Hollow Lindqvist-like-Shaped {V₆} Cluster-Based Metal–Organic Framework for the Highly Efficient Detoxification of Mustard Gas Simulant

Abstract

A polyoxovanadate-based nickel-organic framework, [Ni(bib)₂]{V₂O₆}({V₆}-MOF, bib = 1,4-bis(1<i>H</i>-imidazoly-1-yl)benzene), was facilely prepared under gentle hydrothermal conditions and structurally characterized. Single-crystal X-ray diffraction analysis indicates that the {V₆} cluster in the {V₆}-MOF is constructed of two VO₅ tetragonal pyramids and four VO₄ tetrahedrons via the apex sharing of O atoms, presenting a hollow Linqvist-like structure, which is different from these reported hexanuclear vanadium clusters. The {V₆}-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 ¹H NMR. Using {V₆}-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, {V₆}-MOF exhibits high sustainability, and no obvious reductions in conversion and selectivity are observed after five runs.