文献类型：期刊文献

英文题名：Oxygen vacancies in CoCr-LDH drive electron transfer to peroxymonosulfate for Co(IV)=O-mediated non-radical degradation of oxytetracycline

作者：Ma, Weiyu[1];Sun, Xianbo[1];Liu, Yongdi[1];Ji, Jing[2];Pan, Fei[3];Cai, Zhengqing[1,4]

机构：[1]East China Univ Sci & Technol, Natl Engn Res Ctr Ind Wastewater Detoxicat & Resou, Shanghai 200237, Peoples R China;[2]Beijing Univ Chem Technol, Coll Chem Engn, State Key Lab Organ Inorgan Composites, Beijing 100029, Peoples R China;[3]Wuhan Text Univ, Sch Resources & Environm, Wuhan 430200, Peoples R China;[4]Shanghai Inst Pollut Control & Ecol Secur, Shanghai 200237, Peoples R China

年份：2026

卷号：397

外文期刊名：APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY

收录：;EI(收录号：20262120769055);WOS:【SCI-EXPANDED(收录号:WOS:001788260700001)】；

基金：This work was supported by the Natural Science Foundation of Shanghai [21ZR1415600] , the National Natural Science Foundation of China [41807340] . The authors thank Research Center of Analysis and Test of East China University of Science and Technology for the help on the characterization.

语种：英文

外文关键词：Layered double hydroxide; Peroxymonosulfate; Electron transfer process; Non-radical

摘要：Oxygen vacancy-enriched CoCr-layered double hydroxide (OVs-CoCr-LDH) was successfully synthesized via hydrothermal reduction. The introduction of OVs preserved the LDH framework while inducing partial exfoliation, reducing nanosheet thickness and creating abundant coordinatively unsaturated sites. The OVs-CoCr-LDH/ peroxymonosulfate (PMS) achieved 97.6% oxytetracycline (OTC) removal within 10 min with outstanding salt tolerance (<= 21% inhibition at 1000 mM Cl-/SO42-) and excellent reusing stability. Continuous-flow membrane reactor tests confirmed practical viability, achieving 88.9% OTC removal and 70.2 - 79.9% TOC mineralization over 2400 min. Mechanistic investigations revealed that non-radical pathways dominated, with Co(IV)=O as the primary reactive species (44.7% contribution), followed by 1O2 (33.7%) and center dot O2- (17.1%). DFT calculations revealed OVs as electron-rich centers facilitating PMS adsorption and direct electron transfer; Raman spectroscopy confirmed O-O bond activation without homolytic cleavage; electrochemical analyses and Hammett correlations revealed a directional charge-transfer process where electron-donating ability directly enhances interfacial electron transfer efficiency. Life cycle assessment identified catalyst synthesis and continuous PMS dosing as the main environmental hotspots, providing practical guidance for process optimization. This work establishes an integrated mechanistic-engineering framework for vacancy-directed non-radical oxidation, combining atomistic DFT insights with continuous-flow salt-tolerant operation and life-cycle environmental assessment.