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

作者机构：School of Chemical EngineeringDalian University of TechnologyDalian 116023China 

出 版 物：《Chinese Chemical Letters》 (中国化学快报（英文版）)

年 卷 期：2023年第34卷第7期

页      面：404-408页

核心收录：

学科分类：081702[工学-化学工艺] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

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)。 

主　　题：Polyoxometalate Porous frameworks POMOF Heterogeneous catalysis Sulfide oxidation 

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.