| The development and full utilization of natural clean energy has attracted great attention.Among them,sunlight is considered to be one of the best clean energy sources.Due to the advantages of sustainability and environmental friendliness,photocatalytic reduction of CO2 and photocatalytic conversion of organic matter have become the focus of research in the field of photocatalysis.Among the different types of photocatalysts that have been reported,MOFs materials have shown extremely important research value in photocatalysis due to their rich diversity of structures,modifiability of pores,and adjustability of functions.Based on this,this paper focuses on the photosensitizing complexes to study the structural design and photocatalytic performance of ruthenium-based MOFs materials.Three ruthenium photosensitizing carboxylic acid ligands(H3LRu,H3L2Ru and H6L3Ru)were designed and synthesized,and then four photosensitizing MOFs materials(H3LRu-Co MOF,H3LRu-NiMOF,H3LRu-Zn MOF and H3LRu-ZrMOF)were obtained by coordination self-assembly.According to the structural characteristics of photosensitizing MOFs,the photocatalytic reduction of CO2 and photocatalytic conversion of organic matter were investigated.The thesis is divided into six chapters:Chapter 1:The structural characteristics,synthetic strategies and corresponding properties of photosensitizing MOFs are briefly introduced.The application of photosensitizing MOFs in the field of photocatalysis was mainly investigated.Chapter 2:A photosensitizing carboxylic acid ligand H3LRu was designed and synthesized based on the photosensitizer[Ru（Phen）3]（PF6）.Three photosensitizing MOFs were obtained by self-assembly with Co（II）,Ni（II）,Zn（II）and Zr（IV）ions,respectively,and single crystal structures were obtained.Two photosensitizing ligands H3L2Ru and H6L3Ru were designed and synthesized by extending the ligand size and increasing the coordination sites based on the ligand H3LRu.The synthesized ligands and photosensitizing MOFs were characterized.Chapter 3:Inspired by the photosensitizing H3LRu-Co MOF have strong visible light absorption,relatively negative LUMO energy level,excellent photogenerated charge-separation efficiency and well CO2 adsorption capacity,investigated the application of H3LRu-Co MOF in the photocatalytic CO2 reduction.The reaction active sites in the process of photocatalytic reduction of CO2 were determined,and the reaction mechanism was proved by the synthesis of new photosensitive H3LMeRu-Co MOF.Chapter 4:In order to expand the photocatalytic application range of photosensitizing MOFs,and molecular oxygen can be activated into reactive oxygen species under visible light irradiation in the existence of H3LRu-NiMOF.The photocatalytic performance of H3LRu-NiMOF for photocatalytic oxidation C-N coupling reaction was investigated.The results showed that H3LRu-NiMOF can obtain the corresponding catalytic product of 4-methylaniline in nearly 100%yield within 1h.It is worth noting that H3LRu-NiMOF can also be applied to the gram-scale reaction of photocatalytic oxidation of 4-methylaniline C-N coupling reaction.Chapter 5:The photocatalytic performance of H3LRu-NiMOF was further expanded.The results showed that H3LRu-NiMOF exhibited high photocatalytic activity and wide substrate universality.In addition,after expanding the reaction,H3LRu-NiMOF can still photocatalytic reaction of bis-N-substituted maleimide and N,N-dimethylaniline.Chapter 6:H3LRu-ZrMOF was constructed by using high valence metal ions Zr4+and H3LRu,which is different from the photosensitizing MOFs constructed by other+2valence metal ions.In view of the unique three-dimensional structure of H3LRu-ZrMOF and the rich Zr6-oxygen cluster SBU in the framework,the photocatalytic performance of H3LRu-ZrMOF for the C-C oxidative coupling reaction of maleimide and N,N-dimethylaniline was investigated.Chapter 7:The work of this paper is systematically summarized and prospected. |
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