Development of oxygen vacancies enriched CoAl hydroxide@hydroxysulfide hollow flowers for peroxymonosulfate activation: A highly efficient singlet oxygen-dominated oxidation process for sulfamethoxazole degradation

Abstract

In this study, oxygen vacancies enriched cobalt aluminum hydroxide@hydroxysulfide (CoAl-LDH@CoSx) hollow flowers was synthesized by in-situ etching of CoAl-LDH using sodium sulfide solution. The analysis of SEM, EDS, XRD, and XPS were used to characterize the samples. The as-synthesized 0.2CoAl-LDH@CoSx displayed higher catalysis performance of sulfamethoxazole (SMX) degradation via the activation of PMS than the pristine CoAl-LDH. 98.5 % of SMX (40 μM) was eliminated with 0.1 g/L 0.2CoAl-LDH@CoSx and 0.3 mM PMS at pH 6.0 in 4 min. The degradation fitted with the pseudo-first-order reaction kinetics well with rate constant of 0.89 min−1 for 0.2CoAl-LDH@CoSx/PMS system and 0.55 min−1 for CoAl-LDH/PMS system. Singlet oxygen (1O2) was verified as dominant reactive oxygen species responsible for SMX degradation via quenching tests. Mechanism investigation suggested that the oxygen vacancies, redox cycles of Co(II)/Co(III) and S22−/(S2− and sulfate species) on the surface of 0.2CoAl-LDH@CoSx were crucial for PMS activation. In addition, the plausible degradation pathways of SMX were proposed by analysis of the SMX degradation intermediates. This study not only reveals that 0.2CoAl-LDH@CoSx is an efficient catalyst to activate PMS for SMX degradation, but also shed a novel insight into development of heterogeneous catalysts with oxygen vacancies.