater that NZVI can treat may depend on


the quality of the iron, including the number of times it has been
reused, the type of substrate used (for ex situ use), and the
quality of the water used to make the injectable slurry, including
the amount of oxygen and the amounts and types of particulates
in contains (for in situ use). The effects of reaction conditions
such as reaction time and NZVI concentration on NZVI
characteristics and reactivity were studied.206 The particle size
was dramatically decreased from 87.4 to 9.5 nm under short
reaction time and high reductant concentration. The reactivity of
NZVI (evaluated by a nitrate reduction test) was increased in the
direction of high reductant concentration and fast synthesis,
although deactivation increased in the same direction. Also,
column and batch sedimentation studies were conducted207 to
study the transport of nanoscale NZVI particles stabilized by
three polyelectrolytes: polyvinyl alcohol-co-vinyl acetate-coitaconic acid (PV3A), poly(acrylic acid) (PAA) and soy proteins.
It was revealed that the both PV3A and PAA can increase NZVI
mobility by reducing particle size and generating negative
charged surfaces of NZVI. PV3A stabilized NZVI has the best
transport performance among the three materials. Due to the
large surface area of NZVI, large amounts of polyelectrolytes are
often needed. In addition, to understand more the factors that
limit NZVI mobility, several field-scale tests were performed208
using carboxylmethyl cellulose (CMC) stabilized NZVI.
Regeneration of NZVI reactivity. Iron reducing bacteria (IRB)
survive through the anaerobic metabolism reducing ferric iron,
as electron acceptor, to ferrous iron.209 It helps ZVI remediation
treatment to regenerate the reactivity of iron. NZVI was
researched to improve the reactivity and the mass transfer while
it has been reported that nanoscale particles have toxic effects on
human or nature. It was found that the IRB in NZVI system
were not harmed. Additionally, in ferrozine test, ferrous iron,
which was reduced from ferric iron as electron acceptor for IRB,
was increased in the micro-scale ZVI (MZBI) system. Another
sustainable and cost-effective strategy to improve the longevity
of NZVI treatment zones is through the use of dithionite
(S2O422, described above for creation of FeS/Fe nanoparticles)
as a chemical regenerant.210 It was shown that dithionite can
extend, and in some cases enhance, the removal of two model
groundwater pollutants (1,1,1,2-tetrachloroethane and hexavalent Cr(VI)) in NZVI treatment systems. The efficiency of the
dithionite regeneration process is strongly dependent upon pH
and redox state, which dictate the products of NZVI oxidation,
as well as the redox active species generated from the reaction
between passivated NZVI and dithionite.
Delivery techniques. The delivery of the NZVI to a groundwater aquifer is difficult for a number of reasons:211 delivery of
the particles by way of a slurry injected at multiple injection well
sites is difficult due to aggregation of the particles at the elution
points, many types of iron particles oxidize quickly in the
presence of air, and the nanoparticles are fairly unreactive
towards alkyl chlorocarbons. The problem to resolve is to offer
coatings to allow the particles to travel passively through the soil
while maintaining their reactive integrity. One such approach is
the delivery in the form of foams.212 Foam delivery of remedial
amendments for in situ immobilization of deep vadose zone
RSC Adv., 2012, 2, 93259358 | 9345

View Article Online

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

contaminants can overcome the intrinsic problems associated


with solution-based delivery, such as preferential flow and
contaminant mobilization.213 To study this, carboxyl-modified
polystyrene latex microspheres were used as surrogates for
nanoparticles of remediation purposes. It was demonstrated that
foam can carry significant fractions of zerovalent Fe nanoparticles at concentrations relevant to field remediation conditions
(5.3 g L21).
Scalability. Large-scale applications of NZVI for environmental remediation have been inhibited by the high costs
associated with its conventional production technologies. So,
the optimization of NZVI production is in a permanent progress.
Thus, carbon-supported Fe nanoparticles (CFe; 20100 nm
diameter) were synthesized214 by reacting Fe salts, adsorbed or
impregnated from aqueous solutions on 80 m2 g21 carbon black,
at 600800 uC under Ar. Fe3O4 particles formed at 300500 uC in
the initial stage of the reaction, being reduced to a mixture of aand c-Fe nanoparticles at .600 uC. At a 10 : 3 Fe : Cr mole
ratio, CFe reduced a 10 ppm Cr6+ solution to y1 ppm within
3 days. This method can be made in a scalable process from
inexpensive starting materials by carbo-thermal reduction.
Another approach without any chemical process is as follows.
Unlike conventional methods such as chemical synthesis and
vapor phase condensation, which typically involve toxic chemicals, sophisticated equipment and extensive labor, the precision
milling method relies solely on the mechanical impact forces
generated by stainless steel beads in a high-speed rotary chamber
to break down the iron microparticles.215 The system used
nontoxic solvents, was completely scalable to large-scale
manufacturing. After 8 h of milling, the feed micro iron was
effectively reduced to particles with sizes below 50 nm. A result
of application of such techniques is the use of NZVI at industrial
scale. Thus, application of NZVI technology for remediation of
groundwater at an operating industrial facility, containing
chlorinated solvent contaminant, was offered.216 As a result,
the nonaqueous phase source area in the groundwater was
successfully treated and the chlorinated solvent degraded to
benign byproducts within a year. Use of the nanoscale iron
facilitated distribution of the NZVI into the silty clay soil pores
using high pressure injection. The work was performed adjacent
to active plant buildings and roadways with no loss of plant
production.
Among other studies on NZVI particles, we note their in situ
modification techniques217 and potentiometric detection.218
Tables 46 list examples of examples of pollutant remediation
using NZVI, supported and alloyed NZVI and iron oxides and
FeOOH.

Water disinfection using NZVI and iron oxides


In general, both zerovalent iron (ZVI) and nanoscale ZVI
(NZVI) were found to effectively remove many contaminants
relevant to drinking water, including viruses, bacteria, chlorine,
disinfection byproducts (DBPs), and other chemicals.262 It was
proposed that NZVI can be applied to decentralized drinking
water systems to improve the performance of point-of-use
devices. However, in comparison with use of iron-containing
nanomaterials in remediation of chemical pollutants from water,
9346 | RSC Adv., 2012, 2, 93259358

their use for water disinfection is represented by a considerably


lesser number of examples.
The bactericidal effect of nanoFe is a unique property of
nanoFe, which was considerably less observed in other types of
Fe-based compounds. An observed exception corresponds to
iron coated sands and micro-scale iron powder, which were
reported to adsorb viruses via electrostatic attraction and cause
viruses to disintegrate or become noninfective. In any case,
nanosized iron particles may provide higher efficiency compared
to their bulk or micro-scale counterparts.263 It was established
that NZVI in aqueous solution is able to rapidly inactivate E.
coli.264 A strong bactericidal effect of nanoFe was found under
deaerated conditions, with a linear correlation between log
inactivation and nanoFe dose (0.82 log inactivation/mg L21
nanoFe-h). The inactivation of E. coli under air saturation
required much higher nanoFe doses due to the corrosion and
surface oxidation of nanoFe by dissolved oxygen. The effect that
adsorbed synthetic polymers and natural organic matter and
aging (partial oxidation) have on the bactericidal properties of
NZVI to the Gram-negative bacterium, E. coli, was elucidated.265 Exposure to 100 mg L21 of bare NZVI with 28% Fe0
content resulted in a 2.2-log inactivation after 10 min and a 5.2log inactivation after 60 min. In addition to E. coli, iron oxides
showed a high inactivation capacity of MS2 virus.266 Thus, the
inactivation of MS2 coliphage (MS2) by nanoparticulate NZVI
and ferrous ion (Fe(II)) in aqueous solutions was demonstrated.267 It was established that for NZVI, the inactivation
efficiency of MS2 under air-saturated conditions was greater
than that observed under deaerated conditions, indicating that
reactions (16)(21) associated with the oxidation of NZVI were
mainly responsible for the MS2 inactivation. Under air-saturated
conditions, the inactivation efficiency increased with decreasing
pH for both NZVI and Fe(II), associated with the pH-dependent
stability of Fe(II). The ?OH and Fe(IV) (e.g., FeO2+) are mainly
responsible for the oxidation of organic compounds and
inactivation of pathogenic microorganisms. The authors suggested that the NZVI surfaces interacted directly with the MS2
phages, leading to their inactivation. Also, it was indicated that
NZVI caused more capsid damage than Fe(II).
Fe0s + O2 + 2H+ A Fe(II) + H2O2

(16)

Fe0s + O2 + 2H+ A Fe(II) + H2O

(17)

Fe(II) + H2O2 A Fe(III) + ?OH + OH2

(18)

Fe(II) + H2O2 A Fe(VI) + H2O

(19)

Fe(II) + O2 A Fe(III) + ?O22

(20)

Fe(II) + ?O22 + 2H+ A Fe(III) + H2O2

(21)

Other types of bacteria are also available to eliminate using


NZVI. Thus, cyanobacteria pose a serious threat to water
resources around the world, compounded by the fact that they
are extremely resilient, having evolved numerous protective
mechanisms to ensure their dominant position in their ecosystem. It was just shown (Fig. 12)268 that treatment with NZVI is
an effective and environmentally benign method for destroying
and preventing the formation of cyanobacterial water blooms.
This journal is The Royal Society of Chemistry 2012

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online

These nanoparticles have multiple modes of action, including the


removal of bioavailable phosphorus, the destruction of cyanobacterial cells, and the immobilization of microcystins, preventing their release into the water column. The primary product of
NZVI treatment is nontoxic and highly aggregated Fe(OH)3,
which promotes flocculation and gradual settling of the
decomposed cyanobacterial biomass. As another example, the
bio-toxicity of Fe0 nanoparticles on the denitrifying bacteria
Alcaligenes eutrophus was detected by the two methods of
detecting inhibition of the growth of microorganisms and
nitrification inhibition rate.269 It was shown that Fe0 nanoparticles had (a) obvious toxicity on the growth and nitrification
inhibition rate and (b) distinct relationship between dose and
toxicity of Fe0 nanoparticles. Fe0 nanoparticles had visible
toxicity on the denitrifying bacterial, which could be decreased
by surface coating and decoration of nanometal materials.
For the case of supported NZVI, we note first of all Fe-doped
TiO2. It is known that TiO2 itself possess antimicrobial properties under UV-irradiation. Nonwoven nanofibers of pure and
iron-doped titanium dioxide (TiO2) were tested for evaluation of
their antimicrobial attributes for using them as disinfectant
gauze for wound healing upon brief activation by UV/IR
illumination.270 It was found that the fibers exhibited superior
bactericidal affinity when exposed briefly (312 s) to either
multiphoton laser or IR radiations. On the other hand, exposure
to a UV beam for up to 20 min was not effective in mitigating the
bacterial colonization of the E. coli. In a related report,271 the Fe/
Ce codoped nanometer titanic hydrosol, which could be applied
to indoor antisepsis, was prepared under atmosphere pressure by
a microwave-assisted peptization process and resulted good
antibacterial performance. It was shown that the Fe/Ce codoped
nano-TiO2 hydrosol had better antibacterial performance than
the pure nano-TiO2 hydrosol. The relative antibacterial rate

exceeded 95% when the illumination of natural light irradiation


lasted for 6 h. Finally, yellowish (Fe, N)-doped nanocrystalline
TiO2 powders (anatase in phase, 10 nm size) were prepared using
TiOSO4, CO(NH2)2, Fe(NO3)3?9H2O and CN3H5?HCl as precursors by a hydrothermal method.272 TiO2 powders were mixed
with organic silicon and acrylic syrup to test their antibacterial
performance by the colony counting method. It was shown that
the sterilization ratio of E. coli by the heat-treated (Fe, N)-doped
nanocrystalline TiO2 powders was reached up to 94.5% while
that of the powders without any heat treatment was 91.1%.
All other known examples of use of iron-containing nanomaterials in water disinfection correspond to iron oxides, supported
on distinct materials. Some differences in comparison with NZVI
use have been observed. Thus, a material system composed of
iron oxide (Fe2O3) nanoparticles loaded onto a fiberglass
support displayed excellent antiviral properties against the
model virus, MS2 phage, but is ineffective against bacteria,
specifically E. coli.273,274 To increase the antibacterial properties
and still maintain antiviral activity, silver nanoparticles were
added to this system through an aqueous hydrothermal
reduction process with 0.25 M silver nitrate (AgNO3). It was
revealed that a 0.05 mg mL21 loading of the Ag modified
oligodynamic nanoparticle impregnated fiberglass system consisting of Fe2O3 (9.1 wt%) and Ag (0.1 wt%)/g-fiber, displayed
robust antibacterial activity by achieving a 2 log removal of 106
CFU/mL E. coli in 1 min. Site competition between the Ag and
other species on the surface of the fiberglass was observed. The
fiberglass impregnated with CuO/Ag and FexOy/Ag, both
exhibited synergistic disinfection ability greater than that of
fiberglass impregnated with only Ag, the latter displaying the
highest bactericidal effect. Silver-doped iron oxides were also
used in a series of other related reports due to well-known
antibacterial properties of this metal both in bulk, nanoforms

Fig. 12 (a) SEM images of cyanobacteria before treatment, (b) unused NZVI particles, (c) highly deformed cells after brief exposure to NZVI, and (d)
completely destroyed cells surrounded by ferric oxide aggregates. Reproduced with permission.

This journal is The Royal Society of Chemistry 2012

RSC Adv., 2012, 2, 93259358 | 9347

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online

and Ag+ ion. For instance, silver (10 nm) nanoparticles inlaid
Fe3O4-SiO2 magnetic composite (Fe3O4SiO2Ag) was synthesized and its potential application as an antibacterial material in
water disinfection was investigated.275 The minimum inhibitory
concentrations of Fe3O4SiO2Ag magnetic composite to E-coli
and Staphylococcus aureus were 15.625 and 31.25 mg L21,
respectively, and the minimum bactericidal concentrations were
250 and 500 mg L21, respectively. This disinfectant in normal
saline solution could kill 99.9% of the tested bacteria within
60 min. In addition, the effects of silver(I) and iron(III) doping
contents on photocatalytic performance of the titania thin film
were studied.276 Ag and Fe doping and co-doping contents on
nanotitania photocatalytic bactericidal films were prepared by
solgel method, thus combining three active antibacterial species
(Ag, Fe and TiO2). The photocatalytic activity of titania films
was evaluated by the sterilizing rate of the E. coli. For
fluorescent light irradiation, optimal doping amounts for
silver(I)/titania and iron(III)/titania are 0.05, 0.1%, respectively.
More complex FeAg containing systems (a nano-Nd/Fe/B pipe
containing ZnO and Ag2O) are also known.277
Metal oxides, zeolites and such classic objects of nanotechnology as carbon nanotubes have been applied as supports for iron
oxides. Among metal oxide nanoparticles, zinc oxide demonstrates significant bacterial growth inhibition on a broad
spectrum of bacteria, mainly by catalysis of reactive oxygen
species formation from water and oxygen. Zinc oxide was
combined278 with iron oxide to produce magnetic composite
nanoparticles with improved colloidal aqueous stability, together
with adequate antibacterial activity. The Zn/Fe oxide composite
nanoparticles (containing iron oxide, zinc oxide and zinc ferrite
phases) were synthesized by basic hydrolysis of Fe2+ and Zn2+
ions in aqueous continuous phase containing gelatin. Their

antibacterial activity, tested against Staphylococcus aureus and


E. coli, was found to be dependent on the weight ratio [Zn]/[Fe],
i.e., the higher the ratio, the higher the antibacterial activity. The
activity against Staphylococcus aureus was significantly higher
than that observed against E. coli. The environmental safety
effect of nanosized Fe materials including Fe3O4, Fe3O4-zeolite
composite and Fe-doped zeolite was studied using a
Tetrahymena thermophile model.279 The magnetic nanosized
Fe3O4 is most sensitive to the suppression of the growth of
Tetrahymena thermophile, as compared with the Fe3O4zeolite
composite and Fe-doped zeolite. In addition, a photocatalytic
technique using visible light and carbon nanotubes and
nanosized Fe2O3 powder was used to inhibit pathogenic bacterial
growth in water.280 It was suggested that after careful design, this
system can be used to disinfect drinking water, making it free of
pathogenic bacteria.
A special case is the use of polymer supports (membranes)
containing the NZVI and iron oxides, whose use precisely for
water disinfection has not yet been well developed, in a difference
with remediation of chemical pollutants. In contrast to conventional, passive membrane technologies, an approach, reported in
ref. 281 utilized two independently controlled, nanostructured
membranes in stacked configuration for the generation of the
necessary oxidants to purify water (Fig. 13). These include
biocatalytic and organic/inorganic (polymer/iron) nanocomposite membranes. The bioactive (top) membrane contains an
electrostatically immobilized enzyme for the catalytic production
of one of the main reactants, hydrogen peroxide (H2O2), from
glucose. The bottom membrane contains either immobilized iron
ions or ferrihydrite/iron oxide nanoparticles for the decomposition of hydrogen peroxide to form powerful free radical
oxidants. By permeating a solution containing a model organic

Fig. 13 Schematic of reactive nanostructured stacked membrane system. (A) Setup of stacked membrane system consisting of two membranes of
different functionality operated via convective flow. (B) Pore of top membrane with layer-by-layer polycation/polyanion assembly containing
electrostatically immobilized GOx for the conversion of reactants A + B A C. (C) Pore of bottom membrane consisting of pH-responsive PAA gel with
immobilized iron species in collapsed state. (D) Pore of bottom membrane after exposure to increased pH causing gel to swell; reactive iron species
catalyzes conversion of C A D. Reproduced with permission.

9348 | RSC Adv., 2012, 2, 93259358

This journal is The Royal Society of Chemistry 2012

View Article Online

contaminant, such as trichlorophenol, with glucose in oxygensaturated water through the membrane stack, significant
contaminant degradation was realized. According to the authors,
other applications including disinfection and/or virus inactivation are possible.

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

Toxicity and risks of iron nanomaterials application


The conventional methods for in situ remediation of chlorinated
organic solvents, such as trichloroethylene, tend to produce
undesirable byproducts, whereas the use of nanoscale bimetallic
particles according to the techniques described above has
succeeded in eliminating some of these byproducts.282
However, at present the potential environmental risks of NZVI
in in situ field scale applications are largely unknown at the
present and traditional environmental risk assessment
approaches are not yet able to be completed.283 Therefore, it
may not yet be fully clear how to consider the environmental
benefits and risks of NZVI for in situ applications. At present,
there are no significant grounds on which to form the basis that
NZVI currently possess a significant, apparent risk to the
environment, although the majority of the most serious criteria
(i.e. potential for persistency, bioaccumulation, toxicity) are
generally unknown. Similar discussion could be applied to
SPIONs, including magnetite (Fe3O4), which are widely used in
uses such as hyperthermic malignant cell treatment, magnetic
resonance imaging, targeted drug delivery, tissue engineering,
gene therapy, and cell membrane manipulation.
This is rather new area of research. Several reviews284289 and
reports290294 (some of them described below) on iron-containing
nanoparticles could provide a background to this problem.
However, as noted in a review295 superparamagnetic iron oxide
nanoparticles (SPIONs) are promising materials for various
biomedical applications including targeted drug delivery and
imaging, hyperthermia, magneto-transfections, gene therapy,
stem cell tracking, molecular/cellular tracking, magnetic separation technologies (e.g. rapid DNA sequencing), and detection of
liver and lymph node metastases. The most recent applications
for SPIONs for early detection of inflammatory, cancer, diabetes
and atherosclerosis have also increased their popularity in
academia. Another fundamental discussion of SPIONs concerns
potential toxicity. Neenu Singh et al.,296 have investigated such
aspects as cytotoxicity, proteinSPION interaction, changes in
gene expression, impact on cell proliferation, among others.
NZVI (bare and supported)
Several research groups have studied the factors (size, surface,
supporting material, synthesis conditions, etc.) influence the
possible damage to living cells caused by zerovalent iron
particles. The overall conclusion is that the NZVI do possess
certain toxicity for animal cells (for example iron nanoparticles
showed perturbations in the expression of a set of functional
genes297). However, this toxicity is much lower in comparison
with nanoparticles of some other metals. Among other studies,
the size-dependent properties of inorganic metal (in particular,
Fe0) and metal oxide (boehmite) nanoparticles in relation to
environmental, health and safety perspectives were defined.298
Major risks concern the ignition, combustion and explosion of
the metal particles in reactive atmospheres, like hydrogen and
This journal is The Royal Society of Chemistry 2012

predominantly oxygen and air. So, basic mechanisms of


oxidation and reactions at small scale, classification of combustibility, ignition by when initiated by low-energy ignition sources,
rates of flame propagation, intensity of hydrogen generation at
interaction with water, inflammability initiated by electrostatic
discharge were investigated299 for a series of metals, in particular
iron. In addition, oxidative stress markers with SiO2-Fe induced
cytotoxicity in human endothelial cells were evaluated using
iron-doped nanosilica (16 nm).300 Significant modifications for
all parameters in cells treated with these nanoparticles were
found. Related SiO2/NdFeB nanoparticles had mild toxicity,
and could meet the requirement of the national standard for
medical implantation materials.301 Iron-doped TiO2 nanoparticles were tested302 as photosensitizers to kill tumor cells by
studying the HL60 cells activity with different nanoparticles
dosages, different magnetic field strengths and different conditions of receiving the visible radiation and no radiation. The
nanoparticles exhibited toxic/inhibiting effect on leukemia cells,
the greater the concentration of nanoparticles was, the more the
toxic/inhibiting effect was; while the toxic/inhibiting effect of
magnetic field on cells was dependent on the concentration of
iron-doped and magnetic induction intensity. In addition, it is
necessary to mention that toxicological impacts of iron
nanoparticles on the aquatic ecosystem remain poorly understood. In a study the larvae of medaka fish (Oryzias latipes) were
treated303 with thoroughly characterized solutions containing
CM-cellulose (CMC)-stabilized NZVI, aged nanoscale iron
oxides (nFe-oxides) or ferrous ion Fe(II) for 1214 days aqueous
exposure to assess the causal toxic effect(s) of iron NPs on the
fish. The authors established that with the CMC-NZVI solution
the dissolved oxygen level decreased, and a burst of reactive
oxygen species (ROS) was generated as Fe(II) oxidized to ferric
ion (Fe(III)); with the other two iron solutions, these parameters
did not significantly change.
In case of iron oxides (SPIONs), much more research has been
carried out, especially on doped and supported iron oxides in
distinct nanostructural forms. Thus, to test the hypothesis about
nanoparticle-triggered endothelial dysfunction, iron oxide nanoparticles (Fe2O3 and Fe3O4), as two widely used nanomaterials
and the main metallic components in particulate matter, were
selected to assess their potential risks on human endothelial
system.304 The direct effects of iron oxide nanoparticles on
human aortic endothelial cells (HAECs) and the possible effects
mediated by monocyte (U937 cells) phagocytosis and activation
were investigated. It was revealed (Fig. 14) that intravascular
iron oxide nanoparticles may induce endothelial system inflammation and dysfunction in three ways: (a) nanoparticles may
escape from phagocytosis that interact directly with the
endothelial monolayer; (b) nanoparticles are phagocytized by
monocytes and then dissolved, thus impact the endothelial cells
as free iron ions; or (c) nanoparticles are phagocytized by
monocytes to provoke oxidative stress responses. Similarly, the
SPIONs (612 nm diameter and aggregated clusters of these 612
nm nanoparticles), produced using a flame synthesis method,
were tested in respect of their biocompatibility with endothelial
cells for 24 h.305 It was suggested that flame synthesized iron
oxide nanoparticles are comparable to commercially available
nanoparticles for biological applications.
RSC Adv., 2012, 2, 93259358 | 9349

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online

Fig. 14 Influence of iron oxides on endothelial cells. Reproduced with


permission.

Multiply-replicated cytotoxicity (in vitro) assays utilizing a


human epithelial (lung model) cell line (A549) consistently
demonstrated varying degrees of cell death for essentially all
particulate matter (PM) which was characterized as aggregates
of nanoparticulates or primary nanoparticles.306 Cytokine
release was detected, in particular, for Fe2O3, as well as reactive
oxygen species (ROS) production. Nanoparticulate materials in
the indoor and outdoor environments appear to be variously
cytotoxic. Cytotoxicity of nanoparticles with iron oxide as core
and a biocompatible polymer as first layer was analyzed,307
presenting a broad overview of currently available in vitro and in
vivo toxicity data. It was indicated that the toxicity data obtained
vary significantly depending on size, size distribution, surface
(including coating), and subsequent surface derivatization. The
acute toxicity and the anti-phagocytosis of folic acidO-carboxymethyl chitosans superparamagnetic Fe oxide nanoparticles (FA-OCMCS-SPIO-NPs) and O-carboxymethyl chitosans superparamagnetic Fe oxide nanoparticles (OCMCSSPIO-NPs) were evaluated.308 Apparent toxic reaction and
tissue injury did not occur among the animals. Prussian blue
stain showed that FA-OCMCS-SPIO-NPs could escape from
phagocytosis of liver and spleen completely and most of
OCMCS-SPIO-NPs could while dextran-SPIO-NPs could not.
The toxicities (at both cellular and molecular levels) of three
forms of SPIONs of various surface chemistries (COOH, plain,
and NH2) through the comparison with gene expression patterns
of three cell types (i.e., human heart, brain, and kidney) were
evaluated.309 It was revealed that SPIONs-COOH altered genes
associated with cell proliferative responses due to their reactive
oxygen species (ROS) properties. Uptake, toxicity and degradation of magnetic nanowires (200 nm diameter and lengths
comprised between 1 and 40 mm, fabricated by controlled
assembly of c-Fe2O3 nanoparticles) by NIH/3T3 mouse fibroblasts were studied.310 It was revealed that (a) the wires do not
display acute short-term (,100 h) toxicity towards the cells and
9350 | RSC Adv., 2012, 2, 93259358

(b) the cells are able to degrade the wires and to transform them
into smaller aggregates, even in short time periods (days). The in
vitro cytotoxicity of 100 nm iron oxide particles (Fe2O3) was
evaluated in the human embryonic kidney cell line HEK293.311
Cell viability assays demonstrated that 100 mg mL21 Fe2O3
exhibited 20% reduction in HEK293 cell viability in 24 h.
Comparing the results with those for other targets, at both the
cellular and molecular levels, the toxicity was observed in the
following order: ZnO . Fe2O3-NPs . MCM-41.
Combination of microinjection techniques and Raman spectroscopy was used to investigate the effects of Ag and Fe3O4
nanoparticles on Hela cells.312 The nanoparticles were microinjected inside the cells and these latter ones were probed by
means of Raman spectroscopy after a short incubation time, in
order to highlight the first and impulsive mechanisms developed
by the cells to counteract the presence of the nanoparticles. A
different behavior of the cells treated with nanoparticles in
comparison with the control cells was observed. These differences were supposed to be generated by an emerging oxidative
stress due to the nanoparticles. c-Fe2O3 can cause cell death
within 24 h of exposure, most likely through oxidative stress.313
In vivo exploration suggested that although c-Fe2O3 nanoparticles are rapidly cleared through the urine, they can lead to
toxicity in the liver, kidneys and lungs, while the brain and heart
remain unaffected. c-Fe2O3 could exhibit harmful properties and
therefore surface coating, cellular targeting, and local exposure
should be considered before developing clinical applications.
Acute toxicity tests were selected according to their extensive use
in toxicological studies of iron oxide nanoparticles and included
phytotoxicity using several seeds, Daphnia magna and a
bioluminescent test (Microtox), revealing low toxicity.314 The
toxic effects of inhalation exposure to Fe2O3 nanoparticles
(together with ZnO) in rats were investigated.315 Iron content in
liver and lung tissues was significantly increased at 36 h. The
levels of serum alanine aminotransferase (ALT), aspartate
aminotransferase (AST), alkaline phosphatase (ALP), total
protein (TP), creatine kinase (CK), and lactate dehydrogenase
(LDH) were significantly decreased compared to the unexposed
controls. It was shown that both types of nanoparticles caused
severe damage in liver and lung tissues.
Zeta potential measurements, common in nanotoxicology,
were applied to Fe2O3, among other oxides in respect of to
acquaint the effects of pH and time on nanoparticle zeta
potential, agglomerate size and cellular viability.316 Fe2O3
increased in zeta potential and agglomerate size over time.
Cytotoxicity studies revealed that Fe2O3 caused decreasing
cellular viability over 48 h. It was indicated that alterations in
the pH have a large effect on zeta potential and agglomerate size
which may be used as a predictive measure of nanotoxicity.
Cytotoxicity of SPIONs (bare and poly(ethylene glycol)-cofumarate (PEGF)-coated SPION with narrow size distributions)
and their ability to change cell medium components was
investigated317 in respect with Dulbeccos modified Eagles
medium (DMEM) and primary mouse fibroblast (L929) cell
lines. The potential toxic effects of iron(II,III) oxide nanoparticles
were studied.318 While in vitro MTT assay showed a moderate
cytotoxic effect, the Fe(II,III) nanoparticles proved to be devoid
of mutagenic effect in the bacterial systems tested. In addition,
This journal is The Royal Society of Chemistry 2012

View Article Online

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

peptideSPION complexes were proved to be biocompatible and


are localized around the cells due to their peptide coating.319
In case of other iron-containing nanostructures, there is little
available information on their toxicity. Thus, the toxicity of
Mn0.5Zn0.5Fe2O4 nanoparticles in vitro on L-02 cell was
studied,320 showing that (a) the activity of L-02 cell decreased
with the increasing of Mn0.5Zn0.5Fe2O4 nanoparticle concentration and prolonging of poisoning time and (b) the activity of
L-02 cell became stable after poisoning for 48 h. The toxicity of
the related compound, stoichiometric Mn0.2Zn0.8Fe2O4 monodisperse nanoparticles, was evaluated by viability assays on
human umbilical vein endothelial cells.321

Conclusions
Currently, the use of the NZVI, iron oxides and other Fecontained nanomaterials for remediation of both organic and
inorganic pollutants from groundwater and contaminated soils
could be considered as a relatively hot topic in the nanotechnology. During the last decade, a series of distinct methods
have been offered to synthesize these nanostructures as by
traditional wet chemistry routes and more sophisticated
modern techniques as well as greener methods using plant
extracts. Due to relatively low toxicity of iron-containing
nanoparticles, it has been allowed to apply them in free and
supported forms to reach a considerable decontamination of
the environment.
Evaluation of toxicity of the Fe-containing nanomaterials
remains an object of permanent research and polemics. Since real
long-time effects of the presence of iron-containing nanoparticles
in rivers, groundwater, lakes and oceans are still unknown, the
idea to introduce iron-containing nanoparticles into oceans,322 in
order to stimulate growth of phytoplankton and better adsorption of CO2, was further rejected.
The research field, dedicated to coreshell iron (iron oxide)/
gold nanoparticles, is of a special interest due to possibility to be
controlled by magnetic fields (iron core) and functionalization
(gold shell). These air-stable Nps are protected from the
oxidation and retain most of the favorable magnetic properties,
which possess the potential for applications in drug delivery,
high density memory devices by forming self-assembling
nanoarrays, and a series of other applications.

Acknowledgements
BIK is grateful to the Paicyt-UANL-2012 project for financial
support.

References
1 B. Chertok, B. A. Moffat, A. E. David, F. Yu, C. Bergemann, B. D.
Ross and V. C. Yang, Iron oxide nanoparticles as a drug delivery
vehicle for MRI monitored magnetic targeting of brain tumors,
Biomaterials, 2008, 29(4), 487496.
2 P. M. Tiwari, K. Vig, V. A. Dennis and S. R. Singh, Functionalized
Gold Nanoparticles and Their Biomedical Applications,
Nanomaterials, 2011, 1, 3163.
3 C. S. S. R. Kumar, Magnetic nanomaterials, Wiley-VCH, Weinheim,
2009, 648 pp.
4 An-Hui Lu, E. L. Salabas and F. Schuth, Magnetic Nanoparticles:
Synthesis, Protection, Functionalization, and Application, Angew.
Chem., Int. Ed., 2007, 46, 12221244.

This journal is The Royal Society of Chemistry 2012

5 K. Watlington, Emerging Nanotechnologies for Site Remediation and


Wastewater Treatment. Report for U.S. Environmental Protection
Agency, Office of Solid Waste and Emergency Response Office of
Superfund Remediation and Technology Innovation, Technology
Innovation and Field Services Division, Washington, DC, 2005, 47
pp.
6 T. E. Cloete, M. B. M. de Kwaadsteniet and J. M. Lopez-Romero,
Nanotechnology in water treatment. Applications, Caister Academic
Press, 2010, 196 pp.
7 B. Tansel, New Technologies for Water and Wastewater Treatment:
A Survey of Recent Patents. Recent Patents on Chemical Engineering,
2008, ch. 1, pp. 1726.
8 I. Ali, New Generation Adsorbents for Water Treatment, Chem.
Rev., 2012, DOI: 10.102/cr300133d.
9 X. Q. Li, D. W. Elliott and W. Zhang, Zero-Valent Iron
Nanoparticles for Abatement of Environmental Pollutants: materials and engineering aspects, Crit. Rev. Solid State Mater. Sci., 2006,
31, 111122.
10 M. Hofmann-Amtenbrink, B. von Rechenberg and H. Hofmann,
Superparamagnetic nanoparticles for biomedical applications, in
Nanostructured Materials for Biomedical Applications, 2009,
Transworld Research Network, Kerala, India.
11 M. Mahmoudi, M. A. Sahraian, M. A. Shokrgozar and S. Laurent,
Superparamagnetic Iron Oxide Nanoparticles: Promises for
Diagnosis and Treatment of Multiple Sclerosis, ACS Chem.
Neurosci., 2011, 2, 118140.
12 D. L. Huber, Iron nanoparticles, in Dekker encyclopedia of
nanoscience and nanotechnology, ed. J. A. Schwarz, C. I. Contescu
and K. Putyera, CRC Press, Taylor and Francis Group, Boca
Raton, FL, 2008, vol. 3, pp. 16811687.
13 C. S. Rajan, Nanotechnology in Groundwater Remediation, Int. J.
Environ. Sci. Dev., 2011, 2(3), 182187.
14 S. Cheong, P. Ferguson, I. F. Hermans, G. N. L. Jameson, S.
Prabakar, D. A. J. Herman and R. D. Tilley, Synthesis and Stability
of Highly Crystalline and Stable Iron/Iron Oxide Core/Shell
Nanoparticles for Biomedical Applications, ChemPlusChem, 2012,
77, 135140.
15 U. Harm, J. Schuster and K.-M. Mangold, Modification of iron
nanoparticles for ground water remediation, DECHEMA, KarlWinnacker Institut, 2010, http://kwi.dechema.de/kwi_media/
Downloads/ec/F564_Nanoeisen_Harm.pdf.
16 C. F. Geraldes and S. Laurent, Classification and basic properties of
contrast agents for magnetic resonance imaging, Contrast Media
Mol. Imaging, 2009, 4(1), 123.
17 Y. W. Jun, J. W. Seo and J. Cheon, Nanoscaling laws of magnetic
nanoparticles and their applicabilities in biomedical sciences, Acc.
Chem. Res., 2008, 41(2), 179189.
18 B. Nowack, Chapter 1. Pollution Prevention and Treatment Using
Nanotechnology, Nanotechnology, Volume 2: Environmental
Aspects, ed. H. Krug, Wiley-VCH Verlag GmbH & Co., KGaA,
Weinheim, 2008.
19 J. Bai and J-P. Wang, High-magnetic-moment coreshell-type
FeCo-Au/Ag nanoparticles, Appl. Phys. Lett., 2005, 87(15), 11525021-152502.
20 A. Figuerola, R. Di Corato, L. Manna and T. Pellegrino, From iron
oxide nanoparticles towards advanced iron-based inorganic materials designed for biomedical applications, Pharmacol. Res., 2010,
62(2), 126143.
21 M. Pita, J. M. Abad, C. Vaz-Dominguez and C. Briones et al.,
Synthesis of cobalt ferrite core/metallic shell nanoparticles for the
development of a specific PNA/DNA biosensor, J. Colloid Interface
Sci., 2008, 321, 484492.
22 K. An and T. Hyeon, Synthesis and biomedical applications of
hollow nanostructures, Nano Today, 2009, 4(4), 359373.
23 C. Xu, Z. Yuan, N. Kohler, J. Kim, M. A. Chung and S. Sun, FePt
nanoparticles as an Fe reservoir for controlled Fe release and tumor
inhibition, J. Am. Chem. Soc., 2009, 131(42), 1534615351.
24 J. Gao, G. Liang, B. Zhang, Y. Kuang, X. Zhang and B. Xu,
FePt@CoS2 yolk-shell nanocrystals as a potent agent to kill HeLa
cells, J. Am. Chem. Soc., 2007, 129(5), 14281433.
25 M. Diao and M. Yao, Use of zerovalent iron nanoparticles in
inactivating microbes, Water Res., 2009, 43(20), 52435251.
26 J. Y. Kim, H. J. Park, C. Lee, K. L. Nelson, D. L. Sedlak and J.
Yoon, Inactivation of Escherichia coli by nanoparticulate zerovalent

RSC Adv., 2012, 2, 93259358 | 9351

View Article Online

27

28

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

29

30

31

32
33
34

35
36

37

38

39

40

41

42

43
44

45

46
47
48
49

50

iron and ferrous ion, Appl. Environ. Microbiol., 2010, 76(22),


76687670.
Q. W. Ding, T. W. Qian, H. F. Liu and W. Xue, Preparation of
Zero-Valent Iron Nanoparticles and Study of Dispersion, Appl.
Mech. Mater., 2011, 5557, 17481752.
J.-m. Lee, J.-h. Kim, J.-w. Lee, J.-h. Kim, H.-s. Lee and Y.-s.
Chang, Synthesis of Fe-nano Particles Obtained by Borohydride
Reduction with Solvent. Paper A-068, in: B. M. Sass (Conference
Chair), Remediation of Chlorinated and Recalcitrant Compounds
2008. Proceedings of the Sixth International Conference on
Remediation of Chlorinated and Recalcitrant Compounds
(Monterey, CA, May 2008). ISBN 1-57477-163-9, published by
Battelle, Columbus, OH, www.battelle.org/chlorcon.
A. Khodabakhshi, M. M. Amin and M. Mozaffari, Synthesis of
magnetite nanoparticles and evaluation of its efficiency for arsenic
removal from simulated industrial wastewater, Iran. J. Environ.
Health. Sci. Eng., 2011, 8(3), 189200.
H. Park, P. Ayala, M. A. Deshusses, A. Mulchandani, H. Choi and
N. V. Myung, Electrodeposition of maghemite (c-Fe2O3) nanoparticles, Chem. Eng. J., 2008, 139, 208212.
J. Grabis, G. Heidemane and D. Rasmane, Preparation of Fe3O4
and c-Fe2O3 Nanoparticles by Liquid and Gas Phase Processes,
Mater. Sci. (MEDZIAGOTYRA), 2008, 14(4), 292295.
S. G. Ballard, Apparatus and methods for the production of
powders, US Pat., US20056972115, 2005.
W. -B. Kim, J.-S. Park, C.-Y. Suh, D.-S. Kil and J.-C. Lee, US Pat.,
20070209477, 2007.
J. P. Lei, X. L. Dong and X. G. Zhu et al., Formation and
characterization of intermetallic FeSn nanoparticles synthesized by
an arc discharge method, Intermetallics, 2007, 15(12), 15891594.
M. Gupta, E. Wong and W. Leong, Microwaves and Metals, WileyInterscience, New York, 2007, 256 pp.
S. Komarneni, H. Katsuki, D. Li and A. S. Bhalla, Microwave
polyol process for metal nanophases, J. Phys.: Condens. Matter,
2004, 16, S1305S1312.
M. F. Becker, J. R. Brock and H. Cai et al., Metal nanoparticles
generated by laser ablation, Nanostruct. Mater., 1998, 10(5),
853863.
A. R. Rodrigues, J. M. Soares, F. L. A. Machado, W. M. de
Azevedo and D. D. de Carvalho, Synthesis of a-Fe particles using a
modified metalmembrane incorporation technique, J. Magn. Magn.
Mater., 2007, 310(2), 24972499.
S. J. Klaine, P. J. J. Alvarez, G. E. Batley, T. F. Fernandes, R. D.
Handy, D. J. Lyon, S. Mahendra, M. J. Mclaughlin and J. R. Lead,
Nanomaterials in the environment: behavior, fate, bioavailability,
and effects, Environ. Toxicol. Chem., 2008, 27(9), 18251851.
R. Yuvakkumar, V. Elango, V. Rajendran and N. Kannan,
Preparation and characterization of zerovalent iron nanoparticles,
Dig. J. Nanomater. Biostruct., 2011, 6(4), 17711776.
H. Bonnemann, W. Brijoux, R. Brinkmann, E. Dinjus, T. Joussen
bergangsmetallen in
and B. Korall, Erzeugung von kolloiden U
organischer Phase und ihre Anwendung in der Katalyse, Angew.
Chem., Int. Ed. Engl., 1991, 30, 13121344.
S. Yuan-Pang, L. Xiao-Qin, Z. Wei-Xian and H. P. Wang, A
method for the preparation of stable dispersion of zerovalent iron
nanoparticles, Colloids Surf., A, 2007, 308(13), 6066.
A. Harutyunyan, L. Grigorian and T. Tokune, Method for synthesis
of metal nanoparticles, US Pat., 20056974493, 2005.
C. Klinke and K. Kern, Iron nanoparticle formation in a metal
organic matrix: from ripening to gluttony, Nanotechnology, 2007,
18, 215601.
Y. Lu, Z. Zhu and Z. Liu, Carbon-encapsulated Fe nanoparticles
from detonation-induced pyrolysis of ferrocene, Carbon, 2005,
43(2), 369374.
P. T. Anastas and I. T. Horvath, Green Chemistry for a Sustainable
Future, Wiley, 1st edn, 2012, 350 pp.
C.-J. Li and P. T. Anastas, Handbook of Green Chemistry - Green
Processes, Wiley-VCH, 3 Volume Set edition, 2012, 1326 pp.
V. K. Ahluwalia, Green Chemistry: Environmentally Benign
Reactions, CRC Press, 2nd edn, 2012, 326 pp.
J. T. Patel, O. B. Patel and B. P. Raval, Green Chemistry: New
Avenues in Chemical Research: Focus in Healthcare, LAP
LAMBERT Academic Publishing, 2012, 60 pp.
R. Luque, Green Chemistry, Nova Science Publishers, 2011.

9352 | RSC Adv., 2012, 2, 93259358

51 G. E. Hoag, J. B. Collins, R. S. Varma and M. Nadagouda, Green


synthesis of metal nanoparticles using plant extracts, PCT Int.
Appl., WO 2009140694 A2 20091119, 2009.
52 K. E. Tanui, Green Synthesis and Characterization of Iron
Nanoparticles, http://chemistry.uonbi.ac.ke.
53 G. E. Hoag, J. B. Collins, J. L. Holcomb, J. R. Hoag, M. N.
Nadagouda and R. S. Varma, J. Mater. Chem., 2009, 19(45),
86718677.
54 M. N. Nadagouda, A. B. Castle, R. C. Murdock, S. M. Hussain and
R. S. Varma, Green Chem., 2010, 12, 114122.
55 C. Yao, H. Ma and Y. Tong, Electrochemical preparation and
magnetic study of amorphous nanostructured NdFeCoNiMn
high entropy alloy film, Yingyong Huaxue, 2011, 28(10), 11891194.
56 B.-Y. Yoo, S. C. Hernandez, B. Koo, Y. Rheem and N. V. Myung,
Electrochemically fabricated zerovalent iron, iron-nickel, and ironpalladium nanowires for environmental remediation applications,
Water Sci. Technol., 2007, 55, 149156 (1-2, Wastewater
Reclamation and Reuse for Sustainability).
57 A. V. Glebov, V. A. Glebov and O. I. Popova, Development of
nanofilm Fe-Pt magnets for superdense-recording heads, Tsvetnye
Metally, 2009, 12, 6770.
58 B. Wang, D. C. Berry, Y. Chiari and K. Barmak, Experimental
measurements of the heats of formation of Fe3Pt, FePt, and FePt3
using differential scanning calorimetry, J. Appl. Phys., 2011, 110(1),
013903/11-013903/8.
59 E. P. Yelsukov, G. N. Konygin, V. E. Porsev Voronina and V. Ye,
Mossbauer spectroscopy of Fe-based nanomaterials, Czech. J.
Phys., 2006, 56(S3), E31E44.
60 L. H. Dale, Synthesis, applications, and applications of iron
nanoparticles, Small, 2005, 1(5), 482501.
61 W. L. Zhou, E. E. Carpenter, J. Lin, A. Kumbhar, J. Sims and C. J.
OConnor, Nanostructures of gold coated iron coreshell nanoparticles and the nanobands assembled under magnetic field, Eur. Phys.
J. D: At., Mol. Opt. Phys., 2001, 16(13), 289292.
62 Nanoparticle Assemblies and Superstructures, ed. N. S. Kotov, CRC
Press, 2005, 407 pp.
63 Electrochemical Sensors, Biosensors and their Biomedical
Applications, ed. X. Zhang, H. Ju and J. Wang, Academic Press,
2007, 446 pp.
64 Nanomaterials for Application in Medicine and Biology, ed. M.
Giersig and G. B. Khomutov, Springer, 2008, 99 pp.
65 Handbook of Microscopy for Nanotechnology, ed. N. Yao and Z. L.
Wang, Springer, 2005, 170 pp.
66 Principles of Inorganic Materials Design, ed. J. N. Lalena and D. A.
Cleary, Wiley-Interscience, 2005, 404 pp.
67 Nanocomposite structures and dispersions, ed. I. Capek, Volume 23
(Studies in Interface Science), Elsevier Science, 2006, 155 pp.
68 Modern Supramolecular Gold Chemistry: Gold-Metal Interactions
and Applications, ed. A. Laguna, Wiley-VCH, 2008, 525 pp.
69 L. Guczi, A. Beck, A. Horvath and D. Horvath, From molecular
clusters to metal nanoparticles, Top. Catal., 2002, 19(2), 157163.
70 L. Wang, H.-Y. Park and S. I.-I. Lim et al., Core@shell
nanomaterials: gold-coated magnetic oxide nanoparticles, J.
Mater. Chem., 2008, 18(23), 26292635.
71 S. Grancharov, S. OBrien, G. Held and C. Bruce Murray, Method
of preparation of biomagnetic nanoparticles coated with a noble
metal layer, US Pat., 20060140868, 2006; World Pat., WO/2004/
060580, 2004.
72 T. Hyeon, J. Y. Kim, M-.H. Cho, K. Kim Seong and J. Lee, Use of
coreshell gold nanoparticle which contains magnetic nanoparticles
for MRI T2 contrast agent, cancer diagnostic and therapy, World
Pat., WO 2008048074, 2008.
73 A. Naitabdi and B. R. Cuenya, Formation, thermal stability, and
surface composition of size-selected Au-Fe nanoparticles, Appl.
Phys. Lett., 2007, 91(11), 1131101-1131103.
74 N. Dahal, V. Chikan, J. Jasinski and V. J. Leppert, Synthesis of
Water-Soluble Iron-Gold Alloy Nanoparticles, Chem. Mater., 2008,
20(20), 63896395.
75 H. L. Liu, J. H. Wu, J. H. Min and Y. K. Kim, Synthesis of
monosized magnetic-optical AuFe alloy nanoparticles, J. Appl.
Phys., 2008, 103(7, Pt. 2), 07D52911-07D529/3.
76 K. Sato, B. Bian and Y. Hirotsu, L10 type ordered phase formation
in Fe-Au nanoparticles, Jpn. J. Appl. Phys., 2002, 41(Part 2, No. 1A/
B), L1L3.

This journal is The Royal Society of Chemistry 2012

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online


77 S.-J. Cho, S. M. Kauzlarich and J. Olamit et al., Characterization
and magnetic properties of coreshell structured Fe/Au nanoparticles, J. Appl. Phys., 2004, 95(11), 68046806.
78 J. Lin, W. Zhou and A. Kumbhar et al., Gold-coated iron (Fe/Au)
nanoparticles: synthesis, characterization, and magnetic fieldinduced self-assembly, J. Solid State Chem., 2001, 159(1), 2631.
79 R. P. Andres, Ng, A. T. Fe/Au nanoparticles and methods, World
Pat., WO 2003073444, 2003.
80 M. Chen, S. Yamamuro, D. Farrell and S. A. Majetich, Gold-coated
iron nanoparticles for biomedical applications, J. Appl. Phys., 2003,
93(10), 75517553.
81 A. Zelenakova, J. Kovac, V. Kavecansky and V. Zelenak, Magnetic
study of the Fe coated by Au nanoparticles, Acta Phys. Polonica, A,
2008, 113(1), 533536.
82 O. Pana, C. M. Teodorescu and O. Chauvet et al., Structure,
morphology and magnetic properties of Fe-Au coreshell nanoparticles, Surf. Sci., 2007, 601(18), 43524357.
83 Z. Ban, Y. A. Barnakov, F. Li, V. O. Golub and C. J. OConnor,
The synthesis of coreshell iron@gold nanoparticles and their
characterization, J. Mater. Chem., 2005, 15(43), 46604662.
84 S.-J. Cho, A. M Shahnin and G. J. Long et al., Magnetic and
moessbauer study of core/shell Fe/Au nanoparticles, Chem. Mater.,
2006, 18(4), 960967.
85 B. Ravel, E. E. Carpenter and V. G. Harris, Oxidation of iron in
iron/gold core/shell nanoparticles, J. Appl. Phys., 2002, 91(10),
81958197.
86 D. A. Fleming, M. Napolitano and M. E. Williams, Chemically
functional alkanethiol derivatized magnetic nanoparticles, MRS
Symp. Proc., 2003, 746, 207212.
87 D.-L. Lu, K. Domen and K.-I. Tanaka, Electrodeposited Au-Fe,
Au-Ni, and Au-Co alloy nanoparticles from aqueous electrolytes,
Langmuir, 2002, 18(8), 32263232.
88 M. Mirdamadi-Esfahani, M. Mostafavi and B. Keita et al., Au-Fe
system: application in electro-catalysis, Gold Bull., 2008, 41(2),
98104.
89 W.-S. Chang, J.-W. Park, V. Rawat, T. Sands and G.U. Lee,
Templated synthesis of goldiron alloy nanoparticles using pulsed
laser deposition, Nanotechnology, 2006, 17(20), 51315135.
90 D. B. Akolekar, S. K. Bhargava, G. Foran and M. Takahashi,
Studies on gold nanoparticles supported on iron, cobalt, manganese,
and cerium oxide catalytic materials, J. Mol. Catal. A: Chem., 2005,
238(12), 7887.
91 E. Smolentseva, A. Pestryakov and N. Bogdanchikova et al.,
Influence of Fe introduction method on gold state in NaY zeolite,
Int. J. Mod. Phys. B: Condens. Matter Phys, Stat. Phys, Appl. Phys.,
2005, 19(15, 16 & 17, Pt. 1), 24962501.
92 D. Horvath, M. Polisset-Thfoin, J. Fraissard and L. Guczi, Novel
preparation method and characterization of Au-Fe/HY zeolite
containing highly stable gold nanoparticles inside zeolite supercages,
Solid State Ionics, 2001, 141142, 153156.
93 H. Tada, T. Soejima, S. Ito and H. Kobayashi, Photoinduced
desorption of sulfur from gold nanoparticles loaded on metal
surfaces, J. Am. Chem. Soc., 2004, 126(49), 1595215953.
94 Z. Wang, J. Wang and L. Sun, Method for synthesizing antibodymagnetic nanoparticles with gold shell and iron core for recognition
and separation of tumor cells, CN 101303342, 2008.
95 S.-J. Cho, B. R. Jarrett, A. Y. Louie and S. M. Kauzlarich, Goldcoated iron nanoparticles: a novel magnetic resonance agent for T1
and T2 weighted imaging, Nanotechnology, 2006, 17(3), 640644.
96 S. V. Jadhav, Synthesis and characterization of iron core gold shell
nanoparticles and their application to pathogen detection.
Abstracts, 39th Central Regional Meeting of the ACS, Corvington
KY, USA, May 20232007.
97 H. Liu, S. Li, N. He and Y. Deng, Preparation of streptavidin
coated gold magnetic nanoparticles using cysteamine. Abstracts of
Papers, 235th ACS National Meeting, New Orleans, LA, USA, Apr.
6102008, ANYL-137.
98 K. A. Brown, A. Wijaya, J. D. Alper and K. Hamad-Schifferli,
Synthesis of water-soluble, magnetic Fe/Au nanoparticles, MRS
Symp. Proc., 2006, Volume Date 2005, 900E (Nanoparticles and
Nanostructures in Sensors and Catalysis), Paper #: 0900-O07-01.
99 N. Y. He, Y. F. Guo, Y. Deng, Z. F. Wang, S. Li and H. N. Liu,
Carbon encapsulated magnetic nanoparticles produced by hydrothermal reaction, Chin. Chem. Lett., 2007, 18(4), 487490.

This journal is The Royal Society of Chemistry 2012

100 Z. Wang, P. Xiao and N. He, Synthesis and characteristics of carbon


encapsulated magnetic nanoparticles produced by a hidrotermal
reaction, Carbon, 2006, 44(15), 32773284.
101 C. Femoni, M. C. Iapalucci, G. Longoni, C. Tiozzo and S. Zacchini,
An organometallic approach to gold nanoparticles: synthesis and
X-ray structure of CO-protected Au21Fe10, Au22Fe12, Au28Fe14 and
Au34Fe14 clusters, Angew. Chem., Int. Ed., 2008, 47(35), 66666669.
102 T. Wang, D. Zhang, W. Xu, S. Li and D. Zhu, New approach to the
assembly of gold nanoparticles: formation of stable gold nanoparticle ensemble with chainlike structures by chemical oxidation in
solution, Langmuir, 2002, 18(22), 86558659.
103 I. Narita, T. Oku1, H. Tokoro and K. Suganuma, Synthesis and
structures of iron nanoparticles coated with boron nitride nanomaterials, J. Electron Microsc. Technol., 2006, 55(3), 123127.
104 M. Fan, P. Yuan, F. Bergaya, H. He, T. Chen, J. Zhu and D. Liu, A
critical textural evolution study of zerovalent iron/montmorillonite
nanosized heterostructures under various iron loadings, Clays Clay
Miner., 2011, 59(5), 490500.
105 Y. Kong and H. Zhou, Formation and magnetic characterization of
magnesium oxide / iron nano composite particles, Adv. Mater. Res.,
2011, 236238 (Pt. 2, Application of Chemical Engineering), 1927
1930.
106 F. Wang, M. Malac, R. F. Egerton and A. Meldrum et al.,
Multilayer route to iron nanoparticle formation in an insulating
matrix, J. Appl. Phys., 2007, 101(034314), 7 pp.
107 E. Iwamura and M. Yamaguchi, Nano-structural modification of
amorphous carbon thin films by low-energy electron beam
irradiation, Cailiao Rechuli Xuebao, 2004, 25(5, Pt. 2), 12471252.
108 Q.-X. Li, Z.-y. Sun and T. Wang, A study on preparation,
characterization and photocatalytic activity of iron-doped nanoTiO2 thin films based on self-assembled monolayers, Kuangwu
Xuebao, 2011, 31(1), 102107.
109 Q.-Y. Xu, F. Liu, J.-T. Lu, G. Kong and C.-S. Che, Microstructure
and performance of electroplated Fe-nano ZrO2 composite coating,
Jixie Gongcheng Cailiao, 2007, 31(9), 5154.
110 G. Shi, J. Zhang, D. Yu and L. Chen, Synthesis and microwaveabsorbing properties of Al2O3 coated polyhedral Fe nanocapsules
prepared by arc-discharge method, Adv. Mater. Res., 2011, 299300
(Pt. 2, Materials and Manufacturing), 739742.
111 Q. Wang, J.-H. Lee, S.-W. Jeong, A. Jang, S. Lee and H. Choi,
Mobilization and deposition of iron nano and sub-micrometer
particles in porous media: A glass micromodel study, J. Hazard.
Mater., 2011, 192, 14661475.
112 J. Wang and R. Cheng, Preparation and application of activated
carbon supported iron nanomaterial, with application to pentachlorophenol degradation, CN 101708457, 2010.
113 M. Bystrzejewski, Synthesis of carbon-encapsulated iron nanoparticles via solid state reduction of iron oxide nanoparticles, J. Solid
State Chem., 2011, 184(6), 14921498.
114 Z. Wei, X. Wang and H. Yang, Preparation of carbon-encapsulated
Fe coreshell nanostructures by confined arc plasma, Mater. Sci.
Forum, 2011, 688, 245 (Nano-Scale and Amorphous Materials),
245249.
115 C. N. R. Rao, P. J. Thomas and G. U. Kulkarni, Nanocrystals:
Synthesis, Properties and Applications (Springer Series in Materials
Science), Springer, 2007, 182.
116 X. Bingshe, G. Junjie, W. Xiaomin, L. Xuguang and I. Hideki,
Synthesis of carbon nanocapsules containing Fe, Ni or Co by arc
discharge in aqueous solution, Carbon, 2006, 14(13), 26312634.
117 H. Tokoro, S. Fujii and T. Oku, Iron nanoparticles coated with
graphite nanolayers and carbon nanotubes, Diamond Relat. Mater.,
2004, 13(48), 12701273.
118 M. N. Nadagouda and D. A. Lytle, Microwave-assisted combustion
synthesis of nano iron oxide/iron coated activated carbon,
anthracite, cellulose fiber, and silica, with arsenic adsorption studies,
J. Nanotechnol., 2011, 972486 (8 pp.).
119 Y. An and J. Qiu, Synthesis of carbon encapsulated iron nanoparticles
by carbonization of starch with iron as catalyst, 2007, The American
Carbon Society. http://acs.omnibooksonline.com/data/papers/
2004_C085.pdf.
120 Y. An, X. Wu, Z. Sui, Y. Xia and Y. Liu, A novel method for
synthesis of homogeneous carbon encapsulated Fe nanoparticles
based on natural biopolymer, J. Rare Earths, 2007, 25, 452.
121 G. Huang and J. Weng, Syntheses of carbon nanomaterials by
ferrocene, Curr. Org. Chem., 2011, 15(21), 36533666.

RSC Adv., 2012, 2, 93259358 | 9353

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online


122 O. V. Kharissova, Vertically aligned carbon nanotubes fabricated by
microwaves, Rev. Adv. Mater. Sci., 2004, 7(1), 5054.
123 O. V. Kharissova and J. R. Cardenas, Advance in methods of
forming vertically aligned carbon nanotubes by microwave, Phys.
Status Solidi C, 2005, 2(8), 30633066.
124 J. Huo, H. Song and X. Chen, Preparation of carbon-encapsulated
iron nanoparticles by co-carbonization of aromatic heavy oil and
ferrocene, Carbon, 2004, 42, 31773182.
125 Q. Kong, C. Guo, B. Wang, Q. Ji and Y. Xia, A facile preparation
of carbon-supported nanoscale zerovalent iron fibers, Mater. Sci.
Forum, 2011, 688, 349352.
126 A. Desai, D. Mahajan and M. Rafailovich, Synthesis and
characterization of nanosized iron on a polystyrene support as
potential FischerTropsch catalysts, Prepr. Pap.-Am. Chem. Soc.,
Div. Fuel Chem., 2003, 48(2), 783784.
127 H.-J. Kim, T. Phenrat, R. D. Tilton and G. V. Lowry, Effect of
kaolinite, silica fines and pH on transport of polymer-modified zero
valent iron nano-particles in heterogeneous porous media, J. Colloid
Interface Sci., 2012, 370(1), 110.
128 A. G. Nasibulin, S. Rackauskas, H. Jiang, Y. Tian, P. R. Mudimela,
S. D. Shandakov, L. Nasibulina, J. Sainio, E. I. Kauppinen and Y.
Jiang, Simple and Rapid Synthesis of a-Fe2O3 Nanowires Under
Ambient Conditions, Nano Res., 2010, 2, 373379.9.
129 M. Kooti and L. Matturi, Microwave-Assisted Fabrication of
c-Fe2O3 Nanoparticles from Tris(acetylacetonato) Iron (III), Int.
Nano Lett., 2011, 1(1), 3842.
130 D. Barreca, G. Carraro, A. Devi, E. Fois, A. Gasparotto, R.
Seraglia, C. Maccato, C. Sada, G. Tabacchi, E. Tondello, A. Venzo
and M. Winter, b-Fe2O3 nanomaterials from an iron(II) diketonatediamine complex: a study from molecular precursor to growth
process, Dalton Trans., 2012, 41, 149155.
131 A. Mehrani and A. Morsali, One-dimensional Coordination
Polymer as New Precursor for Preparation of Fe 2 O 3
Nanoparticles, J. Inorg. Organomet. Polym. Mater., 2011, 21(3),
476479.
132 L. Vulicevic, N. Ivanovic, A. Maricic, M. Sreckovic, S. Vardic, M.
P laz in ic and Z. Tomic , Hydrothermal T reatment of
Electrochemically Synthesised Nanocrystalline Magnetic Iron
Oxide Powder, Sci. Sintering, 2007, 39, 8591.
133 L. Duraes, A. Moutinho, I. J. Seabra, B. F. O. Costa, H. C. de
Sousa and A. Portugal, Characterization of iron(III) oxide/hydroxide nanostructured materials produced by solgel technology based
on the Fe(NO3)3.9H2O/ethanol/propylene oxide system, Mater.
Chem. Phys., 2011, 130(12), 548560.
134 Z. Li, M.-H. Wu, J.-Z. Gu, Z. Jiao, S.-L. Lu and De-Q. Wang,
Preparation of nanocrystalline Fe2O3 by radiation technique,
Gaoxiao Huaxue Gongcheng Xuebao, 2006, 20(3), 481484.
135 S. -Q. Liu, K. Furuya,A. Hasegawa,K. Mitsuishi and H.
Hashimoto, Manufacture of iron oxide using electron beam, Jpn.
Pat., JP 2005247669, 2005.
136 S. Mollah, Laser Synthesis of Iron Oxide Nanowires, Asian J.
Chem., 2009, 21(10), S001003.
137 S. Seino, T. Kinoshita, T. Nakagawa, T. Kojima, R. Taniguci, S.
Okuda and T. A. Yamamoto, Radiation induced synthesis of gold/
iron-oxide composite nanoparticles using high-energy electron
beam, J. Nanopart. Res., 2007, 10(6), 10711076.
138 B. I. Kharisov, O. V. Kharissova, M. Jose Yacaman and U. Ortiz
Mendez, State of the art of the bi- and trimetallic nanoparticles on
the basis of gold and iron, Recent Pat. Nanotechnol., 2009, 3(2),
8198.
139 A. Gole, J. W. Stone, W. R. Gemmill, H.-C. zur Loye and C. J.
Murphy, Iron oxide coated gold nanorods: synthesis, characterization, and magnetic manipulation, Langmuir, 2008, 24(12),
62326237.
140 L. Wang, J. Bai, Y. Li and Y. Huang, Multifunctional nanoparticles
displaying magnetization and near-IR absorption, Angew. Chem.,
Int. Ed., 2008, 47(13), 24392442.
141 T. A. Salah El-Din, A. A. Elzatahry, D. M. Aldhayan, A. M. AlEnizi and S. S. Al-Deyab, Synthesis and Characterization of
Magnetite Zeolite Nano Composite, Int. J. Electrochem. Sci.,
2011, 6, 61776183.
142 H. Liu, G. Lan, Y. Yan, H. Tang, H. Liu and Y. Li, Direct
hydrothermal synthesis of novel ordered magnetic mesoporous
nanocomposites with high content of iron, Gongye Cuihua, 2011,
19(8), 1115.

9354 | RSC Adv., 2012, 2, 93259358

143 Y.-F. Shi, X. Zhou, L.-B. Zhong, W.-L. Xu, Y. Wang and Q.-Q.
Zhang, Synthesis and formation mechanism of coreshell Fe3O4
coated gold nanomaterials, Dongnan Daxue Xuebao, Yixueban,
2011, 30(1), 610.
144 X. Liu, M. Xu, R. Zhao and J. Zhong, Iron phthalocyanine
prepolymer/Fe3O4 nano hybrid magnetic material and its preparation method, Faming Zhuanli Shenqing, 2011, CN 102086304.
145 Y. Cai, Y. Shen, A. Xie, S. Li and X. Wang, Green synthesis of soya
bean sprouts-mediated superparamagnetic Fe3O4 nanoparticles, J.
Magn. Magn. Mater., 2010, 322(19), 29382943.
146 W. Lu, Y. Shen, A. Xie and W. Zhang, Green synthesis and
characterization of superparamagnetic Fe3O4 nanoparticles, J.
Magn. Magn. Mater., 2010, 322(13), 18281833.
147 R. H. Bagramov, V. D. Blank, N. R. Serebryanaya, G. A. Dubitsky,
E. V. Tatyanin and V. V. Aksenenkov, High Pressures Synthesis of
Iron Carbide Nanoparticles Covered with Onion-Like Carbon
Shells, Fullerenes, Nanotubes, Carbon Nanostruct., 2012, 20(1),
4148.
148 M. Mohapatra and S. Anand, Synthesis and applications of nanostructured iron oxides/hydroxides a review, Int. J. Eng. Sci.
Technol., 2010, 2(8), 127146.
149 S. P. Gubin, Yu. A. Koksharov, G. B. Khomutov and Y. G.
Yurkov, Magnetic nanoparticles: preparation, structure and properties, Russ. Chem. Rev., 2005, 74(6), 489520.
150 K. A. Revati and B. D. Padney, Microbial synthesis of iron-based
nanomaterialsA review, Bull. Mater. Sci., 2011, 34(2), 191198.
151 O. V. Kharissova and B. I. Kharisov, Synthetic techniques and
applications of activated nanostructurized metals: highlights up to
2008, Recent Pat. Nanotechnol., 2008, 2(2), 103119.
152 C. Noubactep and A. Schoener, Metallic iron: dawn of a new era of
drinking water treatment research?, Fresenius Environ. Bull., 2010,
19(8a), 16611668.
153 Overview and Comparison of Conventional and Nano-Based water
treatment technologies. Meridian Institute Global Dialogue on
Nanotechnology and the Poor: Opportunities and Risks. http://
www.merid.org/nano/watertechpaper..
154 T. B. Scott, Inorganic nanoparticles for environmental remediation,
Inorg. Nanopart., 2011, 393439.
155 J. U. Lee, S. G. Cho, Y. S. Jang, J. H. Kim and S. H. Cho, Method
for purifying soil and groundwater using nZVI and DI-PRB, KR
1027140B1 20110405, 2011.
156 Z. Wei-xian, Nanoscale iron particles for environmental remediation: An overview, J. Nanopart. Res., 2003, 5, 323332.
157 D. W. Elliott, H.-L. Lien and W.-x. Zhang, J. Environ. Qual., 2008,
37(6), 21922201.
158 K. R. Reddy, K. Darko-Kagya and C. Cameselle, Electrokineticenhanced transport of lactate-modified nanoscale iron particles for
degradation of dinitrotoluene in clayey soils, Sep. Purif. Technol.,
2011, 79(2), 230237.
159 A. J. Salter-Blanc and P. G. Tratnyek, Effects of solution chemistry
on the dechlorination of 1,2,3-trichloropropane by zerovalent zinc,
Environ. Sci. Technol., 2011, 45, 40734079.
160 Z. Shi, J. T. Nurmi and P. G. Tratnyek, Effects of nano zerovalent
Iron (nZVI) on oxidation-reduction potential (ORP), Environ. Sci.
Technol., 2011, 45, 15861592.
161 P. G. Tratnyek and A. J. Salter, Response to Comment on
Degradation of 1,2,3-Trichloropropane (TCP): Hydrolysis,
Elimination, and Reduction by Iron and Zinc, Environ. Sci.
Technol., 2010, 44, 31983199.
162 V. Sarathy, P. G. Tratnyek, J. T. Nurmi and R. L. Johnson G. O. B.
Johnson, Degradation of 1,2,3-trichloropropane (TCP): Hydrolysis,
elimination, and reduction by iron and zinc, Environ. Sci. Technol.,
2010, 44, 787793.
163 C. A. Gorski, J. T. Nurmi, P. G. Tratnyek, T. B. Hofstetter and M.
M. Scherer, Redox behavior of magnetite: Implications for
contaminant reduction, Environ. Sci. Technol., 2010, 44, 5560.
164 R. L. Johnson, R. OBrien Johnson, J. T. Nurmi and P. G.
Tratnyek, Natural organic matter enhanced mobility of nano
zerovalent iron, Environ. Sci. Technol., 2009, 43, 54555460.
165 V. Sarathy, P. G. Tratnyek, J. T. Nurmi, D. R. Baer, J. E.
Amonette, C. Chun, R. L. Penn and E. J. Reardon, Aging of iron
nanoparticles in aqueous solution: effects on structure and
reactivity, J. Phys. Chem. C, 2008, 112, 22862293.
166 J.-H. Kim, P. G. Tratnyek and Y.-S. Chang, Rapid dechlorination
of polychlorinated dibenzo-p-dioxins (PCDDs) by bimetallic and

This journal is The Royal Society of Chemistry 2012

View Article Online

167

168

169

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

170

171

172
173

174

175

176

177

178

179

180
181

182

183

184

185

186

nano-sized zerovalent iron, Environ. Sci. Technol., 2008, 42,


41064112.
R. L. Johnson, R. B. Thoms, R. OBrien Johnson, J. T. Nurmi and
P. G. Tratnyek, Mineral precipitation and flow reduction upgradient from a zerovalent iron permeable reactive barrier, Ground
Water Monit. Rem., 2008, 28, 5664.
R. L. Johnson, P. G. Tratnyek, R. Miehr, B. B. Thoms and J. Z.
Bandstra, Reduction of hydraulic conductivity and reactivity in
zerovalent iron columns by oxygen and TNT, Ground Water Monit.
Rem., 2005, 25, 129136.
P. G. Tratnyek, V. Sarathy, J. T. Nurmi and R. L. Johnson, Nano
ZVI vs. conventional ZVI: The effect of particle size, Abstracts of
Papers, 233rd ACS National Meeting, Chicago, IL, United States,
Mar. 2529, 2007, p. IEC-167.
X.-qin Li and W.-xian Zhang, Iron Nanoparticles: the CoreShell
Structure and Unique Properties for Ni(II) Sequestration, Langmuir,
2006, 22(10), 4638462.
M. Auffan, H. J. Shipley, S. Yean, A. T. Kan, M. Tomson, J. Rose
and J.-Y. Bottero, Chapter 10. Nanomaterials as Adsorbents,
inEnvironmental Nanotechnology, McGraw-Hill, 2007, pp. 371392.
D. K. Tiwari, J. Behari and P. Sen, Application of Nanoparticles in
Waste Water Treatment, World Appl. Sci. J., 2008, 3(3), 417433.
C. Uzum, T. Shahwan, A. E. Eroglu, I. Lieberwirth, T. B. Scott and
K. R. Hallam, Application of zerovalent iron nanoparticles for the
removal of aqueous Co2+ ions under various experimental conditions, Chem. Eng. J., 2008, 144(2), 213220.
V. Grover, J. Hu, K. Engates and H. J. Shipley, Sorption of metals
to hematite nanoparticles: Competitive and temperature effects,
Abstracts of Papers, 241st ACS National Meeting & Exposition,
Anaheim, CA, United States, March 2731, 2011, COLL-458.
M. Ahmadi, F. Mashhoon, R. Kaveh and F. Tarkian, Use of
mechanically prepared iron nano particles for nitrate removal from
water, Asian J. Chem., 2011, 23(3), 12051208.
A. Ryu, S.-W. Jeong, A. Jang and H. Choi, Reduction of highly
concentrated nitrate using nanoscale zerovalent iron: Effects of
aggregation and catalyst on reactivity, Appl. Catal., B, 2011, 105(1
2), 128135.
Y.-H. Hwang, D.-G. Kim and H.-S. Shin, Mechanism study of
nitrate reduction by nano zero valent iron, J. Hazard. Mater., 2011,
185(23), 15131521.
H. Kang, T. Li, Z. Xiu, L. Sun, Z. Liu and Z. Jin, Denitrification of
nitrate using bimetallic Ni/Fe nanoparticles. Preprints of Extended
Abstracts presented at the ACS National Meeting, American
Chemical Society, Division of Environmental Chemistry, 2006,
vol. 46(2), pp. 7275.
K.-H. Shin and D. K. Cha, Microbial reduction of nitrate in the
presence of nanoscale zerovalent iron, Chemosphere, 2008, 72(2),
257262.
http://www.msnbc.msn.com/id/16947780/ns/technology_and_scienceinnovation/t/million-prize-awarded-water-purifier/#.T-t7AvVSSyo.
S. Luther, N. Borgfeld, J. Kim and J. G. Parsons, Removal of
arsenic from aqueous solution: A study of the effects of pH and
interfering ions using iron oxide nanomaterials, Microchem. J.,
2012, 101, 3036.
B. A. Manning, J. R. Kiser, H. Kwon and S. R. Kanel,
Spectroscopic Investigation of Cr(III)- and Cr(VI)-Treated
Nanoscale Zerovalent Iron, Environ. Sci. Technol., 2007, 41(2),
586592.
Q. Wang, S. Snyder, J. Kim and H. Choi, Aqueous Ethanol
modified Nanoscale Zerovalent Iron in Bromate Reduction:
Synthesis, Characterization, and Reactivity, Environ. Sci. Technol.,
2009, 43(9), 32923299.
Q. Sun, S. E. Mylon and T. D. Waite, Production of reactive oxygen
species from zerovalent iron nanomaterials. Preprints of Extended
Abstracts presented at the ACS National Meeting, American
Chemical Society, Division of Environmental Chemistry, 2008,
vol. 48(1), pp. 379381.
P. Varanasi, A. Fullana and S. Sidhu, Remediation of PCB
contaminated soils using iron nano-particles, Chemosphere, 2007,
66(6), 10311038.
C. Chen, X. Wang, Y. Chang and H. Liu, Dechlorination of
disinfection by-product monochloroacetic acid in drinking water by
nanoscale palladized iron bimetallic particle, J. Environ. Sci., 2008,
20(8), 945951.

This journal is The Royal Society of Chemistry 2012

187 T. Satapanajaru, P. Anurakpongsatorn, P. Pengthamkeerati and H.


Boparai, Remediation of atrazine-contaminated soil and water by
nano zerovalent iron, Water, Air, Soil Pollut., 2008, 192(14),
349359.
188 E.-J. Kim, J.-H. Kim, A.-M. Azad and Y.-S. Chang, Facile
Synthesis and Characterization of Fe/FeS Nanoparticles for
Environmental Applications, ACS Appl. Mater. Interfaces, 2011,
3(5), 14571462.
189 Y. Xi, M. Megharaj and R. Naidu, Dispersion of zerovalent iron
nanoparticles onto bentonites and use of these catalysts for orange
II decolourisation, Appl. Clay Sci., 2011, 53(4), 716722.
190 J. Ge, J. Tian, L. Zhuo, H. Chen and B. Tang, Fabrication of selfassembled iron oxide hierarchical nanostructures and their application in water treatment, Solid State Sci., 2011, 13(8), 15541559.
191 P. Larese-Casanova, D. M. Cwiertny and M. M. Scherer,
Nanogoethite Formation from Oxidation of Fe(II) Sorbed on
Aluminum Oxide: Implications for Contaminant Reduction,
Environ. Sci. Technol., 2010, 44(10), 37653771.
192 T. Long and C. A. Ramsburg, Encapsulation of nZVI particles
using a Gum Arabic stabilized oil-in-water emulsion, J. Hazard.
Mater., 2011, 189(3), 801808.
193 A. Zaleska, Doped-TiO2: A Review, Recent Pat. Eng., 2008, 2,
157164.
194 M. Aufan, Nanoparticules doxydes mrtalliques: relations entre la
reactivite de surface et des reponses biologiques. http://www.tel.archives-ouvertes.fr/docs/00/30/85/03/PDF/auffan_PhD.pdfSimilares.
195 C. Jing, X. Meng, S. Liu, S. Baidas, R. Patraju, C. Christodoulatos
and G. P. Korfiatis, Surface complexation of organic arsenic on
nanocrystalline titanium oxide, J. Colloid Interface Sci., 2005,
290(1), 1421.
196 J. Zhu, W. Zheng, B. He, J. Zhang and M. Anpo, Characterization
of Fe-TiO2 photocatalysts synthesized by hydrothermal method and
their photocatalytic reactivity for degradation of XRG dye diluted
in water, J. Mol. Catal. A: Chem., 2004, 216, 3543.
197 O. Celebi, C. Uezuem, T. Shahwan and H. N. Erten, A radiotracer
study of the adsorption behavior of aqueous Ba2+ ions on
nanoparticles of zerovalent iron, J. Hazard. Mater., 2007, 148(3),
761767.
198 M. Elsner, M. Chartrand, N. VanStone, G. Lacrampe Couloume
and B. Sherwood Lollar, Identifying Abiotic Chlorinated Ethene
Degradation: Characteristic Isotope Patterns in Reaction Products
with Nanoscale Zero-Valent Iron, Environ. Sci. Technol., 2008,
42(16), 59635970.
199 M. Elsner, G. L. Couloume, S. Mancini, L. Burns and B. S. Lollar,
Carbon isotope analysis to evaluate nanoscale Fe(O) treatment at a
chlorohydrocarbon contaminated site, Ground Water Monit. Rem.,
2010, 30(3), 7995.
200 S. E. Mylon, Q. Sun and T. D. Waite, Process optimization in use of
zero valent iron nanoparticles for oxidative transformations,
Chemosphere, 2010, 81(1), 127131.
201 C. R. Keenan and D. L. Sedlak, Factors affecting the yield of
oxidants from the reaction of nanoparticulate zerovalent iron and
oxygen. Preprints of Extended Abstracts - ACS National Meeting,
American Chemical Society, Division of Environmental Chemistry,
2008, vol. 48(2), pp. 748751.
202 H.-S. Kim, J.-Y. Ahn, K.-Y. Hwang, W.-S. Shin and I. Hwang,
Characteristics of nanoscale zerovalent iron (NZVI) particles
formed under controlled air contact. Preprints of Extended
Abstracts - ACS National Meeting, American Chemical Society,
Division of Environmental Chemistry, 2008, 48(2), pp. 198202.
203 M. B. Allabaksh, B. K. Mandal, M. K. Kesarla, K. S. Kumar and
P. S. Reddy, Preparation of stable zero valent iron nanoparticles
using different chelating agents, J. Chem. Pharm. Res., 2010, 2(5),
6774.
204 A. Tiehm, S. Krassnitzer, Y. Koltypin and A. Gedanken,
Chloroethene dehalogenation with ultrasonically produced airstable nano iron, Ultrason. Sonochem., 2009, 16(5), 617621.
205 K. Moore, B. Forsberg, D. R. Baer, W. A. Arnold and R. L. Penn,
Zero-Valent Iron: Impact of Anions Present during Synthesis on
Subsequent Nanoparticle Reactivity, J. Environ. Eng., 2011, 137(10),
889896.
206 Y.-H. Hwang, D.-G. Kim and H.-S. Shin, Effects of synthesis
conditions on the characteristics and reactivity of nano scale zero
valent iron, Appl. Catal., B, 2011, 105(12), 144150.

RSC Adv., 2012, 2, 93259358 | 9355

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online


207 P. Jiemvarangkul, W.-X. Zhang and H.-L. Lien, Enhanced
transport of polyelectrolyte stabilized nanoscale zerovalent iron
(nZVI) in porous media, Chem. Eng. J., 2011, 170(23), 482491.
208 M. M. Krol, A. J. Oleniuk, D. M. OCarroll and B. E. Sleep,
Modelling field scale nano-zero valent iron transport. 85th ACS
Colloid and Surface Science Symposium, Montreal, QC, Canada,
Jun. 1922, 2011, COLLSYMP-441.
209 Y.-D. Park, C.-S. Park and J.-W. Park, Interaction between iron
reducing bacteria and nano-scale valent iron, Sus. Environ. Res.,
2010, 20(4), 233238.
210 D. M. Cwiertny and Y. Xie, Dithionite as a regenerant for the
reducing capacity of nanoscale zerovalent iron in situ treatmentzones, ed. W. Sigmund, Abstracts of Papers, 238th ACS National
Meeting, Washington, DC, United States, Aug. 1620, 2009,
ENVR-063.
211 A. I. Keller, Y. Sheikhaldeen and I. Rampersaud, Environmental
remediation of contaminated groundwater using zerovalent iron
nanoparticles, ed. M. Laudon and B. Romanowicz, Abstracts, 41st
Central Regional Meeting of the American Chemical Society,
Dayton, OH, United States, Jun. 1619, 2010, CERMACS-387.
212 X. Li, X. Shen and L. Zhong, Method for delivering nanoparticles
series remediation substance into polluted aeration zone using
foams, CN 102225427, 2011.
213 X. Shen, L. Zhao, Y. Ding, B. Liu, H. Zeng, L. Zhong and X. Li,
Foam, a promising vehicle to deliver nanoparticles for vadose zone
remediation, J. Hazard. Mater., 2011, 186(23), 17731780.
214 L. B. Hoch, E. J. Mack, B. W. Hydutsky, J. M. Hershman, J. M.
Skluzacek and T. E. Mallouk, Carbothermal Synthesis of Carbonsupported Nanoscale Zerovalent Iron Particles for the Remediation
of Hexavalent Chromium, Environ. Sci. Technol., 2008, 42(7),
26002605.
215 S. Li, W. Yan and W.-X. Zhang, Solvent-free production of
nanoscale zerovalent iron (nZVI) with precision milling, Green
Chem., 2009, 11(10), 16181626.
216 M. Corbin and J. Wolters, Application of nanoparticle technology
for environmental cleanup at an industrial facility. Abstracts of
Papers, 235th ACS National Meeting, New Orleans, LA, United
States, Apr. 610, 2008, IEC-023.
217 L. Pang, Q. Zhou and X. Su, Progress of in situ modification
techniques of nanoscale zerovalent iron, Huagong Jinzhan, 2011,
30(6), 13611368.
218 Z. Shi, J. T. Nurmi, R. L. Johnson and P. G. Tratnyek,
Potentiometric detection of iron nanoparticles. Abstracts of
Papers, 239th ACS National Meeting, San Francisco, CA, United
States, Mar. 2125, 2010, ENVR-402.
219 R. Singh, V. Misra and R. P. Singh, Removal of Cr(VI) by
Nanoscale Zerovalent Iron (nZVI) From Soil Contaminated with
Tannery Wastes, Bull. Environ. Contam. Toxicol., 2011, 88(2),
210214.
220 Y. Liu, In situ remediation method for heavy metal-polluted soil,
2011, CN 102101123, 2011.
221 H. K. Boparai, M. Joseph and D. M. OCarroll, Cadmium removal
by nano zerovalent iron: Influence of physicochemical parameters.
Abstracts of Papers, 239th ACS National Meeting, San Francisco,
CA, United States, Mar. 2125, 2010, ENVR-385.
222 N. C. Mueller, J. Braun, J. Bruns, M. Cernik, P. Rissing, D.
Rickerby and B. Nowack, Application of nanoscale zero valent iron
(NZVI) for groundwater remediation in Europe, Environ. Sci.
Pollut. Res., 2011, 19(2), 550558.
223 M. G. O. Souza, F. T. Silva and J. F. Oliveira, Organic pollutants in
groundwater: remediation by nanoscale iron particles, WIT Trans.
Ecol. Environ., 2008, I, 105113 (Water Pollution).
224 M. C. Chang and H. Y. Kang, Remediation of pyrene-contaminated
soil by synthesized nanoscale zerovalent iron particles, J. Environ.
Sci. Health, Part A: Toxic/Hazard. Subst. Environ. Eng., 2009, 44,
576582.
225 R. Singh, A.s Singh, V. Misra and R. P. Singh, Degradation of
lindane contaminated soil using zerovalent iron nanoparticles, J.
Biomed. Nanotechnol., 2011, 7(1), 175176.
226 X. Li, Sequestration of malodorous sulfides with zerovalent iron
nanoparticles, ed. M. Laudon and B. Romanowicz, Abstracts of
Papers, 240th ACS National Meeting, Boston, MA, United States,
Aug. 2226, 2010, ENVR-330.
227 S. Comba, D. Dalmazzo, E. Santagata and R. Sethi, Rheological
characterization of xanthan suspensions of nanoscale iron for

9356 | RSC Adv., 2012, 2, 93259358

228
229

230

231

232

233

234

235

236

237

238

239

240

241

242

243

244

245
246

injection in porous media, J. Hazard. Mater., 2011, 185(23),


598605.
Y. Huang, D. Liu, Z. Qin, X. Liu and L. Zhang, As(III) adsorption
from drinking water on nanoscale zerovalent iron (NZVI): Kinetics
and isotherm studies, Integr. Ferroelectr., 2011, 127(1), 3947.
I. Halamova, P. Kvapil and L. Benesova, Use of iron nanoparticles
for remediation of groundwater by in situ chemical reduction of
chlorinated hydrocarbons in the Pisecna landfill locality, Vodni
Hospodarstvi, 2011, 61(7), 265268.
G. Naja, A. Halasz, S. Thiboutot, G. Ampleman and J. Hawari,
Degradation of Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX)
Using Zerovalent Iron Nanoparticles, Environ. Sci. Technol., 2008,
42(12), 43644370.
H.-S. Kim, J.-Y. Ahn, D.T. Le, K.-Y. Hwang, J.-Y. Lee, J.-Y. Chun
and I. Hwang, Effects of anions and organic matter on reactivity
and surface characteristics of nanoscale zerovalent iron particles,
Abstracts of Papers, 242nd ACS National Meeting & Exposition,
Denver, CO, United States, Aug. 28Sep. 1, 2011, COLL-23.
M. Dickinson and T. B. Scott, The effect of vacuum annealing on
the remediation abilities of iron and iron-nickel nanoparticles, J.
Nanopart. Res., 2011, 13(9), 36993711.
R. A. Crane, M. Dickinson, I. C. Popescu and T. B. Scott,
Magnetite and zerovalent iron nanoparticles for the remediation of
uranium contaminated environmental water, Water Res., 2011,
45(9), 29312942.
Y.-T. Wei, S.-C. Wu, C.-M. Chou, C.-H. Che, S.-M. Tsai and H.-L.
Lien, Influence of nanoscale zerovalent iron on geochemical
properties of groundwater and vinyl chloride degradation: A field
case study, Water Res., 2010, 44(1), 131140.
H.-L. Lien, Application and implication of zerovalent iron for
transformation of disinfection by-products: a comparison study
between nanoscale palladium iron and microscale iron, Zhongguo
Huanjing Gongcheng Xuekan, 2005, 15(4), 213221.
Y.-H. Shih, M.-Y. Chen and Y.-F. Su, Pentachlorophenol reduction
by Pd/Fe bimetallic nanoparticles: Effects of copper, nickel, and
ferric cations, Appl. Catal., B, 2011, 105(12), 2429.
N. Sakulchaicharoen, D. M. OCarroll and J. E. Herrera, Enhanced
stability and dechlorination activity of pre-synthesis stabilized
nanoscale FePd particles, J. Contam. Hydrol., 2010, 118(34),
117127.
Y. Zhuang, S. Ahn, A. L. Seyfferth, Y. Masue-Slowey, S. Fendorf
and R. G. Luthy, Dehalogenation of Polybrominated Diphenyl
Ethers and Polychlorinated Biphenyl by Bimetallic, Impregnated,
and Nanoscale Zerovalent Iron, Environ. Sci. Technol., 2011, 45(11),
48964903.
C. Chang, F. Lian and L. Zhu, Simultaneous adsorption and
degradation of c-HCH by nZVI/Cu bimetallic nanoparticles with
activated carbon support, Environ. Pollut., 2011, 159(10),
25072514.
Y. Hong, Y. Rheem, M. Lai, D. M. Cwiertny, S. L. Walker and
N. V. Myung, Electrochemical synthesis of FexNi1-x nanostructures
for environmental remediation, Chem. Eng. J., 2009, 151(13),
6672.
H. Zhou, J. Han, S. A. Baig and X. Xu, Dechlorination of 2,4dichlorophenoxyacetic acid by sodium carboxymethyl cellulosestabilized Pd/Fe nanoparticles, J. Hazard. Mater., 2011, 198, 712.
J. Zhan, B. Sunkara, J. Tang, Y. Wang, J. He, G. L. McPherson and
V. T. John, Carbothermal Synthesis of Aerosol-Based AdsorptiveReactive Iron-Carbon Particles for the Remediation of Chlorinated
Hydrocarbons, Ind. Eng. Chem. Res., 2011, 50(23), 1302113029.
B. Sunkara, J. Zhan, I. Kolesnichenko, Y. Wang, J. He, J. E.
Holland, G. L. McPherson and V. T. John, Modifying Metal
Nanoparticle Placement on Carbon Supports Using an AerosolBased Process, with Application to the Environmental Remediation
of Chlorinated Hydrocarbons, Langmuir, 2011, 27(12), 78547859.
B. Sunkara, Jingjing Zhan, Jibao He, G. L. McPherson, G. Piringer
and V. T. John, Nanoscale Zerovalent Iron Supported on Uniform
Carbon Microspheres for the In situ Remediation of Chlorinated
Hydrocarbons, ACS Appl. Mater. Interf., 2010, 2(10), 28542862.
D. Zhang, S. Wei, C. Kaila, X. Su, J. Wu, A. B. Karki, D. P. Young
and Z. Guo, Carbon-stabilized iron nanoparticles for environmental
remediation, Nanoscale, 2010, 2(6), 917919.
S. Xiao, M. Shen, R. Guo, S. Wang, X. Shi, Immobilization of
zerovalent iron nanoparticles into polymer/carbon nanotube composite nanofibers for environmental applications. Abstracts of

This journal is The Royal Society of Chemistry 2012

View Article Online

247

248
249
250

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

251

252

253
254

255
256

257
258

259

260
261

262

263

264
265

266

Papers, 239th ACS National Meeting, San Francisco, CA, United


States, March 2125, 2010, ENVR-111.
A. N. Bezbaruah, S. S. Shanbhogue, S. Simsek and E. Khan,
Encapsulation of iron nanoparticles in alginate biopolymer for
trichloroethylene remediation, J. Nanopart. Res., 2011, 13(12),
66736681.
T. Liu, L. Zhao, D. Sun and X. Tan, Entrapment of nanoscale
zerovalent iron in chitosan beads for hexavalent chromium removal
from wastewater, J. Hazard. Mater., 2010, 184(13), 724730.
Y. Zhang, Y. Li and X. Zheng, Removal of atrazine by nanoscale
zero valent iron supported on organobentonite, Sci. Total Environ.,
2011, 409(3), 625630.
S. Li, P. Wu, H. Li, N. Zhu, P. Li, J. Wu, X. Wang and Z. Dang,
Synthesis and characterization of organo-montmorillonite supported iron nanoparticles, Appl. Clay Sci., 2010, 50(3), 330336.
X. Zhang, S. Lin, Z. Chen, M. Megharaj and R. Naidu, Kaolinitesupported nanoscale zerovalent iron for removal of Pb2+ from
aqueous solution: Reactivity, characterization and mechanism,
Water Res., 2011, 45(11), 34813488.
C. -C. Lee, I.-L. Kao and R.-A. Doong, Combination of titanate
nanotubes and zerovalent iron for the degradation of mixed
contaminants, Preprints of Extended Abstracts, ACS National
Meeting, American Chemical Society, Division of Environmental
Chemistry, 2007, vol. 47(2), pp. 6972.
Y. Li, T. Li and Z. Jin, Stabilization of Fe0 nanoparticles with silica
fume for enhanced transport and remediation of hexavalent
chromium in water and soil, J. Environ. Sci., 2011, 23(7), 12111218.
J. Zhan, T. Zheng, G. Piringer, C. Day, G. L. McPherson and
Y. Lu, Papadopoulos, Kyriakos; John, Vijay T. Transport
Characteristics of Nanoscale Functional Zerovalent Iron/Silica
Composites for in Situ Remediation of Trichloroethylene, Environ.
Sci. Technol., 2008, 42(23), 88718876.
B. S. Karnik, M. J. Baumann, S. J. Masten and S. H. Davies, AFM
and SEM characterization of iron oxide coated ceramic membranes,
J. Mater. Sci., 2006, 41(20), 68616870.
B. S. Karnik, S. H. Davies, M. J. Baumann and S. J. Masten,
Fabrication of Catalytic Membranes for the Treatment of Drinking
Water Using Combined Ozonation and Ultrafiltration, Environ. Sci.
Technol., 2005, 39(19), 76567661.
H. J. Shipley, K. E. Engates and A. M. Guettner, Study of iron
oxide nanoparticles in soil for remediation of arsenic, J. Nanopart.
Res., 2010, 13(6), 23872397.
R. S. Cutting, V. S. Coker, N. D. Telling, R. L. Kimber, C. I.
Pearce, B. L. Ellis, R. S. Lawson, G. van der Laan, R. A. D. Pattrick
and D. J. Vaughan et al., Optimizing Cr(VI) and Tc(VII)
Remediation through Nanoscale Biomineral Engineering, Environ.
Sci. Technol., 2010, 44(7), 25772584.
G. C. C. Yang and M.-Y. Wu, Injection of nanoscale Fe3O4 slurry
coupled with the electrokinetic process for remediation of NO32 in
saturated soil: Remediation performance and reaction behavior,
Sep. Purif. Technol., 2011, 79(2), 272277.
X. Zhao, X. Guo, Z. Yang, H. Liu and Q. Qian, Phase-controlled
preparation of iron (oxyhydr)oxide nanocrystallines for heavy metal
removal, J. Nanopart. Res., 2010, 13(7), 28532864.
M. Mohapatra, K. Rout, S. K. Gupta, P. Singh, S. Anand and B. K.
Mishra, Facile synthesis of additive-assisted nano goethite powder
and its application for fluoride remediation, J. Nanopart. Res., 2009,
12(2), 681686.
Chunjian Shi, D. E. Pomeroy, P. C. Chiu, Application of nanoscale
zerovalent iron to decentralized drinking water systems. Abstracts
of Papers, 242th ACS National Meeting & Exposition, Denver, CO,
United States, Aug. 28Sep. 1, 2011, ENVR-403.
Q. Li, S. Mahendra, D. Y. Lyon, L. Brunet, M. V. Liga, D. Li and
P. J. J. Alvarez, Antimicrobial nanomaterials for water disinfection
and microbial control: Potential applications and implications,
Water Res., 2008, 42, 45914602.
C. Lee, J. Y. Kim, W. I. L. Lee, K. L. Nelson, J. Yoon and D. L.
Sedlak, Bactericidal Effect of Zero-Valent Iron Nanoparticles on
Escherichia coli, Environ. Sci. Technol., 2008, 42(13), 49274933.
Z. Li, K. Greden, P. J. J. Alvarez, K. B. Gregory and G. V. Lowry,
Adsorbed Polymer and NOM Limits Adhesion and Toxicity of
Nano Scale ZeroValent Iron to E. coli, Environ. Sci. Technol., 2010,
44(9), 34623467.
X. Li, J. Wang, L. A. Gutierrez, T. H. Nguyen and J. Economy,
Iron oxide nanoparticle coating on glass substrates for both arsenic

This journal is The Royal Society of Chemistry 2012

267

268

269

270

271

272

273

274

275

276

277

278

279

280

281

282

283

284

285

and MS2 virus removal. Preprints of Extended Abstracts, ACS


National Meeting, American Chemical Society, Division of
Environmental Chemistry, 2008, vol. 48(1), pp. 444446.
J.-Y. Kim, C.-H. Lee, D. C. Love, D. L. Sedlak, J.-Y. Yoon and
K. L. Nelson, Inactivation of MS2 Coliphage by Ferrous Ion and
Zero-Valent Iron Nanoparticles, Environ. Sci. Technol., 2011,
45(16), 69786984.
B. Marsalek, D. Jancula, E. Marsalkova, M. Mashlan, K. Safarova,
J. Tucek and R. Zboril, Multimodal Action and Selective Toxicity
of Zerovalent Iron Nanoparticles against Cyanobacteria, Environ.
Sci. Technol., 2012, 46(4), 23162323.
M. Dong, X. Wang, F. Huang, Z. Jin and T. Li, Toxicity of Fe0
nanoparticles on the denitrifying bacteria-Alcaligenes eutrophus,
Adv. Mater. Res., 2012, 343344(Pt. 2, Materials for Environmental
Protection and Energy Application), 889894.
A.-M. Azad, R. Hershey, S. Ali and V. Goel, Bactericidal efficacy of
electrospun pure and Fe-doped titania nanofibers, J. Mater. Res.,
2011, 25(9), 17611770.
H. Wang and P. Wang, Preparation and antibacterial property of
Fe/Ce codoped nano-titanic hydrosol, Wuji Huaxue Xuebao, 2009,
25(11), 19281934.
R.-L. He, Y. Wei and W.-B. Cao, Preparation of (Fe, N)-doped
TiO2 powders and their antibacterial activities under visible light
irradiation, J. Nanosci. Nanotechnol., 2009, 9(2), 10941097.
G. Nangmenyi, X. Li, S. Mehrabi, E. Mintz and J. Economy, Silvermodified iron oxide nanoparticle impregnated fiberglass for disinfection of bacteria and viruses in water, Mater. Lett., 2011, 65(8),
11911193.
G. N. Nangmenyi, E. Mintz, X. Li, H. Nguyen and J. Economy,
Antibacterial activity of a novel material system consisting of iron
oxide and Ag nanoparticles on a fiberglass substrate. Preprints of
Extended Abstracts, ACS National Meeting, American Chemical
Society, Division of Environmental Chemistry, 2008, vol. 48(1), pp.
708713.
X. Zhang, H. Niu, J. Yan and Y. Cai, Immobilizing silver
nanoparticles onto the surface of magnetic silica composite to
prepare magnetic disinfectant with enhanced stability and antibacterial activity, Colloids Surf., A, 2011, 375(13), 186192.
J. Han, S.-J. Zhang, Z.-G. Lu and Y.-J. Wang, DopingFe3+ to nanoAg TiO2 for photocatalytic performance improvement, Yingyong
Guangxue, 2010, 31(5), 718723.
Z. Chen, Water treatment device employing nano-neodymium-ironboron pipe containing zinc oxide and silver oxide, and steam shower
room equipped with the same with antiscaling and descaling effects,
CN 101671071, 2010.
T. Gordon, B. Perlstein, O. Houbara, I. Felner, E. Banin and S.
Margel, Synthesis and characterization of zinc/iron oxide composite
nanoparticles and their antibacterial properties, Colloids Surf., A,
2011, 374(13), 18.
W.-X. Zhang, J.-L. Cao, Q. Sun, Y.-Y. Xiang, J.-Y. Qian, M. Yang,
W. Wei and F. Xu, Study on the effect of nano-sized iron materials
on environmental safety using a Tetrahymena thermophila system,
Huaxue Shijie, 2007, 48(6), 341344.
M. Sharon, B. Pal and D. V. Kamat, Photocatalytic killing of
pathogenic bacterial cells using nanosize Fe2O3 and carbon
nanotubes, J. Biomed. Nanotechnol., 2005, 1(3), 365368.
S. R. Lewis, S. Datta, M. Gui, E. L. Coker, F. E. Huggins, S.
Daunert, L. Bachas and D. Bhattacharyya, Reactive nanostructured
membranes for water purification, Proc. Natl. Acad. Sci. U. S. A.,
2011, 108, 85778582, S8577/1-1-S8577/5.
M. A. Omole, I. KOwino and O. A. Sadik, Nanostructured
materials for improving water quality: potentials and risks,
Nanotechnol. Appl. Clean Water, 2009, 233247.
K. D. Grieger, A. Fjordboge, N. B. Hartmann, E. Eriksson, P. L.
Bjerg and A. Baun, Environmental benefits and risks of zerovalent
iron nanoparticles (nZVI) for in situ remediation: Risk mitigation or
trade-off?, J. Contam. Hydrol., 2010, 118(34), 165183.
J. Ai, E. Biazar, M. Jafarpour, M. Montazeri, A. Majdi, S.
Aminifard, M. Zafari, H. R. Akbari and H. G. Rad,
Nanotoxicology and nanoparticle safety in biomedical designs, Int.
J. Nanomed., 2011, 6, 11171127.
A. Adamcakova-Dodd, P. S. Thorne and V. H. Grassian, In vivo
toxicity studies of metal and metal oxide nanoparticles, Handb. Syst.
Toxicol., 2011, 2, 803833.

RSC Adv., 2012, 2, 93259358 | 9357

Downloaded on 26 February 2013


Published on 25 July 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20812A

View Article Online


286 S. J. H. Soenen and M. De Cuyper, Assessing iron oxide
nanoparticle toxicity in vitro: current status and future prospects,
Nanomedicine, 2010, 5(8), 12611275.
287 T. Senthilnathan, Profile of ambient air nano-enviro air pollutant
materials, Indian J. Environ. Protect., 2010, 30(7), 587589.
288 T. R. Pisanic, S. Jin and V. I. Shubayev, Iron oxide magnetic
nanoparticle nanotoxicity: incidence and mechanisms, Nanotoxicity,
2009, 397425.
289 B. Fubini, I. Fenoglio, G. Martra, R. Ceschino, M. Tomatis, R.
Cavalli and M. Trotta, An overview on the toxicity of inhaled
nanoparticles, NATO Sci. Ser. II: Math., Phys. Chem., 2006, 228
(Surface Chemistry in Biomedical and Environmental Science), 241
252.
290 X. Wu, Y. Tan, H. Mao and M. Zhang, Toxic effects of iron oxide
nanoparticles on human umbilical vein endothelial cells, Int. J.
Nanomed., 2010, 385399.
291 K. B. Gregory, G. V. Lowry, Z. Li, P. J. Alvarez, K. Greden,
Engineering polymeric nanoparticle coatings for decreased toxicological impacts of nanoscale zerovalent iron. Abstracts of Papers,
239th ACS National Meeting, San Francisco, CA, United States,
Mar. 2125, 2010, ENVR-549.
292 A. Bajaj, B. Samanta, H. Yan, D. J. Jerry and V. M. Rotello,
Stability, toxicity and differential cellular uptake of protein
passivated-Fe3O4 nanoparticles, J. Mater. Chem., 2009, 19(35),
63286331.
293 S.-J. Choi, J.-M. Oh and J.-H. Choy, Toxicological effects of
inorganic nanoparticles on human lung cancer A549cells, J. Inorg.
Biochem., 2009, 103(3), 463471.
294 L. C. Varanda, M. Imaizumi, F. J. Santos and M. Jafelicci Jr, Iron
oxide versus Fe55Pt45/Fe3O4: improved magnetic properties of core/
shell nanoparticles for biomedical applications, IEEE Trans. Magn.,
2008, 44(11), 44484451.
295 M. Mahmoudi, A. Simchi and M. Imani, Recent advances in surface
engineering of superparamagnetic iron oxide nanoparticles for
biomedical applications, J. Iran. Chem. Soc., 2010, 7(S2), S1S27.
296 N. Singh, G. J. S. Jenkins, R. Asadi and S. H. Doak, Potential
toxicity of superparamagnetic iron oxide nanoparticles (SPION),
NanoReviews, 2010, 1. http://www.nano-reviews.net/index.php/
nano/article/view/5358/6032.
297 S. Maiti, Nanotoxicity of gold and iron nanoparticles, J. Biomed.
Nanotechnol., 2011, 7(1), 65.
298 M. Auffan, J. Rose, J.-Y. Bottero, G. V. Lowry, J.-P. Jolivet and
M. R. Wiesner, Towards a definition of inorganic nanoparticles from
an environmental, health and safety perspective, Nat. Nanotechnol.,
2009, 4(10), 634641.
299 N. Eisenreich, M. Lerner and A. Vorozhtsov, Safety aspects and
approaches to fire hazard classification of metal nanopowders,
International Annual Conference of ICT, ed. N. N. Li, 2008, 39th,
p55/1.
300 D. Napierska, V. Rabolli, L. Thomassen, D. Dinsdale, C. Princen,
L. Gonzalez, K. L. Poels, M. Kirsch-Volders, D. F. Lison and J. A.
Martens et al., Oxidative stress induced by pure and iron-doped
amorphous silica nanoparticles in sub-toxic conditions, Chem. Res.
Toxicol., 2012, 25(4), 828837.
301 Z. Xie, J. Li, J. Qian, S. Huang, Z. Wan, L. Yu, C. Liu and Y. Lu,
Preparation and cytotoxicity of SiO2/Nd-Fe-B coreshelled nanoparticles applied to surgical anastomosis, Zhongguo Zuzhi
Gongcheng Yanjiu Yu Linchuang Kangfu, 2010, 14(42), 78297834.
302 M. Liao, H. He and J. Xiong, Effects of iron-doped TiO2
nanoparticles and constant magnetic field on HL60 leukemia cells
activity, Jiguang Shengwu Xuebao, 2009, 18(3), 324328.
303 P.-J. Chen, C.-H. Su, C.-Y. Tseng, S.-W. Tan and C.-H. Cheng,
Toxicity assessments of nanoscale zerovalent iron and its oxidation
products in medaka (Oryzias latipes) fish, Mar. Pollut. Bull., 2011,
63(512), 339346.
304 M. T. Zhu, B. Wang, Y. Wang, L. Yuan, H. J. Wang, M. Wang, H.
Ouyang, Z. F. Chai, W. Y. Feng and Y. L. Zhao, Endothelial
dysfunction and inflammation induced by iron oxide nanoparticle
exposure: Risk factors for early atherosclerosis, Toxicol. Lett., 2011,
203(2), 162171.

9358 | RSC Adv., 2012, 2, 93259358

305 K. Buyukhatipoglu, T. Miller and A. M. Clyne, In vitro toxicity and


intracellular uptake of flame synthesized iron oxide nanoparticles:
an alternative to wet synthesis methods, AIChE Annual Meeting,
Conference Proceedings, Philadelphia, PA, United States, Nov. 16
21, 2008, 910/1-910/6.
306 L. E. Murr and K. M. Garza, Natural and anthropogenic
environmental nanoparticulates: Their microstructural characterization and respiratory health implications, Atmos. Environ., 2009,
43(17), 26832692.
307 M. Mahmoudi, H. Hofmann, B. Rothen-Rutishauser and A. PetriFink, Assessing the In Vitro and In Vivo Toxicity of
Superparamagnetic Iron Oxide Nanoparticles, Chem. Rev., 2012,
112(4), 23232338.
308 W. Gao, C. Fan and Z. Chen, Evaluation of acute toxicity and antiphagocytosis of tumor-targeting superparamagnetic iron oxide
nanoparticles in mice, Zhongguo Yaofang, 2011, 22(25), 23442346.
309 M. Mahmoudi, S. Laurent, M. A. Shokrgozar and M.
Hosseinkhani, Toxicity Evaluations of Superparamagnetic
IronOxide Nanoparticles: Cell Vision versus Physicochemical
Properties of Nanoparticles, ACS Nano, 2011, 5(9), 72637276.
310 M. Safi, M. Yan, M.-A. Guedeau-Boudeville, H. Conjeaud, V.
Garnier-Thibaud, N. Boggetto, A. Baeza-Squiban, F. Niedergang,
D. Averbeck and J.-F. Berret, Interactions between magnetic
nanowires and living cells: uptake, toxicity and degradation,
Condensed Matter, 2011, 121, arXiv: 1108.2081v1.
311 P. Dua, K. N. Chaudhari, C. H. Lee, N. K. Chaudhari, S. W. Hong,
J.-S. Yu, S. Kim and D.-K. Lee, Evaluation of toxicity and gene
expression changes triggered by oxide nanoparticles, Bull. Korean
Chem. Soc., 2011, 32(6), 20512057.
312 P. Candeloro, L. Tirinato, N. Malara, A. Fregola, E. Casals, V.
Puntes, G. Perozziello, F. Gentile, M. L. Coluccio and G. Das et al.,
Nanoparticle microinjection and Raman spectroscopy as tools for
nanotoxicology studies, Analyst, 2011, 136(21), 44024408.
313 A. Hanini, A. Schmitt, K. Kacem, F. Chau, S. Ammar and J.
Gavard, Evaluation of iron oxide nanoparticle biocompatibility, Int.
J. Nanomed., 2011, 6, 787794.
314 A. Garcia, R. Espinosa, L. Delgado, E. Casals, E. Gonzalez, V.
Puntes, C. Barata, X. Font and A. Sanchez, Acute toxicity of cerium
oxide, titanium oxide and iron oxide nanoparticles using standardized tests, Desalination, 2011, 269(13), 136141.
315 L. Wang, L. Wang, W. Ding and F. Zhang, Acute toxicity of ferric
oxide and zinc oxide nanoparticles in rats, J. Nanosci. Nanotechnol.,
2010, 10(12), 86178624.
316 J. M. Berg, A. Romoser, N. Banerjee, R. Zebda and C. M. Sayes,
The relationship between pH and zeta potential of y30 nm metal
oxide nanoparticle suspensions relevant to in vitro toxicological
evaluations, Nanotoxicology, 2009, 3(4), 276283.
317 M. Mahmoudi, A. Simchi, M. Imani, A. S. Milani and P. Stroeve,
An in vitro study of bare and poly(ethylene glycol)-co-fumaratecoated superparamagnetic iron oxide nanoparticles: a new toxicity
identification procedure, Nanotechnology, 2009, 20(22),
225104225104/8.
318 B. Szalay, E. Tatrai, G. Nyiro, T. Vezer and G. Dura, Potential
toxic effects of iron oxide nanoparticles in in vivo and in vitro
experiments, J. Appl. Toxicol., 2012, 32(6), 446453.
319 S. Sulek, B. Mammadov, D. I. Mahcicek, H. Sozeri, E. Atalar, A. B.
Tekinay and M. O. Guler, Peptide functionalized superparamagnetic iron oxide nanoparticles as MRI contrast agents, J. Mater.
Chem., 2011, 21(39), 1515715162.
320 J. Yin, Q. Wu and D. Zhang, Study on L-02 cells toxicity effect of
Mn0.5Zn0.5Fe2O4 nanoparticles in vitro, Dulixue Zazhi, 2011, 25(2),
111114.
321 Z. Beji, A. Hanini, L. S. Smiri, J. Gavard, K. Kacem, F. Villain, J.M. Greneche, F. Chau and S. Ammar, Magnetic properties of Znsubstituted MnFe2O4 nanoparticles synthesized in polyol as
potential heating agents for hyperthermia. Evaluation of their
toxicity on Endothelial cells, Chem. Mater., 2010, 22(19),
54205429.
322 P. W. Boyd, A. J. Watson, C. S. Law and E. R. Abraham et al., A
mesoscale phytoplankton bloom in the polar Southern Ocean
stimulated by iron fertilization, Nature, 2000, 407, 695702.

This journal is The Royal Society of Chemistry 2012

You might also like