Direct Deposition of Copper Atoms onto Graphitic Step Edges Lowers Overpotential and Improves Selectivity of Electrocatalytic CO2 Reduction

Direct Deposition of Copper Atoms onto Graphitic Step Edges Lowers Overpotential and Improves Selectivity of Electrocatalytic CO2 Reduction | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Direct Deposition of Copper Atoms onto Graphitic Step Edges Lowers Overpotential and Improves Selectivity of Electrocatalytic CO2 Reduction Madasamy Thangamuthu, Tom Burwell, Gazi Aliev, Sadegh Ghaderzadeh, and 8 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3894708/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 20 Jun, 2024 Read the published version in Communications Chemistry → Version 1 posted You are reading this latest preprint version Abstract Minimizing our reliance on bulk precious metals is to increase the fraction of surface atoms and improve the metal-support interface. In this work, we employ a solvent/ligand/counterion-free method to deposit copper in the atomic form directly onto a nanotextured surface of graphitized carbon nanofibers (GNFs). Our results demonstrate that under these conditions, copper atoms coalesce into nanoparticles securely anchored to the graphitic step edges, limiting their growth to 2–5 nm. The resultant hybrid Cu/GNF material displays remarkable electrocatalytic properties in CO 2 reduction reaction (CO 2 RR), exhibiting selectivity for formate production with a faradaic efficiency of ~ 94% at a low overpotential of 0.17 V and an exceptionally high turnover frequency of 2.78×10 6 h − 1 . The Cu nanoparticles adhered to the graphitic step edges significantly enhance electron transfer to CO 2 , with the formation of CO 2 ∙− intermediate identifiedas the rate-determining step. Long-term CO 2 RR tests coupled with atomic-scale elucidation of changes in Cu/GNF reveal nanoparticles coarsening, and a simultaneous increase in the fraction of single Cu atoms. These changes disfavour CO 2 RR, as confirmed by density functional theory calculations, revealing that CO 2 cannot effectively compete with H 2 O for adsorption on single Cu atoms on the graphitic surfaces. Physical sciences/Chemistry/Catalysis/Electrocatalysis Physical sciences/Materials science/Materials for energy and catalysis/Electrocatalysis Physical sciences/Chemistry/Energy Physical sciences/Chemistry/Electrochemistry/Electrocatalysis Physical sciences/Chemistry/Catalysis/Heterogeneous catalysis Electrocatalysis Graphitic carbon nanofiber Copper nanoparticles Single-atom catalysts CO2 reduction Full Text Additional Declarations There is NO Competing Interest. Supplementary Files SupportinginformationUoN.docx Cite Share Download PDF Status: Published Journal Publication published 20 Jun, 2024 Read the published version in Communications Chemistry → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-3894708","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":269077747,"identity":"3c245fc3-18bd-44c3-8354-8813e742b063","order_by":0,"name":"Madasamy 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In this work, we employ a solvent/ligand/counterion-free method to deposit copper in the atomic form directly onto a nanotextured surface of graphitized carbon nanofibers (GNFs). Our results demonstrate that under these conditions, copper atoms coalesce into nanoparticles securely anchored to the graphitic step edges, limiting their growth to 2–5 nm. The resultant hybrid Cu/GNF material displays remarkable electrocatalytic properties in CO\u003csub\u003e2\u003c/sub\u003e reduction reaction (CO\u003csub\u003e2\u003c/sub\u003eRR), exhibiting selectivity for formate production with a faradaic efficiency of ~ 94% at a low overpotential of 0.17 V and an exceptionally high turnover frequency of 2.78×10\u003csup\u003e6\u003c/sup\u003e h\u003csup\u003e− 1\u003c/sup\u003e. The Cu nanoparticles adhered to the graphitic step edges significantly enhance electron transfer to CO\u003csub\u003e2\u003c/sub\u003e, with the formation of CO\u003csub\u003e2\u003c/sub\u003e∙− intermediate identifiedas the rate-determining step. Long-term CO\u003csub\u003e2\u003c/sub\u003eRR tests coupled with atomic-scale elucidation of changes in Cu/GNF reveal nanoparticles coarsening, and a simultaneous increase in the fraction of single Cu atoms. These changes disfavour CO\u003csub\u003e2\u003c/sub\u003eRR, as confirmed by density functional theory calculations, revealing that CO\u003csub\u003e2\u003c/sub\u003e cannot effectively compete with H\u003csub\u003e2\u003c/sub\u003eO for adsorption on single Cu atoms on the graphitic surfaces.\u003c/p\u003e","manuscriptTitle":"Direct Deposition of Copper Atoms onto Graphitic Step Edges Lowers Overpotential and Improves Selectivity of Electrocatalytic CO2 Reduction","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-01-31 09:44:18","doi":"10.21203/rs.3.rs-3894708/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"communications-chemistry","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"commschem","sideBox":"Learn more about [Communications Chemistry](http://www.nature.com/commschem/)","snPcode":"","submissionUrl":"","title":"Communications Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Communications Series","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"59e58606-817d-4624-a941-02fede075df9","owner":[],"postedDate":"January 31st, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":28352371,"name":"Physical sciences/Chemistry/Catalysis/Electrocatalysis"},{"id":28352372,"name":"Physical sciences/Materials science/Materials for energy and catalysis/Electrocatalysis"},{"id":28352373,"name":"Physical sciences/Chemistry/Energy"},{"id":28352374,"name":"Physical sciences/Chemistry/Electrochemistry/Electrocatalysis"},{"id":28352375,"name":"Physical sciences/Chemistry/Catalysis/Heterogeneous catalysis"}],"tags":[],"updatedAt":"2024-06-21T07:08:59+00:00","versionOfRecord":{"articleIdentity":"rs-3894708","link":"https://doi.org/10.1038/s42004-024-01218-y","journal":{"identity":"communications-chemistry","isVorOnly":false,"title":"Communications Chemistry"},"publishedOn":"2024-06-20 04:00:00","publishedOnDateReadable":"June 20th, 2024"},"versionCreatedAt":"2024-01-31 09:44:18","video":"","vorDoi":"10.1038/s42004-024-01218-y","vorDoiUrl":"https://doi.org/10.1038/s42004-024-01218-y","workflowStages":[]},"version":"v1","identity":"rs-3894708","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3894708","identity":"rs-3894708","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}