Use of porphyrin-containing polymers of intrinsic microporosity as selective photocatalysts for oxidative detoxification of chemical warfare agent simulant

Abstract

Porphyrin-based polymers of intrinsic microporosity (PIMs) in photocatalytic degradation of a mustard-gas simulant (2-chloroethyl ethyl sulfide (2-CEES)) was demonstrated. Under blue-ultraviolet (UV) light-emitting diode (LED) irradiation, porphyrin-based PIMs PP-H2 and PP-Zn(II) worked as effective heterogeneous photocatalysts for oxidation of 2-CEES. Solvent played an important role in the conversion and selectivity of 2-CEES oxidation. When AcCN was used as a solvent, PP-H2and PP-Zn(II) demonstrated complete conversion of 2-CEES in 30 and 50 min, respectively, whereas they showed complete conversion at 60 and 70 min, respectively, when MeOH was used as a solvent. Moreover, these PIMs produced 2-chloroethyl ethyl sulfoxide (2-CEESO) as a major product with small amounts of 2-chloroethyl ethyl sulfone (2-CEESO[Formula: see text], ethyl methoxyethyl sulfoxide (EMSO), and vinyl sulfoxide (EVS) as side products in most solvents. However, when MeOH was used as a solvent, highly toxic 2-CEESO2 was not observed as a side product. Furthermore, these PIMs showed no significant changes in photocatalytic activity even after five cycles of reuse, indicating their high stability. Thus, the series of PIMs prepared herein can perform well as heterogeneous catalysts in photooxidation of 2-CEES under blue-UV LED light, with PP-H2 being the most effective oxidation catalyst, leading to fast conversion and high selectivity.

Cobalt tris(4-vinylphenyl)corrole: out of the frying pan into the polymer

“…8 In this regard, recent results on porphyrin-containing polymers showed high specificity for the detoxification of chemical warfare agents by using simulants. 9 Molecularly imprinted polymers have proved their particular advantage as a biomimetic heterogenous catalyst for the oxidation of sulphur derivatives involving vesicants and V nerve agent stimulants. 10 Compared to the many published examples involving porphyrin derivatives, literature on corrole-based polymers is much less abundant.…”