The effect of copper species ratio in Cu/SiO 2 catalyst on its performance in dehydrogenation of sec-butanol

The effect of copper species ratio in Cu/SiO 2 catalyst on its performance in dehydrogenation of sec-butanol | 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 The effect of copper species ratio in Cu/SiO 2 catalyst on its performance in dehydrogenation of sec-butanol Li Zhang, Yunqi Shi, Bingrui He, Xuanyuan Wang, Siyuan Wang, Ziyao Zhao, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7732290/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 A series of Cu/SiO 2 catalyst precursor were prepared via the impregnation method using fumed silica as the support. The precursor was reduced to be applied to the dehydrogenation of sec-butanol (SBA) to methyl ethyl ketone (MEK). The contents of various copper species in the catalysts were quantitatively analyzed to elucidate the correlation between copper species ratio and catalytic performance. Furthermore, DFT calculations were carried out using both pure Cu 0 and Cu 0 /Cu + composite models to investigate the reaction mechanism. The results indicate that the reduction conditions significantly influence the composition of copper species and the catalytic behavior. Increasing of reduction temperature and time leads to higher Cu 0 content, lower Cu + content, decreased conversion of sec-butanol, and increased selectivity toward MEK. The highest catalytic performance was achieved when the ratio of Cu 0 to Cu + approaches 3:1, leading to an MEK yield of 98.2%. DFT calculations reveal that the preferred reaction pathway involves initial O-H bond cleavage to form an alkoxy intermediate, followed by dehydrogenation at the β-carbon (β-C) to produce MEK. The rupture of the O-H bond was identified as the rate-determining step. Compared to the pure Cu 0 model, the Cu 0 /Cu + model exhibits strong adsorption energies for all the relevant species and lower reaction energy barriers, demonstrating that Cu + species play a promotive role and act synergistically with Cu 0 to enhance the dehydrogenation process. Copper-based catalyst sec-butanol methyl ethyl ketone dehydrogenation active site reduction conditions DFT Full Text Additional Declarations No competing interests reported. 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-7732290","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":528687398,"identity":"0a5b4e03-cc9c-42c8-bd0d-3fa1718a9cfb","order_by":0,"name":"Li Zhang","email":"","orcid":"","institution":"Shenyang University of Chemical Technology","correspondingAuthor":false,"prefix":"","firstName":"Li","middleName":"","lastName":"Zhang","suffix":""},{"id":528687403,"identity":"01755a6f-ca79-48d1-a32b-03ea89c8ec70","order_by":1,"name":"Yunqi Shi","email":"","orcid":"","institution":"Shenyang University of Chemical 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sec-butanol","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 Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Copper-based catalyst, sec-butanol, methyl ethyl ketone, dehydrogenation, active site, reduction conditions, DFT","lastPublishedDoi":"10.21203/rs.3.rs-7732290/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7732290/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eA series of Cu/SiO\u003csub\u003e2\u003c/sub\u003e catalyst precursor were prepared via the impregnation method using fumed silica as the support. The precursor was reduced to be applied to the dehydrogenation of sec-butanol (SBA) to methyl ethyl ketone (MEK). The contents of various copper species in the catalysts were quantitatively analyzed to elucidate the correlation between copper species ratio and catalytic performance. Furthermore, DFT calculations were carried out using both pure Cu\u003csup\u003e0\u003c/sup\u003e and Cu\u003csup\u003e0\u003c/sup\u003e/Cu\u003csup\u003e+\u003c/sup\u003e composite models to investigate the reaction mechanism. The results indicate that the reduction conditions significantly influence the composition of copper species and the catalytic behavior. Increasing of reduction temperature and time leads to higher Cu\u003csup\u003e0\u003c/sup\u003e content, lower Cu\u003csup\u003e+\u003c/sup\u003e content, decreased conversion of sec-butanol, and increased selectivity toward MEK. The highest catalytic performance was achieved when the ratio of Cu\u003csup\u003e0\u003c/sup\u003e to Cu\u003csup\u003e+\u003c/sup\u003e approaches 3:1, leading to an MEK yield of 98.2%. DFT calculations reveal that the preferred reaction pathway involves initial O-H bond cleavage to form an alkoxy intermediate, followed by dehydrogenation at the β-carbon (β-C) to produce MEK. The rupture of the O-H bond was identified as the rate-determining step. Compared to the pure Cu\u003csup\u003e0\u003c/sup\u003e model, the Cu\u003csup\u003e0\u003c/sup\u003e/Cu\u003csup\u003e+\u003c/sup\u003e model exhibits strong adsorption energies for all the relevant species and lower reaction energy barriers, demonstrating that Cu\u003csup\u003e+\u003c/sup\u003e species play a promotive role and act synergistically with Cu\u003csup\u003e0\u003c/sup\u003e to enhance the dehydrogenation process.\u003c/p\u003e","manuscriptTitle":"The effect of copper species ratio in Cu/SiO 2 catalyst on its performance in dehydrogenation of sec-butanol","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-10-16 18:31:33","doi":"10.21203/rs.3.rs-7732290/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":"b42d3f22-eb80-40c8-898d-ad5c0b327e5a","owner":[],"postedDate":"October 16th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2025-10-21T07:53:49+00:00","versionOfRecord":[],"versionCreatedAt":"2025-10-16 18:31:33","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-7732290","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7732290","identity":"rs-7732290","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}