Ambidextrous approach in action: Mg(OMe)2-doped hierarchical porous zirconium MOFs for decontaminating toxic chemical agents in nonbuffered systems

[Display omitted] •MOFs with both hierarchically porous structure and basic species are synthesized.•The hierarchical pores and basic species synergistically degrade toxic agents.•Rapid decontamination of DMNP and GD in both aqueous and methanol system are realized.•Rapid decontamination of CEES in aqueous system can also be carried out. Utilizing a ligand-truncation strategy, a hierarchically porous structure was engineered within MOF-808, designated as HP-MOF-808. Furthermore, Mg(OMe)2 doping yielded HP-MOF-808@Mg(OMe)2, materials with both hierarchical porosity and basic character, for decontamination of two types of toxic chemical agents in nonbuffered solutions. In aqueous solution, the HP-808-2 exhibited decontamination rate constants for dimethyl-4-nitrophenyl phosphate (DMNP) and the nerve agent soman (GD) that were 3.13 and 1.98 times higher than MOF-808, respectively. The decontamination half-lives of HP-808-2@Mg(OMe)2 1:2 for DMNP and GD were further reduced by 13.87 and 36.82 times compared to HP-808-2. The material retains its decontamination efficacy for DMNP even after 60-days exposure in air and maintains structural integrity in solvents devoid of labile hydrogen for at least 24 h. In methanol, HP-808-2@Mg(OMe)2 achieved 100% DMNP decontamination in 25 min, outperforming HP-808-2 at 31.8%, marking it as the fastest DMNP decontamination material in methanol. Theoretical simulations confirmed the experimental findings, clearly demonstrating the energy changes during reactions with various nucleophiles and revealing the degradation process and mechanism of DMNP on the active sites of MOFs. Moreover, these materials rapidly degraded 2-chloroethyl ethyl sulfide (CEES) through hydrolysis, dehydrohalogenation, and heterolytic cleavage, demonstrating great potential for dual decontamination of toxic chemical agents in unbuffered systems.