Rulin Li , Shasha Wang , Yingjun Li , Lu Zi , Siqin Zhao , Liming Qi , Baocang Liu , Gejihu De , Jun Zhang
{"title":"KMF3钙钛矿八面体单元中m位电荷对称的破坏导致氨中硝酸盐的电化学还原增强。","authors":"Rulin Li , Shasha Wang , Yingjun Li , Lu Zi , Siqin Zhao , Liming Qi , Baocang Liu , Gejihu De , Jun Zhang","doi":"10.1016/j.jcis.2024.11.219","DOIUrl":null,"url":null,"abstract":"<div><div>Electrochemical production of NH<sub>3</sub> from NO<sub>3</sub><sup>−</sup> offers a solution to the environmental issue of excess NO<sub>3</sub><sup>−</sup> but is challenged by the lack of efficient, sensitive electrocatalysts with high NH<sub>3</sub> yield rate and Faraday efficiency (FE). Herein, a medium-entropy perovskite fluoride (KMF<sub>3</sub>, M = Co/Ni/Fe/Ti) was prepared as efficient electrocatalysts to produce NH<sub>3</sub> via the NO<sub>3</sub><sup>−</sup> reduction reaction (NO<sub>3</sub><sup>−</sup>RR). By introducing various transition metals at the M-sites, the charge distribution at the M-site octahedral units was adjusted to increase the disorder of KMF<sub>3</sub>, resulting in an optimized electronic structure with high intrinsic NO<sub>3</sub><sup>−</sup>RR performance. The presence of different transition metals at the M-sites promoted electron transfer, which inhibited the Co 1s-3d transition and strengthened the Co<img>F bond, leading to a decrease in crystal symmetry. Furthermore, owing to differences in valence state, electronegativity, and ionic radius, the coordination number was reduced, inducing the generation of a local twisted coordination environment. This was conducive to catalyst adsorption and the breaking of N<img>O bonds. As a result, the KMF<sub>3</sub> exhibited a high NH<sub>3</sub> yield rate of 13.9 mg h<sup>−1</sup> cm<sup>−2</sup> with an NH<sub>3</sub> FE close to 100 %. The developed medium-entropy KMF<sub>3</sub> electrocatalysts have the potential to recover NH<sub>3</sub> from nitrate wastewater.</div></div>","PeriodicalId":351,"journal":{"name":"Journal of Colloid and Interface Science","volume":"682 ","pages":"Pages 1175-1184"},"PeriodicalIF":9.7000,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"The breaking of charge symmetry at the M-site in octahedral units of KMF3 perovskite induces enhanced electrochemical nitrate reduction in ammonia\",\"authors\":\"Rulin Li , Shasha Wang , Yingjun Li , Lu Zi , Siqin Zhao , Liming Qi , Baocang Liu , Gejihu De , Jun Zhang\",\"doi\":\"10.1016/j.jcis.2024.11.219\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Electrochemical production of NH<sub>3</sub> from NO<sub>3</sub><sup>−</sup> offers a solution to the environmental issue of excess NO<sub>3</sub><sup>−</sup> but is challenged by the lack of efficient, sensitive electrocatalysts with high NH<sub>3</sub> yield rate and Faraday efficiency (FE). Herein, a medium-entropy perovskite fluoride (KMF<sub>3</sub>, M = Co/Ni/Fe/Ti) was prepared as efficient electrocatalysts to produce NH<sub>3</sub> via the NO<sub>3</sub><sup>−</sup> reduction reaction (NO<sub>3</sub><sup>−</sup>RR). By introducing various transition metals at the M-sites, the charge distribution at the M-site octahedral units was adjusted to increase the disorder of KMF<sub>3</sub>, resulting in an optimized electronic structure with high intrinsic NO<sub>3</sub><sup>−</sup>RR performance. The presence of different transition metals at the M-sites promoted electron transfer, which inhibited the Co 1s-3d transition and strengthened the Co<img>F bond, leading to a decrease in crystal symmetry. Furthermore, owing to differences in valence state, electronegativity, and ionic radius, the coordination number was reduced, inducing the generation of a local twisted coordination environment. This was conducive to catalyst adsorption and the breaking of N<img>O bonds. As a result, the KMF<sub>3</sub> exhibited a high NH<sub>3</sub> yield rate of 13.9 mg h<sup>−1</sup> cm<sup>−2</sup> with an NH<sub>3</sub> FE close to 100 %. The developed medium-entropy KMF<sub>3</sub> electrocatalysts have the potential to recover NH<sub>3</sub> from nitrate wastewater.</div></div>\",\"PeriodicalId\":351,\"journal\":{\"name\":\"Journal of Colloid and Interface Science\",\"volume\":\"682 \",\"pages\":\"Pages 1175-1184\"},\"PeriodicalIF\":9.7000,\"publicationDate\":\"2024-12-06\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Colloid and Interface Science\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0021979724027929\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Colloid and Interface Science","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0021979724027929","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
The breaking of charge symmetry at the M-site in octahedral units of KMF3 perovskite induces enhanced electrochemical nitrate reduction in ammonia
Electrochemical production of NH3 from NO3− offers a solution to the environmental issue of excess NO3− but is challenged by the lack of efficient, sensitive electrocatalysts with high NH3 yield rate and Faraday efficiency (FE). Herein, a medium-entropy perovskite fluoride (KMF3, M = Co/Ni/Fe/Ti) was prepared as efficient electrocatalysts to produce NH3 via the NO3− reduction reaction (NO3−RR). By introducing various transition metals at the M-sites, the charge distribution at the M-site octahedral units was adjusted to increase the disorder of KMF3, resulting in an optimized electronic structure with high intrinsic NO3−RR performance. The presence of different transition metals at the M-sites promoted electron transfer, which inhibited the Co 1s-3d transition and strengthened the CoF bond, leading to a decrease in crystal symmetry. Furthermore, owing to differences in valence state, electronegativity, and ionic radius, the coordination number was reduced, inducing the generation of a local twisted coordination environment. This was conducive to catalyst adsorption and the breaking of NO bonds. As a result, the KMF3 exhibited a high NH3 yield rate of 13.9 mg h−1 cm−2 with an NH3 FE close to 100 %. The developed medium-entropy KMF3 electrocatalysts have the potential to recover NH3 from nitrate wastewater.
期刊介绍:
The Journal of Colloid and Interface Science publishes original research findings on the fundamental principles of colloid and interface science, as well as innovative applications in various fields. The criteria for publication include impact, quality, novelty, and originality.
Emphasis:
The journal emphasizes fundamental scientific innovation within the following categories:
A.Colloidal Materials and Nanomaterials
B.Soft Colloidal and Self-Assembly Systems
C.Adsorption, Catalysis, and Electrochemistry
D.Interfacial Processes, Capillarity, and Wetting
E.Biomaterials and Nanomedicine
F.Energy Conversion and Storage, and Environmental Technologies