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 Lin Yang;Zhong Zhang;Chao-Nan Zhang;Xiu-Li Wang

作者机构：College of Chemistry and Materials EngineeringBohai UniversityJinzhou 121013China Professional Technology Innovation Center of Liaoning Province for Conversion Materials of Solar CellBohai UniversityJinzhou 121013China 

出 版 物：《Rare Metals》 (稀有金属（英文版）)

年 卷 期：2024年第43卷第1期

页      面：236-246页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 081705[工学-工业催化] 0817[工学-化学工程与技术] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0703[理学-化学] 0702[理学-物理学] 

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) 

主　　题：Polyoxometalate Metal-organic complex Viologen Oxidation desulfurization Photocatalytic hydrogen production 

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 ***,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) *** 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 *** 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 *** 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 ***,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 ***,the catalytic activities do not decrease evidently after three cycles,revealing the prominent structural stability and recyclability.