Graphene metal organic framework composites and their potential applications 1

1

Chapter 1: Introduction
1.1 History and properties of graphene
Human beings have been using carbon and its allotropes for a long time. In 1960s,
nanodiamond was first synthesized in Russia using a detonation method.
1
Carbon research was
given a new impetus with the discovery of fullerene,
2
C
60
, in 1985. The Japanese scientist, Sumio
Iijima, discovered carbon nanotubes in 1991 with the help of the transmission electron
microscope.
3
In 2004, two physicists at the University of Manchester first isolated individual
graphene planes using adhesive tape
4
(Figure 1.1(a)).
Graphene is an allotrope of carbon with one-atom-thick planar sheets of sp
2
-bonded carbon
atoms that are densely packed in a honeycomb crystal lattice. The term graphene was coined as a
combination of graphite and the suffix -ene by Hanns-Peter Boehm,
5
who described single-layer
carbon foils in 1962. Graphene is most easily visualized as an atomic-scale thick wire made of
carbon atoms and their bonds. The crystalline or "flake" form of graphite have many graphene
sheets stacked together. The carbon-carbon bond length in graphene is about 0.142 nanometers.
6

Graphene sheets stack to form graphite with an interplanar spacing of 0.335 nm, which means that
a stack of three million sheets would be only one millimeter thick. Graphene is the basic structural
element of some carbon allotropes including graphite, charcoal, carbon nanotubes and fullerenes
(Figure 1.1(b)). It can also be regarded as an indefinitely large aromatic molecule, the limiting
case of the family of flat polycyclic aromatic hydrocarbons.

Graphene is distinguished by its
      
7
   
 
8
   -      
         graphene.


2

         -

com            
9

 storage and conversion devices
10

11

Figure 1.1 (a) Timeline of carbon nanostructure discovery. (b) Schematic representation of graphene,
which is the fundamental starting material for a variety of fullerene materials; bucky balls, carbon
nanotubes, and graphite.
12
Image reproduced from reference 12.

1.2 Synthetic method to produce Graphene
Graphite is made up of adjacent graphene layers that are bound by weak van der Waals
forces
13
. Graphene can be obtained by mechanical exfoliation of graphite using adhesive tapes.

This method was discovered by A.K. Geim and K.S. Novoselov, who have been awarded the
Nobel Prize in Physics for their work on graphene
14
(Figure 1.2(a)). However, an economically
viable method for large scale production is needed to be used in industry and mechanical
exfoliation is clearly unsuitable. Therefore, other methods for the synthesis of graphene have been
developed. These methods can be grouped into two major categories: bottom-up synthesis and
solution-processed synthesis.
3


Figure 1.2 (a) Mechanical exfoliation of graphite by using adhesive tapes (b) CVD method of growing
Graphene sheet.
15
Image reproduced from reference 15.

The bottom-up synthesis of graphene typically uses chemical vapor deposition (CVD)
16

method (Figure 1.2(b)). In this method few-layer graphene sheets are deposited on copper foil or
metal catalyst-coated surfaces such as silicon. Such type of graphene typically show good
electrical properties as can be judged from the presence of quantum hall states, and are used
mainly in bench top experiments by physicists to probe the behavior of Dirac electrons, however
they are not amenable to solution-processing. Unlike the bottom up synthesis, the solution route
typically produces graphene oxide (GO) using the exfoliation and oxidation of graphite, followed
by chemical reduction to convert it to reduced graphene oxide (r-GO).
17
GO can be produced by
the oxidative treatment of graphite via one of these three methods: Brodie,

Hummers, and

18
involves the addition of potassium chlorate (KClO
3
) to a slurry
of graphite in fuming nitric acid. Staudenmaier
19
     
chlorate in multiple aliquots over the course of reaction instead of a single addition as Brodie had
done. This resulted in a similar degree of oxi     
approach. Thereafter, Hummer and Offeman
20
developed an alternate oxidation method by
reacting graphite with a mixture of KMnO
4
and concentrated sulfuric acid (H
2

SO
4
), and achieved
similar oxidation levels as well. The formed GO has a basal plane decorated with epoxide and
hydroxyl groups, while its edges are decorated with carboxyl and carbonyl group (Figure 1.3).
4


Figure 1.3 Scheme showing the chemical route to the synthesis of aqueous graphene dispersions. (1)
Oxidation of graphite to graphite oxide, GO, with greater interlayer distance. (2) Exfoliation of graphite
oxide in water by sonication to obtain GO colloids. (3) Controlled conversion of GO colloids to conducting
graphene colloids by hydrazine reduction.
21
Image reproduced from reference 21.

Solution processed graphene can be scaled up industrially, thus it has the potential for
cost-effective applications. In this thesis, solution-processed graphene is the main ingredient used
for the preparation of composites with Metal Organic Framework (MOF).

1.3 Reactions of Graphene
Graphene can be functionalized covalently or non-covalently to form chemically modified
graphene. GO platelets have chemically reactive oxygen functionalities, such as carboxylic acid at
the periphery and epoxy and hydroxyl groups on the basal planes. The carboxylic acid of GO
sheets can react with thionyl chloride (SOCl
2
),
22
1-ethyl-3-(3-dimethylaminopropyl) carbodiimide
(EDC),
23

 -dicyclohexylcarbodiimide (DCC)
24
. Their nucleophilic species like amines or
hydroxyls can be added to carboxylic groups to form amide or ester bonds with GO. Ring-opening
reactions activate the epoxy group of GO -carbon. For
example, octadecylamine can be attached to GO to make dispersible colloidal suspension of
graphene in organic solvents.
25
Non-covalent functionalization of GO can occur by hydrogen
bonding and electrostatic interaction on its oxygen functionalities, or -
interactions and cation- interaction on the aromatic rings on GO.
26
Reduced GO (rGO) platelets
have partially recovered -conjugation.
27
rGO can undergo covalent interaction by its residual
5

functional groups after reduction, for instance through diazonium reaction. In order to prepare
fuctionalized graphene in this thesis, rGO is linked to functional ligands by diazonuim reaction.
28

In Diels-Alder reaction, graphene can act as diene and dienophile via covalent interaction.
29

Indeed, graphene-based derivative can be modified readily by covalent route to tune the chemical
structure for specific applications. (Figure 1.4).


Figure 1.4 Selection of currently available non-covalent and covalent functionalized graphenes.

30
Image
reproduced from reference 30.

1.4 Graphene-based composites
Graphene has attracted enormous research interest in recent years, due to its interesting
properties. Graphene derivatives such as graphene oxide (GO) and reduced graphene oxide (rGO)
offer various possibilities to synthesize graphene-based functional materials for different
6

applications such as the Li-ion batteries,
31
supercapacitors,
32
fuel cells,
33
photovoltaic devices,
34

photocatalysis,
35
as well as Raman enhancement
36
(Figure 1.5).


Figure 1.5 Schematic naming some grapheme-based composites and their potential applications
37
Image
reproduced from reference 37.

1.4.1 Graphene- polymer composites
Carbon-based materials, such as amorphous carbon and carbon nanotubes (CNTs), are
conventional fillers for enhancing the electronic, mechanical and thermal properties of polymer
matrices.
38
CNT has been rendered as one of the most useful filler materials, although it is relatively
costly. Graphene-based fillers are often promoted as favorable replacement or supplement to CNTs.

To use lower amount of graphene filler, the dispersity and its bonding with the polymer matrix are
important in order to have desirable properties of the composites. Therefore, graphene-filled polymer
composites are usually prepared by solution mixing, melt blending, and in situ polymerization.
37
Graphene fillers can be dispersed in the polymer matrixes in layered structures, which are used in
specific applications, such as the directional load-bearing membranes, and thin films for photovoltaic
applications. For example, GO can be deposited onto poly(allylamine hydrochloride) (PAH) or
poly(sodium 4-styrene sulfonate) (PSS) to form layer-by-layer (LbL) assembling via the Langmuir
7

Blodgett (LB)
39
method (Figure 1.6(a). The resulting composited membrane shows enhanced
directional elastic modulus with 8 vol% loading of the graphene (Figure 1.6(b)).
40



Figure 1.6 (a) Schematic illustration of fabrication and assembly of the free-standing GO-LbL film. (b)
Plot showing the variation of elastic modulus calculated theoretically (under parallel and random
orientation) and that obtained experimentally (using buckling and bulging measurements) with the volume

fraction of GO.
40
Image reproduced from reference 40.


1.4.2 Other graphene-based composites
Other than inorganic nanostructures and polymers, materials such as organic crystals,
41
metal
organic frameworks (MOF),
42
biomaterials,
43
and carbon nanotubes (CNTs)
44
have also been mixed
with graphene derivatives to target various applications. For e -dioctyl-3,4,9,10-
perylenedicarboximide (PDI)graphene core/shell nanowires used in organic solar cells have been
formed through  interaction.
45
MOF, a recently emerging material, is used for gas purification and
storage applications, and has also been used to form composites with GO/rGO sheets.
46
Moreover,
biomaterials like DNA hybridized with GO or rGO are used in fluorescent sensing platforms based on
the fluorescence resonance energy transfer (FRET).
47
GrapheneCNT composites have also been
prepared via solution blending or in situ CVD growth
48

to be applied in Li ion batteries, transparent
conductors,
44
and supercapacitors.
49


8

1.5 Overview of Metal-Organic Frameworks (MOFs)
The design and synthesis of extended network materials has been an area of intense
research over the past decade. Specifically, the porous nature of many of these materials makes
them attractive for numerous applications. This section provides background information on many
areas concerning the chemistry of MOFs including: (1) the design of MOFs from precursors, (2)
various applications of MOF materials, (3) previous works concerning the use of MOF and carbon
composites.
1.5.1 The Design of MOFs
MOFs can be formed through a node and linker approach that was first reported by Yaghi,
Robson,
50
Fujita.
51
This method uses metal ions as nodes and organic molecules as linkers. The
metal ion, with a preferred coordination number and geometry, in combination with divergent
linker molecules, creates an extended network in one, two, or three dimensions. The interactions
of the metal ion and the linker molecule vary widely and have included ionic, covalent, and
coordinate interactions,
52
as well as -
53

Often, the strengths
of these interactions directly influence the overall stability of the resulting framework. As shown
in Figure 1.7, the principles of coordination complexes can be used to construct extended network
assemblies.

Figure 1.7 Illustration of the paradigm shift from molecular coordination chemistry involving terminal
ligands to extended assemblies using diverging ligands.
9

The single metal center used as a node can change the structure owing to the preference for
a specific geometry and coordination environment of the given metal. For example, in the
compound [Cu
2
-bipy
)4
]·(D--bipy)
2
·12H
2
O synthesized by Zhang, et.al., the Cu
2+

metal centers adopt a tetrahedral coordination geometry and assemble into a network via -
bipyridine linkages
54
(Figure 1.8).

Figure 1.8 The Cu
2+
ion in [Cu

2
-bipy)
4
]·(D-- bipy)
2
·12H
2
O adopts a tetrahedral geometry
and acts as the node for the extension of a network linked via -bipyridine.
54
Image reproduced from
reference 54.

In comparison, the compound [Cd(4,4'-bpy)
2
(H
2
O)
2
](ClO
4
)
2
.1.5(4,4'-bpy)], synthesized by
Liu et al., contains Cd
2+
centers that adopt an octahedral geometry.
55
The axial positions of the
octahedron are occupied by terminally water molecules. The equatorial positions are assumed by

-bipyridine which act as the linker molecules. Therefore, a square network is formed as a
result of the geometry around the metal center. (Figure 1.9)

Figure 1.9 The Cd
2+
ion in [Cd(4,4'-bpy)
2
(H
2
O)
2
](ClO
4
)
2
.1.5(4,4'-bpy)] adopts an octahedral geometry by
           -bipyridine molecules.
55
Image
reproduced from reference 55.
10

Yaghi introduced the second approach of the MOF design through the use of secondary
building units (SBUs).
56
This method makes use of many common structural motifs known in
molecular cluster chemistry by incorporating them as nodes for network extension. Two examples
of this strategy are shown in Figure 1.10
common example in this regime, where the acetate anions can be replaced by a variety of
dicarboxylates to provide four points for network extension to form a square net.

57


Figure 1.10 Common transition metal acetate clusters and the divergent linker benzene dicarboxylate
creating SBUs. Top: the copper acetate paddlewheel becomes a square planar SBU. Bottom: The [Zn
4
O]
6+

cluster becomes an octahedral SBU. (Color scheme: Zn, green; Cu, light blue; C, black; N, blue, O, red.)
57

Image reproduced from reference 57.


         
4
O]
6+
cluster and six
acetate anions, is another example of an SBU for framework extension. The acetate anions in this
oxo-centered cluster can be replaced by divergent ligands.
58
This SBU serves as an octahedral
node for the formation of a primitive cubic network. Additionally, SBUs formed from metal
clusters can also be combined with neutral, divergent Lewis basic ligands to provide further points
of extension for network growth. Figure 1.11 shows that these Lewis bases can be replaced by
-bipyridine, to create an octahedral node.
11

Figure 1.11              -
bipyridine creates an octahedral node with two additional points of extension
58
Image reproduced from
reference 58.


1.5.2 Potential Applications of MOFs
MOFs have received considerable interest in recent times due to their potential
applications in areas such catalysis, optics, electronics, small molecule storage, and separation
science.
59
There have been hundreds of reports of hydrogen storage in MOF materials.
60
The
interaction of H
2
and the MOF surface is typically quite weak, being dominated by dispersion
forces. Various strategies for enhancing the H
2
-surface interaction have been explored, including
systematically varying pore structure, minimizing pore size to increase van der Waals contacts
with H
2
, and embedding coordinately unsaturated metal centers within the MOF structure to
interact with H
2
. For example, Yaghi has reported many MOFs based on the [Zn
4

O]
6+
SBU which
are effective in storing H
2
. Probably the most popular MOF, MOF-5 or [Zn
4
O(BDC)
3
]

(BDC =
benzene dicarboxylate), was shown to store 4.5 wt % H
2
at 77K and 1.0 wt % at ambient
temperature.
61

MOFs have shown useful in the storage of other small molecules besides hydrogen gas.
For instance, the gas adsorption of N
2
, CO, CO
2
and CH
4
has been reported.
62,63
MOFs can also be
used in catalysis. For example, Lin reported [Cd
3

Cl
6
L
3
] (L = (R)--dichloro--dihydroxy-
12

-binapthyl--bipyridine) can be covalently modified with titanium isopropoxide. This
material was used to catalyze the enantioselective addition of diethylzinc to aromatic aldehydes.
MOFs also have exciting potential as light-weight molecular selective sieves, due to their
extremely high surface areas, low density, interconnected cavities and very narrow pore size
distributions.
64
Some frameworks are also adaptive materials which respond to external stimuli
(for example, light, electrical field, presence of particular chemical species), promising new
advanced practical applications. However, in order to use MOF in next generation sensing,
separation, catalysis and delivery devices, we may require the introduction of extrinsic
functionality. Incorporation of functional species in MOFs has to date been demonstrated through
post-impregnation mostly of metal nanospecies by chemical vapour deposition and one-pot
synthesis (adding either the functional species or its precursors directly into the MOF growing
medium). Both these approaches cause the doping species to grow inside the MOF cavities and on
the MOF outer surface. The resulting lack of spatial control of the functional components within
the MOF crystals compromises the molecular selectivity of the final composite.
The investigation of MOFs in electrochemistry is quite recent. Important applications of
electrochemistry are energy storage and conversion
65
(supercapacitors, batteries, fuel cells). The
poor electron-conductive properties of most MOFs would limit them from being used as
electrode. Although MOFs have been successfully used as electrode materials for rechargeable
batteries,

66
we need some strategies to overcome their insulating nature. The redox behavior of
metal cations inside MOFs could provide a pathway for electrons. Alternatively, the tuning of the
linker structure may lead to better charge transfer inside the framework. An efficient strategy is to
mix MOFs with conductive phases (metal nanocrystals, carbon nanostructures, fuctionalized
graphene, conductive polymers)
67
.
13

1.6 Literature review on MOFs at carbon interfaces
Carbon-based materials such as activated carbon, fullerene (C60), carbon nanotubes
(CNTs), graphite and graphene are of technological interests because of their mechanical strength,
hydrophobicity, potential in adsorption and catalysis, and interesting electronic properties. Thus,
there have been various composite systems with MOF for myriad applications, ranging from
energy storage to the production of catalyst.
1.6.1 Composite of MOF and Activated carbon
Many studies have been done on MOF and activated carbon composites.
68
As an example,
Seung Jae Yang et al. reported
69
a facile method for the preparation of novel ZnO-based
nanostructured architectures using a metal organic framework (MOF) as a precursor. In this
approach, ZnO nanoparticles and ZnO@C hybrid composites were produced under several
heating and atmospheric (air or nitrogen) conditions. The resultant ZnO nanoparticles formed
hierarchical aggregates with a three-dimensional cubic morphology, whereas ZnO@C hybrid
composites consisted of faceted ZnO crystals embedded within a highly porous carbonaceous
species, as determined by several characterization methods. The newly synthesized nanomaterials
showed relatively high photocatalytic decomposition activity and significantly enhanced

adsorption capacities for organic pollutants.
1.6.2 Composite of MOF and Fullerene (C60)
Fullerene-MOF composites are very promising materials for gas storage applications. A lot
of researches have been focused on the use of these materials for methane and hydrogen storage
materials. For instance the incorporation of magnesium-
frameworks (MOFs) was reported by Aaron W. Thornton.
70
The system is modeled using a novel
14

approach underpinned by surface potential energies developed from Lennard-Jones parameters.
Impregnation of MOF pores with magnesium-decorated Mg-C60 fullerenes, denoted as
          dsorption into intimate
contact with large surface area MOF structures. They predicted a very high hydrogen adsorption
enthalpy of 11 kJ mol

with relatively little decrease as a function of H
2
filling. This value is
close to the calculated optimum value of 15.1 kJ mol

and is achieved concurrently with
saturation hydrogen uptake in large amounts at pressures under 10 atm.
1.6.3 Composite of MOF and Carbon nanotubes (CNTs)
CNTs have also been used as surfaces for MOF growth, particularly for the preparation of
composite materials with enhanced gas storage capacity. Yang et al. have reported
71
the hydrogen
storage properties of MOF-5/CNT composites, including in the presence of Pt. The composites
were prepared by adding acid-treated multi-walled CNTs (MWCNTs) or Pt-loaded MWCNTs

dispersed in DMF to the MOF-5 synthesis mixture. Acid treatment of the MWCNT surface prior
to composite formation introduces carboxylate functionalities for MOF binding.

Figure 1.12 HRTEM micrograph of a MOF-5/CNT composite crystal. (b) Enlarged view of the boxed area
in (a), (c) typical selected area electron diffraction patterns of (a).
72
Image reproduced from reference 72.
15

HRTEM and selected area diffraction of the MOF-5/CNT composites clearly demonstrate
efficient mixing of the two components (Figure 1.12)
72
showing enhanced thermal and moisture
stability and higher Langmuir surface area compared with MOF-5 alone. A recent report by Chen
et al. details the increased moisture and electron beam stability of MOF-5 confined within the
interior of MWCNTs,
73
where stability is dependent on the number of walls.

Hydrogen storage
capacity of MOF-5/CNT at 1 bar and 77 K, increased by 25% compared to the parent MOF as
shown by the isotherms presented in Figure 1.13, which is further enhanced at higher pressures
where a 100% increase is observed (298 K, 95 bar). This increased H
2
capacity under a wide
range of experimental conditions is largely attributed to the increased porosity at the interface and
the improved structural integrity of the MOF component. Pranath et al. have reported enhanced
hydrogen storage capacity at high pressure for MIL-101/SWCNT (single-walled carbon nanotube)
composites.
72

A layer-like structure is observed by TEM indicating growth of the MOF on the
functionalized surface of SWCNTs and N
2
adsorption isotherms reveal an increase in ultra
micropores for the composite, as previously reported for MOF/GO and MOF/MWCNT materials.
For a composite of MIL-101 with 8 wt% SWCNTs, hydrogen uptake at 60 bar was increased by
44% at 77 K and 178% at 298 K over pure MIL-101.

Figure 1.13 H
2
adsorption isotherms measured at 77 K and 1 bar using a volumetric method for MOF-
5/CNT composites compared to the parent MOF and MWCNTs.
72
Image reproduced from reference 72.


16

1.6.4 Composite of MOF and Graphene oxide
Oxidation of graphite increases its hydrophilicity making a water dispersible functional
carbonaceous interface for enhanced interactions with small molecules.
74
Bandosz and co-workers
reported
42
the synthesis and ammonia adsorption properties of a number of MOF-GO
nanocomposites including MOF-5, HKUST-1 and MIL-100(Fe), by simply dispersing GO powder
in the usual MOF synthesis. MOF-5 and HKUST-1 crystallites interact strongly with the
hydroxyl, epoxy and carboxylate groups expressed at the GO surface to readily form MOF/GO
composites.

It is proposed that the MOF-5/GO composites are comprised of a sandwich like
structure of alternating MOF/GO/MOF layers, although the SEM images shown in Figure 14
indicate changes in composite as the content of GO increases; perhaps through preferential MOF
interaction with the carboxylate groups at the edges of the GO sheets.
75


Figure 1.14 SEM images for MOF-5/GO composites at GO loadings of (C) 5 wt%, (D) higher-
magnification of 5 wt% sample, (E) 10 wt% and (F) 20 wt%. A clear change in morphology from the
layer-like structures observed at 5 and 10 wt% of GO is seen on increasing the carbon content.
75
Image
reproduced from reference 75.
17

Composite formation is dependent on the functional groups present on the GO surface. A
related study with HKUST-1 and unfunctionalised graphite reveals only the formation of physical
mixtures. The relative orientation of metal coordination sites on the MOF available for GO
binding is highlighted in Figure 1.14. For example, MIL-100(Fe) forms disordered MOF/GO
composite materials, arising from interaction of its spherical cages with GO layers rather than the
cubic MOF-5 and HKUST-1 structures, where metal coordination sites lie along regular planes.
76

(Figure 1.15).

Figure 1.15 Schematic comparison of the coordination between GO layers and MOF units in different
types of MOF network: MOF-5, HKUST-1 and MIL-100(Fe). For MOF-5 and HKUST-1: the atoms
involved in coordination are indicated. For MIL-100(Fe): the red pyramids represent supertetrahedra units
made of trimers of iron octahedra linked by molecules of BTC.

76
Image reproduced from reference 76.


Ammonia adsorption by the MOF/GO composites is strongly dependent on the porosity
and chemical nature of the MOF, and the nature and synergy of the MOF/GO interface, shown in
Figure 1.16 for HKUST-1/GO composites.
42
Both MOF-5/GO and HKUST-1/GO composites
display increasing ammonia absorption capacity and retention with increasing GO content which
attributed to a synergetic effect between the two components. The high surface of GO and small
18

pore spaces at the interface between the GO and MOF (Figure 1.16) improve both ammonia and
hydrogen physisorption.
77
By contrast, the poor interface between MIL-100(Fe) and GO leads to a
decrease in adsorption capacity with GO content. The specific nature of the MOF also plays a role
in the adsorption process, particularly where there can be strong chemical interactions between
NH
3
and the MOF.
Activated HKUST-1 has open metal sites arising from removal of water molecules bound
to the paddlewheel SBUs; these are known to coordinate a variety of molecules, and bind readily
to ammonia and H
2
S in the HKUST-1/GO composites.

NH
3

and H
2
S adsorption by the HKUST-
1/GO composites follow the same multi-step adsorption behaviour: increased adsorption occurs
due to the MOF/GO interface and reactive binding to the Cu sites, which ultimately leads to an
irreversible reaction between the MOF and the adsorbate. This necessarily makes it difficult to
understand the exact role of the GO in complex adsorption systems. Unlike MOF-5/GO, ammonia
adsorption in HKUST-1/GO composites is enhanced in humid conditions due to dissolution of the
adsorbate, and moist conditions also appear to slow down reaction with the MOF despite an
increased NH
3
concentration, likely resulting from competitive water binding. For MIL-
100(Fe)/GO composites ammonia is also retained by interaction with open metal sites, and
Brønsted interactions with water molecules are also involved.
GO itself has a relatively low density of carboxylate groups on the surface of the sheets;
rather, this functionality tends to be most prevalent on the sheet edges. This has some
consequences for MOF growth as seen in the work of Petit et al.,
74
where MOF-5/GO composites
tend to form layered materials at low GO content but disordered wormlike structures at high GO
loading due to the greater number of carboxylate interactions with increasing GO, favoring edge
growth.
19


Figure 1.16 Simple visualization of the two sites of ammonia adsorptionin HKUST-1/GO composites with
(1) physisorption at the interface between graphene layers and MOF units and (2) binding to the copper
centers of the paddlewheel SBUs. Ammonia molecules are represented by the dark gray circles. Note that
the relative MOF and GO domain sizes are not to scale.
77

Image reproduced from reference 77.

1.7 Scope of study
Solution processed functionalized graphene offers large-scale production of graphene-based
material for various applications. By using functionalized graphene and MOF in the composites, it
is expected that graphene sheets will contribute to the enhancement in the dispersive interactions,
whereas the MOF component will contribute to the expansion of the pore space, in which the
initial property of graphene and MOF can be changed. The main aim of this research is to
investigate the effect of intercalation of functionalizedgraphene on the structure of metal organic
frameworks and its electrochemical performance. Three foremost functionalized groups, pheyl-
COOH and pyridineDye, and oxygen groups were chosen to study the influence of
functionalized graphene on the structure of MOF.
Reduced GO was reacted with a phenyl carboxylic diazonium salt to prepare benzoic-acid
functionalised grapheme (BFG). This produces a 3-fold increase in carboxylate functionalities
over GO, and subsequently this was applied as a template for directing MOF growth. The nitrogen
20

adsorption properties of the MOF/BFG nanowires and the electrical properties of composite
nanowires were investigated in chapter 3.
Pyridine-functionalized graphene flakes were used as building blocks in the assembly of
metal organic framework. By reacting the pyridine-functionalized graphene with iron-porphyrin, a
graphene-metalloporphyrin MOF was synthesized. This composite was used as catalytic material
for the oxidation of cyclohexane (chapter 4) and also for oxygen reduction reactions (ORR)
(Chapter 5).
Oxidation of graphite increases its hydrophilicity through the introduction of differential
surface functionalities and defects, such that the resulting graphite oxide (GO) constitutes a water
dispersible functional interface. In chapter 6, The GO/Cu.MOF hybrid is used as a novel
electrocatalyst for hydrogen evolution, oxygen evolution, and oxygen reduction reaction. The
performance of the composite as a Pt-free cathode in Fuel Cell was also tested
More specifically in this thesis, we sought to examine:

1) Changes in the morphology of metal organic framework after intercalation of graphene;
2) Role played by functionalized groups in MOF for forming composites and in enhancing MOF
activities;
3) Effect of the surface area of graphene on the catalytic activities of MOF.
Here, among myriad applications, we have mainly focused on the catalytic activities of
MOF-graphene composites in different reactions such as cyclohexane oxidation, oxygen reduction
reaction, hydrogen evolution reaction and oxygen evolution reaction.

21

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