Ligating atom modulated metal-oxygen bonds for electrocatalytic water oxidation

Ligating atom modulated metal-oxygen bonds for electrocatalytic water oxidation | 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 Ligating atom modulated metal-oxygen bonds for electrocatalytic water oxidation Zhiyong Tang, Pengqi Yang, Hongjian Ge, Siyang Li, Caoyu Yang, and 16 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7749438/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract Applying a positive potential to break the metal-oxygen (M-O) bonds in the electrocatalysts is essential for generating active sites that boost oxygen evolution reaction (OER). However, precisely modulating the M-O binding energy in traditional transition metal oxides remains an insurmountable challenge due to their robust ionic bonds and inflexible lattices. Here we demonstrate that spatially arranged ligating atoms—structural motifs that coordinate the metal center—can serve as key regulators of M-O bonds. Using terephthalate-derived polydentate ligands, we construct metal-organic frameworks (MOFs), in which heterogeneous ligand fields systematically re-engineer the electronic landscape of cobalt in Co-O linkages. Combined theoretical prediction and experimental evidence establish a monotonic correlation between OER activity and the field strength of ligating atoms, following the order of amino-Co-MOF > hydroxy-Co-MOF > thio-Co-MOF. Specifically, the N-ligating atoms in amino-Co-MOF facilitate the dynamic evolution of Co centers from an octahedral Co(II) initial state to a planar Co(III) active state during electrocatalysis by selectively weakening Co-O interactions. Consequently, amino-Co-MOF achieves an ultrahigh activity of 3 A cm-2 at 1.75 V, as well as exceptional stability at 1 A cm-2 over 2,100 hours with a decay rate of only 0.012 mV/h, in the anion exchange membrane water electrolyzer, surpassing 2026 DOE performance targets. Physical sciences/Chemistry/Electrochemistry/Electrocatalysis Physical sciences/Materials science/Materials for energy and catalysis/Metal–organic frameworks Full Text Additional Declarations There is NO Competing Interest. Supplementary Files SupportingInformation.docx Supplementary Information Cite Share Download PDF Status: Under Review 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-7749438","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":523757015,"identity":"af774eb7-8b76-4a30-ad23-c1c8356e8e06","order_by":0,"name":"Zhiyong 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However, precisely modulating the M-O binding energy in traditional transition metal oxides remains an insurmountable challenge due to their robust ionic bonds and inflexible lattices. Here we demonstrate that spatially arranged ligating atoms—structural motifs that coordinate the metal center—can serve as key regulators of M-O bonds. Using terephthalate-derived polydentate ligands, we construct metal-organic frameworks (MOFs), in which heterogeneous ligand fields systematically re-engineer the electronic landscape of cobalt in Co-O linkages. Combined theoretical prediction and experimental evidence establish a monotonic correlation between OER activity and the field strength of ligating atoms, following the order of amino-Co-MOF \u003e hydroxy-Co-MOF \u003e thio-Co-MOF. Specifically, the N-ligating atoms in amino-Co-MOF facilitate the dynamic evolution of Co centers from an octahedral Co(II) initial state to a planar Co(III) active state during electrocatalysis by selectively weakening Co-O interactions. Consequently, amino-Co-MOF achieves an ultrahigh activity of 3 A cm-2 at 1.75 V, as well as exceptional stability at 1 A cm-2 over 2,100 hours with a decay rate of only 0.012 mV/h, in the anion exchange membrane water electrolyzer, surpassing 2026 DOE performance targets.","manuscriptTitle":"Ligating atom modulated metal-oxygen bonds for electrocatalytic water oxidation","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-10-03 08:21:42","doi":"10.21203/rs.3.rs-7749438/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-energy","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"nenergy","sideBox":"Learn more about [Nature Energy](http://www.nature.com/nenergy/)","snPcode":"","submissionUrl":"","title":"Nature Energy","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Research","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"55923253-5d97-44df-8a85-9112501cea25","owner":[],"postedDate":"October 3rd, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[{"id":55668977,"name":"Physical sciences/Chemistry/Electrochemistry/Electrocatalysis"},{"id":55668978,"name":"Physical sciences/Materials science/Materials for energy and catalysis/Metal\u0026#x2013;organic frameworks"}],"tags":[],"updatedAt":"2026-01-22T16:49:04+00:00","versionOfRecord":[],"versionCreatedAt":"2025-10-03 08:21:42","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-7749438","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7749438","identity":"rs-7749438","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}