Recent progress in oxynitride photocatalysts for visible-light-driven water splitting

Abstract

Photocatalytic water splitting into hydrogen and oxygen is a method to directly convert light energy into storable chemical energy, and has received considerable attention for use in large-scale solar energy utilization. Particulate semiconductors are generally used as photocatalysts, and semiconductor properties such as bandgap, band positions, and photocarrier mobility can heavily impact photocatalytic performance. The design of active photocatalysts has been performed with the consideration of such semiconductor properties. Photocatalysts have a catalytic aspect in addition to a semiconductor one. The ability to control surface redox reactions in order to efficiently produce targeted reactants is also important for photocatalysts. Over the past few decades, various photocatalysts for water splitting have been developed, and a recent main concern has been the development of visible-light sensitive photocatalysts for water splitting. This review introduces the study of water-splitting photocatalysts, with a focus on recent progress in visible-light induced overall water splitting on oxynitride photocatalysts. Various strategies for designing efficient photocatalysts for water splitting are also discussed herein.     

Recent advances in earth-abundant photocatalyst materials for solar H2 production

Harvesting solar energy attracts great attention due to its abundant, clean, and permanent characteristics. Thus, photocatalysts have emerged as promising candidates for converting the solar energy to practically useful hydrogen molecules. Tremendous efforts have been devoted in developments of efficient photocatalysts for water splitting, but most of photocatalysts utilize noble metals to improve photocatalytic performance. Progress in photocatalyst materials for the hydrogen production coupled with a better understanding of the basic catalytic mechanisms has enabled better selection of catalytic nanomaterials with improved performance. In this review, we analyze the current state of the art in photocatalyst materials for photochemical hydrogen production through water splitting using earth-abundant materials. We also explore two main factors involved in both material morphology and sacrificial agent to further improve the activity, efficiency and stability of photocatalysts.     

Hierarchical NiO@N‐Doped Carbon Microspheres with Ultrathin Nanosheet Subunits as Excellent Photocatalysts for Hydrogen Evolution

Achieving highly efficient hierarchical photocatalysts for hydrogen evolution is always challenging. Herein, hierarchical mesoporous NiO@N‐doped carbon microspheres (HNINC) are successfully fabricated with ultrathin nanosheet subunits as high‐performance photocatalysts for hydrogen evolution. The unique architecture of N‐doped carbon layers and hierarchical mesoporous structures from HNINC could effectively facilitate the separation and transfer of photo‐induced electron–hole pairs and afford rich active sites for photocatalytic reactions, leading to a significantly higher H₂ production rate than NiO deposited with platinum. Density functional theory calculations reveal that the migration path of the photo‐generated electron transfer is from Ni 3d and O 2p hybrid states of NiO to the C 2p state of graphite, while the photo‐generated holes locate at Ni 4s and Ni 4p hybrid states of NiO, which is beneficial to improve the separation of photo‐generated electron–hole pairs. Gibbs free energy of the intermediate state for hydrogen evolution reaction is calculated to provide a fundamental understanding of the high H₂ production rate of HNINC. This research sheds light on developing novel photocatalysts for efficient hydrogen evolution.     

Recent progress in oxynitride photocatalysts for visible-light-driven water splitting

Photocatalytic water splitting into hydrogen and oxygen is a method to directly convert light energy into storable chemical energy, and has received considerable attention for use in large-scale solar energy utilization. Particulate semiconductors are generally used as photocatalysts, and semiconductor properties such as bandgap, band positions, and photocarrier mobility can heavily impact photocatalytic performance. The design of active photocatalysts has been performed with the consideration of such semiconductor properties. Photocatalysts have a catalytic aspect in addition to a semiconductor one. The ability to control surface redox reactions in order to efficiently produce targeted reactants is also important for photocatalysts. Over the past few decades, various photocatalysts for water splitting have been developed, and a recent main concern has been the development of visible-light sensitive photocatalysts for water splitting. This review introduces the study of water-splitting photocatalysts, with a focus on recent progress in visible-light induced overall water splitting on oxynitride photocatalysts. Various strategies for designing efficient photocatalysts for water splitting are also discussed herein.     

Utilization of a ZnS(en)0.5 photocatalyst hybridized with a CdS component for solar energy conversion to hydrogen

Photocatalytic solar energy conversion to chemical energy attracts great attention due to its high potential in harvesting renewable energy for the future. A ZnS(en)_0.5 photocatalyst hybridized with a CdS component was synthesized by solvothermal and precipitation methods to compare the effect of preparation methods on photocatalytic performance. The highest hydrogen production rate (559 μmol g^?1 h^?1) was achieved from a solvothermally synthesized ZnS(en)_0.5?CdS composite at 80 wt% of CdS content under standard 1-sun-irradiation condition (1000 W/m²). Photocatalytic hydrogen production rates from ZnS(en)_0.5?CdS photocatalysts were highly associated with degrees of charge separation, crystallinity, reduction power, and light absorption. By comparing two different routes for the synthesis of ZnS(en)_0.5?CdS photocatalysts, solvothermally-fabricated material was shown to have a higher photocatalytic activity compared with material fabricated by a precipitation method. This improvement may be due to its excellent crystalline and charge-separation characteristics.     

Carbon Nitride Loaded with an Ultrafine,Monodisperse, Metallic Platinum-Cluster Cocatalyst for the Photocatalytic Hydrogen-Evolution Reaction

For the realization of a next-generation energy society, further improvement in the activity of water-splitting photocatalysts is essential. Platinum (Pt) is predicted to be the most effective cocatalyst for hydrogen evolution from water. However, when the number of active sites is increased by decreasing the particle size, the Pt cocatalyst is easily oxidized and thereby loses its activity. In this study, a method to load ultrafine, monodisperse, metallic Pt nanoclusters (NCs) on graphitic carbon nitride is developed, which is a promising visible-light-driven photocatalyst. In this photocatalyst, a part of the surface of the Pt NCs is protected by sulfur atoms, preventing oxidation. Consequently, the hydrogen-evolution activity per loading weight of Pt cocatalyst is significantly improved, 53 times, compared with that of a Pt-cocatalyst loaded photocatalyst by the conventional method. The developed method is also effective to enhance the overall water-splitting activity of other advanced photocatalysts such as SrTiO₃ and BaLa₄Ti₄O₁₅.     

Acetylene and Diacetylene Functionalized Covalent Triazine Frameworks as Metal-Free Photocatalysts for Hydrogen Peroxide Production: A New Two-Electron Water Oxidation Pathway

Metal-free polymer photocatalysts have shown great promise for photocatalytic H₂O₂ production via two-electron reduction of molecular O₂. The other half-reaction, which is the two-electron oxidation of water, still remains elusive toward H₂O₂ production. However, enabling this water oxidation pathway is critically important to improve the yield and maximize atom utilization efficiency. It is shown that introducing acetylene ( CC ) or diacetylene ( CC CC ) moieties into covalent triazine frameworks (CTFs) can remarkably promote photocatalytic H₂O₂ production. This enhancement is inherent to the incorporated carbon–carbon triple bonds which are essential in modulating the electronic structures of CTFs and suppressing charge recombinations. Furthermore, the acetylene and diacetylene moieties can significantly reduce the energy associated with OH* formation and thus enable a new two-electron oxidation pathway toward H₂O₂ production. The study unveils an important reaction pathway toward photocatalytic H₂O₂ production, reflecting that precise control over the chemical structures of polymer photocatalysts is vital to achieve efficient solar-to-chemical energy conversion.     

Recent advances in visible light-driven water oxidation and reduction in suspension systems

In order to solve the shortage of sustainable energy and the related concern about combustion of fossil fuels, converting the most abundant solar energy into chemical fuels becomes one of the most promising choices to provide the everlasting and environmentally friendly energy vector along with the minimum impact on environment. Among the methods of converting solar energy into chemical fuels, there is a significant interest in the renewable hydrogen production by photocatalysts from abundant water under visible light irradiation. Therefore, the development of efficient photocatalysts for water reduction and oxidation in a suspension system is the footstone for the development of solar energy conversion. In this review, the fundamental theory of photocatalysis and key factors affecting photocatalysis will be introduced first. Then the new materials development covering inorganic materials (oxides, nitrides and sulfides), carbon-based photocatalysts, and semiconductor-coordination compound photocatalysts developed over the past 10?years will be addressed with discussion about dominating factors in the photochemical process. This review would provide a comprehensive reference to exploring the efficient and novel materials working for the solar energy conversion to affordable and sustainable fuels. Finally, the perspective of the technology is also discussed.     

Supercritical water synthesis of nano-particle catalyst on TiO2 and its application in supercritical water gasification of biomass

ABSTRACT

Hydrogen production by catalytic gasification in supercritical water (SCW) is a promising way to utilise biomass resource. Supercritical water not only provides homogeneous and rapid reaction environment for the biomass gasification but also causes catalyst agglomeration problems. In order to prepare activity and stable catalyst for biomass gasification in supercritical water, supercritical water synthesis method was utilised and the preparation method was investigated. Ni, Co, Zn and Cu metal elements were loaded on TiO₂ particles which was proved to be hythothermally steady in supercritical water. And nano-particles were successfully made. Based on gas chromatography/mass spectrometer (GC/MS), scanning electron microscopy, energy dispersive spectrometer (EDS) and X-ray diffraction analysis methods, it turned out that metal catalysts have a uniform spherical structure with diameter around 30 nm. Metal catalysts synthesised with supercritical hydrothermal method showed certain catalytic effects. Ni catalyst had the best performance in stability while Zn catalyst possessed highest hydrogen yield.     

An Unusual Strong Visible‐Light Absorption Band in Red Anatase TiO2 Photocatalyst Induced by Atomic Hydrogen‐Occupied Oxygen Vacancies

Increasing visible light absorption of classic wide‐bandgap photocatalysts like TiO₂ has long been pursued in order to promote solar energy conversion. Modulating the composition and/or stoichiometry of these photocatalysts is essential to narrow their bandgap for a strong visible‐light absorption band. However, the bands obtained so far normally suffer from a low absorbance and/or narrow range. Herein, in contrast to the common tail‐like absorption band in hydrogen‐free oxygen‐deficient TiO₂, an unusual strong absorption band spanning the full spectrum of visible light is achieved in anatase TiO₂ by intentionally introducing atomic hydrogen‐mediated oxygen vacancies. Combining experimental characterizations with theoretical calculations reveals the excitation of a new subvalence band associated with atomic hydrogen filled oxygen vacancies as the origin of such band, which subsequently leads to active photo‐electrochemical water oxidation under visible light. These findings could provide a powerful way of tailoring wide‐bandgap semiconductors to fully capture solar light.     

太阳能光解水制H2催化剂研究进展

氢气是未来人类社会可持续发展的理想能源,光解水制H2的关键是具有高性能的光催化剂.论述了光解水的机理;综述了近年来有关TiO2、过渡金属氧化物、层状金属氧化物、光生物催化剂以及其它新的复合物在光解水方面的研究进展;讨论了提高其光催化反应活性的途径;对存在的问题和前景进行了展望.     

Hydrogen evolution from water splitting on nanocomposite photocatalysts

The photocatalytic production of H₂ in one step is potentially one of the most promising ways for the conversion and storage of solar energy. The paper overviews our recent studies on the photocatalysts splitting water into hydrogen under irradiation. The attention was mainly focused on the promotion effects of nanosized modifications in the interlayer and surface of photocatalysts for hydrogen evolution with visible light. The photocatalytic activity depended significantly on modification techniques, such as loading, proton exchange, and intercalation. The formation of a ‘‘nest’’ on the particle surface promoted a uniform distribution and strong combination of the nanosized particles on the surface of catalysts. By the methods of intercalation and pillaring as well as by selecting both host and guest, a large variety of molecular designed host–guest systems were obtained. Cadmium sulfide (CdS)-intercalated composites showed higher activity and stability. This activity of K₄Ce₂M₁₀O₃₀ (M = Ta, Nb) evolving H₂ under visible light irradiation was enhanced by the incorporation of Pt, RuO₂ and NiO as co-catalysts. Especially, the nanosized NiO_x (Ni–NiO double-layer structure) greatly prompted the photocatalytic H₂ evolution significantly.     

Au NPs@MoS2 Sub‐Micrometer Sphere‐ZnO Nanorod Hybrid Structures for Efficient Photocatalytic Hydrogen Evolution with Excellent Stability

MoS₂ shows promising applications in photocatalytic water splitting, owing to its uniquely optical and electric properties. However, the insufficient light absorption and lack of performance stability are two crucial issues for efficient application of MoS₂ nanomaterials. Here, Au nanoparticles (NPs)@MoS₂ sub‐micrometer sphere‐ZnO nanorod (Au NPs@MoS₂‐ZnO) hybrid photocatalysts have been successfully synthesized by a facile process combining the hydrothermal method and seed‐growth method. Such photocatalysts exhibit high efficiency and excellent stability for hydrogen production via multiple optical‐electrical effects. The introduction of Au NPs to MoS₂ sub‐micrometer spheres forming a core–shell structure demonstrates strong plasmonic absorption enhancement and facilitates exciton separation. The incorporation of ZnO nanorods to the Au NPs@MoS₂ hybrids further extends the light absorption to a broader wavelength region and enhances the exciton dissociation. In addition, mutual contacts between Au NPs (or ZnO nanorods) and the MoS₂ spheres effectively protect the MoS₂ nanosheets from peeling off from the spheres. More importantly, efficiently multiple exciton separations help to restrain the MoS₂ nanomaterials from photocorrosion. As a result, the Au@MoS₂‐ZnO hybrid structures exhibit an excellent hydrogen gas evolution (3737.4 μmol g^?1) with improved stability (91.9% of activity remaining) after a long‐time test (32 h), which is one of the highest photocatalytic activities to date among the MoS₂ based photocatalysts.     

Embedding Au Quantum Dots in Rimous Cadmium Sulfide Nanospheres for Enhanced Photocatalytic Hydrogen Evolution

Rational design and development of new‐generation photocatalysts with high hydrogen evolution activity is recognized as an effective strategy to settle energy crisis. To this regard, hybrid photocatalysts of Au quantum dots embedded in rimous cadmium sulfide nanospheres are synthesized by using a simple hydrothermal process followed by photoreduction. The rimous cadmium sulfide nanospheres with rough surface and irregular fissures greatly strengthen their adhesion and interaction with Au quantum dots, which effectively facilitates the separation, restrains the recombination, and accelerates the consumption of photoinduced electron‐hole pairs. Impressively, the highest photocatalytic activity for hydrogen generation (601.2 μmol h^?1 g^?1) and organic pollutant degradation (100% degradation in 80 min) is obtained by adjusting the Au mass loading to achieve uniform distribution. This work paves new way to the exploitation of highly efficient metal/semiconductor hybrid photocatalysts for clean energy generation and environment restoration.     

Impact of Pt loading methods over mesoporous-assembled TiO2–ZrO2 mixed oxide nanocrystal on photocatalytic dye-sensitized H2 production activity

In this work, the photocatalytic water splitting under visible light irradiation for hydrogen production was investigated by using Eosin Y-sensitized Pt-loaded mesoporous-assembled TiO₂–ZrO₂ mixed oxide nanocrystal photocatalysts. The mesoporous-assembled TiO₂–ZrO₂ mixed oxide with the TiO₂-to-ZrO₂ molar ratio of 95:5 (i.e. 0.95TiO₂–0.05ZrO₂) was synthesized by using a sol–gel process with the aid of a structure-directing surfactant. The Pt loading was comparatively performed via two different effective methods: single-step sol–gel (SSSG) and photochemical deposition (PCD). The synthesized photocatalysts were methodically characterized by N₂ adsorption–desorption, XRD, UV–visible spectroscopy, SEM–EDX, TEM–EDX, TPR, and H₂ chemisorption analyses. The results revealed that the Pt loading by the PCD method greatly enhanced the photocatalytic hydrogen production activity of the synthesized mesoporous-assembled 0.95TiO₂–0.05ZrO₂ mixed oxide photocatalyst more than that by the SSSG method. The optimum Pt loading by the PCD method was experimentally observed at 0.5 wt.%, which was well associated with the maximum Pt dispersion. In addition, the PCD conditions, i.e. UV light irradiation time and UV light intensity, were investigated and optimized to be 2 h and 44 W, respectively.     

金属有机骨架材料在光催化反应中的应用研究进展

环境问题和能源危机的是当今人类社会面临的两大重要问题。光催化技术被认为是解决环境问题和能源危机的有效途径之一。光催化技术利用的关键就是光催化材料的开发。金属有机骨架材料(Metal-organic frameworks,MOFs)是由金属或金属簇与有机配体构筑的一类具有周期性网络结构的新型多孔晶体材料,具有比表面积大、孔道结构规整、孔尺寸可调、催化活性位丰富等优点,被广泛应用于气体存储、气体分离、多相催化、半导体、仿生矿化等多个领域。近十几年来,众多科研工作者尝试将MOFs材料用于光催化反应,并取得了许多优秀的科研成果。尤其是近几年,MOFs在光催化领域的应用受到了越来越多科研工作者的关注。主要综述了近几年MOFs作为光催化剂在催化产氢、CO_2还原、烷基化反应、有机物氧化、有机还原、交叉脱氢偶联反应和去除环境污染物等方面的应用研究进展,并对未来MOFs光催化材料的发展提出了建议。     

Elaborately Modified BiVO4 Photoanodes for Solar Water Splitting

Photoelectrochemical (PEC) cells for solar‐energy conversion have received immense interest as a promising technology for renewable hydrogen production. Their similarity to natural photosynthesis, utilizing sunlight and water, has provoked intense research for over half a century. Among many potential photocatalysts, BiVO₄, with a bandgap of 2.4–2.5 eV, has emerged as a highly promising photoanode material with a good chemical stability, environmental inertness, and low cost. Unfortunately, its charge transport properties are modest, at most a hole diffusion length (L_p) of ≈70 nm. However, recent rapid developments in multiple modification strategies have elevated it to a position as the most promising metal oxide photoanode material. This review summarizes developments in BiVO₄ photoanodes in the past 10 years, in which time it has continuously broken its own performance records for PEC water oxidation. Effective modification techniques are discussed, including synthesis of nanostructures/nanopores, external/internal doping, heterojunction fabrication, surface passivation, and cocatalysts. Tandem systems for unassisted solar water splitting and PEC production of value‐added chemicals are also discussed.     

Design of Heterostructured Hollow Photocatalysts for Solar‐to‐Chemical Energy Conversion

Direct conversion of solar energy into chemical energy in a sustainable manner is one of the most promising solutions to the energy crisis and environmental issues. Fabrication of highly active photocatalysts is of great significance for the practical applications of efficient solar‐to‐chemical energy conversion systems. Among various photocatalytic materials, semiconductor‐based heterostructured photocatalysts with hollow features show distinct advantages. Recent research efforts on rational design of heterostructured hollow photocatalysts toward photocatalytic water splitting and CO₂ reduction are presented. First, both single‐shelled and multishelled heterostructured photocatalysts are surveyed. Then, heterostructured hollow photocatalysts with tube‐like and frame‐like morphologies are discussed. It is intended that further innovative works on the material design of high‐performance photocatalysts for solar energy utilization can be inspired.     

Tantalum (Oxy)Nitride: Narrow Bandgap Photocatalysts for Solar Hydrogen Generation

Photocatalytic water splitting, which directly converts solar energy into hydrogen, is one of the most desirable solar-energy-conversion approaches. The ultimate target of photocatalysis is to explore efficient and stable photocatalysts for solar water splitting. Tantalum (oxy)nitride-based materials are a class of the most promising photocatalysts for solar water splitting because of their narrow bandgaps and sufficient band energy potentials for water splitting. Tantalum (oxy)nitride-based photocatalysts have experienced intensive exploration, and encouraging progress has been achieved over the past years. However, the solar-to-hydrogen (STH) conversion efficiency is still very far from its theoretical value. The question of how to better design these materials in order to further improve their water-splitting capability is of interest and importance. This review summarizes the development of tantalum (oxy)nitride-based photocatalysts for solar water spitting. Special interest is paid to important strategies for improving photocatalytic water-splitting efficiency. This paper also proposes future trends to explore in the research area of tantalum-based narrow bandgap photocatalysts for solar water splitting.