C 2 Ee 21818 F

Energy & Environmental Science
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REVIEW
A review on nanomaterials for environmental remediation

Downloaded by Centro de Investigaciones Cientficas Isla de la Cartuja on 21 December 2012 Published on 24 May 2012 on http://pubs.rsc.org | doi:10.1039/C2EE21818F
Mya Mya Khin,a A. Sreekumaran Nair,*b V. Jagadeesh Babu,b Rajendiran Murugana and Seeram Ramakrishna*ab
Received 31st March 2012, Accepted 24th May 2012 DOI: 10.1039/c2ee21818f This article gives an overview of the application of nanomaterials in environmental remediation. In the area of environmental remediation, nanomaterials offer the potential for the efcient removal of pollutants and biological contaminants. Nanomaterials in various shapes/morphologies, such as nanoparticles, tubes, wires, bres etc., function as adsorbents and catalysts and their composites with polymers are used for the detection and removal of gases (SO2, CO, NOx, etc.), contaminated chemicals (arsenic, iron, manganese, nitrate, heavy metals, etc.), organic pollutants (aliphatic and aromatic hydrocarbons) and biological substances, such as viruses, bacteria, parasites and antibiotics. Nanomaterials show a better performance in environmental remediation than other conventional techniques because of their high surface area (surface-to-volume ratio) and their associated high reactivity. Recent advances in the fabrication of novel nanoscale materials and processes for the treatment of drinking water and industrial waste water contaminated by toxic metal ions, radionuclides, organic and inorganic solutes, bacteria and viruses and the treatment of air are highlighted. In addition, recent advances in the application of polymer nanocomposite materials for the treatment of contaminants and the monitoring of pollutants are also discussed. Furthermore, the research trends and future prospects are briey discussed.
Introduction
The rapid pace of industrialization and its resulting by-products have affected the environment by producing hazardous wastes
a Department of Mechanical Engineering, National University of Singapore, 117574, Singapore b NUS Centre for Nanobres and Nanotechnology (NUSCNN), Healthcare and Energy Materials Laboratory, National University of Singapore, 117584, Singapore. E-mail: nniansn@nus.edu.sg; seeram@ nus.edu.sg
and poisonous gas fumes and smokes, which have been released to the environment. Conventional technologies have been used to treat all types of organic and toxic waste by adsorption, biological oxidation, chemical oxidation and incineration. Supercritical water oxidation (SCWO) has been proposed as a technology capable of destroying a wide range of organic hazardous waste. It has been receiving attention due to its ability to destroy a large variety of high-risk wastes resulting from munitions demilitarization and complex industrial chemical processing. In the concentration range of 1% to 20% of organic
Broader context
Environmental pollution is a global menace and the magnitude of it is increasing day-by-day due to urbanization, heavy industrialization and the changing lifestyles of people. In view of this, providing clean air and water and a clean environment for people is a challenging task. The advent of nanotechnology has given immense scope and opportunities for the fabrication of desired nanomaterials with large surface-to-volume ratios (and hence excellent chemical reactivities) and unique functionalities to treat pollutants. The nanomaterials play major roles in environmental remediation and are used for purposes such as the treatment of natural waters, soils, sediments, industrial and domestic waste water, mine tailings and the polluted atmosphere. The present review gives an extensive view of the roles of nanomaterials in environmental remediation. Environmental remediation using metal and metal oxide nanomaterials, dendrimers, carbon nanomaterials and polymer nanocomposites by chemical degradation (photocatalysis) and sorption are discussed in detail in addition to water purication by nanobre media. The review article also features a section on nanomaterials in the sensing of heavy metals and poisonous gases. We believe that this in-depth review will serve as a reference guide for scientists in the area and the background information will help in fuelling further innovations on sustainable solutions for environmental remediation.
This journal is The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 80758109 | 8075
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pollutants, SCWO is far less costly than incineration or active carbon treatment. In parallel, the rapid growth of nanotechnology has gained a great deal of interest in the environmental Mya Mya Khin is currently working as a research engineer at the National University of Singapore (NUS). She nished her oral defence recently and she is on course to obtain her PhD degree from NUS. She graduated with M. Eng. degree from NUS in Chemical Engineering. She worked as a lecturer and scientist at Ngee Ann Polytechnic and Food & Nutrition in Singapore (20082011). Her current research involves environmental remediation using electrospun nanobres.
Mya Mya Khin
applications of nanomaterials. The treatment of pollutants in water and air is a great challenge and nanomaterials are important for the environmental remediation. Nanomaterials are excellent adsorbents, catalysts and sensors due to their large specic surface areas and high reactivities. The high surface areato-mass ratio of nanomaterials can greatly improve the adsorption capacities of sorbent materials. Due to its reduced size, the surface area of nanomaterials grows exponentially at the same density as the diameter shrinks. In addition, the mobility of nanomaterials in solution is high and the whole volume can be quickly scanned with small amounts of nanomaterials due to their small size. Because of their reduced size and large radii of curvature, the nanomaterials have a surface that is especially reactive (mainly due to the high density of low-coordinated atoms at the surface, edges and vortices). These unique properties can be applied to degrade and scavenge pollutants in water and air.1 The species adsorbed onto the nanomaterials can be removed by applying mild (and affordable) gravitational (centrifugal) or magnetic force (in the case of magnetic
Dr A. Sreekumaran Nair worked as a research fellow (20082012) at the Healthcare and Energy Materials (HEM) Laboratory of the National University of Singapore. He graduated with a PhD in Chemistry from the Indian Institute of Technology (IIT), Madras (2006) and subsequently became a JSPS postdoctoral fellow (2006 2008) in Japan. His research interests include the fabrication of materials for energy conversion A: Sreekumaran Nair and storage, catalysts for solar hydrogen, nanotechnology-based environmental remediation and probing the charge transport mechanism in monolayer-protected clusters and 3-D superlattices. Dr V. Jagadeesh Babu is currently a research fellow at the NUS Centre for Nanobres & Nanotechnology (NUSCNN) of the National University of Singapore. He graduated with a PhD in Physics from the Indian Institute of Technology (IIT), Madras (2008) and subsequently became a research assistant in the Department of Physics IITMadras from 20082009. From the year 2009 to January 2010, he worked as a postdoctoral fellow in V: Jagadeesh Babu the Gwangju Institute of Science and Technology (GIST), Gwangju, South Korea. His research interests include the fabrication of electrospun nanostructured materials for photocatalysis, photovoltaics, the splitting of water for hydrogen energy and probing electrical charge transport in conducting polymers.
8076 | Energy Environ. Sci., 2012, 5, 80758109
Rajendiran Murugan
Dr Rajendiran Murugan is currently a research fellow at the NUSCNN of the National University of Singapore. He graduated with a PhD in organic chemistry (CLRICSIR Lab) from the University of Madras and subsequently became an associate scientic manager at the Synthetic Chemistry Department in Biocon. His research interests include nanocatalysis, the synthesis of small/conjugated molecules and the fabrication of chemosensors.
Prof. Seeram Ramakrishna, FREng, FNAE, FAAAS is a Professor of Materials Engineering and Director of the HEM Labs (http://serve.me.nus.edu.sg/ seeram_ramakrishna/) at the National University of Singapore. He is an acknowledged global leader for his pioneering work on the science and engineering of nanobres (http://research analytics.thomsonreuters.com/m/ pdfs/grr-materialscience.pdf). He Seeram Ramakrishna has authored ve books and ve hundred peer reviewed papers, which attracted $16 000 citations and h-index of 65. Various international databases including Thomson Reuters Web of Science, Elsevier Scopus and Microsoft Academic place him among the top twenty ve authors and most cited materials scientists in the world. He is an elected International Fellow of Major Professional Societies in Singapore, ASEAN, India, the UK and the USA.
This journal is The Royal Society of Chemistry 2012
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nanoparticles). Nanomaterials in various shapes/morphologies/ forms have a signicant impact on water and air quality in the natural environment.2 Magnetic nanoadsorbents are particularly attractive as they can be easily retained and separated from treated water.3 Nanomaterials also have different distributions of reactive surface sites and disordered surface regions. In addition, several natural and engineered nanomaterials have also been proved to have strong antimicrobial properties, including chitosan, silver nanoparticles (nAg), photocatalytic TiO2, and carbon nanotubes (CNT).48 Nanotechnology is also used for the detection of pesticides and heavy metals (e.g. cadmium, copper, lead, mercury, arsenic, etc.). Furthermore, nanomaterials have enhanced redox and photocatalytic properties.9,10 The fabrication of nanomaterials can be achieved by (1) grinding, milling and mechanical alloying techniques; (2) physical or chemical vapour deposition or vacuum evaporation; (3) solgel chemical synthesis methods; (4) gas-phase synthesis techniques, such as ame pyrolysis, electroexplosion, laser ablasion and plasma synthesis, and (5) microwave techniques or combustion methods or delamination of layered materials (the controlled crystallization from amorphous precursors).11 The functionalization process is applied to nanomaterials by a coating technique or chemical modication in order to (1) improve the surface and optical properties, (2) to avoid aggregation and (3) to eliminate the interaction between the nanomaterials and biological substances. For example, doping with an appropriate dopant can improve the photocatalytic activity and cause a red-shift in the band-gap of TiO2, which leads to its capability to absorb light in the visible range.12 The small particle size of nanoparticles (NPs) brings excessive pressure drops when the NPs are applied in a xed bed or any other ow-through system, as well as certain difculties in their separation and reuse and even a possible risk to ecosystems and human health caused by the potential release of nanoparticles into the environment. Therefore, hybrid nanocomposites have been fabricated by impregnating or coating the ne particles onto solid particles of a larger size to overcome the limitations of NPs. The resultant polymer-based nanocomposite (PNC) retains the inherent properties of the nanoparticles; however, the polymer support materials provide higher stability, processability and improvements thanks to the nanoparticle matrix interaction. In addition, the incorporation of nanoparticles (NPs) into polymeric nanocomposites leads to an enhancement of the mechanical, electrical and optical properties. NP-based membranes can be fabricated by assembling NPs on porous membranes13,14 or blending them with polymeric or inorganic membranes.15 The fabrication of membranes with metal oxide NPs could increase the permeability and foulingresistance as well as the quality of the permeate.13 The improvements to membranes or membrane surfaces using nanomaterials provide several changes in the properties, such as the porosity, the hydrophilicity of the surface properties, its electropositivity or electronegativity and the surface catalytic properties. The possible size grading due to the incorporated nanoporous materials can prevent the passage of a range of contaminants and microorganisms through the membrane. Nanobres can also provide a better ltration with a much smaller porosity and have the capability to trap much smaller contaminants. The internal surface areas of nanobres are much higher than conventional lter materials. Furthermore,
nanobrous materials can have interconnected open pore structures and can potentially allow high ow rates. This paper gives an overview of the application of nanomaterials in the purication of water and air contaminated with toxic metal ions, greenhouse gases, organic and inorganic solutes, bacteria and viruses and their performance in environmental remediation, pollutant sensing and detection, cleaner production and so on.
Environmental remediation technologies

(A) Environmental remediation by chemical degradation One of the widely used environmental remediation methods is chemical degradation. Chemical degradation methods include (1) ozone/UV radiation/H2O2 oxidation, (2) photocatalytic degradation, (3) supercritical water oxidation, (4) the Fenton method, (5) sonochemical degradation, (6) the electrochemical method, (7) the electron beam process, (9) solvated electron reduction, (9) permeable reactive barriers of iron and other zerovalent metals and (10) enzymatic treatment methods. Ozone or UV radiation-based technologies (O3/UV/H2O2) are chemical oxidation processes applicable to water treatment for the degradation of individual pollutants or the reduction of the organic load (chemical oxygen demand, COD) and the biodegradability of waste water could be enhanced by using these techniques. Ozone and UV radiation alone can be used for disinfection purposes. O3/UV/H2O2 techniques generally involve two oxidation/photolysis routes to remove foreign matters present in water. Thus, ozone, hydrogen peroxide and/or UV radiation can react individually or photolyze the organic matters directly in water. However, when ozone or hydrogen peroxide are used in combination with UV radiation, the pollutants can be degraded by an oxidation process through hydroxyl free radicals generated in situ. Hydroxyl radicals have the largest standard redox potential, with the exception of uorine. Among the most common water pollutants, phenols and some pesticides are substances that react rapidly with hydroxyl radicals, whereas organochlorine compounds are less reactive. Another feature of this oxidation process is that it is a destructive type of water/air pollution removal due to the reaction of the pollutants with hydroxyl radicals.16,17 The term photocatalytic degradation involves photons and a catalyst. Electrons pertaining to an isolated atom occupy discrete energy levels. In a crystal, each of these energy levels is split into many energy levels as there are atoms. Consequently, the resulting energy levels are very close and can be regarded as forming a continuous band of energies. For a metal (or conductor), the highest energy band is half-lled and the corresponding electrons need only a small amount of energy to be raised into the empty part of the band, which is the origin of the electrical conductivity at room temperature. In contrast, in insulators and semiconductors, valence electrons completely ll a band, which is thus called the valence band, whereas the next highest energy band (termed the conduction band) is empty, at least at 0 K. In liquid water, two HO2_ radicals can combine if their concentrations allow them to react signicantly, yielding H2O2 and O2 (in a disproportionation reaction). In turn, H2O2 can scavenge an electron from the conduction band or from the superoxide and accordingly can be reduced to a hydroxyl radical
Energy Environ. Sci., 2012, 5, 80758109 | 8077
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(_OH) and a hydroxide ion (OH). Because these reactions known to take place in homogeneous aqueous phases, they believed to occur on the TiO2 surface. In other words, very oxidizing _OH might be produced, in principle, by three-electron reduction of O2: O2 + 2H+ + 3e / OH_ + OH HO2 + RH / H2O2 + R_
are are the the
cobalt manganese oxide nanoparticles, synthesized in situ in the reactor, act as an oxidation catalyst to enhance the oxidation rate of organic compounds. Consequently, either the reaction temperature can be reduced or the residence time can be shortened. The TOC of the waste water was found to be 37 480 ppm and decreased to 200 ppm after the reaction.2123 The term Fenton reagent refers to aqueous mixtures of Fe(II) and hydrogen peroxide via the Fenton method. This method has indicated the following net reaction as the predominant process: Fe2+ + H2O2 / Fe3+ + HO_ + OH (1) where Fe2+ and Fe3+ represent the hydrated species, Fe(H2O)62+ and Fe(H2O)63+, respectively. Reaction (1) is often referred to as the Fenton reaction, although many other reactions occur in Fenton systems. The primary utility of the Fenton reagent in the degradation of pollutants is the formation of _OH. The hydroxyl radical is a very strong, nonselective oxidant capable of degrading a wide array of pollutants.24,25 Sonochemical reactions are related to new chemical species produced during acoustical cavitation, whereas the enhancement of heterogeneous reactions can also be related to mechanical effects induced in the uid system by sonication. These effects include an increase in the surface area between the reactants, a faster renovation of catalyst surfaces and accelerated dissolution and mixing. The peculiar nature of sonochemical reactions offers alternative pathways, providing a faster or environmentally safer degradation of contaminants. Sonochemistry provides a unique, high-temperature gaseous environment inside the cavitation bubbles, where the thermolysis of CCl4 molecules takes place at fast rates, yielding _Cl and _CCl3 radicals as primary intermediate products. These radicals further react with _OH radicals or O2, yielding stable HCl, HOCl, Cl2 and CO2 as the nal degradation products. AuTiO2 nanoparticles were prepared by sonicating (20 kHz) an aqueous solution of HAuCl4$3H2O containing polyvinylpyrrolidone, 1-propanol and TiO2 (Deguzza P-25) at room temperature under a nitrogen atmosphere. The waste water solution was irradiated with light and ultrasound was used for the degradation via sonophotocatalysis.2628 Fig. 1 shows a schematic diagram for the different electrochemical treatments. Fig. 1(A) represents direct electrolysis by anodic oxidation in which the pollutant reacts at the electrode surface with adsorbed _OH produced from water oxidation at a high O2 overpotential anode. Fig. 1(B) represents indirect electrolysis where the pollutant reacts in the solution with an irreversibly electrogenerated reagent (B+) produced from the oxidation of inactive B at the anode. The direct electrolytic processes includes conventional procedures of cathodic reduction and anodic oxidation. The indirect methods deal with the use of redox mediators as reversibly electrogenerated reagents, as well as oxidants as irreversibly electrogenerated reagents at the anode (e.g., O3, ClO, Cl and ClO2) or the cathode (e.g., H2O2). Halogenated organics are usually toxic and their electroreduction can make them easily biodegradable. This is also a common goal in the electrochemical decontamination of organic pollutants in waste waters by anodic oxidation. Although modern processes have seriously reduced the operation costs for cathodic reduction and anodic oxidation, both methods are still too costly to be competitive with biological treatment.2931
where RH is an organic species with a labile H atom; however, this reaction would also compete with H-atom abstraction from RH by the _OH radical. A much more direct way of forming the _OH radical is through the oxidation of an adsorbed water molecule or an OH ion by a valence band hole (h+), (i.e., by an electron transfer from these entities to the photoexcited semiconductor). The chemistry occurring at the surface of a photoexcited semiconductor is based on the radicals formed from O2, H2O and electron-rich organic compounds. In addition, cations in aqueous solution can be directly reduced by conduction band electrons provided that the redox potentials of these cations are adequate (i.e., lying below the conduction band energy).18 The photocatalytic reaction occurs, at least principally, in the adsorbed phase and the overall process can be formally divided into ve steps: 1. The transfer of the reactants from the uid phase to the surface; 2. The adsorption of at least one of the reactants; 3. The reaction in the adsorbed phase; 4. The desorption of the product(s); and 5. The removal of the product(s) from the interfacial region. As the adsorption and desorption rates are temperaturedependent, temperature can have an effect on the photocatalytic reaction rates. Increased rates upon raising the temperature above the ambient temperature have been reported for the gasphase removal of some pollutants and, above all, for their mineralization rate.19,20 The supercritical water oxidation (SCWO) process involves bringing together an aqueous waste stream and oxygen in a heated pressurized reactor operating above the critical point of water (374 C, 22.1 MPa or 218 atm). Under these conditions, the solubility properties of water are reversed (i.e., increased organic solubility and decreased inorganic solubility) and the viscosity of the media is decreased to a value similar to gas-like values, thus enhancing the mass transfer properties. These unique properties of hot pressurized water allow oxygen and organics to be contacted in a single phase in which the oxidation of the organics proceeds rapidly. At 400650 C and 3750 psi, SCWO can be used to achieve complete oxidation of many organic compounds with destruction rate efciencies of 99.99% or higher. Small nanoparticles of metal oxides can be produced by hydrothermal synthesis, which is performed in supercritical water above a critical temperature and pressure due to the properties of supercritical water. The supercritical hydrothermal synthesis of metal oxide nanoparticles is green not only because it requires only water as a solvent but also because the resulting nanomaterials contribute to a sustainable society. During the SCWO of organic acids in waste water containing benzoic acid, p-tolualdehyde and p-toluic acid, and in organic compounds, such as cobalt and manganese acetate,
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Sources of free radicals, principally hydroxyl radicals (_OH), oxidatively decompose pollutants. An excellent source of free radicals for water treatment is ionizing radiation. The irradiation of water produces both reducing and oxidizing species, which allow for a versatile approach for the ultimate treatment of a variety of pollutants. Machine-generated electron beams (e-beams) provide reliable and safe radiation sources for the treatment of owing waste streams on a process-size scale. Process versatility is provided by the continuous, rapid treatment potential and a tolerance for feedstocks of varying qualities. Additionally, modern e-beams have excellent operational reliability. The energy of the electron determines its depth of penetration in water. The number of electrons is referred to as the beam current and is controlled by the cathode size and conguration. The e reacts with numerous organic compounds. Of aq particular interest to the application in waste treatment are the reactions with halogenated compounds. A generalized reaction is shown below: e + RCl / R_ + Cl aq Thus, reactions involving the e often result in the dechloriaq nation of organochlorine compounds. This result may be sufcient for waste treatment purposes. However, further reaction of the resulting organic radical (R_) may also be desirable to mineralize the compound. The e also reacts with many other aq organic compounds and contributes to the removal of these compounds from aqueous solution. The process is nonselective in the destruction of organic chemicals because strongly reducing reactive species (e /H_) and strongly oxidizing reactive species aq (_OH) are formed at the same time and in approximately the same concentration in solution.32,33 In the solvated electron reduction method, deep blue solutions of solvated electrons are formed when Li, Na, K, Ca or other group I and group II metals are dissolved in liquid ammonia (eqn (1)). These media have long been used to reduce organic compounds. Among the many functional groups reduced by this process, chloroorganic compounds are the ones reduced with the highest rates (eqn (2)). Na / Na+ + e RCl + e / R_ + Cl (1) (2)
Fig. 1 A schematic diagram for the different electrochemical treatments of organic pollutants.29 (A) represents direct electrolysis by anodic oxidation and (B) represents indirect electrolysis.
Most solvated electron-treated wastes require post treatment. The rst post treatment involves removing and recovering ammonia from the matrix. This is accomplished by passing hot water or steam through the jacket of the treatment cell and by condensing the ammonia for reapplication.3436 The core function of permeable reactive barriers (PRBs) and many related technologies is to bring the contaminated material in contact with a reactive material that promotes a process that results in decontamination. The processes that are responsible for contaminant removal by zero-valent metals (ZVMs) and PRBs include both a physical removal from solution to an immobile phase and a chemical removal by reaction to form less hazardous products. Sequestration by Fe0 occurs mainly by adsorption, reduction and co-precipitation, although other processes may be involved, such as pore diffusion and polymerization. In most cases, adsorption is the initial step and subsequent transformations help ensure that the process is irreversible. In some cases, however, adsorption is the sequestration process of primary importance. This is certainly true with metals that occur as soluble cations, which can be expected to adsorb fairly strongly to iron oxides, but cannot be reduced to insoluble forms by Fe0: e.g., Mg2+, Mn2+ and Zn2+. The lifetime of PRBs using Fe0 as a reactive medium is limited by precipitation at the barrier.3739 Chemical processes often require the presence of excess quantities of reagents to accomplish transformation to the desired extent. In addition, particularly harsh conditions (e.g., high temperatures or extremes of pH) are sometimes required to facilitate the chemical transformations. This can present a problem once the desired transformation has taken place because the resulting stream may be a low-quality mixture that cannot be released to the environment or reused without subsequent treatment. Finally, many chemical treatment processes are not highly selective in terms of the types of pollutants that are transformed during treatment. Consequently, such processes are usually more economical for the treatment of dilute waste water and are often used as a polishing step before waste discharge into the environment. Biological processes are designed to take advantage of the biochemical reactions that are carried out in living cells. Such processes use the natural metabolism of cells to accomplish the transformation or production of chemical species. The metabolic processes occur as a result of a sequence of reactions conducted inside the cell that are catalyzed by proteins called enzymes. An important advantage of biological systems is that they can be used to carry out processes in which no efcient chemical transformations have taken place. In addition, biological processes can often be conducted without the harsh conditions that are necessary during chemical transformations. However, the use of microorganisms provides many rate-limiting factors. For example, costly and time-consuming methods may be necessary to produce microbial cultures that can degrade the targeted pollutant. Furthermore, severe conditions, such as chemical shock, extremes of pH and temperature, toxins, predators and high concentrations of the pollutants, intermediates and products may irreversibly damage or metabolically inactivate the microbial cells. Thus, the sensitivity of microorganisms to changes in their environment can make these processes difcult to control over the long term. They also require a supply of macro- and micro-nutrients for the support of
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microbial growth and often result in the formation of large quantities of biomass that ultimately must be discarded into the environment. In addition, the biochemical reactions occur at a rate that is limited by the metabolism of the microorganism and, thus, are often slower than chemical processes. Moreover, whereas biological systems are commonly used to remove the bulk organic load in waste waters, these systems often have difculty in removing toxic pollutants to consistently low levels. Therefore, conventional biological processes may not be able to improve water quality sufciently to meet the waste water discharge criteria. In an attempt to overcome some of the problems associated with chemical and biological systems, recent research has focused on developing the environmental applications of enzymes that have been isolated from their parent organisms. Enzymes can be applied to transform targeted contaminants, including many of those that may resist biodegradation. This catalytic action can be carried out on, or in the presence of, many substances that are toxic to microbes. In addition, some enzymes can operate over relatively wide temperatures, pH values and salinity ranges compared to cultures of microorganisms. They can also be used to treat contaminants at high and low concentrations and are not susceptible to shock loading effects associated with changes in contaminant concentrations that can often irreversibly damage or metabolically inactivate microbial cells. Consequently, there are fewer delays associated with shutdown/startup periods that are normally required to acclimatize biomass to waste streams. Importantly, the catalytic action of enzymes enables the development of smaller systems of lower capital cost due to the high reaction rates associated with enzymatic reactions. In addition, because bacterial growth is not required to accomplish waste transformations, sludge production is reduced because no biomass is generated. The following situations are those where the use of enzymes might be most appropriate: (i) the removal of specic chemicals from a complex industrial waste mixture before on-site or off-site biological treatment; (ii) the removal of specic chemicals from dilute mixtures, for which conventional mixed-culture biological treatment might not be feasible; (iii) the polishing of a treated waste water or groundwater to meet limitations on specic pollutants or to meet whole efuent toxicity criteria; (iv) the treatment of wastes generated infrequently or in isolated locations, including spill sites and abandoned waste disposal sites; and (v) the treatment of low-volume, highconcentration waste water at the point of generation in a manufacturing facility to allow reapplication of the treated process waste waters to facilitate recovery of soluble products or to remove pollutants known to cause problems downstream when mixed with other wastes from the plant.40,41 (B) Environmental remediation by metals/metal oxides
For environmental remediation, the most widely studied nanoscale metals (NMs) and metal oxides (NMOs) include silver, iron, gold, iron oxides, titanium oxides, etc. The size and shape of NMs and NMOs are both important factors which affect their performance. Efcient synthetic methods to obtain shapecontrolled, highly stable and monodisperse metal/metal oxide nanomaterials have been widely studied during the last decade. Generally, the synthesis methods can be classied into two
categories: (1) physical approaches, including inert gas condensation, severe plastic deformation, high-energy ball milling, ultrasound shot peening; and (2) chemical approaches, including reverse micelle (or microemulsion), controlled chemical coprecipitation, chemical vapor condensation, pulse electrode position, liquid ame spray, liquid-phase reduction, gasphase reduction, etc. Among these synthesis protocols, coprecipitation,42,43 thermal decomposition and/or reduction and hydrothermal synthesis techniques are used widely and are easily scalable with high yields. In this section, the applications of nanoscale metals and NMOs in environmental remediation are presented. Silver nanoparticles are known for their strong antibacterial effects against a wide array of organisms (e.g., viruses, bacteria, fungi). Therefore, silver nanoparticles are widely used for the disinfection of water.4446 The different mechanisms of antimicrobial activity by nAg+ are shown in Fig. 2. Ag+ ions interact with thiol groups in proteins, which leads to inactivation of respiratory enzymes and the production of reactive oxygen species (ROS).47 It was also shown that Ag+ ions can prevent DNA replication and affect the structure and permeability of the cell membrane.48 Silver ions are also photoactive in the presence of UV irradiation, causing an improvement in the UV inactivation of bacteria and viruses.49,50 To date, several mechanisms have been postulated for the antimicrobial property of silver nanoparticles: (1) the adhesion of nanoparticles to the surface altering the membrane properties. Nano Ag (nAg) particles have been reported to degrade lipopolysaccharide molecules, accumulating inside the membrane by forming pits and causing an increase in the membrane permeability;51 (2) nAg particles could penetrate the bacterial cell, resulting in DNA damage; and (3) the dissolution of nAg releases antimicrobial Ag+ ions.52 Particles of Ag less than 10 nm are more toxic to bacteria such as E. coli and P. aeruginosa.53,54 Silver nanoparticles ranging from 1 to 10 nm inhibit certain viruses from binding to host cells by preferentially binding to the virus glycoproteins. Furthermore, triangular nAg nanoplates were found to be more toxic than nAg rods, nAg spheres and even Ag+ ions. The incorporation of nAg into polymer materials, such as polymethoxybenzyl and poly(L-lactic acid)-co-poly(3-caprolactone) nanobres, have also shown antimicrobial properties against E. Coli, A. Niger, S. aureus and Salmonella entrica.5558 Several materials containing iron, such as iron sulde, iron bearing oxyhydroxides and aluminosilicate minerals, were successfully used in the reduction and precipitation of metal ions. Out of all the iron-based materials, elemental iron was found to be the most successful for ground water remediation.59 With the advent of nanotechnology, iron nanoparticles replaced the use of bulk iron-based systems for water purication.60 After a few years, noble metal nanoparticles were also shown to degrade halocarbons by the same mechanism of reductive dehalogenation.6164 In an investigation by Lisha et al., Hg2+ ions were reduced to a zero-valent state, followed by the alloying of reduced mercury on gold nanoparticle surfaces.64,65 The application of noble metal nanoparticles for the removal of halogenated organics and pesticides from drinking water has also been patented.66,67 Gold nanoparticles also exhibit potential to remove inorganic mercury from drinking water.63 Sulphur dioxide (SO2) is frequently released to the atmosphere by the combustion of fossil-derived fuels in factories, power
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Dabro et al. investigated the dehydrochlorination of pentachlorophenol to phenol or cyclohexanol on supported palladium electrodes.77 The rapid and complete dechlorination of all the chlorinated contaminants was achieved for the water and groundwater slurries using bimetallic nanoparticle systems composed of Pd/Fe.78 Contaminants, such as tetrachloroethane (C2Cl4), could be transformed to ethane by accepting electrons from the oxidation of iron through the following reaction:
C2Cl4 + 4Fe0 + 4H+ / C2H4 + 4Fe2+ + 4Cl
Fig. 2 The different mechanism for the antimicrobial activity of Ag+ ions.47
plants, houses and automobiles. The corrosion of buildings due to acid rain by SO2 is a serious challenge. TiO2 is the most commonly used catalyst to convert SO2 to sulfur through the reaction: SO2 + 2H2S / 2H2O + 3Ssolid. Rodriguez68,69 found that the combination of a gold (Au) and TiO2 system produced highly efcient desulfurization. Metallic gold has a very low chemical and catalytic activity.68,69 However, when gold was dispersed on some metal oxides (MgO, TiO2, MnOx, Fe2O3, Al2O3), it gave the positive effects of catalytic activity due to charge transfer between the oxide and gold and a limited nanoscale size (usually less than 10 nm).69 Rodriguez69 investigated the dissociation effects of SO2 using the combined systems of TiO2/ Au and MgO/Au. On both oxide supports, the largest activity for the full dissociation of SO2 was observed in systems containing Au coverages that were less than 1 mL when the size of the Au nanoparticles was below 5 nm. In addition, the combined system of TiO2/Au provided a more effective dissociation of SO2 than that of MgO/Au so that TiO2 played a direct active role for the dissociation of SO2 as well as modied chemical properties of the supported Au nanoparticles.70 Furthermore, catalytic performance tests, such as (1) tests for the reduction of SO2 by H2S through the reaction: SO2 + 2H2S / 2H2O + 3Ssolid and (2) by carbon monoxide through the reaction: SO2 + 2CO / 2CO2 + Ssolid indicated that the combination of Au/TiO2 is 510 times more active than pure TiO2. Zero-valence state metals, such as Fe0, Zn0, Sn0 and Al0, are effective for the remediation of contaminants in contaminated groundwater.59,71 Bimetallic combination (Fe0/Ni0: the ratio of Fe to Ni being 3 : 1) has provided better degradation rates.72 Bimetallic particles are composed of two types of zero-valent iron (ZVI). The structure of bimetals includes cluster-in-cluster and coreshell structures for nanoscale particles.73 As iron corrodes, protons from water are reduced to adsorbed H atoms and to molecular hydrogen at the catalytic Ni surface. Fig. 3 shows a schematic diagram of the reaction of a chlorinated organic molecule with a bimetallic nanoparticle. Fe or Zn serves as an electron donor while another species (Pt or Pd) serves as a catalyst.74,75 TCE is adsorbed onto the surface of the NiFe particles where the CCl bond is broken and the chlorine atom is replaced by hydrogen. A similar mechanism was applied by Cheng et al.76 for the dehalogenation of 4-chlorophenol to phenol on palladized graphite and iron electrodes.76
The removal efciency was found to be greater than 99% using iron nanoparticles without a palladium coating after 24 h. In addition, bimetallic coupling with a second catalytic metal has also been widely applied for the degradation of contaminants in contaminated water. The degradation rate by bimetallic combinations was found to be faster than that observed for metal iron alone.79,80 Bimetallic Pd/Au nanoparticles consist of two catalytic metals, whereas bimetallic nanoparticles of iron consists of a catalytic material (Pd or Ni) and an electron donating material (i.e. Fe). Bimetallic Pd/Au nanoparticles can increase the catalytic activity by a factor of 15 as compared to Pd nanoparticles, Al-supported Pd nanoparticles and Pd black.81,82 Reducing the size of iron to the nanoscale has been very efcient for enhancing the rate of reaction and reducing the formation of by-products.83 However, the material became less stable with an increase in the reaction activity as zero-valent iron nanoparticles are easy to oxidize in air and hydrolyze in water. Therefore, the efciency of Fe0 particles could be signicantly reduced in large scale environmental remediation. To maintain the stability of Fe0 nanoparticles, immobilization of Fe0 in the membrane or bimetallic Fe0 nanomaterials have been used. Meyer et al. in 2004 found that membrane immobilization for nanoparticles of Fe0 and bimetallic Ni0/Fe0 offered two advantages in the removal process of toxic organic compounds. Those advantages were (1) the polymer membrane controlled growth of zero-valent iron metal nanoparticles and (2) the localization and higher concentration of organic substances in the membrane domain led to a signicant enhancement of the reaction rates.84 Although bimetallic particles of Ni/Fe showed a relatively high reactivity towards chlorinated compounds,85,86 there is still an environmental concern over the toxicity of Ni. Particles of nZVI have been applied for the efcient removal of different metals, such as Cr(VI),87 U(IV) and U(VI)88 and Co(II).89 Choe et al. (2001) reported the reductive denitrication by nanoscale zero-valence
Fig. 3 A nanoscale bimetallic particle for chlorinated solvent removal.75
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iron.90 Ghauch et al.91 reported interesting results on the elimination of antibiotics from water using iron NPs.91 Bimetallic nanoparticles of ZVI and Al have been utilized for the removal of chlorinated organic solvents, nitrate and heavy metals, such as Cr6+ and Cu2+, as well as perchlorate ions from waste water.9299 Bimetallic particles of Fe and Al were found to degrade CCl4 by a factor of 6 as compared to micro-sized Fe ZVI. Bimetallic nanoparticles of Pd/Fe were found to provide a higher degradation of CCl4 than one dimensional ZVI Fe nanoparticles100 due to the catalytic effects of metals (Pd or Ni) through a direct hydrogen reduction101 and the prevention of oxide formation at the iron surface.72 Complete degradation could be obtained with a high surface reactivity, the elimination of toxic intermediates and a durable and stable performance by using bimetallic Pd/Fe nanoparticles.101105 Bimetallic Cu/Al particles have shown a better degradation of CCl4 and CH2Cl2, which was not degraded by most of the ZVI.106 Martin et al. have reported the use of ferric-oxide NPs to remove and recover phosphate from municipal waste waters.107 TiO2 nanoparticles have been extensively used for the oxidative and reductive transformation of organic and inorganic contaminants in air and water.108 TiO2 photocatalysts have been a popular choice for much of the published photocatalysis work. Its large bandgap energy (3.2 eV) requires UV excitation to induce charge separation within the particle. TiO2 is a semiconductor and has three distinct polymorph crystalline structures: rutile, anatase and brookite. Both rutile and anatase have a tetragonal structure, containing 6 and 12 atoms per unit cell with an axial ratio of c/a (c perpendicular axis, a horizontal axis) 0.64 and 2.51, respectively. The brookite has an orthorhombic structure. Both rutile and anatase have been applied in photocatalytic and photoelectrochemical processes due to their easy synthesis by various techniques. TiO2 has been widely applied in heterogeneous photocatalysis to decompose a host of organic pollutants, such as phenolic compounds,109 metal ethylene diamine tetra acetate complexes,110 airborne microbes and odorous chemicals.111 Most of this research involved UV photons as the major exciting light sources. There is 5% of solar irradiation within UV range; therefore, it is necessary to enhance the performance of TiO2 by using photons from the near visible to visible region. This can be achieved by manipulating the particle size of the photocatalyst or by doping the TiO2 with foreign ions.112115 The modication TiO2 with noble metal ions could decrease the TiO2 band gap, which benets the electron transfer from the valence band to the conduction band, which facilitates the formation of oxidative species, such as _OH.116 In addition, the modied surface properties of noble metal-doped TiO2 photocatalysts could attract more cationic dye, i.e. rhodamine B (RB), which could be adsorbed on the Ag-doped TiO2 surface due to an increased number of electron traps. One dimensional TiO2 nanomaterials and doped TiO2 nanomaterials are widely used for the degradation of halogenated compounds, the removal of dyes via photocatalytic oxidation, the removal of metals and some disinfection processes for drinking water and waste water. TiO2 nanoparticles are activated by UV irradiation (radiation at wavelength 320400 nm) and its photocatalytic properties have been utilized in various environmental applications to remove contaminants from both water and air.117 Recent research has
shown that the desired band gap narrowing of TiO2 can be better achieved by using nonmetal elements, such as N, F, S and C. Such modied TiO2 materials exhibited larger absorption in the visible region and enhanced the degradation of organic dyes under visible light irradiation, especially under natural solar light irradiation.118 The relevant mechanisms for the role of nonmetals in modied TiO2 materials in its visible light photoactivity are due to the substitution of oxygen for nitrogen in the TiO2 lattice. The corresponding N(2p) states are located above the valence band edge. Mixing of the N(2p) states with the O(2p) states results in a reduction of the band gap in N-doped TiO2 and the photocatalyst can be active under visible light irradiation.119 Nano-sized TiO2 was also reported to kill viruses, including poliovirus 1,120 the hepatitis B virus,121 the Herpes simplex virus122 and MS2 bacteriophage.123 The concentration of TiO2 required to kill bacteria varies between 100 and 1000 ppm depending on the size of the particles and the intensity and wavelength of the light used.124 The antibacterial activity of TiO2 is related to the ROS production, especially hydroxyl free radicals and peroxide formed under UV-A irradiation via oxidative and reductive pathways, respectively.125 A strong absorption of UV-A activates TiO2 under solar irradiation and signicantly enhances solar-triggered disinfection. In a study by Gelover et al., the complete inactivation of fecal coliforms was achieved in 15 min at an initial concentration of 3000 cfu per 100 mL by exposing water in TiO2-coated plastic containers to sunlight, whereas the same inactivation required 60 min with uncoated containers.126 An attractive characteristic of TiO2 photocatalytic disinfection is its capability of activation by visible light, e.g. sunlight. Metal doping has been shown to improve the visible light absorbance of TiO2127 and increase its photocatalytic activity under UV irradiation.128 Noble metals, especially silver, have received much attention for this purpose. Silver has been shown to enable the visible light excitation of TiO2.129 Recently, it was demonstrated that doping TiO2 with silver greatly improved the photocatalytic inactivation of bacteria130 and viruses.131 Reddy et al. demonstrated that 1 wt% Ag in TiO2 reduced the reaction time required for complete removal of 107 cfu of E. coli per mL from 65 to 16 min under UV-A radiation.132 Silver enhances the photoactivity by facilitating electronhole separation and/or providing more surface area for adsorption.116,133 Visible light absorption by silver surface plasmons is thought to induce electron transfer to TiO2 resulting in charge separation and, thus, activation by visible light.129,134 Ag/TiO2 or Au/TiO2 therefore shows a great potential as a photocatalytic material due to its photoreactivity and visible light response. Table 1 summarizes the application of TiO2 nanomaterials for environmental remediation. TiO2 is widely used for NOx control, whereby NOx is reduced back to N2 or oxidized to NO2 and HNO3. The oxidation of nitric acid converts it into a raw material with useful applications, such as in fertilizers. The activity of TiO2 is improved by the addition of an adsorbate, such as zeolites, which concentrate NO on the surface. A highly selective photoreduction of NO to N2O and N2 is observed on the surface of TiO2. In the work of Skubal et al. the surfaces of titanium dioxide NPs were modied with a bidentate chelating agent, thiolactic acid (TLA), to remove aqueous cadmium from simulated waste waters.135 Amezaga-Madrid et al. tested the effect of TiO2 thin lms deposited on soda lime glass slides by
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solgel techniques.136 After 40 min, a 70% reduction of P. aeruginosa cells was observed. Kuhn et al. reported that bacteria placed on TiO2 coated surfaces were killed in the following order: E. coli > P. aeruginosa > S. aureus > Enterobacter faecium > C. albicans.137 While pure TiO2 had no antibacterial effect in free solution or in agar, silver-doped TiO2 particles were more effective than pure silver nanoparticles of a similar size.138 Inorganic nanoscale ZnO was mostly applied to eliminate H2S as an adsorbant. Recently, nanostructured ZnO could efciently remove heavy metals.147 Lee et al. prepared nanometer size zinc oxide (ZnO) powders by a solutioncombustion method (SCM). Compared with two TiO2 powders, P25 and one prepared by a homogeneous precipitation process at low temperature, the zinc oxide nanopowder showed a higher removal rate of Cu2+ ions from the solution.148 ZnO nanosheets prepared via a hydrothermal approach were used to adsorb Pb2+ and then hydrothermally treated in an aqueous solution containing a sulfur source. Due to the surface hydroxy groups, the resultant ZnO nanosheets exhibited a good capacity of Pb2+, which was found to be 6.7 mg g1.149 The Pb2+-preloaded ZnO nanosheets were put into a Teon-lined stainless steel autoclave containing a sulfur source at 120 C for 12 h and the resulting ZnO/PbS nanocomposite exhibited a potential use in photocatalytic remediation. ZnO nanoparticles exhibit strong antibacterial activities on a broad spectrum of bacteria.150 The penetration of the cell envelope and the disorganization of the bacterial membrane upon contact with ZnO nanoparticles were also indicated to inhibit bacterial growth.151 Other NPs, such as cerium oxide, have been applied for the removal of Cr(VI) through the adsorption of the metal onto the surface of the NPs.152 Various dopants, such as transition metal ions (Fe, Co, Cu), have been used to enhance the photocatalytic activity of TiO2. Metal-doped TiO2 was found to induce the desired red-shift of the adsorption spectrum. However, it has also been documented that the presence of transition metals may increase the probability of electronhole recombination, resulting in a reduction of the semiconductors photocatalytic efciency. Titania doping with nonmetal elements (N, C, S) has also been considered as an effective approach to extend the spectral response of TiO2 towards visible energy wavelengths. In this approach, single and co-doped TiO2 catalysts with Fe and S have been reported to exhibit enhanced photocatalytic activity under visible light.
Recently, emphasis has been given to co-doped TiO2 systems, involving cations and anions, in order to improve the photocatalytic efciency of TiO2. It has been suggested that charge separation between electrons and holes is improved by the co-doping of TiO2 with Fe and S. Under both UV and sunlight irradiation, all synthesized S single or co-doped catalysts showed larger catalytic activities compared to the commercial TiO2, P25. Toluene photo-excitation appears to be favoured at a low S concentration (0.2%) in the nanomaterial but it provided a detrimental effect at 0.4% of S in TiO2 nanomaterials. Co-doping with S and Fe favours the photocatalytic activity of the nanomaterial when it is compared to that of single Fe-doped TiO2. In addition, the single S-doped and co-doped S/FeTiO2 catalysts showed high selectivity (>90%) toward the partial oxidation of toluene (production of benzaldehyde).153 The photocatalytic activity of the prepared TiO2 catalysts doped with Li+, Rb3 and Y3+ under sunlight irradiation was evaluated using 2-naphthol as a pollutant model. The results showed a great enhancement in the photocatalytic efciency with the incorporation of Y3+ in samples synthesized by solid grinding, while in samples synthesized by solgel process either Rb+ or Y3+ dopants greatly improved the photocatalytic activity. The increase in photoactivity may be due to: (i) a decrease of the energy gap, which favors a higher photoexcitation efciency under solar radiation and provides a larger population of excited species (holeelectron pairs); (ii) the small particle size favors the increase in the surfaceto-volume ratio and the scavenging action of the photogenerated electrons by the Y3+ or Rb+ ions results in a prevention of the recombination of electronhole pairs and increases the lifetime of the charge carriers; (iii) the doping ions (Rb+ or Y3+) can act as electron traps, thus facilitating the electronhole separation and subsequent transfer of the trapped electron to the adsorbed O2, which acts as an electron acceptor on the surface of the TiO2; (iv) the dopant prevents the recombination of electronhole pairs and increases the lifetime of the charge carriers. Therefore, photocatalysis activity under sunlight can be improved.154 Increasing amounts of silver in Ag-doped TiO2 signicantly increases the rate of degradation of a model dye, rhodamine. Two possible parallel mechanisms, which may result in electron population of the conduction band of the material, have been suggested: (i) rhodamine absorbs visible light and injects an electron into the conduction band of the TiO2 material or (ii) the material itself absorbs visible light, which is probably facilitated
Table 1 Photocatalytic processes of environmental remediation by one dimensional or ion doped-TiO2 nanoparticles Category Disinfection Metal removal Dye removal/destruction of biological toxins and inactivation of bacteria Metal removal Dye removal Air treatment Disinfection Nutrient removal Nutrient removal Organic removal Target material Water-borne pathogenic virus in drinking water Arsenic Methylene blue, creatinine, biological toxins (microcystin-LR), E. Coli Lead Methylene blue NOx and toluene in air S. aureus and E. Coli in water Nitrate Nitrate 2,4,6-Trichlorophenol Type of nanomaterial Ag-doped TiO2 One dimension TiO2/Fe-doped TiO2 Crystalline TiO2 thin lm/the composite material of TiO2 and Al2O3 One dimension TiO2 Ag-doped TiO2 nanobres Ag-doped TiO2 nanobres Ag-doped TiO2 nanobres Cu/Fe/Ag-doped TiO2 TiO2 NPs doped with Bi3+ Ag-doped TiO2 Ref. 139 140 141 142 143 143 143 144 145 146
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by the surface plasmon absorption of the silver-doped materials. It is probable that the two mechanisms are happening in parallel, indeed some commentators have questioned the suitability of dyes, such as methylene blue, for photocatalytic studies. The role of silver clearly controls the recombination rate and subsequently allows a greater proportion of hydroxyl radicals to form.155 (C) Nanoltration (C-1) Nanoltration by membranes. Membrane technologies are more efcient nowadays due to their reliable contaminant removal without the production of any harmful by-products, especially in water and waste water treatment processes. The basic principle of membrane ltration is to apply semi-permeable membranes to remove uids, gases, particles and solutes. For the separation of materials from water, membranes must be water permeable and less permeable to solutes or other particles. Pressure-driven membrane processes, such as microltration (MF), ultraltration (UF), nanoltration (NF) and reverse osmosis (RO), have been applied for water treatment, reuse and desalination systems throughout the world. Nanoltration (NF), as a promising membrane technology, is a method for removing low molecular weight solutes, such as salts, glucose, lactose and micro-pollutants, in contaminated water.156,157 The availability of clean water has emerged as one of the most serious problems facing the global economy in the 21st century. Water treatment systems typically involve a series of coupled processes, each designed to remove one or more different substances in the source water, with the particular treatment process being based on the molecular size and properties of the target contaminants. RO is very efcient for retaining dissolved inorganic and small organic molecules. NF can effectively remove hardness (i.e., Ca(II)) and natural organic matter. However, a limitation of both RO and NF processes is the requirement of high pressures (1001000 psi) to operate the water treatment. Conversely, UF and MF membranes require lower pressures (560 psi) but those membranes cannot retain dissolved ions and organic solutes. Advances in nanochemistry can provide enhancement of UF and MF processes for recovering dissolved ions from aqueous solutions.158160 Both cellulose acetate and polyamide can be used to form NF membranes. In addition, other polymers (e.g., polyvinyl alcohol (PVA) and sulfonated polysulfone) and inorganic materials (e.g., some metal oxides) can also be used for NF membrane synthesis.161 The typical properties of NF membranes are shown in Table 2. NF membranes selectively reject substances as well as enable the retention of nutrients in water. Therefore, the advantages of NF are comparable to the RO process. The adsorption of pollutants onto the membrane can be (1) physical in nature, which is a completely reversible process, or (2) chemical in nature, which is irreversible for strong chemical bonds, such as polymerization, or reversible for weak secondary chemical bonds, such as hydrogen bonds and complexation or (3) both. NF is capable of removing hardness, natural organic matter, particles and a number of other organic and inorganic substances via one single treatment. Water hardness is caused by calcium and magnesium ions, while strontium and barium rarely occur in substantial concentrations. NF membranes can reject bivalent ions in signicantly high amounts.163,164 The calcium ion rejection was found to be 74.978.9% higher than the expected
results of the manufacturer (in Germany) for a thin lm composite of a polyamide membrane with molecular weight cutoff of 300 Da (NF 200B).165 A better rejection of magnesium ions was also found to be 86.790.3% using the same type of membrane due to the stronger hydration of the Mg2+ ion. Van der Bruggen et al.166 observed that a spiral-wound membrane made of polyamide materials with a molecular weight cut-off of 250 Da (NF 70) could remove the major fraction of hardness from groundwater. When groundwater was treated with a NF 70 membrane for the production of drinking water, it was suggested that the permeate should be mixed with streams that have been treated by traditional methods or, alternatively, hardness should be re-added to the drinking water in order to obtain the desired hardness of 1.5 mmol L1. The separation performance of NF membranes for cations is 60%.166 For anions, the separation efciency obtained with NF was larger. For NF, the ion size plays a role for membranes with small pores, leading to a large selectivity.167 Nitrate rejection was 76% for NF70, which is better than expected anticipated by the manufacturer of NF 70. The higher retention of multivalent ions could be obtained over a wide range of concentrations using a membrane with small pore diameters.168 The pore size distribution of NF membranes have a common feature: the largest fraction of medium-size pores is approximately 0.85 nm, which is primarily responsible for the sieving effect of the membranes. In addition, the NF membranes contain larger fractions of the smallest pores (0.220.254 nm) and there is a signicant fraction of wider pores (1.55 nm) in the skin of the NF membranes.169 Mass transport through a nanoltration membrane can be achieved by two mechanisms: diffusion and convection. When the transmembrane pressure is high, the diffusion mechanism becomes less inuential than the convection mass transport mechanism and, therefore, a better retention of Ca2+ ions is found. The retention of Ca2+ was found to be very high for NF 70 and a membrane made of polypiperazineamide (UTC20) and remained constant when the pressure was above 10 bar. A 90% retention was found for multivalent ions, such as sulfate, calcium and magnesium ions, and 6070% was found for monovalent ions, such as sodium and chloride.168 In NF membranes, electrostatic interactions between the negatively charged membrane and the charged species appear as an important feature over the size effect and salts containing divalent sulfate anions are better rejected by the membrane than salts with a monovalent chloride anion. However, the differences in the retention of the examined chlorides are mostly controlled by the size of the cations. The rejection behaviour of the NF membranes for multivalent ions is due to charge interactions with the membrane and the size exclusion of hydrated ions.170 Monovalent ions tend to have lower rejections unless they are retained to maintain charge neutrality with multivalent counter ions.169 Kouti et al., observed the order of chloride retention as s c follows: RMgCl2 > RCaCl2 > RNaCl, which holds for the two types
Table 2 The typical properties of pressure-driven NF membranes162,163 Pore size (nm) Water permeability (L m-2 h-1 bar-1) Operating pressure (bar) Molecular weight cut off (Da) $2 nm 550 210 >100
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of thin lm polyamide NF membranes with slightly lower retention values for the NF-type membranes. This is caused by the presence of a fraction of large pores in the surfaces of the membrane.169 Such an order was not found for sulfates and this may be due to the ion pairing effect, which is more prevalent in MgSO4 than in Na2SO4 solutions. Orecki et al. observed that the NF process of surface water provided a retention coefcient of 9099% for sulfate and 82% for carbonate, while it rejected 4055% of the covalent salts.171 The total hardness of the surface water could be reduced by 85.2%. The rejection of both divalent dibasic arsenate, HAsO42 and sulfate (SO42) ions was found to be notably higher than the rejection of chloride ions by the charged NF membranes due to the stronger electrostatic repulsion of the former ions than the repulsion of the lesser charged, monovalent chloride ion. This shows that the charge exclusion inuences the retention of ions by the negatively charged NF membranes.172 The NF process has many advantages, including ease of operation, reliability, no requirement of additives and a modular construction that is easy to upscale.166 However, the limitation in NF is membrane fouling. Scaling or the formation of precipitates takes place when the concentration of the ionic salt exceeds its solubility in water. Inorganic foulants in the NF process are found to be carbonate, sulphate and phosphate salts of divalent ions, metal hydroxides, sulphides and silica. Fouling leads to physical damage to the membrane due to the plugging of pores and the inability to remove the scales from the membrane surface.172 However, the addition of hydrochloric or sulphuric acid can prevent the formation of calcium carbonate during the NF process.168 An alternative method to prevent membrane fouling is the addition of antiscalants, i.e. surface active materials which can interfere with precipitation during the NF process via threshold inhibition, crystal modication or dispersion. Common surface active agents are sodium hexametaphosphate, diethylenetriamine-penta-methyl phosphoric acid and 1-hydroxyethylidene-1,1-diphosphonic acid. The high rejection of antiscalants by membranes takes place during the NF process due to their high molecular weight and negative charge.172 The NF process is commonly used for the removal of natural organic matter (NOM) from water. NOM is a polydisperse mixture of individual particles in natural water originating from degraded and partly re-synthesized plant residues. Humic and fulvic acid seem to contribute to the natural color of water, which becomes visible if the concentration of the dissolved organic carbon (DOC) is higher than 5 ppm.172 In addition, a large variety of dyes and chemical additives from textile plant are environmental pollutants.173 The results observed by researchers include the ndings that hydrophobic fractions of NOM appear to be retained best, acidic pH favours a lower rejection of NOM (6075%), while a neutral pH favors a high rejection of NOM (90%). Rejection has also been found to be concentration dependent and ionic species may promote conformational changes in the NOM fractions, which can improve rejection via the NF process.174,175 Braghetta et al. observed a decrease in the rejection of DOC at a low pH and high ionic strength using a sulfonated polysulfone hollow bre NF membrane. The interaction between the membrane polymer (the hydrophobic domain) and the organic solute can inuence the rejection behavior as the hydrophobicity of the organic polymer affects the
sorption of organics onto the membrane surface.176 When adsorption takes place inside the membrane or on the surface, the pore size can become reduced as molecules that have a similar size to the pores block them through permeation. The interactions that occur in a multi-component solution may improve the rejections of NOM by the membrane due to friction coupling; i.e. the effect of coupling the different components. Solutions containing electrolytes, non-electrolytes or solutions of weak acids tend to exhibit strong interactions.177 The total organic carbon (TOC) content of surface water can be reduced by 93.5% via the NF process and removes turbidity by 85.5%.171 However, the gradual plugging of the membrane has been observed in the treatment of surface water with a low initial turbidity and high TOC conducted by the NF process. Flushing of the membrane with permeates from the RO process could prevent membrane plugging and allow a recovery of the initial ux. The fouling of membranes by NOM and a decline of the ux are the major problems associated to the NF techniques in the treatment of drinking water.178 Polysulfone membranes have been used in some studies and have caused adsorptive fouling. The fouling mechanisms are adsorption, precipitation, gel formation and an interaction with multivalent ions. Thus, pretreatment with a coagulant has been suggested to prevent these adverse effects and a combination of a coagulation process and membrane ltration can signicantly reduce the necessary amount of coagulant required, while reducing the turbidity and DOC. Moreover, coagulation has been found to provide an efcient hygienic barrier in combination with membranes.179 However, the removal of NOM has been signicantly affected by the type of coagulant, the coagulation conditions, the type of membrane, the ltration conditions and the characteristics of the treated water. In addition, cartridge ltration and activated carbon adsorption can be used to prevent membrane fouling by NOM.172 New ways of reducing membrane fouling have been suggested for the immobilization of TiO2 photocatalysts on the membrane surface and these have been called composite membranes. The use of nanoparticles, such as nano-alumina, silica, silver, iron oxide, etc., in membrane structures has gained a lot of interest, but their application in water treatment and the possible release of nanoparticles into the water has remained open to debate whilst the application of NF has progressed in the treatment of water.180 Organic micro-pollutants present in natural waters used for drinking water production lead to negative effects on human health. Many pesticides and organohalide compounds have been found to be carcinogenic, even in very low concentrations. The removal of micro-pollutants is traditionally done by activated carbon adsorption. This method is very expensive when large fractions of NOM are present because the adsorption sites are mainly taken by NOM due to its high concentration.181 The removal efciencies largely depend on the membranes used and on the pesticides that have to be removed. Montovay et al. found an 80% removal of atrazine and a 40% removal of metazachlor, which is signicantly lower than the expected result.183 Kiso et al.157 studied the removal of pesticides, such as acaricides, fungicides, insecticides, herbicides and rodenticides, such as atrazine and simazine, together with pyridine and a chlorinated pyridine compounds. Four different (unspecied) membranes produced by NittoDenko were used. The rejections obtained
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with three of these membranes were too low and the rejections with the fourth membrane were very high (over 95%); however, this membrane seemed to be an RO membrane and provided a high NaCl rejection.157 Van der Bruggen et al.184 obtained good results for the removal of atrazine, simazine, diuron and isoproturon. Rejections were all over 90% with NF70 (Dow/Filmtec), but for two other membranes (NF45, a Dow/Filmtec membrane, which is a thin lm composite on a polyester support viable for operation at pH from 2 to 10 and temperatures up to 45 C, and UTC-20, a Toray membrane) relatively low rejections were found for the removal of diuron and isoproturon. This may be due to the high polarity of these compounds, which causes interactions with the charged membrane.183 Van der Bruggen et al.167 also proved that there was no signicant effect of concentration on the rejection of pesticides in water. The rejection of pesticides was higher in river water and tap water than in distilled water, but the water ux was lower.167 This was mainly due to ion adsorption inside the membrane pores. Narrower pore sizes counteracted the effect of the presence of NOM. The NOM was assumed to enhance the adsorption of pesticides onto the membranes surface and an increased size exclusion and electrostatic repulsion was also observed during the NF process.182,184 The rejection of pesticides is reasonably high and correlates positively with the order of their molecular sizes.169 Important factors that must be considered for the selection of an appropriate membrane are (1) the molecular weight cut-off (MWCO), which is expressed in Dalton, (2) the membrane porosity, (3) the degree of membrane desalination, and (4) the charge of the membrane. Membranes with a MWCO varying between 200 and 400 Da are considered to be suitable for the adequate removal of pesticides from water. The rejection of uncharged pesticide molecules has been positively correlated with the pore size distribution and the number of pores on the surface of the membrane. The highest desalting membrane was found to effectively reject almost all pesticides. However, rejection was again found to be a function of the properties of the pesticide, such as hydrophobicity and charge, regardless of the membrane salt rejection performance. In general, the reliability of the membrane desalination degree is not an accurate indicator to assess the removal of hydrophobic organic micro-pollutants. A number of studies conrm that composite polyamide membranes indicate far better rejection performances for several mixtures of micro-pollutants, including pesticides, compared to cellulose acetate membranes (CA).185,186 This behavior may be due to the higher polarity of CA membranes, which is responsible for the poor rejection of the highly polar pesticides. The electrostatic repulsion between negatively charged pesticides and the negative charge of the TFC membrane surface could enhance the overall rejection performance.187 The removal of pesticide is dependent not only on the properties of the membrane but also on the properties of the pesticides, such as (1) the molecular weight and size of the pesticide, (2) the hydrophobicity, and (3) the polarity.156,165,188,189 Ben et al.189 investigated the application tez of NF for the removal of phenyl-urease in natural waters. Two types of membrane were used in their investigation: (1) a thin lm composite (a polypyperazinamide skin layer on a polyester support), which is negatively charged because of its active nanopolymer layer; and (2) a cellulose acetate polymer, which is negatively charged. It was found that the retention order for the
thin lm membranes (with a hydrophilic character) was isoproturon > linuron > chlortoluron > diuron, which showed that the molecule polarity is the main parameter that inuences the retention. On the contrary, the retention efciency for the cellulose acetate membrane (with a hydrophobic character) followed the sequence: linuron > diuron > chlortoluron > isoproturon, which indicates that the main factor responsible for the retention is the MW for the adsorption. Moreover, the mass adsorbed sequence found in both membranes for both mineral and reservoir water was: linuron > diuron > chlortoluron > isoproturon. From the results obtained, it can be concluded that the thin lm membrane was the most adequate for the removal of phenylureas from natural waters, especially for the most polar compounds because higher retention coefcients as well as higher retentions are obtained for DOC and aromatic compounds. They also observed that the additional presence of humic acids and calcium ions increases membrane fouling, which is a consequence of the adsorption of various species (NOM and ions on the membrane) as well as pore blocking and the formation of a cake layer on the membrane surface. However, the effect of humic acids and calcium ions on the retention coefcients is not signicant, especially for the less hydrophobic compounds (chlortoluron and isoproturon).189 Manttari et al.190 investigated the combined treatment of paper mill efuents with the activated sludge process and NF using a membrane made of piperazine and benzene tricarbonyl trichloride, which produced a negatively charged, hydrophilic membrane with a smooth surface and a MWCO of 200300 Da. It was reported that a well operated activated sludge process can be a good pretreatment prior to the NF operation as a high COD removal can be achieved via the activated sludge process and the resulting concentrate, after the NF process, had a lower amount of organic pollutant in the waste efuent compared to the NF operation without the pretreatment. The color rejection of NF after treatment was almost complete and the permeate color was always lower than 10% PtCo. Similar to the color, quite high COD rejections (80100%) were found with NF. Furthermore, the conductivity rejection was around 65% and the permeate conductivity was between 1.98 and 2.67 mS cm1.190 Ducom and Cabassud studied the removal of trichloroethylene, tetrachloroethylene and chloroform by NF. The removal efciency of the former two compounds was satisfactory, but the chloroform rejection was signicantly lower. This effect was attributed to the selective adsorption of chloroform into the membrane structure, which led to higher concentrations in the permeate.191 However, good removal efciencies of chloroform were obtained by Waniek et al.192 Pang et al.193 evaluated the removal efciency of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) in contaminated water using a NF unit of a polyvinylidene uoride (PVDF) membrane. The DDT concentration decreased signicantly from 77.4 mg L1 to 52.2 mg L1, while the cumulated quantity adsorbed reached 506 mg m2. The results show that DDT was easy to adsorbed on the polyvinylidene uoride membrane.192 The removal mechanism of DDT by PVDF could be due to two possible mechanisms: adsorption on the membrane or repulsion (steric and electrostatic) by the membrane. The increase of the initial DDT concentration had a negative effect on the DDT removal and the inuence of pH on the rejection is not obvious. In addition, the rejection of DDT was lower with a
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higher ux. It was difcult to simultaneously achieve a high permeate ux and high DDT rejection; however, DDT can be easily adsorbed by humic acid and can be removed altogether. With the blocking effect of the pores by the ions and the presence of organic matter (humic acid) and inorganic matter (NaCl, CaCl2 and CaSO4), the elimination of DDT can be enhanced. The removal of viruses and bacteria is extremely important in drinking water purication. The removal of the protozoa giardia and cryptosporidium from surface water sources is a main priority for many governments and drinking water companies. Traditional chlorination is still often applied as a disinfection method, but the disadvantages of chlorination were found to be (1) the formation of disinfection by-products (DBPs) and (2) the resistance of cryptosporidium to chlorine and chloramines. Membrane ltration may facilitate an improvement in the disinfection process because it is an extra barrier for viruses and bacteria.181 Bacteria (0.510 mm) and protozoan cysts and oocysts (315 mm) are larger and their removal can be guaranteed with at least 4 log units by using UF membranes. The smaller viruses may be rejected by NF membranes, which have pore sizes below 1 nm. Filtration processes by a membrane with carbon nanotube walls have been reported.193 The ltration membrane consisted of a hollow cylinder with radially aligned carbon nanotube (CNT) walls. Srivastava et al.194 efciently conducted the removal of Escherichia coli from drinking water using the CNT-aligned membrane. Membranes that have CNTs as pores could be used in desalination and demineralization. Those tubes act as the pores in the membrane. A membrane lter possessing both super hydrophobicity and superoleophilicity was synthesized from vertically aligned multi-walled carbon nanotubes on a stainless steel mesh for the possible separation of oil and water. Both super hydrophobicity and superoleophilicity could be obtained due to the dual-scale structure and needle-like nanotube geometry of the mesh with micro-scale pores combined with the low surface energy.194 The nanotube lter could separate diesel and water layers and even surfactant-stabilized emulsions. The successful phase separation of the high viscosity lubricating oil and water emulsions was also carried out. The separation mechanism can be readily expanded to a variety of different hydrophobic and oleophilic liquids, such as brewery waste water, which may have a high content of organic matter in terms of COD (from 1000 mg L1 to 4000 mg L1) and BOD (up to 1500 mg L1). Polymeric membranes have many advantages, such as their easy formation, the selective transfer of chemical species and their relatively low cost.195 However, inorganic membranes are currently in competition with organic membranes for commercial applications because they have a better resistance to chemical attack, good mechanical strength and a high tolerance of extreme pH conditions and oxidation. Inorganic membranes composed of metal oxides have higher durability in many water purication applications. In addition, the increased conversion, better selectivity, milder operating conditions and decreased separation load are some other attractive features which promote inorganic membranes as chemical reactors in many established and novel reaction systems.196 In many of the harsh operational environments, only inorganic membranes can offer advantages. However, inorganic membranes are not used extensively because
of the high costs and relatively poor control in pore size distribution. Besides, the effective membrane layer is very thick in comparison to the mean pore size, which results in a reduced ow rate. Thus, the incorporation of inorganic nanoparticles into the polymeric membranes has been considered as a way to make polymeric membranes more attractive for commercialization. Silver nanoparticles (170 nm) have been blended into polysulfone membranes by dispersing nanoparticles in a casting solution before dissolving them in the polysulfone resin (PSf). The addition of silver nanoparticles did not alter the membrane structure. The impregnation of nAg (0.9% by weight) signicantly decreased the number of Escherichia coli that were able to grow on the membrane surface by 99% after ltration with a dilute bacteria suspension. Furthermore, the silver nanoparticles reduced the attachment of an E. coli suspension to the surface of the immersed membrane by 94%.197 The antibacterial mechanism of silver is related to its interaction with sulfur and phosphorous, most notably the thiol groups (SH) present in cysteine and other compounds. The interaction of ionic silver (which can be released from the silver nanoparticles) with thiol groups and the formation of SAg or disulde bonds can damage bacterial proteins, interrupt the electron transport chain and dimerize deoxyribonucleic acid (DNA).198,199 Singapore began reclamation of domestic sewage in 1998 through the NEWater study. Indirect portable reuse is practised through the introduction of a suitable amount of NEWater into reservoirs that can be further puried by water treatment techniques before supplying to the public. To produce NEWater, primary sedimentation and secondary treatment by activated sludge were rst applied for the clarication of used domestic water. Then, bioltration via MF or UF, reverse osmosis (RO) and UV disinfection processes were applied for applications, such as in manufacturing or industry or recharging into groundwater or blending into reservoirs. The main problem in the reclamation of domestic sewage is biofouling of the RO membranes, which reduces the ux and increases the required frequency of cleaning. Pretreatment prior to RO is needed to prevent biofouling. Recently, an increased number of investigations on the use of NF in reducing dissolved organic matters with molecular weights greater than 200 Da have been attempted. Choi et al.206 used a polyamide NF membrane bioreactor for the reclamation of water from domestic sewage and 0.52.0 mg of TOC per L was found in the permeate. The amount of TOC was much less than the average amount of TOC (5 mg L1) from MF membrane bioreactors. Therefore, the NF membrane provided a better retention of organic matter than the MF membrane, which led to a reduced TOC in the permeate or feed of the RO process.200 An average of 89% rejection for high organic acids from anaerobic efuent was observed using polyamide NF membranes.201 Therefore, application of NF membranes is becoming a potential pretreatment process that reduces the problem of biofouling in the RO process. The salt rejections and organics removal by NF membranes could provide the required water quality for groundwater recharging.202 In addition, higher rejections of emerging contaminants were observed using polypiperazineamide thin lm composite membranes as shown in Table 3. The permeate ux when using NF membranes at 415 485 kPa was three times greater than that of RO membrane.203 Furthermore, energy cost was signicantly reduced by 24 times
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using NF at 415485 kPa compared to RO membranes operating at 10002100 kPa to produce the same permeate ux. The advantages of using NF as a pretreatment prior to RO for the desalination of sea water over sand lters are the use of fewer chemicals and the more consistent quality of the permeate. In addition, NF could reduce fouling in RO as other pretreatments using UF and MF membranes can cause fouling in RO due to their inability to remove TDS. It was observed that NF can remove almost all turbidity and microorganisms and reduces TDS by 37.3%.204 More than an 80% rejection of divalent ions and an 86.5% total rejection have been found (Table 3). Rejection rates for NF membranes for the treatment of tertiary treated efuent201 hardness were achieved using NF prior to the RO process.204 Furthermore, NF pretreatment before the RO of sea water could reduce biofouling and scaling due to the high removal of microorganisms and hardness and the lower required pressure for operating the RO process due to the high removal of TDS, which in turn saves the cost of power consumption.204 The polyamide NF membrane bioreactor was observed to have a high treatment efciency and a satisfactory stability for long term operation compared to NF membrane bioreactors made from cellulose acetate, although the permeate productivity was found to be lower.200 The concentrations of DOC in the permeate of the cellulose acetate NF membrane bioreactor deteriorated after 130 days operation, after which time only 10% of TOC was removed by the membrane. Similarly, the salt rejection rates of monovalent and divalent ions were reduced from 4060% and 7090%, respectively, to less than 10% after 80 days of operation. The increased presence of DOC in the permeate was due to the hydrolysis of cellulose acetate, which may have led to an increase in the membrane pore size and a decrease in the surface charge and hydrophobicity of the membrane. After 71 days of operations, large voids were found on the surface of the cellulose acetate membrane via an AFM image, which showed the deterioration of the membrane.204 The deterioration of the membrane may have been due to biodegradation. Therefore, the selection of a suitable type of membrane is important. NF is widely used for industrial waste water treatments, such as (1) color removal and the recovery of salts from waste water in
the textile industry; (2) the recovery of heavy metals and eluents from waste water in metal processing plants; (3) the removal of organics and the recovery of proteins, enzymes and aromatic compounds from waste water in the food processing industry; (4) the reclamation and reuse of water from waste water pulp and the paper industry; and (5) the removal of organics and multivalent ions from waste water at landll leachate plants.172,205 Fersi et al.207 observed that a 90% retention of bivalent cations and a 60% retention of monovalent cations can be achieved using a NF membrane (pore size $ 2 nm) in the treatment of waste water from the textile industry. In addition, the retention of TDS, the turbidity and the color were found to be greater than 90%. Thus, NF membranes are suitable for removing water soluble dyes with molecular weights ranging from 200 to 1000 Da and divalent salts for softening effects.206,207 The limitation of the NF membrane to remove color from industrial waste water is the declination of the ux due to the combined effect of the concentration polarization, the adsorption and/or the pore blocking caused by high COD and salt concentrations. However, pore enlargement (to 5695%) of the NF membrane was found on the surface of a composite membrane of polyamide and polysulfone in the presence of a dye solution containing 1015 g of Na2SO4 L1 and this was found to due to SO42 pushing through the membrane via transmembrane pressure. To prevent this pore enlargement problem, an optimum operating pressure and the proper selection of the membrane must be carried out to ensure the integrity of the membrane for a long period. (C-2) Nanoltration by nanobre media. Nanobres are essentially dened by their effective diameters (in the range of 1 to 200 nm) and they can be used for ne ltration. The synthetic materials, both organic and inorganic, that are spun from the molten state into the ner bres differ in terms of the equipment downstream of the spinneret, which enables a wide range of bre diameters to be produced. Because these media are capable of removing contaminants to below 0.1 mm, they are usually known as nanomembranes. Fig. 4 shows thiol-functionalized zonal mercaptopropyl silica nanobres. Those nanobres were obtained by the dissolution of electrospun polyacrylonitrile (PAN) nanobres with dimethylformamide. PAN nanobres were prepared by coating with 3-mercaptopropyl trimethoxysilane via a solgel process. The uniform porous channels between the nanobres facilitated Hg2+ transportation in the adsorption process.208 Fine spinning techniques have been used for the production of carbon and ceramic bres as well as the bres of other materials and are obviously used as a lter medium, particularly for air ltration.209 The introduction of an antimicrobial functionality agent in the particulate lters has been explored and it has been found that most microorganisms often become resistant, which could limit the benet of an antimicrobial functionality. Furthermore, most of the microorganisms enter the lter with airborne particulate matter and they grow in size due to accumulation and build up on the lter surface. Metallic silver and silver oxides are safe and effective antimicrobial agents at low levels. Positively charged silver ions attract electronegative bacterial cells and bind with the sulfhydryl group on the cell membrane or bacterial DNA and result in the prevention of proliferation of the microorganisms.210,211 Ionic plasma
Table 3 The typical properties of pressure-driven NF membranes162,163 Rejection rate (%) 96 48 40 40 40 70 80 25 100 90 90 78 90
Constituents TOC Conductivity Sodium Potassium Calcium Magnesium Chloride Pharmaceutically active compounds Salicylic acid Naproxen Gembrozil Ketoprofen Carbamazepine
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processing (IPD) is a suitable method for the coating of surface engineered nanosized silver particles on polymeric surfaces for use in heating, ventilation and air conditioning (HVAC) air lters. Porous electrospun nanobrous scaffolds (porosity larger than 70%) can be used to replace ux limiting asymmetric porous ultraltration membranes (of porosity in the range of 34%). Yoon et al. synthesized polyacrylonitrile nanobrous layers supported on nonwoven microbrous substrates (a melt-blown polyethylene terephthalate mat) and applied a water resistant, but water permeable, coating of chitosan over the nanobrous layer. A high ux and low degree of fouling resulted with the use of this nanobre media.212 It was observed that an electrospun membrane conveniently rejects the microparticles and acts as a screen lter without fouling the membrane, especially when the particles are larger than the largest pore size of the nanobrous membrane. A high surface-to-volume ratio of the nanobrous media increased the degree of fouling. Therefore, the surface modication of the nanobrous screen lter with a suitable hydrophilic or hydrophobic oligomer is often recommended to reduce the fouling effect. A novel alumina nanobre lter, which consists of a single layer of an alumina nanobre grafted onto a microglass bre backbone has shown potential for the effective removal and retention of aerosols from polluted air. The extraction fraction of the nanobre lter was found to be three orders lower than the HEPA lters, demonstrating that viruses were effectively retained in the nanobre lter due to an electrostatic attraction between the electropositive bre surface and the electronegative aerosol particles.212 The addition of polystyrene nanobres to the coalescence lters (glass bres) have shown that the addition of small amounts of polystyrene nanobres signicantly improve the coalescence efciency of the lter but also signicantly increase the pressure drop of the lters.213 Conventional ion exchange resins are normally either a gel structure or a granular structure and are typically made of styrene or acrylic as the structural materials. Granular resinous materials have larger pore volumes and low ion-exchange capacities than gel type materials and additionally have a better mechanical strength. The brous materials are applied as a support for the ion-exchange functionality due to their ease of preparation, contact efciency and the physical requirement for strength and dimensional stability.214 Polymeric nanobre-based ion exchangers have higher swelling behaviors compared to other media because of their high surface area, porosity and capillary motion.215 In
Fig. 4 The assembly of a zonal mercaptopropyl silica nanobre.208
addition, polymer nanobre ion exchangers are found to have extremely rapid kinetics and higher ion-exchange capacities.215 A major trend with regards to lter media is the development of the combination lter, capable of performing two separation tasks at once, such as solidgas separation and the adsorption of a gaseous impurity. These combination lters employ a chemically active agent embedded in the lter medium material, the most common of which is activated carbon as an adsorbent. Recent developments in nanobre lters offer a range of adsorptive and chemical treatments and antimicrobial action via silver zeolite technology. Titanate nanobres have been synthesized via a hydrothermal reaction between a concentrated NaOH solution and TiOSO4. The titanate bres were dispersed in ethanol to form a suspension containing 0.2 wt% titanate nanobres. The suspension was sonicated for 10 min to achieve a homogeneous dispersion, which was used to apply thin layers on the porous substrate using a spin-coater. The separation efciency of the ceramic membranes can be signicantly improved by constructing a top separation layer with TiO2 nanobres. These improvements are due to the radical changes in the texture of the top-layer. It is also found that the top layers of the TiO2 nanobres on the porous glass and alumina support were similar in terms of their structure and performance. They are able to retain more than 95% of 60 nm particles at a very high ux rate of about 900 L m2 h1. Moreover, the fabrication of these membranes is relatively simple and economical with low rejection rates, compared to the conventional ceramic membranes. This approach can be scaled-up for the fabrication of ceramic membranes in practical applications.216 For the ltration of liquids, conventional porous polymeric membranes have their intrinsic limitations; e.g. low ux rates and high fouling. These drawbacks are due to the geometric structure of the pores, the corresponding pore size distribution217 and the formation of undesirable macro-voids across the whole membrane layer.218 It appears that electrospun nanobrous membranes can overcome some of these limitations and, consequently, a polyethersulfone (PES) electrospun nanobre mat has been applied as a membrane for liquid ltration. To increase the mechanical strength of the PES bre, a poly(ethylene terephthalate) (PET) non-woven sub-layer was also used. The composite membrane (PESPET) is illustrated in Fig. 5. The PES/PET electrospun nanobrous membranes (ENMs) indicated that the membranes possess a high initial ux. The turbidity of the permeated suspension was found to decrease signicantly with time.219 Polysulfone (PSU) nanobrous membranes possess much higher porosity and have a high surface area, which results in high ux pre-lters with even higher loading capacities. Such pre-lters can be used in various applications, such as the removal of micro-particles from waste water and in ultraltration, or with nanoltration membranes, to prolong the life of these membranes.220,221 A coat of TiO2/polyvinyl alcohol (PVA) on the polyester lter effectively modies the matrix, narrows the pore size to 10 mm and reduces the contact angles by 40 because of the hydroxyl groups from PVA and TiO2. The improved hydrophilicity and anti-fouling properties of the composite membranes enables a highly stabilized (10 m3 m2 h1 or 10 kPa) pure water ux and a high efuent ux during long term ltration tests in membrane reactor systems for the treatment of simulated waste water in the removal of nitrate/
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Fig. 5 The structure of PES/PET composite membranes.220
ammonium to allow for water reuse in a polyester bre production plant.222 (D) Sorbents Water remediation techniques include (1) adsorption, (2) biotechnology, (3) catalytic processes, (4) membrane processes, (5) ionizing radiation processes, and (6) magnetically assisted processes. In addition, nanomaterials-based processes are becoming promising options for applications in water treatment. The adsorption technique is the most frequently studied method to purify water.221224 Sorption is the transfer of ions from the solution phase to the solid phase. Sorption actually describes a group of processes, which include adsorption and precipitation reactions. Basically, adsorption is a mass transfer process by which a substance is transferred from the liquid phase to the surface of a solid and becomes bound by physical and/or chemical interactions.225 Various low cost adsorbents, derived from agricultural waste, industrial by-products, natural materials, or modied biopolymers, have been developed recently and applied in the removal of heavy metals from metal-contaminated waste water. In general, there are three main steps involved in pollutant sorption onto solid sorbents: (i) the transport of the pollutant from the bulk solution to the sorbent surface; (ii) adsorption on the particle surface; and (iii) transport within the sorbent particle. Technical applicability and cost-effectiveness are the key factors that play major roles in the selection of the most suitable adsorbent to treat waste water.226,227 Magnetic sorbents or magnetic ion exchange (MIEX) resins have been introduced for the removal of natural organic matter (NOM) from ambient raw water and was found to be better than coagulation processes. The ion exchange resin beads contain a magnetized component within their structure, which allows the beads to act as individual magnets. The magnetic component results in the beads forming agglomerates that can settle rapidly or uidize at high hydraulic loading rates. The very small resin bead size could provide a high surface area to allow the rapid exchange of selective ions. Resins with a polyacrylic skeleton with macroporous properties are more suitable for the removal of NOM than gel resins.228,229 In addition, the MIEX process involves adsorbing the DOC onto the MIEX resin in a stirred contactor that disperses the resin beads to achieve a maximum surface area. The magnetic part of the resin
allows the resin to agglomerate into larger and faster settling particles, which allow a recovery rate of greater than 99.9% to be obtained. The MIEX process has been applied for the removal of humic acid,230 low to moderate organic concentrations over wide range of alkalinities and bromide concentrations.231,232 Coagulation removed 60% of the dissolved organic carbon (DOC) associated with the 110 k fraction but had little impact on the DOC concentration of the <1 k fraction. Treatment with MIEX removed approximately 80% of the DOC associated with the 110 k fraction and almost 60% of the DOC associated with the <1 k fraction. The nature of water was varied with differing types of NOM and passed through the MIEX resin. It was observed that an increase in the hydrophobicity of the resin reduced the DOC. Furthermore, the MIEX resin was used for the removal of some specic inorganic ions, such as As(V) and Cr(VI). The MIEX process has also been applied in a pre-treatment step for catalytic processes, such as effective debromination using ozonation.233 Magnetic chitosan gel particles, a magnetite bearing covalently immobilised copper phthalocyanine dye, magnetic charcoal and magnetic alginates have all been applied in the removal process of polycyclic dyes, malachite green, crystal white and other organic dyes from waste waters.234238 Magnetotactic bacteria naturally occur as magnetic sorbent sources in nature. These bacteria have the ability to orient themselves in the direction of the magnetic eld. Magnetotactic bacteria have been applied in the removal of organic pollutants from water by enzymatic reactions.239 Surfactant-coated magnetite nanoparticles have been applied in the extraction of the organic contaminant, 2-hydroxyphenol.240 Floating magnetic sorbents, in the form of polymer-coated vermiculite iron oxide composites, have been formulated. The composites oat on the surface of water and can easily remove spilled oil from oil contaminated water.241 In addition, zero valent iron (nZVI) nanoparticles with a diameter of 1120 nm are able to remove As(III) and As(V) by rapid adsorption followed by precipitation and result in surface corrosion byproducts.242244 The adsorption of As(III) and As(V) by iron nanoparticles is due to the weak electrostatic attraction between the adsorbed species and the binding sites.245 Nanoparticles of nZVI have been prepared by adding freshly made ferric chloride to a reaction vessel containing solid NaBH4.246 Polyvinyl alcohol-co-vinyl acetate-co-itaconic acid has been found to be an effective surfactant for the stability of nZVI nanoparticles. Initially the sites are amorphous Fe(II)/Fe(III) magnetite. As the treatment progresses, the initial reactive sites gradually transform into lepidocrocite and the more crystalline magnetite. Heavy metal ions (e.g. Ni(II)) are adsorbed on the oxide shell as corrosion proceeds and precipitates on the iron core of the nanoparticle. Nanoparticles of nZVIs have higher reactivities due to their larger surface area (average area: 35.5 m2 g1) than commonly used microparticles (average area: 0.9 m2 g1) and they also have reaction rates that are 100 times higher than those of microparticles.247 Since the reactions with organohalides are considered as inner-sphere surface-mediated processes, the application of iron nanoparticles is becoming a real potential.246 Fig. 6 shows the reduction of organic pollutants by chemisoprtion on nZVI nanoparticles. Iron can reduce water and form hydrogen gas under anaerobic conditions as follows:248,249
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Fig. 6 A schematic diagram of the reduction of perchloroethylene on the surface of a nZVI particle.74
Fe0 + 2H2O / Fe2+ + H2 + 2OH In addition, iron can remove chlorine by hydrogenolysis as follows: Fe0 + RCl + H+ / Fe2+ + RH + Cl where Fe0 is oxidized to Fe2+, while perchloroethylene is dechlorinated. The application of bulk zero valent iron metal in environmental remediation has limitations, such as slow reaction rates and the formation of more toxic intermediates resulting from the dechlorination process, which are difcult to destroy.250 Iron nanoparticles have been widely applied in the transformation and detoxication of a wide variety of common environmental contaminants, such as chlorinated organic solvents, organochlorine pesticides and PVBs, due to their large surface area and surface activity.251 The degradation rates of trichloroethylene (TCE) has been signicantly increased to 3 103 L m2 h1 from 6.3 105 L m2 h1, which was obtained when bulk Fe0 particles (>1 micrometer) were used to remove TCE.252 The feasibility of applying nZVI particles in water remediation showed that up to 90% TCE was degraded within 30 min.253 In addition, non-toxic nal products were formed. The capacity of transforming TCE into harmless compounds was found to be higher than that of micro ZVI particles due to the higher specic area. The content of Fe0, the solution pH, the concentration of TCE and the presence of anions, such as nitrate, can signicantly affect the degradation of TCE. Furthermore, the application of nZVI particles could reduce the presence of perchlorate ions in contaminated media by 66% within 336 h via a reduction process on the surface of nZVI and the association of an oxygen molecule from the perchlorate ions with nZVI.254,255 The amount of Ni metal adsorbed by iron-core nanoparticles is higher than by iron oxide nanoparticles (i.e. gFe2O3). The addition of functional materials, such as stable noble metals, metal oxides and low molecular weight organic molecules and polymers, in the preparation of nZVI nanoparticles could deliver higher adsorption capacities for heavy metals that will lead to better remediation.245 Modied nZVI nanoparticles that have been applied in the removal of metal ions from water are shown in Table 4. Hu et al. reported that modied jacobsite (manganese iron oxide) nanoparticles can be applied and regenerated many times without a decrease in their adsorption performance.256 The study by Bezbaruah et al. shows that nZVI entrapment in a
biopolymer matrix (alginate) may increase their overall efcacy in groundwater remediation. The authors have shown that nZVI can be effectively trapped in Ca-alginate beads and the reactivity of the entrapped nZVI toward a model contaminant (nitrate) was comparable to that of one dimensional ZVI.257 The reduction in the nitrate concentration using one dimensional nZVI and trapped nZVI in Ca-alginate beads were 5573% and 5073%, respectively, over a 2 h remediation period. In addition, Caalginate is suitable for the entrapment of nZVI to make the nanoparticles relatively stationary in aqueous media (e.g., groundwater). Thus, the mobility and settlement problems associated with one dimensional nZVI can be overcome and alginate-trapped nZVI can be effectively used in permeable reactive barriers for groundwater remediation. Keum and Li reported the application of Fe0 nanoparticles in the reductive debromination of polybrominated diphenyl ethers (PBDEs). The debromination of PBDEs by nZVI particles has high potential value for the remediation of PBDEs in the environment.263 Kim et al. applied Fe0 in the removal of alachlor and pretilachlor.264 Wang and Zhang reported the utilization of Fe0 nanoparticles in the dechlorination of several chlorinated aliphatic compounds and a mixture of PCB at relatively low metal-to-solution ratios (25 g per 100 mL).265 Up to 25% of PCB could be removed within 17 h by using fresh nZVI particles. Fe0 nanoparticles in environmental remediation has great potential; however, the limitations of using Fe0 nanoparticles are: (1) the high activity leads to the storage of freshly synthesized iron particles becoming a signicant problem; (2) the activity of the iron particles decreases as the reaction proceeds due to the formation of Fe(OH)3, which forms on the surface of the Fe0 nanoparticles and may make the iron core unreactive, therefore blocking further reaction; (3) the freshly fabricated Fe0 can easily form aggregates and this decreases the dispersion ability. Recently, research focus have been on solving the above problems. To improve the stability of Fe0 nanoparticles against aggregation, He and his group members developed palladized iron (FePd) nanoparticles stabilizing on starch265 or sodium carboxymethylcellulose (CMC).266 The results showed that the dispersibility of the nanoparticles increased and, thus, the degree of dechlorination greatly increased. The starch-coated Fe0 nanoparticles exhibited markedly greater reactivity during the dechlorination of TCE or PCB in water. About 98% of TCE and 80% of PCB were found to be decomposed after 1 h and 100 h, respectively. In addition, the degradation rate of TCE by CMC-stabilized nanoparticles was 17 times faster than that of Fe0 nanoparticles. Ag-modied Fe0 nanoparticles (1% Ag)267 could facilitate the dechlorination of tetra-, tri- and di-chlorobenzenes (TeCB, TCB and DCB, respectively) within 24 h at a metal loading of 25 g L1 and the dechlorination rate was found to positively correlate with the amount of silver loaded on the bimetallic particles. Researchers268,269 have done lots of work on the dechlorination of PCBs using nanoparticles with activated carbon and bimetallic nanoparticles. Several kinds of assemblies and bimetallics have been investigated, such as GAC (granular activated carbon)/Fe/ Pd bimetallics, GAC/ZVI, GAC/ZVI/Pd, Pd/Mg bimetallics, etc. The GAC/ZVI/Pd system showed an efcient dechlorination of 2-chlorobiphenyl (2-ClBP) at 90% after 2 days. The high degradation ability of the GAC/ZVI/Pd system is caused by the synergistic and simultaneous function of adsorption and
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Table 4 Previous studies of the environmental remediation using modied nZVI Major binding sites or functional groups for the removal of the heavy metal MnO2 and Fe2O3 are major adsorptive components The major adsorption driving force is the redox reaction between Mn(II) and incoming Cr(VI) Major binding sites are the O-donor atoms and S-donor atoms of PEDOT Thiol groups from dimercaptosuccinic acid play a major role in the binding site Anionic adsorption between positively charged maghemite and MoO42 at pH values below 6 and electrostatic repulsion between negatively charged maghemite and MoO42 The dithiocarbamate group after the derivitization of magnetite plays a major role in the removal of Hg2+
Type of nanoparticle Modied jacobsite (MnFe2O4)

255
Particle size (nm) 10 20 11 6 50
Targeted heavy metal ion Cr(VI) Cr(VI) Ag(I), Hg(II), Pb(II) Hg(II), Co(II), Cu(II), As(V), Ag(I), Cd(II), Ti(III), Pb(II) Mo(VI)
Ferrites (MeFe2O4, where Me Mn, Co, Cu, Mg, Zn or Ni)257
Magnetic nanoparticles encapsulated by poly(3,4-ethylenedioxythiophene) (PEDOT)258 Magnetite nanoparticles modied with dimercaptosuccinic acid259,260 Maghemite (-Fe2O3)261
Silica-coated magnetite (Fe3O4)262
5080
Hg2+
dechlorination of PCB. The perchlorate ion was signicantly reduced by 1.8 and 3.3 fold with starch and CMC-modied nZVI, respectively, when it was compared with nZVI.270 Ge et al. applied modied Fe3O4 magnetic nanoparticles (MNPs) (1520 nm) with 3-aminopropyltriethoxysilane and copolymers of acrylic acid and crotonic acid in the removal of Cd2+, Zn2+, Pb2+, Cu2+ from metal contaminated water.272,273 It was observed that the MNPs could efciently remove the metal ions with a high maximum adsorption capacity at pH 5.5 and could be used as a recyclable adsorbents under convenient conditions.271 Mak and Chen found that methylene blue could be recovered fast and efciently from an aqueous solution by polyacrylic acid-bound iron oxide magnetic nanoparticles (12 nm average diameter) due to their large specic surface area and the absence of internal diffusion resistance.274 The impact of pH on the removal of Mo(VI) from contaminated waste water was studied by Afkhami and Norooz-Asl.275 The surfaces of the metal oxides (Fe2O3 suspension) are generally covered with hydroxyl groups that vary in their form at different pHs. The surface charge is neutral at pHzpc (the zero point charge pH, where the pHzpc of maghemite nanoparticles is around 6.3). Below the pHzpc, the adsorbent surface is positively charged and anion adsorption occurs. With an increase in the pH up to pH 4, the uptake of MnO42 ions increases and remains constant in the pH range of 46. Then, the uptake of Mo(VI) in the form of MoO42 ions decreases at pH values higher than 6 as the adsorption surface becomes negatively charged at pH > pHzpc; this leads to an increasing electrostatic repulsion between the negatively charged species (MoO42) and the negatively charged adsorbent, which releases the adsorbed MoO4. The removal efciency was highly pH dependent and the optimal adsorption was found to be pH 4.06.0.273 The sorbents can also be of mineral, organic or biological origin (e.g. activated carbons, zeolites, clays, silica beads), low cost adsorbents (e.g., industrial by-products, agricultural wastes and biomass) and polymeric materials (e.g., organic polymeric
resins and macroporous hyper-crosslinked polymers).279 In recent years, natural polymer adsorbents have been used (e.g., chitin and starch and their derivatives, chitosan and cyclodextrin).274,275 Polysaccharide-based materials can be used as sorbents in waste water treatment.276 Chitosan has been applied extensively in various research areas of water/waste water treatment.277,278 Chang and Chen modied the chitosan polymer and grafted carboxylic groups. Then, the carboxylated chitosan was covalently bound to magnetic nanoparticles. Afterwards, modied chitosan nanoparticles were used for the removal of metals from waste water.280 Qi and Xu modied the chitosan polymer by ionic gelation with tripolyphosphate (TPP) as an ionic cross linker and both the research groups found that modied chitosan nanoparticles could provide high adsorption capacities of Pb2+.281 However, the limitation of modied chitosan nanoparticles is disintegration in aqueous solution or aggregation in pH 9 alkaline solution due to weak electrostatic interactions between chitosan and TPP molecules. Some NPs are powerful adsorbents due to their unique structure and electronic properties. Dissolved organic carbon and organic colloids in the submicron size range have been recognized as a distinct non-aqueous organic phase to which organic pollutants are adsorbed,280 which leads to a reduction in their bioavailability. Zeolites are the microporous materials (pore size < 2 nm) and consist of a 3-dimensional arrangement of [SiO4]4 and [AlO4]5 polyhedra connected through their oxygen atoms to form large negative lattices with Brnsted and Lewis acid sites. If cations are exchanged by protons, the zeolite acquires considerable Brnsted acidic properties. The application of zeolite materials for environmental remediation has gained great attention due to their selective sorption capacities, non-toxic nature, availability and low cost. Zeolites have been widely applied in the removal of heavy metals, such as Cr3+, Ni2+, Zn2+, Cu2+, Fe2+, Pb2+ and Cd2+ from waste water in the mining industries.281283 The stability of zeolites is high and disintegration was found only at pH values below 2. In addition, zeolites have been applied in the retention
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of methyl-tert-butyl ether, chloroform and TCE in water and they were found to be 812 times more efcient than activated carbon. Mesoporous silica-based materials (pore size 250 nm) have been widely used to remove heavy metals present in waste water. Mesoporous silica with functionalized monolayers have been useful in the removal of mercury and other heavy metals from waste water. Better adsorption capacities were found for amino-functionalized silica in the capture of Cu2+, Zn2+, Ni2+ and Cr2+, whereas Hg2+ was better adsorbed on thio-functionalized silica.284 Activated alumina, a porous form of Al2O3, has a high porosity so it is widely used in ltering components for drinking water purication. Mesoporous alumina, aminated mesoporous alumina and alumina-supported MnO can remove As(V), As(III), Cu(II) and TCE from the contaminated water.285287 Nanoscale diboron trioxide/titanium dioxide composite materials have been used for the separation of trace cadmium ions from polluted water containing cadmium ions. The other pollutant matrix ions had no negative effect on the removal of the cadmium ions. The removal of organic pollutants using inorganic nanoparticles and mesoporous structures can be carried out in two ways: (1) static force (including Lewis adsorption); and (2) weak and chemical bonding through hydrogen bonds/p bonds with the surface functional groups. Modication and chemical treatment of the nanomaterials are essential to enhance the target adsorption ability. The removal efciency of As(III) and As(V) was higher for nanocrystalline TiO2 than fumed TiO2.288,289 Alvaro et al. synthesized mesoporous TiO2 nanoparticles in association with tetraethyl orthosilicate using neutral pluronics as templates. The photocatalytic activity for the degradation of phenol was much higher for mesoporous TiO2 nanoparticles compared to standard P-25 TiO2.291 Many types of polymers have been assembled into nanoparticles via polymerization techniques. PolyN-isopropylacrylamide nanoparticles remove Pb2+ and Cd2+ from waste water. The adsorption of Pb2+ and Cd2+ by the polymer is due to the Coulombic attraction between the carboxylate group on the polymer and the positive charged metal species from waste water.292 However, the utilization of polyN-isopropylacrylamide in waste water treatment is not widespread because the main functional group, isopropylacrylamide, does not show a favorable ability to remove metals. Polymeric nanoparticles synthesized by the copolymerization of a pyridyl monomer with styrene have been used for the removal of metal ions. It was observed that the removal rate of metal ions from the aqueous solution was fast due to the presence of bipyridine-based metal-chelating groups on the surface of the nanoparticles.290 It was found that the poly(vinylpyridine) nanoparticles could selectively remove Cu2+ despite the presence of other competing ion species. Chen et al.293 modied polystyrene nanoparticles with a specic dye molecule called an azo-chromophore. It was observed that the adsorption efciency for the removal of Pb2+ increased due to a modication of the nanoparticle ligand and the nanoparticles could retain their adsorptive capacity after 3 cycles of adsorption/desorption.293 Bell et al. demonstrated that the sequestration selectivity for heavy metals could be altered by grafting a macrocyclic ligand of the polymeric nanoparticles with a core shell structure. The original coreshell structure without grafting can adsorb Hg only, while the modied nanoparticles could
adsorb Co2+ selectively in the presence of other heavy metal ions.294 Therefore, polymeric nanoparticles can be tailored for the remediation of selective heavy metals. Tungittiplakorn et al. found that polyurethane-based nanoparticles could be applied in the desorption and transportation of organic pollutants with the hydrophobic core of the nanoparticles.295,296
(E)
Dendrimers
Metal nanoparticles (NPs) have received great scientic and technological interest in environmental remediation due to their size, unusual crystal shapes and lattice orders.295 Nano-sized metal particles are expected to exhibit much higher reactivity because of their larger surface area than bulk particles. However, the preparation of functionalized NPs using different methods still remains a great challenge. One of the unique approaches used to prepare inorganic NPs is through the use of dendrimers. Dendritic nanopolymers are highly branched 3D globular nanoparticles with controlled compositions and architectures. Dendrimers are relatively monodisperse and highly branched nanoparticles with controlled compositions and design and their sizes are in the range of 1100 nm. Dendrimers are built from a starting atom, such as nitrogen, to which carbon and other elements are added by a repeating series of chemical reactions that produce a spherical branching structure, as shown in Fig. 7, in which divergent or convergent hierarchical assembly strategies are involved. As the process repeats, successive layers are added and the sphere can be expanded to the size required by the investigator. Dendrimers consist of three components: (1) a core, (2) interior branched cells and (3) terminal branched cells.297,298 Ammonia is used as the core molecule and it reacts with methylacrylate in the presence of methanol and then ethylenediamine is added: NH3 + 3CH2CHCOOCH3N(CH2 CH2COOCH3)3 / 3NH2CH2CH2NH2N(CH2CH2CONHCH2CH2H2)3 + 3CH3OH At the end of each branch there is a free amino group that can react with 2 methylacrylate monomers and 2 ethylenediamine molecules. Each complete reaction sequence results in a new dendrimer generation as shown in Fig. 8. Dendrimers are a novel class of polymers with a compact spherical structure and unique behavior and a narrow size distribution that can be used as templates or stabilizers to form relatively monodispersed organic/inorganic hybrid NPs. The crucial role played by dendrimers is in the synthesis of dendrimer-stabilized NPs, in which metal ions are usually complexed with dendrimer ligands (e.g. interior tertiary amines, terminal functional groups) through coordination, electrostatic interaction, etc., followed by a reduction or other reactions to form inorganic NPs stabilized by dendrimers. They are routinely synthesized from a central polyfunctional core by the repeated addition of monomers. The core is characterized by a number of functional groups. The dendrimer generation is created by adding monomers to each functional group in turn, leaving the end groups able to react again. The structure of the polymer is determined by the number of reactive groups of the core, the branch lengths and surface group dimensions. The maximum size is limited by the generation at which the dendrimer becomes tightly packed.300
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Fig. 7 The dendritic structure.298
Poly(amidoamine), or PAMAM, dendrimers have been developed for applications in the remediation of waste water contaminated with a variety of transition metal ions, such as copper (Cu(II)). Diallo et al. rst reported the use of PAMAM dendrimers for copper removal in 1999. Dendritic nanopolymers can encapsulate a broad range of solutes in water, including cations (e.g., copper, silver, gold, iron, nickel, zinc and uranium) by attachment to the functional groups of dendrimers, such as primary amines, carboxylates and hydroxymates.303 They also can deactivate bacteria and viruses after binding. Poly(amidoamine) dendrimers can remove metal ions (Cu(II), Ag(I), Fe(III) and others) by functioning as chelating agents and ultraltraters and the removal capacity can be improved by attaching metal ions to the functional groups of dendrimers, such as primary amines, carboxylates and hydroxymates.299 Dendritic nanopolymers, such as PAMAM dendrimers, have much less tendency to pass through the pores of ultraltration membranes
Fig. 8 A graphical presentation of PAMAM dendrimers (a) PAMAM, (b) poly(glycerol-succinic acid) dendrimer, (c) Boltorn and (d) hyperbranched polyglycerol.301
than linear polymers of a similar molar mass because of their much smaller polydispersity and globular shape. Therefore, dendritic nanopolymers have been used to enhance UF and MF processes for the recovery of dissolved ions from aqueous solutions. First, contaminated water is mixed with a solution of functionalized dendritic nanopolymers and then the mixtures of nanopolymers and bound contaminants is transferred to UF or MF units to recover the clean water. In those units, the bound target substance is separated from the nanopolymers by changing the acidity (i.e., the pH) of the solution. Finally, the recovered concentrated solution of contaminants is collected for disposal or the nanopolymers may be recycled.302 Diallo et al. have combined bench scale measurements of metal ion binding to Gx-NH, PAMAM dendrimers with dead-end UF experiments to assess the performance of dendritic polymer ltration to recover Cu(II) from aqueous solutions. The Cu(II) binding capacities of the PAMAM dendrimers seem to be much larger and more sensitive to the pH of the solution than those of linear polymers with amine groups. Furthermore, metal ion (Cu(II)) trapped PAMAM dendrimers can be regenerated by decreasing the solution pH to 4.05.0, thus enabling the recovery of the bound Cu(II) and the recycling of the dendrimer. PAMAM dendrimers can also be applied in the recovery of perchlorate anions and uranium metals from contaminated groundwater. Polyamidoamine dendrimers (PAMAM), after surface modication with benzoylthiourea groups, are a new and excellent water-soluble chelating ion exchange material with a distinct selectivity for toxic heavy metal ions. Investigations on the removal of Co(II), Cu(II), Ni(II), Pb(II) and Zn(II) have been performed using the PAMAM-supported ltration method. The results showed that all metal ions could be retained almost quantitatively at pH 9. Cu(II) could form the most stable complexes with the benzoylthiourea-modied PAMAM derivatives and complete retention was achieved at pH>4, and could be separated selectively from the other heavy metal ions investigated.303 The key novelty of the dendritic polymer ltration process is the combination of dendritic polymers with multiple chemical functionalities with UF and MF. This may enable the development of a new generation of water treatment processes that are exible, recongurable and scalable.300 Dendritic polymer ltration processes are scalable and could be used to develop small and mobile water treatment systems as well as large and xed treatment systems. Dendritic nanopolymers have also much smaller intrinsic viscosities than linear polymers with the same molar mass because of their globular shape.300 Thus, comparatively lower operating pressures, energy consumption and the loss of ligands by shear-force induced during ltration could be achieved with dendritic polymers in cross-ow UF systems and this dendritic ltration could be applied in industrial water treatment.304 PAMAM dendrimers have great potential as templates for metal composite nanoparticles due to their low toxicity and highly regular, branched and three-dimensional structure, which can host inorganic nanoclusters and form stable dendrimer complexes and nanocomposites.305 In general, the reduction of silver cations with NaBH4 and the template role of the dendrimers ensure well dispersed silver nanoparticles with a relatively small size distribution.306 Investigations have already
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indicated that dendrimer-encapsulated silver nanoparticles possess antimicrobial activity.307 Strong bonding is achieved through a mechanism that involves an interaction with noble metals, such as catalytic palladium nanoparticles in lms of linear poly(ethyleneimine) (PEI) and silver. Platinum and palladium nanoparticles have also been successfully encapsulated within poly(propyleneimine) dendrimers. All of these polymers possess some strong electron-donating centers, such as amino or carboxylate groups, which facilitate metalpolymer complex formation. In these studies, the preparation of polymer/metal nanoparticles needed extra reducing agents, including sodium borohydride (NaHB4), formaldehyde, sodium citrate or hydrazine. An amine-terminated hyper-branched poly(amidoamine) (HPAMAMNH2) has been used to produce antimicrobial silver nanocomposites.308 More importantly, this hyperbranched polymer was found to serve as a highly effective self-reducing agent. The advantages of this method are: (i) no extra reducing agent was needed; (ii) the process was conducted at room temperature and under normal pressure and in an aqueous solution, making it a green route; and (iii) the obtained silver nanoparticles have several excellent properties, such as a longterm dispersion stability, small particle size, a narrow size distribution controlled by the composition and a good antimicrobial activity as tested against E. coli, S. aureus, B. subtilis and K. mobilis. The activity was enhanced with an increasing silver concentration. The bacterial inhibition ratio of the HPAMAM NH2/Ag nanocomposites reached up to 95% at a silver concentration of 2.7 mg mL1. Furthermore, pure HPAMAMNH2 also indicated some limited antimicrobial ability with an inhabitation ratio less than 10%. To increase the metal adsorption capacity and form metal nanoparticles, it is imperative that metal ions are trapped in the interior structure of the dendrimer (to offer protection against agglomeration). This is usually attempted by selective protonation or hydroxylation of the surface amines
Table 5 The applications of dendrimers in environmental remediation Type of composite dendrimer Silica nanoparticles prepared by mixing salicylic acid and hyperbranched poly(propylene imine) PAMAM dendrimer composite membrane with hyaluronic acid in a chitosan gutter layer PAMAM dendrimer composite membrane consisting of chitosan and a dendrimer Ni loaded hydrogel PAMAM PAMAM dendrimer composite membrane consisting of chitosan and a dendrimer Composite membrane PAMAM dendrimer and trimesoyl chloride on poly(ether ketone) (TMC) Impregnation of cross-linked silylated and cyclodextrin dendritic poly(propylene imine) and poly(ethylene imine) on ceramic membranes, such as TiO2, Al2O3 and SiC
(the surface amine is more basic as it is primary in nature).308 The interaction of Cu2+ with PAMAM leads to two changes in the absorption spectrum: a band due to the dd transition gains prominence and shifts to 605 nm and a new band, due to a strong ligand-to-metal interaction, appears at 300 nm. Some effort has been made to synthesize dendrimer-protected silver nanodots exhibiting uorescence.309 It is quite clear that dendrimers play a critical role in stabilizing the cluster/nanoparticle surface and thus dramatically increase the stability of such species. Table 5 shows some applications of dendrimers for environmental remediation. (F) Carbon nanomaterials The use of nanoscale activated carbon may have advantages over conventional materials due to the much larger surface area of the nanoparticles on a mass basis. In addition, their unique structure and electronic properties can make them especially powerful adsorbents.317 Many materials have properties that are dependent on size. The advantages for processes involved in environmental remediation are due to (1) their great capacity to adsorb a wide range of pollutants, (2) their fast kinetics, (3) their good surface area, and (4) their selectivity towards aromatic solutes.276 Activated carbon from various sources, such as coconut coir, jute stick, rice husk, etc., is the most popular of the adsorbents. The treatment of water by adsorption methods uses specic ion exchangers or extractants and a combination of adsorption with catalytic treatment methods, redox processes and magnetic processes. Recently, a new technique in adsorption has been reported that applies carbon nanotube clusters. The unique property of these clusters is their ability to remove bacteria from water by an adsorption method. Adsorption on sorbents has become one of the preferred methods to remove toxic contaminants from contaminated water. Adsorption-based separation
Thickness of membrane/disc (nm) 300 76
Targeted contaminants Removal of polycyclic aromatic hydrocarbons (PAH), such as pyrene and phenanthrene, and Pb2+, Cd2+, Hg2+, Cr2O72 from contaminated aqueous solutions Separation of CO2 from a feed gas mixture of CO2 and N2 on porous substrates Separation of CO2 from fossil fuel emission on porous substrates Separation of Cu2+, Co2+ and Cr3+ from aqueous solutions Separation of CO2 from a feed gas mixture of CO2 and N2 on porous substrates Rejection of salts: MgCl2, MgSO4, NaCl and Na2SO4 Removal of organic pollutants, such as polycyclic aromatic hydrocarbons, trihalogen methane, pesticides and methyl-tert-butyl ether
Ref. 310
300 300 2 mm disc 300 The diameters of the pores in the composite membrane are in the range of nanometers 8 mm pore size for the TiO2 lter and 3 mm pore size for the Al2O3 lter
311 312 313 314 315 316319
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processes are widely applied in the purication of drinking water and natural gas contaminated air. Nanoscale carbon black, with a particle size of 2070 nm, can be modied via oxidized with 65% HNO3 by reuxing 10 g of carbon black with 150 mL HNO3 (65%) in a conical ask at 110 C for 120 min. The modied carbon black is ltered and washed with deionized water until the pH of the ltrate is stable and the product is nally dried in a vacuum oven at 110 C for 24 h. The increased adsorption of Cu2+ and Cd2+ on the modied carbon black is due to the increased amount of functional groups after oxidation of the carbon black surface. Adsorption of Cu2+or Cd2+ on the modied carbon black increases with an increasing pH of the solution. Most of the metals were adsorbed on the modied carbon black when the pH was above 5.5. This might be caused by the surface charge development of the modied carbon black and the concentration distribution of Cu2+or Cd2+, which are both pH dependent. At low pH, the adsorption of Cu2+ or Cd2+ on modied carbon black is low because of the competition between H+ and Cu2+ or Cd2+ for the adsorption sites. The surfaces of modied carbon black have negative charges in a wide pH range and Cu2+ or Cd2+ carry a positive charge, existing as either Cu2+ and Cd2+. When the pH level of the solution increases, the concentration of competitor H+ ions decreases and Cu2+ or Cd2+ adsorption increases. Zhou and coworkers320 investigated the adsorption of Cu(II), Zn(II), Pd(II) and Cd(II) on nanoscale hydroxyapatite and carbon black. The adsorption isotherms indicated that different kinds of heavy metals have different afnities for black and activated carbon. The smaller nanoscale carbon particles had a higher adsorption capacity than larger carbon black and activated carbon because the micropores at the internal surface of the activated carbon are not accessible to humic acid, whereas the nanosized pores of carbon black are more accessible to humic acid.319 Carbon nanomaterials (CNMs) have unique properties for sorption processes. CNMs may exist in several forms, such as single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), carbon beads, carbon bres and nanoporous carbon. CNTs can be considered as cylindrical hollow micro-crystals of graphite.320,324 Because they have a large specic area, CNTs have attracted the interest of researchers as a new type of adsorbent. CNTs are graphitic carbon needles and have an outer diameter ranging from 430 nm and a length of up to 1 mm.321 MWCNTs are made of concentric cylinders with spacings between the adjacent layers322 of about 3.4 A, as shown in Fig. 9(a). SWCNTs (Fig. 9(b)) were discovered by Iijima.323 Li et al. found that oxidized CNTs can be good Cd2+ adsorbents and have great potential applications in environmental protection. The specic area and pore specic volume of CNTs were found to be increased after the oxidation of CNTs with H2O2, KMnO4 and HNO3 as shown in Table 6. The adsorption capacities of all adsorbents were observed to be increase with an increase of the CNT dosage. But it increases very slowly for the as-grown CNTs and is 3.5 mg g1 at a CNT dosage of 0.2 g per 100 mL. The increasing trend for H2O2 and HNO3 oxidized CNTs is almost identical and the adsorption capacities are 8.4 and 11.8 mg g1, respectively, at a CNT dosage of 0.2 g per 100 mL. The obvious larger adsorption degree takes place at CNT dosages of 0.03 to 0.08 g per 100 mL and was found for KMnO4 oxidized CNTs (19 mg g1). The removal efciency for KMnO4 oxidized CNTs
almost arrives at 100% at a CNT dosage of 0.08 g per 100 mL, which suggests that the treatment of CNTs with KMnO4 is an effective method to improve their Cd(II) adsorption capabilities.325 Due to the large specic area, CNTs have shown exceptional adsorption capabilities and high adsorption efciencies for various organic pollutants, such as benzene, 1,2-dichlorobenzene325 and ethyl benzene.326 Generally, adsorption has a long residence time for activated carbon, which is the most commonly used adsorbent to achieve equilibrium conditions (i.e., it took 20 h for an adsorption equilibrium to be reached for phenol from water).327 In contrast, Peng et al. observed that less time (40 min) was required for CNTs to adsorb dichlorobenzene. This may be because CNTs have no porous structure as traditional adsorbents do (e.g., activated carbon), in which the adsorbate has to move from the exterior surface to the inner surface of the pores to achieve the equilibrium.327 The short time needed to achieve equilibrium also suggests that CNTs have very high adsorption efciencies and the potential to remove dichlorobenzene from water. It was also found that CNTs grown by pyrolysis with a mixture of propylenehydrogen and a nickel catalyst at 750 C in a ceramic furnace were better at the adsorption of dichlorobenzene when compared to graphitized CNTs. The reason for this was the rough surface, which makes the adsorption of dichlorobenzene much easier for the as-grown CNTs. For the graphitized CNTs, the heat treatment of the CNTs at 2200 C for 2 h in an inert N2 atmosphere eliminated the defects and the surface of the graphitized CNTs became smooth after the treatment at this high temperature. Thus, the adsorption of dichlorobenzene by
Fig. 9 (Super) structure representations of (a) a MWCNT and (b) a SWCNT.326
Table 6 The porosity and specic surface area of as-grown CNTs and oxidized CNTs325 Specic surface area (m2 g1) 122 130 128 154 Pore volume Vp (cm3 g1) 0.28 0.36 0.32 0.58
Type of sample As grown H2O2 KMnO4 HNO3
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graphitized CNTs was decreased. The results from Bina et al.,328 as shown in Fig. 10, indicated that the equilibrium adsorbed amount for SWCNTs is higher than for hybrid carbon nanotubes (HCNTs) and MWCNTs. With a C0 of 10 mg L1, the SWCNTs showed the greatest adsorption capacity for ethylbenzene (ethylbenzene: 9.98 mg g1). The adsorption of ethylbenzene on CNTs is dependent on the chemical nature of the surface and its porosity characteristics. HCNT associated with silica could result in a more porous structure for MWCNTs and produce a sheet of carbon nanotubes, which have a greater area than MWCNTs for ethylbenzene adsorption. This was the main reason for the enhanced removal of ethylbenzene by HCNTs than MWCNTs. Furthermore, due to the electrostatic interaction between the ethylbenzene molecules and the SWCNT surface, higher ethylbenzene adsorption through the single-walled CNTs than through MWCNT has been observed.327 Because the ethylbenzene molecules are positively charged, the adsorption of ethylbenzene is thus favored for adsorbents with a negative surface charge. This results in more electrostatic attraction and thus leads to a higher ethylbenzene adsorption. Single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) were puried by sodium hypochlorite solutions and were applied as sorbents to study the sorption of Zn2+ from aqueous solutions.328 The amount of Zn2+ adsorbed on the CNTs increased with an increase in the temperature. Using the same conditions, the Zn2+ sorption capacity of the CNTs was much greater than that of commercially available powdered activated carbon, indicating that SWCNTs and MWCNTs are effective sorbents. In addition, the sorption/desorption study showed that the Zn2+ ions could be easily removed from the surface site of SWCNTs and MWCNTs by a 0.1 mol L1 nitric acid solution and the sorption capacity was maintained after 10 cycles of the sorption/desorption process. Therefore, it was suggested that CNTs can be reused several times in water treatment and regeneration. The activation of CNTs plays an important role in enhancing the maximum sorption capacity. Activation causes a modication of the surface morphology and surface functional groups and causes removal of amorphous carbon.326 The activation of CNTs under oxidizing conditions with chemicals such as HNO3, KMnO4, H2O2, NaOCl, H2SO4, KOH and NaOH has been widely reported. During activation, the
Fig. 10 The equilibrium amount of ethylbenzene adsorbed on CNTs with a C0 of 10 mg L1 (adapted from ref. 328).
metallic impurities and catalyst support materials are dissolved and the surface characteristics are altered due to the introduction of new functional groups. After oxidation with nitric acid, adsorption isothermal experiments showed that the CNTs had more defects and they have more functional groups on their surfaces when they are prepared at 650 C. They additionally had higher lead adsorption capabilities and are promising adsorbents for use in waste water treatment. The increased capacity of adsorption was found for the removal of Cd2+ (ref. 325), Ni2+ and Cu2+ by other researchers.328 The amount of cationic dyes, such as methyl violet and methylene blue, adsorbed increased with the pH due to the electrostatic attraction between the negatively charged surface of the CNT adsorbents and the positively charged cationic dyes.329,330 The oxidation of the CNTs with KMnO4 and H2O2 exhibited little enhancement in the specic area, while HNO3 oxidation provided a larger specic area.325 A few studies are available detailing SWNTs with antimicrobial activity towards Gram-positive and Gram-negative bacteria due to either a physical interaction or oxidative stress that compromises the cell membrane integrity.331,332 Carbon nanotubes may therefore be useful for inhibiting microbial attachment and biofouling formation on surfaces. However, the degree of aggregation,333 the stabilization effects by NOM334 and the bioavailability of the nanotubes will have to be considered for these antimicrobial properties to be fully effective.335 The separation of metal ion carriers (i.e. nanoparticles with metal ions) from water after water treatment is a challenging problem. In order to improve the separation of carriers of metal ions from treated water, the metal ions can be bound to polymeric molecules and/or carbon nanoparticles forming nanocarbon conjugates or polymer nanocomposites in water that are able to precipitate rapidly. This leads to a signicant increase in the size of the nanocomposites with the formation of precipitates. The precipitates can be easily removed from water by ltration or centrifugation with the subsequent extraction of the metals. Table 7 shows the application of nanocomposites of carbon materials and the advantages of using them for environmental remediation. Multi-walled carbon nanotubeTiO2 composite catalysts can be used as catalysts in photocatalytic processes for water treatment. The introduction of increasing amounts of CNTs into the TiO2 matrix prevents particles from agglomerating, thus increasing the surface area of the composite materials. A synergy effect on the photocatalytic degradation of phenol was found mostly for the reaction activated by near-UV to visible light irradiation. This improvement on the efciency of the photocatalytic process appeared to be proportional to the shift of the UVvis spectra of the CNTTiO2 composites for longer wavelengths, indicating a strong interphase interaction between carbon and semiconductor phases. This effect was explained in terms of CNTs acting as photosensitizer agents rather than an adsorbents or dispersing agents. Surface defects at the surfaces of carbon nanotubes provide advantages not only for the anchoring of the TiO2 particles but also for the electron transfer process to the semiconductor. Original carbon nanotubes, containing moderate amounts of oxygen surface groups, produced the highest synergistic effect for the degradation of phenol under near-UV to visible irradiation. The efciency of CNTTiO2 catalysts in the photocatalytic oxidation of mono-substituted organic compounds under visible irradiation was dependent
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from the ring activating/deactivating properties of the aromatic molecules. A higher kinetic synergy effect was observed for compounds presenting electron donor groups, such as phenol and aniline. For nitrobenzene and benzoic acid a synergy factor near to 1 was obtained, indicating the inexistence of any synergy effect between the CNTs and TiO2 in the photocatalytic degradation of these pollutants.348 A comparison of the photocatalytic activity of TiO2 and TiO2/CNTs composites for acetone degradation in air shows that the presence of a small amount of CNTs can enhance the photocatalytic activity of TiO2 greatly.345 Electrons excited by TiO2 may easily move to the nanostructure of the CNTs due to the strong interaction between TiO2 and CNTs. Then, CNTs raise the band gap of TiO2, which can prevent recombination of the e/h+ pairs. Moreover, the abundant hydroxyl groups adsorbed on the large surface of the composites can lead to the formation of more_OH radicals, which result in an enhancement of the photocatalytic activity of TiO2.349 In the tricomponent mixture of AgNPsCNTsPAMAM prepared by Yuan et al. the disinfection effect on E. coli cells was observed to be greater than both acid (COOH) modied and PAMAM modied MWCNTs. It was observed that the strength of the antimicrobial effect on bacteria follows the order: AgNPs MWCNTsPAMAM mixture > MWCNTsPAMAM > MWCNTsCOOH. The tricomponent mixture showed the highest disinfection activity due to favoring of the debundling (dispersivity) of MWCNTs by PAMAM and increasing the accessible surface area for bacterial interaction. Moreover, the PAMAM-grafted MWCNTs contain abundant amine terminated groups which leads to the reduction of Ag+ ions and regeneration of the AgNPs once Ag+ ions penetrate through the cell walls of the bacteria.350 (G) Application of polymer supported nanocomposites The application of the NPs in environmental remediation provided excessive pressure drops during operating in xed bed or any other ow-through systems, difcult separation and
limitation to reuse and possible risk to ecosystems and human health caused by the potential release of nanoparticles into the environment. In addition, the use of aqueous suspensions limits their wide applications because of the problems for the separation of the ne particles and the recycling of the catalyst. Immobilization of these nanoparticles onto polymer matrix, such as porous resins, ion exchangers, and polymeric membranes,350,351 has been available to solve the problems to considerable extent, serving for the reduction of particle loss, prevention of particles agglomeration and potential application of convective ow occurring by free-standing particles. The widely used host materials for nanocomposite fabrication include carbonaceous materials, such as granular activated carbon, silica, cellulose, sands and polymers, and polymeric host materials must possess excellent mechanical strength for long term use.351354 The generally used NPs include zero valent metals, metallic oxides, biopolymers and single-enzyme nanoparticles (SENs).355358 These nanoparticles could be loaded onto porous resins, cellulose or carboxymethyl cellulose, chitosan, alginate, etc.359363 The choice of the polymeric support is inuenced by their mechanical and thermal behaviour, hydrophobic/hydrophilic balance, chemical stability, bio-compatibility, optical and/ or electronic properties and their chemical functionalities (i.e. solvation, wettability, templating effect, etc.).364 The common catalytic nanoparticles include nanosized semiconductor materials (such as nano-TiO2, ZnO, CdS), zero valence metals (such as Fe0, Cu0 and Zn0) and bimetallic nanoparticles (such as Fe/Pd, Fe/Ni, Fe/Al, Zn/Pd).365375 They are usually applied as catalysts or redox reagents for degradation of a large variety of environmental contaminants, such as PCBs (polychlorinated biphenyls), azo dyes, halogenated aliphatics, organochlorine pesticides, halogenated herbicides and nitroaromatics. Nanocomposite adsorbents were designed by impregnating the inorganic nanoparticles into conventional polymers, namely, alginate,376 cellulose,377,378 porous resins360 and ion-exchangers,359,379 to avoid issues caused by the ultrane particle size, such as transition loss and excessive pressure drops. Porous polymeric adsorbents or
Table 7 The applications of nanocomposites of CNTs for environmental remediation Material blends in the nanocomposite Nanocarbon colloids and polyethylenimine
Benets Sorption of metal ions takes place simultaneously with the formation of a nanocomposite and the coagulation and ltration of nanocomposites with metal ions can capture other contaminated materials The improvement was observed for antimicrobial properties due to the increased contact surface area Providing high surface area, high quality active sites, the retardation of electronhole recombination and visible light catalysis by modication of the band gap and/or sensitization Improvement in the surface area and adsorption capacity Providing an adequate open porous network comprised of transport pores and micropores and a faster removal rate
Target material Removal of Zn , Cd , Cu , Hg , Ni2+, Cr6+ from waste water

2+ 2+ 2+ 2+
Reference 335
CNT with silver ions and copper nanoparticles CNT with TiO2 nanoparticles and P25 TiO2
Removal of E. coli and S. aureus from contaminated water Removal of organic dyes, phenol and phenol derivatives, humic substances, and metallic ions from contaminated water Removal of Co2+, Sr2+ and Ni2+ from the aqueous solution Removal of polar aromatic compounds (p-cresol) from aqueous solutions
336 and 337 338345
CNT with iron oxide magnetic composites Hybrid diatomite/carbon composites
346 347
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ion exchangers have proved to be ideal alternatives to fabricate similar hybrid adsorbents when considering their excellent mechanical strength and the adjustable surface chemistry of the polymeric supports.359,379 The immobilized charged functional groups bound to the polymeric matrix are believed to enhance the permeation of inorganic pollutants of counter charges. Table 8 summarizes some of immobilized nanoparticles in polymer matrix. Due to the high photocatalytic activity of titanium dioxide nanoparticles, the polymer substrates of the nanocomposite catalysts are expected to be antioxidative under UV or visible light illumination. The reported polymeric substrates are usually saturated carbon chain polymers or uoropolymers, such as poly(dimethylsiloxane) (PDMS),380 polyvinylpyrrolidone (PVP),355 polyethylene (PE),381 polypropylene (PP),382 poly(3-hexylthiophene) (P3HT),383 polyaniline (PANI),384 poly(tetrauoroethylene),385 and Naon. Ameen et al. prepared poly-1-naphthylamine (PNA)/TiO2 nanocomposite by in situ polymerization and observed an enhanced photocatalytic activity for the degradation of methylene blue (MB) dye under visible light illumination. The high photodegradation efcacy of the MB dye may be attributed to the efcient charge separation of the electrons (e) and hole (h+) pairs at the interfaces of PNA
and TiO2, as suggested by the slightly high red shift in the UVvis spectra.388 The schematic illustration of MB dye degradation over the surface of PNA/TiO2 nanocomposites catalyst is shown in Fig. 11. Some nanoscale metals and bimetals, such as Fe0, Cu0, Zn0, Fe/Pd, Fe/Ni, Pd/Zn, etc., are very effective in destroying various organic contaminants,386,387 such as chlorinated methanes, brominated methanes, trihalomethanes, chlorinated ethenes, chlorinated benzenes, other polychlorinated hydrocarbons, pesticides and dyes. Magnetite (Fe3O4), maghemite (Fe2O3) and jacobsite (MnFe2O4) nanoparticles can be loaded on or in the polymer matrix, such as alginate beads. A series of magnetic alginate polymers were prepared and batch experiments were conducted to investigate their ability to remove heavy metal ions403 (Co(II), Cr(VI), Ni(II), Pb(II), Cu(II), Mn(II)) and organic dyes402 (methylene blue and methyl orange) from aqueous solutions. Magnetic particles in the nanocomposites allowed easy isolation of the beads from the aqueous solutions after the sorption process. The montmorillonite-supported magnetite nanoparticles synthesized via a hydrosol method exhibited a better adsorption capacity per unit mass of magnetite and a better stability for storage than their unsupported counterparts. During the adsorption of Cr(VI) onto magnetite
Table 8 The application of polymer supported nanomaterials for environmental remediation Type of nanoparticle Fe0/Pd Polymer matrix Polyacrylic acid (PAA)/ polyvinyl alcohol (PVA) Polyaniline Poly (tetrauoroethylene) Polystyrenedivinylbenzene Poly(3-hexylthiophene) (P3HT) Alginate Carboxymethyl cellulose Poly(vinyl pyrrolidone) Sodium carboxymethyl cellulose Chitosan Cellulose acetate Resin Preparation method Dipping cross-linked electrospun polymer mat in ferric trichloride and palladium chloride solution Polymerization of aniline in the presence of TiO2 nanoparticles Electrophoretic deposition Dipping cross-linked polymer mat in ferric trichloride solution Adding TiO2 nonpartisan to the P3HT solution In situ synthesis of Fe0 in alginate bead from Fe3+ In situ synthesis with FeSO4$7H2O as a precursor Electrospinning In situ synthesis with FeSO4$7H2O and K2PdCl6 as precursors In situ synthesis with Cu(SO4)2$5H2O as a precursor Solvent cast In situ reduction of Sn2+ to Sn0 and then deposition of Pb0 through the reduction of Pb4+ Co-precipitation and hydrosol method Precipitation of iron(III) hydroxides from FeCl3 Precipitation of iron(III) hydroxides from FeCl3 Oxidation of the pre-loaded Mn(II) Mixing Target pollutant Trichloroethylene Ref. 389
TiO2 TiO2 Fe0 TiO2 Fe0 Fe0 Fe0 Fe0/Pd Cu0 Ni/Fe Pd/Sn
Phenol Trichlorobenzene Nitrate Methylene orange Trichloroethylene Cr6+ Bromate para-Nitrochlorobenzene Cr6+ Trichloroethylene Trichloroethylene
384 385 390 391 392 393 355 394 395 396 397
Magnetite Hydrated ferricoxide Hydrated ferric oxide Hydrous Manganese oxide (HMO) Fe3O4
Montmorillonite Polymeric anion exchangers Polymeric cation exchanger Polymeric cation exchanger Alginate
Cr6+ As3+ and As5+ Pb(II), Cu(II), Cd(II) Pb(II), Cd(II), Zn(II) Methylene blue, methyl orange
398 399 400 401 402
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Fig. 11 A schematic illustration of the photocatalytic activity of PNA/ TiO2 nanocomposites.386
nanoparticles, Cr(VI) can not only be reduced to Cr(III), which has less toxicity than Cr(VI), but it can also be xed into the iron oxide. This is of high importance for the application of magnetite in the environmental remediation.398 Water pollution is certainly one of the major problems faced by the world today. Metals, such as Hg, Pb, Cr, Cd and As, in diverse forms constitute some of the major inorganic pollutants and have many harmful effects on humans and environment.404 Mercury exists in three chemical forms, namely elemental (Hg0), inorganic mercurous and mercuric forms (Hg1+ and Hg2+) and organic alkyl mercury. Methyl mercury and dimethyl mercury are the most toxic and stable forms of organomercury. Due to the high toxicity effects, the World Health Organization (WHO) has set the limit of mercury in drinking water as 0.001 mg L1. Sumesh et al.407 found that water soluble silver nanoparticle composites of 9 2 nm and 20 5 nm core diameter, protected by mercaptosuccinic acid (MSA) supported on alumina is an effective system to remove mercuric ions from contaminated water at room temperature (28 1 C). Preparation and performance evaluation of silver nanoparticles were done using two different ratios of silver to MSA: 1 : 3 and 1 : 6. The solution with a concentration 2 ppm Hg2+ was used to evaluate the degree of removal of Hg2+ ions from the solution. The percentage of removal by both the nanoparticle composites is high at pH 56 and the performance decreases with an increasing pH of the solution.405 The reason for the decrease of performance of nanoparticle composite at higher pH was due to forming of stable mercuric hydroxo complexes, which may not interact with the surface of nanoparticle composite. Among these two materials, the 1 : 6 silver nanoparticle composite showed better performance than the 1 : 3 Ag nanoparticle composite. Lisha et al.408 reported that gold NPs supported on alumina were used as adsorbents in order to remove inorganic mercury from drinking water. The coupling of cellulose acetate membrane and Fe0 has contributed the degradation rate of 0.17 L m2 h1 for removal of tetrachloroethane and the rate of degradation was found to be 0.12 L m2 h1 for the removal of TCE. Cellulose acetate membranes were used for this investigation and were 25 cm 25 cm 100 mm with a metal (Fe0) concentration of 1% by weight. In addition, the performance testing of coupling of cellulose acetate and the bimetallic system (the Fe0/Ni0 ratio was
4 : 1) showed that the degradation rate of TCE was found to be 0.028 L m2 h1, which was slower than that of TCE (0.098 L m2 h1) using bimetallics (the Fe0/Ni0 ratio was 3 : 1).406 The limitations of the coupling of a cellulose acetate membrane with metallic nanoparticles for the removal of chlorinated ethanes were found to be (1) the incorporated membrane captured Fe0 or bimetallic (Fe0/Ni0) nanoparticles and prevented them from being released to the environment, and (2) a loading time was required for loading nanoparticles into the membrane before they reached the peak reaction rate. The reduction efciency of nitrobenzene in groundwater by iron NPs immobilized in a PEG/nylon66 membrane was investigated by Tong et al. It was found that the iron NPs immobilized in PEG/nylon66 membrane exhibited a high reactivity towards the removal of nitrobenzene. The concentration of nitrobenzene quickly decreased by 68.9% in the rst 20 min and was moderately decreased by 15% from 20 to 80 min. The decrease in reduction efciency was due to the reaction between iron NPs immobilized in PEG/nylon66 membrane and nitrobenzene as well as H2O, which reduced the reactive sites and led to the oxidation of the Fe0 and Fe2+ during the rst several minutes.407,409 In a biocatalytic enzyme nanocomposite or single enzyme nanocomposites (SENs), each enzyme molecule is surrounded with a porous composite organic/inorganic network of less than a few nm in thickness, as shown in Fig. 12. The fabrication of PEI/TiO2 bionanocomposites has been performed by ultrasonic irradiation techniqus, as shown in Fig. 12. Under ultrasonic conditions, the coupling agent (-amido-propyl-triethoxyl silicane) hydrolyzes to form hydroxyls and then polycondensation occurred to form SiOSi bonds. Commonly, the main effects of sonication are because of cavitation or the growth and explosive disintegration of microscopic bubbles on a microsecond timescale. At the same time, ultrasonic cavitation can generate a rigorous environment of local temperature up to 5000 K and local pressure up to 500 atm. Under such conditions the modied TiO2 nanoparticles, which have polar group of coupling agent and OH group on the surface of TiO2 could be dispersed completely in polymer matrix via different interactions with the functional groups of the obtained PEI. The heat stability of the nanocomposite was improved in the presence of TiO2 nanoparticles. Several polymer supported nanomaterials have been investigated and further studies of interaction between the host polymers and the encapsulated NPs are still required. (H) Nanosensors
Environmental monitoring requires rapid and reliable analytical tools that can perform sample analysis with minimal sample
Fig. 12 A diagram nanocomposites.410
of
the
synthesis
process
for
PEI/TiO2
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handling. Nanoparticle (NP)-based environmental sensors have the potential to detect toxins, heavy metals and organic pollutants in air, water and soil and are expected to play an increasingly important role in environmental monitoring. They can both improve detection and sensing of pollutants and can be used to develop new remediation technologies. Compared to traditional detection methods, NP sensors may have higher selectivity, sensitivity and stability and a lower cost.411 The measurement of harmful gases ,such as NOx, CO2, CO, methanol, CH4, etc. is desirable in environmental monitoring, chemical process controlling and personal safety. Gas sensor devices are traditionally comprised of thin lms of metal oxides, with tin oxide, zinc oxide and indium oxide, etc. With the recent discovery of novel metal oxide nanostructures, sensors comprising nanoarrays or single nanostructures have shown improved performance over the thin lms. The improved response of the nanostructures to different gases has been due to the highly single crystalline surfaces as well as large surface area of the nanostructures. A number of studies support the application of ZnO 1D nanostructures as nanosensors. The studies by researchers indicate that NH3 and CO behave as charge donors, transferring charge from the adsorbate to the surface while NO2, O2 and dioxin behave as charge acceptors, withdrawing charge from the ZnO surface.412414 Nanotube-based sensors include metal oxide tubes, such as Co3O4, Fe2O3, SnO2, and TiO2, and metal tubes, such as Pt nanosensor. Jang et al. applied a poly(3,4-ethylenedioxythiophene) (PEDOT) nanorods nanosensor for the detection of HCl and NH3 vapor. The PEDOT nanorode sensors gave a measurable response to NH3 and HCl vapor concentration as low as 10 and 5 ppm, respectively.415 Comini et al. observed the high sensitivity of a MoO3 nanorods lm sensor to 30 ppm carbon monoxide and 100 ppm ethanol.416 Kim et al. studied a gas sensor based on a non-stoichiometric tungsten oxide nanorod lm. The sensor was fabricated on Si wafers as the substrates by using a microelectromechanical system (MEMS) and silicon technology. The sensor responses were observed to be 2% N2 (or air), 1000 ppm ethanol, 10 ppm NH3 and 3 ppm NO2 in both dry air and a nitrogen atmosphere at room temperature.417 A highly selective and stable ethanol sensor based on single-crystalline divanadium pentoxide nanobelts was reported by Liu and coworkers. The V2O5 nanobelts showed greater sensitivity to ethanol of either low (<10 ppm) or high (1000 ppm) concentrations. The response and recovery times were 3050 s.418 Kong and Li found a highly sensitive and selective CuOSnO2 sensor to H2S gas based on SnO2 nanoribbons.418,419 Comini et al. applied a SnO2 nanobelts lm for gas sensing and proved its capability to sense gases at 30 ppm CO (350 C), 200 ppb NO2 (300 C) and 10 ppm ethanol (350 C).416 Gao and Wang found that the SnO2 nanobelt/CdS nanoparticle coreshell heterostructured sensor had high sensitivity to 100 ppm ethanol vapors in air at 400 C.420 The authors suggested that the CdS nanoparticles may be served as additional electron sources that greatly improved the electron conduction in the SnO2 nanobelts. Tao et al. demonstrated the capability of silver nanowire substrates for the detection of 2,4-dinitrotoluene (2,4-DNT), the most common nitroaromatic compound for detecting buried landmines, and other explosives by utilizing vibrational signatures. A sensitivity of about 0.7 pg was achieved.421 Yang et al. demonstrated the capability of silver nanowire substrates for the detection of 2,4-dinitrotoluene
(2,4-DNT) and other explosives by utilizing vibrational signatures. A sensitivity of about 0.7 pg was achieved.422 Zhang and co-workers also continuously demonstrated detection of NO2 down to ppb levels using transistors based on both single and multiple In2O3 nanowires operating at room temperature. The multiwire sensor showed an even lower detection limit of 5 ppb, compared to the 20 ppb limit of single nanowire sensors. This room temperature detection limit is the lowest level so far achieved with all metal oxide lm or nanowire sensors.423 This improved sensitivity was due to the formation of nanowire/nanowire junctions between the metal electrodes, a feature available in the multiple nanowire devices but junctions are not available in the single nanowire devices. Such junctions, when exposed to NO2, should form a depleted layer around the intersection and thus block the electron ow in a way more prominent than the surface depletion of the single nanowires with metal contacts. When detecting NO2 among other common gases, such as O2, CO and H2, using the multiple nanowire devices, selective response to NO2 was also observed. On the basis of their previous study, it was suggested that a large group of In2O3 nanowires with an appropriate doping level distribution could have two opposite sensing responses cancelling out each other and resulting in the immunity to NH3. This unique property of In2O3 nanowires offers a new way to achieve selectivity, as compared to the conventional technique of using permeable polymer coatings. Chu et al. also evaluated the gas sensing properties of In2O3 nanowires lms. The results revealed that the sensors exhibited higher response and good selectivity to C2H5OH at 370 C. The response time was about 10 s and recovery time was shorter than 20 s.424 Functionalization of MWCNTs multiple-lms with nominally 5 nm thick Pt- and Pd-nanoclusters prepared by magnetron sputtering provided higher sensitivity of signicantly enhanced gas detection for NO2, H2S, NH3 and CO, up to a low limit of sub-ppm level.425 Titanate nanotubes (TNT) were proven to be an efcient supports for the immobilization of methylene blue (MB) for the detection of dopamine.420 Porous TiO2 solgel matrix can be used to construct nitrite sensors by immobilizing partially quaternized poly(4-vinylpyridine) complexed with PVP-Os on an electrode.426 The limitation of nanoparticles in practical applications, such as slow diffusion and aggregation, still exists. Immobilization of nanoparticles by polymer matrix is one of the most efcient approaches to overcome such limitations. Since the chemical and physical properties of polymers may be tailored, they gained importance in the construction of sensor devices.427 Conductive polymer nanomaterials have attracted particular interests as sensors for air-borne volatiles428434 (alcohols, NH3, NO2, CO) because of large surface area, adjustable transport properties and chemical specicities, easy processing and scalable productions. Polyaniline nanobres were developed by interfacial polymerization to sense hydrazine gas and it was found that performance of sensing was better than conventional thin lm due to its high surface area, porosity and small diameter.435 PolyanilineSnO2/ TiO2 nanocomposite ultra thin lms have also been fabricated for CO gas sensing.428 The range of the biosensor was found to be 6.9 1014 to 8.6 1013 mol L1 and the detection limit is 2.3 1014 mol L1. A Pdpolyaniline nanocomposite was developed as a selective methanol sensor.432 The synthesized
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Table 9 Polymer-based nanocomposites for the sensing and detection of pollutants Type of nanoparticle SnO2 SnO2 TiO2 Iron oxide Pd Au Polymer matrix Polystyrene/polyaniline (PSS/PANI) Polyaniline (PANI) Polyaniline (PANI) Polypyrrole Polyaniline Chitosan Preparation method In situ self-assembly Hydrothermal method Chemical polymerization and a solgel method Simultaneous gelation and polymerisation Oxidative polymerization of solution with Pd NPs Mixed in solution Target pollutant CO Ethanol, acetone Trimethylamine CO2, N2, CH4 Methanol Zn2+, Cu2+ Ref. 428 429 430 431 432 433
nanocomposite sensor showed high selectivity and sensitivity to methanol vapors with rapid and reverse response. Some applications of polymer-based nanocomposite sensors are shown in Table 9. Nanosensors have also been applied as biosensors. The application of silica-coated nanosilver as biosensors for the biochemical compounds, such as glucose and hydrogen peroxide, because of their superior properties, such as their nontoxic nature, high surface area, high adsorptivity, high uniformity and excellent biocompatibility. TiO2 nanomaterials have been frequently proposed as a prospective interface for the immobilization of biomolecules. Moreover, titanium forms coordination bonds with the amine and carboxyl groups of enzymes and maintains the enzymes biocatalytic activity.436,437,439441 Formaldehyde is a hazardous air pollutant and prolonged exposure to formaldehyde can cause a nervous system damage as well as asthma. When sensor strip made of nylon 6 nano-bre nets (NFN) was exposed to formaldehyde, the methyl yellow on the tape reacted with sulfuric acid produced by the reaction of hydroxylamine sulfate with formaldehyde to produce a yellowto-red color change as shown in Fig. 13.438 Fig. 14 shows the fabrication of the biosensor, which was done by coating graphenegold nanocomposites (G-AuNP), CdTe CdS coreshell quantum dots (CdTeCdS), gold nanoparticles (AuNPs) and horseradish peroxidase (HRP) in a sequence on the surface of a gold electrode (GE). It was found that sensitivity of the biosensor is more than 11-fold better if G-AuNP, CdTeCdS and AuNPs are used. This could be ascribed to the improvement of the conductivity between the graphene nanosheets in the
G-AuNP due to introduction of the AuNPs. The electrocatalytic synergy of G-AuNP, CdTeCdS and AuNPs remarkably improves the electron relay and accelerates the electrochemical reaction and the AuNPsCS lm offers a favorable microenvironment to keep the bioactivity of the HRP. This biosensor provided the best sensitivity in all biosensors based on graphene materials for detection of hydrogen peroxide. This study remains open as a new challenge and approach to explore the electrochemical features of graphene or its nanocomposites for the potential utilizations.442
Conclusions and future prospects

The application of nanomaterials in the detection and removal of pathogens provides greater sensitivity, a lower cost, shorter turn-around times, smaller sample sizes, in-line and real-time detection, higher throughput and portability in environmental remediation. In addition metal and metal oxide nanomaterials can be used to remove organic pollutants and metals by reduction or oxidation of nanomaterial and degree of removal can be enhanced through functionalization with chemical groups that can capture selectively target pollutants in water and air media. This method is effective and promising and can be used in the engineering of water and air improvements. Nanomembranes have found applications in the production of potable water, water reclamation, the removal of metals, dyes, NOM and the removal of pesticides from contaminated water. Further improvements must be made in the application of environmental remediation to selectively remove materials, have a greater resistance to changes in pH and the concentrations of chemicals present in the contaminated water, greater stability for a longer period of time and cost optimization. Nanobrous media have a low basis weight, high permeability and small pore size that make them appropriate for a wide range of ltration applications. In addition, nanobre membranes offer unique properties, such as a high specic surface area (depending on the diameter of bres and intrabre porosity), good interconnectivity of the pores and the potential to incorporate active chemistry or functionality at a nanoscale. A high ux could be produced via nanobrous prelters with even higher loading capacities. Such pre-lters can be used in various applications, such as the removal of microparticles from waste water and with ultraltration or nanoltration membranes to prolong the life of these membranes. On-going investigations are under way to develop engineered nanomaterials of various bre diameters and morphologies to identify their effects on the performance of nanobres. The environmental applications of polymer supported nanocomposites in photocatalytic/chemical catalysis degradation, the
Fig. 13 An illustration of the colorimetric detection of formaldehyde based on the nylon 6 NFN membranes.438
Fig. 14 The fabrication of AuNPs/Cd-Te-CdS/G-AuNPs/GE.442
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adsorption of pollutants and pollutant sensing and detection result in a greener environment. However, the study of the interaction between the host polymers and the encapsulated NPs and its effect on the dispersion in polluted air and water is necessary. In addition, the large scale production of polymersupported nanocomposites and more practical applications remain open. The extensive application of sorbents in environmental remediation have shown the capability of adsorbing metals and organic pollutants from contaminated water and air. Iron-based nanomaterials, TiO2 nanomaterials and polymeric adsorbents have shown high adsorption capacities and selectivities. The surface modication of sorbents are being studied for process optimization. Enhancing the reusability of sorbents and the extension of their lifespan must be explored to reduce the cost in environmental remediation. Sensors have been developed for sensing gases, chemicals and volatile organic compounds and the detection and identication of bacteria. Further development is necessary in the functional properties of nanomaterials to meet the need for trace detection and the treatment of pollutants in water and air and important fundamental and mechanistic studies are required in order to fully explore their real potentials. One dimensional CNTs with single and multiple layers have shown superior adsorption capacities in the removal of diverse range of biological and chemical contaminants due to their brous shape with high aspect ratio and provision of large external surface area. Small size nanoscale particles composed of CNTs are difcult to separate from aqueous solution. Ultra centrifugation separation method is efcient to separate CNTs. However, high energy is necessary for this method. The membrane ltration method is an alternative and efcient technique to separate CNTs from aqueous solutions. However, the membrane can easily be blocked. The CNTs/metal oxide or magnetic composites are promising materials in environmental pollution management at a large scale. More efforts for the development of practical applications of these CNT composites are required in the future. Dendritic nanopolymers have been developed for low pressure ltration processes to remove perchlorate and uranium from contaminated water and recover metal ions (e.g., copper, silver, nickel and zinc) from industrial waste water. The long-term efciencies of dendritic nanopolymer composites as an important practical aspect have not been reported and should be addressed in the future.
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Energy & Environmental Science

Cite this: Energy Environ. Sci., 2012, 5, 8075 www.rsc.org/ees

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A review on nanomaterials for environmental remediation

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Mya Mya Khin

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Environmental remediation technologies

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are are the the

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This journal is The Royal Society of Chemistry 2012

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C2Cl4 + 4Fe0 + 4H+ / C2H4 + 4Fe2+ + 4Cl

Fig. 3 A nanoscale bimetallic particle for chlorinated solvent removal.75

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Fig. 4 The assembly of a zonal mercaptopropyl silica nanobre.208

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Fig. 5 The structure of PES/PET composite membranes.220

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Type of nanoparticle Modied jacobsite (MnFe2O4)

Particle size (nm) 10 20 11 6 50

Ferrites (MeFe2O4, where Me Mn, Co, Cu, Mg, Zn or Ni)257

Silica-coated magnetite (Fe3O4)262

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Fig. 7 The dendritic structure.298

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Thickness of membrane/disc (nm) 300 76

311 312 313 314 315 316319

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Fig. 9 (Super) structure representations of (a) a MWCNT and (b) a SWCNT.326

Type of sample As grown H2O2 KMnO4 HNO3

This journal is The Royal Society of Chemistry 2012

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Target material Removal of Zn , Cd , Cu , Hg , Ni2+, Cr6+ from waste water

336 and 337 338345

CNT with iron oxide magnetic composites Hybrid diatomite/carbon composites

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