文献类型：期刊文献

英文题名：Mechanistic insights into zero-valent-cobalt-driven self-sustaining Fenton process via selective oxygen reduction to generate hydrogen peroxide

作者：Zhang, Yixin[1];Liu, Mingtao[1];Liu, Yongdi[1];Song, Yanyu[1];Sun, Xianbo[1];Zhao, Dongye[2];Cai, Zhengqing[1,3]

机构：[1]East China Univ Sci & Technol, Natl Engn Res Ctr Ind Wastewater Detoxicat & Resou, Shanghai 200237, Peoples R China;[2]San Diego State Univ, Dept Civil Construct & Environm Engn, San Diego, CA 92182, USA;[3]Shanghai Inst Pollut Control & Ecol Secur, Shanghai 200092, Peoples R China

年份：2026

卷号：14

期号：3

外文期刊名：JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING

收录：;EI(收录号：20261520481787);WOS:【SCI-EXPANDED(收录号:WOS:001736420300001)】；

基金：Financial supports from the National Natural Science Foundation of China (41807340, 22176061) , Natural Science Foundation of Shanghai (21ZR1415600) and the Science and Technology Commission of Shanghai Municipality (21230712000) .

语种：英文

外文关键词：Zero-valent cobalt; Oxygen reduction reaction; Self-sustaining Fenton; Reactive oxygen species; Zero-valent cobalt; Oxygen reduction reaction; H2O2; Self-sustaining Fenton; Reactive oxygen species

摘要：Zero-valent transition metals are capable of generating H2O2, but the performance and mechanism for cobalt-driven H2O2 generation are yet to be explored. This work investigated in-situ generation of H2O2 in cobalt-mediated oxygen reduction reaction (ORR) with commercial & micro;ZVCo, and tested the degradation of oxytetracycline (OTC) in this self-sustaining Fenton-like system. Results from reactive oxygen species (ROS) analysis, dissolved oxygen monitoring, and rotating ring-disc electrodes tests revealed & micro;ZVCo's high ORR activity, which was enabled primarily through a two-step single-electron pathway involving O-2(center dot-). & micro;ZVCo outperformed microscale zero-valent iron in H2O2 generation and was able to yield 30.5 & micro;M of H2O2 in tap water, it is 6.2 times higher than in ultrapure water due to synergistic effects of co-existing ions, especially carbonate and magnesium. There is a key critical point of H2O2 concentration in the system, where the H2O2 decomposition rate (first-order kinetic) exceeds its generation rate (zero-order kinetic), resulting in a decrease in its net concentration. Therefore, the increase of & micro;ZVCo dosages did not proportionally promote the accumulation of H2O2 due to H2O2 decomposition in Fenton-like reaction, evidenced by enhanced OTC degradation rates reflecting faster radical-mediated H2O2 consumption. Based on Density Functional Theory calculation and intermediate analysis, the study further clarified the degradation pathway of OTC. Radical quenching experiments revealed that the key radicals for the OTC degradation follow the order of O-2(center dot-) > O-1(2) > center dot OH. This study provides new insight into the mechanism of zero-valent cobalt in the chemically driven oxygen reduction H2O2 generation and self-sustaining Fenton degradation system.