Unraveling Strain Effects on Ammonia Synthesis over Ruthenium Catalysts via Density Functional Theory and Microkinetic Analysis

Unraveling Strain Effects on Ammonia Synthesis over Ruthenium Catalysts via Density Functional Theory and Microkinetic Analysis | 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 Unraveling Strain Effects on Ammonia Synthesis over Ruthenium Catalysts via Density Functional Theory and Microkinetic Analysis Jaemin Lee, Jinu Choi, Vladimir Efremov, Jong Suk Yoo This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8759732/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 04 Mar, 2026 Read the published version in Korean Journal of Chemical Engineering → Version 1 posted 4 You are reading this latest preprint version Abstract Strain engineering has emerged as a promising strategy for tuning heterogeneous catalyst performance, yet its specific influence on ammonia synthesis over ruthenium remains unclear due to concurrent support-induced effects. Here, density functional theory calculations combined with mean-field microkinetic modeling are used to examine the impact of ±5% biaxial strain on terrace Ru(0001) and stepped Ru(101̅0) surfaces. Tensile strain strengthens adsorption while compressive strain weakens it, with these trends governed by systematic shifts in d-band width. Because the stepped surface relaxes more readily, strain produces smaller energetic changes on Ru(101̅0) than on Ru(0001). Activation barriers follow Brønsted–Evans–Polanyi relationships: tensile strain lowers the barriers for N2 and H2 dissociation but raises those for NHx hydrogenation. Microkinetic analysis shows that N2 dissociation remains rate limiting on Ru(0001), whereas the RDS on Ru(101̅0) varies between NH2 hydrogenation and N2 dissociation depending on reaction conditions, leading to opposite TOF responses to strain across the two facets. When combined to represent a realistic 2– 4 nm Ru nanoparticle, overall activity follows the order pristine > tensile > compressive, indicating that unstrained surfaces yield the highest ammonia production. These results clarify how strain modifies reaction energetics and kinetics on Ru catalysts and provide a quantitative basis for evaluating strain engineering in ammonia synthesis. strain ruthenium ammonia synthesis density functional theory microkinetic modeling Full Text Cite Share Download PDF Status: Published Journal Publication published 04 Mar, 2026 Read the published version in Korean Journal of Chemical Engineering → Version 1 posted Reviewers agreed at journal 05 Feb, 2026 Reviewers invited by journal 05 Feb, 2026 Editor assigned by journal 04 Feb, 2026 First submitted to journal 01 Feb, 2026 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. 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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-8759732","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":586666956,"identity":"00a5f96a-86d9-46be-b5f6-d0c1f3e498d5","order_by":0,"name":"Jaemin Lee","email":"","orcid":"","institution":"University of Seoul","correspondingAuthor":false,"prefix":"","firstName":"Jaemin","middleName":"","lastName":"Lee","suffix":""},{"id":586666957,"identity":"9567ab32-f6f5-4724-a54f-f4d82bf552cc","order_by":1,"name":"Jinu Choi","email":"","orcid":"","institution":"University of Seoul","correspondingAuthor":false,"prefix":"","firstName":"Jinu","middleName":"","lastName":"Choi","suffix":""},{"id":586666958,"identity":"58abd3ac-aa97-46f9-8706-1227f8f365e2","order_by":2,"name":"Vladimir Efremov","email":"","orcid":"","institution":"University of Seoul","correspondingAuthor":false,"prefix":"","firstName":"Vladimir","middleName":"","lastName":"Efremov","suffix":""},{"id":586666959,"identity":"ec08d45b-3d22-4dad-a53c-ef3e5f0808d1","order_by":3,"name":"Jong Suk Yoo","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA0UlEQVRIiWNgGAWjYBACxgYQWcEmBxMwIFLLGT5j4rVA9LXJJTYQrYW5/4zhgw9nzNI3HG9/wPCjhsHYvIGAFsYZOcaGMyrScjecOWPA2HOMwUzmAEEtPGbSPGeO5W64kcPAwNvAYCNB0Bv9Z8ykedv+pxvcSH/A+JcoLQ05IC1sCQY3EgyYgbaYEdYyI63YcMYZNsOZQL8cljkmYUxQi2H/4Y0PPlSwyfMdb3/48E2NjeEMgloaOBAxcYCBgaAdDAzyDOwPCKsaBaNgFIyCkQ0A8T0906uSmEMAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0001-6472-7004","institution":"University of Seoul","correspondingAuthor":true,"prefix":"","firstName":"Jong","middleName":"Suk","lastName":"Yoo","suffix":""}],"badges":[],"createdAt":"2026-02-02 02:43:01","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-8759732/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-8759732/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s11814-026-00683-6","type":"published","date":"2026-03-04T15:57:35+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":104250873,"identity":"cc2f513a-4562-4a98-b389-ba940e6f17c0","added_by":"auto","created_at":"2026-03-09 16:11:02","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":685243,"visible":true,"origin":"","legend":"","description":"","filename":"ManuscriptKJChE.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8759732/v1_covered_45ef41d9-d324-4212-bb80-3e8523de9366.pdf"}],"financialInterests":"","formattedTitle":"Unraveling Strain Effects on Ammonia Synthesis over Ruthenium Catalysts via Density Functional Theory and Microkinetic Analysis","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"korean-journal-of-chemical-engineering","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"kjce","sideBox":"Learn more about [Korean Journal of Chemical Engineering](http://link.springer.com/journal/11814)","snPcode":"11814","submissionUrl":"https://www.editorialmanager.com/kjce/default2.aspx","title":"Korean Journal of Chemical Engineering","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Subscription","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"strain, ruthenium, ammonia synthesis, density functional theory, microkinetic modeling","lastPublishedDoi":"10.21203/rs.3.rs-8759732/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8759732/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"Strain engineering has emerged as a promising strategy for tuning heterogeneous catalyst performance, yet its specific influence on ammonia synthesis over ruthenium remains unclear due to concurrent support-induced effects. Here, density functional theory calculations combined with mean-field microkinetic modeling are used to examine the impact of ±5% biaxial strain on terrace Ru(0001) and stepped Ru(101̅0) surfaces. Tensile strain strengthens adsorption while compressive strain weakens it, with these trends governed by systematic shifts in d-band width. Because the stepped surface relaxes more readily, strain produces smaller energetic changes on Ru(101̅0) than on Ru(0001). Activation barriers follow Brønsted–Evans–Polanyi relationships: tensile strain lowers the barriers for N2 and H2 dissociation but raises those for NHx hydrogenation. Microkinetic analysis shows that N2 dissociation remains rate limiting on Ru(0001), whereas the RDS on Ru(101̅0) varies between NH2 hydrogenation and N2 dissociation depending on reaction conditions, leading to opposite TOF responses to strain across the two facets. When combined to represent a realistic 2– 4 nm Ru nanoparticle, overall activity follows the order pristine \u0026gt; tensile \u0026gt; compressive, indicating that unstrained surfaces yield the highest ammonia production. 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