Facile synthesis of Zn doped Ce/Ag nanocomposites for hydrogen evolution reaction

Hina Tabassum

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INTRODUCTION

In 21st century, technical as well as scientific issues that humanity faced are the supply of
clean, safe and renewable energy resources. Currently, the rate of global energy consumption is
about 18.5 TW[1]. With rapid growth of industrialization and urbanization, this global energy
consumption value will continuously increase. It is estimated that in 2050, this value will
increase to about 27 TW. This value will constantly increase and at the end of this century it
would be about 50 TW [2]. Although, major part (80-85%) of this total energy consumption is
originated by burning of fossil fuels. But, the usage of fossil energy results in considerable
release of green house gases named as CO 2 which in turn, affected global climate[3]. Towards
this end, considerable attempts have been made to replace such energy sources with effective and
sustainable energy route.

Hydrogen as a clean and renewable energy source with enhanced gravimetric energy
(~142 MJ kg−1) can meet the tremendous demand of global energy and referred as an ideal
energy career [4, 5]. Consequently, in last decades researchers have devoted much effort to
establish hydrogen as alternative energy source [6-8]. In this respect, the generation of hydrogen
through efficient, cost effective and green approach is the major challenge over its excessive
exploitation [9-14]. Electrochemical water splitting possess several appealing merits including
conversion of electrical energy into chemical energy and easier coupling with other intermittent
energy sources like solar and wind has been contributed largely to overcome this problem [15].

The production of hydrogen fuel via electrochemical splitting of water is one of the
promising approaches toward renewable energy storage and conversion. Electrochemical water
splitting analyzer comprises of oxygen evolution reaction (OER) and hydrogen evolution
reaction (HER) [16].Although, HER in water splitting is thermodynamically uphill- generating
higher energy consumption owing to large driven overpotential [17-22].

Up to now, numerous Ru, Rh and Pt based materials as sophisticated electrocatalysts

have been employed which in turn, expedite HER process and diminish energy barriers. As
these metals are expensive and scarcity so extensive use of these metals has been restrained [23].
To search for alternatives to precious metal catalysts, a variety of layered transition metal oxides

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[24, 25] , phosphides[26, 27] , chalcogenides [28], nitrides [29], sulfides [30, 31] and composites
[32] have been studied for HER.

The efficiency of electrochemical HER is strongly dependent upon electrocatalyst which

has strong association with number of active sites, structural aspects and electronic conductivity.
There are three main factors which has great impact on activity of HER. 1) The adsorption of
hydrogen on the catalyst should not be much stronger or much weaker. Beside this, Gibbs
adsorption energy of H2 may be influenced by electronic structure of catalyst [33]. 2) The
dispersity of active sites at electrocatalyst surface has also impact on HER activity [9]. 3)
Another important factor is electronic conductivity of catalyst. Because catalyst exhibits
insufficient electronic conductivity leads to schottky barrier at both interfaces (catalyst support
electrode and catalyst electrolyte) which necessitates higher overpotential to overwhelm. In that
case, energy conversion efficiency decreases [34].
LITERATURE REVIEW

A recent study carried out by Majhi et al. has demonstrated the preparation of four
different electrocatalysts for HER over entire range of pH. In this study, hydrothermal approach
has been employed in order to prepare nanocomposites named as CoSe 2/CuSe2, CoTe2/CuTe,
FeSe2/CuSe2 and FeTe2-CuTe. Moreover, electrocatalytic activity of above said nanocomposites
was studied toward HER. It turned out that all four nanocomposites possess good electrocatalytic
activity in all medium (acidic, Basic and neutral) but their efficiency increases in acidic medium.
Owing to small Tafel slope and lower value of overpotential makes CoTe 2/CuTe a promising
candidate as compared to others for HER [35].
The key issue towards HER is development of inexpensive and efficient electrocatalyst.
In order to achieve this goal; Jiang et al. investigated the formation of Ru/MoO 2 through a
general and facile in situ carburization. Experimentally it has confirmed that reported material
exhibited remarkable catalytic activity owing to more electrical conductivity, higher charge
transfer rate, modulated interface electronic structure in addition to economically advantageous
[36]. Additionally, Javan and his coworkers have worked on the synthesis of Ni-Cu which was
decorated on carbon quantum dots (Ni-Cu/CQDs) nanocomposites through electrochemical
approach. The electrocatalytic activity of synthesized material was checked for HER in acidic
medium. It has been revealed that catalytic activity of Ni-Cu/CQDs was significantly higher as

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compared to pure Ni electrode and Ni-Cu/GCE. This improvement was due to higher stability,
less charge transfer resistance, decreased overvoltage, enhanced cathode current density and
lower activation energy [37].
Hafeez et al. have developed InVO4-g-C3N4 which was loaded on reduced graphene oxide
via wet impregnation technique. The structural as well as morphological aspects of
nanocomposites have been determined XPS, FT-IR, TEM, XRD and UV/vis spectroscopy.
Consequently, research interest was focused on measuring hydrogen evolution rate. It has been
found that ternary nanocomposites namely InVO4-g-C3N4-rGO contain 45 times higher hydrogen
evolution rate as compared to InVO4-g-C3N4 nanocomposites [38]. Another study carried out by
Ahmed et al. also explored the synthesis of NiWO4 supported on reduced graphene oxide
(NiWO4/rGO). The successful formation of nanocomposites was confirmed by FT-IR, Raman
and XRD. Substantial progress has been made in the development of improved hydrogen
evolution reaction in comparison of NiWO4 [39].
The efficiency of MoSe2 toward hydrogen production is limited due to poor conductivity
and little quantity of active sites. To overcome this issue, Liu et al. utilized Rh nanoparticles
which were deposited on MoSe2 nanosheets. In this study, electron transfer approach has been
successfully employed in order to tune the electronic structure of active sites which in turn,
enhances the performance of HER of MoSe 2 by combination with Rh. This strategy provides an
insight into design and synthesis of Rh/MoSe2 NPs which have lower overpotential and long
term stability [40].
Ray et al. utilized facile redox mediated hydrothermal approach to synthesize Pd-Mn3O4
nanocomposites having remarkable electrocatalytic activity in acidic medium [41]. Yin et al.
synthesized Pd-Si based nanowires (Pd-SiNW) by means of chemical reduction technique. The
nanocatalyst exhibited small Tafel slope, better stability, higher surface area and lower
overpotential as compared to Pd/C catalyst and used effectively in HER process [22]. Another
investigation has been made by Zhao et al. for the fabrication of cobalt-molybdenum
carbide/graphitic carbon nanocomposites through sol gel approach. The synthesized
nanocomposites contain over potential and enhance electrocatalytic activity [12].
Keeping in view the above investigation, this study will be an attempt to enhance the
electrocatalytic activity by designing ternary nanocomposites via co-precipitation method.

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Various electrochemical techniques will be employed to determine the optimization in various
electrodes for HER.
RESEARCH OBJECTIVES

The objectives for this work will be;

 To understand the detailed mechanism that how to make nanomaterial and
nanocomposites
 To improve the catalytic properties of metals by decreasing particle size
 To Investigate the physical, chemical and electrochemical properties of composite
material
 To study the role of these nanomaterials and their potential applications.
 Utilization of prepared material as bifunctional electrode in water splitting
 Improvement in electrocatalytic activity of synthesized nanocomposites than their bare
counterparts
 To decrease over potential
 To improve conductivity
 To develop an inexpensive, environment friendly, good durability, highly stable and
active electrocatalyst towards HER

RESEARCH METHODOLOGY

Materials
All the required chemicals will be of analytical scale. The chemicals required for this
work will be Ce(NO3)3, AgCl, NiCl2, thiourea. The apparatus and glassware essential for this
work will be conical flasks, volumetric flasks, beakers, test tubes, pipette, hot magnetic plate,
magnetic stirrer, electric oven, measuring cylinder, pH meter, electronic balance, mortar and
pestle, spatula, china dish and watch glass.
Method
The cerium based nanocomposites will be synthesized via co-precipitation approach and will
be carried out in following steps;
 The salts used in the synthesis of Zn doped Ag/Ce nanocomposites will be Ce(NO 3)3,
AgCl and ZnCl2.

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  0.01M solution of cerium nitrate in 250ml of distilled water will be prepared and used as
main salt. Solution will be stirred at temperature of 60 °C. On the other hand, 0.01M
solution of Ag salt in 250ml of distilled water will be prepared in a separate flask.
 In the next step, both solution will be mixed together in a conical flask and further stirred
at 60°C for 9hours and allowed it to cool down at room temperature.
 After that, thiourea solution will be added drop wise to precursor solution to maintain a
pH till 11. The mixture solution will again place at hot magnetic plate maintained at 70°C
for four hours.
 Subsequently, precipitates will be obtained through filtration process and wash three
times with 99% methanol.
 The precipitates will be collected followed by calcinations in order to remove water
contents, N,S and oxides which lead to the formation of nanocomposites
 In another flask, we will prepare 1%solution of zinc and 100 ml of this solution will be
added drop-wise to as-prepared nanocomposites.
 The resulting mixture will be stirred at 60°C at speed of about 120 rpm for 5 hours.
 The mixture will be transferred to a beaker, allow it to cool at room temperature
afterwards. Precipitates will be collected after washing.
 The doped nanocomposites will be obtained after drying in an oven.
 The prepared material will be stored in dry desiccators in order to study their structural,
morphological and electrocatalytic aspects.

Characterization/Facilities available
Nanocomposites will be synthesized in Hefei National laboratory for Physical sciences at
Department of chemistry, University of science and technology of China. Characterization of the
material will be done by available techniques from different institutes.

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 WORK SCHEDULE

2021-2022 2022-2023 2023-2024

Sep- Dec- Mar- Jun- Sep- Dec- Mar- Jun- Sep- Dec- Mar- Jun-Aug
Nov Feb May Aug Nov Feb May Aug Nov Feb May

Arrival at
university and
introduction
Layout and
analyzer of our
lab
Putting order for
chemicals and
instruments
Synthesis of
nanocomposites
Characterization
of
nanocomposites
Electrochemical
characterization
Application of
prepared
material for HER
Data Collection

Analysis of data

Use of sediment
filter on
domestic scale
and
comparison of
results
Making of
prototype
according to
domestic use
Submission
of
project and
report writing

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SIGNIFICANCE OF WORK /EXPECTED OUTCOMES

 This study will provide a new strategy for highly efficient and low cost electrocatalyst.
 This study will also allow understanding of detailed mechanisms towards HER on the
electrochemical performance through experimental and theoretical work, which provide
specific guidelines for fabrication of efficient functional HER catalysts by certain
changes in electronic structure and crystal.
 This study will give detailed investigation of prepared efficient electrocatalyst towards
acidic, basic or neutral medium.
 It will also lies in the category of economic advantage in comparison of commercial Pt/C.

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