Zirconium-based metal-organic frameworks (Zr-MOFs) are highly promising for the catalytic degradation of toxic organophosphate nerve agents. However, their practical application in personal protective equipment is limited because they require external volatile alkaline buffers such as N-2-aminoethylmorpholine (NEM) or basic amines to regenerate active sites during hydrolysis. To overcome this limitation, we mimic phosphotriesterase’s active site and residues by performing post-synthetic modification on two-dimensional Zr-BTB nanosheets and MOF-808 nanoparticles. The process involves sequential surface functionalization with hydrophilic ethylenediaminetetraacetic acid (EDTA), chlorination, and grafting of NEM, yielding multifunctional catalysts Zr-BTB-EDTA-NEM and MOF-808-EDTA-NEM. These composites simultaneously provide high active-site accessibility, strong water vapor adsorption, and an intrinsic alkaline buffer environment, enabling self-buffering catalytic hydrolysis under humid conditions. Notably, Zr-BTB-EDTA-NEM achieves 92% conversion of the nerve agent simulant dimethyl 4-nitrophenyl phosphate (DMNP) under a relative humidity (RH) of 99%. This work demonstrates a single-material platform that efficiently degrades organophosphates via solid-phase catalysis under realistic humid conditions, offering new insights for next-generation protective materials.

Spatial separation of oxidation/reduction cocatalyst is an effective means to improve the efficiency of charge separation in photocatalytic reaction systems. Herein, a yolk–shell Pd@NH₂-UiO-66@Cu₂O heterojunction was designed and synthesized by integration of electron collector Pd and hole collector Cu₂O inside and outside of a photoactive metal-organic framework (MOF) NH₂-UiO-66, respectively. The obtained Pd@NH₂-UiO-66@Cu₂O heterojunction effectively inhibits the electron and hole recombination through the photo-induced electrons and holes flow inward and outward of the composite, and promotes the reduction and oxidation abilities for the oxidative coupling of benzylamine to imines. Compared with Pd/NH₂-UiO-66@Cu₂O, Pd@NH₂-UiO-66, and Pd/NH₂-UiO-66, Pd@NH₂-UiO-66@Cu₂O exhibits the highest photocatalytic activity. More importantly, Pd@NH₂-UiO-66@Cu₂O shows a conversion rate of benzylamine up to 99% either by oxidation under aerobic conditions or by strong adsorption of H atom (H_ads) under anaerobic conditions. In addition, the catalyst shows good stability and can be recycled at least ten times. This work provides useful guidance on construction of MOFs-based composites with spatially separated photoinduced charge carriers to realize efficient oxidation coupling of benzylamine in both aerobic and anaerobic conditions.