Вы находитесь на странице: 1из 68

Preparation and characterization RGO-CdS photocatalyst for

the production of hydrogen from water in the presence of sunlight


A Thesis Submitted In the Partial Fulfillment of the Requirements

For the Degree of

Masters of Technology

In

Chemical Engineering

By

NANDITA DOLOI

Under the Supervision of


Dr. A. S. K. Sinha
(Professor)

Department of Chemical Engineering & Technology

Indian Institute of Technology (Banaras Hindu University)

Varanasi-221005

Roll No: 16042024 July, 2018


UNDERTAKING FROM THE CANDIDATE

I, NANDITA DOLOI, M.Tech. student pursuing my project under the supervision of


Dr. A. S. K. Sinha (Professor), Department of Chemical Engineering & Technology, IIT
(BHU) Varanasi, give undertaking that the thesis entitled “Preparation and

characterization RGO-CdS photocatalyst for the production of


hydrogen from water in the presence of sunlight” submitted for the partial
fulfillment of the requirements for the degree of Masters of Technology (Chemical
Engineering) is the hand-work by me during the period of study.

NANDITA DOLOI

Varanasi Roll No: 16042024

July, 2018 M.Tech. (Chemical Engineering)


CANDIDATE’S DECLARATION

I, Nandita Doloi, M.Tech. student pursuing my project under the supervision of Dr.
A.S.K. Sinha (Professor), Department of Chemical Engineering & Technology, IIT
(BHU) Varanasi, declare that I have faithfully acknowledged given credit to and referred
to the research workers whenever their works have been cited in the text and the body of
the thesis. I further certify that I have not willfully lifted up some other’s work,
paragraph, text, data, results, etc., reported in the journals, books, magazines, reports,
dissertations, thesis, etc., or available at websites and included them in this thesis and
cited as my own work.

NANDITA DOLOI

Varanasi Roll No: 16042024

July, 2018 M.Tech. (Chemical Engineering)


CERTIFICATE

It is certified that the work contained in the thesis entitled “Preparation and
characterization RGO-CdS photocatalyst for the production of
hydrogen from water in the presence of sunlight”, submitted by Ms. Nandita
Doloi, for the partial fulfillment of the requirements for the degree of Masters of
Technology (Chemical Engineering), has been carried out by his under my supervision
and this work has not been submitted elsewhere for any other degree.

I also certify that the statements made by the candidate in the undertaking and declaration
are correct to the best of my knowledge.

(Prof. P. K. Mishra) (Prof. A.S.K Sinha)

Head of the Department Supervisor

Varanasi

July, 2018
ACKNOWLEDGEMENTS
It is my great pleasure to express my heart full gratitude to my research supervisor, Dr. A.S.K
Sinha, Department of Chemical Engineering & Technology, IIT (BHU), Varanasi for his
invaluable guidance and constant support throughout the course. His wide knowledge, logical
way of thinking, understanding and guidance has provided a good basis for the present thesis. I
take this opportunity to salute his supporting attitude that has always led me to think and work
independently and follow them in the proper prospective.

I would like to heart fully thank my head of the department, Prof. P. K. Mishra,
Department of Chemical Engineering & Technology, IIT (BHU) Varanasi, for his
support and motivation by providing necessary facilities throughout my research work. I
also take the opportunity to thank all the teaching staff of the Department of Chemical
Engineering & Technology, IIT (BHU) Varanasi, for their benign nature and support.

I would like to deliver my humble thanks to superior research scholars, Mr. Arvind
Singh, Mr. Zahoor Alam, Mr. Tarun kumar Dixit ,Mr. Rajiv Ranjan and Ms. Shreya
Srivastav for their outstanding support and encouragement which made me proactive and
energized my working capability. I would never fail to mention honest thanks to lab
technicians, Mr. Bhubaneswar Sharma, Mr. Arjun, Mr. Umesh and Mr. Sailendra
Upadhyay and Mr Nayan Pandey who supported me throughout my research by
providing necessary belongings and apparatus.

I sincerely thank my labmate Mr. Rohan Bajpai for his valuable support, love and care
during my good or bad, and seven of my very good friends Akash Rai, Pankaj Mahara,
Abhinit Tiwari, Anubha Joshi for their remarkable technical support which helped me in
every go through out my research.

Last but not the least, I bestow my deep love to my family who motivated me to take up
M.tech, Chemical engineering course in an esteemed institute like IIT (BHU) Varanasi
and supported me throughout the span with utmost love and care.

NANDITA DOLOI

Varanasi Roll No: 16042024

July, 2018 M.Tech. (Chemical Engineering)


ABSTRACT

Cadmium sulfide photocatalysts for H2 production from water using visible light were prepared
by different techniques, i.e., liquid-liquid, gas-liquid, and solid-liquid reactions. The crystallite
size and distribution, band gap, and stoichiometric composition of cadmium sulfide and
consequently the activity were affected by the preparation technique. RGO supported CdS
photocatalysts has been prepared by a two steps method, i.e. impregnation of RGO with CdS
followed by high temperature reaction with H2S gas. The activity of cadmium sulfide showed a
strong correlation with its semiconducting (n- or p-type) behavior. Cadmium sulfide that was
prepared by gas-solid reaction had excess interstitial cadmium ions in the lattice, which had been
attributed to its n-type semiconductor behavior and superior activity. The n-type behavior of
cadmium sulfide has been correlated to its stoichiometry. Detailed microstructure studies were
carried out using FTIR, PL, DRS, XRD, TEM, EDAX, XPS, EIS and MS. A much greater
chemical interaction at the interface of CdS and RGO in the reported catalyst. It has been
concluded that the high temperature reaction with H2S has imparted n-type semi conductivity to
CdS which with p-type RGO and synergy of chemical interaction at the interface has resulted
into formation of p-n heterojunction. The formation of heterojunction and high electron mobility
of RGO has given a superior activity due to an efficient charge separation to the catalyst
prepared by the technique. The improved photocatalyst performance of CdS/RGO was attributed
to enhancement of the connection between CdS and RGO, which accelerates the effect of the
separation of photoinduced electrons and holes by transferring the photoinduced electron to
RGO.
CONTENTS
Certificates

Acknowledgement

CHAPTER 1: INTRODUCTION

1.1General- solar energy, solar energy conversion


1.2 Hydrogen production technique
1.2.1 electrolysis of water
1.2.2 by processing carbonaceous matter
1.3Present scenario for hydrogen production utilizing solar energy
1.3.1 Hydrogen as an energy carrier
1.3.2 photobiological system
1.3.3 photoelectrochemical system
1.4Mechanism
1.4.1 role of Na2 S
1.4.2 role of Na2SO3
1.4.3 effect of temp

CHAPTER 2: LITERATURE REVIEW

2.1 Catalysis and photocatalysis


2.1.1 basic principle of photocatalysis

2.2Hydrogen production by photocatalytic water splitting


2.3Metal oxide photocatalyst for water splitting
2.4RGO/CdS based photocatalyst-
2.4.1 Two phase method
2.4.2 precipitation method
2.4.3 sol gel method
2.4.4 hydrothermal/solvothermal method.
2.5Objective of present work

CHAPTER 3: EXPERIMENTAL
3.1 preparation of photocatalysts
3.2 characterization of catalyst
3.2.1 XRD
3.2.2 FTIR
3.2.3 DRS
3.2.4 PL
3.2.5 TEM
3.2.6 XPS
3.2.7 EIS

CHAPTER 4: RESULT AND DISCUSSION


4.1 Photocatalytic activity
4.2 FTIR studies
4.3 XRD studies
4.4 TEM studies
4.5 EDAX studies
4.6 Diffuse reflectance studies
4.7 Photoluminescence studies
4.8 XPS studies
4.9 EIS studies
4.10 Mott Schottky studies

CHAPTER 5: CONCLUSION

REFERENCES
List of Figures
Fig. 1.1 Schematic diagram of solar energy balance
Fig. 1.2 Electrolysis of water
Fig. 1.3 Schematic diagram of PEM Electrolysis
Fig. 1.4 Flow diagram of steam reforming of hydrocarbon
Fig. 1.5 Schematic flowchart of partial oxidation of hydrocarbons
Fig. 1.6 Flow diagram of autothermal reforming process
Fig. 2.1 Basic principle of Photocatalysis
Fig. 3.1 semi-batch reactor for photocatalyst activity measurement
Fig 4.1 Hydrogen production rate for catalyst 4,5, and 6
Fig 4.2 FTIR Comparison
Fig. 4.3 XRD results of sample 1,2,3,4,5 and 6

Fig. 4.4 TEM images of catalyst-1, catalyst-2, catalyst-3 and catalyst-4

Fig. 4.5 EDS spectra of catalyst-1, catalyst-2, catalyst-3, and catalyst-4

Fig. 4.6 Diffuse reflectance spectra of Bare CdS(catalyst-1,2, and 3) and CdS/RGO(catalyst-4,5
and6)

Fig. 4.7 Bandgap of catalyst-1,2,3,4,5 and 6

Fig. 4.8 Photoluminescence spectra of catalyst-1,2,3 and 4,5 and 6

Fig. 4.9The C 1s XPS spectra of catalyst-4(N1C), catalyst-5(N2C) and catalyst-6(N3C)

Fig. 4.10 The Cd 3d XPS spectra of catalyst-4 (N1 Cd), catalyst-5 (N2 Cd) and catalyst-6 (N3
Cd)

Fig. 4.11 The S 2p XPS spectra of various catalysts-4 (N1S), catalyst-5 (N2S) and catalyst-6
(N3S)

Fig. 4.12 Nyquist plots recorded for various catalysts in electrolyte having sulphide and
sulphite at room temperature
List of Tables
Chapter: 1
INTRODUCTION
1.1 Solar Energy

Non-conventional energy sources that can be effectively utilized involve biomass, wind energy,
tidal energy, ocean currents, nuclear energy, and solar energy. Among the various non-
conventional energy sources, solar energy is abundant, cheap, and clean and thus represents a
potentially feasible non-conventional source. Essentially 100% of the energy that fuels the earth
comes from the sun. To maintain a constant global average temperature, all of the sun’s
radiation that enters Earth’s atmosphere must eventually be sent back to space. This is achieved
through Earth’s energy balance. Figure A depicts how the energy from the sun is absorbed,
reflected, and emitted by the earth.

Fig.1.1 Schematic diagram of solar energy balance

The total solar energy falling on earth, approximately 1.78 × 1017 watt, consists of radiations of
wavelengths primarily between 400-800 nm. About two third of the solar energy reaching the
earth surface is used to heat its surface and about one third is used to maintain the hydrological
cycle. Only a small fraction, (~ 0.1%) is chemically fixed through the process of photosynthesis
and out of this, only 0.5% is consumed as food. Therefore, the sun has more than sufficient
energy to meet the energy demand of the civilized world.

Solar Energy Conversion

Solar energy can be converted to useful forms of energy by two distinct means. One by using the
infrared part (49%) of the solar spectrum (Solar thermal conversion devices) and the other by
utilizing the UV/visible region (51%) of solar spectrum (solar-photon conversion devices). In the
first category, the incident radiation is r using into thermal energy which is subsequently used for
water heating, refrigeration, driving mechanical pumps, thermoelectric generators etc. The
second category includes, the solar energy conversion through photo biological, photochemical,
photovoltaic, and photo-electrochemical methods. This technique utilizes Solar Photovoltaic
(PV) devices or solar cells that convert the sun’s energy into electricity. Photovoltaic devices
produce electricity right from the sunlight through an electronic process that naturally occurs in
particular material types known as semiconductors. Electrons contained in these materials are let
loose by solar rays are stimulated to travel via an electronic circuit, sending power to the grid or
directly powering electrical devices. This form of energy can be used to power solar watches,
calculators or traffic signals. They are often used in locations that are not connected to electricity
grid. The production of hydrogen from water using one of these techniques, based on solar
photon conversion process, is a promising method of harnessing solar energy because of the
various advantages of hydrogen which make it a viable energy source.

1.2 Hydrogen production techniques


Hydrogen can be produced from a variety of feedstocks. These include fossil resources, such as
natural gas and coal, as well as renewable resources, such as biomass and water with input from
renewable energy sources (e.g. sunlight, wind, wave or hydro-power). A variety of process
technologies can be used, including chemical, biological, electrolytic, photolytic and thermo-
chemical. Several technologies are already available in the marketplace for the industrial
production of hydrogen. The first commercial technology, dating from the late 1920s, was the
electrolysis of water to produce pure hydrogen. In the 1960s, the industrial production of
hydrogen shifted slowly towards a fossil-based feedstock, which is the main source for hydrogen
production today.

Hydrogen production by commercially processes are based on: (a) Electrolysis of water, (b)
Processing of carbonaceous materials mainly natural gas or naptha.

1.2.1 Electrolysis of water

A well-known electrochemical method to produce hydrogen H2 using electricity is the water


electrolysis [44-46]. It permits the splitting of water molecule into H2 and O2. In this process, a
chemical reaction i.e.

Fig.1.2 Electrolysis of water

Water electrolysis is taking place by external electric energy in an electrochemical cell. The
reaction, however, is very endothermic thus the required energy input is provided by electricity.
Water decomposition by electrolysis consists of two half reactions that take place at two
electrodes separated by an ion-conducting electrolyte. H2 and O2 are produced at the cathode and
the anode, respectively. An ion conducting separator (diaphragm) is used to separate the two
chambers to keep the produced gases isolated from each other. The electrodes are used to apply a
voltage to water causing the water separation as seen in the following reaction:

H2O H2 + O2 (Eq. 1.1)

The following reactions take place inside the alkaline electrolysis cell:

Electrolyte: 4H2O 4H+ + 4OH– (Eq. 1.2)

Cathode: 4 H+ + 4e– 2H2 (Eq. 1.3)

Anode: 4OH– O2 + 2H2O + 4e– (Eq. 1.4)

Sum: 2H2O O2 + 2H2 (Eq. 1.5)

For the simplest case of electrolysis at 25°C and 1 atm, the potentials of the electrode and
cathode can be written as:

Ec = -0.828 – 0.059 log 𝑎𝑂𝐻− (Eq. 1.6)

Ea = 0.401 – 0.059 log 𝑎𝑂𝐻− (Eq. 1.7)

Where, ‘a’ is the activity. The lowest voltage needed to drive the water splitting reaction is Ea -
Ec = 1.229V (this is called the reversible or equilibrium voltage). Many types of electrolyzers
exist today. In general, Potassium hydroxide (KOH) is used as electrolyte in solution (alkaline
solution). Operating temperature is at about 80°C. Today this technology gives a very low
contribution to the worldwide hydrogen production, because of the high cost of electricity and
the high but not complete conversion efficiency [47].

In electrolysers, because of the low conductivity of water, some chemical solutions must be
added to increase the solution conductivity. Strong acid and strong alkali are applied as an
electrolyte. Due to the severe corrosion of acid, instead of strong acid, the alkaline solutions are
the primary electrolytes for water electrolysis. As an alternative to alkaline electrolysis, PEM( or
polymer electrolyte membrane) electrolysis technology uses solid polymeric ion exchange
materials in the electrolyser (48,49) PEM electrolysers require no liquid electrolyte, which
simplifies the design significantly. The electrolyte is an acidic polymer membrane. PEM
electrolysers can potentially be designed for operating pressures up to several hundred bar, and
are suited for both stationary and mobile applications. The main drawback of this technology is
the limited lifetime of the membranes. The major advantages of PEM over alkaline electrolysers
are the higher turndown ratio5, the increased safety due to the absence of KOH electrolytes, a
more compact design due to higher densities, and higher operating pressures.

Anode: H2O 1/2O2 + 2 H+ + 2e– (Eq. 1.8)

Cathode: 2H+ + 2e– H2 (Eq. 1.9)

Fig. 1.3 Schematic diagram of PEM Electrolysis

With relatively high cost, low capacity, poor efficiency and short lifetimes, the PEM
electrolysers currently available are not as mature as alkaline electrolysers. The major R&D
challenge for the future is to design and manufacture electrolyser equipment at lower costs with
higher energy efficiency. Another problem of electrolysers is the limited lifetime of the
electrolysis cells.
Similar to water electrolysis, High-temperature electrolysis is based on technology from high-
temperature fuel cells. The electrical energy needed to split water at 1000 °C is considerably less
than electrolysis at 100 °C. This means that a high-temperature electrolyser can operate at
significantly higher overall process efficiencies than regular low-temperature electrolysers. A
typical technology is the solid oxide electrolyser cell (SOEC). This electrolyser is based on the
solid oxide fuel cell (SOFC), which normally operates at 700 to 1000 °C. At these temperatures,
the electrode reactions are more reversible, and the fuel cell reaction can more easily be reversed
to an electrolysis reaction. Attempts are currently underway to develop systems in which some of
the electricity consumed by the electrolyser can be replaced with the heat available from
geothermal, solar or natural gas sources, thus reducing the consumption of electricity
significantly. Similar to the main challenges for SOFCs, the main R&D needs for SOECs relate
to materials development and thermo-mechanical stress within the functional ceramic materials.

1.2.2 By processing of carbonaceous matter

Essentially any carbonaceous matter can be processed by the following processes for hydrogen
production

1. Steam reforming
2. Partial oxidation
3. Auto thermal reforming
1. Steam reforming (SR)

Most hydrogen produced today in the world is made via steam-methane reforming, a mature
production process in which high-temperature steam (700°C–1,000°C) is used to produce
hydrogen from a methane source, such as natural gas. Main component of natural gas is methane
(CH4), which hydrocarbon has the highest H/C ratio. SR catalysts are typically nickel based
catalysts [32,33]. A block diagram of the SR process is shown in figure (1.4).
Fig:1.4 Flow diagram of steam reforming of hydrocarbon

Three steps are involved in SR of natural gas: (1) The reaction of feedstock consisting of light
hydrocarbons, usually methane (CH4), with steam at elevated temperature (700°C to 900°C) to
produce syngas- a mixture of hydrogen (H2) and carbon monoxide (CO). (2) a water-gas shift
reaction, the component of the syngas carbon mono oxide reacts with steam to produce
additional H2 and carbon dioxide (CO2). This shift reaction is used to increase the H2 content.
Finally a mixture of CO2 and H2 is sent to a gas purifier where the hydrogen is separated from
CO2 via one of many methods (pressure swing absorption, wet scrubbing or membrane
separation). Initially in this process, sulphur is removed from the hydrocarbon feed stocks
because sulphur is a poison for SR catalysts and process equipment. Steam reforming can also be
used to produce hydrogen from other fuels, such as ethanol, propane, or even gasoline.

Steam-methane reforming reaction

CH4 + H2O (+ heat) → CO + 3H2 (Eq. 1.10)


Water-gas shift reaction

CO + H2O → CO2 + H2 (+ small amount of heat) (Eq. 1.11)

2. Partial oxidation

In partial oxidation, the methane and other hydrocarbons in natural gas react with a limited
amount of oxygen (typically from air) that is not enough to completely oxidize the hydrocarbons
to carbon dioxide and water.

Fig.1.5 Schematic flowchart of partial oxidation of hydrocarbons

With less than the stoichiometric amount of oxygen available, the reaction products contain
primarily hydrogen and carbon monoxide (and nitrogen, if the reaction is carried out with air
rather than pure oxygen), and a relatively small amount of carbon dioxide and other compounds.
Subsequently, in a water-gas shift reaction, the carbon monoxide reacts with water to form
carbon dioxide and more hydrogen.

Partial oxidation is an exothermic process—it gives off heat. The process is, typically, much
faster than steam reforming and requires a smaller reactor vessel. As can be seen in chemical
reactions of partial oxidation, this process initially produces less hydrogen per unit of the input
fuel than is obtained by steam reforming of the same fuel.
Partial oxidation of methane reaction

CH4 + ½O2 → CO + 2H2 (+ heat) (Eq. 1.12)

Water-gas shift reaction

CO + H2O → CO2 + H2 (+ small amount of heat) (Eq. 1.13)

3. Auto thermal reforming

Auto thermal reforming is a combination of both steam reforming and partial oxidation. The total
reaction is exothermic, and so it releases heat. The outlet temperature from the reactor is in the
range of 950 to 1100 °C, and the gas pressure can be as high as 100 bar. Again, the CO produced
is converted to H2 through the water-gas shift reaction. The need to purify the output gases adds
significantly to plant costs and reduces the total efficiency.

Fig.1.6 Flow diagram of autothermal reforming process

A flow diagram of the basic process in auto thermal reforming is presented in Figure [1.6]. The
ATR-FPS is comprised of a reform reactor + CO shift reactor + CO selective remover. Air
equivalent to 3 times the amount of oxygen required for CO combustion after CO shift reaction
(O2/CO = 1.5) is supplied at the inlet to the CO selective remover. In addition, heat balance was
determined from changes in enthalpy arising from compositional changes, on the assumption that
in reactions after CO shift reaction, methanation reaction does not advance, and that discharge
heat loss from the system is zero.
1.3 Present scenario for hydrogen production utilizing solar energy
1.3.1 Hydrogen as an energy carrier

The physical and chemical properties of hydrogen make it ideally suited as an energy carrier. On
combustion, it burns back to water. Thus, unlike carbonaceous fuels, it does not produce harmful
CO2 and hence does not cause the ‘Green House Effect’. Furthermore, since the auto ignition
temperature of hydrogen is only 585K, the formation of harmful nitrogen oxides (NOx),
thermodynamically favored at temperatures above 1400K, is suppressed.

Hydrogen contains 2.75 times as much energy as gasoline. It has a high flame propagation speed,
wide flammability limits, and a high detonation temperature, which provide an improved engine
efficiency. Besides, hydrogen does not suffer from the problems associated with liquid fuels,
such as, cold wall quenching, inadequate vaporization, poor mixing and so forth. Since hydrogen
remains a gas at substantially low temperatures (condensation temperature, 20.13K), there is no
problem in starting an engine even at the coldest winter temperatures.

1.3.2 Photo-biological systems

In this system, either living cells themselves such as algae and photosensitive biological
molecules are used to decompose water. In photosynthetic organisms, production of hydrogen is
an essential step in the overall synthesis of carbohydrates from CO2 and water.

H2O + NADP+ 0.5 O2 + NADPH + H+ (Eq. 1.14)

NADP+ serves as a hydrogen carrier to produce carbohydrates from CO2 in the presence of ATP
as an energizer.

Some bacteria and algae contain an enzyme called hydrogenase that catalyzes the reduction of
hydrogen ions to hydrogen. Development of hydrogen producing bacteria and algae and invitro
production of hydrogen are the current areas of research. (Greenbaum and Ramus, 1983;
Matheron and Baulaige, 1983; Rosen Krans et al. 1983; Sybesma, 1984; singh et al, 1990, 1991;
Kumar and Kumar, 1991).
1.3.3 Photo-electrochemical systems

The photo electrochemical systems require the use of semiconductor materials. They can be in
the form of a single crystal, polycrystalline powders or colloidal systems. The illuminated
particulate system absorbs light and react with the substrate. In contrast to photosynthesized
reactions, it is not just a transfer of energy to the substrate. The substrate can also be adsorbed on
the semiconductor. It is implied that the semiconductor does not undergo any permanent change
excepting photo corrosion.

The basic principle of photo electrochemical cells for the photolysis of water is that, a system
having a redox potential of E°≥ + 0.82V, is thermodynamically capable of oxidizing water (O2
production) and on the other hand, with E°≤ -0.41V, is capable of reducing it (H2 formation).
This fact is based on the following reactions (pH=7) (Getoff, 1990) :

2H+ + 2e- H2 (E° = -0.41V) (Eq. 1.15)

H2O 0.5O2 + 2H+ + 2e- (E° = 0.82V) (Eq. 1.16)

H2O H2 + 0.5O2 (E° = 1.23V) (Eq. 1.17)

Hence systems with appropriate E° values can mediate the formation of H2 or O2 from water by
utilizing solar energy.

1.4 Mechanism

1.4.1 Role of Na2S

Although CdS is an efficient photocatalyst for hydrogen production from water using solar
energy, it has a major drawback. It photo corrodes in aqueous medium (Miller and heller, 1976;
Ellis et al, 1977; Mills and Williams, 1987).

CdS + hυ CdS (ℎ𝑉𝐵 + 𝑒𝐶𝐵 ) (Eq. 1.18)

+ 2+
2ℎ𝑉𝐵 + CdS S + 𝐶𝑑𝑎𝑑 (Eq. 1.19)

+
where ℎ𝑉𝐵 , 𝑒𝐶𝐵 and 𝑆𝑎𝑑 denote a hole in the valence band, an electron in the conduction band,
and a sulphur atom adsorbed on the electrode surface, respectively.
Hence from the stand point of practical application of CdS as a photocatalyst, it is desirable to
stabilize it. The possibility of stabilization of CdS by aqueous solutions of reducing agents such
as Fe(CN)4− - 2-
6 (Memming, 1978), I (Fujishima et al. 1971; Inoue et al. 1977), S (Ellis et al.

1976b, 1977; Minoura et al. 1976, 1978 Inoue et al. 1977; and Buhler et al. 1984) has been
reported.

Sulfide ions have been invariably taken as Na2S. Instead of oxidizing the semiconductor and
decomposing it, the holes in the valance band of the semiconductor are taken up by the S2- ions,
which are oxidized to sulphur or disulphide. The various steps of the reaction are as follows
(Buhler et al. 1984; Borrell et al.1992) :

− +
SC + hυ 𝑒𝐶𝐵 (SC) + ℎ𝑉𝐵 (SC) (Eq. 1.20)

+
2 ℎ𝑉𝐵 (SC) + S2- 𝑆22− (Eq. 1.21)

+
2ℎ𝑉𝐵 (SC) + S2- S (Eq. 1.22)

S + S2- 𝑆22− (Eq. 1.23)


2 𝑒𝐶𝐵 (SC) + 2H2O H2 + 2OH- (Eq. 1.24)

According to Furlong et al. (1986) HS- ions are formed as a result of the hydrolysis of Na2S and
are adsorbed on the semiconductor in the excited state. These HS- ions further break up into
hydrogen and S- radicals. Recombination of two H. leads to the liberation of hydrogen. The
various steps of the overall reaction are as follows:


C* + H𝑆𝑎𝑑𝑠 S- + H. (+C*) (Eq. 1.25)

C* + S- +H2O S° + H. (+C*) + OH- (Eq. 1.26)

H. + H. H2 (Eq. 1.27)

Here C* is considered as a steady state ‘reactive entity’ which may be identified with the photo
generated electron-hole (e – h+) pair.

Inoue at al. (1977) studied the percent dissolution suppression of CdS in eight different reducing
agents of widely differing redox potentials: 𝑆𝑂32− , S2- , S2𝑂32− , Fe(𝐶𝑁)4− - 2+ - -
6 , I , Fe , Br , and Cl .
They showed that the percentage suppression of dissolution by 𝑆𝑂32− , S2-, and S2𝑂32− were quite
high, exceeding 95%. Furthermore, they also showed that, sulphide ions in the electrolyte
solution stabilizes CdS photoanode and give rise to the shift of flat band potential of CdS
electrode by almost -60mV/log[S2-]. Minoura et al. (1976) and furlong et al. (1986) have also
reported that the dissolved cd2+ and S2- ions cause the shift of the flat band potential of CdS and
the CdS photoanode is stabilized by the diffusion of S2- ions to the electrode surface.

1.4.2 Role of Na2SO3

In an alkaline medium, S2- ions are oxidized to disulphide ions which are reduced in competition
with protons at the Pt sites (Buhler et al.1984). Additionally, the yellow disulphide acts as an
optional filter reducing the light absorption by CdS (Buhler et al. 1984). This reaction can be
prevented by adding a reducing agent such as S𝑂32− to the solution. Sulphide oxidation in the
presence of S𝑂32− ions, yields mainly thiosulphate ions:

2S2- + 2h+ 𝑆22− (Eq. 1.28)

𝑆22− + S𝑂32− S2𝑂32− + S2- (Eq. 1.29)

The built up of disulphide ions is extensively suppressed by the addition of S𝑂32− . Compared
with the yellow disulphide, the anodic reaction product, thiosulfate, is colorless, and thus does
not reduce the light absorption of CdS. Furthermore, the thiosulfate ions do not interfere
significantly with protons in the reduction process.

1.4.3 Effect of Temperature

The photocatalytic reactions are in general, not very sensitive to temperature. However,
according to Uchihara et al. (1989), the band bending of CdS particles at the working condition
is strengthened by raising the temperature leading to the efficient electron transfer. Buhler et al.
(1984) have also predicted that a slight shift in the energy levels of both the semiconductor and
electrolyte is possible on raising the temperature. Such small shifts cannot increase the rate,
hence they have attributed the increase in photo-activity with temperature to the increase in the
exchange rate of the electrolyte species at the CdS surface.
CHAPTER:2

LITERATURE REVIEW

2.1 Catalysis and photocatalysis

The act of a catalyst on a reaction is called catalysis. A catalyst is a substance that changes the
rate of reaction without being consumed in the reaction. In general, catalysts speed up a reaction
by decreasing the value of the activation energy by changing the reaction mechanism.

One classification of catalyst on the basis of phases involved in the reaction is:
homogeneous and heterogeneous. The reaction in which reactant and catalyst make same phase
is known as homogeneous catalyst. Example of homogeneous catalyst are acid-base catalysis,
enzyme catalysis. In heterogenous catalysis reactant and catalyst are in different phase.
Ostwald’s process (for making nitric acid) and Haber’s process (for production of ammonia) are
example of heterogeneous catalysis. Metals and semiconductors are used as a catalyst in these
reactions, and reaction happens at the interface between the phases.

“Photocatalysis” was first time introduced in 1930, and frequently used in the literature.
Definition of photocatalysis according to according to IUPAC (International union of pure and
applied chemistry) is “a catalytic reaction involving light absorption by a catalyst or a substrate”.
Heterogeneous photocatalysis by semiconductors is a promising field of study. The only
difference photocatalytic reaction with conventional catalysis is the mode of activation. In
photocatalysis the thermal activation is replaced by photonic activation.

2.1.1 Basic principles of photocatalysis

In general, semiconductors are used as photocatalyst in light induced redox processes in fig 2.1
Fig: 2.1 Basic principle of Photocatalysis

Electronic structure of these semiconductors is characterized by a valence band (VB) and


conduction band (CB). When a photon (hv) of energy equal or more than band gap energy (Eg)
of the semiconductor falls on it, an electron jumps from the VB to CB and leaves a hole behind.
In this excited state, either CB electrons VB holes can recombine and dissipate the energy in
form of heat, or trapped in meta-stable surface states, or react individually with electron donors
and electron acceptor present in a electrolyte at the semiconductor interface. Electron which
jumps to the conduction band can catalyze reduction of water to hydrogen. Whereas the holes are
either utilized for production of oxygen or consumed by some sacrificial agents which get
oxidized.

2.2 Hydrogen production by photocatalytic water splitting

Water splitting refers to the dissociation of water molecules to hydrogen and oxygen gases
according

H2O (l) H2 (g) + O2 (g) Go= 238 kJ/mol (Eq. 2.1)

Go= -nFEo (Eq. 2.2)

Where, n is the number of electrons transferred in the reaction, F is the Faraday constant. Since
the standard Gibbs free energy (at 298 K and 1 atm) is positive the reaction is not spontaneous at
room temperature and atmospheric pressure. Energy need to be supplied to carry out the reaction.
Minimum energy required per electron will be 1.23eV, which corresponds to energy of photon of
wavelength 1100 nm according to above reaction.

E=1240 / λ ev (Eq. 2.3)

Therefore the value of bandgap energy (Eg) of the photocatalyst should be more than 1.23 eV
(<1100) to achieve water splitting.

It means photon of wavelength less than 1100 nm will have sufficient energy to dissociate
water. However, water is transparent to UV and visible light, therefore a semiconductor catalyst
is required to mediate the process. A semiconductor having narrow bandgap where electron-hole
pairs are formed due to activation by photons of wavelength less than 1100 nm can act as a
catalyst. In addition, the conduction band should be more negative compared to reduction
potential of water for electron to carry out the reaction. An electrolyte (typically SO32 + S2-) gets
oxidized by the hole left in the valence band.

The overall water splitting reaction process can be divided into three main steps (i) charge-carrier
(electron/hole) generation following absorption of a photon, (ii) charge carrier separation and
migration of electron to conduction band, (iii) reaction between surface species and the charge
carriers. The first two steps are photo physical processes, while the final step is a chemical
process. In addition, recombination of electron and holes may also take place spontaneously.
Backward reaction in the liquid phase is also possible. Therefore, research is being carried out
for (a) enhancement in solar light harvesting by developing semiconductors (b) rapid charge
separation system and elimination of electron hole recombination. Apart from these, it is also
required to make modification with the materials’s particle morphology and the surface structure
modification to increase the reaction rate of redox couples.

2.3 Metal oxide photocatalyst for water splitting

Water splitting photocatalysis are mainly those transition metal oxide containing metal cations
with do and d10 configurations. The d0 metal oxides are from IVB group (Ti4+, Zr4+), VB group
(Nb5+, Ta5+) and VIB group (Mo6+, W6+) while the d10 metal oxides are from IIIA group (Ga3+,
In3+), IVA group (Ge4+, Sn4+) and VA group (Sb5+).
TiO2 i.e, group IVB metal oxides has been widely investigated photocatalyst for water splitting
reaction. However, TiO2 has a large band gap; and is active under ultraviolet light only. Till now,
a various approaches have been adopted by researcher to synthesis TiO2-based photocatalyst to
produce a visible light response is one of the most commonly reported approaches to improving
the visible light activity.

2.4 RGO/CdS based photocatalysts

In the following pages, we discuss recent work reported on RGO based CdS photocatalysis.
Various review articles have been published to demonstrate the roles of graphene in
photocatalytic hydrogen generation. These provide a comprehensive overview of the recent
research progress on graphene-based materials for hydrogen evolution from light-driven water
splitting. Various catalyst system has been prepared by different technique with enhanced
activity compared to bare CdS. The widely used preparation methods are in situ growth, solution
mixing hydrothermal and solvothermal method.

2.4.1 Two-phase method

Jia et al. prepared CdS-graphene samples by mixing CdS nanoparticles, graphene oxide (GO) in
ethanol, followed by sonication for 2h and stirring for 24h at room temperature. Graphene was
first synthesized by an improved Hummer’s method. Cds was separately synthesized. CdS-
graphene give the highest H2 evolution rate of 3.067ml h-1, which is about 5 times higher than
that of CdS. XRD and TEM had ruled out any new phase formation in this mixture during
preparation. Improved hydrogen production was attributed to a high degree of light harvesting
ability and effective charge transfer between these two nanomaterials through the 2D graphene
structure.

Gao et al reported GO-CdS synthesis by the two-phase method, first CdS was prepared by
mixing solution of cadmium chloride hydrate & sulphur into oleylamine and then heated at 433
K in N2 atmosphere under constant stirring. Finally CdS was dispersed in toluene with as
prepared GO. The morphology and structure of nano-composite was investigated by AFM, TEM,
XRD, FTIR and XPS, confirming the good deposition of CdS and on GO sheets. It contributed to
the effective charge transfer. GO-CdS shows much higher hydrogen evolution activity than CdS
i.e four times higher.

2.4.2 Precipitation method

Wang et al prepared GO doped Zn-CdS by precipitation method. First, GO was prepared by


following the modified Hummer method. Then, in a typical process, required amount of GO
solution was added to 50 ml of DI water with constant stirring. A predetermined amount of
Zn(CH3COO)2 and Cd(CH3COO)2 were added into an aqueous solution of GO under constant
stirring. Afterward, 50ml of aqueous Na2S solution was added dropwise with constant stirring for
1 hr. the mixed solution was washed with DI water and vacuum dried at 333K for 24h. ZnS and
CdS nanoparticles were loaded on the surface of GO nanosheets and formed sheet like
morphology. The photocatalytic hydrogen generation rate of the ZnS-CdS/GO was
approximately twice that of ZnS-CdS. Improved hydrogen production rate was attributed to high
carrier transport property of GO nanosheets that constructed transport carrier channels between
ZnS and CdS nanoparticles. It also enhanced the cooperative effects in the heterostructure.

Peng et al reported the synthesis of GO-CdS by precipitation method. First, graphene was
prepared by modified hummer method. After that typically, required amount of Cd(Ac)2. 2 H2O
and exfoliated GO were added into water to obtain 0.1 M Cd(Ac)2 solution. Then, 100ml of Na2S
solution (0.11 M) was added dropwise under stirring. The resultant mixture was continuously
stirred for 1h. after centrifugation, the product was washed with water and acetone and then dried
at 313 K. GO-CdS composite shows a maximum H2 production rate that was 1.5 times higher
than bare CdS. Enhanced activity attributed to coupling of GO with the CdS nanoparticle. It
could efficiently accept and transport electrons from the excited semiconductor, which
suppressed the charge recombination and improved the interfacial charge transfer process.

2.4.3 Sol gel method

Lv et al prepared CdS-graphene oxide. In this process, first sulphonated graphene was dissolved
in distilled water under ultrasonic. Then aqueous solution Cd-precursor (CdCl2) was added
dropwise under stirring followed by dropwise addition of aqueous solution of Na2S. this resultant
was stirred for 3 h. the resulting CdS-graphene composite was recovered by filtration, rinsed
with deionized water several times, and dried at 70 0C under vacuum. Morphology analysis
confirmed that the obtained graphene-CdS photocatalyst was nanocomposite. Higher
photocatalytic activity of this composite compare to bare CdS attributed to highly dispersion of
graphene on CdS and improved interfacial interactions between the semiconductor and co-
catalyst. Therefore, graphene efficiently accepted and transported electron from the excited CdS
suppressed charge recombination resulting improved interfacial charge transfer processes.

Jia et al studied N-graphene-CdS photocatalyst. It was prepared by adding cadmium chloride into
GO solution of ethanol. Na2S solution was added drop-by-drop into the suspension with stirring,
washed and finally heated in nitrogen atmosphere at 673 K for 2h. the hydrogen evolution rate of
CdS was significantly enhanced by loading N-doped graphene. A H2 production rate was 210
mmol.h-1 exceeding that on pure CdS (40 mmol.h-1) by more than 5 times. The enhanced H2
evolution was attributed to the predominant electrical conductivity of N-graphene, indicating that
the photoinduced electrons transport to the surface of the composite much easily to prevent there
combination between photogenerated electrons and holes. They also reported that crystallinity,
morphology, surface area (particle size) and band gap energy between N2-graphene/CdS and
CdS were not responsible for the remarkable enhancement of H2 production.

2.4.4 hydrothermal/solvothermal method

Many researchers have reported preparation of GO/RGO supported CdS by solvothermal or


hydrothermal techniques.

Hang et al also prepared rGO-CdS by solvothermal method. In a typical process, GO was


ultrasonically dispersed in the aqueous solution of DMF. The Cd precursor Cd(Ac)2.4H2O was
added by following addition of TAA as sulphur source, and kept stirring for 0.5h. This
transparent solution was transferred into a Teflon-lined autoclave at 433 K for 24h. they reported
that hexagonal phase CdS and cubical phase CdS were formed by this method. Enhanced
hydrogen production attributed to formation of connection between CdS and GO, which
exhibited a more efficient transfer of photoinduced electrons than mechanically loaded CdS.

Solvothermal method was to synthesized graphene-CdS photocatalyst by Li et al. in preparation


method, graphene oxide (GO), Cd(Ac)2 as a Cd precursor & dimethyl sulfoxide (DMSO) as a
solvent and sulphur source were used. The activity for hydrogen production increased 4.87 times
rather than CdS alone. They demonstrated that graphene enhanced activity due to its properties
as an excellent supporting material as well as collector and transporter of electron to separate
photogenerated electron-hole pairs.

2.5 Objective of present work

The present work was carried out with the following objectives.

 Developed an active RGO-CdS based photocatalyst for hydrogen production by


photocatalytic dissociation of water utilizing solar radiation.
 Compare the photocatalyst prepared by different preparation method at different
composition on the basis their activity measurement.
 Carry out detailed characterization of photocatalyst to understand microstructure of
catalyst.
 Establish a relation between preparation of catalyst, catalyst microstructure and activity.
CHAPTER: 3

EXPERIMENTAL

3.1 Preparation of photocatalysts

Earlier work carried out in our laboratory had demonstrated that CdS prepared by reacting solid
cadmium sulphate with H2S gas (solid-gas reaction) at 573 K resulted in formation of n-type
CdS. It was concluded that reaction carried out at an elevated temperature yielded the non-
stoichiometric composition of CdS having sulphur deficiency and hence showed n-type semi
conductivity. Therefore, in present study catalyst were prepared by different solvent and
preparation technique followed by solid gas reaction at 773 K.

It was reported in previous study in our laboratory (24-28) that use of ammoniacal solution of
precursor resulted into a more active catalyst compared to when an aqueous solution was used. A
higher concentration of active ingredients was observed near the external surface of the support
when ammonia was used as an impregnation solution, which is desirable for the photocatalytic
reactions, since light cannot penetrate deep inside the porous matrix of the support.

 Synthesis of graphene oxide (GO)


GO was synthesized by most widely adopted method i.e modified Hummer method as
reported in the literature (12,15,17). In this method sulphuric acid and potassium
permanganate are used as a strong oxidizing agent. Sodium nitrate is used as a substitute
for nitric acid.
KMnO4 + 3H2SO4 -------- K+ + MnO3+ + H3O+ +3HSO4- (Eq. 3.1)
MnO3+ + MnO4- --------- Mn2O7 (Eq. 3.2)
2NaNO3 + H2SO4 ------- 2HNO3 + Na2SO4 (Eq. 3.3)

We prepared it by taking, graphite flakes (2g) and sodium nitrate (2g) were well mixed.
Then 92 ml concentrated H2SO4 (98%) was carefully added dropwise into the mixture in
a 500 ml volumetric flask kept an ice bath under constant stirring (using magnetic stirrer).
This suspension was constantly stirred for 1 h on ice bath. Further, KMnO4 (12g) was
slowly added into the suspension under constant stirring. The greenish suspension was
then put in a water bath for 1 day. The temperature og water bath was maintained at 308
K. This suspension was diluted by adding 75 ml H2O with slow addition. During this
step, the temperature of the suspension rapidly rose to nearly 353 K and the colour
gradually became brown. Then additional 180 ml of H2O was added. Finally this
suspension was treated by adding 40 ml of 20% H2O2 and stirred for 30 min. It resulted
into reduction of residual permanganate and manganese dioxide into colourless soluble
manganese sulphate and the appearance of suspension turned bright yellow from brown.
The final product GO was collected by vacuum filtration subsequently washed repeatedly
with 4% HCl solution followed by distilled water. After filtration, the oxidized graphene
was dried under vacuum condition at 333K for 4 days.

 Reduction of Graphene oxide


GO (600mg) was dispersed into H2O (300 ml) and put on a sonication bath for 30 min.
the pH of this suspension was adjusted to 2 by addition of 37% HCl solution. Then
NaBH4 powder (1200 mg) was gradually added in to the suspension and sonication was
continued for 15 min. After the sonication, the top part of the brown suspension turned
transparent. Black precipitates were allowed to settle down. Concentrated HCl (30 ml)
was carefully added into this suspension to dissolved excessive NaBH4 powder.
 Catalyst preparation

Catalyst-1: It was an unsupported CdS, prepared by precipitation method. This crystal was
prepared in an aqueous solvent with a stoichiometric ratio of CdSO4 and Na2S (0.1 M). 50mg of
CdSO4 and 50mg of Na2S were mixed with 100ml of water, continuously under magnetic stirring
for 2hours under room temperature. The colour of the solution changes from white to orange.
The solvents were recovered by vacuum filtration and washed with double distilled water.

Catalyst-2: It was an unsupported CdS, prepared by precipitation method but it was prepared
on ammoniacal solvent.

This crystal was prepared in an ammoniacal solvent with a non- stoichiometric ratio (10%
Excess) of CdSO4 and Na2S (0.1 M). 50 mg of CdSO4 and 55 mg of Na2S were mixed with
changes from white to orange. The solvents were recovered by vacuum filtration and washed
with double distilled water.

Catalyst-3: It was also an unsupported CdS. This crystal was prepared by the gas-solid
reaction. Indispensable amount cadmium sulfate granules was taken into a fixed bed tubular
reactor. The granules placed in the reactor was passed with H2S gas at 4000C for 2 h to convert
Cd precursor to CdS.

Catalyst-4: This catalyst was CdS Aq(S) supported on RGO. The required amount of RGO
was added to a calculated volume of a dilute ammoniacal solution of CdS i.e (catalyst-1) to have
a weight ratio of 2:1(2 part RGO and one part CdS) in the final catalyst The resulting mass was
first dried in a water bath at 850C with stirring and subsequently in oven at 1100C for overnight.
The dried granules were then put into the fixed bed reactor and reacted with with H2S gas in a
similar manner as was done for catalyst-3.

Catalyst-5: This catalyst was CdS NH3 (10% E) supported on RGO. The required amount of
RGO was added to a calculated volume of a dilute ammoniacal solution of CdS i.e (catalyst-2) to
have a weight ratio of 2:1(2 part RGO and one part CdS) in the final catalyst The resulting mass
was first dried in a water bath at 850C with stirring and subsequently in oven at 1100C for
overnight. The dried granules were then put into the fixed bed reactor and reacted with with H2S
gas in a similar manner as was done for catalyst-3.

Catalyst-6: This catalyst was CdS gas-solid(4000C) supported on RGO. The required amount
of RGO was added to a calculated volume of a dilute ammoniacal solution of CdS i.e (catalyst-3)
to have a weight ratio of 2:1(2 part RGO and one part CdS) in the final catalyst The resulting
mass was first dried in a water bath at 850C with stirring and subsequently in oven at 1100C for
overnight. The dried granules were then put into the fixed bed reactor and reacted with withH2S
gas in a similar manner as was done for catalyst-3.

Table 3.1: Preparation method of all the three catalyst


Sr. Catalyst Composition (in Summary of
weight ratio preparation method
CdS:RGO)

1 Catalyst-1 CdS Unsupported Prepared in aqueous


solution in stoichiometric
ratio

2 Catalyst-2 CdS Unsupported Prepared in ammoniacal


solution in non-
stoichiometric ratio (10%E)

3 Catalyst-3 CdS Unsupported Prepared by gas-solid


method at 400oC.

4 Catalyst-4 RGO:CdS 2:1 Impregnation of RGO with


catalyst-1, dried and reacted
with H2S at 573K

5 Catalyst-5 RGO:CdS 2:1 Impregnation of RGO with


catalyst-2, dried and reacted
with H2S at 573K

6 Catalyst-6 RGO:CdS 2:1 Impregnation of RGO with


catalyst-3, dried and reacted
with H2S at 573K

 Experimental set-up for photocatalytic reaction:


Fig 3.1 semi-batch reactor for photocatalyst activity measurement

3.2 Characterization of catalysts


To study the behavior and structural information of catalysts it is essential to understand and
explore the relationship between their photocatalytic activities and microstructures as well as
their preparation techniques. In this present work, appropriate characterization techniques were
applied as given in the following table.

Table:3.2 Characterization techniques

Sr. Characterization technique Characteristics studied


No.

1 X-Ray diffraction (XRD) Crystal structure- Phase identification and


crystallite size

2 Fourier transform infrared Functional group analysis


spectroscopy (FTIR)

3 Diffuse reflectance spectroscopy Visible light absorption and band gap


(DRS) estimation

4 Photoluminescence spectroscopy (PL) Charges recombination study

5 Transmission electron microscope Imaging and particle size

6 X-Ray photoelectron spectroscopy Surface analysis, and depth profiling


(XPS)

7 Electrochemical impedance Study of charge transfer rate and


spectroscopy (EIS) conductivity

3.2.1 X-Ray diffraction (XRD)


X-ray diffraction (XRD) is an effective method for determining the crystal structure of
materials. It detects crystalline materials having crystal domains greater than 3-5 nm. It is used to
characterize bulk crystal structure and chemical phase composition. X-ray is a form of
electromagnetic radiation having range of wavelength from 0.01-0.7 nm which is comparable
with the spacing between lattice planes in the crystal. Spacing between atoms in metals ranges
from 0.2-0.3 nm. When an incident beam of X-rays interacts with the target atom, X-ray photons
are scattered in different directions. Scattering is elastic when there is no change in energy
between the incident photon and the scattered photon. In inelastic scattering the scattered photon
loses energy. These scattered waves may super impose and when the waves are in phase then the
interference is constructive and if out of phase then destructive interference occurs. Atoms in
crystal planes form a periodic array of coherent scatters. Diffraction from different planes of
atoms produces a diffraction pattern, which contains information about the atomic arrangement
within the crystal.

The X-ray beams incident on a crystalline solid will be diffracted by the crystallographic planes.
Bragg's law is a simple model explaining the conditions required for diffraction. It is given as

nλ = 2dhklSinӨ (Eq. 3.4)

Where n is an integer, Ө is an angle at which the constructive reaches the maximum i.e. the
diffraction angle, and λ is wavelength of the incident X-rays. For parallel planes of atoms, with a
spacing dhkl between the planes, constructive interference occurs only when Bragg's law is
satisfied. In diffractometers, the X-ray wavelength is fixed. Consequently, a family of planes
produces a diffraction peak only at a specific angle θ. The spacing between diffracting planes of
the atoms determines the peak positions. The peak intensity is determined by the atoms are in the
diffracting plane.

In present study, X-ray diffraction patterns of the prepared photo-catalysts were obtained from a
Rigaku Ultima 4 diffractometer using Cu-Kα irradiation. The calculated d-values were matched
with standard data for identification of different phases present in various catalysts. The mean
crystalline size of CdS in catalysts was calculated by the measuring the line broadening and
using the Scherrer formula.
Actually, peak broadening arises from three sources: (a) Instrumental contributions, (b) Sample
contributions, (c) strain in the sample. The instrument contribution needs to be “subtracted” from
βtotal by the following equation to get actual broadening due to sample.

β2𝑡𝑜𝑡𝑎𝑙 = β2𝑖𝑛𝑠𝑡𝑟𝑢𝑚𝑒𝑛𝑡 + β2𝑠𝑎𝑚𝑝𝑙𝑒 (Eq. 3.5)

We neglected the broadening due to strain. The instrumental broadening is obtained from the
diffraction pattern of a “standard sample” which consists of large crystallites.

3.2.2 Fourier-transform infrared spectroscopy (FTIR)

Fourier Transform Infrared Spectroscopy, also known as FTIR Analysis or FTIR Spectroscopy,
is an analytical technique used to identify organic, polymeric, and, in some cases, inorganic
materials. The FTIR analysis method uses infrared light to scan test samples and observe
chemical properties. In the present study, a Nicholet 5700 (Thermo electron) FTIR
spectrophotometer was used to record FTIR spectra in mid IR range (4000-600 cm-1). An
average of 16 spectra in diffuse reflectance mode was recorded at room temperature at the
resolution of 8cm-1. KBr was used as a reference material. About 1 mg of the sample and 100mg
of KBr were well ground with the help of pastel and mortar. Spectra were obtained for wave
numbers between 500 and 3500 cm-1.

3.2.3 Diffuse reflectance spectroscopy (DRS)

Diffuse reflectance spectroscopy (DRS) is an effective tool for spectroscopy to determine the
band gap of semiconductor photo-catalyst and the absorbance spectrum. When the powdered
sample is radiated with light, a portion is regularly reflected at a powder surface and the
remaining are either absorbed or transmitted the powder and diffused. As light of particular
wavelength is absorbed by the sample, the measurement of the diffuse reflectance light at
different wavelength yields a spectrum called diffuse reflectance spectrum.

In present study, diffuse reflectance spectroscopy of catalysts was carried out on UV-vis
spectrophotometer (Varian 100Bio) with a total reflection attachment. BaSO4 was used as a
reflectance standard. Diffuse reflectance data can be used for the Tauc plot using the Kubelka-
Munk transformation [23-28], given by:
[𝛼ℎ𝜐]1/𝑛 = A(hυ - Eg) (Eq. 3.6)

Where, h is the plank constant, υ is the frequency of the light source, α is absorption coefficient.
A is a proportional constant, Eg is the band gap, and n signifies the nature of the electron
transition. For direct transition (in case of CdS) value of n is ½, i.e. denoting an allowed direct
transition [12].

According to Eq3, once (αhυ)2 is plotted against hυ. The resulting graph yields a straight line that
can be extrapolated to the x-axis to estimate the band gap (expressed in hυ) of the material.

3.2.4 Photoluminescence spectroscopy (PL)

Photoluminescence (PL) spectroscopy is a powerful and non-destructive technique for


investigating the electronic structure, both intrinsic and extrinsic, of semiconducting and
semi‐insulating materials. In this technique, first photo excitation process is executed by
absorption of the light by a sample. An electron moves to excited state due to photo-excitation,
an electron may jump from the valence band and move to conduction band and subsequently
come back to valence band which is called recombination. During this process, excess energy is
released through emission of light. This excess energy is equal to the energy difference between
the equilibrium and excited states. This emitted light is detected by photon detector through a
spectrometer to give PL spectra. Thus the emission spectra corresponding to band-gap excitation
may yield valuable information about recombination behavior of photo-catalysts. Recombination
behavior of catalysts was studied to establish its relation with photocatalytic activity and
microstructure. In the present study, PL spectra were obtained using Fluorescence
spectrophotometer (Varian, Cary eclipse). Powder samples were placed in a sample holder.
Excitation wavelength was 200nm. Emission wavelength was from 400 to 600 nm.

3.2.5 Transmission electron microscopy (TEM)

The transmission electron microscope is a very powerful tool for material science. A high energy
beam of electrons is shone through a very thin sample, and the interactions between the electrons
and the atoms can be used to observe features such as the crystal structure and features in the
structure like dislocations and grain boundaries. Chemical analysis can also be performed. TEM
can be used to study the growth of layers, their composition and defects in semiconductors. High
resolution can be used to analyze the quality, shape, size and density of quantum wells, wires and
dots. The TEM operates on the same basic principles as the light microscope but uses electrons
instead of light. Because the wavelength of electrons is much smaller than that of light, the
optimal resolution attainable for TEM images is many orders of magnitude better than that from
a light microscope. Thus, TEMs can reveal the finest details of internal structure - in some cases
as small as individual atoms. The measurements were performed in a TecnaiG2 20 make TEM at
200kV accelerating voltage. The powder samples was homogeneously dispersed in pure acetone
by means of an ultrasonic bath and then deposited in the copper grid and the solvent was allowed
to evaporate under vacuum before analysis. Selected area electron diffraction uses diffracted
electrons to elucidate crystallographic information from selected regions of the sample. This
attachment was employed with TEM. The diffraction pattern was recorded from thin sample as
TEM from an aperture. The spacing and orientation of the diffraction spots can be interpreted in
terms of planar spacing similar to XRD.

3.2.6 X-ray photoelectron spectroscopy (XPS)

X-ray Photoelectron Spectroscopy (XPS) also known as Electron Spectroscopy for Chemical
Analysis (ESCA) is the most widely used surface analysis technique because it can be applied to
a broad range of materials and provides valuable quantitative and chemical state information
from the surface of the material being studied. XPS is typically accomplished by exciting a
samples surface with mono-energetic Al kα x-rays causing photoelectrons to be emitted from the
sample surface. An electron energy analyser is used to measure the energy of the emitted
photoelectrons. From the binding energy and intensity of a photoelectron peak, the elemental
identity, chemical state, and quantity of a detected element can be determined. Binding energy
possible by measuring the photoelectron energy. It should be noted that for multi-component
samples the intensities of the peaks are proportional to the concentration of the element within
the sampled region. XPS is a surface sensitive technique. Depth profile of a sample gives very
useful information about the sample. In case of composite and co-catalyst doping, this technique
is used to study the depth of surface interaction between support catalyst and doped catalyst. This
depth profile of the sample can be obtained by combining a sequence of ion gun etch cycles
interleaved with XPS measurement from the current surface. An ion gun is used to etch the
material for a period of time and then XPS spectra are acquired.
In this present study, XPS studies were carried out on AMICUS, Kratos Analytical using
monochromatic MgKα (1253.6eV) as X-Ray source. A vacuum of 2×10-6 kPa was maintained in
the analyzer chamber. For depth profiling, etching of surface was carried out by bombarding
argon ions on the surface for requisite period of time. Argon gas was used with an accelerating
voltage of 20kV. The resultant beam current was 12mA. In ideal case (standard specimen), the
surface of composites can be etched at about 7Ǻ per minute under these conditions. A value of
284.6 eV for the carbon C 1s peak was used as calibration for all measurements. Raw peaks were
deconvoluted accurately using XPS peaks software.

3.2.7 Electrochemical impedance spectroscopy (EIS)

Electrochemical impedance spectroscopy (EIS) is widely used to characterize the charge carrier
transfer and charge storage process. Electrochemical impedance is the response of an
electrochemical system (cell) to an applied potential. Electrical properties of materials as well
their interfaces with surface-modified electrodes can be evaluated by this technique. The
response of electrochemical systems is very nonlinear. The complex response of the system is
usually displayed in Nyquist format, with the reactance inverted (since such systems are
inherently capacitive). Where, Impedance (Z) is a determination of the circuit characteristics to
impede the flow of electrons when exposed to a periodic electrical perturbation. Rs is resistance
due to solution/ electrolyte. Rct is the resistance associated with an electrode reaction i.e. related
to generation of electron and transfer to bulk. Cd is the capacitance crated due bulk and interface.

Impedance spectroscopy was done using an Autolab (PGSTAT 204) electrochemical work
station with impedance analyser in a two-electrode configuration. For the electrode fabrication,
Toray Carbon Paper (TGP-H-60, Alfa Aesar,USA) having 1 cm2 cross-sectional area was used.
Slurry was prepared by dispersing the required quantity of photo-catalyst powder in Nafion
solution with a few drops of DMF followed by sonication in ultrasonic water bath for 1hr for
better dispersion. The slurry was uniformly spread on the carbon paper in the form of a
continuous wet film using a brush. It was then dried in an oven for 4hr at 343K. Before the
impedance scanning experiments, the remaining surface was polished to minimize Ohmic effect.
The electrolyte was a solution of sulphite and sulphide ions. The same solution was used for
photocatalytic activity measurement.
CHAPTER 4:
RESULT AND DISCUSSION
4.1 Photocatalytic activity:

The activities of all catalyst in mL of H2 produced at NTP for 4 h of irradiation is given in table
below. The reported values are average of number of repeated runs. It is order to mention that no
hydrogen production was observed either in the absence of irradiation or without photocatalyst.
Therefore, it was concluded that the hydrogen was produced by photocatalysis of water. Since
the electrolyte contained S2- and SO32-, the overall reaction is represented as given below:

H2O + S2- +SO32--------- H2 + 2OH- + S2O32- (Eq. 4.1)

Activity of photocatalyst:

12

B
10

A
8
B (H2 evolved)

C
6

0
0 1 2 3 4

hydrogen evolved

Fig 4.1 Hydrogen production rate for catalyst 4,5, and 6


It is observed from the graph that the activity of supported catalyst i.e. catalyst-6 CdS/RGO was
low as compared to catalyst -4 and 5, because solvent used and preparation technique is
different. Catalyst-4 and 5 was prepared by precipitation method but different solvents were used
(aqueous and ammoniacal) and for 6th catalyst was prepared by gas-solid method. Since these
are supported CdS-RGO catalyst therefore, the photo-generated electron-holes could be
effectively prevented from recombination. As compared to earlier work done in our laboratory,
activity of the bare CdS (hydrogen evolved per hour) is always lower than supported catalyst.

It is also observed that the activity of CdS is improved significantly by mixing with
RGO. This observation is attributed to the fact that the presence of RGO result into a better
charge separation and greater mobility of charges to the surface. From the table above shows that
the catalyst- 4, 5 and 6 had shows superior activity compared to bare CdS from earlier work done
, Since these are supported catalyst. The better activity of the catalyst was attributed to the fact
that the resulting CdS had a non-stoichiometric composition with sulphur deficiency. The
sulphur deficiency made the CdS to behave like an n-type semi conductivity. The RGO has p-
type semi conductivity. Hence formation of a p-n junction with p-type RGO is likely. It was
already discussed that creation of heterojunction is one of the most efficient way among all
available strategies to separate photogenerated charges resulting in the improvement of
photocatalytic hydrogen production.

4.2 FTIR studies:

Formation of functional groups during the catalysts preparation was analysed by FTIR as shown
in Fig 4.2& 4.3 shows the FTIR spectra of graphite, CdS and CdS/RGO. The presence of
functional groups present in the photocatalyst are shown in figure (4.2).
AQ

635

% Transmittance(a.u) AM

635

513 655
G.S

619

500 550 600 650 700 750 800 850 900


Wavenumber(cm-1)
FTIR comparison of bare CdS

1539 RGO/CdS AQ
Transmittance

1546 RGO/CdS AM
1410

RGO/CdS 400
1551

1200 1400 1600 1800 2000

-1
Wavenumber (cm )
FTIR comparison of CdS/RGO catalysts

Fig 4.2 FTIR Comparison

Another significant observation is appearance of absorption peak at 1539 cm-1 in catalyst-4


which is CdS/RGO and is prepared at aqueous solvent as describe above. The literature reports
C-S stretching frequency at 1570 cm-1.
For catalyst-5 ,two more peaks were observed i.e 1410 cm-1 and 1546 cm-1 and this catalyst is
prepared at ammoniacal solution. We assigned these peaks also to C-S stretching. The 6th
catalyst which is prepared by gas-solid method showed a peak at 1551 cm-1. We assigned this
peak also to C-S stretching.

Earlier researchers have also reported electronic interactions between C and S through π* orbital
of RGO and n-orbital of S of CdS. The FTIR study gives an indication of interaction as discussed
above in catalyst-4,5 and 6. The absorption band may also appear because of doping of sulphur
in RGO since H2S gas was passed at high temperature, such doping is likely. The presence of
these oxygen-containing groups reveals that the graphite has been oxidized.

4.3 XRD studies:


A comparison of calculated d values with the standard data shows that all the peaks observed in
catalyst-1 to 6 corresponds to cadmium sulphide with hcp structure. The characteristic peak of
the cubic phase at d=2.91 Å (310) is not observed in these samples. These catalyst were prepared
by precipitation method for two different solvents(Aqueous and ammoniacal solution) and also
by gas-solid method. Catalyst prepared by these preparation technique does not show and cubic
structure. Actually in the case of cubic structure of CdS, FCC structure was formed by both the S
and Cd ions , individually and therefore the ions of same kind contact each other. However in the
case of wurtzite structure, the position of S ions are hexagonal closed pack. Therefore the
possibility of interaction between atoms of same kind is lower in the wurtzite structure. Since the
ions of same kind do not like to contact each other, therefore, greater ionization is more favoured
with the wurtzite structure. It is also in order to mention that the cubic phase of CdS is reported
to have lower activity than hexagonal phase.

Zhang et al(6-8) has explained that wurtzite CdS has stronger ionic character and consequently
higher charge carrier mobility . Moreover, wurtzite CdS has a low carrier effective mass than
those of Zinc blend CdS, which helped in a higher charge mobility and also suppressed their
recombination rate which results into a higher photocatalytic activity of wurtzite to blend CdS.
2000
6
1600
5
Intensity

1200 4

800

400 3
2
1
0
20 30 40 50 60
2 Theta
Fig: 4.3 XRD results of sample 1,2,3,4,5 and 6

TABLE 4.5: XRD d values of AQ(S), AM(10%E) and GS (400)

Standard values of d and miller indices


Hexagonal Cubic Experimental values of
Miller Indices Hexagonal Miller Cubic d
Phase Indices Phase
hkl d(Å) hkl d(Å) AQ(S)
002 3.35 111 3.36 3.389
110 2.07 220 2.06 2.069
200 1.79 311 1.75 1.756
AM(10%E)
002 3.35 111 3.36 3.339
110 2.07 220 2.06 2.067
200 1.79 311 1.75 1.751
G.S(400)
100 3.58 - - 3.5765
101 3.16 - - 3.2245
102 2.45 - - 2.5294
102 2.45 - - 2.3947
TABLE 4.6: XRD d values of RGO/CdS

Standard values of d and miller


indices Experimental values of d
Hexagonal Cubic
Miller Hexagonal Miller Cubic
Indices Phase Indices Phase
hkl d(Å) hkl d(Å) RGO/CdS(AQ)
110 2.06 220 2.06 2.080
112 1.76 - - 1.7697
RGO/CdS(AM)
002 3.36 111 3.36 3.381
- - 200 2.91 2.955
110 2.06 220 2.06 2.067
RGO/CdS(G.S 400)

002 3.36 111 3.36 3.399


110 2.06 220 2.06 2.096
112 1.76 - - 1.749

Mean crystallite size were estimated by measuring full width at half intensity of selected peaks.
Instrumental broadening was subtracted from the total broadening and the Scherrer equation was
used. Since the highest intensity peak of CdS (002) suffered from interference from diffraction
pattern of RGO, crystallite sizes were calculated by measuring the broadening of the (110) peaks
for all the catalyst. Result is given below in tabular form. It is seen from the table that catalyst-1
prepared by precipitation method have much higher crystallite size (9 nm) as compared to other
catalyst. And also catalyst prepared in gas-solid had lesser crystallite size (4.2 nm) than other
catalyst. Thus, the crystallite size cannot be taken as sole criteria for a better activity. Crystallite
size is calculated by using Scherrer Equation:
(Eq. 4.2)

 D= mean size of the ordered (crystallite) domain, which may be smaller or equal to the grain
size.
 K= dimensionless shape factor whose value is close to unity.
 λ= X-ray wavelength
 β= line broadening at half the maximum intensity (FWHM), after subtracting the
instrumental line broadening in radians.
 θ= Braggs angle.

Unit cell parameter ‘a’ and ‘c’ of the hexagonal CdS were calculated using the formula:

(Eq. 4.3)

TABLE 4.6: XRD crystallite size and c/a ratio of AQ(S), AM(10%E) and GS(400)

Catalyst Unit cell parameters Mean


crystalline size
a(Å) c(Å) c/a (nm)

AQ(S) 4.14 6.712 1.6213 9.2

AM(10%E) 4.14 6.712 1.6213 6.5

GS(400) 4.13 6.685 1.6171 4.2


TABLE 4.7: XRD crystallite size and c/a ratio of RGO/CdS

Catalyst Unit cell parameters Mean


crystalline
a(Å) c(Å) c/a size (nm)

RGO/CdS(AQ) 4.129 6.71 1.62 7.2

RGO/CdS(AM) 4.132 6.74 1.63 8.5

RGO/CdS(400) 4.134 6.68 1.61 8

4.4 TEM (Transmission electron microscopy) Studies


We prepared 4 samples and characterized them using TEM (Transmission electron microscopy)
to measure their particle size, and the results are shown below:

Catalysts Particle size (nm)


CdS (Aq) 10
CdS (Am) 7
CdS (GS) 4
CdS/RGO 8

CdS particles are seen to be uniformly on graphene. In TEM images particles are forming
aggregates, and in these aggregate particles are of similar but minute variations in sizes. Average
particle sizes were also calculated as ~ 10nm, 7nm, 4nm and 8nm for catalyst-1, 2, 3 and 6
respectively (Table above). These particles sizes are almost equal to the crystallite sizes
calculation by XRD which were reported above. Hence, agglomeration of crystallite are
negligible in all the catalysts.
It is in order to mention that the XRD analysis had also revealed that in catalyst-1,2 (which were
bare CdS of AQ and AM) both the phases were present. As reported earlier, the cubic phase has
a lower activity and therefore, the presence of this phase could be one of the reason of observed
lower activity of catalyst-1,2 as compared to catalyst-3 and 4 which contained only hexagonal
phase of CdS. The lower activity of catalyst-1,2 with respect to catalyst-3 and 4 is attributed to
the fact that in the bare CdS we used whereas in the latter RGO, which has a better electrical
conductivity.
Figure 4.4: TEM images of catalyst-1, catalyst-2, catalyst-3 and catalyst-4

4.5 EDAX (Energy dispersive X-ray spectrometry) Studies:


EDAX studies are carried out to find out amount of different components in the composite are
present. From the EDS images and table shown below, give the information about the amount of
the different components in the composition can be obtained. All of the composites contain only
C, Cd, S and O ; this is a evidence that the as prepared composites do not contain any impurity
elements from any of the reactants.
Table 4.9: Composition of catalyst-1, catalyst-2, catalyst-3 and catalyst-6

Elements Atomic %
Catalyst-1 Catalyst-2 Catalyst-3 Catalyst-4
O 18.87 - 53.58 11.08
S 42.93 52.31 24.34 7.02
Cd 38.19 47.69 22.08 3.84
C - - - 78.06
Total 100 100 100 100

Figure 4.5: EDS spectra of catalyst-1, catalyst-2, catalyst-3, and catalyst-4


With reference to the table shown above, we can see that the presence of C in only seen in
Catalyst-6 (which is a CdS/RGO catalyst), no other catalyst had C in their composition. Atomic
% of C present in catalyst-4 is 78.06, and we concluded that, it is because that the catalyst is
prepared by gas-solid method. All the catalyst have O contained except catalyst-2 (which is a
bare CdS prepared in ammoniacal solution).

4.6 DRS (Diffuse reflectance studies) Studies:

The diffuse reflectance spectra of all the catalysts are recorded for the range of 450 to 700nm and
are shown in the figure below. It can be observed from the graph that for catalyst- there is a
sharp increase in the absorbance starting at 540 nm. Such a sharp increase in absorbance
indicates onset of band gap excitation. However, such a sharp rise is not observed in catalysts-
. These catalysts were CdS supported on RGO. It is also observed that RGO supported catalysts
have a rather continuous absorption in the range of visible lights. This effect is most pronounced
in catalyst. In earlier research works, an extended optical absorption has been also observed in
graphene based photocatalyst. Peng et al ascribed the enhanced visible light response due to
increment in surface electric charge of CdS in photocatalyst due to presence of GO/RGO.

Gao et al also attributed that graphene-CdS had a continuous absorbance in the visible range
compared with bare CdS which was because graphene could enhance the surface electrical
charge of CdS. Wang et al also reported that enhancement of absorption in visible-light due to
increment of surface electrical charge of host catalyst in presence of doped carbon material
(MWNT). Xu et al reported that ZnO/graphene composite showed higher absorbance in visible
light region due to an increase of surface electric charge of the oxides in the composite due to
graphene introduction. We also think that a greater photo response observed in catalyst- is due to
surface electric charge on the CdS due to the presence of RGO.
0.10
0.08
0.06
Absorbance 0.04
0.02
0.00 1
2
-0.02
-0.04
-0.06
3
-0.08
400 450 500 550 600
wavelength

0.76
0.75
0.74
0.73
0.72
Absorbance

0.71
4
0.70
0.69
0.68
0.67 5
0.66
0.65
0.64
0.63
0.62 6
0.61
0.60
400 450 500 550 600
Wavelength
Figure 4.6: Diffuse reflectance spectra of Bare CdS(catalyst-1,2, and 3) and
CdS/RGO(catalyst-4,5 and6)

The direct bandgap was also calculated by plotting (αhv) vs hv, where α is the absorbance as
shown in figure below. The intercept on the x-axis yielded the value of band gap. However it
was difficult to estimate the bandgap accurately owing to the continuous increase in the
absorbance in RGO supported catalyst (catalyst- 4,5,6). The calculated values of band gaps are
for the catalyst -1, 2, 3, 4, 5, and 6 respectively.
0.075
0.070
0.065 1
0.060
0.055
2
2 0.050
(hva)^ 0.045
0.040
0.035 3
0.030
0.025
0.020
0.015
0.010
0.005
0.000
2.4 2.5 2.6 2.7 2.8 2.9 3.0 3.1 3.2
hv

6.0
5.5
4
5.0 5

4.5
2
(hva)^

6
4.0
3.5
3.0
2.5
2.0
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2
hv
Figure 4.7: bandgap of catalyst-1,2,3,4,5 and 6

It is seen that incorporation of RGO has resulted into narrowing of bandgap. Narrowing of
bandgap has been also observed by many earlier workers. Pan et al reported that graphene doped
CdS showed higher photocatalytic activity. They reported that absorption edge is red shifted and
band gap is also narrowed due to substitutional doping of carbon within CdS. Wu et al reported
shifting in absorption edge in RGO doped CdS. They explained that this was due to stronger
coupling between RGO and CdS and better distribution of CdS on RGO. Lee et al have reported
that chemical bonding between semiconductor and RGO can introduce a localized state within
the bandgap of the semiconductor causing bandgap narrowing or analogously a red shift in the
absorption edge. We also concluded that the chemical interaction between CdS and RGO has
created a localized state with narrowing of bandgap .

Table 4.12: Bandgap of CdS in various catalyst

Catalyst Band gap


Catalyst-1 2.4
Catalyst-2 2.4
Catalyst-3 2.45
Catalyst-4 1.9
Catalyst-5 2
Catalyst-6 2.2

4.7 Photoluminescence studies:


Fig below shows PL spectra of catalyst-1 to 3 with the excitation wavelength of 200 nm. For the
sake of comparison PL of a physical mixture of CdS and GO/RGO (denoted as catalyst-4,5 and
6) was also recorded. Strong emission peaks at about 530 nm (corresponding to 2.4 ev) were
observed for all catalysts.

300 250 AQ
4
250 AM
200
200
5 GS
150
Intensity

Intensity

150 6

100 100
50
50
0
-50 0

-100 500 510 520 530 540 550 560


500 510 520 530 540 550 560
Wavelength
Wavelength(nm)
Fig 4.8: Photoluminescence spectra of catalyst-1,2,3 and 4,5 and 6
When, CdS is excited by light photons (Ephoton> Ebandgap) or by electron beam, principal emission
are observed at ~520 nm i.e a rather narrow, edge luminescence often know as green
luminescence. Vuylsteke et al. suggested that the green emission at 524 nm occurs through direct
recombination of CB electrons and VB holes. Therefore, the PL intensity has been reported to
correlate with the electron-hole recombination.

A comparison of the PL spectra of various catalysts show that the introduction of GO or


RGO drastically decreased the PL intensities of GO/RGO supported catalyst (catalyst-4,5 and 6)
in comparison to unsupported CdS (catalyst-1,2 and 3). In fact, many photoelectrochemical
measurements have confirmed that GO/RGO serves as electron acceptor and thus can improve
electron transfer properties. Li et al. studied the photocurrent generation capability and the
incident photon to current conversion efficiency of graphene-CdS, the improvement of efficiency
was ascribed to electronic property of graphene and morphology. Cao et al. have reported using
time resolved florescence spectroscopy that the graphene-CdS had a lower time constants due to
electron transfer from the excited CdS to the graphene. Wang et al. also showed by using
transient photo voltage technique that graphene has a high ability to accept electron. Therefore it
can be concluded that coupling GO/RGO with CdS can increase the electron acceptance and
transport rate in the composite and therefore suppress the charge recombination.

Hence, greater the recombination more intense shall be the PL intensity. In other words, if
PL intensity is less, more electron should be available to carry out the reduction of water to
hydrogen. The observation can be explained on the basis of high conductivity and the relative
position of Fermi level of GO and RGO.

It is also observed that catalyst-1,2,3 and catalyst-4,5 and 6 all had same composition still
the PL intensities were different. The lowest PL intensity observed in catalyst- implies that
recombination of electron-hole pairs were minimum. For transfer of electrons from CdS to
GO/RGO an intimate contact at the interface would be necessary.

4.8 XPS STUDIES


X-ray photoelectron spectroscopy (XPS) was carried out for surface characterization of samples.
The C1s peaks are shown in figure below. The peaks are de-convoluted using Lorenutzian
Gaussian fitting. It is clearly seen that carbon atoms are associated with different oxygen
functional groups. The 284.6 ev peak is assigned for the carbon in the non-oxygenated ring, C=C
bonds; at 286.4 ev peak is due to hydroxyl. Xu at al. have reported that the peak at 285.6 ev can
also be due to C-S bond.

60000
40000
C=C N1C C=C N2C
50000 35000

30000
Intensity

Intensity
40000
C-S
25000
C-S
30000
20000

20000 15000

10000
10000
5000
276 278 280 282 284 286 288 290 292 294 280 282 284 286 288 290
B.E(e.v) B.E(e.v)

40000

N3C
35000 C-S

30000
Intensity

C=C
25000

20000
C-OH
15000

10000

5000
280 282 284 286 288 290 292
B.E.(eV)

Fig 4.9: The C 1s XPS spectra of catalyst-4(N1C), catalyst-5(N2C) and


catalyst-6(N3C)

The figure below shows the peak of Cd 3d, where the detected major peaks for catalyst-4
RGO/CdS (Aq) , catalyst-5 which is RGO/CdS (Am 10%E) and catalyst-6 which is RGO/CdS
(G.S 400) at 405.3 eV is because of the Cd3d5/2 and Cd3d3/2 signal. Reported value in the literature
for the Cd2+ in CdS are also 405.1 is for Cdd5/2 and Cdd3/2 respectively. Since these catalysts are
supported catalyst of CdS and RGO, there is positive shift in peak position have been observed
in case of catalyst-4, 5 and 6. The shift in peak position confirms that the chemical interaction
between CdS and supported RGO. From the analysis of the shifts in binding energies it is
observed that the support and the preparation technique both cause shift in binding energies and
hence influence the chemical interaction at the interface.

34000
30000 N2 Cd
N1 Cd
32000 28000
Cd3d5/2 and Cd3d3/2
Cd3d5/2
30000 26000
Intensity

Intensity
28000 24000

22000
26000

20000
24000
18000
22000
16000
401 402 403 404 405 406 407 408 409 401 402 403 404 405 406 407 408 409 410
B.E.(eV) B.E.(eV)

24000 N3Cd
Cd3d5/2 and Cd3d3/2

22000
Intensity

20000

18000

16000

400 402 404 406 408 410


B.E.(eV)

Fig 4.10: The Cd 3d XPS spectra of catalyst-4 (N1 Cd), catalyst-5 (N2 Cd) and catalyst-6
(N3 Cd)

The use of RGO and preparation method involving gas-solid reaction has resulted shift in
binding energy.
12000

N1S 8000
11000 N2S
7500
10000 2p3/2 and 2p1/2 peaks of S
2-
7000
Intensity

9000 2-
6500

Intensity
2p3/2 and 2p1/2 peaks of S
8000 6000

7000 5500

6000 5000

5000 4500

158 159 160 161 162 163 164 165 166 167
158 160 162 164 166 168
B.E.(eV)
B.E.(eV)

7500
N3S
2-
7000 2p3/2 and 2p1/2 peaks of S

6500

6000
Intensity

5500

5000

4500

4000

159 160 161 162 163 164 165 166 167


B.E.(eV)

Figure 4.11: The S 2p XPS spectra of various catalysts-4 (N1S), catalyst-5 (N2S) and
catalyst-6 (N3S)

The S 2p spectra of CdS of catalysts-4, 5 and 6 are shown above . the peaks are carefully
deconvoluted and are also shown in the figure. Since these are RGO supported CdS catalyst
prepared by impregnation followed by gas-solid reaction.
For catalyst-4 there is only one peak of 163.1 and one peak of 162.95 eV. For catalyst-5 there is
one peak of 163.7 and another peak of 161.3 eV. For catalyst-6 there are two peak of 162.95 eV
and 161.3 eV. These all are reported peak in the literature.

These values are match with the reported values of S2- of CdS i.e. 161.3 and 162.5. These values
are close to 2p3/2 and 2p1/2 peaks of S2- of CdS as reported in the literature. Therefore these peaks
has been assigned to S2- of CdS. The binding energy become more positive for RGO supported
CdS from the earlier work done in our laboratory. Such a shift in binding energy conclusive
evidence of interfacial chemical interaction between CdS and RGO through π* orbital of RGO
and n orbital of S or CdS. Due to this chemical interaction, net charge on sulphur ion become
less as compared to that of sulphur ion in unsupported CdS and therefore a positive shift in BE
are observed.

4.9 EIS Studies


Electrochemical impedance spectroscopy (EIS) of catalysts-4, 5 and 6 were carried out. The
Nyquist analysis was performed to study charge carrier transport behaviour of catalysts. The
results are shown in Figure below. The points on the right on the diagram corresponds to high
frequency. It is known that low frequency intercept on the real axis corresponds to charge
transfer resistance. Thus, a lower arc radius implies lower charge transfer resistance. In other
words it means a better electron transfer at solid-solid interface (CdS and support) and a faster
transfer of electron to the solid-liquid interface.

It is seen that the arc radius is smallest for catalyst-5 followed by catalyst-6 and then catalyst-4.
A better charge transfer will not only enhance the rate of reaction at solid-liquid interface but
also result into a lower recombination of photogenerated electron hole pairs and both the factors
shall contribute to the better photocatalytic activity.

We have reported that the photocatalytic activity of catalysts follow the trend, i.e.,
catalyst-5 > catalyst- 4 > catalyst-6 which is in the reverse order of charge transfer resistant, i.e;
catalyst-5 < catalyst- 6 > catalyst-4.
RGO-CDS(AM)
RGO-CDS(G.S) RGO-CDS(AQ)
12000 800 20000
catalyst-6 catalyst-5 catalyst-4

10000
600 15000
8000
B (Z'')

6000 400 10000

4000
200 5000
2000

0 0 0
0 10000 20000 0 1000 0 100002000030000
A (Z') C (Z') E (Z')

Fig 4.12: Nyquist plots recorded for various catalysts in electrolyte having sulphide and
sulphite at room temperature

Therefore, it may be concluded that the catalyst prepared in the ammoniacal solvent i.e catalyst-5
promoted formation of heterojunction by chemical interaction between S and CdS and C of RGO
at the interface of RGO and CdS. This heterojunction facilitated transfer of electrons from the
conduction band of CdS to RGO. Because of this effect of the phenomena, the CdS supported on
RGO which was prepared by impregnation and followed by a gas-solid reaction showed superior
activity.
CHAPTER:5
CONCLUSION
Photocatalytic dissociation of water utilizing solar radiation is a promising technology for
hydrogen production which is considered a future source of energy carrier. CdS is an active
photocatalyst for the reaction as it has a narrow bandgap and also the conduction band edge is
suitable placed with respect to the reduction potential of water. However for high activity the
recombination rate of electrons and holes should be contained. Making composite of CdS with
metals or other semiconductor are established technique to reduce charge recombination rate.
Composite of CdS with RGO are particularly promising because it may affect charge separation
as well as owing to high electron conductivity of RGO, transfer of electron to the solid-liquid
interface becomes fast and hence the activity. However, the activity is reported to be highly
dependent on the microstructure in particular the nature of the interface between CdS and RGO.
Microstructure in turn depends on the details of preparation variables. In present work RGO
supported catalyst were prepared by various techniques, characterization and studied for activity
of the catalyst. Based on the result and discussion presented in previous chapter the following
conclusions are drawn.

The FTIR analysis showed existence of C-S bond in catalyst-4, 5 and 6 which were
RGO-CdS catalyst. Shifting in stretching vibration of Cd-S in catalyst-1,2 and 3. It shows the
chemical interaction between CdS and RGO resulting in change in the bond strength of Cd-S.

The PL spectroscopy revealed that a better charge separation took place in a catalyst-4,5
and 6 which were RGO-CdS photocatalyst. The diffuse reflectance spectroscopy showed a
continuous absorption in the range of visible light due to a greater surface electric charge on the
CdS due to the presence of RGO. Narrowing of bandgap has been also observed due to the
interfacial interaction of CdS with RGO.

The XRD result did not indicate any defect structure and it also showed that activity
may not be directly correlated with crystallite size. The TEM showed that particles in catalyst
were not agglomerated. The XRD results showed existence of only hexagonal phase of CdS in
catalyst prepared by gas-solid reaction.
The XPS analysis revealed doping of sulphur in RGO in catalyst prepared by
impregnation followed by gas-solid reaction. The analysis of S 2p peaks of XPS further revealed
that a chemical interaction has established between CdS and RGO in all the catalysts. Activity of
RGO supported CdS photocatalysts depend on the formation of a heterojunction by a chemical
interaction between S of CdS and C of RGO and the interface of the CdS and support RGO.

The EIS study confirmed that RGO supported catalyst i.e. catalyst-5 have high electron
conductivity which is prepared by RGO-CdS (Am) solution. High conductivity facilitated the
transfer of electron to the solid-liquid interface. Therefore, the restriction of charge
recombination and a greater mobility of electron imparted superior activity to the RGO
supported CdS catalyst prepared by impregnation followed by the gas-solid reaction.
REFERENCES
1. K. Zeng, D. Zhang, Recent progress in alkaline water electrolysis for hydrogen
production and applications, Progress in Energy and Combustion Science, 36(2010) 307-
326
2. S. Trasatti, Water electrolysis: , Journal of electroanalytical Chemistry, 476 (1999) 90-91.
3. A. Ursua, L.M. Gandia, P.Sanchis, Hydrogen production from water electrolysis: current
status and future trends, Proceedings of the IEEE, 100 (2012) 410-426.
4. M.A. Rosen, D.S Scott, Comparative efficiency assessments for a range of hydrogen
production processes, International journal of Hydrogen Energy, 23 (1998) 653-659.
5. M. Carmo, D.L. Fritz, J. Mergel, D. Stolten, A comprehensive review on PEM water
electrolysis, International journal of hydrogen energy, 38 (2013) 4901-4934.
6. F. Barbir, PEM electrolysis for production of hydrogen from renewable energy sources,
Solar energy, 78 (2005) 661-669.
7. W. Balthasar, Hydrogen production and technology: Today, tomorrow and beyond,
International journal of hydrogen energy, 9 (1984) 649-668.
8. T.L. LeValley, A.R. Richard, M. Fan, The progress in water gas shift and steam
reforming hydrogen production technologies- A review, International journal of hydrogen
Energy, 39 (2014) 16983-17000.
9. X. Qiu, Y. Zhao, C. Burda, Synthesisand characterization of nitrogen-doped group IVB
visible-light-photoactive metal oxide nanoparticles, Advanced Materials, 19(2007) 3995-
3999.
10. M.K. Arora, N. Sahu, S.N. Upadhaye, A.S.K Sinha, activity of cadmium sulphide
photocatalysts for hydrogen production from water: role of support, Industrial &
Engineering Chemistry Research, 38 (1999) 2659-2665.
11. N. Sahu, M.K Arora, S.N. Upadhaye, A.S.K Sinha, Phase transformation and activity of
cadmium sulfidephotocatalysts for hydrogen production from water: role of adsorbed
ammonia on cadmium sulfate precursor, Industrial & Engineering Chemistry Research,
37 (1998) 4682-4688.
12. M.K. Arora, N. Sahu, S.N. Upadhaye, A.S.K Sinha, Alumina supported cadmium
sulphide photocatalysts for hydrogen production from water: role of dissolved ammonia
in the impregnating solution, Industrial & Engineering Chemistry Research, 38 (1999)
4694-4699.
13. M.K. Arora, S.N. Upadhaye, A.S.K Sinha, effect of dispersion and distribution on
activity of alumina-supported cadmium sulphide photocatalysts for hydrogen production
from water: role of support, Industrial & Engineering Chemistry Research, 37(1998)
1310-1316.
14. A.S.K Sinha, N. Sahu, M.K Arora, S.N. Upadhaye, preparation of egg shell type Al2O3-
supported CdS photocatalysts for reduction of H2O to H2, catalysis Today, 69 (2001)
297-305.
15. W.S. Hummers, R.E. Offeman, Preparation of graphitic oxide, J. Am. Chem. Soc., 80
(1985) 1339.
16. D.P. Das, R.K Barik, J.Das, P.Mohapatra, K.M Parida, visible light induced photo-
hydroxylation of phenol to catechol over RGO-Ag3 VO4 nanocomposites without the use
of H2O2, RSC advances, 2 (2012) 7377-7379.
17. X. Mei, J. Ouyang, Ultrasonication-assisted ultrafast reduction of graphene oxide by zinc
powder at room teamperature, Carbon, 49 (2011) 5389-5397.
18. J.J. Ramsden, M.Gratzel, Photoluminescence of small cadmium sulphide particles,
journals of the chemical society, Farady Transactions 1: Physical chemistry in condensed
Phases, 80 (1984) 919-933.
19. F.A. Kroger, H.J.G Meyer, The edge emission of ZnS, CdS and ZnO and its relation to
the lattice vibrations of these solids, Physica, 20 (1954) 1149-1155.
20. A.A. Vuylsteke, Y.T. Sihvonen, Sulfur vacancy mechanism in pure CdS, Physical
Review, 113 (1959) 40-42.
21. A. Cao, Z. Liu, S. Chu, M. Wu, Z. Ye, Z. Cai, Y. Chang, S.Wang, Q.Gong, Y.Liu, A
facile one-step method to produce graphene-CdS quantum dot nanocomposites as
promising optoelectronic materials, Advanced Materials, 22 (2010) 103-106.
22. X.-J.Lv, W-F.Fu, H-X. Chang, H. Zhang, J-S. Cheng, G-J. Zhang, Y. Song, C-Y. Hu, J-H
Li, Hydrogen evolution from water using semiconductor nanoparticle/graphene
composite photocatalysts without noble metals, Journal of Materials Chemistry, 22
(2012) 1539-1546.
23. J.J. Ramsden, M. Gratzel, Photoluminescence of small cadmium sulphide particles,
Jpurnal of the chemical society, Farady Transaction 1 : Physical Chemistry in Condensed
Phases, 80 (1984) 919-933.
24. F.A Kroger, H.J.G Meyer, the edge emission of ZnS, CdS and ZnO and its relation to the
lattice vibrations of these solids, Physica, 20 (1954) 1149-1155.
25. A.A. Vuylsteke, Y.T. Sihvonen, Sulfur vacancy mechanism in pure CdS, Physical
Review, 113 (1959) 40-42.
26. H. Chang, X. Lv, H.Zhang, J.Li, Quantum dots senitized graphene: In situ growth and
application in photoelectrochemical cells, Electrochemistry Communications, 12 (2010)
483-487.
27. M.C. Biesinger, B.P. Payne, L.W.M Lau, A. Gerson, R.S.C. Smart, X-ray photoelectron
spectroscopic chemical state quantification of mixed nickel metal, oxide and hydroxide
systems, Surface and interface analysis, 41 (2009) 324-332.
28. Q. Xu, P.Pu, J.Zhao, C.Dong, C. Gao, Y. Chen, J. Chen, Y. Liu, H. Zhou, Preparation of
highly photoluminescent sulphur-doped carbon dots for Fe(III) detection, Journal of
Materials Chemistry A, 3 (2015) 542-546.
29. T. Nakajima, M. Kawaguchi, N. Watanable, Electrical conductivity and chemical bond of
graphite intercalation compound with fluorine and metal fluoride, Solid state Ionics, 11
(1983) 65-69.
30. T.V. Khai, T.D Lam, L.V. Thu, H.W. Kim, A two-step method for the preparation of
highly conductive graphene film and its gas-sensing property, Materials sciences and
applications, 6 11 (2015) 16.
31. J. jin , J. Yu, D. Guo, C. Cui, W. Ho, A Hierachical Z-scheme CdS-WO3 photocatalyst
with enhanced CO2 reduction activity, small, (2015) 5262-5271.
32. S. Yousefzadeh, M. Faraji, Y.T. Nien, A.Z Moshfegh, CdS nanoparticle senitized
titanium dioxide decorated graphene for enhancing visible light induced photoanode,
Applied Surface Science, 320 (2014) 772-779.
33. T. Di, B.Zhu, J. Zhang, B. Cheng, J. Yu, enhance photocatalytic hydrogen production on
CdS nanorod using cobalt-phosphate as oxidation cocatalyst, Applied Surface Science,
389 (2016) 775-782.
34. X. Zong, Z. Xing, H. YU, Y Bai, G.Q. LU, L. Wang, photocatalytic hydrogen production
in a noble metal free system catalysed by in situ grown molybdenum sulphide catalyst,
Journal of Catalysis , 310 (2014) 51-56.
35. M. Ben Ali, W-K Jo, H. Elhouichet, R. Boukherroub, Reduced graphene oxide as an
efficient support for CdS-MoS2 heterostructure foe enhanced photocatalytic hydrogen
evolution. International journal of Hydrogen energy, 42 (2017) 16449-16458.