Perimeter Power: Unveiling the Role of Ni-TiO2 Interface Sites in Enhancing Acetic Acid Ketonization Catalysis

Perimeter Power: Unveiling the Role of Ni-TiO2 Interface Sites in Enhancing Acetic Acid Ketonization Catalysis | 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 Perimeter Power: Unveiling the Role of Ni-TiO 2 Interface Sites in Enhancing Acetic Acid Ketonization Catalysis De Chen, Petter Tingelstad, Evangelos Smith, Nora Corneliussen, and 7 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7809779/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 Catalytic ketonization of biomass-derived carboxylic acids is a key step in upgrad- ing oxygenates, yet achieving high rates with stability on oxides remains challenging. We show that highly dispersed Ni on TiO2 creates Ni–Ti perimeter sites that markedly enhance acetic acid ketonization. A 0.25 wt% Ni/TiO2 catalyst exhibits a 2.3-fold higher turnover frequency than TiO2 at 623 K, while sustaining activity. XRD and TEM reveal no detectable Ni crystallites and CO chemisorption indicates high dispersion; in situ DRIFTS resolves distinct interfacial binding modes. Density functional theory attributes the rate enhancement to lowered barriers for α-C–H activation at Ni–Ti perimeters (0.72 eV) relative to pristine TiO2 (1.10 eV), consistent with kinetics showing accelerated rates and reduced deactivation. Activity displays a volcano-type dependence on Ni loading, reflecting a bifunctional adsorption synergy in which carbonyls bind at the Ni–TiO2 interface while methyl fragments coordinate to metallic Ni. The resulting perimeter environment stabilizes α-hydroxy enolate intermediates that drive efficient C–C coupling to ketone products. These findings establish perimeter engineered Ni/TiO2 as an effective platform for acetic-acid ketonization and provide design principles for robust catalysts that couple oxygenates under thermochemical conditions Scientific community and society/Energy and society/Energy access Business and commerce/Economics Full Text Additional Declarations There is NO Competing Interest. Supplementary Files manuscriptSI.pdf Supplementary Information 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-7809779","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":532779918,"identity":"0d97a2b0-7e0f-4b2f-bd23-b73c392f171b","order_by":0,"name":"De Chen","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAo0lEQVRIiWNgGAWjYDACCSD+QLIWxhkMBgwMbKRoYeYhSQv/7OZjj213/GEwl+89JsG4w4YIS+4cSzfOPWPAYNnGlybBeCaNsBYDiRwz6dw2AwaDYzxmEoxth4nRkv9N2pJELTls0owkaZG4kWYm2dtmzGNwLMfYIrGNCL/wz0h+JvGzTU7O4PAZwxsf24gIMRjgAZMJxGsYBaNgFIyCUYAPAADg6Cz5mrCG1QAAAABJRU5ErkJggg==","orcid":"","institution":"Norwegian University of Science and Technology","correspondingAuthor":true,"prefix":"","firstName":"De","middleName":"","lastName":"Chen","suffix":""},{"id":532779919,"identity":"73df884f-ee4e-4ba4-9025-98d4c19abba7","order_by":1,"name":"Petter Tingelstad","email":"","orcid":"","institution":"Norwegian University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Petter","middleName":"","lastName":"Tingelstad","suffix":""},{"id":532779920,"identity":"c10cbe9c-99bb-4999-a43b-3f04f2cb0046","order_by":2,"name":"Evangelos Smith","email":"","orcid":"","institution":"University of Wisconsin-Madison","correspondingAuthor":false,"prefix":"","firstName":"Evangelos","middleName":"","lastName":"Smith","suffix":""},{"id":532779921,"identity":"97412cf1-2e39-4097-9744-52cbb3971b23","order_by":3,"name":"Nora Corneliussen","email":"","orcid":"","institution":"Norwegian University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Nora","middleName":"","lastName":"Corneliussen","suffix":""},{"id":532779922,"identity":"bcf84105-951e-4d8a-9a88-616f061ed7ed","order_by":4,"name":"Pio Gramazio","email":"","orcid":"","institution":"Norwegian University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Pio","middleName":"","lastName":"Gramazio","suffix":""},{"id":532779923,"identity":"00c6e787-c966-409d-8c05-d938b5da6caf","order_by":5,"name":"Robert Peters","email":"","orcid":"","institution":"Norwegian University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Robert","middleName":"","lastName":"Peters","suffix":""},{"id":532779924,"identity":"5519de3f-003f-40df-818a-37abd88c5d55","order_by":6,"name":"Kishore Rajendran","email":"","orcid":"","institution":"Norwegian University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Kishore","middleName":"","lastName":"Rajendran","suffix":""},{"id":532779925,"identity":"d5d9e727-2272-42d2-bf84-2859d9ca6c75","order_by":7,"name":"Albert miró i Rovira","email":"","orcid":"","institution":"Norwegian University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Albert","middleName":"miró i","lastName":"Rovira","suffix":""},{"id":532779926,"identity":"4e57945e-96c7-443e-a390-60e25403a83a","order_by":8,"name":"Tomasz Skrzydlo","email":"","orcid":"","institution":"University of Stavanger","correspondingAuthor":false,"prefix":"","firstName":"Tomasz","middleName":"","lastName":"Skrzydlo","suffix":""},{"id":532779927,"identity":"26a783a3-333e-4a78-aace-5b3175e7223d","order_by":9,"name":"Wakshum Tucho","email":"","orcid":"","institution":"University of Stavanger","correspondingAuthor":false,"prefix":"","firstName":"Wakshum","middleName":"","lastName":"Tucho","suffix":""},{"id":532779928,"identity":"5987d490-c089-4dc0-ae9a-ef928b62c1a9","order_by":10,"name":"Manos Mavrikakis","email":"","orcid":"https://orcid.org/0000-0002-5293-5356","institution":"University of Wisconsin - Madison","correspondingAuthor":false,"prefix":"","firstName":"Manos","middleName":"","lastName":"Mavrikakis","suffix":""}],"badges":[],"createdAt":"2025-10-08 16:20:21","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-7809779/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-7809779/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":96917974,"identity":"e8362160-9574-4613-8f2c-672754a59fed","added_by":"auto","created_at":"2025-11-27 14:10:53","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4446046,"visible":true,"origin":"","legend":"Article File","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7809779/v1_covered_4bc1ca82-7863-415e-9a24-46e039a7b193.pdf"},{"id":94648644,"identity":"8036e6fc-cd5e-48b5-a6a0-f409de795600","added_by":"auto","created_at":"2025-10-29 09:10:23","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":1637472,"visible":true,"origin":"","legend":"Supplementary Information","description":"","filename":"manuscriptSI.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7809779/v1/2be3f1e0e9eb5c7e33f484b5.pdf"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"\u003cp\u003ePerimeter Power: Unveiling the Role of Ni-TiO\u003csub\u003e2\u003c/sub\u003e Interface Sites in Enhancing Acetic Acid Ketonization Catalysis\u003c/p\u003e","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"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 Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-7809779/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7809779/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"Catalytic ketonization of biomass-derived carboxylic acids is a key step in upgrad- ing oxygenates, yet achieving high rates with stability on oxides remains challenging. We show that highly dispersed Ni on TiO2 creates Ni–Ti perimeter sites that markedly enhance acetic acid ketonization. A 0.25 wt% Ni/TiO2 catalyst exhibits a 2.3-fold higher turnover frequency than TiO2 at 623 K, while sustaining activity. XRD and TEM reveal no detectable Ni crystallites and CO chemisorption indicates high dispersion; in situ DRIFTS resolves distinct interfacial binding modes. Density functional theory attributes the rate enhancement to lowered barriers for α-C–H activation at Ni–Ti perimeters (0.72 eV) relative to pristine TiO2 (1.10 eV), consistent with kinetics showing accelerated rates and reduced deactivation. Activity displays a volcano-type dependence on Ni loading, reflecting a bifunctional adsorption synergy in which carbonyls bind at the Ni–TiO2 interface while methyl fragments coordinate to metallic Ni. The resulting perimeter environment stabilizes α-hydroxy enolate intermediates that drive efficient C–C coupling to ketone products. These findings establish perimeter engineered Ni/TiO2 as an effective platform for acetic-acid ketonization and provide design principles for robust catalysts that couple oxygenates under thermochemical conditions","manuscriptTitle":"Perimeter Power: Unveiling the Role of Ni-TiO2 Interface Sites in Enhancing Acetic Acid Ketonization Catalysis","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-10-29 09:10:18","doi":"10.21203/rs.3.rs-7809779/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":"26feec5c-179d-4d40-a04e-3f86340e8702","owner":[],"postedDate":"October 29th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":57076579,"name":"Scientific community and society/Energy and society/Energy access"},{"id":57076580,"name":"Business and commerce/Economics"}],"tags":[],"updatedAt":"2025-11-26T10:56:41+00:00","versionOfRecord":[],"versionCreatedAt":"2025-10-29 09:10:18","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-7809779","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7809779","identity":"rs-7809779","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}