A bifunctional POM-based Cu-viologen complex with mixed octamolybdate clusters for rapid oxidation desulfurization and effective photogeneration of hydrogen  

作　　者：Lin Yang Zhong Zhang Chao-Nan Zhang Xiu-Li Wang 

机构地区：[1]College of Chemistry and Materials Engineering,Bohai University,Jinzhou 121013,China [2]Professional Technology Innovation Center of Liaoning Province for Conversion Materials of Solar Cell,Bohai University,Jinzhou 121013,China

出　　处：《Rare Metals》2024年第1期236-246,共11页稀有金属（英文版）

基　　金：financially supported by the National Natural Science Foundation of China (Nos.22271021,21901018 and 21971024);the Natural Science Foundation of Liaoning Province (No.2022-MS-373);Liaoning Revitalization Talents Program (No.XLYC1902011)。

摘　　要：The design and synthesis of catalysts for the oxidation desulfurization and production of hydrogen are extremely important for solving environmental pollution and energy shortage.Herein,a novel bifunctional [α-Mo_(8)O_(26)]^(4-)/[β-Mo_(8)O_(26)]^(4-)-based Cu-viologen complex H_(4)[Cu_(2)~ⅠCl_(2)(Hbcbpy)_(4)] [α-Mo_(8)O_(26)] [β-Mo8O_(26)]·H_(2)O(BHU-2,Hbcbpy=1-(4-carboxybenzyl)-4,4'-bipyridinium) was synthesized and characterized by single-crystal X-ray diffraction(XRD),infrared radiation spectra,powder X-ray diffraction(PXRD) and X-ray photoelectron spectroscopy(XPS) spectra.The structural characteristic of BHU-2 is the presence of two types of octamolybdate clusters [α-Mo_(8)O_(26)]^(4-)/[β-Mo_(8)O_(26)]^(4-)and a new binuclear Cu~Ⅰ-Hbcbpy complex linked by Cl-bridges[Cu_(2)ⅠCl_(2)(Hbcbpy)_(4)]^(4+).BHU-2 as a heterogeneous catalyst exhibits excellent activities to the oxidation desulfurization and photocatalytic hydrogen production.At room temperature,BHU-2 can catalyze 96% conversion of methyl phenyl sulfide with 98% selectivity,and the process obeys the pseudo-first-order reaction kinetic with the half-life of9.6 min.The notorious 2-chloroethyl ethyl sulfide can achieve 99% conversion with 98% selectivity within only1 min at the presence of BHU-2,and the turnover frequency(TOF) is up to 7400 h^(-1).BHU-2 also exhibits high catalytic activity for the oxidation of other aromatic and aliphatic thioethers within short time at room temperature.Furthermore,BHU-2 shows a high catalytic activity for visible-light-driven hydrogen evolution with an H_(2) evolution rate of 1677.85 μmol·g^(-1)·h^(-1) within 10 h.Moreover,the catalytic activities do not decrease evidently after three cycles,revealing the prominent structural stability and recyclability.

关 键 词：POLYOXOMETALATE Metal-organic complex VIOLOGEN Oxidation desulfurization Photocatalytic hydrogen production 

分 类 号：O641.4[理学—物理化学] O643.36[理学—化学]