By taking the functional adva ntages of both pyrazolate and carboxylate ligands,a unique dual-functional pyrazolate-carboxylate ligand acid,4-(3,6-di(pyrazol-4-yl)-9-carbazol-9-yl)benzoic acid(H3PCBA) was designed and...By taking the functional adva ntages of both pyrazolate and carboxylate ligands,a unique dual-functional pyrazolate-carboxylate ligand acid,4-(3,6-di(pyrazol-4-yl)-9-carbazol-9-yl)benzoic acid(H3PCBA) was designed and synthesized.Using it,a new Co(Ⅱ)-based metal-organic framework(MOF),Co_(3)(PCBA)_(2)(H_(2)O)_(2)(BUT-75) has been constructed.It revealed a(3,6)-connected net based on the 6-connected linear trinuclear metal node,and showed good chemical stability in a wide pH range from 3 to 12 at room temperature,as well as in boiling water.Due to the presence of rich exposed Co(Ⅱ) sites in pores,BUT-75 presented high selective CO_(2) adsorption capacity over N2 at 298 K.Simultaneously,it demonstrated fine catalytic performance for the cycloaddition of CO_(2) with epoxides into cyclic carbonates under ambient conditions.This work has not only enriched the MOF community through integrating diverse functio nalities into one ligand but also contributed a versatile platform for CO_(2) fixation,thereby pushing MOF chemistry forward by stability enhancement and application expansion.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos.21771012,21601008,51621003)the Science & Technology Project of Beijing Municipal Education Committee (No.KZ201810005004)。
文摘By taking the functional adva ntages of both pyrazolate and carboxylate ligands,a unique dual-functional pyrazolate-carboxylate ligand acid,4-(3,6-di(pyrazol-4-yl)-9-carbazol-9-yl)benzoic acid(H3PCBA) was designed and synthesized.Using it,a new Co(Ⅱ)-based metal-organic framework(MOF),Co_(3)(PCBA)_(2)(H_(2)O)_(2)(BUT-75) has been constructed.It revealed a(3,6)-connected net based on the 6-connected linear trinuclear metal node,and showed good chemical stability in a wide pH range from 3 to 12 at room temperature,as well as in boiling water.Due to the presence of rich exposed Co(Ⅱ) sites in pores,BUT-75 presented high selective CO_(2) adsorption capacity over N2 at 298 K.Simultaneously,it demonstrated fine catalytic performance for the cycloaddition of CO_(2) with epoxides into cyclic carbonates under ambient conditions.This work has not only enriched the MOF community through integrating diverse functio nalities into one ligand but also contributed a versatile platform for CO_(2) fixation,thereby pushing MOF chemistry forward by stability enhancement and application expansion.