多步质子电子转移、多种表面含氧中间体及其与双电层分子之间多样的共吸附和相互作用模式等复杂性，使电化学、谱学和计算模拟等任何单一技术对氧电催化体系的解析都存在极大困难。因此迄今仍有诸多关键问题未解，如高反应超电势的起源、多样pH效应的原因、有效的构效关系模型。这些不仅是电化学基础难题，也是限制燃料电池和电解水等能源技术进步的壁垒。原位谱学和计算模拟方法的最新进步为解析表、界面含氧物种和双电层结构带来机遇。本项目联合国内在原位XPS和振动光谱、理论与计算电化学、基础与单晶电化学领域有优势的课题组，通过实验与多尺度模拟结果的交互补充和印证，降低单一方法处理表界面复杂性存在的困难和不确定性，解析典型催化剂表面含氧物种吸附结构及双电层结构随催化剂组成和反应条件的变化规律，阐释这些结构影响反应热力学和动力学的机制，回答上述关键问题，为设计高效氧电催化剂提供指导，为复杂电催化体系研究提供方法学范例和技术

The oxygen electrocatalytic system involves multiple sequential and/or concerted proton-electron transfer steps, and a multitude of surface oxygen-containing intermediates that are co-adsorbed and interact with other molecules in the electrical double layer (EDL). These complexities make any single approach in electrochemistry, spectroscopy and computational simulations insufficient to fully resolve the oxygen electrocatalysis. Therefore, numerous vexing problems remain unsettled, for instance, origins of the large reaction overpotential, causes of intriguing pH effect, and the formula of effective structure-property relations. These puzzles stand as conundrums in fundamental electrochemistry, and block the development of electrochemical energy technologies such as fuel cells and water electrolyzers as well. Fortunately, the near-ambient pressure XPS (APXPS) opens new opportunities to in-situ probe the oxygen-containing intermediates and the EDL. In this project, prime domestic groups in APXPS, theoretical and computational electrochemistry and single crystalline electrochemistry are combined into a joining force, thus enabling us to reduce the uncertainties arising from the daunting complexities of the oxygen electrocatalytic system through mutual complementation and verification between high-resolution experimentation and hierarchical modeling. This project strives to unravel how the structure of oxygen-adsorbing intermediates and the EDL evolve when varying the catalyst structures and reaction conditions, and further delineate a mechanistic picture of how interfacial structure dictates the thermodynamics and kinetics of reactions. This endeavor will be highly instructive to the design of more efficient oxygen electrocatalysts, as well as will establish a new methodology for future forays into complex electrocatalysis systems.