Aminal‐Linked Porphyrinic Covalent Organic Framework for Rapid Photocatalytic Decontamination of Mustard‐Gas Simulant

Abstract

Covalent organic frameworks (COFs) are appealing photocatalysts for toxic chemical degradation. Great efforts have been devoted to regulate the photocatalytic performance of COFs by tuning their organic building blocks, but the relationship between COF linkage and photochemical properties has rarely been explored. Herein, we report the synthesis and characterisation of a novel aminal-linked porphyrinic COF, namelyPor-Aminal-COF.Por-Aminal-COF (0.25 mol %) showed excellent photocatalytic activity toward the detoxification of the sulfur mustard simulant with a half-life (t 1/2 ) of 5 min, which is far lower than that of traditional imine-linked Por-COF (t 1/2 = 16 min). Transient absorption spectroscopy indicated that the aminal linkages of Por-Aminal-COF facilitated the intersystem crossing process. Thus, Por-Aminal-COF showed higher triplet-state generation efficiency compared with Por-COF, consequently promoting the activation of oxygen molecular to singlet oxygen.

Recent advances in metal-free covalent organic frameworks for photocatalytic applications in energy and environmental fields

“…Therefore, it is important to develop efficient decontamination methods for the removal of mustard gas from the environment. Zang et al 111 reported an amine-linked porphyrin COF with 5,10,15,20- tetrakis(4-benzaldehyde)porphyrin and piperazine as monomers (Fig. 16).…”

Phosphate anion-induced silver-chalcogenide cluster-based metal organic frameworks as dual-functional catalysts for detoxifying chemical warfare agent simulants

“…16,[26][27][28][29] Essentially, the high CEES degradation activity of ZZU-601 and ZZU-602 is related to their photogenerated singlet oxygen ( 1 O 2 ) efficiency. 16,30 Electron paramagnetic resonance (EPR) trapping measurements were initially carried out to monitor the generation of 1 O 2 . As expected, with 2,2,6,6-tetramethylpiperidine (TEMP) as a trapping agent, 16,31 a typical 1 : 1 : 1 triplet signal of the TEMP-1 O 2 adduct was detected in the presence of SCC-MOFs upon light irradiation (Fig.…”

Cooperative Catalysis between Dual Copper Centers in a Metal–Organic Framework for Efficient Detoxification of Chemical Warfare Agent Simulants

“…Extensive work has demonstrated that detoxification of nerve agents through hydrolysis of labile P–X bonds (X = F, CN, S, etc.) is a promising route, − while for the degradation of mustard gas, selective oxidation to sulfoxide is an effective approach. ,,− Realistically, the CWAs deployed in war are usually unknown and deadly; hence, to efficiently prevent harm to human beings caused by CWAs, multifunctional catalysts that simultaneously detoxify various types of CWAs are highly desired. However, the different detoxification pathways make constructing versatile catalysts quite challenging.…”