二硫化钼上单原子催化剂的能级调控与电催化性能研究

The fundamental challenges in electrocatalysis including a lack of low-cost materials, low efficiency, and unclear catalytic active sites and reaction mechanisms yet remain to date. To address these issues, this project will focuse on the construction of high-performance single atom electrocatalysts on the basis of “energy level matching” theory and understanding of electrocatalytic mechanism via analyzing the “electronic metal-support interaction” effect. This project will start with the exploration of a novel synthetic approach using functionalized two-dimensional material MoS2 as the support. Detailed analysis of electronic interactions between the metal and the support using a series of advanced analytical techniques helps to understand the electronic structure and energy level of the single-atom metal. Thus, correlation of the electrocatalytic activity and the electronics structures of the catalyst will assist in the specific construction and modulation of electrocatalysts. In addition, in-situ spectroelectrochemistry techniques will be used to understand the formation and nature of intermediates involved in electrocatalytic reaction. Combined with simulations, the intrinsic mechanism of electrocatalytic reaction will be revealed on the molecular level. Our finding holds great promise as an effective and facile strategy for the design of single-atom electrocatalysts, and sheds insights into the structure-activity relationship of electrocatalysts at atomic and molecular level.

针对电催化剂价格昂贵、活性差以及催化活性位点和催化机理不明确等方面的问题，本项目拟构筑单原子金属电催化剂，从电催化的“能级匹配”原理出发，分析金属-载体电子相互作用效应，揭示单原子电催化反应机理。根据拟定的研究目标，本项目以功能化二硫化钼纳米材料为催化剂载体，构建高性能负载型金属单原子复合物电催化剂，研究单原子可控合成新方法；采用多种分析技术深入探讨载体与金属之间的电子相互作用，剖析金属单原子的电子态结构和能级，将其与电催化性能关联，指导电催化剂的精准构筑和性能调控；利用原位电化学-光谱联用技术，研究电催化反应中间态的形成与种类，结合模拟计算从分子水平揭示单原子电催化剂活性位点结构和催化反应机理。研究成果将为金属单原子催化剂的设计和构建提供理论指导，有利于从原子层面更深入地了解活性位点能级与催化活性间的构-效关系。

研究围绕单原子可控制备、电催化剂能级调控、金属-载体电子相互作用和单原子电催化反应机理及其性能等方面展开研究。建立定点欠电位沉积可控合成单原子金属催化剂的新方法；将能级调控概念引入电催化剂的设计中，深入阐述二维层状化合物载体（例如过渡金属硫化物载体、硫掺杂石墨烯载体）与单原子金属之间的载体-金属电子相互作用机制及其对电催化性能的影响；进一步揭示单原子催化剂电催化反应（氧还原反应、析氢反应）机理。本项目研究内容可归纳为如下三点：1）定点欠电位沉积制备单原子催化剂；2）金属-载体电子相互作用调控铂单原子析氢反应电催化性能研究；3）单原子Pt负载硫掺杂碳材料制备及其电催化氧还原性能和机理研究。研究成果将为金属单原子催化剂的设计和构建提供理论指导，有利于从原子层面更深入地了解活性位点能级与催化剂活性间的构-效关系。