Polyoxovanadate-based metal-organic frameworks consisted of open vanadium sites for selective catalytic oxidation of sulfides  

作　　者：Jin-Lin Zhang Qi-Xin Zhao Meng-Yuan Cheng Wei-Min Xuan Yan Liu 

机构地区：[1]College of Chemistry and Chemical Engineering and State Key Laboratory for Modification of Chemical Fibers and Polymer Materials,Donghua University,Shanghai201620,China [2]School of Chemistry and Chemical Engineering,Frontiers Science Center for Transformative Molecules and State Key Laboratory of Metal Matrix Composites,Shanghai Jiao Tong University,Shanghai 200240,China

出　　处：《Tungsten》2023年第2期261-269,共9页钨科技（英文）

基　　金：supported by the National Natural Science Foundation of China(Nos.92161111,21901037,21901038);Shanghai Pujiang Program(No.19PJ1400200);the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning;International Cooperation Fund of Science and Technology Commission of Shanghai Municipality(No.21130750100)。

摘　　要：Three novel polyoxovanadate-based metal-organic frameworks(POV-MOFs),[Co_(2)(1,4-dtzb)_(3)]{V_(4)O_(12)}(V-Co-MOF_(1),1,4-dtzb=1,4-di(4H-1,2,4-triazol-4-yl)benzene],[Co_(3)(1,3-dtzb)_(2)][{V_(6)O_(18)}(V-Co-MOF_(2),1,3-dtzb=1,3-di(4H-1,2,4-triazol-4-yl)benzene],[Co_(4)(4,4’-bdtzb)_(2)]{V_(8)O_(24)}(V-Co-MOF_(3),4,4’-bdtzb=4,4’-(1,1’-biphenyl)-4,4’-diylbis(4H-1,2,4-triazole)benzene]were facilely synthesized and structurally characterized.Single-crystal X-ray diffraction analysis indicates that all the POV-MOFs possess open V sites lined on POV clusters of{V_(4)O_(12)}/{V_(6)O_(18)}/{V_(8)O_(24)}that uniformly distribute on the robust three-dimensional frameworks.This unique structural feature allows them to show high performance for sulfidesulfoxide transformation when performing the reaction in MeOH at 50℃ for 45 min using H_(2)O_(2) as green oxidant.Notably,V-Co-MOF1 exhibited the highest catalytic efficiency,with a conversion>99% and selectivity up to 97% for a series of sulfide substrates.Control reaction demonstrated the catalytically active centers are the open V sites while the MOF skeleton constructed from Co^(2+)and ligands also contributes to enhance the conversion and selectivity via synergistic effect.Furthermore,V-Co-MOF1 can be used as a stable heterogeneous catalyst,and both the structural integrity and catalytic performance were well reserved after five cycles,demonstrating their great potential for advanced catalytic oxidation.

关 键 词：POLYOXOVANADATES Polyoxometalate-based metal-organic framework Sulfoxide Catalytic oxidation 

分 类 号：O623.83[理学—有机化学] O641.4[理学—化学] O643.36