Chapter No 2

1 Literature Review
With the immense increase in the worlds populations energy reserves are drastically
depleted. To meet the world's energy needs, energy conversion and storage devices have played a
crucial role. Currently, transition metal oxides are widely used as promising electrode materials
as they offered multiple oxidation states that helped to enhance the electrochemical properties.

In this chapter, prior experimental workings on the synthesis of transition metal oxide
nanocomposites for the energy conversion and energy storage applications are discussed.
Research publications related to reduced graphene (rGO) and Carbon Nanotubes (CNTs) added
in transition metal oxide nanocomposites are also enlightened for the above mentioned
applications. Moreover, role of both rGO and CNTs coupled transition metal oxides
nanocomposites are described.

1.1 Photocatalysis

1.1.1 Synthesis of Transition Metal Oxide Nanocomposites for Photocatalysis

Amita et al. [100] prepared pure and Co replaced NiO nanostructures by employing co
precipitation method. FCC structure of NiO nanoparticles was confirmed by using XRD. FTIR
confirmed the functional groups and spherical morphology of nanoparticles was also examined
by using SEM. The optical band gap of the synthesized nanocomposite was also studied by UV-
vis analysis and reduction in the band gap of nanoparticles was observed by increasing Co
concentration. Photo catalytic activity of the prepared nanoparticles using methyl blue was done
under sunlight irradiation. They concluded that that methyl blue dye has shown 94% degradation
in fifty minutes in presence of Ni0.6Co0.4O.

Mohamed et al. [101] used the precipitation technique to prepare pure ZnO
nanoparticles and their composite with Eu 2O3 by varying ratios (5, 10 and 15%). Various
techniques were utilized to analyze the nanostructures. The as-prepared pristine ZnO
nanoparticles were found to exhibit crystalline wurtzite structure while mixed Eu 2O3 and ZnO
nanocomposite showed zinc blend phase of Eu 2O3 plus ZnO wurtzite phase which exhibited
elevated purity and good crystallinity. These pure phases were also confirmed by FTIR and
Raman. Spherical morphology was also monitored by SEM and TEM with particle size ranging
29 to 40 nm. It was observed that addition of Eu 2O3 in ZnO has played the vital role in enhancing
the photocatalytic activity of ZnO nanoparticles. They concluded that 5% Eu 2O3 addition in ZnO
nanoparticles exhibited better degradation efficiency which is 96.5% in comparison with pure
ZnO which showed 80.3% after 180 minutes irradiation of UV. This improvement in
photocatalytic activity is attributed to enhanced surface area and reduction in bandgap.

Maria et al. [102] prepared CeO2/Y2O3 hetero-structured by employing the hydrothermal

method. They claimed that CeO2 is thrilling metal catalyst having excellent redox ability. It can
be used as good oxygen buffer. They analyzed the nanostructures by using various
characterization techniques including SEM, EDX, XRD, UV-Vis, FTIR and HRTEM. The
formation of CeO2/Y2O3 cluster was confirmed with the size of 10 nm. During the synthesis,
temperature and pressure used carefully for controlling the size and shape of prepared composite.
Owing to their stable structure, nature and size, CeO 2/Y2O3 nanoparticles were found to be
superior catalyst for careful reduction of p-nitrophenol and to prepare p-aminophenol.
The photocatalytic activity of the synthesized samples was evaluated by using Rhodamine-B
under UV light irradiation. The dye was degraded 98% in 150 minutes. Moreover, antibacterial
activity was also carried out and results were compared with standard antibiotic.

1.1.2 Synthesis of rGO Supported Transition Metal Oxides Nanocomposites for

Photocatalysis

Khadija et al. [103] synthesized reduced graphene included ternary nanocomposites

WO3-ZnO@rGO via facile ultrasonic fabrication. Their morphology, structure and elemental
properties were studied using various characterization techniques including XRD, SEM, EDX
and FTIR. Optical band gap was studied using UV-vis spectroscopy and it was found that
addition of rGO helped to decrease the band gap. CV measurements confirmed the improved
ohmic response of rGO supported samples as compared to without rGO. These structures were
proved to be better catalysts for degradation of methylene blue dye with an efficiency 94% in 90
minutes under visible light. The proved photocatalytic response was attributed to the synergistic
effects forming at WO3-ZnO@rGO interfaces which have raised quantum efficiency and
effective light provoked electron-hole pair separation and transfered. It also showed remarkable
degradation stability after 4 cycles.
 Mahdikhah et al. [67] prepared CoFe2O4/rGO nanocomposites by co-precipitation
method. They studied the influence of rGO and TX-100 surfactant on structural, morphological,
photochemical, optical attributes and photocatalytic activity of CoFe 2O4. Addition of rGO and
TX-100 was responsible for the reduction in crystallite size to 14nm. Surface area enhanced to
116 m2/g and reduction in band gap energy to 1.75 eV. Addition of rGO decresed the magnetic
properties, while coercivity was enhanced tremendously with the utilization of TX-100
surfactant. This may be attributed to electrostatic interface as a result of van der waals force
between TX-100 surfactant and CoFe2O4. PL, TRF, EIS and photocurrent responses composed
nanocomposites employing TX-100 exhibited good charge carrier transfer ability. The
CoFe2O4/rGO nanocomposite sample showed high degradation efficiency for MB than MO and
RhB dyes owing to its electrostatic field force and charge transfer initiated from the cationic
character of MB dyes. These samples also showed high recycling rate with 83% degradation
value after three cycles.

Meiyan et al. [104] effectively produced Ag/TiO2/rGO nano photocatalyst using

hydrothermal method. The nanocomposite was examined by various characterization techniques
including TEM, DRS, FTIR and XPS. The photocatalytic act of the synthesized nanocomposite
was assessed by the degradation of MB dye under visible-light. The output showed that the
photocatalytic performance of titanium oxide was considerably enhanced by employing graphene
and Ag materials. This improvement in phohtcatalytic activity was attributed to the interface
among anatase nanoparticles and rGO sheet contribution. The surface plasmon resonance of
silver nanoparticles also contributed. This research provided a capable method for novel
materials to extend a new TiO2-based photocatalyst with elevated solar amalgamation and
improved catalytic action.

1.1.3 Synthesis of CNTs Supported Transition Metal Oxides Nanocomposites for

Photocatalysis

Kai et al. [105] synthesized MWCNTs/ZnO hybrid by using large scale reflux
mechanism. They used ethylene glycol and polyvinylpolypyrrolidone during the preparation
process. The morphological and structural properties were examined via different
characterization methods. Slight blue shift was observed in the sample of MWCNTs/ZnO as
compared to pure ZnO. MWCNTs/ZnO hybrid exhibited very good photocatalytic performance
under UV light with kapp of 0.1517 min−1 and great reusability. This might be due to strong
chemical bond between ZnO and CNTs. They concluded that MWCNTs/ZnO hybrid showed
promising behavior and excellent stability, no observable change was observed even after 10
cycles.

Shafei et al. [106] prepared Copper doped titanium oxide-carbon nanotubes

catalyst nanopowder by using sol–gel method. The results of CNTs and copper doping on the
as-prepared amorphous TiO2 was inspected by thermal examination. Anatase phase was
predominantly observed when sample calcination was done at 440 °C. It was observed that the
alteration of TiO2/CNTs after doping with copper helped to had uniform coating of TiO 2 on
CNTs which consequently enlarged the surface area. This will help to enhance the photcatalytic
process. The produced nanocomposite powder comprised of a TiO 2 coating on CNTs with
thickness of 80 nm. It also decreased the band gap energy from 3.2 to 3.05 eV. Band gap was
further decreased to 2.85 eV by doping of copper in TiO 2-CNTs. The photoluminescence
analysis revealed the inferior speed of recombination procedure in the presence of CNTs and Cu
doping. Cu doped TiO2-CNTs catalyst was mainly employed for MB degradation in visible light
irradiation. After sixty minutes irradiation, the photocatalytic activity of Copper doped titanium
oxide-carbon nanotubes was 1.3 and 16.3 times greater than that of titanium oxide-carbon
nanotubes and titanium oxide samples respectively. This improvement in photocatalysis was
credited to CNTs and Copper. Its physical and chemical stability was ascertained by recycling
ability

Sung et al. [107] synthesized SnO2–CNTs nanocomposites by using chemical method.

The coating of SnO2 nanoparticles were carried onto thiolated CNTs top. The formation of
SnO2–CNTs was confirmed by using TEM, XRD, and XPS. The photocatalytic action of the
SnO2–CNTs nanocomposites was done by using the photo deprivation of methylene blue and
methyl orange under UV–vis irradiation. The SnO 2–CNTs showed improved photocatalytic
performance in contrast with bulk SnO2, SnO2 nanoparticles, and marketable P25 titanium oxide.
The better activity was credited to the CNTs contribution. The existence of CNTs successfully
concealed an electron–hole recombination, privileged a reactant and product mass transfer.
Moreover, π-π interactions of CNTs and dyes molecules also enhanced the photocatalytic
activity.
 1.1.4 Synthesis of CNTs and rGO Supported Transition Metal Oxides
Nanocomposites for Photocatalysis

Tian et al. [108] prepared ZnO–RGO–CNTs composites employing microwave-assisted

reduction of a graphite oxide dispersed in ZnNO 3 solution with carbon nanotubes suspension.
Their photocatalytic action in the deprivation of MB was explored and the outcome illustrated
that the addition of CNTs might be an essential part in the enrichment of the photocatalytic
performance. The ZnO–RGO–CNTs composite having 3.9 weight % carbon nanotubes attained a
greatest degradation effectiveness of 96% under UV light irradiation for two hundred and sixty
minute. The inclusion of CNTs in ZnO-RGO composite was liable for the enhancement of
photocatalytic activity. This may be the CNTs increase light absorption and slow down the
process of charge recombination.

Yanzhen et al. [109] synthesized ternary TiO2/ CNTs/ rGO composites by one-pot solve
thermal technique. Its structural and morphological analysis was done by XRD, Raman
spectrometry, SEM and TEM. The photocatalytic performance was detected by the degradation
of RhB under UV-vis light irradiation. The investigated outcomes specified that photocatalytic
action enhanced as the ratio of CNTs:TiO2 varied from 0.5% to 3% but reduced when the ratio
increased to 5% and 10%. The TiO2/CNTs/rGO-3% composites exhibited better photocatalytic
performance in comparison with the binary ones (TiO 2/CNTs, TiO2/rGO) and pure TiO2. The
improved photocatalytic activity can be credited to the inclusion of rGO and CNTs, which
decreased the recombination of light-induced electron-hole pairs. The carbon nanotubes and
reduced graphene oxide having high surface area and high adsorption capability to efficiently
adsorb oxygen, water and organics could raise the hydroxyl ratio of photocataltytic surface.

Zeng et al. [110] produced CNTs/rGO embedded Cu2O composite spheres via an
electrostatic self-assemble with microwave-assisted. SEM and TEM analysis revealed that the
fusion of CNTs and rGO was embedded into Cu 2O medium and created a unique 3D micrometer
sphere. The photocatalytic activity was examined by estimating on photo-degradation of a
contaminant methyl orange. The outcomes showed that this new structural design improved
photocatalytic performance with 99.8% degradation of methyl orange after forty minutes in the
existence of hydrogen peroxide under visible light irradiation. It was higher than pure Cu 2O
powders (67.9%) to a large extent.
1.2 Supercapacitors

1.2.1 Synthesis of Transition Metal Oxide Nanocomposites for Supercapacitors

Ruiting et al. [111] synthesized pristine and transition metal doped

Mn3O4 nanostructures by hydrothermal reduction of potassium permanganate. The synthesized
samples were analyzed by SEM/TEM, XRD, XPS and electrochemical testing. The
consequences disclosed that a reduction was happening in multiple steps and addition of ion
doping produced single-phase Mn3O4 nanocrystals. To evaluate the features of prepared
nanocrystals for supercapacitor usage, CV and GCD tests were carried out. The phase constancy
throughout cyclic process and charge transfer performance was greatly enhanced by doping with
transition metal. Chromium doped Mn3O4 nanostructures showed a maximum specific
capacitance of 272 Fg–1 at a current density of 0.5 Ag –1. They claimed that these could be a
potential electrode materials for high-powered, less expensive and eco-friendly supercapacitors.

Shinde et al. [112] prepared novel nickel cobalt oxide thin films by using SILAR
technique. They varied deposition cycles. It was confirmed by electrochemical studies that these
films exhibited excellent capacitive ability and remarkable cyclic stability. Cubic crystals
structure having flower like shapes were confirmed by structural and morphological analysis.
The maximum specific capacitance of about 1936 and 680 Fg -1 were estimated at scan rates of 5
and 100 mVs-1, respectively, in conjunction with improved cyclic stability. This method was
proved to be simple, and great impact of deposition cycle variation was observed to
electrochemical and morphological properties of synthesized samples.

Justin et al. [113] reported the production and activity of zinc oxide core/manganese
oxide shell, 3D nanostructured planar supercapacitors. Zinc Oxide nanorods were developed
over FTO and afterward deposited manganese oxide nanostructure by using SILAR on Zinc
Oxide. The class of the prepared electrode was improved by depositing MnO2 layer over ZnO
core by varying cycles of deposition. 7 cycles of MnO 2 deposition of electrode showed better
electrochemical performance with area capacitance of 14 mF cm−2. Symmetric planar
supercapacitor was also fabricated at similar conditions. This zinc oxide core/manganese oxide
shell 3D structure planar supercapacitor demonstrated maximum area capacitance of
5 mF cm−2 in 1M sodium sulphate electrolyte with high-quality energy density
4.07 × 10−7 Wh cm−2 and power density 3.19 mW cm−2.
 1.2.2 Synthesis of rGO Supported Transition Metal Oxides Nanocomposites for
Supercapacitor

JinhuiXu et al. [114] synthesized the nickel oxide/ reduced grapheme oxide
nanocomposites using hydrothermal precursor and afterward did calcinations of the
precursors into nanocomposite. First, reduced graphene oxide was prepared from
graphene oxide. After that nickel oxide nanoparticles were detached in-between the sheets of
reduced graphene oxide. They investigated by electrochemical studies that the composite
exhibited the specific capacitance of 171.3 Fg-1 in a 6 mol/L KOH electrolyte with a current
density of 0.5 Ag-1. After two thousand cycles of GCD at 5 Ag -1 current density, average specific
capacitance dropped off by 20.93 percent.

Yong et al. [115] prepared reduced graphene oxide coupled nickel iron oxide
nanohybrids. By varying compositional ratio, nickel iron oxide was coated on reduced graphene
oxide substrate. Inappropriate NiFe2O4 planes (too high or too low) could influence the most
favorable position of electron conduction and ion transfer which consecutively affected the
capacitive performance. Composite had achieved 4 times more weight capacitance as compared
to pristine nickel iron oxide. It also showed excellent rate ability and cyclic stability. They
analyzed the surface charge storage mechanism and also concluded that their work could give the
novel ways to produce supercapacitor electrodes.

Juliet et al. [116] prepared rGO/nickel cobalt oxide@zinc cobalt oxide ternary
composite material using a simple hydrothermal process. They investigated the influence of rGO
concentration on electrochemical properties of composite. It had been observed that specific
capacitance of the material increased as the concentration of rGO increased upto 50 milligrams.
On further addition of rGO the value was found to be decreased. The composite with 50 mg
concentration of rGO showed maximum specific capacity of 1197 Cg –1 at a current density of 1
Ag–1. They also observed that by inclusion of 50 mg rGO in nickel cobalt oxide@zinc cobalt
oxide ternary composite material, the supercapacitor device revealed a highest energy density of
62 Whkg–1. The applied potential was enhanced ahead of the water decomposition range. The
rGO/nickel cobalt oxide@zinc cobalt oxide ternary composite asymmetric device reached the
maximum energy density of 71 Whkg–1 and the analogous power density is 0.98 kWkg–1 .
 1.2.3 Synthesis of CNTs Supported Transition Metal Oxides Nanocomposites for
Supercapacitor

Roy et al. [117] synthesized NiO/CNTs composite and studied its electrochemical
behavior. The composite showed interconnected structure providing plenty of pores and high
surface area as demonstrated by XRD, FESEM, TEM and BET technique. The prepared
composite had a specific capacitance of 878.19 Fg −1 at a scan rate of 2 mVs−1 . It also offered
good cyclic stability. The composite material (positive electrode) and activated carbon (negative
electrode) in 1 M sodium sulphate electrolyte solution were utilized to fabricate asymmetric
supercapacitor. Specific capacitance of as prepared device was 197.7 Fg −1 at scan rate 2 mVs−1. It
showed specific energy and specific power 85.7 Wh kg −1 and 11.2 kW kg−1 respectively. NiO-
CNTs composite also displayed outstanding catalytic ability for oxygen evolution reaction.

Ranjith el al. [118] synthesized zinc oxide / carbon nanotubes composites by chemical
refluxing method. The SEM results revealed the successful fabrication of ZnO nanorods on tube
like carbon nanotubes. Zinc oxide nanorods embedded erected and corresponding on the base
across the carbon nanotubes plane. XRD showed that crystalline zinc oxide nanorods were
heavily encumbered on the surface of carbon nanotubes forming a nanocomposite. Raman
spectroscopy exhibited the decrement in intensity of D and G bands because the loading of zinc
oxide nanorods. CV revealed EDLC behavior of zinc oxide nanorods /carbon nanotubes. Zinc
oxide nanorods / carbon nanotubes revealed a high specific capacitance of 189 Fg -1 at 1 mVs-1.
The cyclic stability of 96% was retained for 1000 cycles. Zinc oxide nanorods /carbon nanotubes
composites also showed a high power density of 2250 Wkg-1.

Bebi et al. [119] delicately developed a coaxial fiber-shaped asymmetric supercapacitor

composed from manganese oxide / carbon nanotubes web paper (cathode) connected with Iron
oxide/carbon fiber (anode ) at a high operating voltage of 2.2 V. The synthesized device showed
a high volumetric energy density of 0.43 mWh cm −3 at a power density of 0.02 W cm−3.
Furthermore, it demonstrated good capability, good cyclic stability, and large volumetric
capacitance of 0.67 F cm−3 with extraordinary flexibility. The capable device exemplified its
prospective for portable and wearable energy storage devices.
 1.2.4 Synthesis of CNTs-rGO Supported Transition Metal Oxides Nanocomposites
for Supercapacitors

Chen et al. [120] successfully synthesized rGO/CNTs/MnO2 nanocomposite by using

EPD, CVD and ECD at same time. These methods were employed to successfully combine the
mechanically stable three dimensional carbon foams, higher surface area of two dimensional
graphene, rapid charge transfer ability of one dimensional carbon nanotubes and greater pseudo
capacitance of MnO2. CV results revealed that CF-rGO/CNTs/MnO2 showed greater capacitance
(332.5 Fg-1 at 0.5 Ag-1 ). It showed remarkable stability as higher as 89.2 percent even after
10000 cycles at 5 Ag-1. Asymmetric supercapacitor was also made by using
CF-rGO/CNTs/MnO2 as +ive electrode and activated carbon as –ive electrode. It was operated at
larger potential window from 0-1.8V. A good energy density of 41.6 Whkg -1 was observed at
power density 513.7Wkg-1. These exceptional CV properties of
CF-rGO/CNTs/MnO2 made him potential candidate to replace conventional energy storage
devices.

Yanyan et al. [121] synthesized VO2(B)/CNTs/rGO by using simple hydrothermal

method. Nano ribbon Vanadium oxide covered the carbon nanotubes and graphene to create
hierarchical porous structure. Owing to their porosity, synergetic effects and electron affinity
nanocomposite showed improved electrochemical properties. It showed capacitance of 649.1 Fg -1
at current density 0.5 Ag-1. The maximum energy density calculated was 32.5 Whkg -1. It also
showed good retention stability of 81.6 present even after 10000 cycles. This study revealed that
VO2(B)/CNTs/rGO may be used as potential material for electrode.

Ramesha et al. [122] prepared hybrid composite of cellulose

fiber/MWCNTs/rGO/Co3O4/SnO2 by using hydrothermal process. XRD, SEM, TEM, FTIR,
EDX were employed to characterized its crystallinity, morphology, functional group and
constituent elemental percentage. CV analysis of the composite showed good capacitance of 215
Fg-1 at 0.2 Ag-1 current density. Moreover, it retained 88 percent of original capacitance after
1000 cycles which depicted its good retention ability and stability. Cellulose
fiber/MWCNTs/rGO/Co3O4/SnO2 is thermally more stable than cellulose fiber/mutiwalled
carbon nanotubes and cellulose fiber/ mutiwalled carbon nanotubes /reduced graphene
composites.
 Refrences of mine:
1. Enhanced Photocatalytic Performance of NiO-Decorated ZnO Nanowhiskers for Methylene Blue
Degradation (Abdul Rahman)
2. Phytogenic Synthesis and Characterization of NiO-ZnO Nanocomposite for the Photodegradation
of Brilliant Green and 4-Nitrophenol (Sirajul Haq)
3. Synthesis, characterization and photocatalytic activity of magnetically separable hexagonal
Ni/ZnO nanostructure (Samarpita Senapati)
4. Recent Developments in Chitosan-Based Adsorbents for the Removal of Pollutants from
Aqueous Environments (Daniele C. da Silva Alves)
5. Chitosan-based nanocomposite films incorporated with NiO nanoparticles: Physicochemical,
photocatalytic and antimicrobial properties (Sina Ardebilchi Marand)
6. Facile synthesis and characterization of chitosan/zinc oxide nanocomposite for enhanced
antibacterial and photocatalytic activity (Gunasekaran Madhan)
7. Bi-functional NiO-ZnO nanocomposite: Synthesis, characterization, antibacterial and photo
assisted degradation study (Debashri Paul)
8. Enhanced bactericidal performance of nickel oxide-zinc oxide nanocomposites synthesized by
facile chemical co-precipitation method (S. Thambidurai )
9. Bio-waste eggshell membrane assisted synthesis of NiO/ZnO nanocomposite and its
characterization: Evaluation of antibacterial and antifungal activity (S. Prashanna Suvaitha)
10. Chitosan/zinc oxide-polyvinylpyrrolidone (CS/ZnO-PVP) nanocomposite for better thermal and
antibacterial activity (M. Karpuraranjith)
11. Eco-biocompatibility of chitosan coated biosynthesized copper oxide nanocomposite for
enhanced industrial (Azo) dye removal from aqueous solution and antibacterial properties
(Selvam Sathiyavimal)
12. Facile synthesis of mesoporous NiCo2O4 fibers with enhanced photocatalytic performance for
the degradation of methyl red under visible light irradiation [Yuchi Wan]
13. RGO-MoS2 Supported NiCo2O4 Catalyst toward Solar Water Splitting and Dye Degradation
[Sankalpita Chakrabarty]
14. Synthesis and characterization of nickel oxide/cobalt oxide nanocomposite for effective
degradation of methylene blue and their comparative electrochemical study as electrode
material for supercapacitor application [Sapna Yadav ]
15. Evaluation of Ni-Doped Tricobalt Tetroxide with Reduced Graphene Oxide: Structural,
Photocatalysis, and Antibacterial Response [ João Otávio Donizette Malafatti]
16. Synthesis and characterization of antibacterial activities nickel doped cobalt oxide nano
particles [M. MAYAKANNAN]
17. Surface antibacterial properties and mechanism of NiCo2O4 against E. Coli [Jiahui Sun]