Combination of Porogen leaching approach and DLP 3D-printing method for fabrication of catalytic monolith with improved accessibility to catalyst

Combination of Porogen leaching approach and DLP 3D-printing method for fabrication of catalytic monolith with improved accessibility to catalyst | 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 Combination of Porogen leaching approach and DLP 3D-printing method for fabrication of catalytic monolith with improved accessibility to catalyst Mahdi Rahebi, Samahe Sadjadi, Amir Masood Rezadoust, Eric Monflier This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-9455905/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract To address shortcomings of 3D-printed catalysts and develop a monolithic catalyst with high efficiency and recyclability for Knoevenagel condensation, chemical functionalization and modification of 3D-printing process were combined as a dual approach. More accurately, halloysite clay was first functionalized with cyclodextrin-containing melamine-based polymer to form HPCD, which was applied as a support for immobilization of silicotungstic acid (SiW) and formation of HPCD-SiW. The electrostatic interactions of SiW with melamine moieties of polymer as well as formation of inclusion complex with cyclodextrin groups suppressed SiW leaching. HPCD-SiW was then 3D-printed to from a monolithic catalyst. To prevent from full coverage of HPCD-SiW within polymeric network and improve accessibility to HPCD-SiW, ethylene glycol (EG) was used as a porogen in the course of 3D-printing. This cost-effective porogen could be easily washed (leached) after printing to impart porosity to the final structure, 3D-HPCD-SiW-EG. Comparison of the features and activity of 3D-HPCD-SiW-EG and EG-free monolith confirmed efficiency of porogen-leaching approach for formation of pores in the 3D-HPCD-SiW-EG and superior activity of 3D-HPCD-SiW-EG, which was ascribed to the more exposed active sites in the former. Furthermore, high mechanical stability and minimal SiW leaching simplify catalyst recovery and improve its recyclability. 3D-printed catalyst Halloysite Silicotungstic acid Full Text Additional Declarations No competing interests reported. Supplementary Files SI.docx Cite Share Download PDF Status: Posted 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-9455905","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":633712111,"identity":"98a619bc-3187-443b-ab59-4b8e87d74b2f","order_by":0,"name":"Mahdi Rahebi","email":"","orcid":"","institution":"Iran Polymer and Petrochemical Institute","correspondingAuthor":false,"prefix":"","firstName":"Mahdi","middleName":"","lastName":"Rahebi","suffix":""},{"id":633712112,"identity":"55433b15-7bbd-4b85-a2de-6dd8439a9159","order_by":1,"name":"Samahe Sadjadi","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA20lEQVRIiWNgGAWjYLACHh4Gxjb2xgYGBgMQl7GBSC08B0nSAlImkUCkm+Qb2B9+eCNjJ9sn+bjtcUEBgzx/A3PbB3xaDA7wGEvO4Uk2bpNObDeeYcBgOOMAY/MMvFqArpLm4WFOBGppk+YxYGDcwMDYTMhhj3/z8NQntkkeBGuxJ6iF4QCDGdCWw4ltEoxgLYkEtRgc5jGznMNz3LiNB+wXieQZhwk5rL398Y23PdWy89uPP3tc8MfGth8ogt9hzEDM2ANmsgHZEhARwuAHXMsoGAWjYBSMAkwAANhyPpcoqlHJAAAAAElFTkSuQmCC","orcid":"","institution":"Iran Polymer and Petrochemical Institute","correspondingAuthor":true,"prefix":"","firstName":"Samahe","middleName":"","lastName":"Sadjadi","suffix":""},{"id":633712116,"identity":"7dd294c0-bd96-4537-b3e4-8c7b41c8ac95","order_by":2,"name":"Amir Masood Rezadoust","email":"","orcid":"","institution":"Iran Polymer and Petrochemical Institute","correspondingAuthor":false,"prefix":"","firstName":"Amir","middleName":"Masood","lastName":"Rezadoust","suffix":""},{"id":633712119,"identity":"b386c342-ba73-461a-94fb-dc8a62169ce4","order_by":3,"name":"Eric Monflier","email":"","orcid":"","institution":"Artois University","correspondingAuthor":false,"prefix":"","firstName":"Eric","middleName":"","lastName":"Monflier","suffix":""}],"badges":[],"createdAt":"2026-04-18 10:23:29","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-9455905/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-9455905/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":108492606,"identity":"695f10f0-613c-49ca-b149-586bfa2598f9","added_by":"auto","created_at":"2026-05-05 09:58:09","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1035591,"visible":true,"origin":"","legend":"","description":"","filename":"Prog.Add.Manuf.Ano.pdf","url":"https://assets-eu.researchsquare.com/files/rs-9455905/v1_covered_e41d818f-50c2-4fb9-a555-d975ee74ca7c.pdf"},{"id":108392797,"identity":"d6c2d39e-f7ca-4bb8-a032-a247d5be8e2d","added_by":"auto","created_at":"2026-05-04 07:18:06","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":341702,"visible":true,"origin":"","legend":"","description":"","filename":"SI.docx","url":"https://assets-eu.researchsquare.com/files/rs-9455905/v1/4b59f7d675bef8d213fbacc9.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Combination of Porogen leaching approach and DLP 3D-printing method for fabrication of catalytic monolith with improved accessibility to catalyst","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"3D-printed catalyst, Halloysite, Silicotungstic acid","lastPublishedDoi":"10.21203/rs.3.rs-9455905/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-9455905/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eTo address shortcomings of 3D-printed catalysts and develop a monolithic catalyst with high efficiency and recyclability for Knoevenagel condensation, chemical functionalization and modification of 3D-printing process were combined as a dual approach. More accurately, halloysite clay was first functionalized with cyclodextrin-containing melamine-based polymer to form HPCD, which was applied as a support for immobilization of silicotungstic acid (SiW) and formation of HPCD-SiW. The electrostatic interactions of SiW with melamine moieties of polymer as well as formation of inclusion complex with cyclodextrin groups suppressed SiW leaching. HPCD-SiW was then 3D-printed to from a monolithic catalyst. To prevent from full coverage of HPCD-SiW within polymeric network and improve accessibility to HPCD-SiW, ethylene glycol (EG) was used as a porogen in the course of 3D-printing. This cost-effective porogen could be easily washed (leached) after printing to impart porosity to the final structure, 3D-HPCD-SiW-EG. Comparison of the features and activity of 3D-HPCD-SiW-EG and EG-free monolith confirmed efficiency of porogen-leaching approach for formation of pores in the 3D-HPCD-SiW-EG and superior activity of 3D-HPCD-SiW-EG, which was ascribed to the more exposed active sites in the former. Furthermore, high mechanical stability and minimal SiW leaching simplify catalyst recovery and improve its recyclability.\u003c/p\u003e","manuscriptTitle":"Combination of Porogen leaching approach and DLP 3D-printing method for fabrication of catalytic monolith with improved accessibility to catalyst","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-05-04 07:17:59","doi":"10.21203/rs.3.rs-9455905/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"ae16831e-1a23-4f1a-ac94-343f8504e7d4","owner":[],"postedDate":"May 4th, 2026","published":true,"recentEditorialEvents":[{"type":"decision","content":"Revision requested","date":"2026-05-16T10:01:59+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-05-16T07:48:28+00:00","index":43,"fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-05-13T07:46:28+00:00","index":42,"fulltext":""},{"type":"reviewerAgreed","content":"252571872772579573842092346456510604221","date":"2026-05-06T02:19:11+00:00","index":41,"fulltext":""},{"type":"reviewerAgreed","content":"209694351053462666054131468013907421777","date":"2026-05-05T18:57:58+00:00","index":40,"fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-05-02T01:41:21+00:00","index":32,"fulltext":""},{"type":"reviewerAgreed","content":"50816927510975269987326900221425910624","date":"2026-05-01T12:52:34+00:00","index":31,"fulltext":""}],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2026-05-16T10:09:21+00:00","versionOfRecord":[],"versionCreatedAt":"2026-05-04 07:17:59","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-9455905","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-9455905","identity":"rs-9455905","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}