Micropore environment regulation of zirconium MOFs for instantaneous hydrolysis of an organophosphorus chemical

Summary Protection from nerve agents is an important societal challenge requiring effective strategies for rapid degradation of these toxic chemicals. Here, we report a series of zirconium-based metal-organic frameworks (MOFs)—NU-912 and its derivatives—with a 4,8-connected scu topology. We explore their activity toward degradation of a nerve agent simulant, dimethyl 4-nitrophenyl phosphate (DMNP), to illustrate the virtues of controlling functional group distribution and regulating the environment across the micropore in heterogeneous catalysis. The micropore environments of these MOFs tuned by functional groups (-Br, -CN, -I, and -NH2) have significant influence on catalytic activity. NU-912-I, NU-912-CN, and NU-912-NH2 have half-lives (t1/2) of less than 3 min using only 3 mol % catalyst loading, which places them among the best zirconium (Zr)-MOF-based heterogeneous catalysts for hydrolysis of DMNP.