A critical review in strategies to improve photocatalytic water splitting towards hydrogen production

Water splitting for hydrogen production under light irradiation is an ideal system to provide renewable energy sources and to reduce global warming effects. Even though significant efforts have been devoted to fabricate advanced nanocomposite materials, the main challenge persists, which is lower efficiency and selectivity towards H₂ evolution under solar energy. In this review, recent developments in photo-catalysts, fabrication of novel heterojunction constructions and factors influencing the photocatalytic process for dynamic H₂ production have been discussed. In the mainstream, recent developments in TiO₂ and g-C₃N₄ based photo-catalysts and their potential for H₂ production are extensively studied. The improvements have been classified as strategies to improve different factors of photocatalytic water splitting such as Z-scheme systems and influence of operating parameters such as band gap, morphology, temperature, light intensity, oxygen vacancies, pH, and sacrificial reagents. Moreover, thermodynamics for selective photocatalytic H₂ production are critically discussed. The advances in photo-reactors and their role to provide more light distribution and surface area contact between catalyst and light were systematically described. By applying the optimum operating parameters and new engineering approach on photoreactor, the efficiency of semiconductor photocatalysts for H₂ production can be enhanced. The future research and perspectives for photocatalytic water splitting were also suggested.     

A review on bismuth-based composite oxides for photocatalytic hydrogen generation

Bismuth-based composite oxides are always considered the best visible-light photocatalysts for oxygen production. However, they are failed to photocatalytic reduce the hydrogen from water, due to their lower conduction band made up by Bi 6p and O 2p. Thus, it is significant to modulate their levels of the conduction and valence bands satisfying the redox potential for both H⁺/H₂ and O₂/H₂O, which will directly lead to discovering new visible-light materials for photocatalytic hydrogen generation. Recent years, some modified bismuth-based composite oxides have been reported to achieve photocatalytic hydrogen production. In this paper, a review of photocatalytic hydrogen generation by bismuth-based composite oxides is presented, mainly including energy band engineering, Z-scheme overall water splitting, and strategies for photocatalytic activity improvement.     

Review on the interface engineering in the carbonaceous titania for the improved photocatalytic hydrogen production

Hydrogen is the prime source of energy with enormous attention in the current research development process as it is safe, clean, eco-friendly, and can be produced from renewable resources through simple catalytic reactions. Scalable production of hydrogen through photocatalysis has been achieved using carbon-modified semiconductors since 2009. In this direction, this review delivers comprehensive understandings into the interface and structural interactions between TiO₂ and carbonaceous materials such as carbon, carbon nanotubes, graphene, activated carbon, graphitic carbon nitride, carbon quantum dots, etc., and their influences toward improving the hydrogen generation activity of these systems. Besides, recently developed carbonaceous materials such as 3-D graphene, carbon nanohorns, and carbon nanocones have also been discussed on their character in the photocatalytic water splitting procedure. In general, the observed improvements in this carbon-modified TiO₂ attributed to the synergetic effects, which offer the active migration of charge carriers and reduced recombination rates in the photocatalyst. Finally, highlighting the future perspectives of the carbonaceous materials in photocatalytic applications are concluded.     

Study of NiFe2O4 nanoparticles optical properties by a six-flux radiation model towards the photocatalytic hydrogen production

At present, synthesis of visible-light active materials for hydrogen production through water splitting has become one of the most important challenges in photocatalysis. Of equal importance, photocatalyst optical properties are essential information in order to determine reaction kinetics involved in water splitting. Transition metals spinel ferrites MFe₂O₄ exhibit remarkable activity under visible light for this reaction. However, their optical properties have not been fully determined in photocatalytic kinetic studies. In this research, synthesized and commercial NiFe₂O₄ nanoparticles were compared. NiFe₂O₄ was synthesized by the Pechini method and both materials were studied: structural, textural and optical characterization was performed through XRD, TEM, TGA, BET surface area and UV/Vis spectroscopy and photocatalytic evaluation was performed for hydrogen production. NiFe₂O₄ optical properties were determined by UV/Vis spectroscopy and using a simplified theoretical model for the Radiative Transfer Equation (RTE) called Six-Flux Model (SFM). All performed characterizations and obtained coefficients for the ferrites were compared finding differences between absorption and scattering coefficients, which were attributed to the porosity of the synthesized ferrite.     

Review on hydrogen production photocatalytically using carbon quantum dots: Future fuel

They are sometimes identified as zero-dimensional (0D) nanoparticles. These particles have gained much attention in water splitting into hydrogen and oxygen through photocatalytic conversion. CQDs act as semiconductor few nm sizes, due to very small size; their optical and electronic properties differ from larger particles. CQDs particle has high stability, mild toxicity besides conductivity. These particles are environmentally friendly due to low toxicity and also have excellent luminescence. Therefore they can be utilized as a potential source for the splitting of water photocatalytically. The parting of water into H₂ and O₂ will enable us to produce or collect hydrogen to be used as a future fuel. The review summarizes the efforts made by various researchers in the field of utilizing carbon quantum dabs for water splitting which may be further followed by future researchers for commercial-scale hydrogen production. Thus, the study concludes the methods for the production of CQDs and their utilization under sunlight by catalytically hydrogen gas production from water.     

Enhancement of photoelectrochemical hydrogen production by using a novel ternary Ag2CrO4/GO/MnFe2O4 photocatalyst

Novel Ag₂CrO₄/GO/MnFe₂O₄ photocatalysts synthesized by precipitation method and fabricated on indium tin oxide surface by electrophoretic deposition technique. The obtained Ag₂CrO₄/GO/MnFe₂O₄ composite has been verified by microscopic study, chemical and structural analyses. Also, the ternary composite showed higher photocurrent response and weaker photoluminescence spectrum than MnFe₂O₄, GO, Ag₂CrO₄ and GO/MnFe₂O₄. Photo-cathodes prepared using semiconductor photocatalyst powders were investigated for visible-light-driven photoelectrochemical hydrogen evolution. The best result of the photoelectrochemical hydrogen production in the presence of Ag₂CrO₄/GO/MnFe₂O₄ composite was determined as 446.93 μmol.cm⁻² in 90 min under visible light illumination. So, the enhanced hydrogen producing over the ternary composite was obtained. This study presents the development of stable visible light active photocatalytic materials and the design of efficient for the advancement of hydrogen production via photoelectrochemical water splitting in the future.     

Rational design and fabrication of surface tailored low dimensional Indium Gallium Nitride for photoelectrochemical water cleavage

Currently several type of energy sources exist in the modern world. The energy makes people's life more comfortable, easy, time savings, fast transformation of information and various modes of transmission. Because of large demand of energy, efforts on production of energy increases day by day which subsequently increase serious environmental concerns such as pollution and lack of existing natural resources. In this respect, several attempts have been proposed for new type of renewable and chemical energy systems to overcome the economic burden, global warming and environmental problems caused by the use of conventional fossil fuels. Hydrogen production via water splitting is a promising and ideal route for renewable energy using the most abundant resources of solar light and water. Cost effective photocatalyst for Photoelectrochemical (PEC) water splitting using semiconductor materials as light absorbers have been extensively studied due to their stability and simplicity. Over the past few decades, various metal oxide photocatalysts for water splitting have been developed and their photocatalytic application was studied under UV irradiation. Alternative semiconductor photocatalyst should harness solar energy in the visible light, one such semiconductor material is indium gallium nitride (InGaN), owing to its suitable and tunable energy band-gap, chemical resistance and notable photoelectrocatalytic activity. This review article is initiated with the brief introduction about the origin and methods of production of hydrogen gas from both renewable and nonrenewable energy sources. Multi-functional properties and applications of InGaN are described along with past and recent efforts of InGaN materials for hydrogen evolution by several investigators are provided in detail. In addition, future prospects and ways to improve the PEC performance of InGaN are presented at the end of this review.     

Multidisciplinary methods (co-precipitation,ultrasonic, microwave,reflux and hydrothermal) for synthesis and characterization of CaMn3O6 nanostructures and its photocatalytic water splitting performance

Production of hydrogen and oxygen from water splitting reaction under visible light is a simple method for conversion of solar-to-hydrogen energy and it is a hopeful clean and renewable method for H₂ fuel generation. However, there is still a lack of potential materials with significant activity under visible light. Because of safety, chemical inertness, low cost, stability and other characteristics, transition metal oxide semiconductors have been widely applied as photocatalysts for hydrogen generation. Albeit, wide usage of semiconductor photocatalysts were prevented by its inability to exploit solar energy of visible region. Here we show synthesis of a nano-sized mixed metal oxide (MMO) Ca₃MnO₆ through wet-chemistry methods such as co-precipitation, ultrasonic, microwave, reflux, and hydrothermal methods. The nano-sized Ca₃MnO₆ has initially selected based on morphology and respective particle diameters. The selected sample shows a well-defined single crystal, free from any impurities, complete structural formation, and a band gap energy (E_g) of around 5.3 eV. The best product synthesized in ultrasonic method which shows the best morphology, purity and the highest efficiency for splitting of water to hydrogen and oxygen. Irrespective of preparation methods and morphologies, all samples split water into hydrogen and oxygen, as confirmed from their respective photocatalytic analysis. When the selected sample combined with (NH₄)₂Ce(NO₃)₆, the single-crystal Ca₃MnO₆ nanoparticles split water into hydrogen and oxygen more efficiently under visible light. Our findings demonstrate the importance of nanostructured Ca₃MnO₆ single-crystal photocatalysts in solar water splitting.     

Recent progress and challenges in photocatalytic water splitting using layered double hydroxides (LDH) based nanocomposites

The worldwide energy demand is steadily increasing and estimated to be doubled by the year 2050 due to a continuous hike in economies and population. A large part of the global energy requirement procures using traditional energy sources such as fossil fuels, which are non-renewable. Also, their excessive consumption imparts negative impacts on the environment by CO₂, and CO emissions, which constantly increase the average global temperature. Therefore, the need for a more reliable, sustainable, inexpensive, renewable and environmentally-friendly form of energy is imperative. From these perspectives, hydrogen energy is emerging as one of the most promising alternatives to overcome rising energy demand with a zero-carbon footprint.Herein, various layered double hydroxides (LDH) nanocomposite owing to their attractive physicochemical properties and synergistic effect with other materials in the field of hydrogen production are reviewed. Why the class of LDHs materials is critical and their ideographic properties which make them promising materials in the field of water splitting via photocatalysis and electrocatalysis are also discussed. The synthetic methods of LDHs based nanocomposites fabrication are summarized. Various challenges and strategies from the viewpoint of a different method of hydrogen production through LDHs are reported. Additionally, multiple techniques like surface plasmon resonance (SPR), heterojunction formation, and doping with co-catalyst to increase the efficiency for photocatalytic hydrogen production are also presented. Hopefully, this review will help the readers explore highly efficient, inexpensive and stable LDH catalysts toward photocatalytic water splitting.     

Design of cocatalyst loading position for photocatalytic water splitting into hydrogen in electrolyte solutions

Photocatalytic water splitting into hydrogen is a very attractive and desirable technology to realize sustainable and renewable green energy conversion. Up to now, many research results have confirmed that cocatalyst such as Pt is essential for a high efficiency photocatalytic H₂ evolution system. In a traditional view, the cocatalyst should be closely combined with the photocatalyst to achieve a high H₂ or O₂ photo-productive rate. In this work, an unusual point has been put forward that the suitable loading position of cocatalyst Pt for film-type TiO₂ catalyst is on the bare Fluorine-doped tin oxide (FTO) substrate instead of on the surface of TiO₂ in the electrolyte solutions. Especially, in acidic electrolyte, the hydrogen production rate of this new designed catalyst with Pt loaded on FTO (TiO₂-Pt/FTO) reaches 2.4 times that of the common catalyst with Pt loaded on TiO₂ (Pt/TiO₂-FTO). According to the experiment results, it is supposed that this loading way of cocatalyst on the substrate can construct a self-bias photocatalytic electrochemical cell system, drive electrolyte ions' movement directionally, and obtain high photocatalytic H₂ production efficiency. The universality of this innovation has been verified by CdS and CdS@TiO₂ film-type catalysts. This study provides a new guide in exploring high-efficiency film-type photocatalytic system for water splitting into hydrogen in the electrolyte solution.     

A visible-light-driven heterojunction for enhanced photocatalytic water splitting over Ta2O5 modified g-C3N4 photocatalyst

The photocatalytic water splitting for generation of clean hydrogen energy has received increasingly attention in the field of photocatalysis. In this study, the Ta₂O₅/g-C₃N₄ heterojunctions were successfully fabricated via a simple one-step heating strategy. The photocatalytic activity of as-prepared photocatalysts were evaluated by water splitting for hydrogen evolution under visible-light irradiation (λ > 420 nm). Compared to the pristine g-C₃N₄, the obtained heterojunctions exhibited remarkably improved hydrogen production performance. It was found that the 7.5%TO/CN heterojunction presented the best photocatalytic hydrogen evolution efficiency, which was about 4.2 times higher than that of pure g-C₃N₄. Moreover, the 7.5%TO/CN sample also displayed excellent photochemical stability even after 20 h photocatalytic test. By further experimental study, the enhanced photocatalytic activity is mainly attributed to the significantly improve the interfacial charge separation in the heterojunction between g-C₃N₄ and Ta₂O₅. This work provides a facile approach to design g-C₃N₄-based photocatalyst and develops an efficient visible-light-driven heterojunction for application in solar energy conversion.     

Recent advances in non-metals-doped TiO2 nanostructured photocatalysts for visible-light driven hydrogen production,CO2 reduction and air purification

The generation of hydrogen and oxygen from the photocatalytic water splitting reaction under visible light is a promisingly renewable and clean source for H₂ fuel. The transition metal oxide semiconductors (e.g. TiO₂, WO_3, ZnO, and ZrO₂) are have been widely used as photocatalysts for the hydrogen generation. Because of safety, low cost, chemical inertness, photostability and other characteristics (bandgap, corrosion resistance, thermal and environmental stability), TiO₂ is considered as a most potential catalyst of the semiconductors being investigated and developed. However, the extensive applications of TiO₂ are hampered by its inability to exploit the solar energy of visible region. Other demerits are lesser absorbance under visible light, and recombination of photogenerated electron-hole pairs. In this review, we focus on the all the possible reactions taking place at the catalyst during photo-induced H₂ from water splitting reaction, which is green and promising technology. Various parameter affecting the photocatalytic water splitting reactions are also studied. Predominantly, this review is focussed on bandgap engineering of TiO₂ such as the upward shift of valence band and downward shift of conduction bands by doping process to extend its light absorption property into the visible region. Furthermore, the recent advances in this direction including various new strategies of synthesis, multiple doping, hetero-junction, functionalization, perspective and future opportunities of non-metals-doped TiO₂-based nanostructured photocatalysts for various photocatalytic applications such as efficient hydrogen production, air purification and CO₂ reduction to valuable chemicals have been discussed.     

Solar water splitting to generate hydrogen fuel—a photothermal electrochemical analysis

Theory¹ and experiment² are derived for highly efficient photothermal electrochemical solar water splitting to provide clean, renewable sources of hydrogen fuel. The theory derives semiconductor band-gap-restricted, thermal enhanced, solar water splitting efficiencies, combining photodriven charge transfer, with excess sub-band-gap insolation to lower the water potential. Fundamental water thermodynamics and solar photosensitizer constraints determine solar to hydrogen fuel conversion efficiencies in the 50% range over a wide range of insolation, temperature, pressure and photosensitizer band-gap conditions. Experimentally, a novel physical chemical process within molten NaOH is demonstrated, in which an external single, small band-gap photosentizer, such as Si, can drive the energetics of water cleavage. This is accomplished by tuning (decreasing) the water splitting electrochemical potential, E_H2O, rather than tuning the photosensitizer band gap; this diminished potential is due to (i) thermodynamic temperature induced decrease of E_H2O with increasing temperature, and (ii) partial recombination of the cleavage products.     

Hydrogen production via solar-aided water splitting thermochemical cycles: Combustion synthesis and preliminary evaluation of spinel redox-pair materials

Redox-pair-based thermochemical cycles are considered as a very promising option for the production of hydrogen via renewable energy sources like concentrated solar energy and raw materials like water. This work concerns the synthesis of various spinel materials of the iron and aluminum families via combustion reactions in the solid and in the liquid-phase and the testing of their suitability as redox-pair materials for hydrogen production by water splitting via thermochemical cycles. The effects of reactants' stoichiometry (fuel/oxidizer) on the combustion synthesis reaction characteristics and on the products' phase composition and properties were studied. By fine-tuning the synthesis parameters, a wide variety of single-phase, pure and well crystallized spinels could be controllably synthesized. Post-synthesis, high-temperature calcination studies under air and nitrogen at the temperature levels encountered during solar-aided thermochemical cyclic operation have eliminated several material families due to phase composition instabilities and identified among the various compositions synthesized NiFe₂O₄ and CoFe₂O₄ as the two most suitable for cyclic water splitting – thermal reduction operation. First such thermochemical cyclic tests between 800 and 1400 °C with NiFe₂O₄ and CoFe₂O₄ in powder form in a fixed bed laboratory reactor have demonstrated capability for cyclic operation and alternate hydrogen/oxygen production at the respective cycle steps for both materials. Under the particular testing conditions the two materials exhibited hydrogen/oxygen yields of the same magnitude and similar temperatures of oxygen release during thermal reduction.     

Separation of hot electrons and holes in Au/LaFeO3 to boost the photocatalytic activities both for water reduction and oxidation

Construction of plasmon-based nanostructures is an effective way to enhance the photocatalytic activities of semiconductor photocatalysts for water-splitting. However, the synergistic effect of plasmon-related hot electrons and holes for water splitting in the plasmon-hybrid photocatalyst is rarely considered. Herein, we construct a plasmon-based Au/LaFeO₃ composite photocatalyst to investigate the complex roles of hot electrons and holes for solar water splitting. Benefiting from the formation of Schottky junction and surface plasmon resonance effect of the Au nanoparticles, the synthesized photocatalyst exhibits an excellent photocatalytic activity for each half-reaction of water splitting, and the rates for H₂ and O₂ generation are obtained as high as 202 μmol g⁻¹ h⁻¹ and 23 μmol g⁻¹ h⁻¹, respectively. Moreover, an in-depth investigation reveals that the improved hydrogen evolution is caused by the hot electron injection from Au to LaFeO₃, and the hot holes in Au induced by the separation of hot charges can initiate the water oxidation directly on the surface of gold. Thus, this work provides a new insight into the synergistic effect of plasmon-related hot electrons and holes for boosting the photocatalytic reactions.     

CuInS2-based photocatalysts for photocatalytic hydrogen evolution via water splitting

The realization of efficient photocatalytic hydrogen evolution (PHE) significantly depends on the development of durable and effective semiconductor photocatalysts. Copper indium sulfide (CuInS₂) is an emerging ternary chalcogenide semiconductor material for solar-to-chemical energy application, because it possesses a suitable bandgap, environment-friendly elements, and a low melting point. CuInS₂-based semiconductor photocatalysts have been investigated for PHE via water splitting, but current PHE performance still has difficulty in meeting commercial application requirements and needs to be further improved. In this review, the basic semiconductor properties of CuInS₂, including its crystal and band structures, are introduced, and its PHE mechanism is discussed in detail. The PHE performance of CuInS₂-based photocatalysts is systematically discussed, with a focus on morphology, engineered structure, and heterojunction construction. Finally, issues and challenges currently encountered in the PHE application of CuInS₂-based photocatalysts and their possible solutions are presented.     

Active and robust novel bilayer photoanode architectures for hydrogen generation via direct non-electric bias induced photo-electrochemical water splitting

Photo-electrochemical (PEC) water splitting is a promising and environmentally benign approach for generation of hydrogen using solar energy with minimum greenhouse gas emissions. The development of semiconductor materials for photoanode with superior optoelectronic properties combined with excellent photoelectrochemical activity and stability is vital for the realization of viable commercial development of PEC water splitting systems. Herein, we report for the very first time, the study of nanoscale bilayer architecture of WO₃ and Nb and N co-doped SnO₂ nanotubes (NTs), wherein WO₃ NTs are coated with (Sn_0.95Nb_0.05)O₂:N-600 (annealed in NH₃ at 600 °C) layer of different thicknesses, as a potential semiconductor photoanode material for PEC water splitting. An excellent long term photoelectrochemical stability under illumination in the acidic electrolyte solution combined with a solar-to-hydrogen efficiency (STH) of ～3.83% (under zero applied potential) is obtained for the bilayer NTs, which is the highest STH obtained thus far, to the best of our knowledge compared to the other well studied semiconductor materials, such as TiO₂, ZnO and Fe₂O₃. These promising results demonstrate the excellent potential of bilayer NTs as a viable and promising photoanode in PEC water splitting.     

A current perspective for photocatalysis towards the hydrogen production from biomass-derived organic substances and water

Recently, an increasing interest has been devoted to produce chemical energy – hydrogen (H₂) by converting sustainable sunlight energy via water splitting and reforming of renewable biomass-derived organic substances. These photocatalytic processes are very promising, sustainable, economic, and environment-friendly. Herein, this article gives a concise overview of photocatalysis to produce H₂ as solar fuel via two approaches: water splitting and reforming of biomass-derived organic substances. For the first approach – photocatalytic water splitting, there are two reaction types have been used, including photoelectrochemical (PEC) and photochemical (PC) cell reactions. For the second approach, biomass-derived oxygenated substrates could undergo selective photocatalytic reforming under renewable solar irradiation. Significant efforts to date have been made for photocatalysts design at the molecular level that can efficiently utilize solar energy and optimize the reaction conditions, including light irradiation, type of sacrificial reagents. Critical challenges, prospects, and the requirement to give more attention to photocatalysis for producing H₂ are also highlighted.     

Hydrogen production from water splitting over Eosin Y-sensitized mesoporous-assembled perovskite titanate nanocrystal photocatalysts under visible light irradiation

The photocatalytic water splitting is a promising process for producing H₂ from two abundant renewable sources of water and solar light, with the aid of a suitable photocatalyst. In this work, a combination of sensitizer addition and noble metal loading was employed to modify perovskite photocatalysts in order to achieve the enhancement of photocatalytic H₂ production under visible light irradiation. The dependence of the H₂ production on type of mesoporous-assembled perovskite titanate nanocrystal photocatalysts (MgTiO₃, CaTiO₃, and SrTiO₃), calcination temperature of photocatalyst, Pt loading, type and concentration of electron donor (diethanolamine, DEA; and triethanolamine, TEA), concentration of sensitizer (Eosin Y, E.Y.), photocatalyst dosage, and initial solution pH, was systematically studied. The experimental results showed that the 0.5 wt.% Pt-loaded mesoporous-assembled SrTiO₃ nanocrystal synthesized by a single-step sol-gel method and calcined at 650 °C exhibited the highest photocatalytic H₂ production activity from a 15 vol% DEA aqueous solution with dissolved 0.5 mM E.Y. Moreover, the optimum photocatalyst dosage and initial solution pH for the maximum photocatalytic H₂ production activity were found to be 6 g/l and 11.6, respectively.     

A critical review on core/shell-based nanostructured photocatalysts for improved hydrogen generation

Photocatalytic water splitting into gaseous hydrogen and oxygen in the presence of semiconductor photocatalysts under a visible spectrum of solar irradiation is one of the most promising processes for plummeting energy demands and environmental pollution. Among the successful photocatalytic materials, the core/shell nanostructures show promising results owing to their fascinating morphology that protects the surface features of the core besides the effective separation of photo-excitons resulting in an enhanced rate of hydrogen production up to 162 mmol h⁻¹g⁻¹_cat, which is a notable highest value reported in the literature. In this review, we have focused on the basic characteristics of the core-shell structure-based semiconductor photocatalytic systems and their efficient water-splitting reactions under light irradiation. Comprehensive detail on various synthesis methods of core-shell nanostructures, shell thickness-dependent properties, charge-transfer reaction mechanisms, and photocatalytic stability are highlighted in this review. Core-shell nanostructured materials have been extensively used as a photocatalyst, co-catalyst, and by coupling with supporting materials to improve the apparent quantum efficiency up to 45.6%. Besides, important photocatalytic properties that influence the redox reactions i.e., effective exciton separation, the effect of different light sources/wavelengths, surface charge modeling, photocatalytic active sites, and turnover frequency (TOF) have also been focused on and extensively described. Finally, the present and future prospects of the core-shell nanostructured photocatalysts for solar energy conversion into green hydrogen production have been expounded.