Lindqvist型钼多酸-杯[4]芳烃配合物的构筑及催化性能研究  

Fabrication and Catalytic Performance of Lindqvist Isopolymolybdate-Resorcin[4]arene-based Complex

作　　者：于明月 高庆平[1] 张倩[1] 王建花 王文政[1] 马天芳[1] 刘津华 Yu Mingyue;Gao Qingping;Zhang Qian;Wang Jianhua;Wang Wenzheng;Ma Tianfang;Liu Jinhua(School of Chemical Engineering,Weifang Vocational College,Weifang,262737;School of Chemistry&Chemical Engineering and Environmental Engineering,Weifang University,Weifang,261061)

机构地区：[1]潍坊职业学院化学工程学院,潍坊262737 [2]潍坊学院化学化工与环境工程学院,潍坊261061

出　　处：《化学通报》2024年第11期1348-1353,共6页Chemistry

基　　金：潍坊市科技发展计划项目(2024GX052,2022GX020,2022GX021);潍坊学院博士科研基金项目(2023BS13);潍坊职业学院博士科研基金项目《高性能多酸基锂离子电池负极材料的制备及电化学性能研究》和潍坊职业学院博士科研基金项目《微驱动器用新型热塑性聚氨酯介电弹性体材料的设计与制备》资助。

摘　　要：开发高效的非均相催化剂用于硫化物的催化氧化是目前催化领域的研究热点。同多钼酸盐作为一类重要的多金属氧簇,具有丰富的催化活性位点,从而展现出优异的氧化还原性能。本研究利用同多钼酸盐与功能化的间苯二酚杯[4]芳烃配体(TMR4A)以及铜离子进行自组装,成功合成了一例Lindqvist型钼多酸-杯[4]芳烃铜(Ⅰ)基配合物,即[Cu_(2)(TMR4A)(CH_(3)CN)_(2)(H_(2)O)_(2)]·[Mo_(6)O_(19)]·CH_(3)CN·3H_(2)O(1-Cu)。1-Cu具有优异的化学稳定性,能稳定存在于pH 0~13的水溶液以及不同有机溶剂(甲醇和二氯甲烷)中。化合物1-Cu不仅能有效催化氧化芥子气模拟物2-氯乙基乙基硫醚(CEES),同时,作为一类活性较高的可循环利用的非均相催化剂,其对噻吩类硫醚底物也呈现较高的催化活性。此外,1-Cu对抗坏血酸(AA)的氧化和溴酸钠(NaBrO_(3))的还原具有双功能电催化性能。Exploring efficient heterogeneous catalysts for catalytic oxidation of sulfides is the hotspot in the field of catalysis.As an important class of polyoxometalate,isopolymolybdates possess abundant catalytic active sites,thus showing excellent redox properties.In this study,a Lindqvist-type isopolymolybdate-resorcin[4]arene-based complex,namely,[Cu_(2)(TMR4A)(CH_(3)CN)_(2)(H_(2)O)_(2)]·[Mo_(6)O_(19)]·CH_(3)CN·3H_(2)O(1-Cu),was synthesized by the selfassembly of isopolymolybdate,functionalized resorcin[4]arene(TMR4A)and copper ions.The complex 1-Cu exhibited excellent chemical stability,and could be stable in water solutions of various pH values(0~13)or different organic solvents(methanol and dichloromethane).Satisfyingly,1-Cu could catalyze the oxidation of mustard gas simulant 2-chloroethyl ethyl thioether(CEES)effectively.Simultaneously,as a class of highly active and recyclable heterogeneous catalyst,1-Cu showed high catalytic activity for thiophene compounds.Moreover,1-Cu exhibited bifunctional electrocatalytic behaviors for the oxidation of ascorbic acid(AA)and the reduction of sodium bromate(NaBrO_(3)).

关 键 词：同多钼酸盐 催化氧化 电催化 

分 类 号：O641.4[理学—物理化学] O643.36[理学—化学]