针对CO2光化学还原面临的科学问题，本项目拟通过自组装的方法，将具有良好氧化还原和CO2活化功能的金属有机大环体系为主体分子，通过主客体化学联结染料光敏剂，构建具有光化学还原CO2功能的新型超分子体系。探索组装过程中催化和还原活性中心的性能保持及作用位点预留等控制机制和影响因素，实现超分子体系的组装与功能可控；考察其空腔大小、构型和作用位点布局对光敏剂分子的识别与作用机制，在保持各功能的基础上实现新型主客体化合物的组装控制，在空间和结构上匹配和关联具有光催化和CO2还原功能单元；调配和优化主客体间电子结构和激发态能级，通过对光诱导电子转移途径的控制和光化学反应与催化转化反应间的动力学匹配，实现温和条件下CO2光催化还原；耦合合适的光氧化过程，保证光催化CO2还原高效率同时，优化氧化的过程与机制，形成完整的模拟体系，在不需要电子牺牲剂和质子源的基础上，实现CO2的固定、转化和资源化。

Carbon dioxide is a significant contributor to global climate change but also a potentially powerful C1 building block for fine and commodity chemicals. The chemical fixation and conversion of CO2 are of special interest from the viewpoint of environmental protection and carbon recycling. In this project, by using the metal-organic complexs with satisfactory redox activity and CO2 activation function as the molecular host, new supramolecular systems with function of photochemical reduction of CO2 was created by encapsulation the photosensitizers within the pocket of the metal-organic architectures. To keep the reserve functions of each part, the size, configuration and layout of the action sites of metal-organic architecture are well modified to matching the requirement of photosensitizer recognition. The pathway of the photoinduced electron transfer is well controlled by optimizing the electronic structure and excited energy level between host and guest. And high efficient supramolecular systems are achieved by further matching functions of photocatalysis and CO2 reduction directly. With coupling the high efficient photocatalytic CO2 reduction with a well-established oxidative reaction, new mimicking systems are created to target the chemical fixation and conversion of CO2 in mild condition without any electronic agent and proton source.