Porphyrinic Silver Cluster Assembled Material for Simultaneous Capture and Photocatalysis of Mustard-Gas Simulant

Abstract

Silver cluster-assembled materials (SCAMs), by virtue of their tunable structure, accessible surface area and excellent stability, hold great promise as highly efficient catalysts. Herein, we report a new SCAM [Ag₁₂(S^<i>t</i>Bu)₆(CF₃COO)₃(TPyP)]_<i>n</i> (denoted as Ag₁₂TPyP) composed of a Ag₁₂ chalcogenolate cluster core stabilized by porphyrinic ligands. Ag₁₂TPyP showed superior sulfur mustard simulant (2-chloroethyl ethyl sulfide, CEES) degradation efficiency and achieved a half lifetime (<i>t</i>_1/2) of 1.5 min with 100% selectivity. The experimental results demonstrated that synergistic effects between the silver cluster and photosensitizer ligand promote the efficiency of the generation of singlet oxygen (¹O₂), which accelerates the decontamination rate. Additionally, benefiting from strong affinity between the silver cluster and CEES, Ag₁₂TPyP exhibits a CEES uptake of 74.2 mg g^-1. This work demonstrates that SCAMs offer a new route to the rational design of novel materials for the detoxification of mustard gas.