Construction of imidazole@defective hierarchical porous UiO-66 and fibrous composites for rapid and nonbuffered catalytic hydrolysis of organophosphorus nerve agents

Jun Dai; Dazhao Wang; Juan Yang; Ran Tian; Qi Wang; Yao Li

doi:10.1016/j.jcis.2023.08.163

Construction of imidazole@defective hierarchical porous UiO-66 and fibrous composites for rapid and nonbuffered catalytic hydrolysis of organophosphorus nerve agents

J Colloid Interface Sci. 2023 Dec 15;652(Pt B):1156-1169. doi: 10.1016/j.jcis.2023.08.163. Epub 2023 Aug 26.

Authors

Jun Dai¹, Dazhao Wang¹, Juan Yang², Ran Tian¹, Qi Wang³, Yao Li⁴

Affiliations

¹ School of Safety Science and Engineering, Henan Polytechnic University, Jiaozuo 454003, China.
² School of Safety Science and Engineering, Henan Polytechnic University, Jiaozuo 454003, China; Institute of Chemical Safety, Henan Polytechnic University, Jiaozuo 454003, China. Electronic address: yangjuan@hpu.edu.cn.
³ School of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou 310018, China.
⁴ School of Safety Science and Engineering, Henan Polytechnic University, Jiaozuo 454003, China; Institute of Chemical Safety, Henan Polytechnic University, Jiaozuo 454003, China.

PMID: 37657216
DOI: 10.1016/j.jcis.2023.08.163

Abstract

Hydrolytic destruction of toxic organophosphorus nerve agents by metal-organic framework (MOF) catalysts is commonly reliant on bulk water and volatile liquid base, preventing real-world implementation. Poor accessibility to MOF-based active sites in heterogeneous catalysis is also a crucial factor since reactants diffusion is limited by inherently small micropores. To overcome these practical limitations, a ligand-selective pyrolysis strategy was used to construct unsaturated Zr defects and additional mesopores in UiO-66(Zr). Owing to synergistic effect of Zr defects and hierarchical pores, hydrolysis rate constant (k) of nerve agent simulant DMNP (dimethyl 4-nitrophenyl phosphate) on optimal DHP-UiO-30% (defective hierarchical porous UiO-66) is 3.2 times higher than counterpart UiO-30% in N-ethylmorpholine buffer. Encapsulating imidazole (Im) into DHP-UiO-30% affords Im@DHP-UiO, mimicking phosphotriesterase. Im-72@DHP-UiO exhibits rapid DMNP detoxification with 99% conversion in 12 min and initial half-life (t_1/2) of 1.8 min in nonbuffered water. As the first example of 'three-in-one' detoxifier, Im@DHP-UiO is further integrated onto nonwoven fabric to construct Im@DHP/Fiber, achieving solid-phase detoxification at ambient humidity with t_1/2 of 19.6 min and final conversion of 91%. This is comparable to many powdered catalysts in aqueous solution buffered by volatile bases. This unified strategy is critical and viable to efficiently hydrolyze nerve agents in practical settings.

Keywords: Catalytic hydrolysis; Hierarchical pores; Nerve agents; Nonbuffered water; Solid-phase detoxification; Zr-MOFs.