Two pseudo-polymorphic porous POM-pillared MOFs for sulfide-sulfoxide transformation: Efficient synergistic effects of POM precursors, metal sites and microstructures  

作　　者：Yanhong Chen Haiyan An Shenzhen Chang Yanqin Li Tieqi Xu Qingshan Zhu Huiyun Luo Yaohui Huang Yuting Wei 

机构地区：[1]School of Chemical Engineering,Dalian University of Technology,Dalian 116023,China

出　　处：《Chinese Chemical Letters》2023年第7期404-408,共5页中国化学快报（英文版）

基　　金：financially supported by the National Natural Science Foundation of China (Nos. 21371027, 20901013);Natural Science Foundation of Liaoning Province (No. 2015020232);Fundamental Research Funds for the Central Universities (Nos. DUT19LK01, DUT15LN18)。

摘　　要：Developing sustainable and powerful heterogeneous catalytic systems to convert sulfides into high-value sulfoxide products has become a particularly appealing field and an arduous challenge.In this work,two porous polyoxometalate-pillared metal-organic frameworks,formulated as H_(3n)[Cu_(3)(pidc)_(2)(H_(2)O)_(2.5)]_(2)[PW_(12)O_(40)]_n·x H_(2)O (n=1.5,x=6 for 1,n=1,x=12 for 2;and H_(3)pidc=2-(3-pyridinyl)-1H-imidazole-4,5-dicarboxylic acid),were consciously manufacture and employed for heterogeneously catalyzed sulfide-sulfoxide transformation.Structural analysis shows that 1 and 2 exhibit similar porous frameworks with nearly identical two-dimensional metal-organic layers further pillared by tetradentate POM ligands with different coordination modes,which also result in the porosity of 1 being almost twice that of 2.In catalyzing the conversion of methyl phenyl sulfide (MPS) to methyl phenyl sulfoxide (MPSO),1 can convert nearly 100%of MPS into MPSO within 30 min,while 2 achieved the similar results requires 50 min.The higher activity of 1 may be attributed to its larger channel that can provide more active sites and more efficient mass transfer process.Systematic structure-activity analyses and mechanistic studies revealed dual-reaction pathways driven by POM sites and metal sites assisted by the structural microenvironment.

关 键 词：POLYOXOMETALATE Porous frameworks POMOF Heterogeneous catalysis Sulfide oxidation 

分 类 号：TQ247.3[化学工程—有机化工]