Insight into the nonradical selective oxidation mechanism for versatile organic pollutants removal by perovskite activated peroxymonosulfate system

Abstract

The heterogeneous catalysis of peroxymonosulfate (PMS) through nonradical pathway has shown many advantages in environmental remediation. It is necessary to unveil the factors affecting oxidation routes and selectivity toward different organic pollutants. Herein, a series of ABO3-type BiFexCo1-xO3 perovskite catalysts were fabricated via simple hydrothermal process to realize the changeover of catalytic activity and mechanism in PMS activation and pollutants oxidation. The as-prepared BiFe0.5Co0.5O3 (BFCO-3) achieved a 98 % removal efficiency of SMZ with a high kinetic constant (kobs = 0.334 min−1) in 10 min. The superior catalytic performance was ascribed to the introduction of bimetals at B-site, which enhanced electron donating capacity to PMS, confirming by d-band center calculations. Several parameters such as inorganic anions and humic acids affected the SMZ degradation slightly, owing that singlet oxygen was verified to be the primary reactive species in the BFCO-3/PMS system. Moreover, twelve organic pollutants including amoxicillin crystalline (AMX), cephalexin hydrate (CFX), ciprofloxacin (CIP), levofloxacin (LFX), Sulfadiazine (SDZ), sulfamethoxazole (SMZ), 4-acetamidophenol (ACP), benzoic acid (BA), bisphenol A (BPA), carbamazepine (CBZ), metronidazole (MNZ) and naproxen (NPX) were utilized to investigate the selective oxidation mechanism. A linear correlation between lnkobs and their half-wave potential (φ1/2) values (except for BA and MNZ) suggesting the dominant role of nonradical catalysis where phenolic compounds with lower anodic potential tend to lose electrons are more easily degraded. Furthermore, the reactive sites of representative SMZ for electrophilic species attack were precisely identified based on the Fukui index. And the degradation intermediates of SMZ were further determined by LC-MS/MS technology for proposing their degradation pathway and predicting ecotoxicity. This study not only provides an efficient advanced oxidation system for organic pollutants removal but also advances our understanding of the selective oxidation mechanism in nonradical-dominated catalytic process.