金属-水界面催化的分子机制:加氢与氧化反应  

Recent advances in the molecular‐level understanding of catalytichydrogenation and oxidation reactions at metal‐aqueous interfaces

作　　者：顾宇 王磊[1] 徐柏庆[2] 施慧 Yu Gu;Lei Wang;Bo-Qing Xu;Hui Shi(School of Chemistry and Chemical Engineering,Yangzhou University,Yangzhou 225009,Jiangsu,China;Innovative Catalysis Program,Key Lab of Organic Optoelectronics&Molecular Engineering,Department of Chemistry,Tsinghua University,Beijing 100084,China)

机构地区：[1]扬州大学化学化工学院,江苏扬州225009 [2]清华大学化学系,有机光电子和分子工程教育部重点实验室,北京100084

出　　处：《Chinese Journal of Catalysis》2023年第11期1-55,共55页催化学报（英文）

基　　金：国家自然科学基金(22072128,22308301,22301267,21932005).

摘　　要：固-水界面及相关现象(吸附、成核、腐蚀、催化等)存在于各类化学、物理和生物体系中.就多相催化的分子机制而言,长期以来主要的研究对象是固-气界面催化,对于催化剂与液体相接触时的固-液界面结构及固-液界面催化(尤其是催化动力学与机理中的溶剂效应的本质)的理解则显著滞后.金属-水界面的催化加氢和氧化反应不仅在化学工业的绿色可持续发展中发挥着关键作用,也会对诸多生物体系的功能产生重要影响.然而,水所特有的理化性质使得固-水界面在催化过程中容易呈现丰富且复杂多变的特性,认识其中的微观机制具有挑战性.本文针对几类重要且典型的催化加氢和催化氧化反应(例如双氧水直接合成、生物质分子加氢脱氧、一氧化碳和醇类分子的氧化等),通过遴选近十年左右的代表性文献,总结并剖析了水分子(作为溶剂和添加剂)以及由水导致的溶解、表面基团电离、分子活化/钝化与解离等衍生形成的中性或离子化物种对表界面催化反应行为、机理和构效关系的影响方式与机制.这些实例共同揭示了氢键相互作用、表面基团的离子化、极性环境中化学键的异裂以及质子耦合电子转移等在调控金属-水界面的催化加氢和催化氧化反应中发挥着重要作用.在总结普遍规律和原理的基础上,还针对不同催化反应体系的特异性(例如除反应物外的界面共吸附物种与溶剂水和/或催化剂表面之间的相互作用对反应物分子的活泼性和反应机理的影响)进行了细致剖析.此外,越来越多的实验证据表明,金属-水界面的热催化加氢和热催化氧化与相应的电催化加氢和电催化氧化在反应机理等方面存在诸多相似性,预示着将两种长期分立的多相催化方法相结合,对多相催化反应中的金属-水界面进行系统深入的研究,有望更全面地理解金属-水界面催化的分子机制.本�Solid-aqueous interfaces and their associated phenomena(adsorption,nucleation,corrosion,catalysis,etc.)are ubiquitous in a multitude of chemical systems linking various sub-fields of chemical science.In the realm of heterogeneous catalysis,where an emphasis has been historically placed on chemical transformations at solid-gas interfaces,our molecular understanding of the structures of catalyst-liquid interfaces and the kinetics and mechanisms of the catalytic reactions unfortunately lags behind the development of catalysts and processes in the liquid phase.Heterogeneously catalyzed hydrogenation and oxidation reactions at metal-aqueous interfaces are among the most important processes in the current chemical industry and in a constant pursuit of a greener and more sustainable future,and they also bear significant relevance for the functioning of biological entities.Molecular-level insights into these reactions,however,are often concealed due to the complexity of the dynamic solid-aqueous interfaces.Accordingly,the primary goal of this review is to summarize recent advances in the fundamental understanding of these interfacial chemical processes,particularly spotlighting research in the last decade on dissecting chemical and mechanistic origins of water effects in the catalytic systems.Specifically,we describe a selection of water-engendered effects on the kinetic behaviors and mechanistic consequences for several prototypical metal-catalyzed hydrogenation and oxidation reactions,and critically assess the general and specific roles of water molecules(as solvent or additive)as well as those of the neutral and ionic moieties(particularly H+and OH–)that are dissolved and solvated in water or equilibrated with the functionalities at the catalyst surfaces.We also show growing evidence that has endorsed close mechanistic connections between thermo-and electrocatalytically enabled redox chemistry at the interfaces,which point to promising strategies of integrating the two historically separated fields.While doing so,sy

关 键 词：固-液界面 金属-水界面 氢键相互作用 质子耦合电子转移 水相反应 催化加氢 催化氧化 

分 类 号：O64[理学—物理化学]