Divergent performances of ZIF-67-derived Fe, Co, and FeCo catalysts in peroxymonosulfate activation: Mechanisms and application in ciprofloxacin degradation

Divergent performances of ZIF-67-derived Fe, Co, and FeCo catalysts in peroxymonosulfate activation: Mechanisms and application in ciprofloxacin degradation | 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 Divergent performances of ZIF-67-derived Fe, Co, and FeCo catalysts in peroxymonosulfate activation: Mechanisms and application in ciprofloxacin degradation Huanxuan Li, Xueheng Wei, Xing Gao, Chen Liu, Ning Li, Chen Xu, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7676782/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 20 Dec, 2025 Read the published version in Journal of Inorganic and Organometallic Polymers and Materials → Version 1 posted 14 You are reading this latest preprint version Abstract The degradation of antibiotics in wastewater treatment poses a major and persistent challenge. In this study, we report the use of zeolitic imidazolate framework-67 (ZIF-67), a metal–organic framework (MOF), as a precursor for synthesizing three distinct catalysts (ZIF-67(Fe)-800, ZIF-67(Co)-800, and ZIF-67(FeCo)-800) through pyrolysis. These catalysts were employed to activate peroxymonosulfate (PMS) for ciprofloxacin (CIP) degradation. Strikingly divergent catalytic performances were observed, with CIP degradation rate constants of 0.0027, 0.0731, and 0.0504 min –1 for ZIF-67(Fe)-800, ZIF-67(Co)-800, and ZIF-67(FeCo)-800, respectively. Compared to PMS activation, these catalysts showed significantly reduced efficacy in activating peroxydisulfate and sodium percarbonate. Mechanistic investigations through electron paramagnetic resonance and quenching tests unambiguously identify hydroxyl radical ( · OH), sulfate radical (SO 4 •− ), and singlet oxygen ( 1 O 2 ) as the dominant reactive species in ZIF-67(Fe)-800/PMS and ZIF-67(Co)-800/PMS systems. The ZIF-67(FeCo)-800/PMS system exhibited distinct behavior, with SO 4 •− as the primary species accompanied by · OH, 1 O 2 , and superoxide radicals (O 2 •− ). Notably, H 2 PO 4 − and HCO 3 − exhibited strong inhibitory effects on CIP degradation, while SO 4 2− and CH 3 COO − leaded to modest rate enhancements. Our findings establish a rational framework for designing MOF-derived catalysts, demonstrating their superior efficacy in advanced oxidation processes for pharmaceutical pollutant removal. Peroxymonosulfate (PMS) ZIF-67 derived catalysts ciprofloxacin (CIP) catalytic mechanism Full Text Additional Declarations No competing interests reported. Supplementary Files Supplementarymaterialsclean.doc Cite Share Download PDF Status: Published Journal Publication published 20 Dec, 2025 Read the published version in Journal of Inorganic and Organometallic Polymers and Materials → Version 1 posted Editorial decision: Revision requested 13 Oct, 2025 Reviews received at journal 12 Oct, 2025 Reviews received at journal 08 Oct, 2025 Reviews received at journal 06 Oct, 2025 Reviewers agreed at journal 29 Sep, 2025 Reviews received at journal 27 Sep, 2025 Reviewers agreed at journal 25 Sep, 2025 Reviewers agreed at journal 24 Sep, 2025 Reviewers agreed at journal 24 Sep, 2025 Reviewers agreed at journal 23 Sep, 2025 Reviewers invited by journal 23 Sep, 2025 Editor assigned by journal 23 Sep, 2025 Submission checks completed at journal 23 Sep, 2025 First submitted to journal 22 Sep, 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. 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-7676782","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":524483147,"identity":"d3059599-4066-499c-a856-f0e9b4166738","order_by":0,"name":"Huanxuan Li","email":"","orcid":"","institution":"Hangzhou Dianzi University","correspondingAuthor":false,"prefix":"","firstName":"Huanxuan","middleName":"","lastName":"Li","suffix":""},{"id":524483148,"identity":"d3aaf4f5-1287-4ea2-a6be-0aea2bb62521","order_by":1,"name":"Xueheng Wei","email":"","orcid":"","institution":"Hangzhou Dianzi University","correspondingAuthor":false,"prefix":"","firstName":"Xueheng","middleName":"","lastName":"Wei","suffix":""},{"id":524483149,"identity":"4867d73a-162d-47ab-9c64-16ea86662b19","order_by":2,"name":"Xing Gao","email":"","orcid":"","institution":"China Aerospace Planning and Design Group Co., Ltd. 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degradation","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":"journal-of-inorganic-and-organometallic-polymers-and-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"joip","sideBox":"Learn more about [Journal of Inorganic and Organometallic Polymers and Materials](https://www.springer.com/journal/10904)","snPcode":"10904","submissionUrl":"https://submission.nature.com/new-submission/10904/3","title":"Journal of Inorganic and Organometallic Polymers and Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Peroxymonosulfate (PMS), ZIF-67 derived catalysts, ciprofloxacin (CIP), catalytic mechanism","lastPublishedDoi":"10.21203/rs.3.rs-7676782/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7676782/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe degradation of antibiotics in wastewater treatment poses a major and persistent challenge. In this study, we report the use of zeolitic imidazolate framework-67 (ZIF-67), a metal\u0026ndash;organic framework (MOF), as a precursor for synthesizing three distinct catalysts (ZIF-67(Fe)-800, ZIF-67(Co)-800, and ZIF-67(FeCo)-800) through pyrolysis. These catalysts were employed to activate peroxymonosulfate (PMS) for ciprofloxacin (CIP) degradation. Strikingly divergent catalytic performances were observed, with CIP degradation rate constants of 0.0027, 0.0731, and 0.0504 min\u003csup\u003e\u0026ndash;1\u003c/sup\u003e for ZIF-67(Fe)-800, ZIF-67(Co)-800, and ZIF-67(FeCo)-800, respectively. Compared to PMS activation, these catalysts showed significantly reduced efficacy in activating peroxydisulfate and sodium percarbonate. Mechanistic investigations through electron paramagnetic resonance and quenching tests unambiguously identify hydroxyl radical (\u003cb\u003e\u0026middot;\u003c/b\u003eOH), sulfate radical (SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e\u0026bull;\u0026minus;\u003c/sup\u003e), and singlet oxygen (\u003csup\u003e1\u003c/sup\u003eO\u003csub\u003e2\u003c/sub\u003e) as the dominant reactive species in ZIF-67(Fe)-800/PMS and ZIF-67(Co)-800/PMS systems. The ZIF-67(FeCo)-800/PMS system exhibited distinct behavior, with SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e\u0026bull;\u0026minus;\u003c/sup\u003e as the primary species accompanied by \u003cb\u003e\u0026middot;\u003c/b\u003eOH, \u003csup\u003e1\u003c/sup\u003eO\u003csub\u003e2\u003c/sub\u003e, and superoxide radicals (O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026bull;\u0026minus;\u003c/sup\u003e). Notably, H\u003csub\u003e2\u003c/sub\u003ePO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e and HCO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e exhibited strong inhibitory effects on CIP degradation, while SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e and CH\u003csub\u003e3\u003c/sub\u003eCOO\u003csup\u003e\u0026minus;\u003c/sup\u003e leaded to modest rate enhancements. Our findings establish a rational framework for designing MOF-derived catalysts, demonstrating their superior efficacy in advanced oxidation processes for pharmaceutical pollutant removal.\u003c/p\u003e","manuscriptTitle":"Divergent performances of ZIF-67-derived Fe, Co, and FeCo catalysts in peroxymonosulfate activation: Mechanisms and application in ciprofloxacin degradation","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-10-06 21:57:32","doi":"10.21203/rs.3.rs-7676782/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-10-13T07:09:11+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-10-13T03:54:07+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-10-08T12:48:42+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-10-06T06:47:06+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"319078033862920115065289724898565551599","date":"2025-09-29T08:12:56+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-09-27T07:23:19+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"218175859172008206441192699334746308744","date":"2025-09-26T02:05:58+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"241410938650841005299290266091707445171","date":"2025-09-24T11:23:37+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"200030787302632400632799553891196868520","date":"2025-09-24T08:28:11+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"223223053412873683757112122203974510643","date":"2025-09-24T02:10:58+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-09-24T01:30:37+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-09-23T12:53:15+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-09-23T05:58:35+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Inorganic and Organometallic Polymers and Materials","date":"2025-09-22T10:19:30+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"journal-of-inorganic-and-organometallic-polymers-and-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"joip","sideBox":"Learn more about [Journal of Inorganic and Organometallic Polymers and Materials](https://www.springer.com/journal/10904)","snPcode":"10904","submissionUrl":"https://submission.nature.com/new-submission/10904/3","title":"Journal of Inorganic and Organometallic Polymers and Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"3b06a5dc-840e-4152-b82e-fc052dce4f10","owner":[],"postedDate":"October 6th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-12-22T16:05:43+00:00","versionOfRecord":{"articleIdentity":"rs-7676782","link":"https://doi.org/10.1007/s10904-025-04130-7","journal":{"identity":"journal-of-inorganic-and-organometallic-polymers-and-materials","isVorOnly":false,"title":"Journal of Inorganic and Organometallic Polymers and Materials"},"publishedOn":"2025-12-20 15:57:49","publishedOnDateReadable":"December 20th, 2025"},"versionCreatedAt":"2025-10-06 21:57:32","video":"","vorDoi":"10.1007/s10904-025-04130-7","vorDoiUrl":"https://doi.org/10.1007/s10904-025-04130-7","workflowStages":[]},"version":"v1","identity":"rs-7676782","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7676782","identity":"rs-7676782","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}