GRAPHITE CARBON NITRATE WITH COPPER OXIDE

FOR SUPERCAPACITOR AND PHOTOCATALYTIC

APPLICATIONS

A THESIS

Submitted by

S. GUGAN

In partial fulfilment for the award of the degree of

MASTER OF SCIENCE

IN

PHYSICS

Guided by

Dr. PRADEEP REDDY VANGA

Assistant Professor

DEPARTMENT OF PHYSICS

SCHOOL OF SCIENCE AND HUMANITIES

MAY 2022
 BONAFIDE CERTIFICATE

Certified that this report “GRAPHITE CARBON NITRATE WITH COPPER

OXIDE FOR PHOTOCATALYTIC AND SUPERCAPACITOR
APPLICATION” is the bonafide work of S. GUGAN (20PHPH0014) who carried
out the work under my supervision. Certified further that to the best of my knowledge
the work reported herein does not form part of any other thesis or dissertation on the
basis of which a degree or award was conferred on an earlier occasion on this or any
other candidate.

Signature of the supervisor Signature of the HOD

Dr. Pradeep Reddy Vanga Dr.D.Senthil kumar
Assistant professor Head and associate professor
Department of physics Department of physics
Veltech Veltech
Chennai-600 062 Chennai-600 062
 CERTIFICATE OF EVALUATION

PROGRAM : Master of Science

BRANCH : Physics

SEMESTER : IV

Name of the Student S. GUGAN

Title of the Project
Name of the Guide
Graphite carbon nitrate with copper oxide for
photocatalytic and supercapacitor application
Dr. Pradeep Reddy Vanga
Assistant professor
Department of physics
Veltech
Chennai-600 062

The report of the project work submitted by the above student in partial fulfillment
for the award of Master of Science in physics of Vel Tech Rangarajan Dr.
Sagunthala R & D Institute of Science and Technology for the Viva – voce
examination held on 23-05-2022 has been evaluated and confirmed to the report
of work done by the above student.

INTERNAL EXAMINER EXTERNAL EXAMINER

Name : Name :
Designation : Desination :
Affilation :
 ABSTRACT

Graphite carbon nitride (g-C3N4) is considered as an intrinsically nitrogen rich system

with lamellar structure. It’s the most stable allotrope of carbon nitride at ambient

atmosphere. But it also has rich surface properties that are attractive for many

applications including supercapacitor and photocatalysis. So we have decided that to

perforn synthesis and characterization of graphite carbon nitrate with copper oxide for

photocatalytic and supercapacitor application. And X-Ray diffraction was done to

know the crystal structure and size of the synthesized material and then UV vis-

spectra was done to determine the band gap of the material we have synthesized.
 ACKNOWLEDGEMENT

The author GUGAN S truthfully acknowledge Dr. PRADEEP REDDY VANGA, for

his great valuable work-full support and help.

 TABLE OF CONTENTS

CHAPTER TITLE PAGE NO

NO
I ABSTRACT

II LIST OF FIGURES

III ACKNOWLEDGMENTS

1 INTRODUCTION

1.1 PHOTOCATALYSIS

1.2 SUPERCAPACITOR

2 LITERATURE REVIEW
3 EXPERIMENTAL
3.1 PREPARATION OF g-C3N4

3.2 PREPARATION OF CuO

3.3 PREPARATION OF CuO/g-C3N4

3 CHARACTERIZATION

4 RESULTS AND ANALYSIS

5 CONCLUSION

6 REFRENCES
 LIST OF FIGURES

Figure.1.1) Chemical blowing gas can blow and separate the g-C3N4 layers to form
sheet like Morphology and meantime CuO particles are formed on these g-C3N4
sheets.

Figure 1.2) CuO/g-C3N4 with enhanced photocatalytic degradation of salicylic acid.

Figure. 1.3) Supercapacitor.

Figure 1.4) Types of supercapacitor.

Figure 3.1) preparation of CuO.

Figure 3.2) preparation of CuO/g-C3N4.

Figure 3.3) preparation of CuO/g-C3N4 at 1.0.5 ratio.

Figure 3.4) preparation of CuO/g-C3N4 at 1:0.25 ratio.

Figure 4.1) Brags law.

Figure 4.2) XRD instrumentation.

Figure 4.3) peak width.

Figure 4.4) effect of lattice strain.

Figure 4.5) formation of cones

Figure 4.6) XRD patterns of CuO.

Figure 4.7) XRD patterns of CuO/g-C3N4.

Figure 4.8) W-H nalysis of CuO/g-C3N4.

 I. Introduction

In recent years, graphitic carbon nitride (g-C3N4) has been widely studied, and has

proven to be a promising metal-free visible-light photocatalyst, owing to its low cost,

narrow band gap, and higher thermal stability. Nonetheless, the photocatalytic activity

of bulk g-C3N4 is far from satisfaction, because of its fast charge-carrier

recombination . To overcome this problem, many efforts have been undertaken by

doping foreign ions , increasing of the surface areas, and coupling with other

semiconductors.

In photocatalysis, semiconductor nanosheet has been considered as an interesting

structure for its large surface area that offers more active sites and ultrathin thickness

that decreases the transfer route of photogenerated carriers. As yet, “top–down”

strategies to prepare g-C3N4 sheets, include ultrasonic exfoliation , sulfuric acid

intercalation , alkali-treating , and thermal oxidation route. However, these methods

result in low product yields , multiple-step operation or structural defects in g-C3N4

framework. Recently, a facial “bottom-top” route has been used to synthesize ultrathin

g-C3N4 sheets, using chemical blowing approach.

As is well known, coupling of g-C3N4 with a narrow band gap semiconductor is a

valid method for increasing the separation of charge-carrier capability. Many

metaloxides have been intensively studied as photocatalysts or energy storage

Fig 1.1) Chemical blowing gas can blow and separate the g-C3N4 layers to form
sheet like Morphology and meantime CuO particles are formed on these g-C3N4
sheets

such as TiO2, MnO2, Co3O4, NiO . Among these materials, copper oxide is an

intriguing material for its narrow band-gap, high visible light adsorption coefficient,

and high natural abundance . CuO/g-C3N4 heterojunction catalyst can promote photo-

induced charge-carrier separation, to produce high catalytic efficiency . However, to

the best of my knowledge, all these catalysts have been were prepared by either

multiple-step, time-consuming procedures or by using expensive precursors. In this

reported work, CuO particles supported on graphitic carbon nitride (g-C 3N4)

nanosheeets was prepared by chemical blowing route. The g-C 3N4 nanosheet material

was obtained by thermal condensation of melamine and copper nitrate in thepresence

of ammonium nitrate. The photocatalytic performance of this material was evaluated

through the degradation of salicylic acid (SAL) under visible-light irradiation. It is

expected that the methodology applied in this work will shed new light on the

preparation of various types of g-C3N4 –based efficient photocatalysts.

(Researchgate.com)

What is g-C3N4?

G-C3N4 is a polymeric material composed of tris-triazine-based patterns

with the C/N ratio=3/4 and small amount of H. Since it exhibits a stacked structure, g-
C3N4 is often considered as sp2-hybridized nitrogen-substituted graphene.

Graphite carbon nitride (g-C3N4) is well known as one of the most

promising materials for photocatalytic activities, such as CO2 reduction and water
splitting, and environmental remediation through the removal of organic pollutants.
On the other hand, carbon nitride also pose outstanding properties and extensive
application forecasts in the aspect of field emission properties. In this mini review, the
novel structure, synthesis and preparation techniques of full-bodied g-C3N4-based
composite and films were revealed. This mini review discussed contemporary
advancement in the structure, synthesis, and diverse methods used for preparing g-
C3N4 nanostructured materials. The present study gives an account of full knowledge
of the use of the exceptional structural and properties, and the preparation techniques
of graphite carbon nitride (g-C3N4) and its applications.

Graphitic carbon nitride, g-C3N4, is a polymeric material consisting of

C, N, and some impurity H, connected via tris-triazine-based patterns. Compared with
the majority of carbon materials, it has electron-rich properties, basic surface
functionalities and H-bonding motifs due to the presence of N and H atoms. It is thus
regarded as a potential candidate to complement carbon in material applications. In
this review, a brief introduction to g-C3N4 is given, the methods used for synthesizing
this material with different textural structures and surface morphologies are described,
and its physicochemical properties are referred.
 In addition, four aspects of the applications of g-C3N4 in catalysis are
discussed,as a base metal-free catalyst for NO decomposition, as a reference material
in differentiating oxygen activation sites for oxidation reactions over supported
catalysts, as a functional material to synthesize nanosized metal particles, and as a
metal-free catalyst for photocatalysis. The reasons for the use of g-C3N4 for such
applications are also given, and we expect that this paper will inspire readers to search
for further new applications for this material in catalysis and in other fields.

Polymeric graphitic carbon nitride (g-C3N4) has become the prime

center for consideration in photocatalysis research . G-C3N4 is a visible-light-
response element with band gap of 2.7 eV, and the energy location of CB and VB is at
− 1.1 and 1.6 eV via normal hydrogen electrode respectively . In addition, g-C3N4 has
the ability to resist attacks from heat, strong acid, and strong alkaline solution . G-
C3N4 has a unique ability to be simply prepared by thermally polycondensing the
cheap N-rich precursors, such as dicyanamide, cyanamide, melamine, melamine
cyanurate, and urea, and this is unlike the other metal-containing photocatalysts that
require costly metal salts for preparation . Thermal condensation, solvothermal,
chemical vapor deposition, microwave-assisted, polymerization, and hydrothermal
synthesis are examples of preparative strategies which have been commendably
applied in the preparation of carbon nitride for distinctive purposes and analysis in the
area of photocatalysis and others.

1.1 Photocatalyst

In the past few decades increasing energy demands have resulted in greater

consumption Of fossil fuels, creating environmental concerns and, in turn, greatly

invigorated efforts into research and development of alternate renewable energy

sources Photocatalysis represents a unique class of chemical transformations. It

utilizes the energy delivered by light and drives reactions that are difficult, sometimes

even impossible, to carry out in dark. When used for thermodynamically uphill

reactions such as photosynthesis, photocatalysis promises a sustainable solution to

large scale solar energy storage. Despite the longstanding interest in this process and

research efforts, existing

Fig 1.2): CuO/g-C3N4 with enhanced photocatalytic degradation of salicylic acid

photocatalysis demonstrations are limited to academic laboratory settings. Chief

among the reasons for the slow progress is the lack of suitable photocatalyst materials

for large scale applications. For the purpose of effective light absorption, charge

separation, and charge transfer, a large number of photocatalytic materials, including

conventional semiconductors and emerging photoelectronic materials such as

nanoscale plasmonic metal particles, quantum dots, and 2D materials. (Rakshita ameta

2018)

1.1.1 Photocatalytic Equaion

 MO + hν → MO (h+ + e−) Oxidative reactions due to photocatalytic effect: h+

+ H2O → H+ + •OH.

1.1.2 Types of photocatalyst

 Homogeneous Photocatalysis

When both the semiconductor and reactant are in the same phase, i.e. gas, solid, or
liquid, such photocatalytic reactions are termed as homogeneous photocatalysis.

 Heterogeneous Photocatalysis

When both the semiconductor and reactant are in different phases, such photocatalytic
reactions are classified as heterogeneous photocatalysis. (sciencedirect.com)

1.1.3 Photocatalytic Applications

Paper production: Large scale photocatalysis by micro-sized ZnO tetrapodal

particles added to pilot paper production. The most common are one-dimensional
nanostructures, such as nanorods, nanotubes, nanofibers, nanowires, but also
nanoplates, nanosheets, nanospheres, tetrapods. ZnO has a strong oxidation ability,
chemical stability, enhanced photocatalytic activity, and a large free-exciton binding
energy. Also, it is non-toxic, earth abundant, biocompatible, biodegradable,
environmentally friendly, low cost, and compatible with simple chemical synthesis.
ZnO has also restrictions to its widespread use in photocatalysis under solar radiation
as previously mentioned. Thus, several approaches have been suggested to overcome
this limitation, including nonmetal and metal doping for reducing the band gap and
improving the charge carrier separation. (Wikipedia)

Separating water into hydrogen and oxygen by photocatalytic water splitting.

Combustion of fossil fuels is causing a huge amount of air pollutants, such as nitrogen
oxides, sulfur oxides, and carbon oxides.Using sunlight as a renewable energy source
is therefore becoming increasingly interesting. In order to continue exploring
photocatalytic hydrogen production efficiency, the most prevalently investigated
titanium dioxide (TiO2), which has limited photocatalytic hydrogen production
efficiency, was further loaded with different amounts of nickel oxide (NiO). From the
results obtained, it can be cоncluded that the addition of NiO leads tо a significant
explоitation of the visible part оf the spectrum. An efficient photocatalyst in the UV
range is based on sodium tantalite (NaTaO 3) doped with lanthanum and loaded with a
cocatalyst nickel oxide. The surface of the sodium tantalite crystals is grooved with
nanosteps that are a result of doping with lanthanum (3–15 nm range, see
nanotechnology). The NiO particles which facilitate hydrogen gas evolution are
present on the edges, with the oxygen gas evolving from the grooves.

Use Of Titanium Dioxide In Self-Cleaning Glass.

Free radicals generated from TiO2 oxidize organic matter.The rough wedge-like TiO2
surface was subsequently modified with a hydrophobic monolayer of
octadecylphosphonic acid (ODP). TiO2 surfaces that were plasma etched for 10
second and subsequent surface modification with ODP showed a water contact angle
greater than 150◦. The surface was converted into a superhydrophilic surface (water
contact angle = 0◦) upon UV illumination, due to rapid decomposition of
octadecylphosphonic acid coating resulting from TiO2 photocatalysis.

1.2. Supercapacitor

The current trend of supercapcitor is to replace rechargeable batteries, offering new

method of stotage for energy based on nanotechnology. Unlike batteries,
supercapacitors can recharge within seconds and withstand virtually unlimited charge
cycles, supercapacitor have a higher energy density than conventional capacitor, but a
lower energy density than the standard batteries used in electronic products such as
IoT devices.
 Fig 1.3) Supercapacitor

Supercapacitors, recognized as a great potential device for next generation energy

storage, exhibit a variety of advantages, such asa high power density, a long cycle life
and a fast charge–discharge process. Generally, electrochemical double layer
capacitance (EDLC) and reversible Faradic reactions (pseudocapacitance) are the
energy storage mechanism of supercapacitors. To meet the requirement of electric
vehicle and renewable-energy storage application, conducting polymers (CPs) and
carbon materials have aroused considerable attention as supercapacitor electrode
materials
The supercapacitor is also known as an ultracapacitor. This capacitor is called an
ultracapacitor since it has a higher capacitance value than other regular capacitors.
The capacitors have low voltage limits. These components are the choice over the
regular type of capacitors since they feature higher power density. These components
consume less power and are absolutely safe and easy to operate. (Wikipedia)

Fig 1.4): Types of supercapacitor

The basic unit of electric capacitance is called the farad (F), named for pioneering
British chemist and physicist Michael Faraday (1791–1867). Typical capacitors used
in electronic circuits store only miniscule amounts of electricity (they're usually rated
in units called microfarads (millionths of a farad), nanofarads (billionths of a farad), or
picofarads (trillionths of a farad). In marked contrast, a typical supercapacitor can
store a charge thousands, millions, or even billions of times bigger (rated in farads).
The biggest commercial supercapacitors made by companies such as Maxwell
Technologies have capacitances rated up to several thousand farads. That still
represents only a fraction (maybe 10–20 percent) of the electrical energy you can pack
into a battery. But the big advantage of a supercapacitor is that it can store and release
energy almost instantly—much more quickly than a battery. That's because a
supercapacitor works by building up static electric charges on solids, while a battery
relies on charges being produced slowly through chemical reactions, often involving
liquids.

You often see batteries and supercapacitors compared in terms of their energy and
power. In everyday speak, these two words are used interchangeably; in science,
power is the amount of energy used or produced in a certain amount of time. Batteries
have a higher energy density (they store more energy per unit mass) but
supercapacitors have a higher power density (they can release energy more quickly).
That makes supercapacitors particularly suitable for storing and releasing large
amounts of energy relatively quickly, but batteries are still king for storing large
amounts of energy over long periods of time.

Although supercapacitors work at relatively low voltages (maybe 2–3 volts), they can
be connected in series (like batteries) to produce bigger voltages for use in more
powerful equipment.

Since supercapacitors work electrostatically, rather than through reversible chemical

reactions, they can theoretically be charged and discharged any number of times
(specification sheets for commercial supercapacitors suggest you can cycle them
perhaps a million times). They have little or no internal resistance, which means they
store and release energy without using much energy—and work at very close to 100
percent efficiency (97–98 percent is typical).

1.2.1 Types Of Supercapacitor

Supercapacitors are classified into three types:

1) Electrostatic double-layer capacitors

2) Pseudo-capacitors
3) Hybrid capacitors
  Electrostatic Double Layer Capacitors

These types of capacitor include two electrodes, a separator, and an electrolyte. The
electrolyte is the mixture that constitutes positive and negative ions dissolved in water.
The two electrodes are separated by a separator. These supercapacitors use carbon
electrodes or derivatives with much higher electrostatic double-layer capacitance. The
separation of charge in electrostatic double-layer capacitors is less than in a
conventional capacitor; it ranges from 0.3–0.8 nm.

 Pseudo Capacitors

Pseudo capacitors are also referred to as electrochemical pseudo-capacitors. These

capacitors make use of metal oxide or conducting polymer electrodes with a high
amount of electrochemical pseudocapacitance. These types of components store
electrical energy by electron charge transfer between electrode and electrolyte. This
can be done by a reduction-oxidation reaction commonly known as a redox reaction.

 Hybrid capacitors

The hybrid capacitors are developed by using the techniques of double-layer

capacitors and pseudo-capacitors. In these components, electrodes with different
characteristics are used. One electrode with the capacity to display electrostatic
capacitance, and the other electrode with electrochemical capacitance.

Examples of hybrid capacitors: the lithium-ion capacitor. (Byjus.com)

1.2.2 Specifications Of Supercapacitor

1) Supercapacitors have high capacitances up to 2 kF.

2) These capacitors store large amounts of energy.
3) Supercapacitors bridge the gap between conventional capacitors and
rechargeable batteries.
4) The charge time of a supercapacitor is 1–10 seconds.
5) These components can store electricity through either electrostatic charge
absorption/desorption.
6) Applications Of Supercapacitors
1.2.3 Supercapacitors are used in the following:

1) Electric cars
2) Wind turbines
3) Photographic flash
4) Flywheel in machines
5) MP3 players
6) Regenerative braking in the automotive industry
7) Static memories (SRAM) (byjus.com)

II. LITERATURE REVIEW

Bicheng zhu (2017) The band structures, electronic properties, optical properties and
work functions of pure and halogen (F, Cl, Br, I) doped monolayer g-C3N4 were
examined and investigated by first-principle calculations. Based on the formation
energies, the halogen atoms preferentially dope into the interstitial space enclosed by
three tri-s-triazine units. The introduction of halogen atoms decreases the band gap
from 1.18 eV to 0.64–1.14 eV. The nature of the band gap of both pure and halogen-
doped monolayer g-C3N4 is characteristic of indirect semiconductor. The F atom
contributes to the valance band while other halogen atoms participate in the
conduction band. Correspondingly, the F atom is involved in the HOMO while other
halogen atoms are located in the LUMO. The halogen doped g-C3N4 systems exhibit
enhanced optical absorption in a wide wavelength range of 200–1000 nm and reduced
work functions. This calculation work provides meaningful instructions for the design
of non-metal doped g-C3N4 photocatalyst.

Penfei xia (2016) A g-C3N4/Ag2WO4composite photocatalyst was synthesized bythe

in situ precipitation of -Ag2WO4on the surface of g-C3N4nanosheets. The g-
C3N4nanosheets acted as a support for the nucleation and growth of-Ag 2WO4and
inhibited the phase trans-formation from metastable-Ag2WO4to stable -Ag2WO4. The
introduction of -Ag2WO4enhanced the light absorption and effectively reduced the
recombination of photo induced electron–hole pairs, thereby endowing the
g-C3N4/Ag2WO4composite a superior photocatalytic activity for MO degradation.
After 150 min of illumination, the degradation rates were 42%, 95%, and 71% in the
presence of g-C3N4, g-C3N4/Ag2WO4, and _-Ag2WO4, respectively .The reactive-
species-trapping experiments revealed that h+,•O2−,and•OH were produced and
involved in the photocatalytic reaction. The proposed direct Z-scheme photocatalytic
mechanism illustrates the generation of these reactive species and the enhanced
separation of photo induced electron–hole pairs.

Jung wan (2020) Co3O4/g-C3N4 composites were successfully synthesized by

combining in-situ sedimentation and carbon-assisted methods. The electrochemical
properties of Co3O4/g-C3N4 nanocomposites as electrode materials for
supercapacitors were evaluated. The specific capacitance of the composite
nanomaterial Co3O4/g-C3N4 was 1071 F g-1 at a current density of 1 A g-1, which
was much higher than the pure Co3O4 electrodes. After 4000 cycles, the Co3O4/g-
C3N4 electrode still showed a capacitance retention of 80%. the asymmetric
supercapacitor of Co3O4/g-C3N4//AC maximum energy density is 20.4 Wh kg-1.
Comparing the specific capacitance of Co3O4 and Co3O4/g-C3N4 in a three-electrode
system, g-C3N4 was found to play an important role in improving electrochemical
performance. Compared with other Co3O4 composites, Co3O4/g-C3N4 composites
have the advantages of high specific capacitance, low internal resistance, good
stability for electrochemistry

Jing xu(2018) g-C3N4/MoS2 heterojunction are synthesized by a facile one-step

process, which exhibits highly enhanced specific capacitance (532.7 F g_1 at a current
density of 1 A g_1) and long cycle life (a reduction of capacitance of about 11.4%
after 1000 cycles) as novel electrode materials for supercapacitor. Moreover, the
enhanced electrochemical properties of g-C3N4/MoS2 heterostructure can be largely
ascribed to the synergistic
effect of g-C3N4 and MoS2.

S.vinoth(2020) synthesized a high-performance HASC was fabricated with in-situ

pyrolytic processed S-gC3N4/CoS2 nanocomposite material and bio-derived carbon.
The electrochemical performance achieved as a high specific capacity of 180 C g_1 at
1 A g_1 current density.The HASC cell delivered high energy of 26.7 Wh kg_1 and a
highpower density of 19.8 kW kg_1 in the aqueous electrolyte with a very high
electrochemical stability of 89% at the current density of 30 A g_1 over 100,000
cycles with the coulombic efficiency of 99.6%. The CoS2 nanoparticles engulfed into
S-gC3N4 provides short transport distance of the ions, strong interfacial interaction,
and improving structural stability of the prepared S-gC3N4/CoS2 electrode materials.

S.V.Prabhakar Vattikutty(2018) synthesized a C/CuO@g-C3N4 ternary hybrid via

in-situ growth using a one-step co-pyrolysis decomposition method for the first time.
The prepared C/CuO@g-C3N4 electrode shows a better specific capacitance of 247.2 F
g−1 compared with the pristine g-C3N4, while possessing good stability, with 92.1% of
the initial capacitance remaining even after 6000 cycles. Therefore, our study offers a
new perspective on enhancing electrochemical performance.

Lei shi (2015) have coupled g-C3N4 with flower-likeNi(OH)2 by using facile hydro
thermal route.Theg-C3N4/Ni(OH)2 composites exhibit a higher capacitance compared
with pure Ni(OH)2. which is due to the special structure of the composite and the good
contact between Ni(OH)2 and g-C3N4.

Soheila senati (2019) g-C3N4 nanosheet CoAl-LDH nano flower composites(GL10,

GL30 and GL50 composites) were synthesized through a convenient solvothermal
method. The synthesized CoAl-LDH has a flowerlike morphology with nano-sized
petals for the obtained product. When the nanocomposites were applied as potential
electrode materials for supercapacitor applications, GL30 outperformed the other
tested materials by exhibiting 343.3 F g−1 specific capacitance at 5 Ag−1 current
density in three-electrode system. The results demonstrated that GL30 possesses a
higher capacity.

Santosh kumar (2018) g-C3N4 nanostructures offer tunable textural, electronic and
optical properties that are amenable to tailoring for solar energy harvesting and
subsequent photocatalytic transformations for energy and environmental applications.
Diverse synthetic methods are available to prepare pure g-C3N4 nanostructures of
different dimensionality and porosity, and to integrate these within multi-functional
nanocomposites with enhanced solar spectral utilization, apparent quantum yields,
charge separation and transport, and ultimately photocatalytic activity and stability.
The sustainable production of H2 as an energy vector from water splitting is perhaps
the most promising application, although issues remain regarding the use of sacrificial
reagents and a lack of interdisciplinary efforts to improve photoreactor design.
Photocatalytic reduction of CO2 is at a more preliminary stage, with improvements in
both activity, and the ability to select specific products for either energy (e.g., CO,
CH4, methanol, and formic acid) or chemicals (e.g., >C2 olefins or alkanes) pre-
requisites to bench scale demonstrations. Wastewater treatment using g-C3N4-based
photocatalysts appears promising; however, a lack of standardization in either reactor
design or experimental protocols hampers quantitative comparisons due to issues such
as decoupling adsorption versus reaction, and photocatalysis from direct
photochemical activation of chromophores.

Shifu chen(2014) The composite photocatalyst WO3(wt.%)-g-C3N4 was fabricated

via ball milling and heat treatment methods. The coupling between g-C3N4 and WO3
may happen on the g-C3N4-{0 0 2} facets. When g-C3N4 is the major part of
composite photocatalyst (namely WO3/g-C3N4), the transfer of the photoexcited
electrons and holes is according to the Z-scheme mechanism. In the system, the
photoexcited holes in the VB of g-C3N4 and electrons in the CB of WO 3 are quickly
combined. The accumulated electrons in the CB of g-C3N4 exhibit high reducibility
to reduce the molecular oxygen to yield •O2−; and the holes in the VB of WO 3 display
high oxidizability to oxidize H2O or OH− to generate abundant active •OH radicals.
So, the WO3/g-C3N4 photocatalysts exhibit excellent photocatalytic activity.
However, when WO3 is the main part of the composite photocatalyst (namely g-
C3N4/WO3), the separation of the photogenerated electrons and holes adopts the
band–band transfer. Meanwhile, the surface of g-C3N4 is covered by WO 3 powder,
and the role of g-C3N4 is not played fully. So, the photocatalytic activity can not be
enhanced greatly for the g-C3N4/WO3 photocatalyst.
Wen guo (2018) A facile low-temperature CVD method was successfully developed
to synthesize g-C3N4 ultrathin film on the surface of NiCo 2O4 NNs. Thanks to this
novel CVD method, the thickness of as-synthesized g-C3N4 film could be definitely
thin, so g-C3N4 ultrathin film and NiCo 2O4 NNs can be brought into full play their
advantages.Plus, due to the unique features of g-C3N4 and novel coreshell
nanostructure, this g-C3N4 ultrathin film which coated on NiCo 2O4 NNs can
significantly enhance the electrochemical performance of the whole integrated
electrode obtained. Electrochemical characterizations show that the as-synthesized
NiCo2O4 NNs@g-C3N4 ultrathin film core-shell nanostructure exhibits a high areal
capacitance of 2.83 F cm-2 at a current density of 1mA cm−2 and excellent cycling
stability (15 mA cm−2 after 10,000 cycles, corresponding to 94% of the initial
capacity), as well as an outstanding rate capability (1.13 F cm-2 at 15mA cm-2). This
work fully demonstrates the functionality of g-C3N4 with ultrathin thickness and its
tremendous potential to hybrid with transition metal oxides as electrode materials for
supercapacitors. More importantly, the easy preparation of g-C3N4 ultrathin film may
pave the way for other applications such as designing new heterojunction
photocatalysts.

Soheila senati (2019) g-C3N4 nanosheet@CoAl-LDH nanoflower composites (GL10,

GL30 and GL50 composites) were synthesized through a convenient solvothermal
method. The synthesized CoAl-LDH has a flowerlike morphology with nano-sized
petals for the obtained product. When the nanocomposites were applied as potential
electrode materials for supercapacitor applications, GL30 outperformed the other
tested materials by exhibiting 343.3 F g−1 specific capacitance at 5 Ag−1 current
density in three-electrode system. The results demonstrated that GL30 possesses a
higher capacity. Electrochemical outperformance of GL30 is a consequence of a
synergic effect between g-C3N4 nanosheets and LDH structures. Furthermore, the
GL30 nanocomposite with high specific surface area hinders the agglomeration of the
individual components, and effectively improves their utilization. Furthermore, the
asymmetric supercapacitor fabricated from GL30 acted as the power supply of a red
LED working for 20 min. Therefore, this study proposes that g-C3N4 nanosheets, as a
novel and efficient carbonaceous matrix, can be employed to obtain some new
nanocomposites with noticeable. Ragone plot of energy density versus power density
for GL30 asymmetric supercapacitor, (b, c) Photograph of the GL30 asymmetric
supercapacitor lighted LED indicator. supercapacitance activity in practical
applications.

Yingxi xu (2019) The SnS2/g-C3N4 composites (SSCN-1~SSCN-4) for

supercapacitor were obtained by a simple hydrothermal route. Comparing with the
pure SnS2, the composite materials show excellent capacitance performance,
especially the SnS2/g-C3N4 composite (SSCN-2) shows a specific capacitance of 552
F g-1 at the current density of 0.5 A g-1, and the capacity retention rate is 95.8% after
15000 cycles, which can be assigned to the synergistic effect of the SnS2 and g-C3N4.
The enhanced electrochemical performance of the SnS 2/g-C3N4 composite can be
attributed to the high-quality heterostructure and the nitrogen in g-C3N4 improving
the conductivity of the composite material. Meanwhile, the g-C3N4 also acts as the
support material to avoid the accumulation of SnS2 which always induce the loss of
cycle life. The SnS2/g-C3N4 composite is proved to be one of the most promising
candidates for the future energy-storage applications.

Shiquan hong (2016) A highly e±cient visible-light-driven g-C3N4/CuO hybrid

nanocomposite is successfully fabricated via a simple liquid phase synthesis process
and applied to the degradation of RhB solution. The results of the photodegradation of
RhB indicate that the g-C3N4/CuO catalyst exhibits improved visible-light
photocatalytic activity than the individual materials. More particularly, the highest
activity is obtained over the composite photocatalyst with a molar ratio of 2:1 (g-
C3N4 to CuO). The excellent photocatalytic activity of g-C3N4/CuO nanocomposite
is mainly attributed to the formation of heterostructure between g-C3N4 and CuO,
which can be described to possible photocatalytic mechanism. The g-C3N4/CuO
nanocomposite exhibits excellent stability and recyclable property toward the
photodegradation of RhB after 5 cycling runs. So g-C3N4/CuO hybrid nanocomposite
can therefore be used as a promising photocatalyst in the applications of waste water
treatment.
Mohammed Abdullah bajiri (2019) CuO/ZnO/g-C3N4 has been successfully
fabricated via solution combustion method. The obtained heterostructure has a
mixture of two morphologies including nanoparticles and flower-like composed of
nanosheets. About 98% and 91% of MB was degraded by CuO/ZnO/g-C3N4 and the
optimized CuO/ZnO, respectively, after 45 min of visible light irradiation. The highest
MB degradation was obtained at pH 10 while the highest adsorption was obtained at
pH 3. The effect of pH on the adsorption capacity and the photodegradation efficiency
of the prepared heterostructure was studied. Furthermore, the CuO/ZnO/g-C3N4
heterostructure exhibited higher photocatalytic activity than CuO/ZnO heterostructure
towards the degradation of ammonia nitrogen.
3. EXPERIMENTAL

3.1. preparation of g-C3N4

To prepare Graphite carbon nitrate, 10 g of melamine (M.W.126.12) in

a alumina crucible was heated in a box furnace at 550 0 C for 3 hours. A yellowish
powder of g-C3N4 was obtained.

2.2. Preparation of CuO

Copper oxide was prepared by initially taking 0.4M of NaOH

dissolved into a beaker containing distilled water and put it in the magnetic stirrer
for15 mins. Then 0.3M of copper nitrate was dissolved in a beaker containing 50ml of
distilled water and stirred for 15 mins. After that sodium hydroxide solution was
added in a dropwise manner with constant stirring Into the copper nitrate solution until
the precipitate get formed. Then the solution was stirred upto 3 hours. Then obtained
solution was get filtered using filter paper. And finally dried sample was collected in
the pestor and morter for grinding. After tht the well grined powder was collected in
the centrifuge tube.
 Fig 3.1) preparation of CuO

3.3. Preparation of CuO/g-C3N4

CuO/g-C3N4 was prepared by Initially 0.2M of copper nitrate

solution was dissolved in a beaker containing 50ml distilled water and stirred for 15
mins. After 20 mins 1g of g-C3N4 was added in that solution and stirred for 15 mins.
Then sodium hydroxide solution was added dropwise with constant stirring until the
dark ash precipitate formed.After that the solution was stirred upto 3 hours.Then the
obtained solution was filtered with filter paper and dried in a room temperature for 24
hours.
 Fig 3.2) preparation of CuO/g-C3N4

3.4. Preparation of Cuo/g-C3N4 at 1:0.5 ratio

CuO/g-C3N4 was prepared by Initially 0.2M of copper nitrate

solution was dissolved in a beaker containing 50ml distilled water and stirred for 15
mins. After 20 mins 0.5 g of g-C3N4 was added in that solution and stirred for 15
mins. Then sodium hydroxide solution was added dropwise with constant stirring until
the dark ash precipitate formed.After that the solution was stirred upto 3 hours.Then
the obtained solution was filtered with filter paper and dried in a room temperature for
24 hours.
 Fig 3.3) preparation of CuO/g-C3N4 at 1:0.5 ratio

3.5. Preparation of Cuo/g-C3N4 at 1:0.25 ratio

CuO/g-C3N4 was prepared by Initially 0.2M of copper nitrate

solution was dissolved in a beaker containing 50ml distilled water and stirred for 15
mins. After 20 mins 0.25 g of g-C3N4 was added in that solution and stirred for 15
mins. Then sodium hydroxide solution was added dropwise with constant stirring until
the dark ash precipitate formed.After that the solution was stirred upto 3 hours.Then
the obtained solution was filtered with filter paper and dried in a room temperature for
24 hours.
 Fig 3.4) preparation of CuO/g-C3N4 at 1:0.25 ratio

4. CHARACTERIZATION

X-RAY DIFFRACTION

The atomic planes of a crystal cause an incident beam of X-rays to interfere with one
another as they leave the crystal. The phenomenon is called X-ray diffraction.
 Fig 4.1. Braggs law

Physicists Sir W.H. Bragg and his son Sir W.L. Bragg developed a relationship in
1913 to explain why the cleavage faces of crystals appear to reflect X-ray beams at
certain angles of incidence (theta, q). The variable d is the distance between atomic
layers in a crystal, and the variable lambda l is the wavelength of the incident X-ray
beam; n is an integer. This observation is an example of X-ray wave interference
commonly known as X-ray diffraction (XRD), and was direct evidence for the
periodic atomic structure of crystals postulated for several centuries.
 Fig 4.2 XRD instrumentation

Why XRD?
• Measure the average spacings between layers or rows of atoms
• Determine the orientation of a single crystal or grain
• Find the crystal structure of an unknown material
• Measure the size, shape and internal stress of small crystalline regions.

Applications of XRD

• XRD is a nondestructive technique

• To identify crystalline phases and orientation
• To determine structural properties: Lattice parameters (10-4Å), strain, grain size,
expitaxy, phase composition, preferred orientation (Laue) order-disorder
transformation, thermal expansion
• To measure thickness of thin films and multi-layers*
• To determine atomic arrangement
 Fig 4.3. peak width

Fig 4.4 effect of lattice strain.

X-Ray Diffraction of CuO/g-C3N4 nanocomposite which determines the crystal
structure of the material was characterized in Vellore institute of technology (VIT)
and analysed with Debye-Scherror equation . Then the Ultra Violet visible
spectroscopy (UV) to determine the band gap of the material was recorded
successfully.

Debye scherror formula

It is a method for studying the structure of finely crystalline substances using X-
ray diffraction . It was named after P. Debye and the  German physicist P. Scherrer,
who proposed this method in 1916. A narrow parallel beam of monochromatic X rays,
upon falling onto a polycrystalline sample and being reflected by the crystallites that 
make up the sample, produces a number of coaxial, that is, having one common axis, 
diffraction cones. 

The direction ofthe primary X ray serves as the axis of the cones. Their vertices lie wit
hin the object under study, and the apex angles are determined according to the Bragg-
Vul’f condition n λ = 2d sin θ (where n is a positive integer, λ is the wavelength of the 
X rays, d is the distance between the parallel planes of the points of the space crystal l
attice, and θ is the angle between the reflecting plane and the incident beam). The con
e’s apex angle is equal to four times the value of the angle of reflection ø. The intensit
y and position of the diffraction cones is recorded on a photographic film or by one of 
the ionization methods .The interaction of the diffracted beams with the photographic 
film leaves a trace inthe form of a series of diffraction lines.

The film in some cameras that are used for making roentgenograms of polycrystals is 
placed on the surface of a cylinder, the axis of which is at right angles to the incident 
X-ray beam, and the sample is placed on the cylinder’s axis.
 Fig4.5)
Formation of coaxial diffraction cones: (1) crystal, (2) monochromatic X rays incident 
on crystal, and (3) diffracted rays; 40 and 40 are apex angles of diffraction cones

D= k λ/ β hkl cosθ

D- Crystal size

Θ-peak position

k- shape factor

λ-wavelength of X-Ray

β- full width half maximum

Fig 4.6). XRD patterns of CuO
Fig 4.7) XRD patterns of CuO/g-C3N4
Fig 4.8) W-H analysis of g-C3N4/CuO
 5. RESULT AND ANALYSIS

Fig. 5a shows the ray diffraction (XRD) pattern of the synthesized CuO
nanocomposite material and the analysed results shows that the formation of CuO
with monoclinic structure. The observed XRD pattern are well coincide with the
JCPDS value of CuO. Then the crystal size parameters of CuO nanocomposite was
determined by the Debye-Scherror equation and the calculated average crystal size of
CuO nanocomposite is 0.13 nm.

Fig. 5b shows the ray diffraction (XRD) pattern of the synthesized CuO/g-C3N4
nanocomposite material and the analysed results shows that the formation of CuO
with monoclinic structure and The impurity of g-C3N4 did not produce any
secondary phase. The observed XRD pattern are well coincide with the JCPDS value
of CuO/gC3N4. Then the crystal size parameters of CuO/g-C3N4 nanocomposite was
determined by the Debye-Scherror equation and the calculated average crystal size of
CuO/g-C3N4 nanocomposite is 0.12 nm.
 6. CONCLUSION

The CuO/g-C3N4 nanocomposite was successfully synthesized using co-

precipitation method. And XRD analysis shows the formation of perfect crystal.
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