Enhancing Oxygen Reduction Reaction on Mn-Doped ZnO Catalysts: Structural, Electronic, and Mechanistic Insights for Selective Peroxide Production

Enhancing Oxygen Reduction Reaction on Mn-Doped ZnO Catalysts: Structural, Electronic, and Mechanistic Insights for Selective Peroxide Production | 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 Enhancing Oxygen Reduction Reaction on Mn-Doped ZnO Catalysts: Structural, Electronic, and Mechanistic Insights for Selective Peroxide Production Carlos A. Quiñones Martínez, Alannisse M. Santos-Rivera, Ninoshca M. García, and 8 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7518552/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 In this work, we investigate manganese-doped ZnO catalysts for the oxygen reduction reaction (ORR) in alkaline media, combining structural characterization, electrochemical analysis, and density functional theory (DFT) calculations. XRD confirms that Mn doping preserves the wurtzite ZnO structure while inducing lattice distortions and vibrational shifts indicative of manganese incorporation. XPS analysis reveals that Mn 3 ⁺ is the dominant surface species, which is confirmed by x-ray absorption and emission spectroscopic measurements. Electrochemically, Mn-doped ZnO exhibits enhanced catalytic performance, with increased limiting current density and slight improvements in onset potential compared to pure ZnO. DFT calculations indicate that, while the overall thermodynamics of peroxide formation remain similar, the incorporation of Mn significantly stabilizes the *–OOH intermediate, thereby reducing the energy requirement for this key step. Together, these findings demonstrate that manganese doping improves ORR activity by modifying the electronic structure and enhancing reaction kinetics, offering valuable insights for the design of efficient ZnO-based electrocatalysts for selective H₂O₂ production. Full Text Additional Declarations No competing interests reported. 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. 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-7518552","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":519688704,"identity":"fd12450d-3e14-4805-9ee2-44a806ec9df9","order_by":0,"name":"Carlos A. Quiñones Martínez","email":"","orcid":"","institution":"University of Puerto Rico at Humacao","correspondingAuthor":false,"prefix":"","firstName":"Carlos","middleName":"A. Quiñones","lastName":"Martínez","suffix":""},{"id":519688706,"identity":"07932c0b-39fc-4b28-9bf2-e9605ba8df56","order_by":1,"name":"Alannisse M. 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Production","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research 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XRD confirms that Mn doping preserves the wurtzite ZnO structure while inducing lattice distortions and vibrational shifts indicative of manganese incorporation. XPS analysis reveals that Mn\u003csup\u003e3\u003c/sup\u003e⁺ is the dominant surface species, which is confirmed by x-ray absorption and emission spectroscopic measurements. Electrochemically, Mn-doped ZnO exhibits enhanced catalytic performance, with increased limiting current density and slight improvements in onset potential compared to pure ZnO. DFT calculations indicate that, while the overall thermodynamics of peroxide formation remain similar, the incorporation of Mn significantly stabilizes the *\u0026ndash;OOH intermediate, thereby reducing the energy requirement for this key step. Together, these findings demonstrate that manganese doping improves ORR activity by modifying the electronic structure and enhancing reaction kinetics, offering valuable insights for the design of efficient ZnO-based electrocatalysts for selective H₂O₂ production.\u003c/p\u003e","manuscriptTitle":"Enhancing Oxygen Reduction Reaction on Mn-Doped ZnO Catalysts: Structural, Electronic, and Mechanistic Insights for Selective Peroxide Production","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-09-26 11:53:32","doi":"10.21203/rs.3.rs-7518552/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":"6b020941-7780-4401-968f-dd4b8cac7c9d","owner":[],"postedDate":"September 26th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2025-11-14T14:53:46+00:00","versionOfRecord":[],"versionCreatedAt":"2025-09-26 11:53:32","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-7518552","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7518552","identity":"rs-7518552","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}