Four unprecedented V_(14)clusters as highly efficient heterogeneous catalyst for CO_(2)fixation with epoxides and oxidation of sulfides

作     者：Ji-Lei Wang Jia-Peng Cao Yin-Hua Zhu Qin Wang Ning-Fang Li Xin-Rong Fan Hua Mei Yan Xu 

作者机构：State Key Laboratory of Materials-Oriented Chemical EngineeringCollege of Chemical EngineeringNanjing Tech UniversityNanjing210009China State Key Laboratory of Coordination ChemistryCoordination Chemistry InstituteNanjing UniversityNanjing 210093China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2023年第66卷第1期

页      面：107-116页

核心收录：

学科分类：081705[工学-工业催化] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：supported by the Natural Science Foundation of Jiangsu(BK20191359) the National Natural Science Foundation of China(92161109) the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX22_1343) the Social Science Foundation of Jiangsu(19TQB002) 

主　　题：V_(14)clusters heterogeneous catalyst CO_(2)fixation oxidation of sulfides 

摘      要：Chemical fixation of carbon dioxide(CO_(2))is an energy-saving method for alleviating the greenhouse gas emissions,whereas it persists a challenge posed by the demand for efficient ***,four unprecedented examples of tetradecanuclear vanadium clusters,namely,[(C_(2)H_(8)N_(2))6(CH_(3)O)8(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)](V_(14)-1),[(C_(3)H_(10)N_(2))_(6)(CH_(3)O)_(8)(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)](V14^(-2)),[(C_(6)H_(14)N_(2))6(CH_(3)O)8(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)]·5H_(2)O(V14^(-3))and[(C_(4)H_(12)N_(2)O)_(4)(C_(4)H_(11)N_(2)O)_(2)(CH_(3)O)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(28)]·6H_(2)O(V_(14)-4),have been triumphantly designed and constructed under solvothermal *** them,compounds V_(14)-1–4 are the first cases of tetradecanuclear vanadium clusters without the introduction of inorganic acid radical *** main units[V_(10)^(Ⅳ)V_(4)ⅤO_(26)]8+and[V10ⅣV4ⅤO28]4+represent brand-new configurations of tetradecanuclear vanadium *** the fact that the presence of V^(Ⅳ)/V^(Ⅴ)can potentially facilitate electron transfer and consequently expedite catalytic reactions,we explored the catalytic activities of these ***,V_(14)-1 was further used as a heterogeneous catalyst in the CO_(2)fixation into cyclic carbonates under milder conditions(60℃,0.5 MPa)and exhibited higher catalytic ***,the experimental results indicated that V_(14)-1 could efficiently catalyze the sulfoxidation,which could fully convert most sulfides within 40 min at room ***,as a stable heterogeneous catalyst employed in CO_(2)fixation with epoxides and oxidation of sulfides,V_(14)-1 could be consecutively used multiple cycles without losing its catalytic activity.