Metal cluster-regulated switching of reactive oxygen species within ionic porphyrin cages for efficient chemical warfare agent detoxification

Metal cluster (MC) sites confined within discrete porous molecular cages have been extensively utilized in heterogeneous catalysis. However, studies on how encapsulated MCs influence the catalytic performance of their containers are scarce. Herein, by leveraging an eco-friendly alcohol reduction method, we fabricated an organic cage-encapsulated MC complex, abbreviated as Au⊂TPPCage·Cl. Notably, the charge transfer between the Au clusters and the porphyrin cage skeleton significantly modifies the electronic structure of the porphyrin units, thereby enhancing cages’ photophysical properties. This results in a distinct O₂ activation ability, switching from ¹O₂ to O₂^•−. Consequently, this hybrid exhibits superior performance in the catalytic degradation of the blister agent simulant CEES, with a half-life of 2.0 min under visible light. The Lindqvist-type POM anions introduced by ion exchange endow this hybrid with additional hydrolysis sites, enabling the efficient detoxification of nerve agent simulant DECP, with a half-life of 4.2 min. Furthermore, a facile and universal method is advanced to tightly load the cage-encapsulated MC complex onto different types of fibers, leading to fiber composites that enhance practical applicability compared to untreated parent fibers, including extended protection duration and increased degradation efficiency. This work pioneers a new perspective involving MC-regulated switching reactive oxygen species within cage-type containers, while offering exciting opportunities for developing advanced catalysts for chemical warfare agent detoxification.