Porphyrin-Moiety-Functionalized Metal-Organic Layers Exhibiting Catalytic Capabilities for Detoxifying Nerve Agent and Blister Agent Simulants

The development of very efficient bifunctional catalysts for the simultaneous detoxification of two kinds of the deadliest chemical warfare agents (CWAs), nerve agent and blister agent, is highly desirable. In this study, two porphyrin-based ligands [tetrakis(4-carboxyphenyl) porphyrin (TCPP) and protoporphyrin IX (PPIX)] are introduced into (MOLs), composed of six-connected Zr-6 nodes and the tritopic carboxylate ligand BTB, by a solvent-assisted ligand incorporation method. The loads of TCPP and PPIX are 6.4 and 10.9 wt %, respectively. The detoxification of simulants of the nerve agent and the blister agent was conducted to investigate the catalytic activity of porphyrin-moiety-functionalized MOLs. The reaction half-life of optimal TCPP-functionalized MOL catalyzing the hydrolysis of a nerve agent simulant is only 2.8 min, meanwhile, the half-life of the selective catalytic oxidation of a blister agent simulant is only 1.2 min under LED illumination. More importantly, such a degradation half-life is only about 4 min under natural sunlight (similar to 60 mW/cm(2)). To our knowledge, TCPP-functionalized MOL is by far the most efficient catalyst for blister agent simulant degradation under solar light. Therefore, 2D ultrathin MOLs on demand appear to be a promising and efficient material platform for the development of bifunctional catalysts for CWA protection.

Automated summary

This study aims to develop highly efficient bifunctional catalysts for the simultaneous detoxification of nerve agent and blister agent, two of the deadliest chemical warfare agents. By introducing two porphyrin-based ligands (TCPP and PPIX) into two-dimensional ultrathin metal-organic framework materials (MOLs), the catalytic activity of the MOLs for nerve agent and blister agent simulants was investigated. The results showed that TCPP-functionalized MOL exhibited the highest catalytic activity for the degradation of blister agent simulant under solar light.