Active site proximity regulates selectivity in ammonia oxidation reactions

Active site proximity regulates selectivity in ammonia oxidation reactions | 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 Active site proximity regulates selectivity in ammonia oxidation reactions Javier Ruiz-Martinez, Yan Wang, Polina Lavrik, Shouwei Zuo, Teng Li, and 8 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7320698/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 Metal-oxide catalysts have attracted significant attention in ammonia (NH 3 ) oxidation reactions, including selective catalytic reduction (SCR) of nitrogen oxides (NOx) and selective catalytic oxidation (SCO) of NH 3 . However, minimizing the formation of nitrous oxide (N 2 O) remains a key challenge. In this study, we demonstrate that the oxidation behavior and consequently N 2 O selectivity can be effectively tailored by controlling the nuclearity of supported metal oxides. Comparative studies between isolated Mn single sites and MnOx nanoclusters with similar oxidation states, coordination numbers, and supported in the same substrate, reveal that isolated Mn sites significantly suppressed the formation of N 2 O. In contrast, MnOx nanoclusters generate higher amounts of N 2 O. This structure-selectivity relationship extends beyond the Mn/TiO 2 system, with similar proximity-dependent behavior observed in Co- and Ni-oxide materials in NH3-SCR of NO reaction. These findings offer valuable insights for the rational design of metal-oxide catalysts with reduced N 2 O emissions in NH 3 oxidation processes. Physical sciences/Chemistry/Catalysis/Heterogeneous catalysis Physical sciences/Materials science/Materials for energy and catalysis/Porous materials Full Text Additional Declarations There is NO Competing Interest. Supplementary Files WangetalSupplementaryinformation.pdf 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-7320698","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":502854419,"identity":"ff762d4b-951e-466b-8b79-8ea158c2d2a9","order_by":0,"name":"Javier 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reactions","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"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":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-7320698/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7320698/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"Metal-oxide catalysts have attracted significant attention in ammonia (NH\u003csub\u003e3\u003c/sub\u003e) oxidation reactions, including selective catalytic reduction (SCR) of nitrogen oxides (NOx) and selective catalytic oxidation (SCO) of NH\u003csub\u003e3\u003c/sub\u003e. However, minimizing the formation of nitrous oxide (N\u003csub\u003e2\u003c/sub\u003eO) remains a key challenge. In this study, we demonstrate that the oxidation behavior and consequently N\u003csub\u003e2\u003c/sub\u003eO selectivity can be effectively tailored by controlling the nuclearity of supported metal oxides. Comparative studies between isolated Mn single sites and MnOx nanoclusters with similar oxidation states, coordination numbers, and supported in the same substrate, reveal that isolated Mn sites significantly suppressed the formation of N\u003csub\u003e2\u003c/sub\u003eO. In contrast, MnOx nanoclusters generate higher amounts of N\u003csub\u003e2\u003c/sub\u003eO. This structure-selectivity relationship extends beyond the Mn/TiO\u003csub\u003e2\u003c/sub\u003e system, with similar proximity-dependent behavior observed in Co- and Ni-oxide materials in NH3-SCR of NO reaction. These findings offer valuable insights for the rational design of metal-oxide catalysts with reduced N\u003csub\u003e2\u003c/sub\u003eO emissions in NH\u003csub\u003e3\u003c/sub\u003e oxidation processes.","manuscriptTitle":"Active site proximity regulates selectivity in ammonia oxidation reactions","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-08-21 07:32:33","doi":"10.21203/rs.3.rs-7320698/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"32c4a9d7-af1b-40b6-a65a-a54d8743b01f","owner":[],"postedDate":"August 21st, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[{"id":53414878,"name":"Physical sciences/Chemistry/Catalysis/Heterogeneous catalysis"},{"id":53414879,"name":"Physical sciences/Materials science/Materials for energy and catalysis/Porous materials"}],"tags":[],"updatedAt":"2026-04-16T06:57:24+00:00","versionOfRecord":[],"versionCreatedAt":"2025-08-21 07:32:33","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-7320698","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7320698","identity":"rs-7320698","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}