Photocatalytic Water Splitting for Solar Hydrogen Production Using the Carbonate Effect and the Z‐Scheme Reaction

The development of innovative technologies for solar energy conversion and storage is important for solving the global warming problem and for establishing a sustainable society. The photocatalytic water‐splitting reaction using semiconductor powders has been intensively studied as a promising technology for direct and simple solar energy conversion. However, the evolution of H₂ and O₂ gases in a stoichiometric ratio (H₂/O₂ = 2) is very difficult owing to various issues, such as an unfavorable backward reaction and mismatched band potentials. Two important findings have widened the variety of photocatalysts available for stoichiometric water‐splitting, viz. the carbonate anion effect and the Z‐scheme photocatalytic reaction using a redox mediator. The bicarbonate anion has been found to act as a redox catalyst via preferential peroxide formation and subsequent decomposition to O₂. As the Z‐scheme reaction using a redox mediator mitigates band potential mismatches, it is widely applicable for various visible‐light‐active photocatalysts. This review describes the development of photocatalytic water‐splitting for solar hydrogen production using the carbonate anion effect and the Z‐scheme reaction. Moreover, recent developments in photocatalysis–electrolysis hybrid systems, an advanced Z‐scheme reaction concept, are also reviewed for practical and economical hydrogen production.     

Layered Double Hydroxide Nanostructured Photocatalysts for Renewable Energy Production

An enormous research effort is currently being directed towards the development of efficient visible‐light‐driven photocatalysts for renewable energy applications including water splitting, CO₂ reduction and alcohol photoreforming. Layered double hydroxide (LDH)‐based photocatalysts have emerged as one of the most promising candidates to replace TiO₂‐based photocatalysts for these reactions_, owing to their unique layered structure, compositional flexibility, controllable particle size, low manufacturing cost and ease of synthesis. By introducing defects into LDH materials through the control of their size to the nanoscale, the atomic structure, surface defect concentration, and electronic and optical characteristics of LDH materials can be strategically engineered for particular applications. Furthermore, through the use of advanced characterization techniques such as X‐ray absorption fine structure, positron annihilation spectrometry, X‐ray photoelectron spectroscopy, electron spin resonance, density‐functional theory calculations, and photocatalytic tests, structure‐activity relationships can be established and used in the rational design of high‐performance LDH‐based photocatalysts for efficient solar energy capture. LDHs thus represent a versatile platform for semiconductor photocatalyst development with application potential across the energy sector.     

g‐C3N4‐Based Heterostructured Photocatalysts

Photocatalysis is considered as one of the promising routes to solve the energy and environmental crises by utilizing solar energy. Graphitic carbon nitride (g‐C₃N₄) has attracted worldwide attention due to its visible‐light activity, facile synthesis from low‐cost materials, chemical stability, and unique layered structure. However, the pure g‐C₃N₄ photocatalyst still suffers from its low separation efficiency of photogenerated charge carriers, which results in unsatisfactory photocatalytic activity. Recently, g‐C₃N₄‐based heterostructures have become research hotspots for their greatly enhanced charge carrier separation efficiency and photocatalytic performance. According to the different transfer mechanisms of photogenerated charge carriers between g‐C₃N₄ and the coupled components, the g‐C₃N₄‐based heterostructured photocatalysts can be divided into the following categories: g‐C₃N₄‐based conventional type II heterojunction, g‐C₃N₄‐based Z‐scheme heterojunction, g‐C₃N₄‐based p–n heterojunction, g‐C₃N₄/metal heterostructure, and g‐C₃N₄/carbon heterostructure. This review summarizes the recent significant progress on the design of g‐C₃N₄‐based heterostructured photocatalysts and their special separation/transfer mechanisms of photogenerated charge carriers. Moreover, their applications in environmental and energy fields, e.g., water splitting, carbon dioxide reduction, and degradation of pollutants, are also reviewed. Finally, some concluding remarks and perspectives on the challenges and opportunities for exploring advanced g‐C₃N₄‐based heterostructured photocatalysts are presented.     

Enhanced Photocatalytic Activity for H2 Evolution under Irradiation of UV–Vis Light by Au-Modified Nitrogen-Doped TiO2

Background Purpose

Photocatalytic water splitting for hydrogen evolution is a potential way to solve many energy and environmental issues. Developing visible-light-active photocatalysts to efficiently utilize sunlight and finding proper ways to improve photocatalytic activity for H₂ evolution have always been hot topics for research. This study attempts to expand the use of sunlight and to enhance the photocatalytic activity of TiO₂ by N doping and Au loading.

Methods

Au/N-doped TiO₂ photocatalysts were synthesized and successfully used for photocatalytic water splitting for H₂ evolution under irradiation of UV and UV–vis light, respectively. The samples were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PL), and photoelectrochemical characterizations.

Results

DRS displayed an extension of light absorption into the visible region by doping of N and depositing with Au, respectively. PL analysis indicated electron-hole recombination due to N doping and an efficient inhibition of electron-hole recombination due to the loaded Au particles. Under the irradiation of UV light, the photocatalytic hydrogen production rate of the as-synthesized samples followed the order Au/TiO₂ > Au/N-doped TiO₂ > TiO₂ > N-doped TiO₂. While under irradiation of UV–vis light, the N-TiO₂ and Au/N-TiO₂ samples show higher H₂ evolution than their corresponding nitrogen-free samples (TiO₂ and Au/TiO₂). This inconsistent result could be attributed to the doping of N and the surface plasmonic resonance (SPR) effect of Au particles extending the visible light absorption. The photoelectrochemical characterizations further indicated the enhancement of the visible light response of Au/N-doped TiO₂.

Conclusion

Comparative studies have shown that a combination of nitrogen doping and Au loading enhanced the visible light response of TiO₂ and increased the utilization of solar energy, greatly boosting the photocatalytic activity for hydrogen production under UV–vis light.     

2D Metal Organic Framework Nanosheet: A Universal Platform Promoting Highly Efficient Visible‐Light‐Induced Hydrogen Production

2D metal organic frameworks (MOF) have received tremendous attention due to their organic–inorganic hybrid nature, large surface area, highly exposed active sites, and ultrathin thickness. However, the application of 2D MOF in light‐to‐hydrogen (H₂) conversion is rarely reported. Here, a novel 2D MOF [Ni(phen)(oba)]_n·0.5nH₂O (phen = 1,10‐phenanthroline, oba = 4,4′‐oxybis(benzoate)) is for the first time employed as a general, high‐performance, and earth‐abundant platform to support CdS or Zn_0.8Cd_0.2S for achieving tremendously improved visible‐light‐induced H₂‐production activity. Particularly, the CdS‐loaded 2D MOF exhibits an excellent H₂‐production activity of 45 201 µmol h^?1 g^?1, even exceeding that of Pt‐loaded CdS by 185%. Advanced characterizations, e.g., synchrotron‐based X‐ray absorption near edge structure, and theoretical calculations disclose that the interactive nature between 2D MOF and CdS, combined with the high surface area, abundant reactive centers, and favorable band structure of 2D MOFs, synergistically contribute to this distinguished photocatalytic performance. The work not only demonstrates that the earth‐abundant 2D MOF can serve as a versatile and effective platform supporting metal sulfides to boost their photocatalytic H₂‐production performance without noble‐metal co‐catalysts, but also paves avenues to the design and synthesis of 2D‐MOF‐based heterostructures for catalysis and electronics applications.     

A Floating Sheet for Efficient Photocatalytic Water Splitting

Solar photocatalytic water splitting has been a promising way to provide clean hydrogen energy. There are two weaknesses in the typical photocatalytic process in which photocatalysts are generally dispersing in water under stir. One is the inadequate utilization of light energy and the other one is the cumbersome operation in the recycling procedure. This study demonstrates an efficient solar photocatalytic water splitting using a floating sheet with a novel WSe₂ cocatalyst. The sheet is fabricated by laser‐depositing WSe₂ film on a carbon foam (CF) substrate and drop‐casting of the synthesized nanodiamond‐embedded Cu₂O (NEC) photocatalysts. This is a new‐type artificial photocatalytic system that overcomes the above‐mentioned weaknesses of a powder‐dispersing system. The WSe₂ cocatalyst acts as an electron sink to promote electron–hole separation, resulting in the further improvement of photocatalytic performance. This floating NEC/WSe₂/CF structure achieves efficient water splitting upon simulated solar irradiation with an increased H₂ evolution rate, which is 13.2 times that of the powder‐dispersing system. This study offers a strategy for the design of new‐type photocatalytic system and discovery of alternative noble metal‐free cocatalysts.     

Leaf‐Mosaic‐Inspired Vine‐Like Graphitic Carbon Nitride Showing High Light Absorption and Efficient Photocatalytic Hydrogen Evolution

Green plants use solar energy efficiently in nature. Simulating the exquisite structure of a natural photosynthesis system may open a new approach for the construction of desirable photocatalysts with high light harvesting efficiency and performance. Herein, inspired by the excellent light utilization of “leaf mosaic” in plants, a novel vine‐like g‐C₃N₄ (V‐CN) is synthesized for the first time by copolymerizing urea with dicyandiamide‐formaldehyde (DF) resin. The as‐prepared V‐CN exhibits ultrahigh photocatalytic hydrogen production of 13.6 mmol g^?1 h^?1 under visible light and an apparent quantum yield of 12.7% at 420 nm, which is ≈38 times higher than that of traditional g‐C₃N₄, representing one of the highest‐activity g‐C₃N₄‐based photocatalysts. This super photocatalytic performance is derived from the unique leaf mosaic structure of V‐CN, which effectively improves its light utilization and affords a larger specific surface area. In addition, the introduction of DF resin further optimizes the energy band of V‐CN, extends its light absorption, and improves its crystallinity and interfacial charge transport, resulting in high performance. It is an easy and green strategy for the preparation of broad‐spectrum, high‐performance g‐C₃N₄, which presents significant advancement for the design of other nanophotocatalysts by simulating the fine structure of natural photosynthesis.     

Dramatic Enhancement of CO2 Photoreduction by Biodegradable Light‐Management Paper

Photocatalytic reduction of CO₂ with H₂O vapor is gaining increased interest because it is a promising “green chemistry” route for the direct conversion of CO₂ to value‐added chemicals driven by solar energy. To increase the efficiency of photocatalytic conversion, most efforts are made by exploring various photocatalysts while little effort on advanced light management. For the first time, it is demonstrated that bio‐degradable transparent paper with excellent light diffusivity can effectively enhance the light utilization of photocatalytic reactions when attached on the device surface, and thus greatly increase the conversion efficiency. As a proof‐of‐concept, a graphitic carbon nitride (g‐C₃N₄) photocatalyst with transparent paper attached, exhibited 1.5 times higher photocatalytic activity than bare g‐C₃N₄ in the reduction of CO₂ under visible light irradiation. The improved catalytic performance can be ascribed to the (1) refractive index matching and (2) enhanced light absorption via prolonged light traveling path in transparent paper, which decreases the light reflection at surface and traps the absorbed light inside, leading to an increased light absorption at the active layer of the device. The transparent paper with a controllable light management behavior has an unprecedented potential for applications in photocatalysis as a general method for improved light utilization.     

Nitrogen‐Doped Carbon‐Coated CuO‐In2O3 p–n Heterojunction for Remarkable Photocatalytic Hydrogen Evolution

CuO as a catalyst has shown promising application prospects in photocatalytic splitting of water into hydrogen (H₂). However, the instability of CuO in amine aqueous solution limits the applications of CuO‐based photocatalysts in the photocatalytic H₂ evolution. In this work, a novel dodecahedral nitrogen (N)‐doped carbon (C) coated CuO‐In₂O₃ p–n heterojunction (DNCPH) is designed and synthesized by directly pyrolyzing benzimidazole‐modified dodecahedral Cu/In‐based metal‐organic frameworks, showing long‐term stability in triethanolamine (TEOA) aqueous solution and excellent photocatalytic H₂ production efficiency. The improved stability of DNCPH in TEOA solution is ascribed to the alleviation of electron deficiency in CuO by forming the p–n heterojunction and the protection with coated N‐doped C layer. Based on detailed theoretical calculations and experimental studies, it is found that the improved separation efficiency of photogenerated electron/hole pairs and the mediated adsorption behavior (|?G_H*|→0) by coupling N‐doped C layer with CuO‐In₂O₃ p–n heterojunction lead to the excellent photocatalytic H₂ production efficiency of DNCPH. This work provides a feasible strategy for effectively applying CuO‐based photocatalysts in photocatalytic H₂ production.     

Graphene‐Based Nanocomposites for Energy Storage

Since the first report of using micromechanical cleavage method to produce graphene sheets in 2004, graphene/graphene‐based nanocomposites have attracted wide attention both for fundamental aspects as well as applications in advanced energy storage and conversion systems. In comparison to other materials, graphene‐based nanostructured materials have unique 2D structure, high electronic mobility, exceptional electronic and thermal conductivities, excellent optical transmittance, good mechanical strength, and ultrahigh surface area. Therefore, they are considered as attractive materials for hydrogen (H₂) storage and high‐performance electrochemical energy storage devices, such as supercapacitors, rechargeable lithium (Li)‐ion batteries, Li–sulfur batteries, Li–air batteries, sodium (Na)‐ion batteries, Na–air batteries, zinc (Zn)–air batteries, and vanadium redox flow batteries (VRFB), etc., as they can improve the efficiency, capacity, gravimetric energy/power densities, and cycle life of these energy storage devices. In this article, recent progress reported on the synthesis and fabrication of graphene nanocomposite materials for applications in these aforementioned various energy storage systems is reviewed. Importantly, the prospects and future challenges in both scalable manufacturing and more energy storage‐related applications are discussed.     

Microwave‐Induced Metal Dissolution Synthesis of Core–Shell Copper Nanowires/ZnS for Visible Light Photocatalytic H2 Evolution

A microwave‐induced metal dissolution strategy is developed for in situ synthesis of copper nanowires/ZnS (CuNWs/ZnS) hybrids with core–shell structure. The CuNWs are used as microwave antennas to create local “super‐hot” surfaces to further initiate ZnS crystallization with full coverage on CuNWs. With the help of S^2?, the hot metal surface further results in the CuNWs dissolution with promoted Cu⁺ diffusion and incorporation into the ZnS lattice. With the narrowed bandgap of ZnS and the strongly coupled interface between CuNWs and ZnS created by microwaves, the as‐prepared hybrid composites exhibit an enhanced activity and stability in visible light for the photocatalytic H₂ evolution. The corresponding H₂ evolution rate reaches up to 10722 µmol h^?1 g^?1 with apparent quantum efficiency (AQE) of 69% under 420 nm LED irradiation, showing a remarkably high AQE among the noble‐metal free visible light‐driven photocatalysts and demonstrating a promising potential in practical applications to deal with the energy crisis.     

In Situ Phase‐Induced Spatial Charge Separation in Core–Shell Oxynitride Nanocube Heterojunctions Realizing Robust Solar Water Splitting

Efficient spatial charge separation is critical for solar energy conversion over solid photocatalysts. The development of efficient visible‐light photocatalysts has been of immense interest, but with limited success. Here, multiband core–shell oxynitride nanocube heterojunctions composed of a tantalum nitride (Ta₃N₅) core and nitrogen‐doped sodium tantalate (NaTaON) shell have been constructed via an in situ phase‐induced etching chemical strategy. The photocatalytic water splitting performance of sub‐20‐nm Ta₃N₅@NaTaON junctions exhibits an extraordinarily high photocatalytic activity toward oxygen and hydrogen evolution. Most importantly, the combined experimental results and theoretical calculations reveal that the strong interfacial Ta? O? N bonding connection as a touchstone among Ta₃N₅@NaTaON junctions provides a continuous charge transport pathway rather than a random charge accumulation. The prolonged photoexcited charge carrier lifetime and suitable band matching between the Ta₃N₅ core and NaTaON shell facilitate the separation of photoinduced electron–hole pairs, accounting for the highly efficient photocatalytic performance. This work establishes the use of (oxy)nitride heterojunctions as viable photocatalysts for the conversion of solar energy into fuels.     

Exceptional Visible‐Light‐Driven Cocatalyst‐Free Photocatalytic Activity of g‐C3N4 by Well Designed Nanocomposites with Plasmonic Au and SnO2

In this work, plasmonic Au/SnO₂/g‐C₃N₄ (Au/SO/CN) nanocomposites have been successfully synthesized and applied in the H₂ evolution as photocatalysts, which exhibit superior photocatalytic activities and favorable stability without any cocatalyst under visible‐light irradiation. The amount‐optimized 2Au/6SO/CN nanocomposite capable of producing approximately 770 μmol g^?1 h^?1 H₂ gas under λ > 400 nm light illumination far surpasses the H₂ gas output of SO/CN (130 μmol g^?1), Au/CN (112 μmol g^?1 h^?1), and CN (11 μmol g^?1 h^?1) as a contrast. In addition, the photocatalytic activity of 2Au/6SO/CN maintains unchanged for 5 runs in 5 h. The enhanced photoactivity for H₂ evolution is attributed to the prominently promoted photogenerated charge separation via the excited electron transfer from plasmonic Au (≈520 nm) and CN (470 nm > λ > 400 nm) to SO, as indicated by the surface photovoltage spectra, photoelectrochemical I–V curves, electrochemical impedance spectra, examination of formed hydroxyl radicals, and photocurrent action spectra. Moreover, the Kelvin probe test indicates that the newly aligned conduction band of SO in the fabricated 2Au/6SO/CN is indispensable to assist developing a proper energy platform for the photocatalytic H₂ evolution. This work distinctly provides a feasible strategy to synthesize highly efficient plasmonic‐assisted CN‐based photocatalysts utilized for solar fuel production.     

3D‐Branched ZnO/CdS Nanowire Arrays for Solar Water Splitting and the Service Safety Research

Modulation of broadband light trapping through assembly of 3D structures and modification with narrow band‐gap semiconductors provide an effective way to improve the photoelectrochemical (PEC) performance. Here, 3D‐branched ZnO nanowire arrays (NWAs) modified with cadmium sulfide (CdS) nanoparticles are designed and synthesized via solution chemical routes. The 3D‐branched ZnO NWA–CdS nanoparticle photoanodes show an excellent PEC performance in UV and visible region and the maximum photo‐to‐hydrogen conversion efficiency reaches to 3.1%. The high performance of 3D‐branched ZnO NWA–CdS composites is mainly attributed to the excellent carrier collection capability and high light‐trapping ability of 3D‐branched ZnO NWAs as well as the excellent photocatalytic activity of CdS nanoparticles in the visible region. In addition, the photocorrosion mechanism of 3D‐branched ZnO NWA–CdS photoanodes is systematically investigated, and a protective TiO₂ layer is deposited onto the photoanodes to elevate the PEC stability. The results benefit a deeper understanding of the role of 3D‐branched structures decorated with narrow band‐gap semiconductors in solar water splitting.     

Photo/Electrochemical Applications of Metal Sulfide/TiO2 Heterostructures

Developing efficient and affordable catalysts is of great significance for energy and environmental sustainability. Heterostructure photocatalysts exhibit a better performance than either of the parent phases as it changes the band bending at the interfaces and provides a driving force for carrier separation, thus mitigating the effects of carrier recombination and back‐reaction. Herein, the photo/electrochemical applications of a variety of metal sulfides (MS_x) (MoS₂, CdS, CuS, PbS, SnS₂, ZnS, Ag₂S, Bi₂S₃, and In₂S₃)/TiO₂ heterojunctions are summarized, including organic degradation, water splitting, and CO₂ reduction conversion. First, a general introduction on each MS_x material (especially bandgap structures) will be given. Then the photo/electrochemical applications based on MS_x/TiO₂ heterostructures are reviewed from the perspective of light harvesting ability, charge carrier separation and transportation, and surface chemical reactions. Special focus is given to CdS/TiO₂ and PbS/TiO₂‐based quantum dot sensitized solar cells. Ternary composites by taking advantages of positive synergetic effects are also well summarized. Finally, conclusions are made regarding approaches for structure design, and the authors' perspective on future architectural design and electrode construction is given. This work will make up the gap for TiO₂ nanocomposites and shed light on the fabrication of more efficient MS_x‐metal oxide junctions in photo/electrochemical applications.     

Single‐Crystalline Nanomesh Tantalum Nitride Photocatalyst with Improved Hydrogen‐Evolving Performance

Tantalum nitride (Ta₃N₅) with a suitable bandgap (≈2 eV) is regarded as one of the most promising photocatalysts for efficient solar energy harvesting and conversion. However, Ta₃N₅ suffers from low hydrogen production activity due to the low carrier mobility and fast carrier recombination. Thus, the design of Ta₃N₅ nanostructures to facilitate charge carrier transport and improve photocatalytic performance remains a challenge. This study reports a new type of ultrathin (≈2 nm) Ta₃N₅ nanomesh with high specific surface area (284.6 m² g^?1) and excellent crystallinity by an innovative bottom‐up graphene oxide templated strategy. The resulting Ta₃N₅ nanomeshes demonstrate drastically improved electron transport ability and prolonged lifetime of charge carriers, due to the nature of high surface area and excellent crystallinity. As a result, when used as photocatalysts, the Ta₃N₅ nanomeshes exhibit a greater than tenfold improvement in solar hydrogen production compared to bulk counterparts. This work provides an effective and generic strategy for designing 2D ultrathin nanomesh structures for nonlayered materials with improved catalytic activity.     

Long‐Lived,Visible‐Light‐Excited Charge Carriers of TiO2/BiVO4 Nanocomposites and their Unexpected Photoactivity for Water Splitting

Different mole ratios of TiO₂/BiVO₄ nanocomposites with effective contacts have are fabricated by putting BiVO₄ nanoparticles into the TiO₂ sol, followed by thermal treatment at 450 °C. Based on the transient‐state surface photovoltage responses and the atmosphere‐controlled steady‐state surface photovoltage spectra, it is concluded that the photogenerated charge carriers in the TiO₂/BiVO₄ nanocomposite with a proper mole ratio (5%) display much longer lifetime and higher separation than those in the BiVO₄ alone. This is responsible for the unexpected activity for photoelectrochemical oxidation of water, for photocatalytic production of H₂, and for photocatalytic degradation of phenol as a model pollutant under visible irradiation. Moreover, it is suggested that the prolonged lifetime and increased separation of photogenerated charges in the fabricated TiO₂/BiVO₄ nanocomposite is attributed to the unusual spatial transfer of visible‐excited high‐energy electrons of BiVO₄ to TiO₂. This work will provide feasible routes to synthesize visible‐light responsive nanomaterials for efficient solar utilization.     

3D Graphene‐Based H2‐Production Photocatalyst and Electrocatalyst

Hydrogen (H₂) has been deemed as the most promising and valuable alternative to nonrenewable fossil fuels. Photocatalytic and electrocatalytic water splitting are considered to be the most efficient and environmentally friendly approaches for the sustainable H₂ evolution reaction (HER). Graphene with a 3D framework has been utilized for the HER due to its unique structure and properties, including its hierarchical network, large specific surface area, diverse pore distribution, outstanding light absorption ability, and excellent electrical conductivity. The large specific surface area and hierarchically porous structure of 3D graphene can not only maximize the exposure of active sites but also promote electron transfer and gas product diffusion. In addition, the free‐standing 3D graphene monolith is easily recycled compared with powder phase support, which can prevent the loss of active catalysts. By making full use of the aforementioned merits, 3D graphene‐based composite materials show great promise as high‐performance catalysts toward photocatalytic and electrocatalytic HER. In this review, recent advances in fabricating 3D graphene‐based composite materials and their applications in both photocatalytic and electrocatalytic HER are summarized and discussed. Furthermore, the current challenges and future vision associated with the design, fabrication, and integration of 3D graphene‐based composite materials toward HER are put forward.     

Recent Advancement of p‐ and d‐Block Elements,Single Atoms,and Graphene‐Based Photoelectrochemical Electrodes for Water Splitting

Solar‐assisted photoelectrochemical (PEC) water splitting to produce hydrogen energy is considered the most promising solution for clean, green, and renewable sources of energy. For scaled production of hydrogen and oxygen, highly active, robust, and cost‐effective PEC electrodes are required. However, most of the available semiconductors as a PEC electrodes have poor light absorption, material degradation, charge separation, and transportability, which result in very low efficiency for photo‐water splitting. Generally, a promising photoelectrode is obtained when the surface of the semiconductor is modified/decorated with a suitable co‐catalyst because it increases the light absorbance spectrum and prevents electron–hole recombination during photoelectrode reactions. In this regard, numerous p‐ and d‐block elements, single atoms, and graphene‐based PEC electrodes have been widely used as semiconductor/co‐catalyst junctions to boost the performances of PEC overall water splitting. This review enumerates the recent progress and applications of p‐ and d‐block elements, single atoms, and graphene‐based PEC electrodes for water splitting. The focus is placed on fundamental mechanism, efficiency, cells design, and various aspects that contribute to the large‐scale prototype device. Finally, future perspectives, summary, challenges, and outlook for improving the activity of PEC photoelectrodes toward whole‐cell water splitting are addressed.     

Bismuth Tantalum Oxyhalogen: A Promising Candidate Photocatalyst for Solar Water Splitting

As wide range of light absorption and suitable redox potentials are prerequisites for photocatalytic water splitting, exploring new semiconductor‐based materials with proper band structures for water splitting still calls for longstanding efforts. In this work, a series of photocatalysts, bismuth tantalum oxyhalide, Bi₄TaO₈X (X = Cl, Br), with valence band and conduction band positions at ≈?0.70 and ≈1.80 eV versus the reversible hydrogen electrode (RHE), respectively, are found to be capable for both water oxidation and reduction under visible light irradiation. Using flux synthetic methods, Bi₄TaO₈X (X = Cl, Br) with microplatelet morphology can be successfully prepared. The photocatalyst based on these materials shows an apparent quantum efficiency as high as 20% at 420 nm for water oxidation. In addition, a Z‐scheme system coupling Bi₄TaO₈Br with Ru/SrTiO₃:Rh is successfully achieved for overall water splitting with a stoichiometric ratio of H₂ and O₂ evolutions. This work demonstrates a new series of semiconductors Bi₄TaO₈X (X = Cl, Br) with the promising application in the field of solar energy utilization.