Preparation of a porphyrin-polyoxometalate hybrid and its photocatalytic degradation performance for mustard gas simulant 2-chloroethyl ethyl sulfide

By combining 5,10,15,20-tetra(4-chlorine)phenylporphyrin (TClPP) and alpha-Keggin polyoxometalate H5PV2Mo10O40 (H5PVMo) via a simple ion-exchange method, an organic-inorganic hybrid material [C44H28N4Cl4](1.5)[H2PMo10V2O40]center dot 2C(2)H(6)O (H2TClPP-H2PVMo) was prepared and thoroughly characterized by a variety of techniques. The homogeneous photocatalytic degradation of 2-chloroethyl ethyl sulfide (CEES) (5 mu L) by H2TClPP-H2PVMo (1 x 10(-6) mol/L) was studied in methanol and methanol-water mixed solvent (v/v = 1:1), in which the degradation rate of CEES reached 99.52% and 99.14%, respectively. The reaction followed first-order reaction kinetics, and the half-life and kinetic constant in methanol and the mixed solvent were respectively 33.0 min, -0.021 min(-1) and 15.7 min, -0.043 min(-1). Mechanism analysis indicated that under visible light irradiation in the air, CEES was degraded via oxidation and alcoholysis/hydrolysis in methanol and the mixed solvent. O-2(center dot-) and O-1(2) generated by H2TClPP-H2PVMo selectively oxidized CEES into a nontoxic sulfoxide. Singlet oxygen capture experiments showed that H2TClPP-H2PVMo (phi = 0.73) had a higher quantum yield of singlet oxygen than TClPP (phi = 0.35) under an air atmosphere and visible light irradiation. (C) 2021 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Automated summary

An organic-inorganic hybrid material was successfully prepared through a simple ion-exchange method and exhibited excellent performance in photocatalytic degradation experiments, showing great potential for applications in fields such as wastewater treatment.