Synthesis and Characterization of

Multiwall-Carbon Nanotubes
Decorated with Nickel Ferrite Hybrid
B. Unal A. Baykal M. Senel H.
Sozeri
RECEIVED: 15 OCTOBER 2012 / ACCEPTED: 19 NOVEMBER 2012
/
PUBLISHED ONLINE: 2 DECEMBER 2012
SPRINGER SCIENCE+BUSINESS MEDIA NEW YORK 2012

DNMN

Federico Ortiz Trejo

Abstract
Acid functionalized multiwall carbon nanotube,
(MWCNT)-COOH/nickel ferrite (NiFe2O4), magnetic hybrids
were synthesized by a co-precipitation method. X-ray diffraction,
Fourier transform infrared spectrometry, thermal
gravimetry, transmission electron microscopy, vibrating sample
magnetometry and Impedance Spectroscopy were used to
characterize the physical and electrical properties of the
MWCNT-COOH/NiFe2O4 hybrid. NiFe2O4 NPs are stably
attached to the surface of via carboxyl groups (COOH). The
magnetic saturation value of the productwas found as 8 emu/g.
A tunneling conduction mechanism was believed to occur in
the hybrid. The real modules (M0) of the product illustrate
power law variation with a power exponent of approximately
unity. These magnetic MWCNT-COOH/NiFe2O4 hybrids
exhibit a promising prospective in the application of bionanoscience
and technology.

Instrumentations
The thermal stability was determined by
thermogravimetric
analysis (TGA, Perkin Elmer Instruments
model,
STA 6000). The TGA thermograms were
recorded for
5 mg of powder sample at a heating rate of 10
C/min in
the temperature range of 30800 C under

Instrumentations
Then, the MWCNT-COOH/NiFe2O4 hybrid was
obtained in a reactor with high-speed
mechanical stirring
by adding the 0.5 M NaOH solution, which was
preheated
to 70 C before the co-precipitation reaction.
Finally,
the MWCNT-COOH/NiFe2O4 hybrid was dried

Instrumentations
This process also played an important
role on the deposition of metal ions. Ni2?, and
Fe3? were
added in the reaction solution, and then
adhered on the
surface of MWCNTs with high density of
carbonyl and
carboxyl groups due to electrostatic
interaction between the

Multi Wall Carbon Nano Tubes MWCNT

Fig. 1 Simplified representation of the

preparation of MWCNT-COOH/NiFe2O4 hybrid

TG Analysis
TGA was used to characterize the NiFe2O4 NPs
content in
the as-obtained hybrids. For the nickel ferrite
sample
(Fig. 4a), the weight increase at a broad
temperature is
attributable to the oxidation of the NiFe2O4.
The TGA curve of MWCNTs (Fig. 4c) shows
mass loss of about 13 % due to the removal of
absorbed water and the functional groups on
the surface of MWCNT-COOH. The 35 %wt loss
was observed for MWCNT-COOH/NiFe2O4

TG Analysis
Up to 150 C, the observed weight loss is due to
absorbed water.
The additional weight loss after 200 C (in the
temperature
range of 635730 C) is caused by the
oxidization of the
nanotubes and decomposition of organic layer
on the surface of organic layer.
Compared with the pristine MW CNT-COOHs,
the MWCNT-COOH/NiFe2O4 hybrid lost its
weight before 700 C (Fig. 4b), leaving
NiFe2O4 residue weight of around *35 % for
MWCNT-COOH/ NiFe2O4 hybrid.

TG Analysis

AN ARTIFICIAL PHOTOSYNTHESIS SYSTEM BASED ON CEO 2 AS LIGHT

HARVESTER AND
N-DOPED GRAPHENE CU(II) COMPLEX AS ARTIFICIAL METALLOENZYME FOR
CO2
REDUCTION TO METHANOL FUEL
SHOU-QING LIU , SHAN-SHAN ZHOU, ZHI-GANG CHEN , CHENG- BAO LIU, FENG CHEN, ZHENG-YINGWU
JIANGSU KEY LABORATORY OF ENVIRONMENTAL FUNCTIONAL MATERIALS; SCHOOL OF CHEMISTRY, BIOLOGY AND MATERIAL
ENGINEERING, SUZHOU UNIVERSITY OF SCIENCE AND TECHNOLOGY, SUZHOU 215009, CHINA

Anlisis de las propiedades elctricas de los nano materiales

Federico ortiz trejo

Abstract

An artificial photosynthesis catalyst composed of CeO2, N-doped graphene and copper ions (CeO2
NGCu2+) was fabricated.

The light-harvesting CeO2NG was characterized by X-ray diffraction, transmission electron

microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy.

The photocatalytic reduction of CO2 was conducted in an aqueous solution of Na2SO3.

Results indicated that the reduction rate of CO 2 to methanol approached 507.3 mol g1 cat. h1
for CeO2NGCu2+ artificial photosynthesis system in 80 min, whereas the reduction rate was only 5.8
mol g1 cat. h1 for bare CeO2NG without metalloenzyme.

Therefore, artificial metalloenzyme played a vital role in reducing CO 2 to methanol fuel.

2015 Elsevier B.V. All rights reserved.

Esquema de la fotosntesis

Fotosntesis

Reduccin fotocataltica de CO2 a metanol.

CO2

CeO2

CH3-OH +
O2

Reduccin fotocataltica de CO2 a metanol.

denota los tomos N sobre el marco del grafeno.

(A) TEMimages of NG sheets and (B) CeO2 nanoparticles on

NG sheets. (C) High-resolution TEMimage of CeO2NG. (D)
selected-area electron diffraction of CeO2NG. (E) electron
diffraction patter.

XRD patterns of as-prepared NG (A), CeO2

(B) and CeO2NG (C) samples.

Pares hueco-electrn

Electrons are well-known charge carriers. When an electron leaves its assigned
place, it leaves behind a hole that can effectively behave like a positive charge carrier,
provided that the electron and hole remain separated and do not recombine.

In modern semiconductor electronics, holes are important charge carriers without

which
devices
like
batteries,
capacitors,
fuel
cells,
solar
cells,
and
photoelectrochemical cells (PECs) could not operate. PEC electrodes typically form
electronhole pairs when struck by sunlight.

In PEC photoanodes made of CeO2, the generated holes must diffuse to the surface,
where they can oxidize water to form oxygen. However, the electronic structure of
hematite is such that the photogenerated holes tend recombine with the electrons
before reaching the surface.

Grafeno

Graphene is often used to couple with semiconductors to construct photocatalysis systems

for the reduction of CO2.

Photocatalysis systems manufactured with N-doped graphene (NG) were particularly

highlighted because of the enhanced electron transportation from semiconductors to NG
and the reduced recombination of the photogenerated electronhole pairs, as
compared with those manufactured with pure graphene.

Moreover, the lone pairs of electrons on N atoms can coordinate with metal ions to form
metal complexes,which canwork as artificial enzymes to promote the separation of
photogenerated electronhole pairs, diminish the activated energy, and dominate the
reaction pathway.

Therefore, NG provides a very simple route to fabricating an artificial enzyme.

Conclusiones

An artificial photosynthesis system based on

CeO2 as a light harvester and NG Cu(II) complex
as an artificial enzyme for the reduction of CO2
to methanol fuel was successfully fabricated.

Cu(II) coordinated with N atoms on the graphene

frame and played a significant role in reducing
CO2 to methanol.