二氧化碳还原反应和析氧反应电化学催化剂设计的理论研究

CO2 reduction reaction (CO2RR) and oxygen evolution reaction (OER), which are the two half reactions for realizing artificial photosynthesis via electrochemical routes, have been among the focus of energy and environmental research in recent years, and the key issue is the design of highly efficient and selective electrocatalysts. Theoretical modeling can elucidate the atomistic mechanisms underlying the catalytic performance observed in experiments, and thus provide insights and guidelines for the rational design of novel electrocatalysts. This proposal will first develop a new accurate and yet practical multi-scale theoretical method for modeling the electrochemical interface, which combines the theoretical method based on joint density functional theory (JDFT) and the reactive force field (ReaxFF) method to properly describe the electrochemical interface with explicit inclusion of electrolyte. Based on our previous studies on the mechanisms for CO2RR and OER and the novel concept of single-cluster catalyst (SCC) design, this proposal will then explore and predict a series of new highly efficient and selective electrocatalysts for CO2RR and OER, with transition metal oxides and N-doped carbon materials as supports, in order to advance the realization of artificial photosynthesis via electrochemical routes.

二氧化碳还原反应(CO2RR)和析氧反应(OER)是构成电化学方法实现人工光合作用反应的两个半反应，近年来成为了能源和环境领域的热点课题。其研究关键是设计高效高选择性的电化学催化剂，而理论模拟能为实验发现提供微观机理的认识，并由此提供改进或创新电化学体系设计的新思路。本项目拟首先发展一套兼具准确性和实用性的电化学界面理论模拟多尺度方法，结合基于联合密度泛函理论(JDFT)的电化学界面理论方法和反应力场方法(ReaxFF)来模拟包含电解质结构的复杂电化学界面。然后基于申请人之前工作对CO2RR和OER反应机理的理解以及所提出的新型的单团簇催化剂(SCC)设计概念，通过理论模拟来探索并预测分别以过渡金属氧化物和N掺杂的碳材料为载体，一系列新的以SCC为设计思路的高效和高选择性的CO2RR和OER电化学催化剂设计，从而推动电化学方法实现人工光合作用反应的发展。

近年来，电化学催化成为了能源和环境领域的热点课题，具有广泛的潜在应用价值。其研究关键之一是设计高性能的电化学催化剂，而理论模拟可以提供新认识和新思路。本项目围绕基于单原子催化剂（SAC）和单团簇催化剂（SCC）设计概念的电化学催化剂的理论设计：提出了SAC和SCC的电化学稳定性理论，发展了一套基于电化学势窗口的理论模拟方法来预测SAC和SCC在特定载体上的负载稳定性；预测了一系列热力学或动力学稳定的新型SCC，可应用于高效催化电化学还原反应；分析了过渡金属SAC上的吸附能趋势与d能带理论的矛盾，阐明了其中的理论图像。本项目的研究成果为高性能SAC和SCC电化学催化剂的理性设计提供了新认识和新思路。