V=O Functionalized {Tm2}-Organic Framework Designed by Postsynthesis Modification for Catalytic Chemical Fixation of CO2 and Oxidation of Mustard Gas

In terms of recently documented references, the introduction of V.O units into porous MOF/COF frameworks can greatly improve their original performance and expand their application prospects due to a change in their electronegativity. In this work, by a cation-exchange strategy, a consummate combination of separate 4f [Tm2(CO2)8] SBUs and 3d [VIVO(H2O)2] units generated the functionalized porous metal-organic framework {(Me2NH2) 2[VO( H2O)][Tm2(BDCP)2]center dot 3DMF center dot 3H2O} n (NUC-11), in which [Tm2(CO2)8] SBUs constitute the fundamental 3D host framework of {[Tm2](BDCP)2} n along with [VIVO(H2O)2] units being further docked on the inner wall of channels by covalent bonds. Significantly, NUC-11 represents the first example of V.O modified porous MOFs, in which uncoordinated carboxylic groups (-CO2H) further grasp the functional [VIVO(H2O)2] units on the initial basic skeleton along with the formation of covalent bonds as fixed ropes. Furthermore, activated samples of NUC-11 displayed a good catalytic performance for the chemical synthesis of carbonates from related epoxides and CO2 with high conversion rate. Moreover, by employing NUC-11 as a catalyst, a simulator of mustard gas, 2-chloroethyl ethyl sulfide, could be quickly and efficiently oxidized into low-toxicity products of oxidized sulfoxide (CEESO). Thus, this study offers a brand new view for the design and synthesis of functional-units-modified porous MOFs, which could be potentially applied as an excellent candidate in the growing field of efficient catalysis.