| Designed synthesis and applications of emerging porous materials have been a hot topic in coordination chemistry and materials chemistry,such as metal-organic framework materials(MOFs),covalent-organic framework materials(COFs)and polyoxometalates(POMs)-based compounds constructed from polyacid anions and inorganic clusters.These functional porous materials exhibit a variety of physical and chemical properties derived from their variable structural configurations and features,and constituent moieties.More importantly,it is of great value to design and synthesize different kinds of biomimetic ligands and construct biomimetic metal-organic frameworks with different inorganic metal ions for biomimetic heterogeneous catalysis inspired from the catalytic mechanisms of biological enzymes.In this thesis,we have synthesized two metalloporphyrinic ligands 5,10,15,20-tetrakis(3,5-dicarboxypheny1)porphyrin(H10OCPP)and 5,10,15,20-tetraaminophenyl porphyrin(H2TAPP)as functional building blocks,assembling with different metals and organic ligands for the construction of six porphyrinic MOFs and COFs.Simultaneously,a 2D polyoxometalate framework(CZJ-11)was constructed from sandwich-type POM,[WZn{Cu(H2O)}2(ZnW9O34)2]12-and Gd3+,which underwent a single-crystal-to-single-crystal structural transformation to obtain a 3D porous material CZJ-12.In addition,the above porous materials were characterized by single crystal X-ray diffraction,powder X-ray diffraction,solid-state NMR,FT-IR,UV,thermogravimetry,elemental analysis,SEM,TEM and AAS etc.Moreover,because of the different topological and pore structures,and catalytic centers of these porous compunds,we conducted in-depth study on the biomimetic catalytic activation of molecular oxygen with different influencing factors such as structure,metal nodes and catalytic sites of the biomimetic framewoks.Meanwhile,we also studied their heterogeneous catalytic nature,catalytic mechanisms,size effect,turnover numbers,brilliant catalytic effects were obtained,especially in the fields of olefin epoxidation,selective oxidation of alkylbenzenes and aliphatic alcohols. |
