Shuai Mao , Peng Zhao , Yi Wu, Chun Liu, Mingzhu Xia, Fengyun Wang
{"title":"通过羟基化促进Co(OH)2/g-C3N4的电荷迁移以改善PMS活化:催化剂设计、DFT计算和机理分析","authors":"Shuai Mao , Peng Zhao , Yi Wu, Chun Liu, Mingzhu Xia, Fengyun Wang","doi":"10.1016/j.cej.2022.138503","DOIUrl":null,"url":null,"abstract":"<div><p>Cobalt-based materials were considered as promising catalysts for peroxymonosulfate (PMS) activation, while few reactive sites and ion leaching limit its environmental application. Herein, Co(OH)<sub>2</sub> nanosheets in-situ anchored hydroxylated hollow tubular g-C<sub>3</sub>N<sub>4</sub> (Co/CNH) was successfully fabricated by a facile impregnation method, and used to activate PMS for enrofloxacin hydrochloride (ERF) degradation. Compared with neat Co(OH)<sub>2</sub> and CNH, the optimum catalyst (10 %Co/CNH) exhibited higher ERF degradation efficiency for 95.6 % within 30 min. The enhanced performance was attributed to the synergistic effect between Co(OH)<sub>2</sub> and CNH. CNH can not only provide numerous nucleation sites for Co(OH)<sub>2</sub> to inhibit its agglomeration, but also provide abundant OH<sup>−</sup> for formation of the key PMS activation species CoOH<sup>+</sup>. Furthermore, DFT-based electron density difference elucidated that the sp<sup>3</sup> hybridization introduced by OH<sup>−</sup> greatly facilitated charge transfer from 10 %Co/CNH to PMS. A series of characterization verified that <sup>1</sup>O<sub>2</sub> dominated the degradation of ERF (nonradical pathway), SO<sub>4</sub><sup>•−</sup> and •OH (radical pathway) as well as electron transfer also contributed to this process. Fukui index (<em>f</em><sup>−</sup>) and bond degree (BD) indicated that reactive oxygen species tend to attack atoms with higher <em>f</em><sup>−</sup> and scavenge covalent bonds with larger BD in the process of ERF degradation.</p></div>","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":null,"pages":null},"PeriodicalIF":13.3000,"publicationDate":"2023-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"23","resultStr":"{\"title\":\"Promoting charge migration of Co(OH)2/g-C3N4 by hydroxylation for improved PMS activation: Catalyst design, DFT calculation and mechanism analysis\",\"authors\":\"Shuai Mao , Peng Zhao , Yi Wu, Chun Liu, Mingzhu Xia, Fengyun Wang\",\"doi\":\"10.1016/j.cej.2022.138503\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Cobalt-based materials were considered as promising catalysts for peroxymonosulfate (PMS) activation, while few reactive sites and ion leaching limit its environmental application. Herein, Co(OH)<sub>2</sub> nanosheets in-situ anchored hydroxylated hollow tubular g-C<sub>3</sub>N<sub>4</sub> (Co/CNH) was successfully fabricated by a facile impregnation method, and used to activate PMS for enrofloxacin hydrochloride (ERF) degradation. Compared with neat Co(OH)<sub>2</sub> and CNH, the optimum catalyst (10 %Co/CNH) exhibited higher ERF degradation efficiency for 95.6 % within 30 min. The enhanced performance was attributed to the synergistic effect between Co(OH)<sub>2</sub> and CNH. CNH can not only provide numerous nucleation sites for Co(OH)<sub>2</sub> to inhibit its agglomeration, but also provide abundant OH<sup>−</sup> for formation of the key PMS activation species CoOH<sup>+</sup>. Furthermore, DFT-based electron density difference elucidated that the sp<sup>3</sup> hybridization introduced by OH<sup>−</sup> greatly facilitated charge transfer from 10 %Co/CNH to PMS. A series of characterization verified that <sup>1</sup>O<sub>2</sub> dominated the degradation of ERF (nonradical pathway), SO<sub>4</sub><sup>•−</sup> and •OH (radical pathway) as well as electron transfer also contributed to this process. Fukui index (<em>f</em><sup>−</sup>) and bond degree (BD) indicated that reactive oxygen species tend to attack atoms with higher <em>f</em><sup>−</sup> and scavenge covalent bonds with larger BD in the process of ERF degradation.</p></div>\",\"PeriodicalId\":270,\"journal\":{\"name\":\"Chemical Engineering Journal\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":13.3000,\"publicationDate\":\"2023-01-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"23\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemical Engineering Journal\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1385894722039845\",\"RegionNum\":1,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"ENGINEERING, CHEMICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Engineering Journal","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1385894722039845","RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ENGINEERING, CHEMICAL","Score":null,"Total":0}
Promoting charge migration of Co(OH)2/g-C3N4 by hydroxylation for improved PMS activation: Catalyst design, DFT calculation and mechanism analysis
Cobalt-based materials were considered as promising catalysts for peroxymonosulfate (PMS) activation, while few reactive sites and ion leaching limit its environmental application. Herein, Co(OH)2 nanosheets in-situ anchored hydroxylated hollow tubular g-C3N4 (Co/CNH) was successfully fabricated by a facile impregnation method, and used to activate PMS for enrofloxacin hydrochloride (ERF) degradation. Compared with neat Co(OH)2 and CNH, the optimum catalyst (10 %Co/CNH) exhibited higher ERF degradation efficiency for 95.6 % within 30 min. The enhanced performance was attributed to the synergistic effect between Co(OH)2 and CNH. CNH can not only provide numerous nucleation sites for Co(OH)2 to inhibit its agglomeration, but also provide abundant OH− for formation of the key PMS activation species CoOH+. Furthermore, DFT-based electron density difference elucidated that the sp3 hybridization introduced by OH− greatly facilitated charge transfer from 10 %Co/CNH to PMS. A series of characterization verified that 1O2 dominated the degradation of ERF (nonradical pathway), SO4•− and •OH (radical pathway) as well as electron transfer also contributed to this process. Fukui index (f−) and bond degree (BD) indicated that reactive oxygen species tend to attack atoms with higher f− and scavenge covalent bonds with larger BD in the process of ERF degradation.
期刊介绍:
The Chemical Engineering Journal is an international research journal that invites contributions of original and novel fundamental research. It aims to provide an international platform for presenting original fundamental research, interpretative reviews, and discussions on new developments in chemical engineering. The journal welcomes papers that describe novel theory and its practical application, as well as those that demonstrate the transfer of techniques from other disciplines. It also welcomes reports on carefully conducted experimental work that is soundly interpreted. The main focus of the journal is on original and rigorous research results that have broad significance. The Catalysis section within the Chemical Engineering Journal focuses specifically on Experimental and Theoretical studies in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. These studies have industrial impact on various sectors such as chemicals, energy, materials, foods, healthcare, and environmental protection.