电催化剂设计中表面和界面工程的最新进展（英文）

电催化已发展为一种涉及电化学、表面科学、材料科学和催化科学等众多科学分支的交叉学科和综合技术,在工农业生产、经济和国防建设、能源开发和环境保护等方面发挥了不可或缺的作用.金属纳米催化剂的可控合成和创新构建,极大地推动了电催化的广泛应用和巨大进展.过渡金属尤其是贵金属Pt、Pd等电催化剂,在电催化中表现出良好的选择性、活性和稳定性,很难完全被其他材料所取代.制约电催化可持续发展的瓶颈问题是,如何设计、合成和构建高性能低成本的金属纳米催化剂.为实现这一目标,人们付出了大量的努力并取得了一些可喜的进展.电催化是发生在电解质与电极材料表面和界面的异相催化反应,金属纳米电催化剂的性能与其形貌、结构、尺寸和组成相关.本文着力总结和探讨如何从表面工程和界面工程角度设计、合成和构筑金属纳米结构及其复合结构,以实现金属电催化剂性能和成本的双优化.本文提出了在金属纳米结构及其复合结构的设计、合成和构筑过程中需要考虑的几个重要的表面和界面因素,即表面面积、表面晶面、活性位点和界面结构等.首先,有效表面面积越大,越有利于电催化反应.我们总结了增大催化剂有效活性面积的四种有效方法,包括减小颗粒尺寸、制成薄层二维纳米结构、增大粗糙度、形成中空、多孔或介孔及框架结构等.其次,表面晶面也可决定电催化的性能.我们简单总结了低指数晶面和高指数晶面在表面能、晶面形成和催化活性上的"挑战与机遇"矛盾关系,并简要阐述了晶面选择性即晶面效应以及晶面与尺寸的依赖关系.再次,活性位点一般指的是低配位表面原子位点,是电催化反应的决定因素之一.我们描述了活性位点与表面和界面结构特征、纳米晶表面晶面、表面缺陷和空穴、表面面积和粒子尺寸等的依赖关系.最后,界面结构工程是调控电催化性能的最丰稔因素.我们简述了界面结构的形成、分类及其对优化界面活性位点的成分和几何结构、表面悬键和原子配位数、电子结构与电子传递、质子传输和物种交换等方面调控作用,并在界面工程的基础上推介了贵金属基复合结构的合成、组装的几种典型方式.本文以具体示例的形式,分别从表面工程和界面工程的角度,扼要介绍了本课题组最近在甲酸氧化、氧还原、析氢等电催化反应体系中贵金属基纳米结构及其复合纳米结构电催化剂的设计、合成与构筑的具体做法.我们分别介绍了低指数晶面和高指数晶面的表面设计对于提高催化剂性能的关键作用.对于低指数晶面,我们重点介绍了如何获得相似尺寸的不同表面晶面以研究其晶面效应,如何维持相同晶面调节尺寸以研究其尺寸效应,如何建造与电极有良好电学接触的低指数晶面纳米结构,以利于提升其电催化性能.对于高指数晶面,介绍了几种形成高指数晶面的途径,并阐明了其晶面对电催化性能的影响.另一方面,我们从金属纳米结构及其复合结构的成分和结构调控策略介绍了界面构建对于提升电催化性能的奇妙作用,包括建造多金属纳米结构、与二维材料负载组装和利用界面极化.由此,本文总结了表面和界面工程对于电催化剂设计、合成和构筑目前面临的三个关键挑战.     

高指数晶面纳米催化剂的电化学制备及应用

催化剂的性能与其表面结构及组成密切相关,高指数晶面纳米晶的表面含有高密度的台阶原子等活性位点而表现出较高的催化活性. 本文综述了电化学方波电位方法用于Pt、Pd、Rh等贵金属高指数晶面结构纳米晶催化剂的制备、形成机理及其电催化性能的研究. 针对贵金属利用率问题,还着重介绍了具有较高质量活性的小粒径Pt二十四面体的制备. 在此基础上,还介绍了电化学方波电位方法用于低共熔溶剂中制备高指数晶面纳米晶,以及高指数晶面纳米催化剂的表面修饰及应用;最后对高指数晶面纳米催化剂的发展做出了展望.     

化学功能化增强贵金属纳米晶电催化性能（英文）

基于电催化过程的可再生和清洁能源的生产、转换和储存技术(如水电解和燃料电池)是缓解全球能源短缺和环境污染问题的有效手段.目前,水电解和燃料电池技术的实际应用缺乏高效、稳定的电催化剂来驱动动力学迟缓的阴极和阳极反应.贵金属纳米晶由于其独特的电子结构和高化学惰性而具有高电催化活性和稳定性.为了提升贵金属纳米晶的本征电催化性能,大量研究聚焦在利用面积效应、晶面效应和不同组分之间的协同效应来调控贵金属的粒径、形貌和化学成分.事实上,贵金属纳米晶的电催化性能也与其表/界面性质密切相关.电催化剂表面的化学功能化可以改变电极/电解质界面结构,从而提高电催化活性和选择性,这对开发新型高效的电催化剂具有重要的理论意义.本文系统介绍了本课题组开发的聚胺(PAM)功能化贵金属纳米电催化剂的合成方法及其在燃料电池和电解池等能源转换装置中的应用,具体包括:通过引入PAM控制反应动力学来调控纳米晶体的结构和形态,构建界面功能化贵金属纳米电催化剂;利用金属表面修饰的PAM分子改变表面催化位点的电子结构、配位环境等物理化学性质来控制反应物和中间体等的吸附行为,从而达到调节催化活性的目的;采用PAM分子来隔离特定活性位...     

具特定晶面且大比表面积贵金属纳米晶催化基元的构筑

贵金属纳米晶在电催化等领域具有广泛应用. 其催化活性往往与纳米晶体的表面结构直接相关,而催化剂的贵金属原子利用率与比表面积密切相关. 因小尺寸纳米晶难以保留特定的晶面,而具有特定表面的纳米晶通常结晶成尺寸较大、比表面积比较小的晶体,调控纳米晶的尺寸和表面结构两种策略似乎相互矛盾. 如何可控合成同时具有特定表面结构和大比表面积的贵金属纳米晶具有重要的意义. 本综述从形貌调控角度详细介绍提高贵金属纳米晶原子利用率的方法策略;总结调控单贵金属及其合金同时具有特定晶面和大比表面积的研究现状;最后,对纳米晶的形貌调控领域未来的发展趋势提出展望.     

钯纳米晶体在电催化甲酸氧化反应中的形貌效应

本文基于课题组前期工作,选用适当的金属前驱物、还原剂、稳定剂和保护剂,通过调控氧化刻蚀和反应动力学等,成功合成了形貌和尺寸均不相同的Pd纳米晶.经过认真的纳米粒子清洗和电极修饰组装,考察了它们在电催化甲酸氧化反应中的形貌与性能的关系.研究结果表明,Pd纳米晶样品的最大电流密度以纳米八面体（nanooctahedra）、纳米线（nanowires）、纳米立方体（nanocubes）、纳米瓜子（nanotapers）、凹面纳米立方体（concave nanocubes）的顺序递增,催化甲酸氧化反应的起始氧化电位均小于0.2V.研究结果印证了Pd纳米晶催化甲酸氧化反应的催化性能在尺寸效应上主要受活性表面积的影响,扣除表面积效应后的催化性能与其尺寸没有明确关系.该系列Pd纳米晶的催化性能主要取决于其表面结构,得出Pd纳米晶催化甲酸氧化反应遵循{111}晶面〈{100}晶面〈高指数晶面的性能活性顺序.综合最大电流密度和最小操作电位因素发现,Pd凹面纳米立方体和Pd纳米瓜子具有相对较好的商用价值.     

铜-氧化铈界面:几何及电子结构

纳米催化材料的性能主要由粒子尺寸、形貌和界面决定,即活性位点的电子及几何结构.尺寸、形貌可控的纳米催化材料的合成及其反应性能的研究,即催化剂的构效关系,一直是催化领域的研究热点.氧化物负载的金属催化剂广泛应用于多相催化反应过程.基于氧化铈优异的氧化还原性能, Cu/CeO2催化剂在CO氧化、N2O消除、水气变换、甲醇合成等反应中表现出优异性能.其中,通过铜物种与氧化铈表面化学键合形成的金属-载体界面通常被认为是催化活性中心.铜物种和氧化铈的相互作用主要体现在氧化铈固定铜物种,而铜物种促进氧化铈的氧化还原能力,涉及Cu^2+/Cu^+/Cu^0和Ce^3+/Ce^4+之间电子的传输和转移.Cu/CeO2催化剂活性位的原子结构与金属-载体相互作用程度密切相关.氧化铈形貌和铜负载量是决定界面电子和几何结构的重要因素.常见的纳米氧化铈形貌包括纳米粒子(多面体)、纳米棒和纳米立方体,可分别选择性暴露(111)、(110)和(100)晶面;这些晶面上原子配位环境和化学性能决定了铜-氧化铈的键合方式和界面结构.与暴露{100}晶面的纳米立方体相比,主要暴露{100}/{110}镜面的氧化铈纳米棒、暴露{111}/{100}晶面的纳米粒子与铜物种具有更强的金属-载体相互作用程度,也更有利于铜物种的分散.铜的负载量也显著影响铜物种在特定氧化铈表面的分散度和化学状态;随着铜负载量的增加,可在氧化铈表面形成层状铜、铜团簇和铜纳米粒子.通常情况下,低负载量有利于单层、双层铜物种的形成,高负载量时则出现多层铜和铜纳米粒子.催化活性位通常是由铜原子与氧化铈上的氧空穴相互作用产生,与氧化铈表面氧空穴的数量和密度密切相关,即氧化铈形貌.本文总结了Cu/CeO2催化剂的研究进展,讨论了氧化铈形貌和铜负载量对铜物种分散度和化学状态的影响规律,总结了铜氧化铈界面结构的多维度表征结果,比较了Cu/CeO2催化剂在CO氧化、水气变换及甲醇合成中的活性位结构和反应机制.     

铜-氧化铈界面:几何及电子结构（英文）

纳米催化材料的性能主要由粒子尺寸、形貌和界面决定,即活性位点的电子及几何结构.尺寸、形貌可控的纳米催化材料的合成及其反应性能的研究,即催化剂的构效关系,一直是催化领域的研究热点.氧化物负载的金属催化剂广泛应用于多相催化反应过程.基于氧化铈优异的氧化还原性能, Cu/CeO_2催化剂在CO氧化、N_2O消除、水气变换、甲醇合成等反应中表现出优异性能.其中,通过铜物种与氧化铈表面化学键合形成的金属-载体界面通常被认为是催化活性中心.铜物种和氧化铈的相互作用主要体现在氧化铈固定铜物种,而铜物种促进氧化铈的氧化还原能力,涉及Cu~(2+)/Cu~+/Cu~0和Ce~(3+)/Ce~(4+)之间电子的传输和转移.Cu/CeO_2催化剂活性位的原子结构与金属-载体相互作用程度密切相关.氧化铈形貌和铜负载量是决定界面电子和几何结构的重要因素.常见的纳米氧化铈形貌包括纳米粒子(多面体)、纳米棒和纳米立方体,可分别选择性暴露(111)、(110)和(100)晶面;这些晶面上原子配位环境和化学性能决定了铜-氧化铈的键合方式和界面结构.与暴露{100}晶面的纳米立方体相比,主要暴露{100}/{110}镜面的氧化铈纳米棒、暴露{111}/{100}晶面的纳米粒子与铜物种具有更强的金属-载体相互作用程度,也更有利于铜物种的分散.铜的负载量也显著影响铜物种在特定氧化铈表面的分散度和化学状态;随着铜负载量的增加,可在氧化铈表面形成层状铜、铜团簇和铜纳米粒子.通常情况下,低负载量有利于单层、双层铜物种的形成,高负载量时则出现多层铜和铜纳米粒子.催化活性位通常是由铜原子与氧化铈上的氧空穴相互作用产生,与氧化铈表面氧空穴的数量和密度密切相关,即氧化铈形貌.本文总结了Cu/CeO_2催化剂的研究进展,讨论了氧化铈形貌和铜负载量对铜物种分散度和化学状态的影响规律,总结了铜氧化铈界面结构的多维度表征结果,比较了Cu/CeO_2催化剂在CO氧化、水气变换及甲醇合成中的活性位结构和反应机制.     

Ru修饰Pd二十四面体纳米晶的合成及其甲醇电催化氧化性能

表面结构控制和表面异种金属修饰是调控催化剂反应性的重要方法。因此,我们结合高指数晶面结构的高反应性与表面修饰异种金属,合成具有{730}高指数晶面的钯二十四面体纳米晶,并通过循环伏安扫描电沉积法得到Ru修饰的钯二十四面体纳米晶。电化学测试结果表明,低的Ru覆盖度(θ_(Ru)=0.08)可显著提高对碱性介质中甲醇电氧化的催化性能。电化学原位红外光谱结果表明,少量Ru的修饰没有减少CO的生成,而是促进了低电位下甲醇氧化成甲酸根。     

贵金属纳米框架设计合成及电催化性能的研究进展

由超薄边框相互连接形成的贵金属纳米框架以负载量低、活性高等优势在多相催化领域受到了广泛关注.纳米框架独特的三维开放可及性结构不仅能够在边缘和顶点处暴露出更多的活性位点,提高贵金属活性位点利用率,还可以将反应底物限制在纳米范围内,增加底物分子碰撞的几率.本文综合评述了贵金属纳米框架材料的合成策略,总结了近年来贵金属纳米框架催化剂在电催化领域的研究进展,并对其未来发展方向和面临的挑战进行了展望.     

高效氧化铜-二氧化铈催化剂的研究进展

二氧化铈(CeO_2)因其独特的储存和释放氧的能力,通过调控晶畴尺寸和表面结构,可与活性组分形成结构稳定且化学性质活泼的界面相互作用,显著提高催化剂的性能,从而被广泛应用.对于活性组分的选择,氧化铜因其价廉易得、活性和稳定性良好等特点成为贵金属的优良替代品.因此,氧化铜-二氧化铈(CuO-CeO_2)复合材料成为当下催化多种工业反应如一氧化碳氧化、水煤气变换反应等经济有效的催化剂.然而,由于CeO_2的形貌、尺寸以及暴露晶面等都会对金属载体间的相互作用产生影响,导致催化剂的结构十分复杂,造成了对活性位点及其作用机理的认知不充分.本文总结了本课题组对CuO-CeO_2体系中的活性位点进行精确指认的策略,以及以此为基础对活性位点的调控,探讨了新的反应机理,并对其未来发展方向进行了展望.     

Material and Interface Engineering for High‐Performance Perovskite Solar Cells: A Personal Journey and Perspective

Hybrid organic‐inorganic perovskite solar cells (PSCs) have become a shining star in the photovoltaic field due to their spectacular increase in power conversion efficiency (PCE) from 3.8 % to over 23 % in just few years, opening up the potential in addressing the important future energy and environment issues. The excellent photovoltaic performance can be attributed to the unique properties of the organometal halide perovskite materials, including high absorption coefficient, tunable bandgap, high defect tolerance, and excellent charge transport characteristics. The authors entered this field when pursuing research on dye‐sensitized solar cells (DSCs) by leveraging nanorods arrays for vectorial transport of the extracted electrons. Soon after, we and others realized that while the organometal halide perovskite materials have excellent intrinsic properties for solar cells, interface engineering is at least equally important in the development of high‐performance PSCs, which includes surface defect passivation, band alignment, and heterojunction formation. Herein, we will address this topic by presenting the historical development and recent progress on the interface engineering of PSCs primarily of our own group. This review is mainly focused on the material and interface design of the conventional n‐i‐p, inverted p‐i‐n and carbon electrode‐based structure devices from our own experience and perspective. Finally, the challenges and prospects of this area for future development will also be discussed.     

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.     

缺陷位工程在二维材料电催化析氢反应中的研究进展

面对不可再生资源的快速消耗和环境污染的日益加重,寻找清洁可再生能源势在必行.氢能是一种清洁可再生的能源,是目前最有希望替代化石燃料的一种能源.电化学水分解可用来产生高纯氢气,其中析氢催化剂起着至关重要的作用.尽管贵金属铂基催化剂表现出优异的析氢性能,然而稀缺性和高成本限制了其大规模应用.因此,开发高效和地球存量丰富的电...     

Tuning Reconstruction Level of Precatalysts to Design Advanced Oxygen Evolution Electrocatalysts

Surface reconstruction engineering is an effective strategy to promote the catalytic activities of electrocatalysts, especially for water oxidation. Taking advantage of the physicochemical properties of precatalysts by manipulating their structural self-reconstruction levels provide a promising methodology for achieving suitable catalysts. In this review, we focus on recent advances in research related to the rational control of the process and level of surface transformation ultimately to design advanced oxygen evolution electrocatalysts. We start by discussing the original contributions to surface changes during electrochemical reactions and related factors that can influence the electrocatalytic properties of materials. We then present an overview of current developments and a summary of recently proposed strategies to boost electrochemical performance outcomes by the controlling structural self-reconstruction process. By conveying these insights, processes, general trends, and challenges, this review will further our understanding of surface reconstruction processes and facilitate the development of high-performance electrocatalysts beyond water oxidation.     

Defective NiFe2O4 Nanoparticles for Efficient Urea Electro‐oxidation

Urea is an important organic pollutants in sewage and needs to be removed for environmental protection. Here, we report defective NiFe₂O₄ (NFO) nanoparticles with excellent performance for urea electro‐oxidation. The results show that defects can be effectively implanted at the surface of NFO nanoparticles by a facile and versatile lithium reduction method without affecting its main crystal structure and grain size. The defective NFO‐5Li nanoparticles displayed a significantly improved urea electro‐oxidation performance compared with NFO‐Pristine nanoparticles. Particularly, the NFO‐Pristine and NFO‐5Li show a potential of 1.398 and 1.361 V at the current density of 10 mA cm^?2 and Tafel slope of 37.3 and 31.4 mV dec^?1, respectively. In addition, the NFO‐5Li nanoparticles also revealed outstanding electrocatalytic stability. The superior performance can be attributed to the designed tunable surface defect engineering. Furthermore, the defect engineering strategy as well as the defective NFO nanoparticles hold great potential for applications in other materials and areas.     

促进组织生长的聚合物骨架工程材料

对组织工程中影响细胞生长规律的两个主要因素：材料的表面性质和表面形貌进行了讨论，指出材料的生物相容性应同时包括表面相容性和结构相容性。对于可促进组织生长的聚合物骨架材料的结构设计，必须同时兼顾材料的表面工程和结构２工程，二者必不可少且不可分割。     

Surface/interface engineering of high-efficiency noble metal-free electrocatalysts for energy-related electrochemical reactions

To date,much efforts have been devoted to the high-efficiency noble metal-free electrocatalysts for hydrogen-and oxygen-involving energy conversion reactions,due to their abundance,low cost and nultifunctionally.Surface/interface engineering is found to be effective in achieving novel physicochemical properties and synergistic effects in nanomaterials for electrocatalysis.Among various engineering strategies,heteroatom-doping has been regarded as a most promising method to improve the electrocatalytic performance via the regulation of electronic structure of catalysts,and numerous works were reported on the synthesis method and mechanism investigation of heteroatom-doping electrocatalysts,though the heteroatom-doping can only provide limited active sites.Engineering of other defects such as vacancies and edge sites and construction of heterostructure have shown to open up a potential avenue for the development of noble metal-free electrocatalysts.In addition,surface functionalization can attach various molecules onto the surface of materials to easily modify their physical or chemical properties,being as a promising complement or substitute for offering materials with catalytic properties.This paper gives the insights into the diverse strategies of surface/interface engineering of the highefficiency noble metal-free electrocatalysts for energy-related electrochemical reactions.The significant advances are summarized.The unique advantages and mechanisms for specific applications are highlighted.The current challenges and outlook of this growing field are also discussed.     

Multi‐Anion Intercalated Layered Double Hydroxide Nanosheet‐Assembled Hollow Nanoprisms with Improved Pseudocapacitive and Electrocatalytic Properties

Electrochemically active hollow nanostructured materials hold great promise in diverse energy conversion and storage applications, however, intricate synthesis steps and poor control over compositions and morphologies have limited the realization of delicate hollow structures with advanced functional properties. In this study, we demonstrate a one‐step wet‐chemical strategy for co‐engineering the hollow nanostructure and anion intercalation of nickel cobalt layered double hydroxide (NiCo‐LDH) to attain highly electrochemical active energy conversion and storage functionalities. Self‐templated pseudomorphic transformation of cobalt acetate hydroxide solid nanoprisms using nickel nitrate leads to the construction of well‐defined NiCo‐LDH hollow nanoprisms (HNPs) with multi‐anion intercalation. The unique hierarchical nanosheet‐assembled hollow structure and efficiently expanded interlayer spacing offer an increased surface area and exposure of active sites, reduced mass and charge transfer resistance, and enhanced stability of the materials. This leads to a significant improvement in the pseudocapacitive and electrocatalytic properties of NiCo‐LDH HNP with respect to specific capacitance, rate and cycling performance, and OER overpotential, outperforming most of the recently reported NiCo‐based materials. This work establishes the potential of manipulating sacrificial template transformation for the design and fabrication of novel classes of functional materials with well‐defined nanostructures for electrochemical applications and beyond.     

Electrochemical interfaces for chemical and biomolecular separations

The design of molecularly selective interfaces can lead to efficient electrochemically-mediated separation processes. The fast growing development of electroactive materials has resulted in new electroresponsive adsorbents and membranes, with enhanced selectivity, higher uptake capacities, and improved energy performance. Here, we review progress on the interfacial design for electrochemical separations, with a focus on chemical and biological applications. We discuss the development of new electrode materials and the underlying mechanisms for selective molecular binding, highlighting areas of growing interest such as metal recovery, waste recycling, gas purification, and protein separations. Finally, we emphasize the need for integration between molecular level interface design and electrochemical engineering for the development of more efficient separation processes. We envision that electrochemical separations can play a key role towards the electrification of the chemical industry and contribute towards new approaches for process intensification.