Graphene composites: The materials for the future

Sreemanta Mitra1,2 , Sourish Banerjee2 , Anindya Datta 3 , and Dipankar Chakravorty1,

1

MLS Prof.of Physics Unit,

arXiv:1207.1995v1 [cond-mat.mes-hall] 9 Jul 2012

Indian Association for the Cultivation of Science,

Kolkata-700032, India.

Department of Physics, University of Calcutta,

Kolkata-700009, India.
and

University School of Basic and Applied Science (USBAS),

Guru Govind Singh Indraprastha University,
New Delhi, India

The exotic physical properties of graphene have led to intense research activities on the
synthesis and characterization of graphene composites during the last decade. In this article the methods developed for preparation of such materials and the different application
areas are reviewed. The composites discussed are of two types, viz; graphene/polymer and
inorganic/ graphene. The techniques of ex-situ hybridization and in-situ hybridization have
been pointed out. Some of the application areas are batteries and ultracapacitor for energy
storage and fuel cell and solar cell for energy generation and some of the possible future
directions of research have been discussed.

I.

INTRODUCTION

lus ( 1T P a)3 high thermal conductivity (

5000W m1 K 1 )4 and high mobility of charge

Since its discovery1 the first two dimen- carriers( 200000cm2 V 1 s1 )5 . These intrigusional material, graphene, which consists of sp2 ing properties of graphene, tempted researchers
bonded carbon atoms in honeycomb network,has to fabricate composites with the same.

been in the limelight of research in condensed nanocomposite is a combination of multiple mamatter physics.

Synthesis of graphene belied terials, out of which one has a nanometer di-

the argument of Peirls and Landau, that two mension, and the property may reflect that of a
dimensional materials could not sustain ther- weighted average of the components or a commodynamic fluctuation, and hence would be pletely new one. Previously, another well known
unstable.2 The unique properties of graphene carbon based material viz; carbon nanotube
arise due to the long range conjugation (CNT) was used to synthesize nanocomposites,
which results in high value of Youngs modu-

which showed interesting properties. Graphene in and bands which cross at K and K point
has quite a few properties similar to those of and give a linear dispersion. By first nearest
CNTs.

It also shows some distinctly differ- neighbor tight binding model,the E-K relation

ent behavior, like quantum Hall effect both of these electrons has been shown to be given
anomalous and fractional, due to the ballis- by,20
tic nature of its charge carriers.1,6,7 A number of graphene based nanocomposites with in-

E =

1 + 4 cos

organic matrices811 , organic crystals12,13 , biomaterials14 ,polymers (both conducting and non
conducting)1518 have been studied for various
applications, such as supercapacitors, photocatalysis,sensors etc. In this article, we review
the work carried out on graphene based com-

ky a
ky a
3kx a
cos
+ 4cos2
2
2
2
(1)

where, represents a positive constant, known

as transfer integral, and is the matrix element
between the orbitals of the neighboring carbon atoms. The positive and negative signs in
equation (1) signify fully empty anti-bonding
and fully filled bonding band respectively.Up

posites.

to first approximation, for small k, the equation

(1) is reduced to,
II.

PROPERTIES

E (~k) = 0~k

(2)

Before starting the discussion on graphene ~

k is measured with respect to the K points

based composites, we briefly describe the elecand 0 = vf = 3a

2 , and vf is the Fermi
tronic properties of graphene, as these are the
group velocity. This linear dispersion relation
important aspects which determine its applicain graphene, allows one to leave Schr
odingers
tions. In 1946, P.R.Wallace was the first to show
equation as used in most condensed matter systheoretically, that graphene is semi-metallic in
tems, and consider Dirac equation instead to
nature, and the low energy excitations are simidemonstrate the particle behavior. The idea has
lar to those of Dirac fermions. The chemical poa direct consequence to replace the effective mass
tential crosses exactly the Dirac point and hence
by cyclotron mass and it has also been found
19
gives rise to a linear dispersion spectrum . The
that m is directly proportional to the electron
hexagonally arranged carbon atoms in graphene
density6 .
can be visualized as a triangular lattice with two
atoms per unit cell, as a basis. The s, px , and py

III.

GRAPHENE IN COMPOSITE

orbitals of a carbon atom make bond with the

neighboring carbon atom. The hybridization of

The method of preparation of graphene as

pz orbitals of neighboring carbon atoms results developed by Geim and Novoselov1 , viz; The

3
scotch tape method produces high quality (as
observed from Raman spectroscopy and AFM
images ) graphene but this is not suitable for
large scale production.

Hence, the technique

could not be used for composite synthesis. Apart

from this Nobel winning method, five other
widely used methods have been reported for
the synthesis of graphene, namely, (a) chemical
vapor deposition21,22 , (b)epitaxial growth2325 ,
(c)chemical reduction of graphite derivative26,27 ,
(d) Unzipping of CNTs28,29 , (e) organic synthesis technique30 . Out of these methods, the
chemical reduction of graphite derivatives has

FIG.

1.

Electrical

conductivity

of

the

graphene/polystyrene composites as a function

of filler volume fraction. Reprinted with permission

been employed mostly for synthesizing compos- from39 , Nature Publishing Group.
ites based on graphene.This strategy has become
popular, since it not only yields large amount of of GO to RGO can be done by using several rechemically modified graphene, but also can be ducing agents; viz, hydrazine hydrate26 sodium
used to functionalize it suitably for practical ap- borohydride3133 ,hydroquinone34 etc. Hydrazine
has mostly been used as the reducing agent.

plication.

At present most of the composites based Many environment friendly chemicals have been
on graphene use reduced graphene oxide used to reduce GO to form RGO, such as
(RGO),which is obtained by the exfoliation and alcohols, sodium citrate, tea, solar radiation
3538 .
chemical reduction of graphite oxide (GO), a etc.

graphite derivative.

Of several methods pre-

scribed,modified Hummers method has mostly

A.

Classifications

been used to synthesize graphite oxide by treating graphite with strong mineral acids. Though

The synthesis of first ever graphene based

the structure of graphite oxide is a point of de- composites, viz; graphene/polystyrene was rebate till date, oxidation of graphite will destroy ported in 2006, by R.S.Ruoff and co-workers39 .
the sp2 hybridization and increase the interlayer Their main observation was low percolation
separation. As a result, the Van-der Waals force threshold, which they had computed to be 0.1
between the layers gets much weaker, and it be- vol% of graphene for the composite. The obsercomes easy to exfoliate. The chemical reduction vation have been given in Fig. 1.

4
This work attracted considerable attention
which led to the further development of different composites with graphene. Broadly, we
can classify graphene composites under two major groups viz;(a)graphene/polymer composite
(b)graphene/inorganic material composites.
We briefly discuss below the work carried out
on the above two categories of graphene composites.

1.

Graphene/Polymer composites

Graphene has been successfully used as a

filler material, similar to the CNT in polymers.

These can be sub categorized in to

two parts,(i)graphene/non-conducting polymer

composite and (ii)graphene/conducting polymer
composites.
FIG. 2. Uniaxial tensile testing. (a) Ultimate tensile strength for the baseline epoxy and GPL/epoxy,

In the polymer matrix; graphene fillers of

MWNT/epoxy, and SWNT/epoxy nanocomposites.

different volume fractions can substantially im- The weight fraction of nanofillers for all of the
prove the properties, e.g. electrical,thermal & nanocomposite samples tested was fixed at 0.1%.
mechanical.

Due to their high aspect ratio (b) Youngs modulus of nanocomposite samples with

and large interface graphene/polymer compos- 0.1% weight of GPL, 0.1% weight of SWNT, and
ites show much enhanced properties at low concentration than CNT/polymer composites40,41 .

0.1% weight of MWNT is compared with the pristine

(i.e., unfilled) epoxy matrix. Reprinted with permission from40 , American Chemical Society.

The summarized results have been described in

Fig. 2.
The

most

simple

and

straightforward is important. GO is easily dispersed in water,

method to fabricate polymer composites is due to its oxygen functionality, but RGO has
solution mixing.

To achieve good dispersion, very low solubility, hence RGO in water was

the compatibility of the polymer and filler regularly sonicated in water in an ultrasonic
(graphene in this case) in the required solvent bath, to achieve good dispersion before mixing

5
it with different aqueous solutions of polymers, has a moderate role to play in this operation.
e.g.

(poly)methyl methacrylate (PMMA)42 , Along with the electrical conductivity, the

(poly)aniline

(PANI)43 ,(poly)urethene44

and thermal conductivity of the polymer matrices

(poly)vinyl alcohol(PVA)45 .

with graphene as fillers have been shown to

An unavoidable situation of re-stacking and increase substantially. The high room temperaggregation of graphene sheets develops in the ature (RT) thermal conductivity of single layer
above method of synthesizing graphene/polymer graphene,viz;(
composites.

5000W m1 K 1 ) showed a

This could be taken care of by prominent effect when only 0.25 volume% RGO

surface functionalization of the RGO before in silicon foam matrix, increased its thermal
conductivity by 6%52 . This increase of thermal

mixing with polymers.

Another approach of synthesis is in-situ poly- conductivity,surpasses

merization technique4650 .

different

conventional

fillers like Ag, which need around 50% loading

Alternatively, by the method of in-situ anodic to achieve the same value. Apart from these,
polymerization51

graphene/PANI

was fabricated.

Apart from this, graphene different polymers with graphene fillers have

composite mechanical properties and thermal stability of

was also included as fillers in different polymer shown increase compared to that of the polymatrices such as silicone52 via this method.

mers themselves. Being the strongest material

Enhancement of some properties or ob- till date, graphenes incorporation in isocyanate

taining a completely new property is the PU matrix increased the Youngs modulus and
44
primary objective of fabricating composites. hardness by 900% and 327% respectively .

Graphene/polymer

composites

objectives satisfactorily.

attain

55
these Rao et.al. have shown that,SWNT/PVA com-

posites exhibit superior mechanical proeper-

The electrical conductivity of different polymers ties as compared to that of graphene/PVA

filled with graphene have shown enormous composites. They have reported that composimprovement. Percolation threshold has been ites comprising of two different nanocarbon
found to be very low in different types of insu- (graphene/SWNT),

(SWNT/Nanodiamond)

lating polymers as matrices in composites, e.g. and (Nanodiamond/graphene) reinforced in

0.15 volume% RGO in (poly)vinyl chloride/vinyl polymer show a large enhancement of the meacetate co-polymer composite53 , 0.47% filler in chanical property. Functional polymers another
graphene/PET composites54 .

This is due to important property, viz; thermal stability was

graphenes large surface area and conjugated also improved by incorporating graphene (as it
2D surface. Also filler/matrix interaction medi- has a superior properties) in the polymer. To
ated by surface functional groups of graphene name a few,the glass transition temperature

6
(temperature above which the chains of a ther-

2.

Graphene/Inorganic composite

moplastic polymer begin to flow) of 0.05 wt.%

loaded graphene in PMMA increased by 30K and

Nanoparticles or nanostructures of different

1 wt.% loaded graphene in (poly)acrylonitrile shapes and sizes have got increasing attenGraphene/elastomer composite tion from research point of view during the

by 40K18 .

showed better thermal stability viz; an in- last decade, because of their interesting propercrease of the degradation temperature by 55K ties. Several nanoparticles of metals, metal ox(0.25%RGO/silicone)52 and 10K (0.5% exfoli- ides,and other inorganic compounds have been
ated graphite/PLA)56 .

The strong interlayer made into a composite structure with graphene

cohesive energy and surface area along with to further enhance their properties. The materi10
61
62
strong filler/matrix interaction have been shown als included in the list are Au, Ag , Ni , Cu ,

Ru, Rh63 T iO2 64 , ZnO9 , M nO2 65 , Co3 O4 43 ,

to be responsible for this enhancement.

66
67
The highly hydrophilic PVA became highly NiO , F e3 O4 etc. The scheme for prepar-

hydrophobic by incorporation of graphene fillers ing M nO2 /graphene composite has been shown
schematically in fig. 3.

in it57

In general,

the synthetic methods for

graphene/inorganic nanostructures can be classified into two categories, (a) ex-situ hybridizaIn addition to the polymer composites with tion and (b)in-situ hybridization.
randomly distributed graphene as a filler in

(a) Ex-situ hybridization: assembly on

polymer matrices, layered graphene/polymer graphene

composite was also fabricated for specific Ex-situ hybridization technique is probably
application purposes e.g.
films58 .Employing
technique,

photovoltaic thin much more simplistic than the in-situ one. In

Langmuir-Blodgett

(LB) general, graphene and a pre synthesized or

GO sheets were deposited on commercially available nanocrystals are mixed

(poly)allylamine

hydrochloride

which eventually,

multilayer, in solutions. For better mixing, surface mod-

showed enhancement of ification of either or both of the nanocrystals

directional elastic modulus, by an order of and the graphene was done.

magnitude59 .

However, this

For photovoltaic applications functionalization is not a regular procedure. In

(poly)3-hexylthiophene(P3H7)/phenyl-C61-

this process, the - stacking via some linking

butyric acid (PCBM)/GO were deposited on molecule is one of the mechanisms involved.
the ITO coated substrate in which GO acted as The - stacking serves here as an adhesive
a hole transport segment60 .

layer to absorb the nanoparticle. Out of the

7
nanoparticle/graphene

composites71 .Apart

from - stacking (a non-covalent interaction)

covalent interaction has also been used to
fabricate composites.

For this GO, instead

of RGO was used, since it (GO) has a large

number of oxygen containing groups which
in turn can be used to link with other functional groups.

In this approach, tetraethyl

orthosilicate and (3-aminopropyl) triethoxysilane treated F e3 O4 was reacted with GO, in

presence of 1-ethyl-3-(3-dimethylaminopropyl)
carbodiimide

and

N-hydroxysuccinnimide

to form F e3 O4 /GO composite.

The amino

groups introduced on functionalized F e3 O4

reacted with carboxylic groups of GO72 . Amide
bonds of 4-aminothiophenol functionalized CdS
FIG. 3. Scheme for preparing graphene/M nO2 com- nanoparticles were used to link with acylated
posite. Reprinted with permission from65 , American GO sheets to form CdS/GO composite73 . By
Chemical Society.

this covalent interaction, aminated CNTs and

acid chloride activated GO were linked to form

74
several examples, 2-mercaptopyridine modified CNT/GO composite . Also by the method of

gold

nanoparticles68

or

benzyl

mercaptan Fisher esterification between hydroxyl groups

capped CdS nanoparticles69 were successfully on fullerenes,

GO/fullerene composite was

75
added to graphene (RGO) which have several synthesized .

Electrostatic interactions were

applications e.g. in catalysis, surface enhanced also used to prepare composites of graphene
Raman spectroscopy (SERS) etc. Alternatively, and inorganic nanoparticles. Due to the ionmodified or functionalized graphene has also ization of the oxygen containing functional
been used for attaching nanoparticles to it. groups on GO or RGO, they were negatively
For example, adhesive polymer nafion coated charged, and this was exploited to assemble
RGO has been used to prepare RGO/T iO2 positively charged inorganic nanoparticles on
composites70 , or bovine serum albumin (a bio- them via electrostatic interaction. RGO/F e3 O4
76
polymer) has been employed to modify RGO for composite was synthesized by this route . In

the fabrication of silver, palladium, or platinum the case of negatively charged nanoparticles,

8
the RGO/GO surface had to be changed to a the in-situ technique gave uniform surface coverpositively charged configuration for the electro- age by controlling the nucleation sites on RGO
static interaction to take place.

For this the through surface modification.

RGO was coated with cationic polyelectrolytes Out of several possibilities, chemical reduction
e.g.

PQ11 treated RGO was attached with method has been the most popular technique

negatively charged silver (Ag) nanoparticles77 , to grow metal nanostructures on graphene. Noand (poly) diallyldimethyl ammonium chloride ble metals precursors, e.g. AgN O3 , K2 P tCl4 ,
(PDDA) coated RGO acted as host for citrate H2 P dCl6 can be easily reduced in-situ by
capped gold nanoparticles, and thioglycolic acid chemical reducing agents e.g.
functionalized CdSe quantum dots78,79 .
Another

exciting

method

of

sodium boro-

hydride (N aBH4 ), amines and ascorbic acid.

synthesizing Au nanoparticle/graphene composite was syn-

graphene/inorganic nanoparticle composite was thesized by reducing HAuCl4 with N aBH4 in

layer by layer self assembly, where one graphene a octadecylamine solution of RGO82 .

Along

layer was sandwiched between two layers of with nanoparticles, anisotropic nanostructures
nanoparticle assembly. In comparison to other of metals on graphene have also been syntheknown

methods

of

multilayer

fabrication, sized using the method of chemical reduction.

where composites were prepared in advance, In the latter, self directing surfactants have been
this technique allowed one to synthesize two used to get desired nanostructures on graphene.
components simultaneously, and the thickness For example, Au nanorods were prepared on
could be controlled with high precision in seed modified RGO, by using cetyl trimethythe nanoscale80 . The electrostatic interaction lammonium bromide (CTAB) as a shape dibetween the alternating layers of graphene and rected surfactant83 or 2.4 nm thick hexagoother materials was used to fabricate the LBL nal close packed structured Au nanosheets on
self assembled composite. Negatively charged GO84 .

Photochemical reduction method has

M nO2 and negatively charged (poly)sodium also been applied for the synthesis of nanostruc4-styrenesulfonate (PSS) functionalized RGO tured metal/graphene composite. In this techwas attached with positively charged PDDA to nique, fluorescent gold nanodots on thiol modifabricate 3d multilayer nanostructures

fied RGO surface were grown by in-situ reduc-

(PDDA/PSS-RGO/PDDA/M nO2 )81 .

tion of HAuCl4 under light irradiation85 .

(b) In-situ hybridization

In this in-situ reaction method, apart from the

86
Achieving uniform surface coverage of nanocrys- metal particles, metal oxides, such as, SnO2 ,
65
tals on RGO is very difficult in the ex-situ M nO2 have also been synthesized on RGO

method of composite synthesis. In comparison, surface. In-situ microwave irradiation technique

9
was used to prepare metal nanoparticles as well also synthesized by the same group of workers92 .
as metal oxides, on RGO, such as Cu, Au,
Ag62

or Co3 O4

87 .

In-situ anodic electro-deposition of M nO2

In spite of large scale pro- nanoflowers on RGO electrodes was also carried

duction, this method does not give good con- out to fabricate M nO2 /RGO composite. For
trol over size and distribution of the nanopar- this RGO paper was first prepared by vacuum
ticles on RGO surface. This problem has re- filtration of the RGO solution followed by its
cently been overcome by combining microwave use in desired shape as electrode for M nO2
irradiation technique with ionic liquid assisted electro-deposition93 .
dispersion of RGO. In this modified method, Apart from electrochemical depositions and
Ru/RGO and Rh/RGO composites with nar- electro-less deposition, which was previously
row size distribution of Ru and Rh nanoparticles observed for single walled carbon nanotube
were synthesized63 .

(SWCNTs) with Au and Pt nanoparticles94 ,

Recently, a novel, green approach, viz; elec- GO/RGO has also been used as templates
trochemical approach was used to fabricate for synthesizing Ag nanoparticles on them8 .
graphene/inorganic composite.

This method Since the SWCNT has a higher Fermi level

consisted of two steps; graphene sheets were (less negative) than the redox potential of
first assembled on electrodes, which was followed the metals Au or Pt, it act like cathode to
by the immersion of graphene coated electrode donate electrons for the reduction of the metal
in the electrolyte solution of the metallic pre- ions and its nucleation of the corresponding
cursors, for the electrochemical synthesis. Sev- nanoparticles. For GO, the oxygen containing
eral high purity noble metals such as gold88,89 functional groups provide more nucleation sites
platinum90 and alloy of gold/platinum91 were for the nanoparticles rather than the RGOs,
reduced electrochemically on graphene, by ap- which are relatively free from the oxygen
plying an electric potential.

Apart from the functionalities. Among the in-situ methods of

metals, metal oxides were also synthesized with preparing graphene/metal oxide composites,
graphene using this method.

P-type and n- sol-gel method (which consists essentially of

type Cu2 O films and ZnO nanorods were syn- hydrolysis and poly condensation reactions ) has
thesized on (poly) ethylene tetraphthalate sup- also been used to prepare T iO2 SiO2 , F e3 O4
ported RGO films8 . In case of the Cu2 O de- nanostructures on RGO86,95,96 .

The OH

position the reduction of Cu2+ and the pH of groups in the surface of GO/RGO play a key
the electrolyte solution determined whether the role and act as nucleation sites for the nanoparsemiconductor would be p-type or n-type. The ticles.

Along with graphene/metal oxides

chlorine doped n-type Cu2 O on graphene was composite fabrication by the sol-gel technique

10
RGO/silica composite was also prepared by PVD or physical vapor deposition technique is
Ruoff and co-workers at Texas, by the hydrolysis used to deposit material by condensation of the
of TMOS and water-ethanol dispersion of GO, vaporized form of the material on a substrate.
which was then subsequently reduced to RGO The technique can be of two types, viz; (a)
by putting the composite film in a hydrazine vacuum deposition and (b) sputtering deposihydrate vapor atmosphere overnight. The films tion. The advantage of these methods is that
showed a very low percolation threshold and they could use the graphene (not the chemibehaved as a transparent conductor97 .

cally modified one) with all its interesting properties, as the substrate. Gold (Au) film has been

Another green method for the synthesis of grown on micro-mechanically cleaved graphene
o 1 under a
graphene/inorganic composite is hydrothermal layer at a rate of deposition 1A s
4
synthesis technique, in which high temperatures pressure of 10 Pa, and then subjecting it to a

in a confined space generate high pressure and fi- heat treatment at 1533 K. The Au film morpholnally give highly crystalline nanostructures, and ogy depended on the number of graphene layers
also reduce GO to RGO. In this technique, and for lower number of layers, the particle size
CdS/RGO98 was synthesized by using Cd(Ac)2 , of Au nanoparticle was smaller and therefore,
GO, N a2 S as precursors.

100
The Cd(Ac)2 was yielded high density . The theoretically pre-

1/3
dissolved in the aqueous solution of GO and dicted scaling law is given by D n , where

then N a2 S was added drop wise. The mixture D is the mean particle diameter and n is numwas subjected to a hydrothermal treatment in ber of layers of the graphene film. Moire pata Teflon coated autoclave shell at 453 K for tern has also been observed for Ir, Pt, W, Re,
101,102 and Pt, Pd, Rh, Co,
40h. Similarly, by using Cd(CH3 COO)2 and on graphene/Ir(111)
103,104 .
GO in dimethyl sulfoxide (DMSO) in an auto- Au on graphene/Ru(0001)

clave at 453 K for 18h, CdS/RGO composite was CVD or chemical vapor deposition process has
synthesized99 . The DMSO here acted as a source the same objective as the previous technique,
of sulfur and also a reducing agent to reduce GO but has some advantages, e.g.
to RGO.

inexpensive,

controllable and high deposition rate, over

Deposition technique is another one which is PVD. This technique has also been employed
105
widely used to synthesize inorganic materials to fabricate graphene supported CdSe , ZnO
106
107
on different substrates. Physical vapor deposi- nanorod and ZnS nanowires . The observed

tion, chemical vapor deposition and atomic layer cathodoluminescence effect for ZnS/graphene
deposition techniques were used to synthesize composite has been described schematically in
graphene/inorganic material composites.

Fig. 4.

11
basis of surface reactions. SnO2 coated RGO
has been synthesized by ALD by using SnCl4
& H2 O as precursors. By adjusting the growth
temperatures to 473 K and 673 K respectively,
amorphous and crystalline SnO2 nanoparticles
were achieved by Meng and co-workers111 . Also
by adjusting the cycling numbers the morphology of the SnO2 could be changed from nanoparticle to nanosheets.

IV.

FIG. 4. CL spectrum of ZnS:Te NWs grown on a

APPLICATIONS

MGF without catalysts. Reproduced with permission from107 , Institute of Physics Publishing.

As discussed previously, graphene was successfully composited with different inorganic

A representative example would be CdSe materials as well as polymers and CNTs. The
nanoparticle on RGO with cadmium shot and main objective for the preparation of composites
selenium shot as precursors. GO was at first is to use them for some practical applications.
reduced to RGO by thermal annealing at 773K In this section we discuss about the various
for 1h. under Ar flow. CdSe was prepared by applicabilities of these materials.
CVD at 773 K under atmospheric pressure and
RGO coated substrate was used to collect CdSe
nanoparticles under a flow of Ar, which was used
as a carrier gas. Another useful material that has

A.

Batteries and Ultracapacitors: energy

storage

been fabricated using CVD is CNT/graphene

composite in which CNT was grown vertically

Energy is the most important issue these

on graphene108 . For this synthesis Ni109 or Co110 days all around the world, and graphene
was used as catalyst. The amount of these cata- composites may give a possible solution to
lysts controlled the length and amount of CNTs this ever-increasing requirement. For low cost
on graphene along with the deposition times.

energy conversion and storage material, lithium

Atomic layer deposition or ALD is different from ion batteries (LiB) have no competitor these
the CVD process. In ALD, alternate and cyclic days. This is because of its high potential with
supply of the gaseous precursors with sequential respect to standard hydrogen cell (-3.04 eV)
half reactions, allows the film to grow on the and large energy density of theoretical value

12
4000W hkg1 112 . Graphene and its derivatives cycles.

It was also seen that the structure

do not host Li like bulk graphite , but they and crystallinity of the nanoparticles remained
can store Li via surface adsorption, which unaltered after many charging and discharging
then have high conductivity and surface area. cycles. Similarly, graphene coated metal oxide
So, different metal oxide nanostructures e.g. nanoparticles have also proved to be very good
SnO2 86 , Co3 O4 43 , M nO2 113 , F e3 O4 96 have anode material for LiBs. For example, graphene
been composited with graphene for lithium wrapped Co3 O4 with very low C content,
ion battery applications.

For bare metal provides excellent capacity of 1000mAhg1

oxides, the problem arises due to the rapid for more than 130 cycles114 .

Bare graphene

decay of the capacity, which is caused by poor due to large specific surface area shows quite
conductivity of the materials.

After being a high specific capacity 540mAhg1 ), the

attached with graphene, the hybrid electrodes graphene composite with other carbon material,
have excellent conducting network, as already e.g.
observed113 .

CNTs, increase the separation between

To explain, we can take the graphene stacks and hence increase the specific

example of the M n3 O4 /graphene anode. Being capacity by 40%.

a low cost and high capacity (theoretical value Apart from lithium ion batteries, ultracapacitor
of 936mAhg1 ) system, M n3 O4 would be is another type of electrochemical energy storage
considered as a possible candidate for the anode device, which gives high power density, long cymaterial in LiB. But the low conductivity has cling life, in comparison to conventional battery
limited its practical applications. The growth device. By their operational mechanisms, ultra
of M n3 O4 nanoparticles on graphene not only or supercapacitors are of two types;
solves this problem of conductivity directly, but (a) Electrical double layer capacitor (EDLC),
also provides a specific capacity value, which which stores energy via electrostatic process,
is close to the theoretical one, and more than viz;
double that observed in pure M n3 O4 .

charge accumulation occurs at elec-

Also trolyte/electrode interface due to polarization.

the graphene/metal oxide composite provides a EDLC thus requires an electrode material with
large surface area for the nanoparticles to grow, high conductivity and large surface area. The
hence the agglomeration of the nanoparticles is RGO is a promising candidate since it provides
reduced. The specific capacity is enhanced in an open pore structure which allows the
the composites due to this large active surface of electrolyte ions to move in and form electric
the nanoparticles. This large surface allows the double layers115 .
nanoparticles to participate more efficiently in (b) Pseudo capacitor is based on the rapid redox
Li/electron diffusion, during discharge/charge reaction of the chemical species in the electrode.

13
Usually, metal oxides and conducting polymers graphene/conducting polymer composites were
have been used in these electrodes.

But the also used as supercapacitors. They have mod-

high cost and relatively low conductivity of the erate conductivity and fast charge-discharge
metal oxides and conducting polymers, have kinetics. Also the flexibility for thin film based
limited their uses. Graphene derivatives may electronics, added a new interest to them. (Poly)
offer a solution to these problems.

aniline has been used mostly with RGO/GO

Though graphene has been used as the elec- to be used as supercapacitors42 . It has been
trode materials of supercapacitors116 , graphene reported that 1% GO loading in the backbone of
composited with different metal oxides e.g. (poly) aniline gives an enhanced conductivity of
ZnO117 , Co3 O4 87 , RuO2 118 have also been 10Scm1 and specific capacitance of 531F g1 ,
used to enhance the effect.

The metal oxide whereas for pure (poly) aniline the conduc-

nanoparticles contribute to the energy storage tivity and specific capacitance are reported
and the RGO sheets provide the capacitance to be 2Scm1 and 260F g 1 respectively42 .
by the electron double layer mechanism at The cycling stability was also enhanced in
the carbon surface.

The RGOs also create comparison to pure (poly) aniline as the GO

the conducting network for the nanoparti- underwent the mechanical deformation during
cles. For example, M nO2 /graphene composite charging-discharging cycles119 .
electrode showed high specific capacitance
( 310F g1 at2mV s1 ), which was 3 times
higher than that observed for pure RGO or
M nO2 .

Cheng and others43 had worked on

graphene/metal oxide hybrid electrode,

B.

Fuel cell and solar cell: energy

generation

to

improve the energy density of the supercapac-

Along with the storage of energy (as done by

itor while maintaining its high power density. batteries and ultracapacitor) the generation of
They had used graphene as negative electrode energy is also a problem of interest. Fuel cells
and M nO2 nanowire/graphene composite as generate electricity by the reaction between fuel
positive electrode and observed high energy and oxidant, which act as anode and cathode redensity, which is the square of the operating spectively. Starting with hydrogen/oxygen fuel
voltage across the cell.

This asymmetric ca- cells, a number of different combinations have

pacitor system showed much higher energy been tried so far for the fuel cell fabrication. One
density ( 30.4W hkg1 ) in comparison to the of the most popular and widely used materials
symmetric one.

for low temperature fuel cells is platinum. But

Apart from metal oxide /graphene composites, the problem with Pt-based catalysts is that Pt is

14
very costly, hence its uses should be minimized, of the nanotubes, reduced the film connectivand on the other hand, decreasing Pt content ity and conductivity significantly.
hampers the performance of the fuel cell.

Graphene,

on the other hand has a large surface continu-

Large effective area of graphene makes it ity and its properties can be tuned by doping
a possible candidate for fuel cell applica- and functionalization. The graphene sheets of
tions. Pt/Graphene composite has been used 100m size, on n-Si with 100% coverage (prein methanol oxidation cells120,121 and oxygen pared in CVD method) have been used to make
reduction cells122,123 .

The 2D structure of Schottky junction solar cell127 , which showed

graphene makes both sides of the material ex- 1.5% efficiency with a fill factor (obtained maxposed to the solution, hence increases the ef- imum power/ theoretical power) of 56%. The
fective surface area, which enhances the effi- graphene film behaves as a semi-transparent
ciency. The residual oxygen functionality (how- electrode and generate a built-in voltage of 0.55
ever small) of RGO removes the carbonaceous V for the electron-hole separation127 . Although
species and hence it shows better tolerance the graphene based solar cell systems show reato carbon monoxides, which is evolved dur- sonable value of efficiency, it is still less than
ing methanol oxidation121 . Also the nitrogen that of pure Si-based solar cells.

Hence, in-

doped graphene, with higher conductivity has creasing of the efficiency is one of the major asbeen used for the fuel cell application124 . This pects of graphene based solar cell devices, where
enhanced electronic conductivity essentially in- graphene-based composites may give better recreases the electrocatalytic activities of N-RGO- sults.

The graphene based polymer compos-

Pt catalysts. In methanol fuel cell, these exhibit ites have been incorporated as electrodes, elecoxidation current of 135mAmg 1 , which is al- tron and hole transports for photovoltaic device
most double that of bare RGO-Pt catalyst.

applications9,60,128 .

For solar cell applications, amorphous carbon has been used for several years, as ptype semiconductor with silicon as n-type
semiconductor125 .

V.

CONCLUSIONS AND FUTURE

DIRECTIONS

Apart from this, CNT has

also been employed with silicon heterojunction

The unique electronic, mechanical and ther-

for the solar cell application126 . But both of mal properties of graphene and its derivatives
these had several drawbacks, which did not al- along with its low cost mass production make
low for wide usage. For amorphous carbon the it a promising material for composites with diftuning of the electronic properties was the main ferent polymers, metals, metal oxides, and other
obstacle, whereas for the CNTs the bundling carbon based materials.

15
Starting with simple solution mixing to CVD of hydrogen has been observed in graphene129 ,
synthesis a number of methods have been em- it would be profitable to explore the possibilployed to fabricate the graphene composite for ity of increase the storage capacity by suitable
several application purposes. Some of the inves- graphene composites.
tigations on graphene and graphene based composites have been highlighted in this review article. We have discussed the most important

ACKNOWLEDGEMENTS

of todays scientific challenge, The energy genThe authors thank Department of Science

eration and its storage and its possible solu-

tions from the point of view of graphene com- and Technology, New Delhi, India for the
posites. With a large number of new research funding through an Indo-Australian project on
being reported and it would not be an overes- Nanocomposite and Clean Energy. Sreemanta
timation,to expect several new fabrication tech- Mitra thanks University grants Commission,
niques to evolve. Harvesting of solar energy by New Delhi, India, for Senior research fellowship
the graphene composite has not been achieved in and Dipankar Chakravorty thanks Indian Nalaboratories. So it would be one of the key prob- tional Science Academy for Honorary Scientists
lems for the next decade or so. Also the storage position.

sreemanta85@gmail.com

Solid State Communications 146, 351 (2008)

mlsdc@iacs.res.in

K. S. Novoselov, A. K. Geim, S. V. Morozov,

D. Jiang, M. I. Katsnelson, I. V. Grigorieva,

D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grig-

S. V. Dubonos, and A. A. Firsov, Nature 438,

orieva, and A. A. Firsov, Science 306, 666 (2004)

2

K. S. Novoselov, D. Jiang, F. Schedin, T. J.

197 (2005)
7

zov, V. I. Falko, M. I. Katsnelson, U. Zeitler,

A. K. Geim, Proc. Natl. Acad. Sci. U.S.A. 102,

D. Jiang, F. Schedin, and A. K. Geim, Nat. Phys.

10451 (2005)

2, 177 (2006)

C. Lee, X. Wei, J. W. Kysar, and J. Hone, Sci-

A. A. Balandin, S. Ghosh, W. Bao, I. Calizo,

Lett. 8, 902 (2008)

S. Wu, Z. Yin, Q. He, X. Huang, X. Zhou, and

H. Zhang, J. Phys. Chem. C 114, 11816 (2010)

D. Teweldebrhan, F. Miao, and C. N. Lau, Nano

K. S. Novoselov, E. McCann, S. V. Moro-

Booth, V. V. Khotkevich, S. V. Morozov, and

ence 321, 385 (2008)

4

K. S. Novoselov, A. K. Geim, S. V. Morozov,

Z. Yin, S. Wu, X. Zhou, X. Huang, Q. Zhang,

F. Boey, and H. Zhang, Small 6, 307 (2010)

10

X. Zhou, X. Huang, X. Qi, S. Wu, C. Xue,

K. I. Bolotin, K. J. Sikes, Z. Jiang, M. Klima,

F. Y. C. Boey, Q. Yan, P. Chen, and H. Zhang,

G. Fudenberg, J. Hone, P. Kim, and H. Stormer,

J. Phys. Chem. C 113, 10842 (2009)

16
11

R. Muszynski, B. Seger, and P. V. Kamat, J.

24

Phys. Chem. C Lett. 112, 5263 (2008)

12

13

S. Wang, B. M. Goh, K. K. Manga, Q. Bao,

Mater. 7, 406 (2008)

25

L. Herman, M. Chandrashekhar, J. Park, P. L.

(2010)

McEuen, J. M. Parpia, H. G. Craighead, and

T. H. Han, W. J. Lee, D. H. Lee, J. E. Kim, E.-

M. G. Spencer, Nano Lett. 9, 3100 (2009)

26

(2010)

16

(2009)
28

D. V. Kosynkin, A. L. Higginbotham, A. Sinitskii, J. R. Lomeda, A. Dimiev, B. K. Price, and

X. Qi, K.-Y. Pu, X. Zhou, H. Li, B. Liu, F. Boey,

J. M. Tour, Nature 458, 872 (2009)

29

H. Yang, Q. Zhang, C. Shan, F. Li, D. Han, and

L. Niu, Langmuir 26, 6708 (2010)

18

S. Park and R. S. Ruoff, Nat. Nanotech. 4, 217

Angew. Chem. Int. Ed. 49, 9426 (2010)

W. Huang, and H. Zhang, Small 6, 663 (2010)

17

Nguyen, and R. S. Ruoff, Carbon 45, 1558 (2007)

27

X. Qi, K.-Y. Pu, H. Li, X. Zhou, S. Wu, Q.-L.

Fan, B. Liu, F. Boey, W. Huang, and H. Zhang,

S. Stankovich, D. A. Dikin, R. D. Piner, K. A.

Kohlhaas, A. Kleinhammes, Y. Jia, Y. Wu, S. T.

Y. Wang, Z. Li, D. Hu, C.-T. Lin, J. Li, and

Y. Lin, J. Am. Chem. Soc. 132, 9274 (2010)

15

S. Shivaraman, R. A. Barton, X. Yu, J. Alden,

P. Yang, and K. P. Loh, ACS Nano 438, 6180

Y. Choi, and K. Sang Ouk, Adv. Mater. 22, 2060

14

P. W. Sutter, J.-I. Flege, and E. A. Sutter, Nat.

H. Dai, Nature 458, 877 (2009)

30

T. Ramanathan, A. A. Abdala, S. Stankovich,

D. A. Dikin, M. Herrera-Alonso, R. D. Pinar,

31

J. Shen, Y. Hu, M. Shi, X. Lu, C. Qin, C. Li,

and M. Ye, Chem. Mater. 21, 3514 (2009)

32

PrudHomme, and L. C. Brinson, Nat. Nanotech.

306, 327 (2008)

X. Yan, X. Cui, and L.-s. Li, J. Am. Chem. Soc.

132, 5944 (2010)

D. H. Adamson, H. C. Schniepp, X. Chen,

R. S. Ruoff, S. T. Nguyen, I. A. Aksay, R. K.

L. Jiao, L. Zhang, X. Wang, G. Diankov, and

D. Li, M. B. Muller, S. Gilje, R. B. Kaner, and

G. G. Wallace, Nat. Nanotech. 3, 101 (2008)

33

H.-J. Shin, K. K. Kim, A. Benayad, S.-M. Yoon,

19

P. R. Wallace, Phys. Rev. 71, 622 (1947)

H. K. Park, I.-S. Jung, M. H. Jin, H.-K. Jeong,

20

A. H. C. Neto, F. Guinea, N. M. R. Peres, K. S.

J. M. Kim, J.-Y. Choi, and Y. H. Lee, Adv.

Novoselov, and A. K. Geim, Rev. Mod. Phys. 81,

Funct. Mater. 19, 1987 (2009)

109 (2009)
21

34

A. Reina, X. Jia, J. Ho, D. Nezich, H. Son,

H. Liu, and J. Yao, J. Phys. Chem. C 112, 8192

V. Bulovic, M. S. Dresselhaus, and J. Kong,

Nano Lett. 9, 30 (2009)
22

23

G. Wang, J. Yang, J. Park, X. Gou, B. Wang,

(2008)
35

D. R. Dreyer, S. Murali, Y. Zhu, R. S. Ruoff,

C. Mattevi, H. Kim, and M. Chhowalla, J.

and C. W. Bielawski, J. Mater. Chem. 21, 3443

Mater. Chem. 21, 3324 (2011)

(2011)

W. A. de Heer, C. Berger, X. Wu, P. N. First,

36

Z. Zhang, H. Chen, C. Xing, M. Guo, F. Xu,

E. H. Conrad, X. Li, T. Li, M. Sprinkle, J. Hass,

X. Wang, H. J. Gruber, B. Zhang, and J. Tang,

M. L. Sadowski, M. Potemski, and G. Martinez,

Nano Res. 4, 599 (2011)

Solid State Communications 143, 92 (2007)

37

Y. Wang, Z. Shi, and J. Yin, ACS Appl. Mater.

Interfaces 3, 1127 (2011)

17
38

V.

Eswaraiah,

S.

S.

J.

Aravind,

and

S. Ramaprabhu, J. Mater. Chem. 21, 6800

39

and H.-M. Cheng, ACS Nano 3, 1745 (2009)

52

(2011)

Perez, J. A. de Saja, and M. A. Lopez-Manchado,

S. Stankovich, D. A. Dikin, G. H. B. Dommett,

J. Mater. Chem. 18, 2221 (2008)

K. M. Kohlhaas, E. J. Zimney, E. A. Stach, R. D.

53

Piner, S. T. Nguyen, and R. S. Ruoff, Nature

442, 282 (2006)
40

54

M. A. Rafiee, J. Rafiee, Z. Wang, H. Song, Z.-Z.

42

J. Liang, Y. Huang, L. Zhang, Y. Wang, Y. Ma,

Polymer 51, 1191 (2010)

55

and C. N. R. Rao, Proc. Natl. Acad. Sci. U.S.A.

2297 (2009)

106, 13186 (2009)

T. Ramanathan, S. Stankovich, D. A. Dikin,

56

Q. Wu, Y. Xu, Z. Yao, A. Liu, and G. Shi, ACS

57

58

59

46

60

47

48

49

61

62

H. M. A. Hassan, V. Abdelsayed, A. E. R. S.

7565 (2007)

Khder, K. M. AbouZeid, J. Terner, M. S. El-

X. Xiao, T. Xie, and Y.-T. Cheng, J. Mater.

Shall, S. I. Al-Resayes, and A. A. El-Azhary, J.

Chem. 20, 3508 (2010)

Mater. Chem. 19, 3832 (2009)

M. A. Rafiee, J. Rafiee, I. Srivastava, Z. Wang,

63

D. Marquardt,

C. Vollmer,

R. Thomann,

H. Song, Z.-Z. Yu, and N. Koratkar, Small 6, 179

P. Steurer, R. M. lhaupt, E. Redel, and C. Ja-

(2010)

niak, Carbon 49, 1326 (2011)

X. Zhou, T. Wu, B. Hu, G. Yang, and B. Han,

64

K. Zhang, L. L. Zhang, X. S. Zhao, and J. Wu,

D.-W. Wang, F. Li, J. Zhao, W. Ren, Z.-G.

Chen, J. Tan, Z.-S. Wu, I. Gentle, G. Q. Lu,

J. Liu, H. Bai, Y. Wang, Z. Liu, X. Zhang, and

D. D. Sun, Adv. Funct. Mater. 20, 4175 (2010)

65

Chem. Mater. 22, 1392 (2010)

51

H. Wang, J. T. Robinson, G. Diankov, and

H. Dai, J. Am. Chem. Soc. 132, 3270 (2010)

Chem. Commun. 46, 3663 (2010)

50

S.-S. Li, K.-H. Tu, C.-C. Lin, C.-W. Chen, and

M. Chhowalla, ACS Nano 4, 3169 (2010)

A. Yu, P. Ramesh, M. E. Itkis, E. Bekyarova,

and R. C. Haddon, J. Phys. Chem. C Lett. 111,

D. D. Kulkarni, I. Choi, S. S. Singamaneni, and

V. V. Tsukruk, ACS Nano 4, 4667 (2010)

S. Banerjee, and D. Chakravorty, J. Phys. Chem.

C 115, 14285 (2011)

Y. Xu, G. Long, L. Huang, Y. Huang, X. Wan,

Y. Ma, and Y. Chen, Carbon 48, 3308 (2010)

20, 085712 (5pp) (2009)

S. Mitra, O. Mondal, D. R. Saha, A. Datta,

J. Wang, X. Wang, C. Xu, M. Zhang, and

X. Shang, Polym Int 60, 816 (2011)

Nano 4, 1963 (2010)

D. Cai, K. Yusoh, and M. Song, Nanotechnology

I.-H. Kim and Y. G. Jeong, Journal of Polymer

Science: Part B: Polymer Physics 48, 850 (2010)

mer Physics 45, 2097 (2007)

45

K. E. Prasad, B. Das, U. Maitra, U. Ramamurty,

T. Guo, and Y. Chen, Adv. Funct. Mater. 19,

son, Journal of Polymer Science: Part B: Poly-

44

H.-B. Zhang, W.-G. Zheng, Q. Yan, Y. Yang,

J.-W. Wang, Z.-H. Lu, G.-Y. Ji, and Z.-Z. Yu,

H. Liu, H. Shen, S. T. Nguyen, and L. C. Brin-

43

T. Wei, G. Luo, Z. Fan, C. Zheng, J. Yan, C. Yao,

W. Li, and C. Zhang, Carbon 47, 2290 (2009)

Yu, and N. Koratkar, ACS Nano 3, 3884 (2009)

41

R. Verdejo, F. Barroso-Bujans, M. A. Rodriguez-

S. Chen, J. Zhu, X. Wu, Q. Han, and X. Wang,

ACS Nano 4, 2822 (2010)

66

J. Y. Son, Y.-H. Shin, H. Kim, and H. M. Jang,

ACS Nano 4, 2655 (2010)

18
67

68

J. Shen, Y. Hu, M. Shi, N. Li, H. Ma, and M. Ye,

S. Li, C. L. Gan, F. Boey, C. A. Mirkin, and

J. Huang, L. Zhang, B. Chen, N. Ji, F. Chen,

H. Zhang, Nat. Communn 2, 292 (2011)

71

M. Feng, R. Sun, H. Zhan, and Y. Chen, Nan-

(2010)
86

L. V. Saraf, D. Hu, J. Zhang, G. L. Graff, J. Liu,

96, 083113 (3pp) (2010)

M. A. Pope, and I. A. Aksay, ACS Nano 4, 1587

J. Liu, S. Fu, B. Yuan, Y. Li, and Z. Deng, J.

(2010)
87

F. He, J. Fan, D. Ma, L. Zhang, C. Leung, and

T. A. Pham, B. C. Choi, and Y. T. Jeong, Nan-

75

Y.-K. Kim and D.-H. Min, Carbon 48, 4283

6973 (2010)
88

20, 9253 (2010)

89

Y. Zhang, L. Ren, S. Wang, A. Marathe,

250 (2010)
90

G. Zhu, Y. Liu, Z. Xu, T. Jiang, C. Zhang, X. Li,

91

79

(2011)
92

Y. Fang, S. Guo, C. Zhu, Y. Zhai, and E. Wang,

Langmuir 26, 11277 (2010)

81

82

83

J. Xiang and L. T. Drzal, ACS Appl. Mater. In-

Q. Cheng, J. Tang, J. Ma, H. Zhang, N. Shinya,

and L.-C. Qin, Carbon 49, 2917 (2011)

94

869 (2011)
80

S. Wu, Z. Yin, Q. He, G. Lu, X. Zhou, and

H. Zhang, J. Mater. Chem. 21, 3467 (2011)

93

L.-L. Li, K.-P. Liu, G.-H. Yang, C.-M. Wang, J.R. Zhang, and J.-J. Zhu, Adv. Funct. Mater. 21,

Y. Hu, H. Zhang, P. Wu, H. Zhang, B. Zhou,

and C. Cai, Phys. Chem. Chem. Phys. 13, 4083

S. Liu, J. Tian, L. Wang, H. Li, Y. Zhang, and

X. Sun, Macromolecules 43, 10078 (2010)

S. Liu, J. Wang, J. Zeng, J. Ou, Z. Li, X. Liu,

and S. Yang, J. Power Sources 195, 4628 (2010)

and G. Qi, ChemPhysChem 11, 2432 (2010)

78

C. Fu, Y. Kuang, Z. Huang, X. Wang, N. Du,

J. Chen, and H. Zhou, Chem. Phys. Lett. 499,

5386 (2011)

77

M. Du, T. Yang, and K. Jiao, J. Mater. Chem.

(2010)

J. Chaudhuri, and G. Li, J. Mater. Chem. 21,

76

J. Yan, T. Wei, W. Qiao, B. Shao, Q. Zhao,

L. Zhang, and Z. Fan, Electrochimica Acta 55,

otechnology 21, 465603 (10pp) (2010)

74

D. Wang, R. Kou, D. Choi, Z. Yang, Z. Nie, J. Li,

S. Sun, L. Gao, and Y. Liu, Appl. Phys. Lett.

H. L. Chan, Carbon 48, 3139 (2010)

73

X. Huang, X. Zhou, S. Wu, Y. Wei, X. Qi,

J. Zhang, F. Boey, and H. Zhang, Small 6, 513

Am. Chem. Soc. 132, 7279 (2010)

72

85

(2010)

otechnology 21, 075601 (7pp) (2010)

70

X. Huang, S. Li, Y. Huang, S. Wu, X. Zhou,

J. Phys. Chem. C 114, 1498 (2010)

Y. Zhang, and Z. Zhang, Nanoscale 2, 2733

69

84

H. C. Choi, M. Shim, S. Bangsaruntip, and

H. Dai, J. Am. Chem. Soc. 124, 9058 (2002)

95

Y.-B. Tang, C.-S. Lee, J. Xu, Z.-T. Liu, Z.-H.

terfaces 3, 1325 (2011)

Chen, Z. He, Y.-L. Cao, G. Yuan, H. Song,

Z. Li, J. Wang, X. Liu, S. Liu, J. Ou, and

L. Chen, L. Luo, H.-M. Cheng, W.-J. Zhang,

S. Yang, J. Mater. Chem. 21, 3397 (2011)

I. Bello, and S.-T. Lee, ACS Nano 4, 3482 (2010)

R. Muszynski, B. Seger, and P. V. Kamat, J.

96

G. Zhou, D.-W. Wang, F. Li, L. Zhang, N. Li,

Phys. Chem. C Lett. 112, 5263 (2008)

Z.-S. Wu, L. Wen, G. Q. (Max)Lu, and H.-M.

Y.-K. Kim, H.-K. Na, and D.-H. Min, Langmuir

Cheng, Chem. Mater. 22, 5306 (2010)

26, 13065 (2010)

19
97

S. Watcharotone, D. A. Dikin, S. Stankovich,

R. Piner, I. Jung, G. H. B. Dommett, G. Evme-

98

99

3723 (2010)
111

nenko, S.-E. Wu, S.-F. Chen, C.-P. Liu, S. T.

Y. Zhang, R. Li, and X. Sun, J. Phys. Chem.

Nguyen, and R. S. Ruoff, Nano Lett. 7, 1888

C 114, 18330 (2010)

(2007)

112

M. R. Palacn, Chem. Soc. Rev. 38, 2565 (2009)

A. Ye, W. Fan, Q. Zhang, W. Deng, and

113

H. Wang, L.-F. Cui, Y. Yang, H. S. Casalongue,

Y. Wang, Catal. Sci. Technol. 2, 969 (2012)

J. T. Robinson, Y. Liang, Y. Cui, and H. Dai, J.

A. Cao, Z. Liu, S. Chu, M. Wu, Z. Ye, Z. Cai,

Am. Chem. Soc. 132, 13978 (2010)

Y. Chang, S. Wang, Q. Gong, and Y. Liu, Adv.

114

Mater. 22, 103 (2010)

100

H. Zhou, C. Qiu, Z. Liu, H. Yang, L. Hu, J. Liu,

132, 944 (2010)

115

116

103

Electroanalytical Chem. 634, 68 (2009)

118

Y. Pan, M. Gao, L. Huang, F. Liu, and H.-J.

2867 (2010)
119

Z. Zhou, F. Gao, and D. W. Goodman, Surface

120

121

107

108

122

123

Y. Shao, S. Zhang, C. Wang, Z. Nie, J. Liu,

S. Kim, H. Choi, M. Jung, S.-Y. Choi, and S. Ju,

Y. Wang, and Y. Lin, Journal of Power Sources

Nanotechnology 21, 425203 (6pp) (2010)

195, 4600 (2010)

D. Kondo, S. Sato, and Y. Awano, Appl. Phys.

124

L. L. Zhang, Z. Xiong, and X. S. Zhao, ACS Nano

Z. Fan, J. Yan, L. Zhi, Q. Zhang, T. Wei, J. Feng,

M. Zhang, W. Qian, and F. Wei, Adv. Mater. 22,

L.-S. Zhang, X.-Q. Liang, W.-G. Song, and Z.-Y.

Wu, Phys. Chem. Chem. Phys. 12, 12055 (2010)

125

4, 7030 (2010)
110

R. I. Jafri, N. Rajalakshmi, and S. Ramaprabhu,

J. Mater. Chem. 20, 7114 (2010)

Exp. 1, 074003(3pp) (2008)

109

Y. Li, W. Gao, L. Ci, C. Wang, and P. M.

Ajayan, Carbon 48, 1124 (2010)

J. Zhong, X. Jing, M. Ozkan, and C. S. Ozkan,

Small 6, 2448 (2010)

L. Dong, R. R. S. Gari, Z. Li, M. M. Craig, and

S. Hou, Carbon 48, 781 (2010)

2703 (2011)
J. Lin, M. Penchev, G. Wang, R. K. Paul,

H. Wang, Q. Hao, X. Yang, L. Lu, and X. Wang,

ACS Appl. Mater. Interfaces 2, 821 (2010)

K. Yu, G. Lu, S. Mao, K. Chen, H. Kim, Z. Wen,

and J. Chen, ACS Appl. Mater. Interfaces 3,

106

F. Kim, J. Luo, R. Cruz-Silva, L. J. Cote,

K. Sohn, and J. Huang, Adv. Funct. Mater. 20,

Science 604, L31 (2010)

105

Y. Zhang, H. Li, L. Pan, T. Lu, and Z. Sun, J.

Physics 11, 103045 (19pp) (2009)

Gao, Appl. Phys. Lett. 95, 093106 (3pp) (2009)

104

J. Chem. Sci 120, 9 (2008)

117

A. T. NDiaye, T. Gerber, C. Busse, J. Myslivecek, J. Coraux, and T. Michely, New Journal of

S. R. C. Vivekchand, C. shekhar Rout, K. S. Subrahmanyam, A. Govindaraj, and C. N. R. Rao,

T. Michely, Phys. Rev. Lett. 97, 215501 (4pp)

102

C. Liu, F. Li, L.-P. Ma, and H.-M. Cheng, Adv.

Mater. 22, E28 (2010)

A. T. NDiaye, S. Bleikamp, P. J. Feibelman, and

(2006)

S. Yang, X. Feng, S. Ivanovici, and K. M

ullen,
Angew. Chem. Int. Ed. 49, 8408 (2010)

H. Yang, C. Gu, and L. Sun, J. Am. Chem. Soc.

101

X. Meng, D. Geng, J. Liu, M. N. Banis,

Z. Q. Ma and B. X. Liu, Solar Energy Materials

& Solar Cells 69, 339 (2001)

126

Y. Jia, J. Wei, K. Wang, A. Cao, Q. Shu, X. Gui,

Y. Zhu, D. Zhuang, G. Zhang, B. Ma, L. Wang,

20
W. Liu, Z. Wang, J. Luo, and D. Wu, Adv.

127

K. S. Subrahmanyam, P. Kumar, U. Maitra,

Mater. 20, 4594 (2008)

A. Govindaraj, K. P. S. S. Hembram, U. V.

X. Li, H. Zhu, K. Wang, A. Cao, J. Wei, C. Li,

Waghmare, and C. N. R. Rao, Proc. Natl. Acad.

Y. Jia, Z. Li, X. Li, and D. Wu, Adv. Mater. 22,

Sci. U.S.A. 108, 2674 (2011)

2743 (2010)
128

129

D. Yu, Y. Yang, M. Durstock, J.-B. Baek, and

L. Dai, ACS Nano 4, 5633 (2010)