电催化CO2还原可利用间歇性可再生清洁能源，将温室气体转化为具有高工业附加值的化工原料，因此，其已成为当前的研究热点。然而CO2深度还原反应机制尚不明确，严重限制了人们通过精准设计催化剂结构以进一步提高多碳产物的活性及选择性。有机配体分子表面修饰是一种全新的、非常有前景的提高金属催化剂电催化还原CO2性能的策略，本项目拟设计一系列基于咪唑、吡啶及苯胺的有机配体分子，系统调控其官能团疏水性、给电子能力、亲氧特性等，通过同步辐射软X射线吸收谱及光电子能谱技术，探索有机配体分子对Cu基金属纳米催化剂表面电子结构及电催化产物活性及选择性调控，重点利用高亮度、高分辨率同步辐射原位红外光谱技术，结合同位素标记及密度泛函理论，给出电催化CO2深度还原中间体及其与有机配体分子作用的谱学证据，揭示有机配体分子调控电催化还原CO2机理，为高活性、高选择性催化剂在原子、分子尺度的精准设计奠定基础。

By utilizing clean and renewable energy, greenhouse gas carbon dioxide could be converted into value-added fuels and feedstocks by electrochemical reduction, thus rendering it the focus of the international research community. However, the mechanism of the deep reduction of CO2 to multi-carbon products remains unraveled, thus severely limiting the rational design of metal catalysts and enhancement of selectivity and activity towards them. Surface functionalization of the metal catalysts with organic capping ligands has been demonstrated as a novel and effective strategy to enhance the catalytic performance. Here in this proposal, a series of organic ligands based on imidazole, pyridine and aniline would be developed and the organic functional groups would be tuned systematically in terms of hydrophobicity, electronegativity and oxophile ability. The impact of the surface functionalization of the organic ligands on the atomic and electronic structures, and the catalytic activity and selectivity towards multi-carbon products on the metal catalyst would be explored by soft X-Ray absorption and photoelectron spectroscopies. The intermediates of deep reduction of CO2 to multi-carbon products and their bonding interaction with the organic capping ligands would be examined by the synchrotron-based in-situ infrared spectroscopy, as well as the isotopic labeling and density functional theory (DFT). The combined characterization techniques would unravel the reduction reaction path of CO2 to multi-carbon products and the mediating mechanism by organic capping ligands, thus paving ways for the rational design of high performance electrocatalysts at molecular scale.