双位点钴基氧化物定向构筑及其耦合增强电催化析氧性能研究

电催化析氧反应(OER)是决定电解水、二氧化碳还原等多种能源转换效率的关键反应，但OER多步反应涉及的中间基团(*OH/*O/*OOH)吸附能线性相关导致过电势较高。目前研究局限于调控限速步骤对应的基团吸附能，而有关同步优化多个基团吸脱附的研究鲜有报道。本项目选取具有应用前景的钴基氧化物(CoOx)为研究对象，提出采用金属元素掺杂调控电子结构以优化*OH/*O吸附能，同时掺入非金属作为质子受体稳定*OOH吸附的研究思路，实现CoOx中双位点构筑，协同优化多个基团吸附能以降低OER过电势，并利用电解水等探针反应表征所制备催化剂的性能。结合微观动力学模型、DFT计算和原位表征等技术，探究电子结构与吸附能的构效关系，理清双位点在OER多步反应中互利耦合的物理图像，阐明打破吸附能线性关系的设计原则，实现双位点的靶向调控和大电流密度下催化材料理性构建，为高效、稳定析氧催化剂设计及其商业应用夯实基础。

Oxygen evolution reaction (OER) is a vital reaction in many technologies for energy conversion, such as water splitting and CO2 electroreduction. However, the linear free energy scaling relationships involving intermediates of *OH, *O and *OOH have restricted OER catalytic activity. The current researchs have been devoted to regulating intermediates adsorption energy of rate-determining step, and few researchs focus on the synergetic optimization for *OH, *O, and *OOH adsorption. In this project, we take cobalt-based oxides (CoOx) as the research object, the electron states and *OH/*O adsorption energy are modulated by transition metal doping. Meanwhile, the proton acceptor is introduced by nonmetal elements doping to decrease the *OOH adsorption energy, which was used to construct dual active sites and optimize synchronously *OH, *O, and *OOH adsorption energy, the electrocatalytic activity is characterized by probe reaction such as water splitting. Combining the microstructure kinetic, DFT resuts and in-situ characterization techniques to establish the correlation between intrinsic electronic structure and *OH/*O adsorption energy. Moreover, the synergistic catalytic mechanism and design rules of dual-sites are revealed, and the modified CoOx catalysts by dual-sites are prepared and applied at high current density. This project can provides technical and theoretical support for the high efficiency and stable OER catalysts and their commercial application.