卟啉MOFs材料的构筑及可见光催化CO2转化性能研究

Exploiting novel efficient visible-light-responsive photocatalytic materials for converting CO2 into valuable fuels, is of great significance to alleviate environmental pollution and energy shortage pressure. This project intends to prepare visible-light-responsive porous porphyrin MOFs using diverse photosensitized porphyrin ligands coordinated with high redox active non-noble metals, and to construct POMs-based porphyrin MOFs by introducing POMs building blocks with excellent catalytic properties. Characterizing the structures of the porphyrin MOFs by various modern techniques, studying the photoelectrochemical properties of the porphyrin MOFs and the adsorption properties of CO2 through UV, fluorescence, electrochemical and gas adsorption methods. The influence of different structures and different reaction conditions on the catalytic performance of visible-light-driven photocatalytic reduction of CO2 of porphyrin MOFs will be analyzed. We will utilize density functional theory to elucidate the intrinsic relationship between different structures and spectra expansion and bandgap control, to reveal the reaction mechanism of photocatalytic reduction of CO2, and to seek for reusable visible-light-responsive porphyrin MOFs photocatalysts for photocatalytic conversion of CO2 with high efficiency and high selectivity. The research results will enrich varieties of porphyrin MOFs and provide new ideas for the preparation of novel photocatalytic materials.

研制新型高效可见光响应的催化材料，进行光催化还原CO2将其转化为有价值的燃料，对缓解环境污染和能源短缺问题具有重要意义。本项目拟利用结构多样的光敏卟啉配体与氧化还原活性高的非贵金属配位，制备可见光响应的多孔卟啉MOFs；引入催化性能优异的POMs建筑块构筑多酸基卟啉MOFs。运用多种现代技术对所制备的卟啉MOFs进行结构表征，通过紫外、荧光、电化学测试及气体吸附等方法研究卟啉MOFs的光电化学性质和对CO2的吸附性能等。分析不同结构、不同反应条件对卟啉MOFs可见光催化还原CO2性能的影响；结合密度泛函理论阐明不同结构与光谱拓展、带隙调控之间的关系，揭示光催化还原CO2的反应机理；获得可重复使用的可见光响应的新型卟啉MOFs光催化剂，实现高效、高选择性光催化转化CO2。该研究结果将丰富卟啉MOFs种类，为制备新型光催化材料提供新思路。

开发新型高效的多孔材料进行CO2的存储和转化，对缓解环境污染和能源短缺问题具有重要的科学意义。本项目选用三苯胺基光敏配体、苯基羧酸及含氮配体与多种金属配位原位自组装构筑了几例MOFs材料，通过使用卟啉类、四苯乙烯类及噻吩基单体制备了一些多孔有机聚合物COFs和CMPs材料。运用多种现代技术对所制备的MOFs、COFs及CMPs材料进行结构表征，通过紫外、荧光、电化学测试及气体吸附等方法研究材料的光电化学性质和对CO2的吸附性能等。分析不同结构、不同反应条件合成的COFs及CMPs材料对CO2吸附性能的影响。制备的光敏Zn-MOF和Cd-MOF可以作为荧光探针，实现对硝基芳香性爆炸物和重金属离子的高效特异性检测；Co-MOF可作为出色的非均相催化剂，通过活化PMS来高效降解甲基橙（MO）染料，在4.5 min内降解率可达98%以上并且具有很好的稳定性。结合密度泛函理论阐明荧光检测机理，结合自由基捕获解释催化降解反应机理。该研究结果丰富了MOFs种类，为制备新型稳定的多孔功能材料提供新思路。