A review on H2 production through photocatalytic reactions

via water splitting using various nanoparticles

Abstract:
In this review we discussed about process of Hydrogen evolution through various nanoparticles
which are used industrially. We describe the advantages & Disadvantages of these nanoparticles
and also about the affect of product which is explained on the last of the whole experiment on the
environment. In this we discuss about various processes used for the production of Hydrogen.
The hydrogen is used for the production of HCl. We discussed several methods were developed
to enhance photocatalysts efficiency, primarily by modifying its morphology, crystallization, and
electrical properties. Photocatalytic H2 generation via water splitting is increasingly gaining
attention as a viable alternative for improving the performance of H2 production for solar energy
conversion. We summarize recent achievements in the synthesis and application of various
photocatalysts. At the end of this review we discussed about the future perspectives and various
innovative methods for the production of Hydrogen evolution through various nanoparticles.

Why we need Hydrogen?

 H2 is environmentally friendly, renewable, and considered to be an ideal candidate for an

economically and socially sustainable fuel and was previously regarded as an alternative energy
source [1]. Interestingly, H2-rich water has neuron effects owing to its antioxidant properties.
The sun provides an energy output of ~3 × 1024 J per year, which is approximately 12,000 times
higher than the current energy demand [2]. Therefore, solar energy can act as a sustainable
alternative energy source in the future. To date, the transformation of solar energy into H 2 via
water splitting is deemed as a desirable H 2preparation method to solve the energy crisis. The
proper use of H2 requires insight into the physical properties of H 2 molecules. As we know, the
lengths and strengths of hydrogen bonds are exquisitely sensitive to temperature and pressure.
Meanwhile, the charges of H2molecules also vary with temperature because the spin direction of
the nucleus in the H2 molecule changes depending on the temperature, and an energy difference
occurs between H2 molecules. As we know, H2 gas, often called molecular H2, is a highly
flammable gas with a wide range of concentrations between 4% and 75% by volume. Hydrogen
fuel is a zero-emission fuel when burned with oxygen. It can be used in electrochemical cells or
internal combustion engines to power vehicles or electric devices.
Photocatalysts for Water Splitting
Many photocatalysts were created as photocatalysts for hydrogen evolution. Based on these
species, they can be divided into three major parts:
(1) graphene-based photocatalyst;
(2) graphitic carbon nitride (g-C3N4)-based photocatalysts; and
(3) Heterojunction photocatalysts (semiconductor–semiconductor or semiconductor–(metal,
element)).
Types of Photo catalysis
Graphene-Based Photocatalysts
Recently, graphene-based photocatalysts attracted significant attention for enhancing photocatalytic
H2production performance. Graphene is used to enhance photocatalytic efficiency owing to its novel
structure and electrochemical properties. Graphene is a well-known two-dimensional (2D) material,
which can improve surface area, and its 2D membrane-like structure imparts unique electrochemical
properties

Molybdenum disulfide (MoS2):

Molybdenum disulfide (MoS2) has been widely studied as a potential earth‐abundant

electrocatalyst for the hydrogen‐evolution reaction (HER). Defects engineering and hetero‐
elemental doping are effective methods to enhance the catalytic activity for HER, so exploring
an efficient route to achieve in‐plane vacancy engineering and elemental doping of MoS2
simultaneously is necessary. 

Titanium dioxide (TiO2)

It is a well semi conducting material for photocatalysis and has promise in solar energy
conversion. TiO2 exists in three mineral forms: anatase, Rutile, and Brookite.

 Anatase type TiO2 has a crystalline structure that corresponds to the tetragonal system
(with bipyramidal habit) and is used mainly as a photocatalyst under UV irradiation.
 Rutile type TiO2 also has a tetragonal crystal structure (with prismatic habit). This type
of Titania is mainly used as white pigment in paint
 Brookite type TiO2 has an orthorhombic crystalline structure. TiO2, therefore is a
versatile material that has applications in various products such as paint pigments,
sunscreen lotions, electrochemical electrodes, capacitors, solar cells, and even as a food
coloring agent and in toothpastes.
g-C3N4-Based Photocatalysts
Currently, carbon-nitride-based photocatalysts receive significant attention for their
photocatalytic H2 generation owing to a unique electronic structure. This section summarizes
recent significant achievements in building C3N4-based photocatalysts for H2 evolution. Methods
including nanostructure regulation, band-gap modification, dye sensitization, and heterojunction
fabrication are highlighted herein.

Metal-Loading-Based Photocatalysts
Metal loading is also regarded as a useful method for photocatalytic enhancement
constructed Ag-rGO-TiO2 composite photocatalysts in 2018. In order to analyze the
photocatalytic mechanism of the architectural Ag-TiO2 and Ag-rGO-TiO2 composites, their
structures with Ag nanocubes for light absorption and TiO 2 nanosheets were well displayed. The
difference between Ag-TiO2 and Ag-rGO-TiO2 is the interface between Ag nanocubes and
TiO2 nanosheets, which enhances the electron transfer capability. For Ag-TiO2, the direct contact
between the two materials results in the formation of Ag (100)/(001) TiO 2 interface. Meanwhile,
for Ag-rGO-TiO2, both Ag(100)/rGO and rGO/(001) TiO 2 interfaces are formed by rGO. As
mentioned above, the synergistic effect of Ag(100)/rGO and rGO/(001)TiO2 interfaces, rather
than the Ag(100)/(001) TiO2 interface, offers quicker electron transfer.

Synthesis of Nano-TiO2 via Different Methods:

 Hydrothermal Method.
 Solvothermal Method.
 Sol-Gel Method.
 Direct Oxidation Method.
 Chemical Vapor Deposition.
 Electrodeposition.
 Sonochemical Method.
 Microwave Method.

2.1. Hydrothermal Method

Hydrothermal synthesis is normally conducted in steel pressure vessels called autoclaves

with or without Teflon liners under controlled temperature or pressure with the reaction in
aqueous solutions. The temperature can be elevated above the boiling oint of water, reaching
 the pressure of vapor saturation. The temperature and the amount of solution added to the
autoclave largely determine the internal pressure produced. It is a method that is widely used
for the production of small particles in the ceramics industry.

2.2. Solvothermal Method

The solvothermal method is almost identical to the hydrothermal method except that the
solvent used here is nonaqueous. However, the temperature can be elevated much higher than
that in hydrothermal method, since a variety of organic solvents with high boiling points can
be chosen. The solvothermal method normally has better control than hydrothermal methods
of the size and shape distributions and the crystallinity of the TiO2 nanoparticles. The
solvothermal method has been found to be a versatile method for the synthesis of a variety of
nanoparticles with narrow size distribution and dispersity. The solvothermal method has been
employed to synthesize TiO2 nanoparticles [23-25]. Fig.6 show a typical TEM image of the
TiO2 nanoparticles prepared with the solvothermal method.

2.3. Sol-Gel Method

The sol-gel method is a versatile process used inmaking various ceramic materials. In a
typical sol-gel process, a colloidal suspension, or a sol, is formed from the hydrolysis and
polymerization reactions of the precursors, which are usually inorganic metal salts or metal
organic compounds such as metal alkoxides. Complete polymerization and loss of solvent
leads to the transition from the liquid sol into a solid gel phase. Thin films can be produced
on a piece of substrate by spin-coating or dip-coating. A wet gel will form when the sol is
cast into a mold, and the wet gel is converted into a dense ceramic with further drying and
heat treatment. A highly porous and extremely low- density material called an aerogel is
obtained if the solvent in a wet gel is removed under a supercritical condition.

2.4. Direct Oxidation Method

Nanostructured TiO2 can be obtained by oxidation of titanium metal using oxidants or under
anodization. Crystalline TiO2 nanorods have been obtained by direct oxidation of a titanium
metal plate with hydrogen peroxide [28-30]. Typically, TiO2 nanorods on a Ti plate are
obtained when a cleaned Ti plate is put in 50 mL of a 30 wt% H2O2 solution at 353 ◦ K for
72 h.
2.5. Chemical Vapor Deposition

Vapor deposition refers to any process in which materials in a vapor state are condensed to
form a solid-phase material. These processes are normally used to form coatings to alter the
mechanical, electrical, thermal, optical, corrosion resistance, and wear resistance properties
of various substrates. In CVD processes, thermal energy heats the gases in the coating
chamber and drives the deposition reaction. In CVD, flow rate, gas composition, deposition
temperature, pressure and deposition chamber geometry are the process parameters by which
deposition can be controlled to have nanoforms of the desired material.

2.6. Electrodeposition

Electrodeposition is commonly employed to produce a coating, usually metallic, on a surface

by the action of reduction at the cathode. The substrate to be coated is used as cathode and
immersed into a solution which contains a salt of the metal to be deposited. The metallic ions
are attracted to the cathode and reduced to metallic form. With the use of the template of an
anodic alumina membrane (AAM), TiO2 nanowires can be

obtained by electrodeposition.

2.7. Sonochemical Method

Ultrasound has been very useful in the synthesis of a wide range of nanostructured materials,
including high-surface area transition metals, alloys, carbides, oxides, and colloids. The
chemical effects of ultrasound do not come from a direct interaction with molecular species.
Instead, sonochemistry arises from acoustic cavitation: the formation, growth, and implosive
collapse of bubbles in a liquid. In a typical procedure for preparation of TiO2 nanoparticles,
0.5 g TiO2 pellets were dissolved into 30 ml NaOH solution (10 M) under vigorous stirring
at room temperature for 2 h. Then the yellowish solution was irradiated in an ultrasonic bath
(Power Sonic 405, 40 kHz and 350 W) for 2h in ambient temperature.

2.8. Microwave Method

A dielectric material can be processed with energy in the form of high-frequency

electromagnetic waves. The principal frequencies of microwave heating are between 900 and
 2450 8 M. Malekshahi Byranvand et al./ JNS 3 (2013) 1-9 MHz At lower microwave
frequencies, conductive currents flowing within the material due to the movement of ionic
constituents can transfer energy from the microwave field to the material. At higher
frequencies, the energy absorption is primarily due to molecules with a permanent dipole
which tend to reorientate under the influence of a microwave electric field.

Summary and Perspectives:

We observed over the last several decades that photocatalysis was shown to be a promising
method for H2 production. Even though the principles controlling photocatalytic activity in the
developed semiconductors were identified, several aspects remain unclear. Therefore, practical
applications and the commercialization of photocatalytic H 2 production require further research.
Meanwhile, the charge transfer among photocatalysts due to the influence of structure and
electrochemical properties is also not very clear, while the influence of various preparation
methods on the catalytic performance is not well understood. The development of improved
photocatalysts will benefit from advances in science. Improved building of novel co-catalysts
will arise from using efficient catalysts. Many researches are underway investigating new
synthesis methods for sample preparation and novel system construction. Herein, we concluded
the most prominent achievements associated with H 2 production via photocatalysis. We hope this
report will assist further research efforts regarding the development of photocatalysts. 

Results and Discussion:

References
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