Magnussen Olaf M, Groß Axel
Institute of Experimental and Applied Physics , Kiel University , Olshausenstr. 40 , 24098 Kiel , Germany.
Institute of Theoretical Chemistry , Ulm University , Albert-Einstein-Allee 11 , 89081 Ulm , Germany.
J Am Chem Soc. 2019 Mar 27;141(12):4777-4790. doi: 10.1021/jacs.8b13188. Epub 2019 Feb 27.
For the knowledged-based development of electrochemical processes, a better fundamental understanding of the interfaces between electrodes and electrolytes is necessary. This requires insight into the interface structure and dynamics on the atomic-scale, including that of the liquid electrolyte in the near-surface region, i.e., in the inner and outer part of the electrochemical double layer. This perspective describes current studies of simple and well-defined electrochemical interfaces by first-principles electronic structure calculations and in situ structure-sensitive methods. It is shown that these experimental and theoretical studies are now approaching a level, where they can operate on the same footing, making direct comparison of the obtained results feasible. Using selected examples, progress in clarifying the structure and dynamics of the double layer, of adsorbed species on electrode surfaces, and of initial steps in electrochemical phase formation processes is discussed.
对于基于知识的电化学过程开发，有必要对电极与电解质之间的界面有更深入的基本理解。这需要在原子尺度上洞察界面结构和动力学，包括近表面区域液体电解质的界面结构和动力学，即在电化学双层的内层和外层。本视角通过第一性原理电子结构计算和原位结构敏感方法描述了对简单且明确的电化学界面的当前研究。结果表明，这些实验和理论研究目前正在接近一个水平，即在这个水平上它们可以在相同的基础上开展工作，使得对所获结果进行直接比较成为可能。通过选定的示例，讨论了在阐明双层结构和动力学、电极表面吸附物种以及电化学相形成过程初始步骤方面取得的进展。
