共价键合双核金属配合物和光敏剂实现二氧化碳还原均相光催化体系有序异相化研究

可见光催化二氧化碳（CO2）还原是解决能源危机和缓解全球变暖的理想途径。针对CO2还原分子催化剂在催化过程中遇到的稳定性不高和循环利用不够理想等问题，本项目拟采用共价有机框架材料（COFs）的构建策略，以双核金属配合物分子催化剂和分子光敏剂作为COFs的构筑单元，利用席夫碱醛胺缩合反应将两个构筑单元共价连接，控制合成集催化剂和光敏剂于一体的二维（2D）高结晶性COFs材料，实现光催化CO2还原均相催化体系的异相化；运用X-射线粉末衍射解析和模拟异相化COFs催化剂的晶体结构，并在结构表征的基础上，研究异相化催化剂的光电性质和光催化CO2还原性能，重点研究分子催化剂和光敏基团两者的匹配性对催化活性的影响，分析催化活性与催化剂结构之间的关系，总结异相化催化剂的合成规律；最后结合理论计算，揭示光催化CO2还原的催化机理，为性能优异的光催化CO2还原催化剂的设计提供新的研究思路和参考。

Catalytic carbon dioxide (CO2) reduction driven by visible light is an ideal approach to solve the energy crisis and alleviate global warming. In view of the low stability and unsatisfactory recycling of molecular catalysts in the catalytic CO2 reduction process, we plan to heterogeneity of homogeneous photocatalytic CO2 reduction system by the strategy of covalent organic frameworks (COFs) construction, to obtain two-dimensional high-crystallinity photocatalysts. The binuclear complex molecular catalyst and photosensitizer will be used as the construction units, which will be connected together through the Schiff base aldehyde amine condensation reaction. X-ray powder diffraction is used to analyze and simulate the crystal structure of the obtained COFs photocatalysts. On the basis of structure characterization, the photoelectric properties and photocatalytic CO2 reduction performance of the photocatalysts will be studied. Emphasis will be placed on the influence of the match between the photocatalyst and the photosensitizer on the catalytic activity of the resulted photocatalysts. The relationship between the catalytic activity and the catalyst structure will be analyzed, and the synthesis rule of COFs photocatalyst will be summarized. Finally, the catalytic mechanism of photocatalytic CO2 reduction will be revealed by theoretical calculation. The results will provide a new research direction and reference for the design of high-performance photocatalytic CO2 reduction catalysts.