CO2电还原制多碳醇：石墨炔基催化剂设计策略及CO增强偶联机制探究

电催化CO2还原为高附加值C2+多碳醇一般是由CO2首先转化为吸附的CO中间体（*CO）引发的，但具体反应机制尚不清楚。由于铜基催化剂存在多碳醇选择性低、耐久性差等问题，本项目拟设计一种新型的具备高度有序凹凸结构的无铜氮掺杂石墨炔材料（N-OG），系统探究sp-N掺杂类型和杂化碳结构对CO2RR生成醇类活性的影响，突破现有铜基材料研究的局限；并以此为着力点，深入研究CO覆盖密度、吸附强度及反应速率对多碳醇反应途径的影响规律，厘清*CO的真实配位状态与增强偶联机制。同时，构筑Au/N-OG串联催化体系，借助Au位点还原CO2产生的局部高浓度CO微环境进一步增强C-C偶联效率。利用电化学-单分子荧光显微镜技术，在单粒子水平上实时跟踪量化单个Au/N-OG位点上CO中间体的生成、脱附、迁移及还原的动态变化过程与微观分布，建立C-C偶联反应的精准CO调控机制，为CO2RR制多碳醇提供新思路和指导。

The electrocatalytic reduction of CO2 (CO2RR) into highly valuable C2+ alcohols is generally initiated by converting CO2 to adsorbed CO intermediates (the first step), but the specific reaction pathway and mechanism are yet unclear. Considering that copper-based catalysts have been suffering from some serious issues for CO2RR into C2+ alcohols, such as low selectivity and poor durability, in this project, a new type of copper-free nitrogen-doped graphdiyne materials with highly ordered concave-convex structure (N-OG) would be designed to systematically study the effects of sp-N doping type and hybrid carbon structure on CO2RR into alcohols activity, breaking through the limitations of existing copper-based researches. With this as the research objects, we proposed to further explore the impacts of CO coverage density, adsorption strength and reaction rate on the reaction pathway of C2+ alcohols, so as to clarify the real coordination environment and enhanced coupling mechanism of CO intermediate (*CO). Simultaneously, a tandem catalyst (Au/N-OG) will be designed to generate local high-concentration CO microenvironment at Au sites that could further enhance C-C coupling efficiency. By using unique electrochemical single-molecule fluorescence microscopy (EC-SMFM) at single-particle level, we propose to trace and quantify the dynamic process of formation, desorption, migration and reduction of CO intermediates formed on single Au/N-OG site in real-time, and establishing a precise CO regulation mechanism of C-C coupling reaction. Our project will provide new insights and guidance for CO2RR into C2+ alcohols.