Haifang Mao , Yang Liu , Zhenmin Xu , Zhenfeng Bian
{"title":"MOFs 上缺陷诱导的原位电子-金属-支撑相互作用可加速铁(III)还原,从而实现高效芬顿反应","authors":"Haifang Mao , Yang Liu , Zhenmin Xu , Zhenfeng Bian","doi":"10.1016/S1872-2067(24)60047-1","DOIUrl":null,"url":null,"abstract":"<div><p>The inefficient reduction of Fe<sup>3+</sup> and activation of H<sub>2</sub>O<sub>2</sub> in the Fenton reaction severely limit its application in practical water treatment. In this study, we developed defective NH<sub>2</sub>-UiO-66 (d-NU) with coordinated unsaturated metal sites by adjusting the coordination configuration of Zr, creating a solid-liquid interface to facilitate Fe<sup>3+</sup> reduction and the sustainable generation of •OH from H<sub>2</sub>O<sub>2</sub> activation. The d-NU/Fe<sup>3+</sup>/H<sub>2</sub>O<sub>2</sub>/Vis system demonstrated highly efficient removal of various organic pollutants, with a rapid Fe<sup>2+</sup> regeneration rate and exceptional stability over ten cycles. The degradation rate constant of d-NU (0.16112 min<sup>–1</sup>) was 11 times higher than that of NH<sub>2</sub>-UiO-66 (NU) (0.01466 min<sup>–1</sup>) without defects. Characterization combined with density functional calculations revealed that defects induced coordination unsaturation of the Zr sites, leading to <em>in situ</em> electron-metal-support interactions between Fe<sup>3+</sup> and the support <em>via</em> Zr–O–Fe bridges. This accumulation of electrons from the unsaturated Zr sites enabled the adsorption of Fe<sup>3+</sup> at the solid-liquid interface, promoting the formation of Fe<sup>2+</sup> across a wide pH range with a reduced energy barrier. This study introduces a promising strategy for accelerating Fe<sup>3+</sup> reduction in the solid-liquid interfacial Fenton process for the degradation of organic pollutants.</p></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"61 ","pages":"Pages 247-258"},"PeriodicalIF":15.7000,"publicationDate":"2024-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Defect-induced in situ electron-metal-support interactions on MOFs accelerating Fe(III) reduction for high-efficiency Fenton reactions\",\"authors\":\"Haifang Mao , Yang Liu , Zhenmin Xu , Zhenfeng Bian\",\"doi\":\"10.1016/S1872-2067(24)60047-1\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The inefficient reduction of Fe<sup>3+</sup> and activation of H<sub>2</sub>O<sub>2</sub> in the Fenton reaction severely limit its application in practical water treatment. In this study, we developed defective NH<sub>2</sub>-UiO-66 (d-NU) with coordinated unsaturated metal sites by adjusting the coordination configuration of Zr, creating a solid-liquid interface to facilitate Fe<sup>3+</sup> reduction and the sustainable generation of •OH from H<sub>2</sub>O<sub>2</sub> activation. The d-NU/Fe<sup>3+</sup>/H<sub>2</sub>O<sub>2</sub>/Vis system demonstrated highly efficient removal of various organic pollutants, with a rapid Fe<sup>2+</sup> regeneration rate and exceptional stability over ten cycles. The degradation rate constant of d-NU (0.16112 min<sup>–1</sup>) was 11 times higher than that of NH<sub>2</sub>-UiO-66 (NU) (0.01466 min<sup>–1</sup>) without defects. Characterization combined with density functional calculations revealed that defects induced coordination unsaturation of the Zr sites, leading to <em>in situ</em> electron-metal-support interactions between Fe<sup>3+</sup> and the support <em>via</em> Zr–O–Fe bridges. This accumulation of electrons from the unsaturated Zr sites enabled the adsorption of Fe<sup>3+</sup> at the solid-liquid interface, promoting the formation of Fe<sup>2+</sup> across a wide pH range with a reduced energy barrier. This study introduces a promising strategy for accelerating Fe<sup>3+</sup> reduction in the solid-liquid interfacial Fenton process for the degradation of organic pollutants.</p></div>\",\"PeriodicalId\":9832,\"journal\":{\"name\":\"Chinese Journal of Catalysis\",\"volume\":\"61 \",\"pages\":\"Pages 247-258\"},\"PeriodicalIF\":15.7000,\"publicationDate\":\"2024-06-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chinese Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1872206724600471\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chinese Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1872206724600471","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
Defect-induced in situ electron-metal-support interactions on MOFs accelerating Fe(III) reduction for high-efficiency Fenton reactions
The inefficient reduction of Fe3+ and activation of H2O2 in the Fenton reaction severely limit its application in practical water treatment. In this study, we developed defective NH2-UiO-66 (d-NU) with coordinated unsaturated metal sites by adjusting the coordination configuration of Zr, creating a solid-liquid interface to facilitate Fe3+ reduction and the sustainable generation of •OH from H2O2 activation. The d-NU/Fe3+/H2O2/Vis system demonstrated highly efficient removal of various organic pollutants, with a rapid Fe2+ regeneration rate and exceptional stability over ten cycles. The degradation rate constant of d-NU (0.16112 min–1) was 11 times higher than that of NH2-UiO-66 (NU) (0.01466 min–1) without defects. Characterization combined with density functional calculations revealed that defects induced coordination unsaturation of the Zr sites, leading to in situ electron-metal-support interactions between Fe3+ and the support via Zr–O–Fe bridges. This accumulation of electrons from the unsaturated Zr sites enabled the adsorption of Fe3+ at the solid-liquid interface, promoting the formation of Fe2+ across a wide pH range with a reduced energy barrier. This study introduces a promising strategy for accelerating Fe3+ reduction in the solid-liquid interfacial Fenton process for the degradation of organic pollutants.
期刊介绍:
The journal covers a broad scope, encompassing new trends in catalysis for applications in energy production, environmental protection, and the preparation of materials, petroleum chemicals, and fine chemicals. It explores the scientific foundation for preparing and activating catalysts of commercial interest, emphasizing representative models.The focus includes spectroscopic methods for structural characterization, especially in situ techniques, as well as new theoretical methods with practical impact in catalysis and catalytic reactions.The journal delves into the relationship between homogeneous and heterogeneous catalysis and includes theoretical studies on the structure and reactivity of catalysts.Additionally, contributions on photocatalysis, biocatalysis, surface science, and catalysis-related chemical kinetics are welcomed.