Unlocking the Transition of Electrochemical Water Oxidation Mechanism Induced by Heteroatom Doping

Heteroatom doping has emerged as a highly effective strategy to enhance the activity of metal-based electrocatalysts toward the oxygen evolution reaction (OER). It is widely accepted that the doping does not switch the OER mechanism from the adsorbate evolution mechanism (AEM) to the lattice-oxygen-mediated mechanism (LOM), and the enhanced activity is attributed to the optimized binding energies toward oxygen intermediates. However, this seems inconsistent with the fact that the overpotential of doped OER electrocatalysts (<300 mV) is considerably smaller than the limit of AEM (>370 mV). To determine the origin of this inconsistency, we select phosphorus (P)-doped nickel-iron mixed oxides as the model electrocatalysts and observe that the doping enhances the covalency of the metal-oxygen bonds to drive the OER pathway transition from the AEM to the LOM, thereby breaking the adsorption linear relation between *OH and *OOH in the AEM. Consequently, the obtained P-doped oxides display a small overpotential of 237 mV at 10 mA cm⁻². Beyond P, the similar pathway transition is also observed on the sulfur doping. These findings offer new insights into the substantially enhanced OER activity originating from heteroatom doping.     

Dimension Engineering in Noble-Metal-Based Electrocatalysts for Water Splitting

Dimension engineering plays a critical role in determining the electrocatalytic performance of catalysts towards water electrolysis since it is highly sensitive to the surface and interface properties. Bearing these considerations into mind, intensive efforts have been devoted to the rational dimension design and engineering, and many advanced nanocatalysts with multidimensions have been successfully fabricated. Aiming to provide more guidance for the fabrication of highly efficient noble-metal-based electrocatalysts, this review has focused on the recent progress in dimension engineering of noble-metal-based electrocatalysts towards water splitting, including the advanced engineering strategies, the application of noble-metal-based electrocatalysts with distinctive geometric structure from 0D to 1D, 2D, 3D, and multidimensions. In addition, the perspective insights and challenges of the dimension engineering in the noble-metal-based electrocatalysts is also systematically discussed.     

Strategies for Promoting Catalytic Performance of Ru-Based Electrocatalysts towards Oxygen/Hydrogen Evolution Reaction

Ru-based materials hold great promise for substituting Pt as potential electrocatalysts toward water electrolysis. Significant progress is made in the fabrication of advanced Ru-based electrocatalysts, but an in-depth understanding of the engineering methods and induced effects is still in their early stage. Herein, we organize a review that focusing on the engineering strategies toward the substantial improvement in electrocatalytic OER and HER performance of Ru-based catalysts, including geometric structure, interface, phase, electronic structure, size, and multicomponent engineering. Subsequently, the induced enhancement in catalytic performance by these engineering strategies are also elucidated. Furthermore, some representative Ru-based electrocatalysts for the electrocatalytic HER and OER applications are also well presented. Finally, the challenges and prospects are also elaborated for the future synthesis of more effective Ru-based catalysts and boost their future application.     

Biological Exploitation of Solar Energy by Photosynthetic Water Splitting

The cleavage of water by solar radiation into dioxygen and metabolically bound hydrogen during photosynthesis is of central importance for the existence of higher forms of life on earth. The realization of this process in biological organisms made possible the use of the earth's huge water reservoir for the exploitation of solar energy and, at the same time, led to the creation of an aerobic atmosphere. The dioxygen thereby formed is a powerful oxidant which permits an energetically highly efficient nutrient turnover. In recent years considerable progress has been made in understanding the functional and structural organization of photosynthetic water splitting. This article attempts to give a review of our current state of knowledge with special emphasis on the oxidation of water to O₂ in biological systems.     

Halogen-Driven Bandgap Opening in Graphdiyne for Overall Photocatalytic Water Splitting

In this work, we studied the electronic band structure of the halogen (F, Cl, and Br) functionalized graphdiynes (GDYs) by using hybrid density functional theory. The results revealed that the bandgap energies of modified GDYs increase as the number of halogen atoms increases. It is also found that the position of the valence band maximum (VBM) is influenced by the electronegativity of halogen atoms. The higher the electronegativity, the deeper the VBM of the GDYs modified by the same number of halogen atoms. Importantly, our results revealed that the bandgap of GDY could be effectively tuned by mixing types of halogen atoms. The new generated conduction band and valence band edges are properly aligned with the oxidation and reduction potentials of water. Further thermodynamic analysis confirms that some models with mixing types of halogen atoms exhibit higher performance of overall photocatalytic water splitting than non-mixing models. This work provides useful insights for designing efficient photocatalysts that can be used for overall water splitting.     

Atomic‐Layer‐Confined Doping for Atomic‐Level Insights into Visible‐Light Water Splitting

A model of doping confined in atomic layers is proposed for atomic‐level insights into the effect of doping on photocatalysis. Co doping confined in three atomic layers of In₂S₃ was implemented with a lamellar hybrid intermediate strategy. Density functional calculations reveal that the introduction of Co ions brings about several new energy levels and increased density of states at the conduction band minimum, leading to sharply increased visible‐light absorption and three times higher carrier concentration. Ultrafast transient absorption spectroscopy reveals that the electron transfer time of about 1.6 ps from the valence band to newly formed localized states is due to Co doping. The 25‐fold increase in average recovery lifetime is believed to be responsible for the increased of electron–hole separation. The synthesized Co‐doped In₂S₃ (three atomic layers) yield a photocurrent of 1.17 mA cm^?2 at 1.5 V vs. RHE, nearly 10 and 17 times higher than that of the perfect In₂S₃ (three atomic layers) and the bulk counterpart, respectively.     

Phosphating-induced charge transfer on CoO/CoP interface for alkaline H2 evolution

Designing non-noble metal electrocatalysts toward alkaline hydrogen evolution reaction (HER) with high performance at a large current density is urgent. Herein, a CoO/CoP heterostructure catalyst (termed POZ) was designed by a phosphating strategy. The strong electron transfer on the interface of CoO/CoP was experimentally and theoretically proven. POZ showed a low overpotential of 236 mV at 400 mA/cm², which was 249 mV lower than non-phosphated sample. It also exhibited a remarkable solar-to-hydrogen conversion efficiency of 10.5%. In this work, the construction of CoO/CoP interface realized by a simple phosphating strategy could provide an important reference to boost the HER performance on those materials not merely metal oxides.     

光催化全解水助催化剂的设计与构建

能源和环境危机是当今社会面临的两大关键课题,利用太阳光驱动化学反应、将太阳能转化为化学能是解决上述问题的重要措施。通过光催化分解水是直接利用太阳能生产氢燃料的有效策略。光催化水分解过程可以分为三个基元步骤:光吸收、电荷分离与迁移、以及表面氧化还原反应。助催化剂可有效提高电荷分离效率、提供反应活性位点并抑制催化剂光腐蚀的发生,进而提高水分解效率。助催化剂也可以通过活化水分子以提高表面氧化还原动力学,进而提升整体光催化反应的太阳能转换效率。本文综述了助催化剂在光催化反应中的重要作用以及目前常用的助催化剂类型,详细说明了在光催化全解水过程中双助催化剂体系的构建及作用机理,并根据限制全解水的关键因素提出了新型助催化剂的设计策略。     

Enhancing the Water Splitting Efficiency of Sn‐Doped Hematite Nanoflakes by Flame Annealing

The effect of flame annealing on the water‐splitting properties of Sn decorated hematite (α‐Fe₂O₃) nanoflakes has been investigated. It is shown that flame annealing can yield a considerable enhancement in the maximum photocurrent under AM 1.5 (100 mW cm^?2) conditions compared to classic furnace annealing treatments. Optimizing the annealing time (10 s at 1000 °C) leads to a photocurrent of 1.1 mA cm^?2 at 1.23 V (vs. RHE) with a maximum value 1.6 mA cm^?2 at 1.6 V (vs. RHE) in 1 M KOH. The improvement in photocurrent can be attributed to the fast direct heating that maintains the nanoscale morphology, leads to optimized Sn decoration, and minimizes detrimental substrate effects.     

光电催化分解水的光阳极改性策略

Photoelectrochemical water splitting is to utilize collected photo-generated carrier for direct water cleavage for hydrogen production. It is a system combining photoconversion and energy storage since converted solar energy is stored as high energy-density hydrogen gas. According to intrinsic properties and band bending situation of a photoelectrode, hydrogen tends to be released at photocathode while oxygen at photoanode. In a tandem photoelectrochemical chemical cell, current passing through one electrode must equals that through another and electrode with lower conversion rate will limit efficiency of the whole device. Therefore, it is also of research interest to look into the common strategies for enhancing the conversion rate at photoanode. Although up to 15% of solar-to-hydrogen efficiency can be estimated according to some semiconductor for solar assisted water splitting, practical conversion ability of state-of-the-art photoanode has yet to approach that theoretical limit. Five major steps happen in a full water splitting reaction at a semiconductor surface:light harvesting with electron excitations, separated electron-hole pairs transferring to two opposite ends due to band bending, electron/hole injection through semiconductor-electrolyte interface into water, recombination process and mass transfer of products/reactants. They are closely related to different proposed parameters for solar water splitting evaluation and this review will first help to give a fast glance at those evaluation parameters and then summarize on several major adopted strategies towards high-efficiency oxygen evolution at photoanode surface. Those strategies and thereby optimized evaluation parameter are shown, in order to disclose the importance of modifying different steps for a photoanode with enhanced output.     

Phosphorene-Based van der Waals Heterojunction for Solar Water Splitting

As a clean and renewable future energy source, hydrogen fuel can be produced via solar water splitting. Two-dimensional (2D) black phosphorene (black-P) can harvest visible light due to the desirable band gap, which promises it as a metal-free photocatalyst. However, black-P can be only used to produce hydrogen since the oxidation potential of water locates lower than the position of the valence band maximum. To improve the photocatalytic performance of black-P, here, using black-P and blue phosphorene (blue-P) monolayers, we propose a 2D van der Waals (vdW) heterojunction. Theoretical results, including the band structures, density of states, Bader charge population, charge density di erence, and optical absorption spectra, clearly reveal that the visible light absorption ability is obviously improved, and the band edge alignment of the proposed vdW heterojunction displays a typical type-II feature to effectively separate the photogenerated carriers. At the same time, the built-in interfacialelectric field prevents the electron-hole recombination. These predictions suggest that the examined phosphorene-based vdW heterojunction is an efficient photocatalyst for solar water splitting.     

Common Pitfalls of Reporting Electrocatalysts for Water Splitting

Rigorous assessment of heterogeneous electrocatalysts for electrochemical water splitting has been a critical issue mainly due to insufficient standard protocols to measure and report experimental data. In this perspective, we highlight some common pitfalls when measuring and reporting electrocatalytic data, which should be avoided to ensure the accuracy and reproducibility and to advance the water splitting field. We advocate to prevent the introduction of artefacts from the counter and reference electrodes, as well as the impurities in the electrolyte when conducting electrocatalyst activity measurements. In addition, we encourage the use of the electrochemically active surface area(ECSA)-normalized current densities to represent the intrinsic activity of the reported catalysts for a better comparison with previously known materials. Suitable ECSA measurement methods should be employed based on the nature of catalysts. Recommendations made in this perspective will hopefully assist in identifying advanced catalysts for water splitting research.     

Control of Spatially Homogeneous Distribution of Heteroatoms to Produce Red TiO2 Photocatalyst for Visible-Light Photocatalytic Water Splitting

The strong band-to-band absorption of photocatalysts spanning the whole visible-light region (400–700 nm) is critically important for solar-driven photocatalysis. Although it has been actively and widely used as a photocatalyst for various reactions in the past four decades, TiO₂ has a very poor ability to capture the whole spectrum of visible light. In this work, by controlling the spatially homogeneous distribution of boron and nitrogen heteroatoms in anatase TiO₂ microspheres with a predominance of high-energy {001} facets, a strong visible-light absorption spectrum with a sharp edge beyond 680 nm has been achieved. The red TiO₂ obtained with homogeneous doping of boron and nitrogen shows no increase in defects like Ti³⁺ that are commonly observed in doped TiO₂. More importantly, it has the ability to induce photocatalytic water oxidation to produce oxygen under the irradiation of visible light beyond 550 nm and also the photocatalytic reduction of water to produce hydrogen under visible light. These results demonstrate the great promise of using red TiO₂ for visible-light photocatalytic water splitting and also reveal an attractive strategy for realizing the wide-spectrum visible-light absorption of wide-band-gap oxide photocatalysts.     

Photocatalytic Water Splitting Under Visible Light with Particulate Semiconductor Catalysts

Photocatalytic water splitting (PWS) is the most promising technology to produce H₂ energy directly from renewable water and solar light. PWS has made a remarkable progress last decades under ultra-violet (UV) light, but there are many technical challenges remaining for PWS under visible light. Several approaches are taken in search of photocatalysts efficient for PWS under visible light: (i) to find new single phase materials, (ii) to decorate UV-active photocatalysts with a photosensitizer absorbing visible light, (iii) to tune the band gap energy by modifying cations or anions of UV-active photocatalysts with substitutional doping, and (iv) to fabricate multi-component photocatalysts by forming composites or solid solutions. This article discusses the above approaches based on our experimental results as well as data available in the literature. At the moment, the greatest challenge to the progress of visible light PWS is the low efficiency of light utilization. Finding new photocatalytic materials with unique structure and phase is still the key to the success. In addition, the synthesis of these materials with high crystallinity and high surface area is also important, because these properties exert great impact on the activity of the material of the same structure and phase. Finally, smart combination and modification of known materials could also be fruitful.     

Acceptor-Doping Accelerated Charge Separation in Cu2O Photocathode for Photoelectrochemical Water Splitting: Theoretical and Experimental Studies

Cu₂O is a typical photoelectrocatalyst for sustainable hydrogen production, while the fast charge recombination hinders its further development. Herein, Ni²⁺ cations have been doped into a Cu₂O lattice (named as Ni-Cu₂O) by a simple hydrothermal method and act as electron traps. Theoretical results predict that the Ni dopants produce an acceptor impurity level and lower the energy barrier of hydrogen evolution. Photoelectrochemical (PEC) measurements demonstrate that Ni-Cu₂O exhibits a photocurrent density of 0.83 mA cm⁻², which is 1.34 times higher than that of Cu₂O. And the photostability has been enhanced by 7.81 times. Moreover, characterizations confirm the enhanced light-harvesting, facilitated charge separation and transfer, prolonged charge lifetime, and increased carrier concentration of Ni-Cu₂O. This work provides deep insight into how acceptor-doping modifies the electronic structure and optimizes the PEC process.     

Surface and interface engineering in transition metal–based catalysts for electrochemical water oxidation

A tremendous effort has been provided in last two decades to develop efficient transition metal–based heterogeneous catalysts for the electrochemical water oxidation. Several approaches such as composition modulation, heteroatom doping, morphological development, particle size tuning, surface area enhancement, and control over electronic structure have been explored for the designing of the materials with improved water oxidation activity. As the electrochemical process is a surface phenomenon, surface structure plays a crucial role in controlling the water oxidation activity. Rational engineering of the catalyst surface by composition modulation, crystal facet tuning, and generating functional overlayer has been reported to enhance the water oxidation activity. Heteroatom doping, cationic and anionic deficiencies, and ultrathin 2D morphology are also found to promote electrochemical performance. In addition, engineering in the interface provides intrinsic improvement of the catalytic activity and stability for the electrochemical water oxidation. Although, surface and interface engineering of the catalyst has come out as the major factors in the electrochemical water oxidation, no dedicated review is available in this field. In this review, we have described the strategies of improving water oxidation activity of the catalysts by surface and interface engineering. The progress in this field discussed in detail; the challenges have been identified and addressed to attain a clear understanding in this field.     

Solid-State Conversion Synthesis of Advanced Electrocatalysts for Water Splitting

Electrolytic water technology is promising for sustainable energy utilization, but the lack of efficient electrocatalysts retards its application. The intrinsic activity of electrocatalysts is determined by its electronic structure, whereas the apparent activity can be further optimized by reasonable design on micro-/nanostructures of electrocatalysts. The core goal of electrocatalytic research is to reveal the relationship between the structure and performance of electrocatalysts, which is also the basis of reasonable design and construction of efficient electrocatalysts. Traditional synthetic methods, namely bottom-up and top-down routes, usually induce the change of different structural parameters at the same time. The solid-state conversion strategy, which is converts solid precursors into target materials through chemical reactions, has been widely adopted to produce materials with precisely controllable structures. In this Minireview, we focus on recent advances in the solid-state conversion synthesis of water-splitting electrocatalysts. First, the basis of solid-state conversion chemistry is introduced. Then, the specific methods of precise control of electronic structure by solid-state conversion and the relationship between electronic structure and performance are summarized. Based on the understanding of the electronic structure–performance relationship, synergistic regulation of electronic structure and micro-/nanostructures by solid-state conversion to achieve the copromotion of intrinsic activity and apparent activity are described. Finally, the remaining challenges in this field are discussed, and future research directions are proposed as well.     

A Doping Technique that Suppresses Undesirable H2 Evolution Derived from Overall Water Splitting in the Highly Selective Photocatalytic Conversion of CO2 in and by Water

Photocatalytic conversion of CO₂ to reduction products, such as CO, HCOOH, HCHO, CH₃OH, and CH₄, is one of the most attractive propositions for producing green energy by artificial photosynthesis. Herein, we found that Ga₂O₃ photocatalysts exhibit high conversion of CO₂. Doping of Zn species into Ga₂O₃ suppresses the H₂ evolution derived from overall water splitting and, consequently, Zn‐doped, Ag‐modified Ga₂O₃ exhibits higher selectivity toward CO evolution than bare, Ag‐modified Ga₂O₃. We observed stoichiometric amounts of evolved O₂ together with CO. Mass spectrometry clarified that the carbon source of the evolved CO is not the residual carbon species on the photocatalyst surface, but the CO₂ introduced in the gas phase. Doping of the photocatalyst with Zn is expected to ease the adsorption of CO₂ on the catalyst surface.     

不同压力下光热催化分解水制氢行为研究

随着世界能源消耗总量的急剧增加和随之带来的环境污染问题的日趋严重,开发清洁的可再生能源已迫在眉睫.氢作为一种清洁的能源载体,使用后的产物仅为水,不会造成二次污染.将水转变为氢也是最好的太阳能的化学储存方式之一[1～6].     

冷等离子体处理制备NiO/SrTiO3及其光催化水分解制氢性能研究

利用辉光放电等离子体处理改进常规浸渍法制备了NiO/SrTiO3光催化剂. XRD、XPS和TEM分析证明, 金属颗粒在载体表面的分散性得到极大提高, 并在反应中具有很好的稳定性. XPS、热重和XRD分析表明, 等离子体处理使浸渍的Ni(NO3)2在常温下分解为晶化度较低的NiO团簇, 该团簇可能与载体具有较强的相互作用. 在光催化反应中, 高分散的金属可以促进电荷传递, 并提供更多的表面活性位. 对于水分解制氢和甲醇溶液转化制氢反应, 该催化剂的活性分别是常规催化剂的1.3倍和1.8倍.