CO2 Reduction with High Bulk Turnover Numbers at Small Overpotentials by a fac-Mn(bpy)(CO)3L Complex with a Redox-Active, Electron Reservoir Ligand

CO2 Reduction with High Bulk Turnover Numbers at Small Overpotentials by a fac-Mn(bpy)(CO)3L Complex with a Redox-Active, Electron Reservoir Ligand | 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 Research Article CO 2 Reduction with High Bulk Turnover Numbers at Small Overpotentials by a fac-Mn(bpy)(CO) 3 L Complex with a Redox-Active, Electron Reservoir Ligand Andy Galvez-Rodriguez, Octavio Martinez-Perez, Steven H. Bergens This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5784204/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The electrocatalytic CO 2 reduction reaction (CRR) is required to convert CO 2 into useful commodity chemicals with renewable energy thereby reducing global greenhouse gas emissions. We report significantly enhanced CRR activity by incorporating the s-donating, e - reservoir ligand Imdye (1-imidazole-2,4,6-tri(carbazol-9-yl)-3,5-dicyanobenzene) within the complex fac -[Mn I (bpy)(CO) 3 (Imdye)] + (bpy = 2,2'-bipyridine). The reduction potentials of Imdye, Mn I/0 , and CO 2 to CO are close, allowing the active catalyst [Mn 0 (bpy)(CO) 2 (Imdye - )] - to provide 2e - to CO 2 at small overpotentials. This system reduces CO 2 to CO with bulk turnover numbers up to 830 very near the CRR reduction potential. This CRR activity arose from Imdye promoting the CRR at small overpotentials, and from utilizing the electrooxidation of CH 3 OH/H 2 O to CO 2 , 6H + and 6e - at the Pt counter electrode, neutralizing pH changes from the CRR. These strategies will apply to most CRR electrocatalytic systems. Full Text Additional Declarations The authors declare no competing interests. Supplementary Files SupplementaryInformation.docx Cite Share Download PDF Status: Posted 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. 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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-5784204","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":399088375,"identity":"87a6f425-b6a7-4e5b-b2db-7792ac5b6c6e","order_by":0,"name":"Andy Galvez-Rodriguez","email":"","orcid":"","institution":"University of Alberta","correspondingAuthor":false,"prefix":"","firstName":"Andy","middleName":"","lastName":"Galvez-Rodriguez","suffix":""},{"id":399088376,"identity":"a436dc05-ec69-4ddb-82de-2a0a6872871d","order_by":1,"name":"Octavio Martinez-Perez","email":"","orcid":"","institution":"University of Alberta","correspondingAuthor":false,"prefix":"","firstName":"Octavio","middleName":"","lastName":"Martinez-Perez","suffix":""},{"id":399088377,"identity":"3e136784-7b4a-4565-9d19-1c3d7226540d","order_by":2,"name":"Steven H. 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We report significantly enhanced CRR activity by incorporating the s-donating, e\u003csup\u003e-\u003c/sup\u003e reservoir ligand Imdye (1-imidazole-2,4,6-tri(carbazol-9-yl)-3,5-dicyanobenzene) within the complex \u003cem\u003efac\u003c/em\u003e-[Mn\u003csup\u003eI\u003c/sup\u003e(bpy)(CO)\u003csub\u003e3\u003c/sub\u003e(Imdye)]\u003csup\u003e+\u003c/sup\u003e (bpy = 2,2'-bipyridine). The reduction potentials of Imdye, Mn\u003csup\u003eI/0\u003c/sup\u003e, and CO\u003csub\u003e2\u003c/sub\u003e to CO are close, allowing the active catalyst [Mn\u003csup\u003e0\u003c/sup\u003e(bpy)(CO)\u003csub\u003e2\u003c/sub\u003e(Imdye\u003csup\u003e-\u003c/sup\u003e)]\u003csup\u003e-\u003c/sup\u003e to provide 2e\u003csup\u003e-\u003c/sup\u003e to CO\u003csub\u003e2\u003c/sub\u003e at small overpotentials. This system reduces CO\u003csub\u003e2\u003c/sub\u003e to CO with bulk turnover numbers up to 830 very near the CRR reduction potential. This CRR activity arose from\u003cstrong\u003e \u003c/strong\u003eImdye promoting the CRR at small overpotentials, and from utilizing the electrooxidation of CH\u003csub\u003e3\u003c/sub\u003eOH/H\u003csub\u003e2\u003c/sub\u003eO to CO\u003csub\u003e2\u003c/sub\u003e, 6H\u003csup\u003e+\u003c/sup\u003e and 6e\u003csup\u003e-\u003c/sup\u003e at the Pt counter electrode, neutralizing pH changes from the CRR. These strategies will apply to most CRR electrocatalytic systems. \u0026nbsp;\u003c/p\u003e","manuscriptTitle":"CO2 Reduction with High Bulk Turnover Numbers at Small Overpotentials by a fac-Mn(bpy)(CO)3L Complex with a Redox-Active, Electron Reservoir Ligand","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-01-09 04:15:34","doi":"10.21203/rs.3.rs-5784204/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"a2d4c28a-2d97-4a67-879a-0d69e0836618","owner":[],"postedDate":"January 9th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2025-01-09T04:15:34+00:00","versionOfRecord":[],"versionCreatedAt":"2025-01-09 04:15:34","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-5784204","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5784204","identity":"rs-5784204","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}