Oxygen Vacancy Rich La-Doped NiFe₂O₄ as a Visible-Light Peroxydisulfate Activator for Rapid Degradation of Tetracycline

Oxygen Vacancy Rich La-Doped NiFe₂O₄ as a Visible-Light Peroxydisulfate Activator for Rapid Degradation of Tetracycline | 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 Oxygen Vacancy Rich La-Doped NiFe₂O₄ as a Visible-Light Peroxydisulfate Activator for Rapid Degradation of Tetracycline Prabal Barua, Nahida Nargis, Saeid Eslamian This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8194910/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 14 You are reading this latest preprint version Abstract Antibiotic residues in water are persistent and promote antimicrobial resistance, demanding efficient, solar-driven advanced oxidation. UV–Vis diffuse reflectance revealed a slight red shift and a narrowed band gap relative to NiFe₂O₄, while diminished PL intensity, smaller EIS semicircles, and higher transient photocurrent indicated suppressed recombination and improved charge transport. Under visible light (λ > 420 nm) with PDS (1 mM) and catalyst loadings of 0.2–0.3 g L⁻¹, NiLa₀․₂Fe₁․₈O₄ removed ∼90% TCH in 60 min and followed pseudo-first-order kinetics with an apparent rate constant ~ 1.5× that of pristine NiFe₂O₄. Optimal performance occurred at mildly acidic pH (~ 4); increasing initial TCH concentration slowed kinetics, and common anions, especially HCO₃⁻, partially inhibited degradation. Scavenger tests (EtOH, IPA, AO, BQ) identified SO₄•⁻ and •OH as the dominant oxidants, with contributions from h⁺ and O₂•⁻. The catalyst was magnetically recoverable and retained ~ 90% of its initial activity after four cycles; post-use XRD/XPS showed intact spinel and stable Ni/Fe/La valences with a modest decrease in surface-adsorbed oxygen. The synergy between oxygen-vacancy–rich surfaces and PDS activation under visible light underpins the high activity and durability. These findings position NiLa₀․₂Fe₁․₈O₄ as a practical, recyclable photocatalyst for antibiotic abatement and provide guidance for defect/dopant engineering of spinel ferrites for water remediation. Peroxydisulfate (persulfate PDS) activation Sulfate radicals (SO₄•⁻) Oxygen vacancies La-doped NiFe₂O₄ (NiLa₀.₂Fe₁.₈O₄) Spinel ferrite Tetracycline hydrochloride degradation Advanced oxidation processes (AOPs) Water remediation Full Text Additional Declarations No competing interests reported. Cite Share Download PDF Status: Under Review Version 1 posted Editorial decision: Revision requested 18 Dec, 2025 Reviews received at journal 16 Dec, 2025 Reviews received at journal 14 Dec, 2025 Reviews received at journal 10 Dec, 2025 Reviewers agreed at journal 08 Dec, 2025 Reviewers agreed at journal 05 Dec, 2025 Reviewers agreed at journal 04 Dec, 2025 Reviewers agreed at journal 03 Dec, 2025 Reviewers agreed at journal 03 Dec, 2025 Reviewers invited by journal 03 Dec, 2025 Editor assigned by journal 03 Dec, 2025 Editor invited by journal 02 Dec, 2025 Submission checks completed at journal 01 Dec, 2025 First submitted to journal 01 Dec, 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. 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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-8194910","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":555440823,"identity":"6de5ab8e-7ebc-46e9-bb6a-f129fe3ac569","order_by":0,"name":"Prabal 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Tetracycline","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":"discover-chemistry","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"Learn more about [Discover Chemistry](https://link.springer.com/journal/44371)","snPcode":"44371","submissionUrl":"https://submission.nature.com/new-submission/44371/3","title":"Discover Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Discover Series","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"Peroxydisulfate (persulfate, PDS) activation, Sulfate radicals (SO₄•⁻), Oxygen vacancies, La-doped NiFe₂O₄ (NiLa₀.₂Fe₁.₈O₄), Spinel ferrite, Tetracycline hydrochloride degradation, Advanced oxidation processes (AOPs), Water remediation","lastPublishedDoi":"10.21203/rs.3.rs-8194910/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8194910/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eAntibiotic residues in water are persistent and promote antimicrobial resistance, demanding efficient, solar-driven advanced oxidation. UV\u0026ndash;Vis diffuse reflectance revealed a slight red shift and a narrowed band gap relative to NiFe₂O₄, while diminished PL intensity, smaller EIS semicircles, and higher transient photocurrent indicated suppressed recombination and improved charge transport. Under visible light (λ\u0026thinsp;\u0026gt;\u0026thinsp;420 nm) with PDS (1 mM) and catalyst loadings of 0.2\u0026ndash;0.3 g L⁻\u0026sup1;, NiLa₀․₂Fe₁․₈O₄ removed \u0026sim;90% TCH in 60 min and followed pseudo-first-order kinetics with an apparent rate constant\u0026thinsp;~\u0026thinsp;1.5\u0026times; that of pristine NiFe₂O₄. Optimal performance occurred at mildly acidic pH (~\u0026thinsp;4); increasing initial TCH concentration slowed kinetics, and common anions, especially HCO₃⁻, partially inhibited degradation. Scavenger tests (EtOH, IPA, AO, BQ) identified SO₄\u0026bull;⁻ and \u0026bull;OH as the dominant oxidants, with contributions from h⁺ and O₂\u0026bull;⁻. The catalyst was magnetically recoverable and retained\u0026thinsp;~\u0026thinsp;90% of its initial activity after four cycles; post-use XRD/XPS showed intact spinel and stable Ni/Fe/La valences with a modest decrease in surface-adsorbed oxygen. The synergy between oxygen-vacancy\u0026ndash;rich surfaces and PDS activation under visible light underpins the high activity and durability. These findings position NiLa₀․₂Fe₁․₈O₄ as a practical, recyclable photocatalyst for antibiotic abatement and provide guidance for defect/dopant engineering of spinel ferrites for water remediation.\u003c/p\u003e","manuscriptTitle":"Oxygen Vacancy Rich La-Doped NiFe₂O₄ as a Visible-Light Peroxydisulfate Activator for Rapid Degradation of Tetracycline","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-12-05 14:34:15","doi":"10.21203/rs.3.rs-8194910/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-12-18T08:24:43+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-12-17T03:40:38+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-12-14T21:17:18+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-12-10T20:43:24+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"236509594038451598716892510995096937816","date":"2025-12-09T02:22:28+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"181499890241098351397123468382015194758","date":"2025-12-05T18:01:45+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"39427497591573451428097851336640264637","date":"2025-12-04T18:59:48+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"191740278921973391796445361968181783628","date":"2025-12-03T20:33:27+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"301385891066397533267641235221019850595","date":"2025-12-03T13:03:54+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-12-03T12:59:29+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-12-03T12:55:39+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"","date":"2025-12-02T15:50:24+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-12-01T13:42:03+00:00","index":"","fulltext":""},{"type":"submitted","content":"Discover Chemistry","date":"2025-12-01T13:05:41+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"discover-chemistry","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"Learn more about [Discover Chemistry](https://link.springer.com/journal/44371)","snPcode":"44371","submissionUrl":"https://submission.nature.com/new-submission/44371/3","title":"Discover Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Discover Series","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"610a8659-b720-46fe-b3de-98a8e08e94a1","owner":[],"postedDate":"December 5th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2026-04-20T15:40:17+00:00","versionOfRecord":[],"versionCreatedAt":"2025-12-05 14:34:15","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8194910","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8194910","identity":"rs-8194910","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}