Water motifs in zirconium metal-organic frameworks induced by nanoconfinement and hydrophilic adsorption sites

Water motifs in zirconium metal-organic frameworks induced by nanoconfinement and hydrophilic adsorption sites | 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 Water motifs in zirconium metal-organic frameworks induced by nanoconfinement and hydrophilic adsorption sites Veronique Van Speybroeck, Aran Lamaire, Sven Rogge, Jelle Wieme This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3749314/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 19 Nov, 2024 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract The intricate hydrogen bond network of water gives rise to various structures with anomalous properties at different thermodynamic conditions. Nanoconfinement can further modify the water structure and properties, and induce specific water motifs, which are instrumental for technological applications such as atmospheric water harvesting. However, so far, a causal relationship between nanoconfinement and the presence of specific hydrophilic adsorption sites is lacking, hampering the further design of nanostructured materials for water templating. Therefore, this work investigates the organisation of water in a series of zirconium-based metal-organic frameworks (MOFs), with varying topologies, pore sizes, and chemical composition, to extract design rules to shape water. The highly tuneable pores and hydrophilicity of MOFs makes them ideally suited for this purpose. We find that small nanopores favour orderly water clusters that nucleate at hydrophilic adsorption sites. Favourably positioning the secondary adsorption sites, hydrogen-bonded to the primary adsorption sites, allows larger clusters to form. To disentangle the importance of nanoconfinement and hydrophilic nucleation sites in this process, we introduce an analytical model with precise control of the adsorption sites. This sheds a new light on design parameters to induce specific water clusters and hydrogen-bonded networks, thus rationalising the application space of water in nanoconfinement. Physical sciences/Chemistry/Materials chemistry/Metal–organic frameworks Physical sciences/Materials science/Theory and computation/Computational methods Physical sciences/Chemistry/Theoretical chemistry/Structure prediction Full Text Additional Declarations There is NO Competing Interest. Supplementary Files SI.pdf Cite Share Download PDF Status: Published Journal Publication published 19 Nov, 2024 Read the published version in Nature Communications → 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-3749314","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":265880479,"identity":"0feb4191-488a-47f5-b76e-00ed1dab8cba","order_by":0,"name":"Veronique Van Speybroeck","email":"data:image/png;base64,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","orcid":"https://orcid.org/0000-0003-2206-178X","institution":"Ghent University","correspondingAuthor":true,"prefix":"","firstName":"Veronique","middleName":"Van","lastName":"Speybroeck","suffix":""},{"id":265880480,"identity":"4d31fad0-6c7d-430d-a835-3e97ce2ad9cd","order_by":1,"name":"Aran Lamaire","email":"","orcid":"https://orcid.org/0000-0003-0093-5490","institution":"Ghent University","correspondingAuthor":false,"prefix":"","firstName":"Aran","middleName":"","lastName":"Lamaire","suffix":""},{"id":265880481,"identity":"ecc5f314-dd41-4282-88b8-82ddacbc0fff","order_by":2,"name":"Sven Rogge","email":"","orcid":"https://orcid.org/0000-0003-4493-5708","institution":"Ghent University","correspondingAuthor":false,"prefix":"","firstName":"Sven","middleName":"","lastName":"Rogge","suffix":""},{"id":265880482,"identity":"4b09d432-b0e4-4253-bab0-fb2933dc34b0","order_by":3,"name":"Jelle Wieme","email":"","orcid":"https://orcid.org/0000-0002-4841-2608","institution":"Ghent University","correspondingAuthor":false,"prefix":"","firstName":"Jelle","middleName":"","lastName":"Wieme","suffix":""}],"badges":[],"createdAt":"2023-12-13 16:02:11","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3749314/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3749314/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41467-024-54358-z","type":"published","date":"2024-11-19T05:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":69326185,"identity":"533c22a3-5a01-423c-aa17-d75afa88d0b1","added_by":"auto","created_at":"2024-11-19 08:07:01","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2015701,"visible":true,"origin":"","legend":"","description":"","filename":"Article.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3749314/v1_covered_2be044df-25b2-4f15-8133-ba1c2691e2b2.pdf"},{"id":49344820,"identity":"3925c5aa-6030-4695-afc3-758e3fbb2044","added_by":"auto","created_at":"2024-01-09 04:10:54","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":21283306,"visible":true,"origin":"","legend":"","description":"","filename":"SI.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3749314/v1/525705d34f9aba672ec282f6.pdf"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Water motifs in zirconium metal-organic frameworks induced by nanoconfinement and hydrophilic adsorption sites","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":"[email protected]","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-3749314/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3749314/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"The intricate hydrogen bond network of water gives rise to various structures with anomalous properties at different thermodynamic conditions. Nanoconfinement can further modify the water structure and properties, and induce specific water motifs, which are instrumental for technological applications such as atmospheric water harvesting. However, so far, a causal relationship between nanoconfinement and the presence of specific hydrophilic adsorption sites is lacking, hampering the further design of nanostructured materials for water templating. Therefore, this work investigates the organisation of water in a series of zirconium-based metal-organic frameworks (MOFs), with varying topologies, pore sizes, and chemical composition, to extract design rules to shape water. The highly tuneable pores and hydrophilicity of MOFs makes them ideally suited for this purpose. We find that small nanopores favour orderly water clusters that nucleate at hydrophilic adsorption sites. Favourably positioning the secondary adsorption sites, hydrogen-bonded to the primary adsorption sites, allows larger clusters to form. To disentangle the importance of nanoconfinement and hydrophilic nucleation sites in this process, we introduce an analytical model with precise control of the adsorption sites. This sheds a new light on design parameters to induce specific water clusters and hydrogen-bonded networks, thus rationalising the application space of water in nanoconfinement.","manuscriptTitle":"Water motifs in zirconium metal-organic frameworks induced by nanoconfinement and hydrophilic adsorption sites","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-01-09 04:10:48","doi":"10.21203/rs.3.rs-3749314/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"caf1e7b3-dffb-4b53-a7f2-69a0d38a9cdd","owner":[],"postedDate":"January 9th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":28008984,"name":"Physical sciences/Chemistry/Materials chemistry/Metal\u0026#x2013;organic frameworks"},{"id":28008985,"name":"Physical sciences/Materials science/Theory and computation/Computational methods"},{"id":28008986,"name":"Physical sciences/Chemistry/Theoretical chemistry/Structure prediction"}],"tags":[],"updatedAt":"2024-11-19T08:06:52+00:00","versionOfRecord":{"articleIdentity":"rs-3749314","link":"https://doi.org/10.1038/s41467-024-54358-z","journal":{"identity":"nature-communications","isVorOnly":false,"title":"Nature Communications"},"publishedOn":"2024-11-19 05:00:00","publishedOnDateReadable":"November 19th, 2024"},"versionCreatedAt":"2024-01-09 04:10:48","video":"","vorDoi":"10.1038/s41467-024-54358-z","vorDoiUrl":"https://doi.org/10.1038/s41467-024-54358-z","workflowStages":[]},"version":"v1","identity":"rs-3749314","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3749314","identity":"rs-3749314","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}