Photoexcited Hole and Electron-Polaron Entangled Photocatalytic Reaction on Metal Oxide Surface

Photoexcited Hole and Electron-Polaron Entangled Photocatalytic Reaction on Metal Oxide Surface | 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 Photoexcited Hole and Electron-Polaron Entangled Photocatalytic Reaction on Metal Oxide Surface Jin Zhao, Chang Gao, Shijing Tan, Weibin Chu, Bing Wang, Hrvoje Petek, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5603672/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 Analyzing dynamics at both temporal and spatial scales of surface photocarrier interactions is pivotal for optimizing the photocatalytic chemical activity. Taking the photocatalytic conversion of CH3OH to HCOOCH3 on TiO2 surface as a prototypical system, we elucidate the correlated time- and spatial- evolution of photoexcited electron-hole (e-h) pairs, defining the polaron-catalyzed molecule-surface chemistry at the ab initio theory level. The photocatalytic process is driven by two photoexcited holes, each inducing C-H bond cleavage via a proton coupled electron transfer (PCET). It leads to the formation of HCOOCH3, with a pair of protons adsorbed on bridge oxygen atoms and the release of two electrons, forming two small polarons. The entire reaction occurs on picosecond timescale. Photoexcited electrons do not directly participate in the reaction but form small polarons in TiO2 within tens of femtoseconds, which lowers reactant energy and suppress the photocatalytic efficiency. This study illuminates novel insights on the design and optimization of surface photocatalytic reactions. Physical sciences/Chemistry/Photochemistry/Photocatalysis Physical sciences/Chemistry/Physical chemistry/Electron transfer Physical sciences/Chemistry/Theoretical chemistry/Molecular dynamics Physical sciences/Chemistry/Surface chemistry Physical sciences/Physics/Chemical physics Full Text Additional Declarations There is NO Competing Interest. 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-5603672","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":391854779,"identity":"008c279c-9bce-4847-923e-87b1f818a48a","order_by":0,"name":"Jin Zhao","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA10lEQVRIiWNgGAWjYDACCRA2YJCDcpmJ12IMVU2sFiBIbCBai/zs5ocPLArupG84f/7gB4YK68QG9rMH8GphnHPM2EDC4FnuhhvJzBIMZ9ITG3jyEvBqYZZIMJOQMDgM1MLMxsDYdjixQYLHAK8WNon0byAt6QbnDwO1/CNCC49EDtiWBIMDyUAtDURokZDIKQb65bDhzBvJxhIJx9KN23hy8GuRn5G+8bHEn8PyfOcPPvzwocZatp/9DH4tIMAsAWMlgHxHUD0QMH4gRtUoGAWjYBSMXAAAD+c/FisDFLMAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0003-1346-5280","institution":"University of Science and Technology of China","correspondingAuthor":true,"prefix":"","firstName":"Jin","middleName":"","lastName":"Zhao","suffix":""},{"id":391854780,"identity":"dcb77d4b-c98f-4024-b3de-1237c46781ec","order_by":1,"name":"Chang Gao","email":"","orcid":"","institution":"University of Science and Technology of China","correspondingAuthor":false,"prefix":"","firstName":"Chang","middleName":"","lastName":"Gao","suffix":""},{"id":391854781,"identity":"b6f117af-1bfb-4fad-a8dd-9ff3fd1062f9","order_by":2,"name":"Shijing Tan","email":"","orcid":"https://orcid.org/0000-0002-8537-9528","institution":"University of Science and Technology of China","correspondingAuthor":false,"prefix":"","firstName":"Shijing","middleName":"","lastName":"Tan","suffix":""},{"id":391854782,"identity":"87ef72a7-4ae6-41ad-9b89-62e0cb8d0e56","order_by":3,"name":"Weibin Chu","email":"","orcid":"https://orcid.org/0000-0001-5951-0337","institution":"Fudan University","correspondingAuthor":false,"prefix":"","firstName":"Weibin","middleName":"","lastName":"Chu","suffix":""},{"id":391854783,"identity":"27d567cc-6296-4ce7-be97-39135f03ee72","order_by":4,"name":"Bing Wang","email":"","orcid":"https://orcid.org/0000-0002-2953-2196","institution":"Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China","correspondingAuthor":false,"prefix":"","firstName":"Bing","middleName":"","lastName":"Wang","suffix":""},{"id":391854784,"identity":"cee4e014-9825-4f9b-b282-8ba3fb23b78d","order_by":5,"name":"Hrvoje Petek","email":"","orcid":"https://orcid.org/0000-0001-9605-2590","institution":"University of Pittsburgh","correspondingAuthor":false,"prefix":"","firstName":"Hrvoje","middleName":"","lastName":"Petek","suffix":""},{"id":391854785,"identity":"992df5b3-9170-48e6-93e7-504f397ca05f","order_by":6,"name":"Qijing Zheng","email":"","orcid":"https://orcid.org/0000-0003-0022-3442","institution":"University of science and technology of China","correspondingAuthor":false,"prefix":"","firstName":"Qijing","middleName":"","lastName":"Zheng","suffix":""}],"badges":[],"createdAt":"2024-12-08 15:35:06","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5603672/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5603672/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Photoexcited Hole and Electron-Polaron Entangled Photocatalytic Reaction on Metal Oxide Surface","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-5603672/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5603672/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"Analyzing dynamics at both temporal and spatial scales of surface photocarrier interactions is pivotal for optimizing the photocatalytic chemical activity. Taking the photocatalytic conversion of CH3OH to HCOOCH3 on TiO2 surface as a prototypical system, we elucidate the correlated time- and spatial- evolution of photoexcited electron-hole (e-h) pairs, defining the polaron-catalyzed molecule-surface chemistry at the ab initio theory level. The photocatalytic process is driven by two photoexcited holes, each inducing C-H bond cleavage via a proton coupled electron transfer (PCET). It leads to the formation of HCOOCH3, with a pair of protons adsorbed on bridge oxygen atoms and the release of two electrons, forming two small polarons. The entire reaction occurs on picosecond timescale. Photoexcited electrons do not directly participate in the reaction but form small polarons in TiO2 within tens of femtoseconds, which lowers reactant energy and suppress the photocatalytic efficiency. This study illuminates novel insights on the design and optimization of surface photocatalytic reactions.","manuscriptTitle":"Photoexcited Hole and Electron-Polaron Entangled Photocatalytic Reaction on Metal Oxide Surface","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-12-19 06:43:46","doi":"10.21203/rs.3.rs-5603672/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":"bd23fcd7-c732-4047-a4f3-2383c13f47dd","owner":[],"postedDate":"December 19th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":41768161,"name":"Physical sciences/Chemistry/Photochemistry/Photocatalysis"},{"id":41768162,"name":"Physical sciences/Chemistry/Physical chemistry/Electron transfer"},{"id":41768163,"name":"Physical sciences/Chemistry/Theoretical chemistry/Molecular dynamics"},{"id":41768164,"name":"Physical sciences/Chemistry/Surface chemistry"},{"id":41768165,"name":"Physical sciences/Physics/Chemical physics"}],"tags":[],"updatedAt":"2025-01-31T09:45:47+00:00","versionOfRecord":[],"versionCreatedAt":"2024-12-19 06:43:46","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-5603672","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5603672","identity":"rs-5603672","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}