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Abstract Electrochemical water splitting is a promising approach towards a sustainable and renewable energy source. However, the demand for high anodic potential and sluggish kinetics of oxygen evolution reaction (OER) restrict the efficiency and feasibility of the water-splitting process. In this quest, transition metal oxides and alloys are considered potential candidates owing to their natural occurrence and high redox potential for OER. However, many associated challenges in their use are still there to be addressed. Here, we designed a new class of bismuth-doped iron oxide on exfoliated graphene oxide by optimizing the metal loading on the conductive support to facilitate the flow of charge during catalysis. The catalytic ability of the synthesized Bi-doped nanocomposites was evaluated in activating the OER under extreme alkaline conditions (1 MKOH). On screening different combinations, 20Bi–Fe2O3@GO was identified as the most efficient and sustainable electrocatalyst even under harsh operating conditions, with an onset potential of 1.48 V and a Tafel slope of 65 mV/dec. The current study offers a new class of Bi-doped electrocatalysts, where the precise doping of Bi and the optimized loading of metal was found the key to achieving low onset potential and high current density to initiate OER. Graphical abstract

Zinc oxide (ZnO) has been utilized for photocatalytic water splitting due to its excellent performance, low cost, non-toxicity, thermal stability, and chemical stability. However, despite these remarkable properties, ZnO has significant drawbacks, such as photocorrosion and an inability to utilize visible light due to its wide band gap of 3.3-3.4 eV. Structurally, ZnO exists in three different forms: rocksalt, cubic blende, and hexagonal wurtzite. It has been reported that the wurtzite structure produces more H2 compared to its counterparts. Herein, we discuss several techniques for synthesizing zinc oxide and how incorporating zinc oxide nanoparticles with metal oxides, sulfides, and other materials can enhance its performance in the visible light region. Recently, integrating ZnO with TiO2 –Ag using an S-scheme heterostructure boosted the H2 activity rate to approximately 60.0 mmol/g/h, which is about 166 times superior to pristine ZnO. This improvement is attributed to the enhanced light absorption and charge transfer facilitated by Ag doping. This review examines ZnO-based photocatalytic H2 generation via water splitting with different modification strategies and explores future outlooks for improving performance of ZnO.

In this work, samarium doped Ni-Zn catalysts with a composition of Ni0.9Zn0.1SmyFe2-yO4 (y = 0–0.03) are made by inorganic sol–gel auto-combustion (SC) route. These Ni-Zn materials depict the forming of typical cubic crystal structure (Fd3m) and it is affirmed by the X-ray diffraction plots. The existence of cubic, spherical, and aggregated shaped grains with an average grain size that falls in between the range of 188 to 316 nm are confirmed from the FESEM images of prepared materials. According to the photo catalytic water splitting research findings, the total hydrogen yield for the Ni-Zn1, Ni-Zn2, Ni-Zn3, and Ni-Zn4 catalysts after four hours are 16.17, 15.02, 23.47 and 24.99 mmol gcat-1. Among all the compositions, the Ni-Zn4 photocatalyst exhibits the maximum photocatalytic performance of 24.99 mmol gcat-1. However, the Ni-Zn4 sample also shows the high electro catalytic hydrogen evolution reaction (HER) performance. With their outstanding photo/electro performance, the synthesized Sm-doped Ni-Zn nanoferrites shows great promise as potential candidates for the green hydrogen generation.

A very simple electrochemical top-down procedure was employed to obtain pure graphene quantum dots (GQDs) in water and using only graphite as carbonaceous precursor. The graphitic structure of the GQDs has been clearly observed by high-resolution transmission electronic microscopy (HRTEM). Then, the synthesis of N-doped GQDs was allowed by the addition of ammonia in the solution. The nitrogen doping was plainly evidenced by X-ray photoelectron (XPS) and Raman spectroscopies. The role of the electrolytic solution employed during the synthesis has been also discussed. Finally, these N-doped and non-doped GQDs were further used to prepare hybrids by grafting them onto ZnO semi-conductors, and their photocatalytic properties towards water-splitting were investigated. Interestingly, a very important enhancement of the amount of dihydrogen produced was observed with N-doped GQDs, compared to ZnO alone or to hybrids prepared with non-doped GQDs.

Abstract Tuning the electronic properties of transition metals using pyrophosphate (P2O7) ligand moieties can be a promising approach to improving the electrochemical performance of water electrolyzers and supercapacitors, although such a material’s configuration is rarely exposed. Herein, we grow NiP2O7, CoP2O7, and FeP2O7 nanoparticles on conductive Ni-foam using a hydrothermal procedure. The results indicated that, among all the prepared samples, FeP2O7 exhibited outstanding oxygen evolution reaction and hydrogen evolution reaction with the least overpotential of 220 and 241 mV to draw a current density of 10 mA/cm2. Theoretical studies indicate that the optimal electronic coupling of the Fe site with pyrophosphate enhances the overall electronic properties of FeP2O7, thereby enhancing its electrochemical performance in water splitting. Further investigation of these materials found that NiP2O7 had the highest specific capacitance and remarkable cycle stability due to its high crystallinity as compared to FeP2O7, having a higher percentage composition of Ni on the Ni-foam, which allows more Ni to convert into its oxidation states and come back to its original oxidation state during supercapacitor testing. This work shows how to use pyrophosphate moieties to fabricate non-noble metal-based electrode materials to achieve good performance in electrocatalytic splitting water and supercapacitors.

The water oxidation reaction in photosystem II (PS II) produces most of the molecular oxygen in the atmosphere, which sustains life on Earth, and in this process releases four electrons and four protons that drive the downstream process of CO2 fixation in the photosynthetic apparatus. The catalytic center of PS II is an oxygen-bridged Mn4Ca complex (Mn4CaO5) which is progressively oxidized upon the absorption of light by the chlorophyll of the PS II reaction center, and the accumulation of four oxidative equivalents in the catalytic center results in the oxidation of two waters to dioxygen in the last step. The recent emergence of X-ray free-electron lasers (XFELs) with intense femtosecond X-ray pulses has opened up opportunities to visualize this reaction in PS II as it proceeds through the catalytic cycle. In this review, we summarize our recent studies of the catalytic reaction in PS II by following the structural changes along the reaction pathway via room-temperature X-ray crystallography using XFELs. The evolution of the electron density changes at the Mn complex reveals notable structural changes, including the insertion of OX from a new water molecule, which disappears on completion of the reaction, implicating it in the O—O bond formation reaction. We were also able to follow the structural dynamics of the protein coordinating with the catalytic complex and of channels within the protein that are important for substrate and product transport, revealing well orchestrated conformational changes in response to the electronic changes at the Mn4Ca cluster.

Climatic changes are reaching alarming levels globally, seriously impacting the environment. To address this environmental crisis and achieve carbon neutrality, transitioning to hydrogen energy is crucial. Hydrogen is a clean energy source that produces no carbon emissions, making it essential in the technological era for meeting energy needs while reducing environmental pollution. Abundant in nature as water and hydrocarbons, hydrogen must be converted into a usable form for practical applications. Various techniques are employed to generate hydrogen from water, with solar hydrogen production—using solar light to split water—standing out as a cost-effective and environmentally friendly approach. However, the widespread adoption of hydrogen energy is challenged by transportation and storage issues, as it requires compressed and liquefied gas storage tanks. Solid hydrogen storage offers a promising solution, providing an effective and low-cost method for storing and releasing hydrogen. Solar hydrogen generation by water splitting is more efficient than other methods, as it uses self-generated power. Similarly, solid storage of hydrogen is also attractive in many ways, including efficiency and cost-effectiveness. This can be achieved through chemical adsorption in materials such as hydrides and other forms. These methods seem to be costly initially, but once the materials and methods are established, they will become more attractive considering rising fuel prices, depletion of fossil fuel resources, and advancements in science and technology. Solid oxide fuel cells (SOFCs) are highly efficient for converting hydrogen into electrical energy, producing clean electricity with no emissions. If proper materials and methods are established for solar hydrogen generation and solid hydrogen storage under ambient conditions, solar light used for hydrogen generation and utilization via solid oxide fuel cells (SOFCs) will be an efficient, safe, and cost-effective technique. With the ongoing development in materials for solar hydrogen generation and solid storage techniques, this method is expected to soon become more feasible and cost-effective. This review comprehensively consolidates research on solar hydrogen generation and solid hydrogen storage, focusing on global standards such as 6.5 wt% gravimetric capacity at temperatures between −40 and 60 °C. It summarizes various materials used for efficient hydrogen generation through water splitting and solid storage, and discusses current challenges in hydrogen generation and storage. This includes material selection, and the structural and chemical modifications needed for optimal performance and potential applications.

Hydrogen generation by photocatalytic water-splitting holds great promise for addressing the serious global energy and environmental crises, and has recently received significant attention from researchers. In this work, a method of assembling GeC/MXY (M = Zr, Hf; X, Y = S, Se) heterojunctions (HJs) by combining GeC and MXY monolayers (MLs) to construct direct Z-scheme photocatalytic systems is proposed. Based on first-principles calculations, we found that all the GeC/MXY HJs are stable van der Waals (vdW) HJs with indirect bandgaps. These HJs possess small bandgaps and exhibit strong light-absorption ability across a wide range. Furthermore, the built-in electric field (BIEF) around the heterointerface can accelerate photoinduced carrier separation. More interestingly, the suitable band edges of GeC/MXY HJs ensure sufficient kinetic potential to spontaneously accomplish water redox reactions under light irradiation. Overall, the strong light-harvesting ability, wide light-absorption range, small bandgaps, large heterointerfacial BIEFs, suitable band alignments, and carrier migration paths render GeC/MXY HJs highly efficient photocatalysts for overall water decomposition.

Hydrogen, one of the most promising forms of new energy sources, due to its high energy density, low emissions, and potential to decarbonize various sectors, has attracted significant research attention. It is known that electrocatalytic hydrogen production is one of the most widely investigated research directions due to its high efficiency in the conversion of electricity to H2 gas. However, given the limited reserves and high cost of precious metals, the search for non-precious metal-based catalysts has been widely explored, for example, transition metal phosphides, oxides, and sulfides. Despite this interest, a detailed survey unveils that the surface and internal structures of the alternative catalysts, including their surface reconstruction, composition, and electronic structure, are poorly studied. As a result, a disconnection in the structure–property relationship severely hinders the rational design of efficient and reliable non-precious metal-based catalysts. In this review, by focusing on Ni5P4, a bifunctional catalyst for water splitting, we systematically summarize the material motifs pertaining to the different synthetic methods, surface characteristics, and hydrolysis properties. It is believed that a cascaded correlation may provide insights toward understanding the fundamental catalytic mechanism and design of robust alternative catalysts for hydrogen production.

Hydrogen is considered a promising substitute for traditional fossil fuels because of its widespread sources, high calorific value of combustion, and zero carbon emissions. Electrocatalytic water-splitting to produce hydrogen is also deemed to be an ideal approach; however, it is a challenge to make highly efficient and low-cost electrocatalysts. Single-atom catalysts (SACs) are considered the most promising candidate to replace traditional noble metal catalysts. Compared with SACs, dual-atom catalysts (DACs) are capable of greater attraction, including higher metal loading, more versatile active sites, and excellent catalytic activity. In this review, several general synthetic strategies and structural characterization methods of DACs are introduced, and recent experimental advances in water-splitting reactions are discussed. The authors hope that this review provides insights and inspiration to researchers regarding DACs in electrocatalytic water-splitting.

The world's energy crisis and environmental problems could be addressed via solar fuel (hydrogen) generation. Thus, the development of non-toxic, inexpensive and high-efficiency photocatalysts is crucial. Spinel ferrite with general formula MFe2O4 (where M=Mg2+, Co2+, Ni2+, Zn2+, e.t.c.) has gained enormous interest in the field of solar energy conversion and storage especially solar fuel (hydrogen) generation via photocatalytic water-splitting. Spinel ferrites are considered as ideal materials for solar fuel (hydrogen) generation due to its promising magnetic recovery, suitable band gap energy, low toxicity, strong thermal stability, affordability, simple preparation method, and magnetic retrieval ability. However, the solar-to-hydrogen (STH) conversion efficiency of spinel ferrite materials is still low due to high rate of photogenerated electron-hole pair recombination, resulting in poor photocatalytic performance. Herein, preparation approach for spinel ferrites is reviewed in details. Importantly, the solar H2 production improvements achieved in the study of the spinel ferrites material as main photocatalyst not a co-catalyst were exclusively reviewed and discussed. Thus, this review would likely motivate researchers to broaden the applications for spinel ferrites-based materials in solar fuel (hydrogen) generation in an economical and eco-friendly approach.

Recently, TiO2(B) has been extensively used in catalytic and energy fields owing to its exceptional crystal structure. But being a metastable state, TiO2(B) is transformed easily into other stable crystalline forms like anatase or rutile phase, and the low crystallinity limits the application of the material in catalysis. A combination of TiO2(B) with anatase, which is benefitted by a homojunction, is proven to be blessed with high activity. Herein, hydrogen production via photocatalytic water-splitting is presented using Cu modified biphasic titania nanotubes achieved by a facile hydrothermal procedure. The systems are well characterized using SEM, TEM, XRD analysis, N2 adsorption study, FTIR, DR-UV, Raman, Photoluminescence, and X-ray photoelectron spectral analysis. The homo-junction developed in titania due to anatase –TiO2 (B), as well as the heterojunction created by the co-catalyst, tune the photocatalytic activity of TiO2 nanotubes positively, as evident from the enhanced hydrogen production over the system.

Hydrogen energy from solar water-splitting is known as an ideal method with which to address the energy crisis and global environmental pollution. Herein, the first-principles calculations are carried out to study the photocatalytic water-splitting performance of single-layer GaInSe3 under biaxial strains from −2% to +2%. Calculations reveal that single-layer GaInSe3 under various biaxial strains has electronic bandgaps ranging from 1.11 to 1.28 eV under biaxial strain from −2% to +2%, as well as a completely separated valence band maximum and conduction band minimum. Meanwhile, the appropriate band edges for water-splitting and visible optical absorption up to ~3 × 105 cm−1 are obtained under biaxial strains from −2% to 0%. More impressively, the solar conversion efficiency of single-layer GaInSe3 under biaxial strains from −2% to 0% reaches over 30%. The OER of unstrained single-layer GaInSe3 can proceed without co-catalysts. These demonstrate that single-layer GaInSe3 is a viable material for solar water-splitting.

Abstract Introducing amorphous and ultrathin nanosheets of transition bimetal phosphate arrays that are highly active in the oxygen evolution reaction (OER) as shells over an electronically modulated crystalline core with low hydrogen absorption energy for an excellent hydrogen evolution reaction (HER) can boost the sluggish kinetics of the OER and HER in alkaline electrolytes. Therefore, in this study, ultrathin and amorphous cobalt‐nickel‐phosphate (CoNiPOx) nanosheet arrays are deposited over vanadium (V)‐doped cobalt‐nitride (V3%‐Co4N) crystalline core nanowires to obtain amorphous‐shell@crystalline‐core mesoporous 3D‐heterostructures (CoNiPOx@V‐Co4N/NF) as bifunctional electrocatalysts. The optimized electrocatalyst shows extremely low HER and OER overpotentials of 53 and 270 mV at 10 mA cm−2, respectively. The CoNiPOx@V3%‐Co4N/NF (+/−) electrolyzer utilizing the electrocatalyst as both anode and cathode demonstrates remarkable overall water‐splitting activity, requiring a cell potential of only 1.52 V at 10 mA cm−2, 30 mV lower than that of the RuO2/NF (+)/20%‐Pt/C/NF (−) electrolyzer. Such impressive bifunctional activities can be attributed to abundant active sites, adjusted electronic structure, lower charge‐transfer resistance, enhanced electrochemically active surface area (ECSA), and surface‐ and volume‐confined electrocatalysis resulting from the synergistic effects of the crystalline V3%‐Co4N core and amorphous CoNiPOx shells boosting water splitting in alkaline media.

This study focuses on the generation of solar thermochemical fuel (hydrogen, syngas) from CO2 and H2O molecules via two-step thermochemical cycles involving intermediate oxygen-carrier redox materials. Different classes of redox-active compounds based on ferrite, fluorite, and perovskite oxide structures are investigated, including their synthesis and characterization associated with experimental performance assessment in two-step redox cycles. Their redox activity is investigated by focusing on their ability to perform the splitting of CO2 during thermochemical cycles while quantifying fuel yields, production rates, and performance stability. The shaping of materials as reticulated foam structures is then evaluated to highlight the effect of morphology on reactivity. A series of single-phase materials including spinel ferrite, fluorite, and perovskite formulations are first investigated and compared to state-of-the-art materials. NiFe2O4 foam exhibits a CO2-splitting activity similar to its powder analog after reduction at 1400 °C, surpassing the performance of ceria but with much slower oxidation kinetics. On the other hand, although identified as high-performing materials in other studies, Ce0.9Fe0.1O2, Ca0.5Ce0.5MnO3, Ce0.2Sr1.8MnO4, and Sm0.6Ca0.4Mn0.8Al0.2O3 are not found to be attractive candidates in this work (compared with La0.5Sr0.5Mn0.9Mg0.1O3). In the second part, characterizations and performance evaluation of dual-phase materials (ceria/ferrite and ceria/perovskite composites) are performed and compared to single-phase materials to assess a potential synergistic effect on fuel production. The ceria/ferrite composite does not provide any enhanced redox activity. In contrast, ceria/perovskite dual-phase compounds in the form of powders and foams are found to enhance the CO2-splitting performance compared to ceria.

The depletion of fossil fuels is a worldwide problem that has led to the discovery of alternative energy sources. Solar energy is the focus of numerous studies due to its huge potential power and environmentally friendly nature. Furthermore, one such area of study is the production of hydrogen energy by engaging photocatalysts using the photoelectrochemical (PEC) method. 3-D ZnO superstructures are extensively explored, showing high solar light-harvesting efficiency, more reaction sites, great electron transportation, and low electron-hole recombination. However, further development requires the consideration of several aspects, including the morphological effects of 3D-ZnO on water-splitting performance. This study reviewed various 3D-ZnO superstructures fabricated through different synthesis methods and crystal growth modifiers, as well as their advantages and limitations. Additionally, a recent modification by carbon-based material for enhanced water-splitting efficiency has been discussed. Finally, the review provides some challenging issues and future perspectives on the improvement of vectorial charge carrier migration and separation between ZnO as well as carbon-based material, using rare earth metals, which appears to be exciting for water-splitting.

Porous high-entropy alloys (HEAs) have emerged as promising electrocatalysts for water-splitting reactions, owing to their rich dissimilar active sites, elemental diversity, and multiple functionalities. The rational design of HEAs for water-splitting attracted great interest in improving their current performance, so it is essential to provide timely updates on this field. This review emphasizes the preparation methods of porous HEAs and the effect of their salient features like high configurational entropy, cocktail effect, lattice distortion, and sluggish diffusion on oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). This mini-review also provides some insights into the current limitations and future perspectives to direct research on the development of ideal HEAs for OER and HER.

The development of earth-abundant element-based highly active and efficient catalysts for the oxygen evolution reaction (OER) is crucial for sustainable energy conversion technologies. In this work, we successfully used the Ni-modified Keggin-type polyoxometalate ([PNi(H2O)W11O39]5-) as a precursor to chemically modify the zeolitic imidazolate framework ZIF 67 via a facile one-pot method. The resulting composite catalyst shows promising electrocatalytic OER performance in a 1 M aqueous KOH solution with high faradaic efficiency. Higher reactivity is observed compared with several reference composites. This synthetic approach could provide access to designing a new class of highly reactive catalysts for targeted reactions.

Herein, hydrothermal fabrication of CdO-g-C3N4 photocatalyst for a substantially better photocatalytic recital in water splitting is presented. The XRD analysis confirms the cubic phase of CdO-g-C3N4, whereas FTIR and UV-VIS studies revealed the presence of respective groups and a median band gap energy (2.55 eV) of the photocatalyst, respectively, which further enhanced its photo-electrochemical (PEC) properties. The SEM displays the oblong structures of g-C3N4 sheets and nano rod-like morphology of CdO and CdO-g-C3N4, respectively. The HR-TEM exhibits morphology & orientation of the grains and substantiates the polycrystal-line nature of CdO-g-C3N4 nanocomposite. The photocatalytic water-splitting concert is evaluated by PEC experiments under 1 SUN visible light irradiation. Linear sweep voltammetry (LSV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) comprehend the CdO-g-C3N4 as a hydrogen evolution photocatalyst. A photocurrent density beyond ≥5 mA/cm2 is recorded from CdO-g-C3N4, which is 5–6 folds greater than pure CdO and g-C3N4. The efficient separation and transfer of charges allocated to CdO-g-C3N4 and fabricating heterojunctions between g-C3N4 and CdO suppresses the unfavorable electron-hole pairs recombination process. Thus, it recesses charge transfer resistance, augmenting enhanced photocatalytic performance under 1 SUN irradiation.

The solar thermochemical two-step splitting of H2O and CO2 based on metal oxide compounds is a promising path for clean and efficient generation of hydrogen and renewable synthetic fuels. The two-step process is based on the endothermic solar thermal reduction of a metal oxide releasing O2 using a high-temperature concentrated solar heat source, followed by the exothermic oxidation of the reduced oxide with H2O and/or CO2 to generate pure H2 and/or CO. This pathway relates to one of the emerging and most promising processes for solar thermochemical fuel production encompassing green H2 and the recycling/valorization of anthropogenic greenhouse gas emissions. It represents an efficient route for solar energy conversion and storage into renewable and dispatchable fuels, by directly converting the whole solar spectrum using heat delivered by concentrating systems. This eliminates the need for photocatalysts or intermediate electricity production, thus bypassing the main limitations of the low-efficient photochemical and electrochemical routes currently seen as the main green methods for solar fuel production. In this context, among the relevant potential redox materials, thermochemical cycles based on volatile and non-volatile metal oxides are particularly attractive. Most redox pairs in two-step cycles proceed with a phase change (solid-to-gas or solid-to-liquid) during the reduction step, which can be avoided by using non-stoichiometric oxides (chiefly, spinel, fluorite, or perovskite-structured materials) through the creation of oxygen vacancies in the lattice. The oxygen sub-stoichiometry determines the oxygen exchange capacity, thus determining the fuel production output per mass of redox-active material. This paper provides an overview of the most advanced cycles involving ZnO/Zn, SnO2/SnO, Fe3O4/FeO, ferrites, ceria, and perovskites redox systems by focusing on their ability to perform H2O and CO2 splitting during two-step thermochemical cycles with high fuel production yields, rapid reaction rates, and performance stability. Furthermore, the possible routes for redox-active material integration and processing in various solar reactor technologies are also described.

A new supramolecular electrocatalyst for Oxygen Evolution Reaction (OER) was synthesized from a central multibridging cobalt tetrapyridylporphyrazine (CoTPyPz) species by attaching four [Ru(bpy)2Cl]+ groups. Both CoTPyPz and the tetraruthenated cobalt porphyrazine species, TRuCoTPyPz, form very homogenous molecular films just by dropcasting their methanol solutions onto GCE electrodes. Such films exhibited low overpotentials for O2 evolution, e.g., 560 e 340 mV, respectively, displaying high stability, typically exceeding 15 h. The kinetic parameters obtained from the Tafel plots showed that the peripheral complexes are very important for the electrocatalytic activity. Hyperspectral Raman images taken along the electrochemical process demonstrated that the cobalt center is the primary active catalyst site, but its performance is enhanced by the ruthenium complexes, which act as electron-donating groups, in the supramolecular system.

Phosphides of transition metals (TMPs) are a developing class of materials for hydrogen evolution reaction (HER) as an alternative to expensive noble metals to produce clean energy. Herein, the nitrogen-doped molybdenum oxide (MoOx) is developed via a facile and simple hydrothermal method, followed by annealing in the N2 atmosphere and phosphorization to form a nitrogen-doped oxygenated molybdenum phosphide (N-MoP) sphere-shaped structure. The developed N-doped phosphide structure depicts enhanced HER activity by reaching a current density of 10 mA cm−2 at a very low overpotential of only 87 mV, which is much better than annealed nitrogen-doped molybdenum oxide (A-MoOx) 138 mV in alkaline medium. N-MoP is a highly efficient electrocatalyst for HER attributed to a more exposed surface, large electrode/electrolyte interface and appropriate binding energies for reactants. This study extends the opportunity of developing nitrogen-doped TMPs, which can display exceptional properties as compared to their oxides.

In this study, zinc-doped (α-Fe2O3:Zn), silver-doped (α-Fe2O3:Ag) and zinc/silver co-doped hematite (α-Fe2O3:Zn/Ag) nanostructures were synthesized by spray pyrolysis. The synthesized nanostructures were used as photoanodes in the photoelectrochemical (PEC) cell for water-splitting. A significant improvement in photocurrent density of 0.470 mAcm−2 at 1.23 V vs. reversible hydrogen electrode (RHE) was recorded for α-Fe2O3:Zn/Ag. The α-Fe2O3:Ag, α-Fe2O3:Zn and pristine hematite samples produced photocurrent densities of 0.270, 0.160, and 0.033 mAcm−2, respectively. Mott–Schottky analysis showed that α-Fe2O3:Zn/Ag had the highest free carrier density of 8.75 × 1020 cm−3, while pristine α-Fe2O3, α-Fe2O3:Zn, α-Fe2O3:Ag had carrier densities of 1.57 × 1019, 5.63 × 1020, and 6.91 × 1020 cm−3, respectively. Electrochemical impedance spectra revealed a low impedance for α-Fe2O3:Zn/Ag. X-ray diffraction confirmed the rhombohedral corundum structure of hematite. Scanning electron microscopy micrographs, on the other hand, showed uniformly distributed grains with an average size of

For the emerging Janus transition metal dichalcogenides (TMD) layered water-splitting photocatalysts, stacking the monolayers to form bilayers has been predicted to be an effective way to improve their photocatalytic performances. To achieve this, the stacking pattern plays an important role. In this work, by means of the density functional theory calculations, we comprehensively estimate energetical stability, light absorption and redox capacity of Janus WSSe bilayer with different stacking patterns. Unfortunately, the Janus WSSe bilayer with the most stable configuration recover the out-of-plane symmetry, which is not in favor of the photocatalytic reactions. However, rolling the Janus WSSe bilayer into double-walled nanotube could stabilize the appropriate stacking pattern with an enhanced instinct dipole moment. Moreover, the suitable band edge positions, high visible light absorbance, outstanding solar-to-hydrogen efficiency (up to 28.48%), and superior carrier separation promise the Janus WSSe double-walled nanotube the potential for the photocatalytic water-splitting application. Our studies not only predict an ideal water-splitting photocatalyst, but also propose an effective way to improve the photocatalytic performances of Janus layered materials.

Hydrogen produced from water using photocatalysts driven by sunlight is a sustainable way to overcome the intermittency issues of solar power and provide a green alternative to fossil fuels. TiO2 has been used as a photocatalyst since the 1970s due to its low cost, earth abundance, and stability. There has been a wide range of research activities in order to enhance the use of TiO2 as a photocatalyst using dopants, modifying the surface, or depositing noble metals. However, the issues such as wide bandgap, high electron-hole recombination time, and a large overpotential for the hydrogen evolution reaction (HER) persist as a challenge. Here, we review state-of-the-art experimental and theoretical research on TiO2 based photocatalysts and identify challenges that have to be focused on to drive the field further. We conclude with a discussion of four challenges for TiO2 photocatalysts—non-standardized presentation of results, bandgap in the ultraviolet (UV) region, lack of collaboration between experimental and theoretical work, and lack of large/small scale production facilities. We also highlight the importance of combining computational modeling with experimental work to make further advances in this exciting field.

Due to its physical and chemical properties, the n-type tungsten oxide (WO3) semiconductor is a suitable photoanode for water decomposition reaction. The responses of the photoelectrochemical PEC water-splitting properties as an effect of structural and optical changes of WO3 thin films, as well as the nature of electrolyte solutions, were studied in this work. The WO3 thins films have been obtained by pulsed laser deposition (PLD) on silicon (Si(001)) covered with platinum substrates using three different laser wavelengths. As the XRD (X-ray diffraction) and XTEM (cross-section transmission electron microscopy) analysis shows, the formation of highly crystalline monocline WO3 phase is formed for the film deposited at 1064 nm wavelength and poor crystalline phases with a large ordering anisotropy, characteristic of 2D structures for the films deposited at 355 nm and 193 nm wavelengths, respectively. The photogenerated current densities Jph depend on the laser wavelength, in both alkaline and acidic electrolyte. The maximum values of the photocurrent density have been obtained for the sample prepared with laser emitting at 355 nm. This behavior can be correlated with the coherent crystallized atomic ordering that appear for long distances (10–15 nm) in the (001) plane of the monoclinic WO3 phase structure films obtained at 355 nm laser wavelength. All the samples show poor current density in dark conditions and they are very stable in both acidic and alkaline solutions. The highest photocurrent density value is obtained in acidic solution for the WO3 thin film prepared by 355 nm laser (29 mA/cm2 at 1.6 V vs. RHE (1.35 V vs. Ag/AgCl)).

Sulfur-doped carbon nanohorns (S-CNHs) were prepared by an easy one-pot solvothermal process and were employed as efficient electrocatalysts towards water splitting. Initially, oxidation of CNHs followed by thermal treatment with the Lawesson’s reagent resulted in the formation of S-CNHs with the sulfur content determined as high as 3%. The S-CNHs were thoroughly characterized by spectroscopic, thermal and electron microscopy imaging means and then electrocatalytically screened. Specifically, S-CNHs showed excellent activity and durability for both O2 and H2 evolution reactions, by showing low overpotential at 1.63 and −0.2 V vs. RHE for oxygen and hydrogen evolution reaction, respectively. Additionally, S-CNHs showed significantly lower Tafel slope value and lower current resistance compared to oxidized and pristine CNHs for both electrocatalytic reactions. The outstanding electrocatalytic properties and high conductivity, along with the high S-doping level, render S-CNHs a promising bifunctional electrocatalyst for water splitting.

This review focuses on tungsten oxide (WO3) and its nanocomposites as photoactive nanomaterials for photoelectrochemical cell (PEC) applications since it possesses exceptional properties such as photostability, high electron mobility (~12 cm2 V−1 s−1) and a long hole-diffusion length (~150 nm). Although WO3 has demonstrated oxygen-evolution capability in PEC, further increase of its PEC efficiency is limited by high recombination rate of photogenerated electron/hole carriers and slow charge transfer at the liquid–solid interface. To further increase the PEC efficiency of the WO3 photocatalyst, designing WO3 nanocomposites via surface–interface engineering and doping would be a great strategy to enhance the PEC performance via improving charge separation. This review starts with the basic principle of water-splitting and physical chemistry properties of WO3, that extends to various strategies to produce binary/ternary nanocomposites for PEC, particulate photocatalysts, Z-schemes and tandem-cell applications. The effect of PEC crystalline structure and nanomorphologies on efficiency are included. For both binary and ternary WO3 nanocomposite systems, the PEC performance under different conditions—including synthesis approaches, various electrolytes, morphologies and applied bias—are summarized. At the end of the review, a conclusion and outlook section concluded the WO3 photocatalyst-based system with an overview of WO3 and their nanocomposites for photocatalytic applications and provided the readers with potential research directions.

A 316-grade woven stainless-steel mesh membrane was investigated as a gas-separation membrane for alkaline water-splitting electrolysis. Its resistance was measured using electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV), with the conclusion that it presented approximately half the resistance of a comparable commercial alternative (ZirfonTM). Its gas-separation performance was analysed using gas chromatography (GC) at 140 mA cm−2, where it achieved 99.25% purity at the hydrogen outlet of the electrolyser. This fell to 97.5% under pumped circulation, which highlights that it is sensitive to pressure differentials. Nevertheless, this mixture is still more than a factor two inside the upper flammability limit of hydrogen in oxygen. It is hoped that such a low-cost material may bring entry-level electrolysis to many hitherto discounted applications.

Mesoporous titanium dioxide materials were prepared using a nanocasting technique involving silica SBA-15 as the hard-template. At an optimal loading of titanium precursor, the hexagonal periodic array of pores in SBA-15 was retained. The phases of titanium dioxide could be easily varied by the number of impregnation cycles and the nature of titanium alkoxide employed. Low number of impregnation cycles produced mixed phases of anatase and TiO2(B). The mesoporous TiO2 materials were tested for solar hydrogen production, and the material consisting of 98% anatase and 2% TiO2(B) exhibited the highest yield of hydrogen from the photocatalytic splitting of water. The periodicity of the pores was an important factor that influenced the photocatalytic activity. This study indicates that mixed phases of titania containing ordered array of pores can be prepared by using the nanocasting strategy.

Solar thermochemical processes have the potential to efficiently convert high-temperature solar heat into storable and transportable chemical fuels such as hydrogen. In such processes, the thermal energy required for the endothermic reaction is supplied by concentrated solar energy and the hydrogen production routes differ as a function of the feedstock resource. While hydrogen production should still rely on carbonaceous feedstocks in a transition period, thermochemical water-splitting using metal oxide redox reactions is considered to date as one of the most attractive methods in the long-term to produce renewable H2 for direct use in fuel cells or further conversion to synthetic liquid hydrocarbon fuels. The two-step redox cycles generally consist of the endothermic solar thermal reduction of a metal oxide releasing oxygen with concentrated solar energy used as the high-temperature heat source for providing reaction enthalpy; and the exothermic oxidation of the reduced oxide with H2O to generate H2. This approach requires the development of redox-active and thermally-stable oxide materials able to split water with both high fuel productivities and chemical conversion rates. The main relevant two-step metal oxide systems are commonly based on volatile (ZnO/Zn, SnO2/SnO) and non-volatile redox pairs (Fe3O4/FeO, ferrites, CeO2/CeO2−δ, perovskites). These promising hydrogen production cycles are described by providing an overview of the best performing redox systems, with special focus on their capabilities to produce solar hydrogen with high yields, rapid reaction rates, and thermochemical performance stability, and on the solar reactor technologies developed to operate the solid−gas reaction systems.

The chemical challenge of economically splitting water into molecular hydrogen and oxygen requires continuous development of more efficient, less-toxic, and cheaper catalyst materials. This review article highlights the potential of iron sulfide-based nanomaterials as electrocatalysts for water-splitting and predominantly as catalysts for the hydrogen evolution reaction (HER). Besides new synthetic techniques leading to phase-pure iron sulfide nano objects and thin-films, the article reviews three new material classes: (a) FeS2-TiO2 hybrid structures; (b) iron sulfide-2D carbon support composites; and (c) metal-doped (e.g., cobalt and nickel) iron sulfide materials. In recent years, immense progress has been made in the development of these materials, which exhibit enormous potential as hydrogen evolution catalysts and may represent a genuine alternative to more traditional, noble metal-based catalysts. First developments in this comparably new research area are summarized in this article and discussed together with theoretical studies on hydrogen evolution reactions involving iron sulfide electrocatalysts.

Z-scheme heterostructures have attracted much attention for their prominent photocatalytic performance. However, the charge transfer mechanism is still ambiguous, and how to design the high-speed channel for interfacial charge transfer is still a big challenge. In the present work, the energy band structure and charge transfer of the MoS _2 /g–C _3 N _4 heterojunction are studied systematically. MoS _2 /g–C _3 N _4 heterojunction could be demonstrated to form a direct Z-scheme system via the analysis of the interfacial band bending. Regrettably, this heterojunction has a low tunneling possibility at the surface, seriously limiting the photocatalytic efficiency. To solve this problem, we try to build high-speed channel between the layers with suitable metal. We make a thorough inquiry of the interface of M–C _3 N _4 and M–MoS _2 heterojunctions (M = Ag, Al, Au, and Pt). Our results reveals that Ag could improve the recombination efficiency of the majority carriers at the interface, which could pretty explain the enhanced photoactivity for g–C _3 N _4/ Ag/MoS _2 system found in experiments. More notably, both Schottky and tunneling barriers vanish at the Al–C _3 N _4 interface, forming an ohmic contact, which predicts a higher performance for electron transport. So that aluminum with the more excellent performance and higher abundance is a promising candidate for sliver in the Z-scheme system.