铜基纳米团簇电催化性能调控及其催化CO2高效转化为烃类物质的机理和应用研究

The reutilization of carbon-based energy and high-performance conversion of CO2 to hydrocarbon compounds are the significant demands in the fields of chemical production and environmental protection. In the present project, novel electroctalytic surface/interface will be fabricated based on copper-based nanoclusters/3D carbon materials to study the electroreduction of CO2. The highly efficient and selective conversion of CO2 to hydrocarbon compounds will be achieved by taking advantage of the highly electrocatalytic activity of Cu-based catalysts, large surface/interface area and the tunable electronic structure and properties of copper-based nanoclusters, and the highly stable structure, good electronic conductivity and high porosity of the 3D carbon supports. Various ex-situ and in- situ spectroscopic electrochemical techniques will be used to study the mechanism and dynamics of CO2 transform on the copper-based nanoclusters/3D carbon catalysts. This project will focus on the controlled syntheses of Cu-based nanoclusters and 3D carbons with different compositions and structures, detailed structure characterization, studies of electron transfer mechanism, catalyst-dependent process of CO adsorption and desorption, and the catalytic selectivity etc. This research will be helpful for systematically understanding the mechanism of CO2 electroreduction on copper-based nanoclusters/3D carbon catalysts and the selective conversion of CO2. Moreover, this project will provide reliable experimental results and theoretical foundation for the application of sub-nanometer sized copper nanoclusters in the conversion of CO2 to hydrocarbon compounds with high performance and selectivity.

碳基能源的重复利用和CO2高效转化为烃类化合物是化工生产和环境保护领域的重大需求。本项目利用铜基电催化剂对CO2转化为烃化物的高催化性能，铜基纳米簇的高表界面效应及其电子结构和性能可调控性，以及三维多孔碳材料的结构稳定性、良好导电性和高孔隙度等独特性能，通过电化学原位谱学等技术研究铜基纳米簇-三维多孔碳复合结构对CO2电化学还原的性能、催化机理及应用，构建性能优异的CO2还原电催化表界面新体系，实现具有产物选择性的CO2高效转化。本项目将对不同组成和比例的铜基纳米簇、不同形貌的三维碳复合材料制备、结构表征、电子传递机制、CO解吸附控制及催化选择性等内容进行全面和深入研究。研究结果将会对基于铜基纳米簇复合材料的CO2电催化还原机理及CO2到烃化物的选择性转化等方面有系统性认识，从而为亚纳米量级的铜纳米簇催化材料应用于CO2到烃类物质的选择性、高效转化应用方面提供可靠的实验结果和理论依据。

通过本项目的实施，我们成功设计和可控制备了原子水平结构明确的Cu、Ag、Pt、Pd、Ni等金属团簇和Fe、FeCu单原子催化剂材料。掌握了制备高分散、电化学催化性能优良的团簇基金属催化剂的实验条件和关键技术，并对其结构和性能进行了系统研究。在此基础上，通过原子掺杂和表面功能化等方法对金属团簇等纳米结构进行功能调控和拓展，设计了新型电催化材料，应用于CO2还原、氧还原、甲酸氧化、葡萄糖和过氧化氢电化学检测等。通过对上述纳米材料结构和电化学催化性能研究，深刻认识了团簇基材料结构与其催化性能之间的构效关系。在对团簇催化剂结构和性能优化的基础上，针对不同的催化反应过程和检测对象，筛选出具有高活性和高稳定性的电极材料。本项目的研究成果对理性、高效设计电催化纳米催化剂、拓展金属团簇的应用领域以及深入认识团簇结构-性能的内在关联性提供了可靠的实验结果和理论依据。