{"title":"通过配体支持-金属中心质子耦合电子转移†实现可持续制氢的 pdc 针状铜配合物","authors":"Meena Chettri, Subhajit Saha, Nilankar Diyali, Rakesh Debnath, Harshita Bagdwal, Monika Singh and Bhaskar Biswas","doi":"10.1039/D4SE00953C","DOIUrl":null,"url":null,"abstract":"<p >A water-stable <strong>[Cu(pdc)(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>]</strong> complex, promising functional mimics of hydrogenase active sites and promoting sustainable hydrogen production in acidic water, was designed and synthesised using an ONO-type pincer ligand, 2,6-pyridine dicarboxylic acid (<strong>pdc</strong>), and copper(<small>II</small>) nitrate. X-ray crystallographic analysis reveals that <strong>[Cu(pdc)(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>]</strong> crystallizes in a triclinic crystal system with square pyramidal geometry. The complex shows an excellent faradaic efficiency of 91% with remarkable stability up to 60 equivalents of acetic acid (AcOH), relative to <strong>[Cu(pdc)(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>]</strong>. Moreover, comprehensive spectroscopic, analytical, electrochemical, and computational analyses were performed to validate the proton-coupled electron transfer reaction. <strong>pdc</strong> coordinated with the Cu centre offers a delicate balance in shuttling <em>syn</em>-conformational proton coupling (H<small><sub>pdc</sub></small><small><sup><em>δ</em>+</sup></small>⋯H<small><sub>Cu</sub></small><small><sup><em>δ</em>−</sup></small>, 2.1 Å), promoting sustainable hydrogen production in water. Further, the scope of the electrocatalytic fate of <strong>[Cu(pdc)(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>]</strong> towards industrial prospects was ensured by examining the electrocatalytic capacity of <strong>[Cu(pdc)(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>]</strong> in 0.5 M H<small><sub>2</sub></small>SO<small><sub>4</sub></small>. The complex exhibits a significant elevation in cathodic current with H<small><sub>2</sub></small>SO<small><sub>4</sub></small> in water collected from the Relli river (27.066668° N, 88.466667° E), Kalimpong, West Bengal, envisioning its true-catalytic capacity in pilot-scale application and real prospect for industrial use.</p>","PeriodicalId":104,"journal":{"name":"Sustainable Energy & Fuels","volume":" 23","pages":" 5553-5560"},"PeriodicalIF":5.0000,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A pdc-pinched copper complex for sustainable hydrogen production through ligand supported-metal centric proton-coupled electron transfer†\",\"authors\":\"Meena Chettri, Subhajit Saha, Nilankar Diyali, Rakesh Debnath, Harshita Bagdwal, Monika Singh and Bhaskar Biswas\",\"doi\":\"10.1039/D4SE00953C\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >A water-stable <strong>[Cu(pdc)(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>]</strong> complex, promising functional mimics of hydrogenase active sites and promoting sustainable hydrogen production in acidic water, was designed and synthesised using an ONO-type pincer ligand, 2,6-pyridine dicarboxylic acid (<strong>pdc</strong>), and copper(<small>II</small>) nitrate. X-ray crystallographic analysis reveals that <strong>[Cu(pdc)(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>]</strong> crystallizes in a triclinic crystal system with square pyramidal geometry. The complex shows an excellent faradaic efficiency of 91% with remarkable stability up to 60 equivalents of acetic acid (AcOH), relative to <strong>[Cu(pdc)(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>]</strong>. Moreover, comprehensive spectroscopic, analytical, electrochemical, and computational analyses were performed to validate the proton-coupled electron transfer reaction. <strong>pdc</strong> coordinated with the Cu centre offers a delicate balance in shuttling <em>syn</em>-conformational proton coupling (H<small><sub>pdc</sub></small><small><sup><em>δ</em>+</sup></small>⋯H<small><sub>Cu</sub></small><small><sup><em>δ</em>−</sup></small>, 2.1 Å), promoting sustainable hydrogen production in water. Further, the scope of the electrocatalytic fate of <strong>[Cu(pdc)(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>]</strong> towards industrial prospects was ensured by examining the electrocatalytic capacity of <strong>[Cu(pdc)(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>]</strong> in 0.5 M H<small><sub>2</sub></small>SO<small><sub>4</sub></small>. The complex exhibits a significant elevation in cathodic current with H<small><sub>2</sub></small>SO<small><sub>4</sub></small> in water collected from the Relli river (27.066668° N, 88.466667° E), Kalimpong, West Bengal, envisioning its true-catalytic capacity in pilot-scale application and real prospect for industrial use.</p>\",\"PeriodicalId\":104,\"journal\":{\"name\":\"Sustainable Energy & Fuels\",\"volume\":\" 23\",\"pages\":\" 5553-5560\"},\"PeriodicalIF\":5.0000,\"publicationDate\":\"2024-10-11\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Sustainable Energy & Fuels\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/se/d4se00953c\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Sustainable Energy & Fuels","FirstCategoryId":"88","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/se/d4se00953c","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
A pdc-pinched copper complex for sustainable hydrogen production through ligand supported-metal centric proton-coupled electron transfer†
A water-stable [Cu(pdc)(H2O)2] complex, promising functional mimics of hydrogenase active sites and promoting sustainable hydrogen production in acidic water, was designed and synthesised using an ONO-type pincer ligand, 2,6-pyridine dicarboxylic acid (pdc), and copper(II) nitrate. X-ray crystallographic analysis reveals that [Cu(pdc)(H2O)2] crystallizes in a triclinic crystal system with square pyramidal geometry. The complex shows an excellent faradaic efficiency of 91% with remarkable stability up to 60 equivalents of acetic acid (AcOH), relative to [Cu(pdc)(H2O)2]. Moreover, comprehensive spectroscopic, analytical, electrochemical, and computational analyses were performed to validate the proton-coupled electron transfer reaction. pdc coordinated with the Cu centre offers a delicate balance in shuttling syn-conformational proton coupling (Hpdcδ+⋯HCuδ−, 2.1 Å), promoting sustainable hydrogen production in water. Further, the scope of the electrocatalytic fate of [Cu(pdc)(H2O)2] towards industrial prospects was ensured by examining the electrocatalytic capacity of [Cu(pdc)(H2O)2] in 0.5 M H2SO4. The complex exhibits a significant elevation in cathodic current with H2SO4 in water collected from the Relli river (27.066668° N, 88.466667° E), Kalimpong, West Bengal, envisioning its true-catalytic capacity in pilot-scale application and real prospect for industrial use.
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Sustainable Energy & Fuels will publish research that contributes to the development of sustainable energy technologies with a particular emphasis on new and next-generation technologies.
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