Unraveling the role of Fe and Ni in oxygen evolution reaction on pentlandite using three generations of computational surface models

Unraveling the role of Fe and Ni in oxygen evolution reaction on pentlandite using three generations of computational surface models | 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 Unraveling the role of Fe and Ni in oxygen evolution reaction on pentlandite using three generations of computational surface models Maksim Sokolov, Kai S. Exner This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7096145/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 22 Jan, 2026 Read the published version in npj Computational Materials → Version 1 posted 13 You are reading this latest preprint version Abstract Oxygen evolution reaction (OER) – 2H 2 O → O 2 + 4H + + 4e − – remains the primary bottleneck in electrochemical water splitting for green hydrogen production. Pentlandite, a bimetallic chalcogenide mineral, has recently shown promise under alkaline conditions, although the elementary processes at the atomic level remain largely unclear. Using density functional theory calculations, we report three generations of pentlandite surface models with varying complexity to decipher the contributions of Fe and Ni sites to OER activity. The first-generation model is based on the pristine pentlandite surface and purports that no OER catalytic activity is observed. The second-generation model takes surface coverage by adsorbed oxygen or hydroxyl into account and suggests that Fe corresponds to the active site in the OER. In contrast, the third-generation model considers not only the surface coverage but also the surface oxidation of pentlandite by exchanging lattice sulfur atoms with oxygen, as observed experimentally. Only this extension shows that both Fe and Ni sites are active centers for OER and that Fe and Ni exhibit distinct limiting steps depending on applied bias, as determined by a degree of span control analysis. Our results demonstrate that when assessing pentlandite with regard to OER, surface oxidation and coverage effects must be explicitly considered in addition to the mechanistic breadth. The reported modeling approach provides the basis for the rational design of next-generation catalysts by highlighting the importance of considering surface oxidation in the theoretical description of energy conversion processes. Physical sciences/Chemistry Physical sciences/Energy science and technology Physical sciences/Materials science DFT OER Pentlandite Theoretical Electrocatalysis Bimetallic Chalcogenide Full Text Additional Declarations No competing interests reported. Supplementary Files SIpnmechanismsandoxidationnpj.pdf Cite Share Download PDF Status: Published Journal Publication published 22 Jan, 2026 Read the published version in npj Computational Materials → Version 1 posted Editorial decision: Revision requested 18 Sep, 2025 Reviews received at journal 15 Sep, 2025 Reviews received at journal 01 Sep, 2025 Reviewers agreed at journal 01 Sep, 2025 Reviewers agreed at journal 26 Aug, 2025 Reviews received at journal 21 Aug, 2025 Reviewers agreed at journal 04 Aug, 2025 Reviewers agreed at journal 29 Jul, 2025 Reviewers agreed at journal 25 Jul, 2025 Reviewers invited by journal 23 Jul, 2025 Editor assigned by journal 22 Jul, 2025 Submission checks completed at journal 14 Jul, 2025 First submitted to journal 10 Jul, 2025 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. 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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-7096145","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":489773185,"identity":"47c85bea-2892-47a2-b56d-69cd7cb69e54","order_by":0,"name":"Maksim Sokolov","email":"","orcid":"","institution":"University Duisburg-Essen","correspondingAuthor":false,"prefix":"","firstName":"Maksim","middleName":"","lastName":"Sokolov","suffix":""},{"id":489773186,"identity":"67c1c55f-fc1a-4ac8-a3c4-f8ae8069b304","order_by":1,"name":"Kai S. 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Pentlandite, a bimetallic chalcogenide mineral, has recently shown promise under alkaline conditions, although the elementary processes at the atomic level remain largely unclear. Using density functional theory calculations, we report three generations of pentlandite surface models with varying complexity to decipher the contributions of Fe and Ni sites to OER activity. The first-generation model is based on the pristine pentlandite surface and purports that no OER catalytic activity is observed. The second-generation model takes surface coverage by adsorbed oxygen or hydroxyl into account and suggests that Fe corresponds to the active site in the OER. In contrast, the third-generation model considers not only the surface coverage but also the surface oxidation of pentlandite by exchanging lattice sulfur atoms with oxygen, as observed experimentally. Only this extension shows that both Fe and Ni sites are active centers for OER and that Fe and Ni exhibit distinct limiting steps depending on applied bias, as determined by a degree of span control analysis. Our results demonstrate that when assessing pentlandite with regard to OER, surface oxidation and coverage effects must be explicitly considered in addition to the mechanistic breadth. The reported modeling approach provides the basis for the rational design of next-generation catalysts by highlighting the importance of considering surface oxidation in the theoretical description of energy conversion processes.\u003c/p\u003e","manuscriptTitle":"Unraveling the role of Fe and Ni in oxygen evolution reaction on pentlandite using three generations of computational surface models","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-07-25 11:22:21","doi":"10.21203/rs.3.rs-7096145/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-09-18T16:57:57+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-09-15T21:27:58+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-09-01T18:30:28+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"294268090283322818682770345799935134975","date":"2025-09-01T18:26:17+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"33845267353645779525823603493603237961","date":"2025-08-26T21:25:54+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-08-21T19:51:59+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"242567715822607018063574816744730688859","date":"2025-08-04T14:33:22+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"159132938228789268952183485752908790033","date":"2025-07-29T16:08:39+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"294268090283322818682770345799935134975","date":"2025-07-25T13:03:19+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-07-23T12:55:24+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-07-22T19:38:18+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-07-14T14:28:43+00:00","index":"","fulltext":""},{"type":"submitted","content":"npj Computational Materials","date":"2025-07-10T21:16:01+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"npj-computational-materials","isNatureJournal":false,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"npjcompumats","sideBox":"Learn more about [npj Computational Materials](http://www.nature.com/npjcompumats/)","snPcode":"41524","submissionUrl":"https://mts-npjcompumats.nature.com/","title":"npj Computational Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"NPJ","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"b549b13f-1acf-4d2c-bfc5-85723997ada4","owner":[],"postedDate":"July 25th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":51998754,"name":"Physical sciences/Chemistry"},{"id":51998755,"name":"Physical sciences/Energy science and technology"},{"id":51998756,"name":"Physical sciences/Materials science"}],"tags":[],"updatedAt":"2026-01-26T16:12:28+00:00","versionOfRecord":{"articleIdentity":"rs-7096145","link":"https://doi.org/10.1038/s41524-026-01961-x","journal":{"identity":"npj-computational-materials","isVorOnly":false,"title":"npj Computational Materials"},"publishedOn":"2026-01-22 15:58:22","publishedOnDateReadable":"January 22nd, 2026"},"versionCreatedAt":"2025-07-25 11:22:21","video":"","vorDoi":"10.1038/s41524-026-01961-x","vorDoiUrl":"https://doi.org/10.1038/s41524-026-01961-x","workflowStages":[]},"version":"v1","identity":"rs-7096145","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7096145","identity":"rs-7096145","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}