Tian Hong-Rui, Zhang Zhong, Dang Tian-Yi, Liu Shu-Mei, Lu Ying, Liu Shu-Xia
Key Laboratory of Polyoxometalate Science of the Ministry of Education, College of Chemistry, Northeast Normal University, Changchun, Jilin 130024, P. R. China.
Inorg Chem. 2021 Jan 18;60(2):840-845. doi: 10.1021/acs.inorgchem.0c02890. Epub 2021 Jan 6.
A polyoxovanadate-based nickel-organic framework, [Ni(bib)]{VO}({V}-MOF, bib = 1,4-bis(1-imidazoly-1-yl)benzene), was facilely prepared under gentle hydrothermal conditions and structurally characterized. Single-crystal X-ray diffraction analysis indicates that the {V} cluster in the {V}-MOF is constructed of two VO tetragonal pyramids and four VO tetrahedrons via the apex sharing of O atoms, presenting a hollow Linqvist-like structure, which is different from these reported hexanuclear vanadium clusters. The {V}-MOF not only expands the structure of polyoxovanadates (POVs) but also catalyzes the rapid detoxification of mustard gas simulant (2-chloroethyl ethyl sulfide, CEES) at 25 °C. The catalytic results were determined by means of GC, GC-MS, and H NMR. Using {V}-MOF as a heterogeneous catalyst, CEES underwent catalyzed oxidation to only nontoxic product 2-chloroethyl ethyl sulfoxide (CEESO) within 40 min, and the conversion and selectivity were almost 100%. In addition, {V}-MOF exhibits high sustainability, and no obvious reductions in conversion and selectivity are observed after five runs.
一种基于多金属氧钒酸盐的镍有机框架化合物[Ni(bib)]{VO}（{V}-MOF，bib = 1,4-双(1-咪唑基-1-基)苯），在温和的水热条件下简便合成并进行了结构表征。单晶X射线衍射分析表明，{V}-MOF中的{V}簇由两个VO四方锥和四个VO四面体通过O原子的顶点共享构成，呈现出一种类似林奎斯特结构的中空结构，这与已报道的六核钒簇不同。{V}-MOF不仅扩展了多金属氧钒酸盐（POV）的结构，还能在25℃下催化芥子气模拟物（2-氯乙基乙基硫醚，CEES）的快速解毒。催化结果通过气相色谱（GC）、气相色谱-质谱联用（GC-MS）和核磁共振氢谱（H NMR）测定。以{V}-MOF作为多相催化剂，CEES在40分钟内催化氧化仅生成无毒产物2-氯乙基乙基亚砜（CEESO），转化率和选择性几乎均为100%。此外，{V}-MOF表现出高可持续性，五次循环后转化率和选择性没有明显降低。
