Adsorptive Behavior of Poly (vinylidene fluoride) Membranes for the Recovery of Lignin-derived Hydrophobic Deep Eutectic Solvents

Adsorptive Behavior of Poly (vinylidene fluoride) Membranes for the Recovery of Lignin-derived Hydrophobic Deep Eutectic Solvents | 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 Adsorptive Behavior of Poly (vinylidene fluoride) Membranes for the Recovery of Lignin-derived Hydrophobic Deep Eutectic Solvents Odianosen I. Ewah, Yuxuan Zhang, Jian Shi, Isabel C. Escobar This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6909022/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 01 Sep, 2025 Read the published version in Scientific Reports → Version 1 posted 12 You are reading this latest preprint version Abstract Recently, membrane technology has gained significant traction as an energy-efficient alternative to traditional thermal processes for solvent recovery. Deep eutectic solvents (DESs) have emerged as sustainable alternatives to conventional organic solvents, yet a systematic methodology for selecting compatible membrane materials for their recovery remains underdeveloped. This study established a predictive framework for membrane material selection in hydrophobic DES applications using Hansen Solubility Parameters (HSP) with inverted criteria targeting materials with relative energy difference (RED) values greater than 1.0. Flat sheet membranes were fabricated via the non-solvent induced phase separation (NIPS) technique. Four NIPS fabricated polymer membranes were evaluated: polysulfone, cellulose acetate, polyvinylidene fluoride (PVDF) fabricated with polyethylene glycol (PEG) as a pore-forming agent, and polybenzimidazole (PBI). The HSP approach successfully predicted membrane-solvent compatibility, with polysulfone (RED = 0.6) and cellulose acetate (RED = 0.9) dissolving completely within 24 hours, while PVDF (RED = 1.9) and PBI (RED = 1.1) maintained structural integrity throughout a 7-day exposure period. Furthermore, PVDF demonstrated superior performance with minimal weight gain (3.0%), hydrophobic surface characteristics (122° water contact angle), and enhanced mechanical properties following DES exposure. Comprehensive chemical and morphological characterization confirmed PVDF's chemical stability and revealed a surface-selective interaction mechanism involving simultaneous PEG (pore-forming agent) extraction and DES component adsorption. Adsorption kinetics followed pseudo-first-order behavior with reversible characteristics, best described by the Temkin isotherm model (R² = 0.9987). PVDF membranes-maintained separation functionality with average lignin rejection (75.2 ± 7.69%) and demonstrated filtration permeability of 2.0 ± 0.34 LMH/bar. This methodology provides a rational approach for membrane selection in emerging solvent systems, contributing to the advancement of sustainable separation technologies for DES-based biomass processing applications. Physical sciences/Engineering Physical sciences/Materials science Hydrophobic deep eutectic solvents polyvinylidene fluoride Hansen solubility parameters membrane separations lignin separation adsorption kinetics solvent-resistant membranes Full Text Additional Declarations No competing interests reported. Supplementary Files PaperManuscriptSupplementaryMaterial.docx Cite Share Download PDF Status: Published Journal Publication published 01 Sep, 2025 Read the published version in Scientific Reports → Version 1 posted Editorial decision: Revision requested 28 Jul, 2025 Reviews received at journal 21 Jul, 2025 Reviews received at journal 21 Jul, 2025 Reviewers agreed at journal 16 Jul, 2025 Reviewers agreed at journal 14 Jul, 2025 Reviewers agreed at journal 11 Jul, 2025 Reviewers agreed at journal 30 Jun, 2025 Reviewers invited by journal 26 Jun, 2025 Editor invited by journal 26 Jun, 2025 Editor assigned by journal 25 Jun, 2025 Submission checks completed at journal 21 Jun, 2025 First submitted to journal 21 Jun, 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-6909022","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":476781549,"identity":"0a18b021-aa3c-4445-9011-ba8ea556cf6f","order_by":0,"name":"Odianosen I. Ewah","email":"","orcid":"","institution":"University of Kentucky","correspondingAuthor":false,"prefix":"","firstName":"Odianosen","middleName":"I.","lastName":"Ewah","suffix":""},{"id":476781550,"identity":"ac62c209-c799-45e7-ac57-c4a1106da3a5","order_by":1,"name":"Yuxuan Zhang","email":"","orcid":"","institution":"University of Kentucky","correspondingAuthor":false,"prefix":"","firstName":"Yuxuan","middleName":"","lastName":"Zhang","suffix":""},{"id":476781551,"identity":"15cfabc0-4a69-417b-a804-82a6d291c93b","order_by":2,"name":"Jian Shi","email":"","orcid":"","institution":"University of Kentucky","correspondingAuthor":false,"prefix":"","firstName":"Jian","middleName":"","lastName":"Shi","suffix":""},{"id":476781552,"identity":"4c2a9150-3bd7-4649-a235-f5122970224d","order_by":3,"name":"Isabel C. Escobar","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA9UlEQVRIiWNgGAWjYBACNjAqgLEZbBgkQEwegloM4FrSCGthQNNymLAWPv7Dzx58MGCQk28/fOzBzz3nE2fOSGB88LYNjxUSaeaGMwwYjA3OpKUb9jy7nThbIoHZcC5eLQxm0jwGDIkbJHjMJHgO3E6cJ5HAJs2LTwv/8W/SfwwY6ufP4DGT/HPgHEgL+2+8WhhyzKSB3k9guMEDtO7AAZDD2JjxapHIKTfsMZAw3AD0i7HMgWTjmT0PmyXnnMOtRb7/+LYHPyps5EEh9vDNATvZGceTD354U4ZbCxRIILEFEhsIqkcD/AdI1TEKRsEoGAXDHAAAI1JLNzdhkKkAAAAASUVORK5CYII=","orcid":"","institution":"University of Kentucky","correspondingAuthor":true,"prefix":"","firstName":"Isabel","middleName":"C.","lastName":"Escobar","suffix":""}],"badges":[],"createdAt":"2025-06-17 00:38:16","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6909022/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6909022/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41598-025-18164-x","type":"published","date":"2025-09-01T15:57:19+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":90827938,"identity":"c4cda1ff-c754-4dda-bc6e-0a4cd22669de","added_by":"auto","created_at":"2025-09-08 16:03:44","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2196945,"visible":true,"origin":"","legend":"","description":"","filename":"PaperManuscriptFinalDraftTem.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6909022/v1_covered_f4178753-80ad-490f-8510-bb5e870a5bec.pdf"},{"id":85748092,"identity":"16ab2c16-c1cf-4024-bc53-0cca99f792e9","added_by":"auto","created_at":"2025-07-01 09:43:27","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":1399221,"visible":true,"origin":"","legend":"","description":"","filename":"PaperManuscriptSupplementaryMaterial.docx","url":"https://assets-eu.researchsquare.com/files/rs-6909022/v1/9bb5909bd5fd2e0480fdfe37.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Adsorptive Behavior of Poly (vinylidene fluoride) Membranes for the Recovery of Lignin-derived Hydrophobic Deep Eutectic Solvents","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":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"Hydrophobic deep eutectic solvents, polyvinylidene fluoride, Hansen solubility parameters, membrane separations, lignin separation, adsorption kinetics, solvent-resistant membranes","lastPublishedDoi":"10.21203/rs.3.rs-6909022/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6909022/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eRecently, membrane technology has gained significant traction as an energy-efficient alternative to traditional thermal processes for solvent recovery. Deep eutectic solvents (DESs) have emerged as sustainable alternatives to conventional organic solvents, yet a systematic methodology for selecting compatible membrane materials for their recovery remains underdeveloped. This study established a predictive framework for membrane material selection in hydrophobic DES applications using Hansen Solubility Parameters (HSP) with inverted criteria targeting materials with relative energy difference (RED) values greater than 1.0. Flat sheet membranes were fabricated via the non-solvent induced phase separation (NIPS) technique. Four NIPS fabricated polymer membranes were evaluated: polysulfone, cellulose acetate, polyvinylidene fluoride (PVDF) fabricated with polyethylene glycol (PEG) as a pore-forming agent, and polybenzimidazole (PBI). The HSP approach successfully predicted membrane-solvent compatibility, with polysulfone (RED\u0026thinsp;=\u0026thinsp;0.6) and cellulose acetate (RED\u0026thinsp;=\u0026thinsp;0.9) dissolving completely within 24 hours, while PVDF (RED\u0026thinsp;=\u0026thinsp;1.9) and PBI (RED\u0026thinsp;=\u0026thinsp;1.1) maintained structural integrity throughout a 7-day exposure period. Furthermore, PVDF demonstrated superior performance with minimal weight gain (3.0%), hydrophobic surface characteristics (122\u0026deg; water contact angle), and enhanced mechanical properties following DES exposure. Comprehensive chemical and morphological characterization confirmed PVDF's chemical stability and revealed a surface-selective interaction mechanism involving simultaneous PEG (pore-forming agent) extraction and DES component adsorption. Adsorption kinetics followed pseudo-first-order behavior with reversible characteristics, best described by the Temkin isotherm model (R\u0026sup2; = 0.9987). PVDF membranes-maintained separation functionality with average lignin rejection (75.2\u0026thinsp;\u0026plusmn;\u0026thinsp;7.69%) and demonstrated filtration permeability of 2.0\u0026thinsp;\u0026plusmn;\u0026thinsp;0.34 LMH/bar. This methodology provides a rational approach for membrane selection in emerging solvent systems, contributing to the advancement of sustainable separation technologies for DES-based biomass processing applications.\u003c/p\u003e","manuscriptTitle":"Adsorptive Behavior of Poly (vinylidene fluoride) Membranes for the Recovery of Lignin-derived Hydrophobic Deep Eutectic Solvents","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-07-01 09:43:22","doi":"10.21203/rs.3.rs-6909022/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-07-28T18:45:09+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-07-22T03:50:28+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-07-21T08:59:58+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"113108276529635782622061522078270195437","date":"2025-07-17T01:45:05+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"91499888074985765928810112304058681010","date":"2025-07-14T11:08:46+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"217159315149393421869916617678649867928","date":"2025-07-11T14:58:04+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"307374084439871047828183592591377328096","date":"2025-06-30T12:51:22+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-06-26T06:00:20+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"","date":"2025-06-26T05:43:23+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-06-25T06:05:47+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-06-21T17:18:22+00:00","index":"","fulltext":""},{"type":"submitted","content":"Scientific Reports","date":"2025-06-21T17:14:20+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"1aeb6c7e-547d-47c3-8f4e-4839e89a8836","owner":[],"postedDate":"July 1st, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":50629078,"name":"Physical sciences/Engineering"},{"id":50629079,"name":"Physical sciences/Materials science"}],"tags":[],"updatedAt":"2025-09-08T15:59:40+00:00","versionOfRecord":{"articleIdentity":"rs-6909022","link":"https://doi.org/10.1038/s41598-025-18164-x","journal":{"identity":"scientific-reports","isVorOnly":false,"title":"Scientific Reports"},"publishedOn":"2025-09-01 15:57:19","publishedOnDateReadable":"September 1st, 2025"},"versionCreatedAt":"2025-07-01 09:43:22","video":"","vorDoi":"10.1038/s41598-025-18164-x","vorDoiUrl":"https://doi.org/10.1038/s41598-025-18164-x","workflowStages":[]},"version":"v1","identity":"rs-6909022","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6909022","identity":"rs-6909022","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}