{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,13]],"date-time":"2026-10-13T16:35:31Z","timestamp":1791909331924,"version":"4.3.4"},"reference-count":50,"publisher":"American Chemical Society (ACS)","issue":"35","license":[{"start":{"date-parts":[[2019,8,23]],"date-time":"2019-08-23T00:00:00Z","timestamp":1566518400000},"content-version":"vor","delay-in-days":14,"URL":"https:\/\/pubs.acs.org\/page\/policy\/authorchoice_ccbyncnd_termsofuse.html"}],"funder":[{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["DMR \u2013 1419807"],"award-info":[{"award-number":["DMR \u2013 1419807"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["DMR-1452612"],"award-info":[{"award-number":["DMR-1452612"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000015","name":"U.S. Department of Energy","doi-asserted-by":"publisher","award":["DE-AC02-06CH11357"],"award-info":[{"award-number":["DE-AC02-06CH11357"]}],"id":[{"id":"10.13039\/100000015","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/na","name":"J-WAFS","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2019,9,4]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>The reversible capture of water vapor at low humidity can enable transformative applications such as atmospheric water harvesting and heat transfer that uses water as a refrigerant, replacing environmentally detrimental hydro- and chloro-fluorocarbons. The driving force for these applications is governed by the relative humidity at which the pores of a porous material fill with water. Here, we demonstrate modulation of the onset of pore-filling in a family of metal\u2013organic frameworks with record water sorption capacities by employing anion exchange. Unexpectedly, the replacement of the structural bridging Cl\u2013 with the more hydrophilic anions F\u2013 and OH\u2013 does not induce pore-filling at lower relative humidity, whereas the introduction of the larger Br\u2013 results in a substantial shift toward lower relative humidity. We rationalize these results in terms of pore size modifications as well as the water hydrogen bonding structure based on detailed infrared spectroscopic measurements. Fundamentally, our data suggest that, in the presence of strong nucleation sites, the thermodynamic favorability of water pore-filling depends more strongly on the pore diameter and the interface between water in the center of the pore and water bound to the pore walls than the hydrophilicity of the pore wall itself. On the basis of these results, we report two materials that exhibit record water uptake capacities in their respective humidity regions and extended stability over 400 water adsorption\u2013desorption cycles.<\/jats:p>","DOI":"10.1021\/jacs.9b06246","type":"journal-article","created":{"date-parts":[[2019,8,9]],"date-time":"2019-08-09T19:49:33Z","timestamp":1565380173000},"page":"13858-13866","source":"Crossref","is-referenced-by-count":184,"title":["Record-Setting\nSorbents for Reversible Water Uptake\nby Systematic Anion Exchanges in Metal\u2013Organic Frameworks"],"prefix":"10.1021","volume":"141","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9890-1346","authenticated-orcid":true,"given":"Adam J.","family":"Rieth","sequence":"first","affiliation":[{"name":"Massachusetts Institute of Technology , , 77 Massachusetts Avenue , , ,","place":["Cambridge, Massachusetts, United States, 02139"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9475-2638","authenticated-orcid":true,"given":"Ashley M.","family":"Wright","sequence":"additional","affiliation":[{"name":"Massachusetts Institute of Technology , , 77 Massachusetts Avenue , , ,","place":["Cambridge, Massachusetts, United States, 02139"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Grigorii","family":"Skorupskii","sequence":"additional","affiliation":[{"name":"Massachusetts Institute of Technology , , 77 Massachusetts Avenue , , ,","place":["Cambridge, Massachusetts, United States, 02139"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jenna L.","family":"Mancuso","sequence":"additional","affiliation":[{"name":"University of Oregon , , , ,","place":["Eugene, Oregon, United States, 97403"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7132-768X","authenticated-orcid":true,"given":"Christopher H.","family":"Hendon","sequence":"additional","affiliation":[{"name":"University of Oregon , , , ,","place":["Eugene, Oregon, United States, 97403"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1262-1264","authenticated-orcid":true,"given":"Mircea","family":"Dinca\u0306","sequence":"additional","affiliation":[{"name":"Massachusetts Institute of Technology , , 77 Massachusetts Avenue , , ,","place":["Cambridge, Massachusetts, United States, 02139"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2019,8,9]]},"reference":[{"issue":"50","key":"2026090305123978400_cit1","doi-asserted-by":"publisher","first-page":"17591","DOI":"10.1021\/jacs.8b09655","article-title":"Tunable Metal\u2013Organic\nFrameworks\nEnable High-Efficiency Cascaded Adsorption Heat Pumps","volume":"140","author":"Rieth","year":"2018","journal-title":"J. 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Energy"},{"issue":"32","key":"2026090305123978400_cit5","doi-asserted-by":"publisher","first-page":"4775","DOI":"10.1002\/adma.201502418","article-title":"Design of Hydrophilic Metal Organic Framework Water Adsorbents for\nHeat Reallocation","volume":"27","author":"Cadiau","year":"2015","journal-title":"Adv. Mater."},{"issue":"5","key":"2026090305123978400_cit6","doi-asserted-by":"publisher","first-page":"790","DOI":"10.1021\/cm304055k","article-title":"Water Sorption Cycle Measurements on Functionalized\nMIL-101Cr for Heat Transformation Application","volume":"25","author":"Khutia","year":"2013","journal-title":"Chem. Mater."},{"issue":"20","key":"2026090305123978400_cit7","doi-asserted-by":"publisher","first-page":"10148","DOI":"10.1039\/C2JM15615F","article-title":"MIL-100(Al, Fe) as\nWater Adsorbents for Heat Transformation Purposes\u2500a Promising\nApplication","volume":"22","author":"Jeremias","year":"2012","journal-title":"J. Mater. 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Ed."},{"issue":"33","key":"2026090305123978400_cit29","doi-asserted-by":"publisher","first-page":"27868","DOI":"10.1021\/acsami.8b09333","article-title":"Tuning\nWater Sorption in Highly Stable Zr(IV)-Metal-Organic Frameworks through\nLocal Functionalization of Metal Clusters","volume":"10","author":"Zhang","year":"2018","journal-title":"ACS\nAppl. Mater. Interfaces"},{"issue":"7425","key":"2026090305123978400_cit30","doi-asserted-by":"publisher","first-page":"582","DOI":"10.1038\/nature11570","article-title":"Water Structural\nTransformation at Molecular Hydrophobic Interfaces","volume":"491","author":"Davis","year":"2012","journal-title":"Nature"},{"issue":"6849","key":"2026090305123978400_cit31","doi-asserted-by":"publisher","first-page":"802","DOI":"10.1038\/35090532","article-title":"Formation of Ordered\nIce Nanotubes inside Carbon Nanotubes","volume":"412","author":"Koga","year":"2001","journal-title":"Nature"},{"issue":"6149","key":"2026090305123978400_cit32","doi-asserted-by":"publisher","first-page":"1230444","DOI":"10.1126\/science.1230444","article-title":"The Chemistry and\nApplications of Metal-Organic Frameworks","volume":"341","author":"Furukawa","year":"2013","journal-title":"Science"},{"issue":"6","key":"2026090305123978400_cit33","doi-asserted-by":"publisher","first-page":"1588","DOI":"10.1021\/acs.accounts.9b00062","article-title":"Adsorption-Based Atmospheric Water\nHarvesting: Impact of Material and Component Properties on System-Level\nPerformance","volume":"52","author":"LaPotin","year":"2019","journal-title":"Acc. Chem. Res."},{"key":"2026090305123978400_cit34","doi-asserted-by":"publisher","first-page":"289","DOI":"10.1007\/s10450-005-5939-y","article-title":"Temperature\nEffect on Adsorption\/Desorption\nIsotherms for a Simple Fluid Confined within Various Nanopores","volume":"11","author":"Coasne","year":"2005","journal-title":"Adsorption"},{"key":"2026090305123978400_cit35","doi-asserted-by":"publisher","first-page":"97","DOI":"10.1351\/pac196306010097","article-title":"Fast Elementary\nSteps in Chemical Reaction Mechanisms","volume":"6","author":"Eigen","year":"1963","journal-title":"Pure\nAppl. Chem."},{"issue":"30","key":"2026090305123978400_cit36","doi-asserted-by":"publisher","first-page":"9401","DOI":"10.1021\/jacs.6b05723","article-title":"High and Reversible Ammonia Uptake\nin Mesoporous Azolate Metal-Organic Frameworks with Open Mn, Co, and\nNi Sites","volume":"138","author":"Rieth","year":"2016","journal-title":"J. Am. Chem. Soc."},{"issue":"9","key":"2026090305123978400_cit37","doi-asserted-by":"publisher","first-page":"3461","DOI":"10.1021\/jacs.8b00313","article-title":"Controlled\nGas Uptake in Metal-Organic Frameworks with\nRecord Ammonia Sorption","volume":"140","author":"Rieth","year":"2018","journal-title":"J. Am. Chem. Soc."},{"issue":"1","key":"2026090305123978400_cit38","doi-asserted-by":"publisher","first-page":"38","DOI":"10.1021\/jacs.7b10107","article-title":"Hydroxide Ligands Cooperate with Catalytic Centers\nin Metal-Organic Frameworks for Efficient Photocatalytic CO2 Reduction","volume":"140","author":"Wang","year":"2018","journal-title":"J. Am. Chem. Soc."},{"issue":"1","key":"2026090305123978400_cit39","doi-asserted-by":"publisher","first-page":"373","DOI":"10.1021\/ja01145a126","article-title":"The Determination\nof Pore Volume\nand Area Distributions in Porous Substances. I. Computations from\nNitrogen Isotherms","volume":"73","author":"Barrett","year":"1951","journal-title":"J. Am. Chem. Soc."},{"issue":"23","key":"2026090305123978400_cit40","doi-asserted-by":"publisher","first-page":"6267","DOI":"10.1021\/la970776m","article-title":"Application of Large Pore MCM-41\nMolecular Sieves To Improve Pore Size Analysis Using Nitrogen Adsorption\nMeasurements","volume":"13","author":"Kruk","year":"1997","journal-title":"Langmuir"},{"issue":"37","key":"2026090305123978400_cit41","doi-asserted-by":"publisher","first-page":"1704304","DOI":"10.1002\/adma.201704304","article-title":"Metal-Organic\nFrameworks for Water Harvesting from Air","volume":"30","author":"Lenzen","year":"2018","journal-title":"Adv.\nMater."},{"issue":"33","key":"2026090305123978400_cit42","doi-asserted-by":"publisher","first-page":"10437","DOI":"10.1021\/jacs.6b02635","article-title":"Water in Carbon Nanotubes:\nThe Peculiar Hydrogen Bond Network Revealed by Infrared Spectroscopy","volume":"138","author":"Dalla Bernardina","year":"2016","journal-title":"J. Am. Chem. Soc."},{"issue":"22","key":"2026090305123978400_cit43","doi-asserted-by":"publisher","first-page":"6329","DOI":"10.1039\/C6AN01717G","article-title":"Depth Profiles\nof Hydrogen Bound\nWater Molecule Types and Their Relation to Lipid and Protein Interaction\nin the Human Stratum Corneum: In Vivo","volume":"141","author":"Choe","year":"2016","journal-title":"Analyst"},{"issue":"37","key":"2026090305123978400_cit44","doi-asserted-by":"publisher","first-page":"12090","DOI":"10.1021\/ja057856u","article-title":"Unusual Hydrogen\nBonding in Water-Filled Carbon Nanotubes","volume":"128","author":"Byl","year":"2006","journal-title":"J.\nAm. Chem. Soc."},{"issue":"47","key":"2026090305123978400_cit45","doi-asserted-by":"publisher","first-page":"10754","DOI":"10.1021\/acs.jpcb.8b09910","article-title":"Disentangling\nCoupling Effects in\nthe Infrared Spectra of Liquid Water","volume":"122","author":"Hunter","year":"2018","journal-title":"J. Phys.\nChem. 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A"},{"issue":"3","key":"2026090305123978400_cit49","doi-asserted-by":"publisher","first-page":"1208","DOI":"10.1021\/acs.cgd.6b01597","article-title":"Synthesis\nof Highly Crystalline NH2-MIL-125 (Ti) with S-Shaped Water Isotherms\nfor Adsorption Heat Transformation","volume":"17","author":"Sohail","year":"2017","journal-title":"Cryst. Growth\nDes."},{"issue":"3","key":"2026090305123978400_cit50","doi-asserted-by":"publisher","first-page":"582","DOI":"10.1021\/acs.chemmater.7b04891","article-title":"AlPO-78: A 24-Layer\nABC-6 Aluminophosphate Synthesized Using a Simple Structure-Directing\nAgent","volume":"30","author":"Yuhas","year":"2018","journal-title":"Chem. 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