Activating Inert,Nonprecious Perovskites with Iridium Dopants for Efficient Oxygen Evolution Reaction under Acidic Conditions

Simultaneous realization of improved activity, enhanced stability, and reduced cost remains a desirable yet challenging goal in the search of oxygen evolution electrocatalysts in acid. Herein we report iridium‐containing strontium titanates (Ir‐STO) as active and stable, low‐iridium perovskite electrocatalysts for the oxygen evolution reaction (OER) in acid. The Ir‐STO contains 57 wt % less iridium relative to the benchmark catalyst IrO₂, but it exhibits more than 10 times higher catalytic activity for OER. It is shown to be among the most efficient iridium‐based oxide electrocatalysts for OER in acid. Theoretical results reveal that the incorporation of iridium dopants in the STO matrix activates the intrinsically inert titanium sites, strengthening the surface oxygen adsorption on titanium sites and thereby giving nonprecious titanium catalytic sites that have activities close to or even better than iridium sites.     

Recent advances in one-dimensional nanostructures for energy electrocatalysis

Catalysts play decisive roles in determining the energy conversion efficiencies of energy devices. Up to now, various types of nanostructured materials have been studied as advanced electrocatalysts. This review highlights the application of one-dimensional (1D) metal electrocatalysts in energy conversion, focusing on two important reaction systems—direct methanol fuel cells and water splitting. In this review, we first give a broad introduction of electrochemical energy conversion. In the second section, we summarize the recent significant advances in the area of 1D metal nanostructured electrocatalysts for the electrochemical reactions involved in fuel cells and water splitting systems, including the oxygen reduction reaction, methanol oxidation reaction, hydrogen evolution reaction, and oxygen evolution reaction. Finally, based on the current studies on 1D nanostructures for energy electrocatalysis, we present a brief outlook on the research trend in 1D nanoelectrocatalysts for the two clean electrochemical energy conversion systems mentioned above.     

Activating Inert,Nonprecious Perovskites with Iridium Dopants for Efficient Oxygen Evolution Reaction under Acidic Conditions

Simultaneous realization of improved activity, enhanced stability, and reduced cost remains a desirable yet challenging goal in the search of oxygen evolution electrocatalysts in acid. Herein we report iridium‐containing strontium titanates (Ir‐STO) as active and stable, low‐iridium perovskite electrocatalysts for the oxygen evolution reaction (OER) in acid. The Ir‐STO contains 57 wt % less iridium relative to the benchmark catalyst IrO₂, but it exhibits more than 10 times higher catalytic activity for OER. It is shown to be among the most efficient iridium‐based oxide electrocatalysts for OER in acid. Theoretical results reveal that the incorporation of iridium dopants in the STO matrix activates the intrinsically inert titanium sites, strengthening the surface oxygen adsorption on titanium sites and thereby giving nonprecious titanium catalytic sites that have activities close to or even better than iridium sites.     

Amorphous Oxide Nanostructures for Advanced Electrocatalysis

Amorphous oxides have attracted special attention as advanced electrocatalysts owing to their unique local structural flexibility and attractive electrocatalytic properties. With abundant randomly oriented bonds and surface-exposed defects (e.g., oxygen vacancies) as active catalytic sites, the adsorption/desorption of reactants can be optimized, leading to superior catalytic activities. Amorphous oxide materials have found wide electrocatalytic applications ranging from hydrogen evolution and oxygen evolution to oxygen reduction, CO₂ electroreduction and nitrogen electroreduction. The amorphous oxide electrocatalysts even outperform their crystalline counterparts in terms of electrocatalytic activity and stability. Despite of the merits and achievements for amorphous oxide electrocatalysts, there are still issues and challenges existing for amorphous oxide electrocatalysts. There are rarely reviews specifically focusing on amorphous oxide electrocatalysts and therefore it is imperative to have a comprehensive overview of the research progress and to better understand the achievements and issues with amorphous oxide electrocatalysts. In this minireview, several general preparation methods for amorphous oxides are first introduced. Then, the achievements in amorphous oxides for several important electrocatalytic reactions are summarized. Finally, the challenges and perspectives for the development of amorphous oxide electrocatalysts are outlined.     

导电MOFs在能源转化中的应用

可再生能源供应方案包括析氢反应(HER)、析氧反应(OER)、氧还原反应(ORR)和二氧化碳还原反应(CO2RR)等多种反应,电催化剂对这些反应至关重要。到目前为止,已有一系列导电MOFs作为与能源相关电催化电极材料的报道。本文从提高MOFs导电能力和对产物的选择性、增强MOFs的化学稳定性及增加MOFs的反应活性位点等方面介绍了导电MOFs作为电催化剂的设计策略,重点综述了其在能源转化涉及的HER、OER、ORR以及CO2RR方面的应用,并从材料制备和应用需求角度出发, 对高性能导电MOFs材料在电催化领域所面临的挑战和前景进行了展望。     

氧还原电化学催化剂研究的最新进展

燃料电池可以在接近室温条件下将氢或烃类中蕴含的巨大化学能通过电化学途径直接转化为清洁、稳定、可持续的电能,因而被视为极有前景的、能够满足日益增长的世界能源需求的终极解决方案之一.在一个典型的氢燃料电池中,氢在正极氧化而氧在负极还原,从动力学角度说,氧还原反应(ORR)比氢氧化反应进行的慢得多.无论是在酸性还是碱性条件下,氧的还原都可以一个四电子过程或是两个双电子过程进行,当然在酸性和碱性环境中反应的机理不同.铂一直是最有效的ORR催化剂,但受到价格昂贵、稳定性差和易中毒等因素的制约,目前非铂催化剂成为越来越引人瞩目的发展方向.本综述试图从分子催化剂、金属纳米材料催化剂、金属氧化物催化剂和新兴的二维材料催化剂等方面,选取近十年来最能代表ORR电化学催化剂方面成就的例子分析其优缺点,并为今后该领域的研究提供一些有益的思路.典型的分子催化剂是卟啉类化合物,当这种四齿的N4配体与过渡金属特别是铁、钴络合时,往往显示出良好的ORR催化性能,多数情况下其中的过渡金属中心、配体和碳支撑体系共同组成催化剂的活性中心.在另一些报道中,邻菲罗啉或是连吡啶型N2化合物也可以作为配体使用.第四和第五副族的很多金属形成的不同价态的氧化物都具有氧还原活性,比如MnOx,CoOx,TiOx,ZrOx,IrOx等.金属氧化物表现出易于修饰,不容易团聚和抗腐蚀等诸多优点,而其良好的ORR性能与表面的缺陷密切相关,因此钙钛矿型氧化物ABOx也引起人们的广泛关注,人们可以通过调节氧化物的晶型、尺寸和组成来获得更好的催化性能.近年来随着液相合成技术的发展,人们可以制备出理想形状和尺寸的单分散纳米粒子,然后通过旋涂、自组装等手段将其修饰到合适的电极上以获得增强性能的ORR催化剂.通过形状与尺寸调控,或组合成其它复杂的纳米结构,都有可能提高催化活性或是稳定性,因此有关纳米催化剂的研究日趋增多.在此基础上,考虑到石墨烯的可修饰性和良好的电化学性能,纳米材料复合石墨烯所形成的二维或三维结构也可提供很好的氧还原催化性能,而MoS2代替石墨烯作为支撑物所构成的二维催化剂也是值得注意的研究方向.综上所述,尽管现有的非铂催化剂仍难以完全满足商业化的要求,设计理念和合成方法的快速发展有望在不远的将来解决这一难题.而设计合成可控尺寸、形状、组成和表面形貌的纳米催化剂在很大程度上将加速这一进程.     

Unravelling the Structure of Electrocatalytically Active Fe–N Complexes in Carbon for the Oxygen Reduction Reaction

Non‐precious Fe/N co‐modified carbon electrocatalysts have attracted great attention due to their high activity and stability in oxygen reduction reaction (ORR). Compared to iron‐free N‐doped carbon electrocatalysts, Fe/N‐modified electrocatalysts show four‐electron selectivity with better activity in acid electrolytes. This is believed relevant to the unique Fe–N complexes, however, the Fe–N structure remains unknown. We used o,m,p‐phenylenediamine as nitrogen precursors to tailor the Fe–N structures in heterogeneous electrocatalysts which contain FeS and Fe₃C phases. The electrocatalysts have been operated for 5000 cycles with a small 39 mV shift in half‐wave potential. By combining advanced electron microscopy and Mössbauer spectroscopy, we have identified the electrocatalytically active Fe–N₆ complexes (FeN₆, [Fe^III(porphyrin)(pyridine)₂]). We expect the understanding of the FeN₆ structure will pave the way towards new advanced Fe–N based electrocatalysts.     

Electrocatalyst Fabrication Using Metal Nanoparticles Prepared in Ionic Liquids

Metal nanoparticle-based electrocatalysts are widely used in electronic devices, which serve for electrochemical reactions like oxygen reduction reaction, alcohol oxidation and CO₂ reduction reaction. These catalyst-dependent reactions are the key of the emerging clean energy systems. Catalyst design and synthesis therefore have received keen attention in past decades. We are motivated to study synthesis approaches of metal nanoparticle-based electrocatalysts using ionic liquids (ILs), which are promising solvents for the nanoparticle preparation because of their unique physicochemical properties. In this personal account, we review our previous and present works on nanoparticle preparation in IL and utilization of the obtained nanoparticles as electrocatalysts.     

Advances in efficient electrocatalysts based on layered double hydroxides and their derivatives

The explore and development of electrocatalysts have gained significant attention due to their indispensable status in energy storage and conversion systems, such as fuel cells, metal–air batteries and solar water splitting cells. Layered double hydroxides(LDHs) and their derivatives(e.g., transition metal alloys, oxides, sulfides, nitrides and phosphides) have been adopted as catalysts for various electrochemical reactions, such as oxygen reduction, oxygen evolution, hydrogen evolution, and CO_2 reduction, which show excellent activity and remarkable durability in electrocatalytic process. In this review, the synthesis strategies, structural characters and electrochemical performances for the LDHs and their derivatives are described. In addition, we also discussed the effect of electronic and geometry structures to their electrocatalytic activity. The further development of high-performance electrocatalysts based on LDHs and their derivatives is covered by both a short summary and future outlook from the viewpoint of the material design and practical application.     

Recent Approaches to Design Electrocatalysts Based on Metal–Organic Frameworks and Their Derivatives

Rational design and synthesis of efficient electrocatalysts are important constituents in addressing the currently growing provision issues. Typical reactions, which are important to catalyze in this respect, include CO₂ reduction, the hydrogen and oxygen evolution reactions as well as the oxygen reduction reaction. The most efficient catalysts known up‐to‐date for these processes usually contain expensive and scarce elements, substantially impeding implementation of such electrocatalysts at a larger scale. Metal‐organic frameworks (MOFs) and their derivatives containing affordable components and building blocks, as an emerging class of porous functional materials, have been recently attracting a great attention thanks to their tunable structure and composition together with high surface area, just to name a few. Up to now, several MOFs and MOF‐derivatives have been reported as electrode materials for the energy‐related electrocatalytic application. In this review article, we summarize and analyze current approaches to design such materials. The design strategies to improve the Faradaic efficiency and selectivity of these catalysts are discussed. Last but not least, we discuss some novel strategies to enhance the conductivity, chemical stability and efficiency of MOF‐derived electrocatalysts.     

Single-atom Catalysts for Polymer Electrolyte Membrane Fuel Cells

Searching for high-activity, stability and highly cost-effective electrocatalysts for acid oxygen reaction reduction(ORR) has always been an urgent problem in polymer electrolyte membrane fuel cells(PEMFCs). Nonetheless, the electrochemical properties of various systems have their intrinsic limits and tremendous efforts have been paid out to search for highly efficient electrocatalysts by more rational control over the size, morphology, composition, and structure. In particular, single-atom catalysts(SACs) have attracted extensive interest due to theirs excellent activity, stability, selectivity and the highest metal utilization. In recent years, the number of papers in the field of SACs has increased rapidly, indicating that SACs have made great progress. This review focuses on SACs electrochemical applications in the acid ORR and introduces innovative syntheses, fuel cell performance and long-time durability.     

Recent advances in oxygen electrocatalysts based on tunable structural polymers

Due to their high energy density, great safety and eco-friendliness, zinc-air batteries (ZABs) attract much attention. During the process of charging and discharging, the two key processes viz. oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) limit their efficiency. In general, the noble metal-based electrocatalysts (ORR: platinum (Pt); OER: iridium (IV) oxide [IrO₂] and ruthenium oxide [RuO₂]) have long been used. Nonetheless, these noble metal electrocatalysts also have their limitations owing to high cost and poor stability. As alternatives, polymers are found to be most promising on account of their tunable structure, uniform network, high surface morphology and strong durability. Polymers are capable catalysts. In this review, recent advances as well as insight into the architecture of covalent organic polymers (COPs), metal coordination polymers (MCPs) and pyrolysis-free polymers (PFPs) are duly outlined.     

Advances in Understanding Mechanisms of Perovskites and Pyrochlores as Electrocatalysts using In‐Situ X‐ray Absorption Spectroscopy

Metal oxides are some of the most promising candidates as electrocatalysts for electrical‐energy‐storage (EES) systems. Particularly, perovskite and pyrochlore oxides have been intensively investigated as bifunctional electrocatalysts because of their superior catalytic activities during the oxygen‐reduction and ‐evolution reactions. However, the origin of the outstanding catalytic activities and structural changes of the materials are not clear, in part due to the difficulty in identification during electrocatalysis. In this Minireview, we present a critical overview of recent progress in understanding catalytic mechanisms of perovskite and pyrochlore oxides, highlighting the innovative in‐situ X‐ray absorption spectroscopy (XAS) analysis for electrochemical tests.     

Nickel-iron borate coated nickel-iron boride hybrid for highly stable and active oxygen evolution electrocatalysis

The development of efficient and cost-effective electrocatalysts toward anodic oxygen evolution reaction (OER) is crucial for the commercial application of electrochemical water splitting. As the most promising electrocatalysts, the OER performances of nickel-iron-based materials can be further improved by introducing metalloid elements to modify their electron structures. Herein, we developed an efficient hybrid electrocatalyst with nickel-iron boride (NiFeB) as core and amorphous nickel-iron borate (NiFeB_i) as shell (NiFeB@NiFeB_i) via a simple aqueous reduction. The obtained NiFeB@NiFeB_i exhibits a small overpotential of 237 mV at 10 mA/cm² and Tafel slope of 57.65 mV/dec in 1.0 mol/L KOH, outperforming most of the documented precious-metal-free based electrocatalysts. Benefiting from the in situ formed amorphous NiFeBi layer, it shows excellent stability toward the oxygen evolution reaction (OER). These findings might provide a new way to design advanced precious-metal-free electrocatalysts for OER and the application of electrochemical water splitting.     

Constructing Built-in Electric Field in Heterogeneous Nanowire Arrays for Efficient Overall Water Electrolysis

Efficient bifunctional electrocatalysts for hydrogen and oxygen evolution reactions are key to water electrolysis. Herein, we report a built-in electric field (BEF) strategy to fabricate heterogeneous nickel phosphide-cobalt nanowire arrays grown on carbon fiber paper (Ni₂P-CoCH/CFP) with large work function difference (ΔΦ) as bifunctional electrocatalysts for overall water splitting. Impressively, Ni₂P-CoCH/CFP exhibits a remarkable catalytic activity for hydrogen and oxygen evolution reactions to obtain 10 mA cm⁻², respectively. Moreover, the assembled lab-scale electrolyzer driven by an AAA battery delivers excellent stability after 50 h electrocatalysis with a 100 % faradic efficiency. Computational calculations combining with experiments reveal the interface-induced electric field effect facilitates asymmetrical charge distributions, thereby regulating the adsorption/desorption of the intermediates during reactions. This work offers an avenue to rationally design high-performance heterogeneous electrocatalysts.     

碱性介质中碳纳米管FeNi复合物上电催化析氧反应(英文)

Non-noble metals such as Fe and Ni have comparable electrocatalytic activity and stability to that of Ir and Ru in an oxygen evolution reaction (OER). In this study, we synthesized carbon nanofibers with embedded FeNi composites (FeNi-CNFs) as OER electrocatalysts by a facile route comprising electrospinning and the pyrolysis of a mixture of metal precursors and a polymer solution. FeNi-CNFs demonstrated catalytic activity and stability that were better than that of 20 wt% Ir on Vulcan carbon black in oxidizing water to produce oxygen in an alkaline media. Physicochemical and electrochemical characterization revealed that Fe and Ni had synergistic roles that enhanced OER activity by the uniform formation and widening of pores in the carbon structure, while the CNF matrix also contributed to the increased stability of the catalyst.     

Recent Progress in Precious Metal-Free Carbon-Based Materials towards the Oxygen Reduction Reaction: Activity,Stability, and Anti-Poisoning

The large-scale application of polymer electrolyte membrane fuel cells (PEMFCs) depends heavily on the development of high-performance and cost-effective oxygen reduction reaction (ORR) electrocatalysts to replace the traditional Pt-based materials. Among the numerous candidates of ORR electrocatalysts, precious metal-free carbon-based materials have received ever-increasing attention for their unique electronic features, tunable nanostructures, and robustness. Although tremendous efforts have been devoted to raising the intrinsic properties of precious metal-free carbon-based materials, there exists a lot of room for them to be improved in activity, stability, and poison-tolerance. In this Minireview, the latest strategies for enhancing activity by increasing the accessible active sites and promoting the intrinsic activity have been summarized. In addition, with special emphasis on devastating catalyst poisoning, up-to-data tactics for elevating the stability and poison-tolerance are introduced. Finally, conclusions and perspectives are also presented.     

Ion‐Exchange‐Assisted Synthesis of Pt‐VC Nanoparticles Loaded on Graphitized Carbon: A High‐Performance Nanocomposite Electrocatalyst for Oxygen‐Reduction Reactions

Carbide‐based electrocatalysts are superior to traditional carbon‐based electrocatalysts, such as the commercial Pt/C electrocatalysts, in terms of their mass activity and stability. Herein, we report a general approach for the preparation of a nanocomposite electrocatalyst of platinum and vanadium carbide nanoparticles that are loaded onto graphitized carbon. The nanocomposite, which was prepared in a localized and controlled fashion by using an ion‐exchange process, was an effective electrocatalyst for the oxygen‐reduction reaction (ORR). Both the stability and the durability of the Pt‐VC/GC nanocomposite catalyst could be enhanced compared with the state‐of‐the‐art Pt/C. This approach can be extended to the synthesis of other metal‐carbide‐based nanocatalysts. Moreover, this straightforward synthesis of high‐performance composite nanocatalysts can be scaled up to meet the requirements for mass production.     

钙钛矿型稀土氧化物的合成及其能源转化储存应用研究进展

钙钛矿型稀土氧化物价格低廉、结构可控、性质多样,在催化领域有着广阔的应用前景。本文从钙钛矿型稀土氧化物的结构类型、合成方法及电化学催化反应出发,总结了传统高温合成方法、火焰喷雾法、静电纺丝法和脉冲激光沉积法等几种最常用的合成方法,以及提升其氧析出反应(OER),氢析出反应(HER)和氧还原反应(ORR)催化能力的典型有效方法,概述了近年来钙钛矿型稀土氧化物在电解水、金属空气电池和固体氧化物燃料电池等能源转化储存装置的主要研究进展,进而对钙钛矿型稀土氧化物在能源转化储存领域的应用进行了展望。     

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.