Near infrared-driven photoelectrochemical water splitting: Review and future prospects

Photoelectrochemical (PEC) water splitting supplies an environmentally friendly, sustainable approach to generating renewable hydrogen fuels. Oxides semiconductors, e.g. TiO₂, BiVO₄, and Fe₂O₃, have been widely developed as photoelectrodes to demonstrate the utility in PEC systems. Even though significant effort has been made to increase the PEC efficiency, these materials are still far from practical applications. The main issue of metal oxides is the wide bandgap energy that hinders effective photons harvesting from sunlight. In solar spectrum, over 40% of the energy is located in the near-infrared (NIR) region. Developing sophisticated PEC systems that can be driven by NIR illumination is therefore essential. This review gives a concise overview on PEC systems based on the use of NIR-driven photoelectrodes. Promising candidates as efficient yet practical NIR-responsive photoelectrodes are suggested and discussed. Future outlooks on the advancement of PEC water splitting are also proposed.     

提高氧化铁光电催化分解水效率的策略进展

为了解决能源危机与环境污染问题,发展一种可再生的清洁能源至关重要.太阳能是一种取之不尽用之不竭的清洁能源,而氢气是一种良好的能源载体.利用太阳能光电催化水分解制氢,是一项有望能够解决能源与环境问题的技术,具有很大的应用前景.其中,氧化铁因为具有合适的能带位置与带隙、良好的稳定性与廉价无毒等优点,成为一种理想的光阳极材料.但是,在实际的测试中,氧化铁仅仅只能得到一个较低的光电转换效率,这可能是因为其较短的空穴扩散距离、较低的电导率以及极度缓慢的水氧化反应动力学所致.整个光电催化水氧化可分为三个过程,即光吸收过程、电荷分离过程以及表面空穴注入过程.这三个过程的效率共同决定了器件的太阳能转化效率.鉴于此,本文将从如何提高这三个效率的角度出发,总结近期研究报道中提高氧化铁光电催化分解水效率的一些策略.光吸收过程是指半导体中价带的电子在吸收具有一定能量的光子后发生跃迁,产生空穴-电子对的过程.其光子的损失主要来源于光的反射、透射以及半导体吸收边的限制.提高光吸收效率的主要策略包括制备具有特定纳米结构的氧化铁电极、利用表面等离子体共振效应以及组成双光吸收系统和掺杂等.电荷分离过程指的是受光激发产生的空穴电子对,在内建电场的作用下发生电荷分离,即光生空穴流向电极表面,光生电子流向半导体内部并从外电路导出.电荷分离效率的损失主要来源于光生载流子在迁移过程中的复合.因此,为了提高电荷分离效率,常见的策略是提高载流子在电荷分离过程中的复合时间τ₁和减少电荷迁移到表面(空穴)或者基底(电子)的时间τ₂.具体的策略包括制备特定的纳米结构(缩短体表相距离,减少τ₂)、构建异质结(增强能带弯曲,提高τ₁和减少τ₂)、掺杂(减少τ₂)和钝化复合中心(提高τ₁)等.表面空穴注入是指到达表面的光生空穴发生水氧化反应生成氧气的过程.除了空穴注入外,表面还可能存在复合与逆反应过程.因此,为了提高表面空穴注入效率,我们既可以提高水氧化反应动力学,具体的手段包括引入水氧化催化剂、F掺杂和碱处理等;也可以采用减少复合反应的策略,具体的方法包括引入钝化层、酸处理和高温热处理等;还可以采用减少逆反应的方法,最常见的手段就是在基底与氧化铁层之间引入电子阻挡层.上述三种途径都能提高表面空穴注入效率.最后,通过结合上述的一些策略,目前得到的最高性能的氧化铁电极在1.23 V(相对于可逆氢电极)能够达到6 mA cm^?2的光电催化分解水电流,但这个值依然明显低于氧化铁的理论值(12.6 mA cm^?2).这可能是由于体相复合所致.除此之外,氧化铁表面的水氧化机理现在依然不清晰,这些都是需要我们在未来解决的问题.     

Iron Oxide Photoelectrode with Multidimensional Architecture for Highly Efficient Photoelectrochemical Water Splitting

Nanostructured metal oxide semiconductors have shown outstanding performances in photoelectrochemical (PEC) water splitting, but limitations in light harvesting and charge collection have necessitated further advances in photoelectrode design. Herein, we propose anodized Fe foams (AFFs) with multidimensional nano/micro-architectures as a highly efficient photoelectrode for PEC water splitting. Fe foams fabricated by freeze-casting and sintering were electrochemically anodized and directly used as photoanodes. We verified the superiority of our design concept by achieving an unprecedented photocurrent density in PEC water splitting over 5 mA cm⁻² before the dark current onset, which originated from the large surface area and low electrical resistance of the AFFs. A photocurrent of over 6.8 mA cm⁻² and an accordingly high incident photon-to-current efficiency of over 50 % at 400 nm were achieved with incorporation of Co oxygen evolution catalysts. In addition, research opportunities for further advances by structual and compositional modifications are discussed, which can resolve the low fill factoring behavior and improve the overall performance.     

TiO_2纳米阵列光阳极光电催化水分解研究进展

光电催化水分解制氢是目前解决能源危机与环境污染最理想的技术之一.设计和构筑高效的光阳极是实现光电催化技术实际应用的关键.在众多半导体光阳极材料中,TiO_2纳米阵列由于其快的电荷传输速率,高的光热稳定性,无毒和成本低等优点,已经被广泛用于光电催化水分解反应的研究.但是TiO_2本征的光吸收范围窄、光生电荷复合率高、表面水氧化动力学缓慢严重地制约了其太阳能-氢能转换效率.我们结合近年来国内外及本课题组的研究工作详细论述了TiO_2纳米阵列的改性策略,主要包括利用元素掺杂来拓展TiO_2的光吸收范围并提高导电性,构筑异质结促进光电极电荷的分离与转移,半导体敏化增加光电极的可见光吸收并促进电荷转移,表面处理用于增加表面水氧化反应速率.最后指出了该材料发展现状,并对其发展前景做出展望.我们为进一步提高TiO_2纳米阵列的光电催化水分解活性提供了理论指导和实践借鉴.     

Emerging materials for plasmon-assisted photoelectrochemical water splitting

Energy production and environmental pollution are the two major problems the world is facing today. The depletion of fossil fuels and the emission of harmful gases into the atmosphere leads to the research on clean and renewable energy sources. In this context, hydrogen is considered an ideal fuel to meet global energy needs. Presently, hydrogen is produced from fossil fuels. However, the most desirable way is from clean and renewable energy sources, like water and sunlight. Sunlight is an abundant energy source for energy harvesting and utilization. Recent studies reveal that photoelectrochemical (PEC) water splitting has promise for solar to hydrogen (STH) conversion over the widely tested photocatalytic approach since hydrogen and oxygen gases can be quantified easily in PEC. For designing light-absorbing materials, semiconductors are the primary choice that undergoes excitation upon solar light irradiation to produce excitons (electron-hole pairs) to drive the electrolysis. Visible light active semiconductors are attractive to achieve high solar to chemical fuel conversion. However, pure semiconductor materials are far from practical applications because of charge carrier recombination, poor light-harvesting, and electrode degradation. Various heteronanostructures by the integration of metal plasmons overcome these issues. The incorporation of metal plasmons gained significance for improving the PEC water splitting performance. This review summarizes the possible main mechanisms such as plasmon-induced resonance energy transfer (PIRET), hot electron injection (HEI), and light scatting/trapping. It also deliberates the rational design of plasmonic structures for PEC water splitting. Furthermore, this review highlights the advantages of plasmonic metal-supported photoelectrodes for PEC water splitting.     

Flame spray pyrolysis for the one-step fabrication of transition metal oxide films: Recent progress in electrochemical and photoelectrochemical water splitting

Developing large scale deposition techniques to fabricate thin porous films with suitable opto-electro nic properties for water catalysis is a necessity to mitigate climate change and have a sustainable environment.In this review,flame spray pyrolysis(FSP)technique,a rapid and scalable methodology to synthesize nanostructured transitional metal oxide films with designed functionalities,is firstly introduced.Furthermore,applications in electrochemical(EC)and photoelectrochemical(PEC)water splitting for the production of hydrogen fuel is also presented.The high combustion temperature and the aggregation of flame aerosol ensure that the FSP-made films possess high crystallinity,tunable porosity and high surface areas,making this method suitable either as catalysts for EC water splitting or as efficient semiconductor materials for PEC water splitting.Finally,a perspective on the next generation FSP engineered films with potential applications in energy storage and conversion is described.     

Identifying Copper Vacancies and Their Role in the CuO Based Photocathode for Water Splitting

Metal oxides are an important family of semiconductors for effective photoelectrodes in solar‐to‐chemical energy conversion. Defect engineering, such as modification of oxygen vacancy density, has been extensively applied in tailoring the optoelectric properties of photoelectrodes. Very limited attention has been paid to the influence of metal vacancies. Herein, we study metal vacancies in a typical CuO photocathode for photoelectrochemical (PEC) water splitting. The Cu vacancies can improve the charge carrier concentration, and facilitate the charge separation and transfer in the CuO photocathode. By changing the O₂ partial pressure, the density of Cu vacancies can be tuned, which leads to improved PEC performance. The CuO photocathode prepared in pure O₂ exhibits a 100 % photocurrent increase compared to that prepared in air. The promotion effect of Cu vacancies on the PEC is also observed in other Cu based photocathodes, showing the generic role of metal vacancies in efficient photocathodes.     

构筑先进二维异质结构Ag/WO3−x用于提升光电转化效率

Solar energy, which is clean, affordable and reliable, can help alleviate the current environmental pollution and energy crisis efficiently. In the past few decades, great progress has been made in harvesting and converting solar energy into chemical energy. Among various technologies, plasmon-induced photoelectrochemistry has been proposed as a promising alternative for solar energy conversion. The hot electrons generated from plasmon excitation and transfer from metal nanostructures to semiconductors is a potential new paradigm for solar energy conversion. However, the ultrafast decay of the hot carriers is unfavorable for the improvement of photocatalytic efficiency. Therefore, finding more efficient photocatalysts, with enhanced light absorption and a longer carrier lifetime, is of paramount importance for improving the conversion efficiency of solar energy, but their fabrication is challenging. In this work, a plasmonic metal/semiconductor heterostructure based on Ag nanoparticles embedded in two-dimensional (2D) amorphous sub-stoichiometric tungsten trioxide (a-WO_3−x), followed by annealing, was successfully fabricated. Firstly, the peculiar nanostructure of 2D a-WO_3−x was successfully constructed from WS₂ nanosheets with supercritical CO₂ (SC CO₂) at 200 ℃. Secondly, the Ag/a-WO_3−x heterostructure was synthesized using an in situ reduction method. Finally, the obtained 2D heterostructure of Ag/WO_3−x was annealed at 400 ℃ in N₂ to further improve its stability and conductivity. X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure, morphology, and composition of the material, respectively. UV-Vis spectra were also measured to evaluate light adsorption. Characterization results show that the amorphous structure can effectively anchor metal nanoparticles, and the metal nanoparticles are uniformly dispersed in the amorphous region and have a small size. The as-prepared nanocomposites showed efficient photoelectrochemical (PEC) water splitting when serving as photoelectrode materials, and efficient PEC activity towards photo-oxidation degradation currents under excitation of Ag localized surface plasmon resonance (LSPR). The photocurrent response of the Ag/WO_3−x heterostructure was approximately five times greater than that of a-WO_3−x. Moreover, the PEC degradation efficiency of Ag/WO_3−x reached 96.7% for MO under Vis light illumination (after reaction for 120 min), while the PEC degradation efficiency of WO_3−x was only 63.6%. The high PEC performance of the composite photoanode can be ascribed to the local surface plasmon resonance (LSPR) effect of the Ag nanoparticles, which can enhance the light absorption and hot electron transformation. Moreover, the construction of local crystalline-amorphous interfaces can further promote the separation efficiency of the photogenerated electron-hole pairs, and thus increase conductivity. This work provides a positive strategy for the fabrication of advanced photocatalysts, and a new perspective on understanding of the synergistic effects of structural and electronic regulations.     

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.     

Ligand‐Assisted Co‐Assembly Approach toward Mesoporous Hybrid Catalysts of Transition‐Metal Oxides and Noble Metals: Photochemical Water Splitting

A bottom‐up synthetic approach was developed for the preparation of mesoporous transition‐metal‐oxide/noble‐metal hybrid catalysts through ligand‐assisted co‐assembly of amphiphilic block‐copolymer micelles and polymer‐tethered noble‐metal nanoparticles (NPs). The synthetic approach offers a general and straightforward method to precisely tune the sizes and loadings of noble‐metal NPs in metal oxides. This system thus provides a solid platform to clearly understand the role of noble‐metal NPs in photochemical water splitting. The presence of trace amounts of metal NPs (≈0.1 wt %) can enhance the photocatalytic activity for water splitting up to a factor of four. The findings can conceivably be applied to other semiconductors/noble‐metal catalysts, which may stand out as a new methodology to build highly efficient solar energy conversion systems.     

光催化分解水制氢反应中助催化剂的作用及机理（英文）

近年来,随着一次能源过度消耗所带来的能源和环境问题日益突出,开发廉价、可持续的清洁能源备受关注.光催化分解水制氢可利用太阳能普遍率高和几乎免费等特点制取燃烧热值高、燃烧产物无污染的氢气能源.自从1972年日本的Fujishima教授和Honda教授首次发现TiO2单晶电极光催化分解水可以产生氢气以来,光催化制氢被认为是实现可持续制氢最有潜力的方法之一.有效地将太阳能转换为化学能的关键是设计高效的电荷分离和运输结构.然而,现有的大多数半导体光催化剂因缺少活性位点、光生载流子易复合等缺点而无法达到较高的转换效率.因此,如何提高半导体光催化产氢的转换效率是现阶段面对的重要问题.在众多解决方法中,助催化剂的引入可以为光催化制氢反应增加活性位点,促进光生载流子的有效分离,进而有效地提高半导体光催化产氢速率.本文总结了多种不同类型的助催化剂应用于光催化产氢研究的最新进展,详细讨论了助催化剂在增强光吸收、提供活性位点、增加催化剂稳定性和促进电荷分离等方面的作用,阐明了助催化剂在光催化分解水制氢中的反应机理,同时还提出了光催化制氢的未来研究和预测.本文将助催化剂分为以下几种类别进行讨论:(1)单一助催化剂,包括金属/合金、金属氧化物/氢氧化物、金属磷化物、金属硫化物、碳基材料等助催化剂材料;(2)双助催化剂;(3)Z-Scheme助催化剂;(4)MOFs助催化剂.近年来,助催化剂材料在光催化产氢中应用的发展趋势从当初价格昂贵的贵金属趋于价格相对低廉的非贵金属,从单一体系趋于更复杂的体系.虽然现阶段关于助催化剂与基底之间的匹配还需要进一步研究,但我们相信随着技术的发展,这些问题都可以迎刃而解.希望在不久的将来,可以精确设计和构建出具有高效光催化产氢活性的催化剂体系,开发出更多新的可再生清洁能源,从而缓解能源紧缺和环境恶化等棘手问题.     

Metal-Organic Framework Glass Catalysts from Melting Glass-Forming Cobalt-Based Zeolitic Imidazolate Framework for Boosting Photoelectrochemical Water Oxidation

Sluggish oxygen evolution kinetics and serious charge recombination restrict the development of photoelectrochemical (PEC) water splitting. The advancement of novel metal–organic frameworks (MOFs) catalysts bears practical significance for improving PEC water splitting performance. Herein, a MOF glass catalyst through melting glass-forming cobalt-based zeolitic imidazolate framework (Co-a_gZIF-62) was introduced on various metal oxide (MO: Fe₂O₃, WO₃ and BiVO₄) semiconductor substrates coupled with NiO hole transport layer, constructing the integrated Co-a_gZIF-62/NiO/MO photoanodes. Owing to the excellent conductivity, stability and open active sites of MOF glass, Co-a_gZIF-62/NiO/MO photoanodes exhibit a significantly enhanced photoelectrochemical water oxidation activity and stability in comparison to pristine MO photoanodes. From experimental analyses and density functional theory calculations, Co-a_gZIF-62 can effectively promote charge transfer and separation, improve carrier mobility, accelerate the kinetics of oxygen evolution reaction (OER), and thus improve PEC performance. This MOF glass not only serves as an excellent OER cocatalyst on tunable photoelectrodes, but also enables promising opportunities for PEC devices for solar energy conversion.     

铁基多相助催化剂光电化学水氧化研究进展

The use of fossil fuels has caused serious environmental problems such as air pollution and the greenhouse effect. Moreover, because fossil fuels are a non-renewable energy source, they cannot meet the continuously increasing demand for energy. Therefore, the development of clean and renewable energy sources is necessitated. Hydrogen energy is a clean, non-polluting renewable energy source that can ease the energy pressure of the whole society. The sunlight received by the Earth is 1.7× 10¹⁴ J in 1 s, which far exceeds the total energy consumption of humans in one year. Therefore, conversion of solar energy to valuable hydrogen energy is of significance for reducing the dependence on fossil fuels. Since Fujishima and Honda first reported on TiO₂ in 1972, it has been discovered that semiconductors can generate clean, pollution-free hydrogen through water splitting driven by electricity or light. Hydrogen generated through this approach can not only replace fossil fuels but also provide environmentally friendly renewable hydrogen energy, which has attracted considerable attention. Photoelectrochemical (PEC) water splitting can use solar energy to produce clean, sustainable hydrogen energy. Because the oxygen evolution reaction (OER) over a photoanode is sluggish, the overall energy conversion efficiency is considerably low, limiting the practical application of PEC water splitting. A cocatalyst is, thus, necessary to improve PEC water splitting performance. So far, the synthesis of first-row transition-metal-based (e.g., Fe, Co, Ni, and Mn) cocatalysts has been intensively studied. Iron is earth-abundant and less toxic than other transition metals, making it a good cocatalyst. In addition, iron-based compounds exhibit the properties of a semiconductor/metal and have unique electronic structures, which can improve electrical conductivity and water adsorption. Various iron-based catalysts with high activity have been designed to improve the efficiency of PEC water oxidation. This article briefly summarizes the research progress related to the structure, synthesis, and application of iron oxyhydroxides, iron-based layered double hydroxides, and iron-based perovskites and discusses the evaluation of the performance of these cocatalysts toward photoelectrochemical water oxidation.      

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.     

Subsurface Engineering Induced Fermi Level De-pinning in Metal Oxide Semiconductors for Photoelectrochemical Water Splitting

Photoelectrochemical (PEC) water splitting is a promising approach for renewable solar light conversion. However, surface Fermi level pinning (FLP), caused by surface trap states, severely restricts the PEC activities. Theoretical calculations indicate subsurface oxygen vacancy (sub-O_v) could release the FLP and retain the active structure. A series of metal oxide semiconductors with sub-O_v were prepared through precisely regulated spin-coating and calcination. Etching X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), and electron energy loss spectra (EELS) demonstrated O_v located at sub ∼2–5 nm region. Mott–Schottky and open circuit photovoltage results confirmed the surface trap states elimination and Fermi level de-pinning. Thus, superior PEC performances of 5.1, 3.4, and 2.1 mA cm⁻² at 1.23 V vs. RHE were achieved on BiVO₄, Bi₂O₃, TiO₂ with outstanding stability for 72 h, outperforming most reported works under the identical conditions.     

Improving intrinsic electrocatalytic activity of layered transition metal chalcogenides as electrocatalysts for water splitting

Electrochemical water splitting has been considered an important method for facilitating renewable and sustainable energy conversion. For the practical application of water electrocatalysis, it is important to develop a non-noble metal-based, earth-abundant, highly efficient, and stable electrocatalysts for water splitting. Among the various non-noble metal-based electrocatalysts, layered transition metal chalcogenides (TMCs) have emerged as fascinating materials for electrochemical water splitting. The unique structural and electronic properties of layered TMCs make them very attractive for understanding the fundamental principles of electrocatalysis, as well as for developing highly efficient and stable electrocatalysts for the practical application of water electrocatalysis. In this mini review, we present a comprehensive overview of recent developments to improve the intrinsic electrocatalytic activity of layered transition metal chalcogenide (TMC)-based electrocatalysts for practical applications in water splitting.     

Recent Progress in LDH@Graphene and Analogous Heterostructures for Highly Active and Stable Photocatalytic and Photoelectrochemical Water Splitting

Photocatalytic (PC) and photoelectrochemical (PEC) water splitting is a plethora of green technological process, which transforms copiously available photon energy into valuable chemical energy. With the augmentation of modern civilization, developmental process of novel semiconductor photocatalysts proceeded at a sweltering rate, but the overall energy conversion efficiency of semiconductor photocatalysts in PC/PEC is moderately poor owing to the instability ariseing from the photocorrosion and messy charge configuration. Particularly, layered double hydroxides (LDHs) as reassuring multifunctional photocatalysts, turned out to be intensively investigated owing to the lamellar structure and exceptional physico-chemical properties. However, major drawbacks of LDHs material are its low conductivity, sluggish mass transfer and structural instability in acidic media, which hinder their applicability and stability. To surmount these obstacles, the formation of LDH@graphene and analogus heterostructures could proficiently amalgamate multi-functionalities, compensate distinct shortcomings, and endow novel properties, which ensure effective charge separation to result in stability and superior catalytic activities. Herein, we aim to summarize the currently updated synthetic strategies used to design heterostructures of 2D LDHs with 2D/3D graphene and graphene analogus material as graphitic carbon nitride (g-C₃N₄), and MoS₂ as mediator, or interlayer support, or co-catalyst or vice versa for superior PC/PEC water splitting activities along with long-term stabilities. Furthermore, latest characterization technique measuring the stability along with variant interface mode for imparting charge separation in LDH@graphene and graphene analogus heterostructure has been identified in this field of research with understanding the intrinsic structural features and activities.     

Recent advances in bismuth vanadate-based photocatalysts for photoelectrochemical water splitting

Photoelectrochemical(PEC) technology is considered to be a promising approach for solar-driven hydrogen production with zero emissions. Bismuth vanadate(BiVO_4) is a kind of photocatalytic material with strong photoactivity in the visible light region and appropriate band gap for PEC water splitting.However, the solar-to-hydrogen efficiency(STH) of BiVO_4 is far away from the 10% target needed for practical application due to its poor charge separation ability. Therefore, this review attempts to summarize the strategies for improving the photocurrent density and especially hydrogen production of BiVO_4 materials through PEC techniques in the last three years, such as doping nonmetal and metal elements, depositing noble metals, constructing heterojunctions, coupling with carbon and metalorganic framework(MOF) materials to further enhance the PEC performance of BiVO_4 photoanode. This review aims to serve as a general guideline to fabricate highly efficient BiVO_4-based materials for PEC water splitting.     

GaP/GaPN核壳纳米线阵列修饰的硅光阴极的光电化学制氢反应（英文）

能够大规模同时提升电极的催化效率和稳定性对光电化学分解水系统的开发具有重要意义.硅是一种地球储量丰富且成熟的工业材料,由于其合适的带隙(1.1 eV)和优异的导电性,已被广泛用于光电化学制氢反应.然而,缓慢的表面催化反应和在电解液中的不稳定性限制了其在太阳能制氢中的实际应用.III-IV族半导体材料也具有较高的载流子传输特性且被广泛用于光电器件.其中,GaP的直接带隙和间接带隙分别为2.78和2.26 eV,可与硅组成串联型光电极用于光电化学分解水.然而,GaP的光腐蚀电位位于禁带中,很容易在光电催化过程中发生光腐蚀而导致性能大幅下降.本文报道了一种新型的GaP/GaPN核/壳纳米线修饰的p型硅(p-Si)串联型光阴极,同未修饰的p-Si相比,其光电化学制氢性能更高.这可归因于以下几点:(1)p-Si和GaP纳米线之间形成的p-n结促进了电荷分离;(2)GaPN相对于GaP具有更低的导带边位置,进一步促进了光生电子向电极表面的转移;(3)纳米线结构既缩短了光生载流子的收集距离,又增加了比表面积,从而加快了表面反应动力学.此外,在GaP中引入氮元素还提高了体系的光吸收和稳定性.我们所提出的高效、简便的改进策略可应用于其他的太阳能转换体系.利用简单的化学气相沉积法制备GaP/GaPN核/壳纳米线修饰的p-Si光阴极.首先在p-Si衬底上利用Au纳米颗粒作为催化剂生长GaP纳米线;然后,去除Au催化剂,并在氨气中退火便形成了GaP/GaPN核壳纳米线.高分辨透射电子显微镜,拉曼光谱和X射线光电子谱的表征结果均证实了氨气退火使得GaP纳米线表面形成了GaPN的薄壳层,同时证明了GaP/GaPN核壳纳米线具有可调的核壳结构.在模拟太阳光下作为光阴极用于光解水制氢反应时,GaP/GaPN核壳纳米线修饰的p-Si光阴极的起始电位为~0.14 V,而未修饰的p-Si电极的起始电位大约在?0.77 V.而且,GaP/GaPN核/壳纳米线修饰的p-Si光阴极比未修饰的p-Si光阴极具有更高的光电流密度,在水的还原电位下,其光电流密度为?0.3 mA cm^-2,且饱和光电流密度在?0.76 V时达到了?8.8 mA cm^-2.此外,GaP/GaPN核/壳纳米线修饰的p-Si光阴极的光电化学活性在10 h内没有发生明显下降.由此可见GaP/GaPN核/壳纳米线可以规模化有效地提升Si光电极的催化效率和稳定性.     

Recent Progress on Nickel-Based Oxide/(Oxy)Hydroxide Electrocatalysts for the Oxygen Evolution Reaction

Developing clean and sustainable energies as alternatives to fossil fuels is in strong demand within modern society. The oxygen evolution reaction (OER) is the efficiency-limiting process in plenty of key renewable energy systems, such as electrochemical water splitting and rechargeable metal–air batteries. In this regard, ongoing efforts have been devoted to seeking high-performance electrocatalysts for enhanced energy conversion efficiency. Apart from traditional precious-metal-based catalysts, nickel-based compounds are the most promising earth-abundant OER catalysts, attracting ever-increasing interest due to high activity and stability. In this review, the recent progress on nickel-based oxide and (oxy)hydroxide composites for water oxidation catalysis in terms of materials design/synthesis and electrochemical performance is summarized. Some underlying mechanisms to profoundly understand the catalytic active sites are also highlighted. In addition, the future research trends and perspectives on the development of Ni-based OER electrocatalysts are discussed.