Vertically Aligned Porous Nickel(II) Hydroxide Nanosheets Supported on Carbon Paper with Long‐Term Oxygen Evolution Performance

Vertically aligned Ni(OH)₂ nanosheets were grown on carbon paper (CP) current collectors through a simple and cost‐effective hydrothermal approach. The as‐grown nanosheets are porous and highly crystallized. If used as a monolithic electrode for electrochemical water oxidation in alkaline solution, the carbon paper supported Ni(OH)₂ nanosheets [CP@Ni(OH)₂] exhibit high electrocatalytic activity and excellent long‐term stability. The electrode can attain an anodic current density of 20 mA cm⁻² at a low overpotential of 338 mV, comparable to that of state‐of‐the‐art RuO₂ nanocatalysts supported on CP (CP/RuO₂) with the same catalyst loading. Significantly, CP@Ni(OH)₂ shows much better long‐term stability than CP/RuO₂ upon continuous galvanostatic electrolysis, particularly at a high industry‐relevant current density such as 100 mA cm⁻². CP@Ni(OH)₂ can sustain water oxidation at 100 mA cm⁻² for 50 h without any degradation, whereas the performance of CP/RuO₂ is much poorer and deteriorates gradually over time. CP@Ni(OH)₂ electrodes hold substantial promise for use as low‐costing water oxidation anodes in electrolyzers.     

Improving the Electrocatalytic Activity of a Nickel-Organic Framework toward the Oxygen Evolution Reaction through Vanadium Doping

Metal-organic frameworks (MOFs) have been considered as potential oxygen evolution reaction (OER) electrocatalysts owning to their ultra-thin structure, adjustable composition, high surface area, and high porosity. Here, we designed and fabricated a vanadium-doped nickel organic framework (V_1−x−Ni_xMOF) system by using a facile two-step solvothermal method on nickel foam (NF). The doping of vanadium remarkably elevates the OER activity of V_1−x−Ni_xMOF, thus demonstrating better performance than the corresponding single metallic Ni-MOF, NiV-MOF and RuO₂ catalysts at high current density (>400 mA cm⁻²). V_0.09−Ni_0.91MOF/NF provides a low overpotential of 235 mV and a small Tafel slope of 30.3 mV dec⁻¹ at a current density of 10 mA cm⁻². More importantly, a water-splitting device assembled with Pt/C/NF and V_0.09−Ni_0.91MOF/NF as cathode and anode yielded a cell voltage of 1.96 V@1000 mA cm⁻², thereby outperforming the-state-of-the-art RuO₂⁽⁺⁾||Pt/C⁽⁻⁾. Our work sheds new insight on preparing stable, efficient OER electrocatalysts and a promising method for designing various MOF-based materials.     

高结晶度硼酸镍纳米棒的制备及其电催化析氧性能研究

氢能被视为21世纪最具发展潜力的能源. 电解水制氢具有诸多优点,如原料来源广泛、操作简便、产品纯度高、无污染,已成为最具有应用前景的方法之一,但其阳极氧析出反应动力学缓慢,严重制约电解水制氢的效率. 因此,发展氧析出电催化剂尤为重要. 本文利用高温煅烧法制备了硼酸镍纳米棒,长度约为2 μm,直径约为200 nm. 与文献报道的低结晶度或无定型硼酸盐析氧催化剂不同,硼酸镍纳米棒的结晶度较高,并且具有较好的OER催化活性和稳定性. 其催化活性可以通过与其他导电材料复合或进一步减小其尺寸等方式提升.     

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.     

Heteroatom‐doped MoSe2 Nanosheets with Enhanced Hydrogen Evolution Kinetics for Alkaline Water Splitting

Electrochemical water splitting for hydrogen generation is a vital part for the prospect of future energy systems, however, the practical utilization relies on the development of highly active and earth‐abundant catalysts to boost the energy conversion efficiency as well as reduce the cost. Molybdenum diselenide (MoSe₂) is a promising nonprecious metal‐based electrocatalyst for hydrogen evolution reaction (HER) in acidic media, but it exhibits inferior alkaline HER kinetics in great part due to the sluggish water adsorption/dissociation process. Herein, the alkaline HER kinetics of MoSe₂ is substantially accelerated by heteroatom doping with transition metal ions. Specifically, the Ni‐doped MoSe₂ nanosheets exhibit the most impressive catalytic activity in terms of lower overpotential and larger exchange current density. The density functional theory (DFT) calculation results reveal that Ni/Co doping plays a key role in facilitating water adsorption as well as optimizing hydrogen adsorption. The present work paves a new way to the development of low‐cost and efficient electrocatalysts towards alkaline HER.     

In-Situ Generated Trimetallic Molybdate Nanoflowers on Ni Foam Assisted with Microwave for Highly Enhanced Oxygen Evolution Reaction

Oxygen evolution reaction (OER) is considered as a critical half-cell reaction of water splitting, the kinetics of which is sluggish even not favored, thus requiring highly active electrocatalysts to shrink the reaction energy barrier and improve the energy conversion efficiency. In this study, In-situ generated trimetallic molybdate nanoflowers on Ni foam by a straightforward and time-saving solvothermal method assisted with microwave, not only bring synergistic effect into full play between multiple metals, but also construct a well-defined nanoflower-like structure accompanied by larger specific area (273.3 m² g⁻¹) and smaller size than the pristine NiMoO₄. The resulting Ni_0.9Al_0.1MoO₄-NF requires a relatively low overpotential of 266 mV for OER at 10 mA cm⁻², which outperforms commercial RuO₂ catalysts (274 mV). Such excellent performance compares favorably to most previously reported NiMoO₄-based electrocatalysts for OER. This work not only supplies a facile method to construct a well-defined nanoflower-like structure on foam, but also broadens our horizons into the mechanism of OER in alkaline conditions.     

Adjustable Ternary FeCoNi Nanohybrids for Enhanced Oxygen Evolution Reaction

Water splitting as a greatly desired technology to produce clean renewable energy, but is hampered by the sluggish oxygen evolution reaction. So, the development of highly active and durable water oxidation electrocatalysts is of primarily significance for energy conversion. Here, a facial strategy to synthesize FeCoNi nanohybrids with adjustable morphological structures by using fluorine is introduced. The morphology and electrocatalytic activity of the sample is determined by the innovative introduction of fluorine. Among them, the overpotential at 10 mA cm⁻² of the best sample is approximately 97 mV lower than the commercial RuO₂ toward the oxygen evolution reaction in 1 m KOH. Additionally, the catalysts also have low Tafel slopes and remarkable stability.     

Efficient Hydrogen and Oxygen Evolution Catalysis Using 3D-Structured Nickel Phosphosulfide Nanosheets in Alkaline Media

Water electrolysis offers a zero-carbon route to generate renewable energy conversion systems. Herein, a self-supported nickel phosphosulfide nanosheet (NS) electrocatalyst was fabricated at a low temperature on carbon cloth, which was then subjected to Ar etching to enhance its catalytic activity. Etching resulted in better hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performance than other samples, with overpotentials of 103.1 mV (at 10 mA cm⁻²) and 278.9 mV (at 50 mA cm⁻²), respectively. The characterization results confirmed that Ar etching created a thin amorphous layer around the NiPS₃ NSs, which increased the number of active sites and modulated their electronic structures. These 3D-structured NiPS₃ NSs and their subsequent Ar etching process show promise for applications in overall water splitting in alkaline media.     

钨掺杂的铁镍基层状氢氧化物用于电催化析氧和析氢反应

采用简便的一步水热合成法,在泡沫镍上原位生长微量W~(6+)掺入的Fe_(0.2)Ni(OH)_2双金属层状氢氧化物(LDH),以此来降低铁镍材料的过电势。通过场发射扫描电子显微镜(FESEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)和拉曼光谱(Raman)等分析方法对材料形貌、组成、结构等进行表征,发现钨掺杂使催化剂材料的晶体结构和电子结构发生变化,W_(0.03)Fe_(0.2)Ni(OH)_2LDH表现出优异的电化学析氧(OER)和析氢(HER)性能。电化学测试表明该催化剂在25 mA·cm~(-2)电流密度下OER和HER过电势分别仅有271和208 mV,塔菲尔斜率分别为61和181 mV·dec~(-1)。此外,经过长达20 h计时电位稳定性测试后,材料的催化性能未见明显下降。     

Robust Polyoxometalate/Nickel Foam Composite Electrodes for Sustained Electrochemical Oxygen Evolution at High pH

The development of technologically viable electrodes for the electrochemical oxygen evolution reaction (OER) is a major bottleneck in chemical energy conversion. This article describes a facile one‐step hydrothermal route to deposit microcrystals of a robust Dexter–Silverton polyoxometalate oxygen evolution catalyst, [Co_6.8Ni_1.2W₁₂O₄₂(OH)₄(H₂O)₈], on a commercial nickel foam electrode. The electrode shows efficient and sustained electrochemical oxygen evolution at low overpotentials (360 mV at 10 mA cm⁻² against RHE, Tafel slope 126 mV dec⁻¹, faradaic efficiency (96±5) %) in alkaline aqueous solution (pH 13). Post‐catalytic analyses show no mechanical or chemical degradation and no physical detachment of the microcrystals. The results provide a blueprint for the stable “wiring” of POM catalysts to commercial metal foam substrates, thus giving access to technologically relevant composite OER electrodes.     

CoOx@Co-NC Catalyst with Dual Active Centers for Enhanced Oxygen Evolution: Breaking Trade-Off of Particle Size and Metal Loading

Increasing the metal loading and downsizing the metal particle size are two effective ways to boost the electrochemical performance of catalysts. However, it is difficult to simultaneously increase the metal loading and reduce the particle size since isolated individual atoms are easy to aggregate into nanoparticles when increasing the metal loading. To tackle this contradiction, we report a bottom-up ligand-mediated strategy to facilely prepare ultrafine CoO_x nanoclusters anchored on a Co-N-containing carbon matrix (CoO_x@Co-NC). The co-exist of N and O atoms prevent Co atoms agglomerating into large particles and allowing the formation of ultrafine dispersed Co species with large Co loading (up to 20 wt.%). Since the relationship between ultrasmall size and large metal loading is well balanced, the CoO_x nanoclusters have no inhibitory effect, but facilitate the catalytic performance of Co-N₄ sites during OER process. Consequently, due to the synergistic effect of ultrafine CoO_x nanoclusters and Co-N₄ macrocycles, the as-synthesized CoO_x@Co-NC exhibit promising OER activity (η₁₀=370 mV, Tafel plot=40 mV/dec), bettering than that of benchmark RuO₂ (η₁₀=411 mV, Tafel plot=72 mV/dec). This ligand-mediated strategy to synthesize carbonaceous materials containing dual active centers with large metal loading is promising for developing active and stable catalysts for electrocatalytic applications.     

Bifunctional Catalysts for Reversible Oxygen Evolution Reaction and Oxygen Reduction Reaction

Metal-air batteries (MABs) and reversible fuel cells (RFCs) rely on the bifunctional oxygen catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Finding efficient bifunctional oxygen catalysts is the ultimate goal and it has attracted a great deal of attention. The dilemma is that a good ORR catalyst is not necessarily efficient for OER, and vice versa. Thus, the development of a new type of bifunctional oxygen catalysts should ensure that the catalysts exhibit high activity for both OER and ORR. Composites with multicomponents for active centers supported on highly conductive matrices could be able to meet the challenges and offering new opportunities. In this Review, the evolution of bifunctional catalysts is summarized and discussed aiming to deliver high-performance bifunctional catalysts with low overpotentials.     

Rapid Synthesis of Cobalt Nitride Nanowires: Highly Efficient and Low‐Cost Catalysts for Oxygen Evolution

Electrochemical splitting of water to produce hydrogen and oxygen is an important process for many energy storage and conversion devices. Developing efficient, durable, low‐cost, and earth‐abundant electrocatalysts for the oxygen evolution reaction (OER) is of great urgency. To achieve the rapid synthesis of transition‐metal nitride nanostructures and improve their electrocatalytic performance, a new strategy has been developed to convert cobalt oxide precursors into cobalt nitride nanowires through N₂ radio frequency plasma treatment. This method requires significantly shorter reaction times (about 1 min) at room temperature compared to conventional high‐temperature NH₃ annealing which requires a few hours. The plasma treatment significantly enhances the OER activity, as evidenced by a low overpotential of 290 mV to reach a current density of 10 mA cm^?2, a small Tafel slope, and long‐term durability in an alkaline electrolyte.     

经由[Ni(en)3](SeO3)配合物电镀制备的硒化镍高效电催化水分解反应

电催化水分解是一种高效制备清洁氢气能源的有效方法. 开发高效、稳定、廉价、双功能的电催化剂用于水的氧化与还原反应一直以来都是具有挑战的课题. 在这篇论文中,作者报道了一种生长在碳布上高活性的硒化镍微球. 该催化剂通过对同时包含镍和硒元素的亚硒酸镍配合物进行电解制备. 由于前驱分子同时含有两种有效元素,制备得到的硒化镍具有很好的形貌和元素分步均一性. 制备得到的NiSe-EA/CC电极能够双功能催化水的氧化与还原. 在154 mV析氢过电势下能达到10 mA·cm^-2的催化电流. 同时,在250 mV析氧过电势下能达到20 mA·cm^-2电催化电流. 用该电极材料同时作为阴极和阳极制备的全电解水电解池能在1.53 V的电压下实现10 mA·cm^-2的稳定电解电流.     

用于电催化析氧反应电极的制备策略

随着能源枯竭和环境污染等问题的日益严重,开发清洁可再生能源及相关新型技术迫在眉睫。近年来,水分解、金属-空气电池等电化学能源储存和转换技术得到人们的广泛关注。电催化析氧反应(Oxygen evolution reaction,OER)是其中的一个关键反应,大量高性能的OER电催化剂不断见诸报道。除了材料本征催化活性的影响,不同的电极制备方式同样会对催化剂性能的发挥起到重要作用,越来越多的研究者致力于探索高效OER电极的设计与制备方法。本综述从方法论的角度,详细介绍了目前高效OER电极的制备策略,讨论了各类制备方式的优势和不足,总结了相关工作的最新研究进展,概述了新型电极的制备方法。最后,对电极制备策略的发展方向进行了总结与展望。     

Design of Multi-Metallic-Based Electrocatalysts for Enhanced Water Oxidation

Electrochemical water splitting by renewable energy resources is an efficient and green approach for hydrogen gas production. However, the anodic oxygen evolution reaction (OER) largely impedes the industrial application due to its sluggish four-electron-transition kinetics. Although various materials have been developed to accelerate the OER rate, still some issues should be addressed to meet the industrial demand: (i) considerable 200–300 mV overpotential as extra onset energy input, (ii) limited survival and performance in acidic electrolyte for the majority of oxide/hydroxide composite materials, (iii) unsatisfying long-term durability and (iv) the need for facile and scalable preparation methods. Here, we emphasize on multi-metallic composites with enhanced OER activity based on both precious and nonprecious elements that outperform the unary and binary composites. The regulation effect from multi-metal incorporation is also summarized systematically: (i) introducing foreign metal atoms to the host material boosts the physical properties such as conductivity, surface area, defect density, morphology, wettability, etc., (ii) metal doping can synergistically regulate the electronic features of the host material, e. g. oxygen vacancy, e_g orbit filling, coordinative number and covalence state, which can optimize the absorption/desorption energy of the M−O intermediate, (iii) chaotic impact from the added atoms twists the catalyst lattice into a more aggressive and higher energy state, which is more feasible to transform to an active intermediate with lower required energy supply. This review aims to provide a practical approach to further improve the OER performance via multi-metallic-based catalysts.     

镍铁水滑石电催化氧析出研究进展

氧析出反应(Oxygen evolution reaction, OER)是电解水制氢、二氧化碳还原、二次金属-空气电池等能源储存和转化技术中的关键半反应。镍铁水滑石类材料(NiFe layered double hydroxide, NiFe-LDH)具有独特的层状结构、优异的催化性能和成本低廉等优点,是一类极具潜力的OER催化材料。但电导率低、活性位点暴露不充分等缺点也限制了其催化性能的进一步提高。本文综述了包括引入缺陷、片层剥离、元素掺杂、表面修饰和原位生长等针对NiFe-LDH的改性方法,这些方法能有效提升反应活性位点数量、增强导电性并促进反应动力学过程。最后,讨论了对NiFe-LDH改性中存在的问题以及对后续研究的展望。     

Plasma‐Engraved Co3O4 Nanosheets with Oxygen Vacancies and High Surface Area for the Oxygen Evolution Reaction

Co₃O₄, which is of mixed valences Co²⁺ and Co³⁺, has been extensively investigated as an efficient electrocatalyst for the oxygen evolution reaction (OER). The proper control of Co²⁺/Co³⁺ ratio in Co₃O₄ could lead to modifications on its electronic and thus catalytic properties. Herein, we designed an efficient Co₃O₄‐based OER electrocatalyst by a plasma‐engraving strategy, which not only produced higher surface area, but also generated oxygen vacancies on Co₃O₄ surface with more Co²⁺ formed. The increased surface area ensures the Co₃O₄ has more sites for OER, and generated oxygen vacancies on Co₃O₄ surface improve the electronic conductivity and create more active defects for OER. Compared to pristine Co₃O₄, the engraved Co₃O₄ exhibits a much higher current density and a lower onset potential. The specific activity of the plasma‐engraved Co₃O₄ nanosheets (0.055 mA cm^?2_BET at 1.6 V) is 10 times higher than that of pristine Co₃O₄, which is contributed by the surface oxygen vacancies.     

Controllable Synthesis of Fe-Doped NiCo2O4 Nanobelts as Superior Catalysts for Oxygen Evolution Reaction

As one of the promising clean and renewable technologies, water splitting has been a hot topic, especially the half-reaction of oxygen evolution reaction (OER) due to its sluggish and complex kinetics. Hence, Fe-doped NiCo₂O₄ nanobelts were designed and prepared as catalysts toward OER. By increasing the Fe amount, the catalytic performances of the as-synthesized products went up and then decreased. Profiting from the synergistic effect between Fe atom and NiCo₂O₄, all the Fe-NiCo₂O₄ catalysts exhibited superior catalytic activities to the corresponding NiCo₂O₄. In addition, the characteristic nanobelt architecture facilitates the conduction of electrons and the exposure of active sites. With the optimal Fe content, the 9.1 % Fe-NiCo₂O₄ yielded the smallest overpotential and Tafel slope among the catalysts, distinctly lower than that of RuO₂.     

Core–Shell NiO@Ni‐P Hybrid Nanosheet Array for Synergistically Enhanced Oxygen Evolution Electrocatalysis: Experimental and Theoretical Insights

Cost‐effective and highly‐efficient electrocatalysts for the oxygen evolution reaction are crucial for electrolytic hydrogen production. Here, we report core–shell NiO@Ni‐P nanosheet arrays as a high‐performance 3D catalyst for water oxidation electrocatalysis. Such nanoarrays demand overpotentials of 292 and 350 mV to drive geometrical catalytic current densities of 10 and 100 mA cm^?2, respectively, with an activity superior to its NiO and Ni‐P counterparts. Notably, this catalyst also shows a high long‐term electrochemical durability with a Faradaic efficiency of 98.1 %. Density functional theory calculation reveals that the superior activity benefits from the synergistic effect between NiO and Ni‐P.