{"paper_id":"23f3b887-b212-4333-95f4-41e508312dde","body_text":"Oxygen Evolution Catalysis by Manganese Oxides Resilient to Voltage Fluctuations | 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 Oxygen Evolution Catalysis by Manganese Oxides Resilient to Voltage Fluctuations Ryuhei Nakamura, Ailong Li, Hideshi Ooka, Shuang Kong, Kiyohiro Adachi, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5973633/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 20 Oct, 2025 Read the published version in Nature Sustainability → Version 1 posted You are reading this latest preprint version Abstract Renewable energy sources, such as solar and wind power, fluctuate on time scales of seconds to hours. Chemical synthesis powered by these sources requires electrocatalysts that can cope with fluctuating conditions. Here, we report an electrochemical oxygen evolution reaction (OER) system that is tolerant to voltage fluctuations through the design of catalytic pathways. By leveraging the redox chemistry of manganese oxide, we integrated the Guyard reaction (4Mn 3+ + Mn 7+ → 5Mn 3+ ) as a regeneration pathway into the catalytic cycle. Unlike other 3d-block metal catalysts, which rapidly degrade under fluctuating conditions, the constructed manganese oxide system shows resilience to voltage fluctuations by alternating between decomposition and regeneration. When the voltage is switched between 1.68 and 3.00 V repeatedly, the catalyst can maintain an OER current of 250 mA cm-2 at pH 2 for more than 2000 h, highlighting the importance of pathway design for sustainable energy conversion from intermittent renewable sources. Physical sciences/Chemistry/Catalysis/Electrocatalysis Physical sciences/Materials science/Materials for energy and catalysis/Electrocatalysis Full Text Additional Declarations There is NO Competing Interest. Supplementary Files CRNSI20250206.pdf Supplementary Information MovieS1WithoutregenerationunderfluctuationwithoutPi.mp4 Supplementary Video/Movie 1 MovieS2Withregenerationunderfluctuation.mp4 Supplementary Video/Movie 2 Cite Share Download PDF Status: Published Journal Publication published 20 Oct, 2025 Read the published version in Nature Sustainability → 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-5973633\",\"acceptedTermsAndConditions\":true,\"allowDirectSubmit\":false,\"archivedVersions\":[],\"articleType\":\"Article\",\"associatedPublications\":[],\"authors\":[{\"id\":419086738,\"identity\":\"7ce1e144-d90e-486d-a8e2-76393049d006\",\"order_by\":0,\"name\":\"Ryuhei Nakamura\",\"email\":\"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAABAElEQVRIiWNgGAWjYHACNgYGAyDFA+HJMTCzQUWJ1WJMpBYGhJbEBvyqGRjMZ+SYPfhQwJDH33P46WbePXbp29vZEh8XMPDl4dIicyPH3HCGAUOxxNk2s9s8z5Jz5xxmO2w8g4GtGJcWCYkcM2keA6B7zjMAtRxgzp3BzN4mzcPABnQhHi1/gFrmn2f/BtRSny7BzN7+m6AWYIglbjjbA7LlcIIEM9sxZrxaeJ6VSfYYSCRuPHOm7OacA8cNZzCzJQOdiscv7MnbJH78sUmcdyZ92403B6rlJfiPGX7mqTiGM8QYBBLAOtGFDY4l4NTCfwC7eA1uLaNgFIyCUTDSAABhYE3A5/fkJQAAAABJRU5ErkJggg==\",\"orcid\":\"https://orcid.org/0000-0003-0743-8534\",\"institution\":\"RIKEN Center for Sustainable Resource\",\"correspondingAuthor\":true,\"prefix\":\"\",\"firstName\":\"Ryuhei\",\"middleName\":\"\",\"lastName\":\"Nakamura\",\"suffix\":\"\"},{\"id\":419086739,\"identity\":\"aeb6fc59-6652-473a-8946-ace4fec2f73a\",\"order_by\":1,\"name\":\"Ailong Li\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"RIKEN\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Ailong\",\"middleName\":\"\",\"lastName\":\"Li\",\"suffix\":\"\"},{\"id\":419086740,\"identity\":\"1027da5b-692f-463c-8ffd-951eb010922b\",\"order_by\":2,\"name\":\"Hideshi Ooka\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"RIKEN\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Hideshi\",\"middleName\":\"\",\"lastName\":\"Ooka\",\"suffix\":\"\"},{\"id\":419086741,\"identity\":\"89e73d6e-7f1d-4c1f-8ca7-f030e1271129\",\"order_by\":3,\"name\":\"Shuang Kong\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"RIKEN\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Shuang\",\"middleName\":\"\",\"lastName\":\"Kong\",\"suffix\":\"\"},{\"id\":419086742,\"identity\":\"1fcb9f81-d9a8-4f00-bbf0-510ec0655acb\",\"order_by\":4,\"name\":\"Kiyohiro Adachi\",\"email\":\"\",\"orcid\":\"https://orcid.org/0000-0002-8224-8602\",\"institution\":\"RIKEN\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Kiyohiro\",\"middleName\":\"\",\"lastName\":\"Adachi\",\"suffix\":\"\"},{\"id\":419086743,\"identity\":\"27b4d464-66c6-4af6-8524-fa15add0b4ec\",\"order_by\":5,\"name\":\"Sun Hee Kim\",\"email\":\"\",\"orcid\":\"https://orcid.org/0000-0001-6557-1996\",\"institution\":\"Korea Basic Science Institute\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Sun\",\"middleName\":\"Hee\",\"lastName\":\"Kim\",\"suffix\":\"\"},{\"id\":419086744,\"identity\":\"42fa03bd-a451-48a7-8073-0e881e8b809b\",\"order_by\":6,\"name\":\"Daisuke Hashizume\",\"email\":\"\",\"orcid\":\"\",\"institution\":\"RIKEN\",\"correspondingAuthor\":false,\"prefix\":\"\",\"firstName\":\"Daisuke\",\"middleName\":\"\",\"lastName\":\"Hashizume\",\"suffix\":\"\"}],\"badges\":[],\"createdAt\":\"2025-02-06 12:45:14\",\"currentVersionCode\":1,\"declarations\":\"\",\"doi\":\"10.21203/rs.3.rs-5973633/v1\",\"doiUrl\":\"https://doi.org/10.21203/rs.3.rs-5973633/v1\",\"draftVersion\":[],\"editorialEvents\":[{\"content\":\"https://doi.org/10.1038/s41893-025-01665-y\",\"type\":\"published\",\"date\":\"2025-10-20T04:00:00+00:00\"}],\"editorialNote\":\"\",\"failedWorkflow\":false,\"files\":[{\"id\":93996761,\"identity\":\"15d32d22-5039-41e5-8857-499fa3c28a00\",\"added_by\":\"auto\",\"created_at\":\"2025-10-21 07:10:32\",\"extension\":\"pdf\",\"order_by\":1,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"manuscript-pdf\",\"size\":1997694,\"visible\":true,\"origin\":\"\",\"legend\":\"Article File\",\"description\":\"\",\"filename\":\"CRNMS20250206.pdf\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-5973633/v1_covered_b95510b1-d6ee-49b9-b676-47e4d9dd6760.pdf\"},{\"id\":79170067,\"identity\":\"16eb2ce1-29b3-49d9-bbf8-6cd40bbcf9cf\",\"added_by\":\"auto\",\"created_at\":\"2025-03-25 09:15:19\",\"extension\":\"pdf\",\"order_by\":1,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"supplement\",\"size\":953257,\"visible\":true,\"origin\":\"\",\"legend\":\"Supplementary Information\",\"description\":\"\",\"filename\":\"CRNSI20250206.pdf\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-5973633/v1/7481d5fdc63a708128846682.pdf\"},{\"id\":79168787,\"identity\":\"26d5bc7d-acc4-456b-9e66-e2c2a0e06f0a\",\"added_by\":\"auto\",\"created_at\":\"2025-03-25 09:07:20\",\"extension\":\"mp4\",\"order_by\":2,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"supplement\",\"size\":2433077,\"visible\":true,\"origin\":\"\",\"legend\":\"Supplementary Video/Movie 1\",\"description\":\"\",\"filename\":\"MovieS1WithoutregenerationunderfluctuationwithoutPi.mp4\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-5973633/v1/5fd66d06e7fd0ff8b3adb020.mp4\"},{\"id\":79168786,\"identity\":\"8207149b-3a97-43d0-8009-8a3a84a1242e\",\"added_by\":\"auto\",\"created_at\":\"2025-03-25 09:07:19\",\"extension\":\"mp4\",\"order_by\":3,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"supplement\",\"size\":3005380,\"visible\":true,\"origin\":\"\",\"legend\":\"Supplementary Video/Movie 2\",\"description\":\"\",\"filename\":\"MovieS2Withregenerationunderfluctuation.mp4\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-5973633/v1/c36e7bafe8ab11d5b5978c1a.mp4\"}],\"financialInterests\":\"There is \\u003cb\\u003eNO\\u003c/b\\u003e Competing Interest.\",\"formattedTitle\":\"Oxygen Evolution Catalysis by Manganese Oxides Resilient to Voltage Fluctuations\",\"fulltext\":[],\"fulltextSource\":\"\",\"fullText\":\"\",\"funders\":[],\"hasAdminPriorityOnWorkflow\":false,\"hasManuscriptDocX\":false,\"hasOptedInToPreprint\":true,\"hasPassedJournalQc\":\"\",\"hasAnyPriority\":true,\"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\":\"info@researchsquare.com\",\"identity\":\"nature-portfolio\",\"isNatureJournal\":true,\"hasQc\":false,\"allowDirectSubmit\":false,\"externalIdentity\":\"\",\"sideBox\":\"\",\"snPcode\":\"\",\"submissionUrl\":\"\",\"title\":\"Nature Portfolio\",\"twitterHandle\":\"\",\"acdcEnabled\":false,\"dfaEnabled\":false,\"editorialSystem\":\"ejp\",\"reportingPortfolio\":\"\",\"inReviewEnabled\":true,\"inReviewRevisionsEnabled\":false},\"keywords\":\"\",\"lastPublishedDoi\":\"10.21203/rs.3.rs-5973633/v1\",\"lastPublishedDoiUrl\":\"https://doi.org/10.21203/rs.3.rs-5973633/v1\",\"license\":{\"name\":\"CC BY 4.0\",\"url\":\"https://creativecommons.org/licenses/by/4.0/\"},\"manuscriptAbstract\":\"\\u003cp\\u003eRenewable energy sources, such as solar and wind power, fluctuate on time scales of seconds to hours. Chemical synthesis powered by these sources requires electrocatalysts that can cope with fluctuating conditions. Here, we report an electrochemical oxygen evolution reaction (OER) system that is tolerant to voltage fluctuations through the design of catalytic pathways. By leveraging the redox chemistry of manganese oxide, we integrated the Guyard reaction (4Mn\\u003csup\\u003e3+\\u003c/sup\\u003e + Mn\\u003csup\\u003e7+\\u003c/sup\\u003e → 5Mn\\u003csup\\u003e3+\\u003c/sup\\u003e) as a regeneration pathway into the catalytic cycle. Unlike other 3d-block metal catalysts, which rapidly degrade under fluctuating conditions, the constructed manganese oxide system shows resilience to voltage fluctuations by alternating between decomposition and regeneration. When the voltage is switched between 1.68 and 3.00 V repeatedly, the catalyst can maintain an OER current of 250 mA cm-2 at pH 2 for more than 2000 h, highlighting the importance of pathway design for sustainable energy conversion from intermittent renewable sources.\\u003c/p\\u003e\",\"manuscriptTitle\":\"Oxygen Evolution Catalysis by Manganese Oxides Resilient to Voltage Fluctuations\",\"msid\":\"\",\"msnumber\":\"\",\"nonDraftVersions\":[{\"code\":1,\"date\":\"2025-03-25 09:07:14\",\"doi\":\"10.21203/rs.3.rs-5973633/v1\",\"editorialEvents\":[],\"status\":\"published\",\"journal\":{\"display\":true,\"email\":\"info@researchsquare.com\",\"identity\":\"nature-sustainability\",\"isNatureJournal\":true,\"hasQc\":false,\"allowDirectSubmit\":false,\"externalIdentity\":\"natsustain\",\"sideBox\":\"Learn more about [Nature Sustainability](http://www.nature.com/natsustain/)\",\"snPcode\":\"\",\"submissionUrl\":\"\",\"title\":\"Nature Sustainability\",\"twitterHandle\":\"\",\"acdcEnabled\":true,\"dfaEnabled\":true,\"editorialSystem\":\"ejp\",\"reportingPortfolio\":\"Nature Research\",\"inReviewEnabled\":true,\"inReviewRevisionsEnabled\":false}}],\"origin\":\"\",\"ownerIdentity\":\"66b62ffe-efce-4bb0-96c5-732572aed5dc\",\"owner\":[],\"postedDate\":\"March 25th, 2025\",\"published\":true,\"recentEditorialEvents\":[],\"rejectedJournal\":[],\"revision\":\"\",\"amendment\":\"\",\"status\":\"published-in-journal\",\"subjectAreas\":[{\"id\":44685284,\"name\":\"Physical sciences/Chemistry/Catalysis/Electrocatalysis\"},{\"id\":44685285,\"name\":\"Physical sciences/Materials science/Materials for energy and catalysis/Electrocatalysis\"}],\"tags\":[],\"updatedAt\":\"2025-10-21T07:10:23+00:00\",\"versionOfRecord\":{\"articleIdentity\":\"rs-5973633\",\"link\":\"https://doi.org/10.1038/s41893-025-01665-y\",\"journal\":{\"identity\":\"nature-sustainability\",\"isVorOnly\":false,\"title\":\"Nature Sustainability\"},\"publishedOn\":\"2025-10-20 04:00:00\",\"publishedOnDateReadable\":\"October 20th, 2025\"},\"versionCreatedAt\":\"2025-03-25 09:07:14\",\"video\":\"\",\"vorDoi\":\"10.1038/s41893-025-01665-y\",\"vorDoiUrl\":\"https://doi.org/10.1038/s41893-025-01665-y\",\"workflowStages\":[]},\"version\":\"v1\",\"identity\":\"rs-5973633\",\"journalConfig\":\"researchsquare\"},\"__N_SSP\":true},\"page\":\"/article/[identity]/[[...version]]\",\"query\":{\"redirect\":\"/article/rs-5973633\",\"identity\":\"rs-5973633\",\"version\":[\"v1\"]},\"buildId\":\"8U1c8b4HqxoKbykW_rLl7\",\"isFallback\":false,\"isExperimentalCompile\":false,\"dynamicIds\":[84888],\"gssp\":true,\"scriptLoader\":[]}","source_license":"CC-BY-4.0","license_restricted":false}