Construction And Catalytic Carbon Dioxide Conversion Of Metal Cluster Base Metal-Organic Frameworks

Carbon dioxide?CO₂?is the most common green-house gas in human life.With the development of industry,the raising carbon dioxide emission has caused a series of environmental problems,such as global warming,sea-level rise,the increase of diseases and insect pests.However,CO₂ is also an important C1 resource in chemical industries.It is a crucial task to convert CO₂ into economically value-added chemical industrial products under mild conditions.Metal-organic framework?MOFs?is a novel porous crystalline material.It has the characteristics of easy separation,recovery and reuse of heterogeneous catalysts,high selectivity and adjustable of homogeneous catalysts,and is an excellent heterogeneous catalyst.MOFs has many properties such as porous,large specific surface area and polymetallic sites,so it has been widely used in chemical and chemical fields.Based on this idea,a new type of MOFs material was prepared in this paper,which realized efficient and selective catalytic conversion of carbon dioxide.?1?We designed and synthesized a new heterogeneous porous silver-catalysts,with in-situ formed Ag-S rods as connecting nodes and thiosemicarbazide-functionalized linear ligands,used in both?-and?-catalytic transformation.Strong Ag-S bonds bypassed the loss of noble silver elements and inhibited the formation of non-porous silver particles which always led to decrease of yields in homogenous reactions.Furthermore,various derivates of propargylamines and phenylacetylenes were applicated as both?and?-active substrates with moderate to good yields.?2?Through solvothermal methods,Fe₂M-TATAB?M=Cu,Co,Zn,Fe,Mn,Ni?MOFs by incorporating H₃TATAB moiety with Fe₂M??₃-O??CH₃COO?₆ has been synthesized with a quadrilateral channel of 19.8 x 15.2?² along a axis.Fe₂M-TATAB?M=Cu,Co,Zn,Fe,Mn,Ni?MOFs containing potential lewis acid sites has been employed to catalyze the cycloaddition of epoxides with carbon dioxide with high efficiency and selectivity.Influencing factors of the catalytic process such as temperature,pressure,time and co-catalyst were studied systematically.