表界面化学调控低维氧化亚铜优化其电催化CO2还原性能研究

Designing low-cost and efficient electrocatalysts is critical to driving electrocatalytic CO2 reduction to valuable multi-carbon products and realizing commercial application of this green energy conversion technology. This project aims to use low-dimensional copper oxide material as the research object. By virtue of the high specific surface area of low-dimensional system to guarantee the optimal exposure of catalytic active sites. Surface/interface chemical regulation strategies, such as surface ion/molecular modification, designing surface defects or heterojunctions and introducing interfacial strain/bridged bonds, etc, are used to modulate the electronic structure and surface properties of low-dimensional cuprous oxide material for synergistically optimizing the catalytic active sites, adsorption free energy of the reaction intermediates and conductivity, and finally improve the catalytic activity and selectivity of C≥2+ products (C2H4, C2H5OH, etc.) for electrocatalytic CO2 reduction. Moreover, the spectroscopy characterization methods and theoretical calculation are used to reveal how surface/interface chemical regulation strategies modulate the electronic structure and surface properties of low-dimensional cuprous oxide, and the microscopic mechanism of the electrocatalytic CO2 reduction reaction process is expounded. The development of this project provides theoretical and methodological guidance to design efficient catalysts for electrocatalytic CO2 reduction.

设计低成本且高效的电催化剂对于推动电催化CO2还原转换为有价值的多碳产物并实现这种绿色能源转换技术工业化应用至关重要。本项目拟以低维氧化亚铜材料为研究对象，利用低维体系的高比表面积特性，在催化活性位点得到最大程度暴露的基础上，构建新型的表界面化学调控策略如表面离子/分子修饰，设计表面缺陷或异质结，引入界面应力或桥键等方法对低维氧化亚铜材料的电子结构和表面特性进行调制，实现对其催化活性位点、反应中间体的吸附自由能和电导率的协同优化，提升其电催化CO2还原转化为多碳产物（C2H4,C2H5OH等）的催化活性及选择性。在此基础上，利用光谱学表征方法和理论计算揭示表界面化学调控策略调制其电子结构和表面特性的调控规律，阐述电催化CO2还原反应过程的微观机制。本项目的开展有望为设计高效的电催化CO2还原催化剂提供理论和方法指导。

在本项目开展过程中，项目负责人对基于非贵金属电催化剂体系的表界面化学调控方法进行了系统的研究，发展了基于Co，Ni，Mo和Cu等元素的功能性催化材料体系，提出了表面单/双阴离子修饰，Ni，S双缺陷策略，多金属异质界面设计等调控方法，对无机固体材料的本征电子结构及表面特性实现协同优化，从而显著提升该系列材料的电催化活性及稳定性，使该类材料展现了在电解水制氢和电催化CO2还原领域的显著应用前景。该一系列原创性成果为项目负责人今后研究领域的拓展及延申奠定了良好的基础。基于此，项目负责人在 ACS Sustain. Chem. Eng.；ChemSusChem; J. Colloid Interface Sci, Chem. Commun等化学、材料类高水平期刊发表论文 20 篇，很好完成了基金预期的相关研究计划。