Research Progress of Ferrite Materials for Photoelectrochemical Water Splitting

Photoelectrochemical(PEC)water splitting is an effective strategy to convert solar energy into clean and renewable hydrogen energy.In order to carry out effective PEC conversion,researchers have conducted a lot of exploration and developed a variety of semiconductors suitable for PEC water splitting.Among them,metal oxides stand out due to their higher stability.Compared with traditional oxide semiconductors,ferrite-based photoelectrodes have the advantages of low cost,small band gap,and good stability.Interestingly,due to the unique characteristics of ferrite,most of them have various tunable features,which will be more conducive to the development of efficient PEC electrode.However,this complex metal oxide is also troubled by severe charge recombination and low carrier transport efficiency,resulting in lower conversion efficiency compared to theoretical value.Based on this,this article reviews the structure,preparation methods,characteristics and modification strategies of various common ferrites.In addition,we analyzed the future research direction of ferrite for PEC water splitting,and looked forward to the development of more efficient catalysts.     

Visible‐Light‐Responsive Photoanodes for Highly Active,Stable Water Oxidation

Solar energy is a natural and effectively permanent resource and so the conversion of solar radiation into chemical or electrical energy is an attractive, although challenging, prospect. Photo‐electrochemical (PEC) water splitting is a key aspect of producing hydrogen from solar power. However, practical water oxidation over photoanodes (in combination with water reduction at a photocathode) in PEC cells is currently difficult to achieve because of the large overpotentials in the reaction kinetics and the inefficient photoactivity of the semiconductors. The development of semiconductors that allow high solar‐to‐hydrogen conversion efficiencies and the utilization of these materials in photoanodes will be a necessary aspect of achieving efficient, stable water oxidation. This Review discusses advances in water oxidation activity over photoanodes of n‐type visible‐light‐responsive (oxy)nitrides and oxides.     

Perovskite Oxide Based Electrodes for High‐Performance Photoelectrochemical Water Splitting

Photoelectrochemical (PEC) water splitting is an attractive strategy for the large‐scale production of renewable hydrogen from water. Developing cost‐effective, active and stable semiconducting photoelectrodes is extremely important for achieving PEC water splitting with high solar‐to‐hydrogen efficiency. Perovskite oxides as a large family of semiconducting metal oxides are extensively investigated as electrodes in PEC water splitting owing to their abundance, high (photo)electrochemical stability, compositional and structural flexibility allowing the achievement of high electrocatalytic activity, superior sunlight absorption capability and precise control and tuning of band gaps and band edges. In this review, the research progress in the design, development, and application of perovskite oxides in PEC water splitting is summarized, with a special emphasis placed on understanding the relationship between the composition/structure and (photo)electrochemical activity.     

Tuning the Composition and Structure of Ni@MoC Nanosheets for Highly Active and Stable Electrocatalysis in Water Splitting

The conventional electrolytic water-splitting process for hydrogen production is plagued by high energy consumption, low efficiency, and the requirement of expensive catalysts. Therefore, finding effective, affordable, and stable catalysts to drive this reaction is urgently needed. We report a nanosheet catalyst composed of carbon nanotubes encapsulated with MoC/Mo₂C, the Ni@MoC-700 nanosheet showcases low overpotentials of 275 mV for the oxygen evolution reaction and 173 mV for the hydrogen evolution reaction at a current density of 10 mA ⋅ cm⁻². Particularly noteworthy is its outstanding performance in a two-electrode system, where a cell potential of merely 1.64 V is sufficient to achieve the desired current density of 10 mA ⋅ cm⁻². Furthermore, the catalyst demonstrates exceptional durability, maintaining its activity over a continuous operation of 40 hours with only minimal attenuation in overpotential. These outstanding activity levels and long-term stability unequivocally highlight the promising potential of the Ni@MoC-700 catalyst for large-scale water-splitting applications.     

Cerium-Doped Iron Oxide Nanorod Arrays for Photoelectrochemical Water Splitting

In this work, a simple one-step hydrothermal method was employed to prepare the Ce-doped Fe₂O₃ ordered nanorod arrays (CFT). The Ce doping successfully narrowed the band gap of Fe₂O₃, which improved the visible light absorption performance. In addition, with the help of Ce doping, the recombination of electron/hole pairs was significantly inhibited. The external voltage will make the performance of the Ce-doped sample better. Therefore, the Ce-doped Fe₂O₃ has reached superior photoelectrochemical (PEC) performance with a high photocurrent density of 1.47 mA/cm² at 1.6 V vs. RHE (Reversible Hydrogen Electrode), which is 7.3 times higher than that of pristine Fe₂O₃ nanorod arrays (FT). The Hydrogen (H₂) production from PEC water splitting of Fe₂O₃ was highly improved by Ce doping to achieve an evolution rate of 21 μmol/cm²/h.     

Acid Treatment Enables Suppression of Electron–Hole Recombination in Hematite for Photoelectrochemical Water Splitting

We report a strategy for efficient suppression of electron–hole recombination in hematite photoanodes. Acid‐treated hematite showed a substantially enhanced photocurrent density compared to untreated samples. Electrochemical impedance spectroscopy studies revealed that the enhanced photocurrent is partly due to improved efficiency of charge separation. Transient absorption spectroscopic studies coupled to electrochemical measurements indicate that, in addition to improved bulk electrochemical properties, acid‐treated hematite has significantly decreased surface electron–hole recombination losses owing to a greater yield of the trapped photoelectrons being extracted to the external circuit.     

光催化分解水的研究进展

阐述了利用光催化剂分解水获取氢气的原理和国内外的研究进展,特别对近几年来在开发新型高效半导体催化材料及拓展对可见光的响应等方面的研究工作进行了评述, 阐述了光催化分解水在解决能源紧缺和环境污染等方面的应用前景和今后的研究方向.     

Recent Progress of Transition Metal Compounds as Electrocatalysts for Electrocatalytic Water Splitting

Hydrogen has enormous commercial potential as a secondary energy source because of its high calorific value, clean combustion byproducts, and multiple production methods. Electrocatalytic water splitting is a viable alternative to the conventional methane steam reforming technique, as it operates under mild conditions, produces high-quality hydrogen, and has a sustainable production process that requires less energy. Electrocatalysts composed of precious metals like Pt, Au, Ru, and Ag are commonly used in the investigation of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Nevertheless, their limited availability and expensive cost restrict practical use. In contrast, electrocatalysts that do not contain precious metals are readily available, cost-effective, environmentally friendly, and possess electrocatalytic performance equal to that of noble metals. However, considerable research effort must be devoted to create cost-effective and high-performing catalysts. This article provides a comprehensive examination of the reaction mechanism involved in electrocatalytic water splitting in both acidic and basic environments. Additionally, recent breakthroughs in catalysts for both the hydrogen evolution and oxygen evolution reactions are also discussed. The structure-activity relationship of the catalyst was deep-going discussed, together with the prospects of current obstacles and potential for electrocatalytic water splitting, aiming at provide valuable perspectives for the advancement of economical and efficient electrocatalysts on an industrial scale.     

Shape-Controlled First-Row Transition Metal Vanadates for Electrochemical and Photoelectrochemical Water Splitting

Transition metal vanadates (MVs) possess abundant electroactive sites, short ion diffusion pathways, and optical properties that make them suitable for various electrochemical (EC) and photoelectrochemical (PEC) applications. While these materials are commonly used in energy storage devices like batteries and capacitors, their shape-controlled 1D and 2D morphologies have gained equal popularity in water splitting (WS) technology in recent times. This review focuses on recent progress made on various first-row (3d, 4 s) transition metal vanadates (t-MVs) having controlled one-dimensional (fiber, wire, or rod) and two-dimensional (layered or sheet) morphologies with a specific emphasis on copper vanadates (CuV), cobalt vanadates (CoV), iron vanadates (FeV), and nickel vanadates (NiV). The review covers different aspects of shape-controlled 1D and 2D t-MVs including optoelectrical properties, wet chemistry synthesis, and electrochemical (EC-WS) and photoelectrochemical water splitting (PEC-WS) performance in terms of onset potential, overpotential, and long-term stability or high cyclic performance. The review concludes by providing some possible thoughts on how to promote the water-splitting attributes of shape-controlled t-MVs more effectively.     

光电化学分解水电池的电极性能提高方法及光阴极研究进展

光电化学水分解电池能够将太阳能直接转化为氢能,是一种理想的太阳能利用方式. p-n叠层电池具有理论转换效率高、成本低廉、材料选择灵活等优势,被认为是最有潜力的一类光电化学水分解电池. 然而,目前这类叠层电池的太阳能转化效率还不高,主要原因是单个电极的效率太低. 本文介绍了几种提高光电极分解水性能的方法--减小光生载流子的体相复合、表面复合以及抑制背反应等,同时综述了国内外关于几种p型半导体光阴极的研究进展,如Si、InP、CuIn_1-x GaxS(Se)₂、Cu₂ZnSnS₄等. 通过总结,作者提出一种p-Cu₂ZnSnS₄(CuIn_1-xGaxS(Se)₂)/n-Ta₃N₅(Fe₂O₃) 组装方式,有望获得高效低成本叠层光电化学水分解电池.     

Modulating Benzothiadiazole-Based Covalent Organic Frameworks via Halogenation for Enhanced Photocatalytic Water Splitting

Two-dimensional covalent organic frameworks (2D COFs), an emerging class of crystalline porous polymers, have been recognized as a new platform for efficient solar-to-hydrogen energy conversion owing to their pre-designable structures and tailor-made functions. Herein, we demonstrate that slight modulation of the chemical structure of a typical photoactive 2D COF (Py-HTP-BT-COF) via chlorination (Py-ClTP-BT-COF) and fluorination (Py-FTP-BT-COF) can lead to dramatically enhanced photocatalytic H₂ evolution rates (HER=177.50 μmol h⁻¹ with a high apparent quantum efficiency (AQE) of 8.45 % for Py-ClTP-BT-COF). Halogen modulation at the photoactive benzothiadiazole moiety can efficiently suppress charge recombination and significantly reduce the energy barrier associated with the formation of H intermediate species (H*) on polymer surface. Our findings provide new prospects toward design and synthesis of highly active organic photocatalysts toward solar-to-chemical energy conversion.     

半导体光解水制氢研究:现状、挑战及展望

通过半导体光催化分解水反应实现太阳能向清洁能源氢能的转化,是解决人类面临的能源和环境危机的终极途径之一。该过程的关键是开发宽光谱响应、高效的光催化剂,到目前为止,调控能带结构、制备活性晶面、构建异质结构、负载助催化剂等诸多方法被广泛应用于扩展半导体材料的吸光范围和提高其光催化活性。本文介绍了半导体光解水制氢的基本原理,并综述了该领域的研究进展,重点关注提高半导体光催化活性的方法及其所面临的挑战和瓶颈问题,并结合相关课题组的研究工作提出可能的应对策略。     

半导体光解水制氢研究:现状、挑战及展望

通过半导体光催化分解水反应实现太阳能向清洁能源氢能的转化,是解决人类面临的能源和环境危机的终极途径之一。该过程的关键是开发宽光谱响应、高效的光催化剂,到目前为止,调控能带结构、制备活性晶面、构建异质结构、负载助催化剂等诸多方法被广泛应用于扩展半导体材料的吸光范围和提高其光催化活性。本文介绍了半导体光解水制氢的基本原理,并综述了该领域的研究进展,重点关注提高半导体光催化活性的方法及其所面临的挑战和瓶颈问题,并结合相关课题组的研究工作提出可能的应对策略。     

光电化学水分解中铁酸盐光阴极的制备与改性

由n型半导体光阳极和p型半导体光阴极组成的无偏压光电化学电池通过太阳能可以将水直接转化为高能量密度的氢气,为解决太阳能利用过程中存在的间歇性和储存问题提供了一种潜在的经济有效的解决途径。金属氧化物具有低成本和易制备等优势,相比于发展较成熟的n型光阳极金属氧化物材料,传统的p型光阴极金属氧化物材料由于金属离子易受到光电腐蚀的影响,光电极寿命的提升是个很大的挑战。作为新型的金属氧化物光阴极材料,铁酸盐具有合适的带隙、较好的光稳定性、较正的起始电位以及较低的制备成本,正在成为光电化学电池实际应用中的有力竞争者。本文阐述了光电化学水分解的基本原理与提升光电极性能的一般方法,总结了近年来颇受关注的代表性铁酸盐光阴极材料CuFeO₂、CaFeO₄与LaFeO₃在制备方法、元素掺杂以及表面修饰等方面取得的重要进展,并对铁酸盐光阴极的未来发展趋势做了展望。     

Application of Novel Calix[4]arene Metal-free Sensitizers in Dye-sensitized Photoelectrochemical Cells for Water Splitting

A series of novel calix[4]arene metal-free dyes, featuring macrocyclic structure and unique conical conformation, has been introduced into photoanode-based dye-sensitized electrochemical cell system as photosensitizers. The electrochemical properties of the corresponding sensitized photoanodes were systematically studied in the absence/presence of water oxidation catalyst(WOC). Furthermore, the visible-light-driven overall water-splitting reactions were conducted by fully assembled devices, obtaining a performance trend of Calix-3 > Calix-2 > Calix-1. The corresponding device of Calix-3 exhibited the best photoactivity, giving an initial photocurrent density of ca. 300 μA/cm², an IPEC peak value of ca. 9.0% at 365 nm and a wide photo-respond band up to ca. 620 nm. The best performance of Calix-3 can be attributed to its most effective light-harvesting ability, best ICT transition property, highest oxidation potential and thus best ability of activating WOC. This work offers an inspiration for the application of new-type effective metal-free sensitizers in photocatalytic water-splitting device.     

Photocatalytic Z-scheme Overall Water Splitting: Insight into Different Optimization Strategies for Powder Suspension and Particulate Sheet Systems

Achieving solar light-driven photocatalytic overall water splitting is the ideal and ultimate goal for solving energy and environment issues. Photocatalytic Z-scheme overall water splitting has undergone considerable development in recent years; specific approaches include a powder suspension Z-scheme system with a redox shuttle and a particulate sheet Z-scheme system. Of these, a particulate sheet has achieved a benchmark solar-to-hydrogen efficiency exceeding 1.1 %. Nevertheless, owing to intrinsic differences in the components, structure, operating environment, and charge transfer mechanism, there are several differences between the optimization strategies for a powder suspension and particulate sheet Z-scheme. Unlike a powder suspension Z-scheme with a redox shuttle, the particulate sheet Z-scheme system is more like a miniaturized and parallel p/n photoelectrochemical cell. In this review, we summarize the optimization strategies for a powder suspension Z-scheme with a redox shuttle and particulate sheet Z-scheme. In particular, attention has been focused on choosing appropriate redox shuttle and electron mediator, facilitating the redox shuttle cycle, avoiding redox mediator-induced side reactions, and constructing a particulate sheet. Challenges and prospects in the development of efficient Z-scheme overall water splitting are also briefly discussed.     

Intercalation of Highly Dispersed Metal Nanoclusters into a Layered Metal Oxide for Photocatalytic Overall Water Splitting

Metal nanoclusters (involving metals such as platinum) with a diameter smaller than 1 nm were deposited on the interlayer nanospace of KCa₂Nb₃O₁₀ using the electrostatic attraction between a cationic metal complex (e.g., [Pt(NH₃)₄]Cl₂) and a negatively charged two‐dimensional Ca₂Nb₃O₁₀^? sheet, without the aid of any additional reagent. The material obtained possessed eight‐fold greater photocatalytic activity for water splitting into H₂ and O₂ under band‐gap irradiation than the previously reported analog using a RuO₂ promoter. This study highlighted the superior functionality of Pt nanoclusters with diameters smaller than 1 nm for photocatalytic overall water splitting. This material shows the greatest efficiency among nanosheet‐based photocatalysts reported to date.     

Black Phosphorus-Based Semiconductor Heterojunctions for Photocatalytic Water Splitting

Solar-to-hydrogen (H₂) conversion has been regarded as a sustainable and renewable technique to address aggravated environmental pollution and global energy crisis. The most critical aspect in this technology is to develop highly efficient and stable photocatalysts, especially metal-free photocatalysts. Recently, black phosphorus (BP), as a rising star 2D nanomaterial, has captured enormous attention in photocatalytic water splitting owing to its widespread optical absorption, adjustable direct band gap, and superior carrier migration characteristics. However, the rapid charge recombination of pristine BP has seriously limited its practical application as photocatalyst. The construction of BP-based semiconductor heterojunctions has been proven to be an effective strategy for enhancing the separation of photogenerated carriers. This Minireview attempts to summarize the recent progress in BP-based semiconductor heterojunctions for photocatalytic water splitting, including type-I and type-II heterojunctions, Z-Scheme systems, and multicomponent heterojunctions. Finally, a brief summary and perspective on the challenges and future directions in this field are also provided.     

全固态Z-Scheme光催化材料应用于二氧化碳还原和光催化分解水研究进展

由两种不同的半导体催化剂和电子传输介质建立的Z-Scheme光催化体系,通过在可见光照射下分别在两种半导体催化剂上进行氧化反应和还原反应,实现两步法光催化分解水和二氧化碳还原.相较于离子型Z-Scheme光催化体系,全固态Z-Scheme光催化体系具有适用范围广、无副反应、光源利用率高等特性,具有更加广阔的应用前景.在此,我们简述了Z-Scheme光催化体系的反应机理,综述了全固态Z-Scheme光催化体系在光催化分解水和光催化还原CO₂领域的应用,并对未来全固态Z-Scheme光催化体系的发展进行了展望.