{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,31]],"date-time":"2026-08-31T09:18:16Z","timestamp":1788167896993,"version":"build-2803163510"},"reference-count":35,"publisher":"American Chemical Society (ACS)","issue":"33","license":[{"start":{"date-parts":[[2026,8,12]],"date-time":"2026-08-12T00:00:00Z","timestamp":1786492800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,8,12]],"date-time":"2026-08-12T00:00:00Z","timestamp":1786492800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,8,12]],"date-time":"2026-08-12T00:00:00Z","timestamp":1786492800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/100020994","name":"Centre national d'?tudes spatiales","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/100020994","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100004795","name":"Institut Universitaire de France","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/501100004795","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100010190","name":"Grand ?quipement National De Calcul Intensif","doi-asserted-by":"publisher","award":["A0180907613"],"award-info":[{"award-number":["A0180907613"]}],"id":[{"id":"10.13039\/501100010190","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100024807","name":"Centre Informatique National de l?Enseignement Sup?rieur","doi-asserted-by":"publisher","award":["A0180907613"],"award-info":[{"award-number":["A0180907613"]}],"id":[{"id":"10.13039\/501100024807","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/na","name":"Balard Plate-forme d?Analyses et de Caract?risations","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":[[2026,8,24]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Volatile siloxanes are persistent molecular contaminants in industrial gas streams and represent a significant concern in aerospace environments, where trace-level outgassing can lead to deposition on sensitive surfaces and performance degradation. While Metal\u2013Organic Frameworks (MOFs) have emerged as promising adsorbents for siloxane capture, the adsorption behavior of structurally distinct linear and cyclic siloxanes under dilute conditions remains poorly understood, particularly in relation to pore architecture-dependent mechanisms. Here, we combine very low-pressure gravimetric adsorption measurements at 303 K with Grand Canonical Monte Carlo (GCMC) simulations to investigate the adsorption of hexamethyldisiloxane (L2) and octamethylcyclotetrasiloxane (D4) in three MOFs with contrasting pore structures: PCN-777(Zr), DUT-4(Al), and MIL-101(Cr). The results indicate that siloxane adsorption is governed by distinct mechanistic regimes depending on framework topology rather than a single adsorption pathway. DUT-4(Al) exhibits a confinement-driven regime characterized by ultralow-pressure uptake and strong host\/guest interactions, associated with limited reversibility and enhanced retention, particularly for D4. PCN-777(Zr) follows a cooperative pore-filling regime at higher pressures, which limits its efficiency under trace conditions. MIL-101(Cr) displays intermediate adsorption onset with improved reversibility, resulting in a balanced uptake-regeneration behavior. Across all frameworks, D4 consistently adsorbs more strongly than L2, reflecting enhanced stabilization of cyclic siloxanes in confined environments, while remaining sensitive to pore architecture. Overall, this study provides a mechanistic description of siloxane adsorption in MOFs under trace conditions and highlights the role of pore topology in governing adsorption regimes and regenerability.<\/jats:p>","DOI":"10.1021\/acs.inorgchem.6c03471","type":"journal-article","created":{"date-parts":[[2026,8,12]],"date-time":"2026-08-12T10:02:00Z","timestamp":1786528920000},"page":"19612-19618","source":"Crossref","is-referenced-by-count":0,"title":["Framework-Dependent\nAdsorption Regimes of Linear and\nCyclic Siloxanes in Metal\u2013Organic Frameworks under Trace Concentrations"],"prefix":"10.1021","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6488-2001","authenticated-orcid":true,"given":"Pedro Freire","family":"Bra\u0302ntuas","sequence":"first","affiliation":[{"name":"Institut Charles Gerhardt Montpellier (ICGM), UMR 5253 \u2212 CNRS\/UM\/ENSCM, Pole Chimie Balard Recherche , ,","place":["Montpellier Cedex 5, France, 34293"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Joy","family":"Ekka","sequence":"additional","affiliation":[{"name":"Institut Charles Gerhardt Montpellier (ICGM), UMR 5253 \u2212 CNRS\/UM\/ENSCM, Pole Chimie Balard Recherche , ,","place":["Montpellier Cedex 5, France, 34293"]},{"name":"Centre National d\u2019Etudes Spatiales , , 18 Avenue Edouard Belin , ,","place":["Toulouse Cedex 09, France, 31401"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ezgi","family":"Gulcay-Ozcan","sequence":"additional","affiliation":[{"name":"Institut Charles Gerhardt Montpellier (ICGM), UMR 5253 \u2212 CNRS\/UM\/ENSCM, Pole Chimie Balard Recherche , ,","place":["Montpellier Cedex 5, France, 34293"]},{"name":"Sabanc\u0131 U\u0308niversitesi , Orta Mahalle, , ,","place":["Tuzla, I\u0307stanbul, Turkey, 34956"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guillaume","family":"Rioland","sequence":"additional","affiliation":[{"name":"Centre National d\u2019Etudes Spatiales , , 18 Avenue Edouard Belin , ,","place":["Toulouse Cedex 09, France, 31401"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2096-0450","authenticated-orcid":true,"given":"Guillaume","family":"Maurin","sequence":"additional","affiliation":[{"name":"Institut Charles Gerhardt Montpellier (ICGM), UMR 5253 \u2212 CNRS\/UM\/ENSCM, Pole Chimie Balard Recherche , ,","place":["Montpellier Cedex 5, France, 34293"]},{"name":"Institut Universitaire de France (IUF) , ,","place":["Paris, France, 75005"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3812-7379","authenticated-orcid":true,"given":"Sabine","family":"Devautour-Vinot","sequence":"additional","affiliation":[{"name":"Institut Charles Gerhardt Montpellier (ICGM), UMR 5253 \u2212 CNRS\/UM\/ENSCM, Pole Chimie Balard Recherche , ,","place":["Montpellier Cedex 5, France, 34293"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,12]]},"reference":[{"key":"2026083104352395600_cit1","doi-asserted-by":"publisher","DOI":"10.1016\/B978-0-125-20750-8.X5001-5","volume-title":"Chemistry and Technology\nof Silicones","author":"Noll","year":"1968"},{"key":"2026083104352395600_cit2","doi-asserted-by":"publisher","first-page":"97","DOI":"10.1016\/j.progpolymsci.2018.06.001","article-title":"PDMS with Designer Functionalities\u2500Properties,\nModifications Strategies, and Applications","volume":"83","author":"Wolf","year":"2018","journal-title":"Prog. Polym. Sci."},{"key":"2026083104352395600_cit3","volume-title":"Silicones & Industry:\na Compendium for Practical Use, Instruction and Reference","author":"Tomanek","year":"1993"},{"key":"2026083104352395600_cit4","doi-asserted-by":"publisher","first-page":"112631","DOI":"10.1016\/j.ecoenv.2021.112631","article-title":"Review of Recent Findings on Occurrence\nand Fates of Siloxanes in Environmental Compartments","volume":"224","author":"Xiang","year":"2021","journal-title":"Ecotoxicol. Environ. Saf."},{"issue":"1","key":"2026083104352395600_cit5","doi-asserted-by":"publisher","first-page":"466","DOI":"10.1021\/cr500319v","article-title":"Environmental Chemistry of Organosiloxanes","volume":"115","author":"Ru\u0308cker","year":"2015","journal-title":"Chem. Rev."},{"issue":"20","key":"2026083104352395600_cit6","doi-asserted-by":"publisher","first-page":"8835","DOI":"10.1021\/acs.est.3c10752","article-title":"Concentrations\nof Volatile Methyl Siloxanes in New York City Reflect Emissions from\nPersonal Care and Industrial Use","volume":"58","author":"Brunet","year":"2024","journal-title":"Environ. Sci.\nTechnol."},{"issue":"13","key":"2026083104352395600_cit7","doi-asserted-by":"publisher","first-page":"1711","DOI":"10.1016\/j.enconman.2005.10.016","article-title":"Energy Use of Biogas Hampered by\nthe Presence of Siloxanes","volume":"47","author":"Dewil","year":"2006","journal-title":"Energy Convers. Manage."},{"key":"2026083104352395600_cit8","volume-title":"The Incidence and\nFate of Volatile Methyl Siloxanes in a Crewed Spacecraft Cabin","author":"Perry","year":"2017"},{"key":"2026083104352395600_cit9","volume-title":"Process Development For Removal Of\nSiloxanes From ISS Atmosphere","author":"Carter","year":"2015"},{"issue":"1","key":"2026083104352395600_cit10","doi-asserted-by":"publisher","first-page":"012018","DOI":"10.1088\/1757-899X\/1287\/1\/012018","article-title":"Euclid Cleanliness\nand Contamination Control","volume":"1287","author":"Portaluppi","year":"2023","journal-title":"IOP Conf Ser. Mater.\nSci. Eng."},{"issue":"1","key":"2026083104352395600_cit11","doi-asserted-by":"publisher","first-page":"389","DOI":"10.1007\/s11207-013-0290-z","article-title":"On-Orbit Degradation\nof Solar Instruments","volume":"288","author":"BenMoussa","year":"2013","journal-title":"Sol Phys."},{"issue":"12","key":"2026083104352395600_cit12","doi-asserted-by":"publisher","first-page":"1245","DOI":"10.1016\/j.tibtech.2021.05.003","article-title":"Volatile Siloxanes Emissions: Impact\nand Sustainable Abatement Perspectives","volume":"39","author":"Pascual","year":"2021","journal-title":"Trends\nBiotechnol."},{"issue":"19","key":"2026083104352395600_cit13","doi-asserted-by":"publisher","first-page":"23259","DOI":"10.1007\/s13399-023-04478-1","article-title":"Adsorptive\nRemoval of Siloxanes from Biogas: Recent Advances in Catalyst Reusability\nand Water Content Effect","volume":"14","author":"Vali","year":"2024","journal-title":"Biomass Conv. Bioref."},{"issue":"45","key":"2026083104352395600_cit14","doi-asserted-by":"publisher","first-page":"19375","DOI":"10.1021\/acs.iecr.4c02052","article-title":"A Review on Adsorption in Nanoporous\nAdsorbents for Gas Decontamination: Space Applications and Beyond","volume":"63","author":"Aumond","year":"2024","journal-title":"Ind. Eng. Chem. Res."},{"issue":"5","key":"2026083104352395600_cit15","doi-asserted-by":"publisher","first-page":"78","DOI":"10.1007\/s10450-025-00631-6","article-title":"Molecular Simulation of Fluid Adsorption\nin Nanoporous Adsorbents: Simple Descriptors for Space Decontamination\nApplications","volume":"31","author":"Manokaran","year":"2025","journal-title":"Adsorption"},{"issue":"10","key":"2026083104352395600_cit16","doi-asserted-by":"publisher","first-page":"1073","DOI":"10.1080\/09593330903057540","article-title":"Siloxane Treatment\nby Adsorption into Porous Materials","volume":"30","author":"Ortega","year":"2009","journal-title":"Environ.\nTechnol."},{"issue":"3","key":"2026083104352395600_cit17","doi-asserted-by":"publisher","first-page":"859","DOI":"10.1016\/j.cej.2010.10.032","article-title":"Purification of Landfill\nBiogases\nfrom Siloxanes by Adsorption: A Study of Silica and 13X Zeolite Adsorbents\non Hexamethylcyclotrisiloxane Separation","volume":"165","author":"Montanari","year":"2010","journal-title":"Chem.\nEng. J."},{"key":"2026083104352395600_cit18","doi-asserted-by":"publisher","first-page":"118","DOI":"10.1016\/j.micromeso.2015.04.016","article-title":"Adsorption of Octamethylcyclotetrasiloxane\n(D4) on Silica Gel (SG): Retention Mechanism","volume":"213","author":"Sigot","year":"2015","journal-title":"Microporous Mesoporous Mater."},{"key":"2026083104352395600_cit19","doi-asserted-by":"publisher","first-page":"112327","DOI":"10.1016\/j.micromeso.2022.112327","article-title":"Electrospun Al-MOF Fibers\nas D4 Siloxane Adsorbent: Synthesis, Environmental\nImpacts, and Adsorption Behavior","volume":"348","author":"Pioquinto-Garci\u0301a","year":"2022","journal-title":"Microporous\nMesoporous Mater."},{"key":"2026083104352395600_cit20","doi-asserted-by":"publisher","first-page":"230","DOI":"10.1016\/j.renene.2019.01.096","article-title":"Chromium-Based\nMIL-101 Metal Organic Framework as a Fully Regenerable D4 Adsorbent\nfor Biogas Purification","volume":"138","author":"Gargiulo","year":"2019","journal-title":"Renewable Energy"},{"issue":"27","key":"2026083104352395600_cit21","doi-asserted-by":"publisher","first-page":"7885","DOI":"10.1039\/c3ta11217a","article-title":"Siloxane D4\nCapture by Hydrophobic\nMicroporous Materials","volume":"1","author":"Mito-Oka","year":"2013","journal-title":"J. Mater. Chem. A"},{"issue":"6","key":"2026083104352395600_cit22","doi-asserted-by":"publisher","first-page":"106601","DOI":"10.1016\/j.jece.2021.106601","article-title":"Environmental\nAssessment of Metal-Organic Framework DUT-4 Synthesis and Its Application\nfor Siloxane Removal","volume":"9","author":"Pioquinto-Garci\u0301a","year":"2021","journal-title":"J. Environ. Chem. Eng."},{"issue":"21","key":"2026083104352395600_cit23","doi-asserted-by":"publisher","first-page":"12711","DOI":"10.1039\/D1TA02275J","article-title":"Breaking the Upper Bound of Siloxane\nUptake: Metal\u2013Organic Frameworks as an Adsorbent Platform","volume":"9","author":"Gulcay-Ozcan","year":"2021","journal-title":"J. Mater. Chem. A"},{"issue":"15","key":"2026083104352395600_cit24","doi-asserted-by":"publisher","first-page":"17531","DOI":"10.1021\/acsami.2c02607","article-title":"MIL-101(Cr)\nMOF as an Effective Siloxane Sensor","volume":"14","author":"Iacomi","year":"2022","journal-title":"ACS Appl.\nMater. Interfaces"},{"issue":"31","key":"2026083104352395600_cit25","doi-asserted-by":"publisher","first-page":"37828","DOI":"10.1021\/acsami.3c07158","article-title":"Quantitative Simulations\nof Siloxane Adsorption in\nMetal\u2013Organic Frameworks","volume":"15","author":"Chng","year":"2023","journal-title":"ACS Appl. Mater.\nInterfaces"},{"issue":"1","key":"2026083104352395600_cit26","doi-asserted-by":"publisher","first-page":"910","DOI":"10.1021\/acs.jpcc.4c07065","article-title":"Kinetic Separation of Siloxanes in Metal\u2013Organic\nFrameworks","volume":"129","author":"Chng","year":"2025","journal-title":"J. Phys. Chem. C"},{"issue":"37","key":"2026083104352395600_cit27","doi-asserted-by":"publisher","first-page":"16844","DOI":"10.1021\/acs.jpcc.5c04283","article-title":"Equilibrium Separation\nof Siloxanes in Metal\u2013Organic\nFrameworks","volume":"129","author":"Chng","year":"2025","journal-title":"J. Phys. Chem. C"},{"issue":"3","key":"2026083104352395600_cit28","doi-asserted-by":"publisher","first-page":"266","DOI":"10.1021\/je00045a002","article-title":"Vapor Pressures\nof Poly(Dimethylsiloxane) Oligomers","volume":"31","author":"Flaningam","year":"1986","journal-title":"J. Chem.\nEng. Data"},{"issue":"1","key":"2026083104352395600_cit29","doi-asserted-by":"publisher","first-page":"149","DOI":"10.1002\/anie.201409334","article-title":"A Highly\nStable Zeotype Mesoporous Zirconium Metal\u2013Organic Framework\nwith Ultralarge Pores","volume":"54","author":"Feng","year":"2015","journal-title":"Angew. Chem. Int. Ed."},{"issue":"2","key":"2026083104352395600_cit30","doi-asserted-by":"publisher","first-page":"81","DOI":"10.1080\/08927022.2015.1010082","article-title":"RASPA: Molecular\nSimulation Software for Adsorption and Diffusion in Flexible Nanoporous\nMaterials","volume":"42","author":"Dubbeldam","year":"2016","journal-title":"Mol. Simul."},{"key":"2026083104352395600_cit31","doi-asserted-by":"publisher","DOI":"10.1016\/C2017-0-01796-2","volume-title":"Physics of Cryogenics","author":"Zohuri","year":"2018"},{"issue":"7","key":"2026083104352395600_cit32","doi-asserted-by":"publisher","first-page":"1107","DOI":"10.1021\/ct700342k","article-title":"Computing the Heat\nof Adsorption Using Molecular Simulations:\nThe Effect of Strong Coulombic Interactions","volume":"4","author":"Vlugt","year":"2008","journal-title":"J. Chem. Theory Comput."},{"issue":"25","key":"2026083104352395600_cit33","doi-asserted-by":"publisher","first-page":"10024","DOI":"10.1021\/ja00051a040","article-title":"UFF, a\nFull Periodic Table Force Field for Molecular Mechanics and Molecular\nDynamics Simulations","volume":"114","author":"Rappe","year":"1992","journal-title":"J. Am. Chem. Soc."},{"issue":"8","key":"2026083104352395600_cit34","doi-asserted-by":"publisher","first-page":"2844","DOI":"10.1021\/ct3002199","article-title":"Improved Atoms-in-Molecule Charge Partitioning Functional\nfor Simultaneously Reproducing the Electrostatic Potential and Chemical\nStates in Periodic and Nonperiodic Materials","volume":"8","author":"Manz","year":"2012","journal-title":"J. Chem. Theory Comput."},{"issue":"3","key":"2026083104352395600_cit35","doi-asserted-by":"publisher","first-page":"253","DOI":"10.1002\/andp.19213690304","article-title":"Die Berechnung\nOptischer Und Elektrostatischer Gitterpotentiale","volume":"369","author":"Ewald","year":"1921","journal-title":"Ann. Phys."}],"container-title":["Inorganic Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.inorgchem.6c03471","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/inocaj\/article-pdf\/65\/33\/19612\/66507341\/acs.inorgchem.6c03471.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/inocaj\/article-pdf\/65\/33\/19612\/66507341\/acs.inorgchem.6c03471.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,8,31]],"date-time":"2026-08-31T08:36:20Z","timestamp":1788165380000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/inocaj\/article\/65\/33\/19612\/5253216\/Framework-Dependent-Adsorption-Regimes-of-Linear"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,8,12]]},"references-count":35,"journal-issue":{"issue":"33","published-online":{"date-parts":[[2026,8,12]]},"published-print":{"date-parts":[[2026,8,24]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.inorgchem.6c03471","relation":{},"ISSN":["0020-1669","1520-510X"],"issn-type":[{"value":"0020-1669","type":"print"},{"value":"1520-510X","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,8,12]]}}}