Rapid pollutant degradation by peroxymonosulfate via an unusual mediated-electron transfer pathway under spatial-confinement

Nano-confinement systems offer various extraordinary chemical/physical properties, due to the spatial restriction and the electronic interaction between the confined species and the surrounding medium. They are, therefore, providing rich opportunities for the design of efficient catalytic reaction systems for pollutant removal. Herein, a highly efficient mediated-electron transfer pathway is identified on a spatially-confined zero valent cobalt for abatement of the organic pollutants by PMS. The catalyst showed efficient catalytic performance in both batch and a flow reactor for degradation of various pollutants, e.g., a degradation reaction constant of 0.052 s⁻¹ for sulfamethoxazole and 0.041 s⁻¹ for BPA. Regulated by the spatial-confinement, a distinctive inverse relationship between PMS decomposition rate and the electron density of the pollutant molecule was experimentally substantiated, e.g., in the presence of the electron-rich sulfamethoxazole, PMS decomposed slower than that with BPA, while in the presence of electron deficient diphenhydramine, PMS decomposed faster than that with BPA. The unique reaction mechanism endows the spatially-confined cobalt with the capability of eliminating the priority pollutants in the complex water matrix with pervasive halide ions and natural organic matter (NOM) via PMS activation.

A highly efficient mediated-electron transfer process of PMS activation on Co was achieved by construction of a spatially-confined reaction environment.