Li Ji-Kun, Dong Jing, Wei Chuan-Ping, Yang Song, Chi Ying-Nan, Xu Yan-Qing, Hu Chang-Wen
Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic, School of Chemistry and Chemical Engineering, Beijing Institute of Technology , Beijing 100081, P.R. China.
College of Chemistry and Chemical Engineering, Taishan University , Tai'an 271021, Shandong, P.R. China.
Inorg Chem. 2017 May 15;56(10):5748-5756. doi: 10.1021/acs.inorgchem.7b00366. Epub 2017 Apr 21.
Six alkoxohexavanadate-based Cu- or Co-POVs [Cu(dpa)(acac)(HO)][VO(OMe)] (1), [Cu(phen)(acac)(MeOH)][VO(OMe)] (2), [Co(dpa)(acac)][VO(OMe)]·2MeOH (3), [Co(phen)(acac)][VO(OMe)] (4), [Cu(dpa)(acac)][VVO(OMe)] (5), and [Cu(dpa)(acac)(MeOH)][VVO(OMe)] (6) (POV = polyoxovanadate; dpa = 2,2'-dipyridine amine; phen = 1,10-phenanthroline; acac = acetylacetone anion) have been synthesized by controlling the reaction conditions and characterized by single-crystal X-ray diffraction and powder X-ray diffraction analyses, FT-IR spectroscopy, element analyses, and X-ray photoelectron spectroscopy. In compounds 1-4 and 6, Cu or Co complexes and alkoxohexavanadate anions are assembled through electrostatic interactions. Differently, in compound 5, seven-methoxo-substituted Lindqvist-type [VO(OMe)] are bridged to Cu complex via terminal O atoms by coordination bonds. All compounds 1-6 exhibit excellent heterogeneous catalytic performance in oxidative desulfurization and CEES ((2-chloroethyl) ethyl sulfide, a sulfur mustard simulant) abatement with HO as oxidant. Among them, the catalytic activity of 6 [conv. of DBT (dibenzothiophene) up to 100% in 6 h; conv. of CEES reached 100% and selectivity of CEESO ((2-chloroethyl) ethyl sulfoxide) up to 85% after 4 h] outperforms others and can be reused without losing its activity.
通过控制反应条件合成了六种基于烷氧基六钒酸盐的铜或钴多钒酸盐[Cu(dpa)(acac)(HO)][VO(OMe)] (1)、[Cu(phen)(acac)(MeOH)][VO(OMe)] (2)、[Co(dpa)(acac)][VO(OMe)]·2MeOH (3)、[Co(phen)(acac)][VO(OMe)] (4)、[Cu(dpa)(acac)][VVO(OMe)] (5)和[Cu(dpa)(acac)(MeOH)][VVO(OMe)] (6)（POV = 多钒酸盐；dpa = 2,2'-联吡啶胺；phen = 1,10-菲咯啉；acac = 乙酰丙酮阴离子），并通过单晶X射线衍射和粉末X射线衍射分析、傅里叶变换红外光谱、元素分析和X射线光电子能谱对其进行了表征。在化合物1 - 4和6中，铜或钴配合物与烷氧基六钒酸根阴离子通过静电相互作用组装在一起。不同的是，在化合物5中，七甲氧基取代的Lindqvist型[VO(OMe)]通过端基氧原子与铜配合物通过配位键相连。所有化合物1 - 6在以HO作为氧化剂的氧化脱硫和消除CEES（(2-氯乙基)乙基硫醚，一种硫芥模拟物）方面均表现出优异的多相催化性能。其中，6的催化活性（6小时内二苯并噻吩（DBT）的转化率高达100%；4小时后CEES的转化率达到100%，CEESO（(2-氯乙基)乙基亚砜）的选择性高达85%）优于其他化合物，并且可以重复使用而不丧失其活性。
