{"title":"金属有机框架中的聚钒酸盐诱导多通道电子转移,促进过一硫酸盐活化","authors":"Ming-Yan Lan, Yu-Hang Li, Chong-Chen Wang, Xin-Jie Li, Jiazhen Cao, Linghui Meng, Shuai Gao, Yuhui Ma, Haodong Ji, Mingyang Xing","doi":"10.1038/s41467-024-51525-0","DOIUrl":null,"url":null,"abstract":"<p>Catalytic peroxymonosulfate (PMS) activation processes don’t solely rely on electron transfer from dominant metal centers due to the complicated composition and interface environment of catalysts. Herein the synthesis of a cobalt based metal-organic framework containing polyvanadate [V<sub>4</sub>O<sub>12</sub>]<sup>4−</sup> cluster, Co<sub>2</sub>(V<sub>4</sub>O<sub>12</sub>)(bpy)<sub>2</sub> (bpy = 4,4’-bipyridine), is presented. The catalyst demonstrates superior degradation activity toward various micropollutants, with higher highest occupied molecular orbital (HOMO), via nonradical attack. The X-ray absorption spectroscopy and density functional theory (DFT) calculations demonstrate that Co sites act as both PMS trapper and electron donor. In situ spectral characterizations and DFT calculations reveal that the terminal oxygen atoms in the [V<sub>4</sub>O<sub>12</sub>]<sup>4−</sup> electron sponge could interact with the terminal hydrogen atoms in PMS to form hydrogen bonds, promoting the generation of SO<sub>5</sub>* intermediate via both dynamic pull and direct electron transfer process. Further, Co<sub>2</sub>(V<sub>4</sub>O<sub>12</sub>)(bpy)<sub>2</sub> exhibits long-term water purification ability, up to 40 h, towards actual wastewater discharged from an ofloxacin production factory. This work not only presents an efficient catalyst with an electron sponge for water environmental remediation via nonradical pathway, but also provides fundamental insights into the Fenton-like reaction mechanism.</p>","PeriodicalId":19066,"journal":{"name":"Nature Communications","volume":null,"pages":null},"PeriodicalIF":14.7000,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Multi-channel electron transfer induced by polyvanadate in metal-organic framework for boosted peroxymonosulfate activation\",\"authors\":\"Ming-Yan Lan, Yu-Hang Li, Chong-Chen Wang, Xin-Jie Li, Jiazhen Cao, Linghui Meng, Shuai Gao, Yuhui Ma, Haodong Ji, Mingyang Xing\",\"doi\":\"10.1038/s41467-024-51525-0\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Catalytic peroxymonosulfate (PMS) activation processes don’t solely rely on electron transfer from dominant metal centers due to the complicated composition and interface environment of catalysts. Herein the synthesis of a cobalt based metal-organic framework containing polyvanadate [V<sub>4</sub>O<sub>12</sub>]<sup>4−</sup> cluster, Co<sub>2</sub>(V<sub>4</sub>O<sub>12</sub>)(bpy)<sub>2</sub> (bpy = 4,4’-bipyridine), is presented. The catalyst demonstrates superior degradation activity toward various micropollutants, with higher highest occupied molecular orbital (HOMO), via nonradical attack. The X-ray absorption spectroscopy and density functional theory (DFT) calculations demonstrate that Co sites act as both PMS trapper and electron donor. In situ spectral characterizations and DFT calculations reveal that the terminal oxygen atoms in the [V<sub>4</sub>O<sub>12</sub>]<sup>4−</sup> electron sponge could interact with the terminal hydrogen atoms in PMS to form hydrogen bonds, promoting the generation of SO<sub>5</sub>* intermediate via both dynamic pull and direct electron transfer process. Further, Co<sub>2</sub>(V<sub>4</sub>O<sub>12</sub>)(bpy)<sub>2</sub> exhibits long-term water purification ability, up to 40 h, towards actual wastewater discharged from an ofloxacin production factory. This work not only presents an efficient catalyst with an electron sponge for water environmental remediation via nonradical pathway, but also provides fundamental insights into the Fenton-like reaction mechanism.</p>\",\"PeriodicalId\":19066,\"journal\":{\"name\":\"Nature Communications\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":14.7000,\"publicationDate\":\"2024-08-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Nature Communications\",\"FirstCategoryId\":\"103\",\"ListUrlMain\":\"https://doi.org/10.1038/s41467-024-51525-0\",\"RegionNum\":1,\"RegionCategory\":\"综合性期刊\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"MULTIDISCIPLINARY SCIENCES\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Nature Communications","FirstCategoryId":"103","ListUrlMain":"https://doi.org/10.1038/s41467-024-51525-0","RegionNum":1,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MULTIDISCIPLINARY SCIENCES","Score":null,"Total":0}
Multi-channel electron transfer induced by polyvanadate in metal-organic framework for boosted peroxymonosulfate activation
Catalytic peroxymonosulfate (PMS) activation processes don’t solely rely on electron transfer from dominant metal centers due to the complicated composition and interface environment of catalysts. Herein the synthesis of a cobalt based metal-organic framework containing polyvanadate [V4O12]4− cluster, Co2(V4O12)(bpy)2 (bpy = 4,4’-bipyridine), is presented. The catalyst demonstrates superior degradation activity toward various micropollutants, with higher highest occupied molecular orbital (HOMO), via nonradical attack. The X-ray absorption spectroscopy and density functional theory (DFT) calculations demonstrate that Co sites act as both PMS trapper and electron donor. In situ spectral characterizations and DFT calculations reveal that the terminal oxygen atoms in the [V4O12]4− electron sponge could interact with the terminal hydrogen atoms in PMS to form hydrogen bonds, promoting the generation of SO5* intermediate via both dynamic pull and direct electron transfer process. Further, Co2(V4O12)(bpy)2 exhibits long-term water purification ability, up to 40 h, towards actual wastewater discharged from an ofloxacin production factory. This work not only presents an efficient catalyst with an electron sponge for water environmental remediation via nonradical pathway, but also provides fundamental insights into the Fenton-like reaction mechanism.
期刊介绍:
Nature Communications, an open-access journal, publishes high-quality research spanning all areas of the natural sciences. Papers featured in the journal showcase significant advances relevant to specialists in each respective field. With a 2-year impact factor of 16.6 (2022) and a median time of 8 days from submission to the first editorial decision, Nature Communications is committed to rapid dissemination of research findings. As a multidisciplinary journal, it welcomes contributions from biological, health, physical, chemical, Earth, social, mathematical, applied, and engineering sciences, aiming to highlight important breakthroughs within each domain.