Hydrophobic post-functionalization of a water instable bioMOF: Effect on CO2 and water adsorption

The preparation of highly porous metal organic frameworks (MOFs) chemically resistant to water is essential for the forthcoming use of these materials as adsorbents in applications of gas separation under moisture or for wastewater remediation. However, most of the synthesized MOFs have a framework...

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Authors: Rosado, Albert, Borrás, Alejandro, Suárez García, Fabián, Vallcorba, Oriol, López Periago, Ana M., Ayllón, José A., Domingo Pascual, M. Concepción
Format: article
Status:Published version
Publication Date:2025
Country:España
Institution:Consejo Superior de Investigaciones Científicas (CSIC)
Repository:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/392319
Online Access:http://hdl.handle.net/10261/392319
https://api.elsevier.com/content/abstract/scopus_id/85214335193
Access Level:Open access
Keyword:Aerogel
BioMOF
Gas adsorption
Green chemistry
Hydrophobicity
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dc.title.none.fl_str_mv Hydrophobic post-functionalization of a water instable bioMOF: Effect on CO2 and water adsorption
title Hydrophobic post-functionalization of a water instable bioMOF: Effect on CO2 and water adsorption
spellingShingle Hydrophobic post-functionalization of a water instable bioMOF: Effect on CO2 and water adsorption
Rosado, Albert
Aerogel
BioMOF
Gas adsorption
Green chemistry
Hydrophobicity
title_short Hydrophobic post-functionalization of a water instable bioMOF: Effect on CO2 and water adsorption
title_full Hydrophobic post-functionalization of a water instable bioMOF: Effect on CO2 and water adsorption
title_fullStr Hydrophobic post-functionalization of a water instable bioMOF: Effect on CO2 and water adsorption
title_full_unstemmed Hydrophobic post-functionalization of a water instable bioMOF: Effect on CO2 and water adsorption
title_sort Hydrophobic post-functionalization of a water instable bioMOF: Effect on CO2 and water adsorption
dc.creator.none.fl_str_mv Rosado, Albert
Borrás, Alejandro
Suárez García, Fabián
Vallcorba, Oriol
López Periago, Ana M.
Ayllón, José A.
Domingo Pascual, M. Concepción
author Rosado, Albert
author_facet Rosado, Albert
Borrás, Alejandro
Suárez García, Fabián
Vallcorba, Oriol
López Periago, Ana M.
Ayllón, José A.
Domingo Pascual, M. Concepción
author_role author
author2 Borrás, Alejandro
Suárez García, Fabián
Vallcorba, Oriol
López Periago, Ana M.
Ayllón, José A.
Domingo Pascual, M. Concepción
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia, Innovación y Universidades (España)
Ministerio de Ciencia e Innovación (España)
Agencia Estatal de Investigación (España)
Rosado, Albert [0000-0003-3222-9566]
Borrás, Alejandro [0000-0002-0725-421X]
Vallcorba, Oriol [0000-0001-6499-7688]
Ayllón, José A. [0000-0001-7965-7424]
Domingo Pascual, M. Concepción [0000-0002-6976-8283]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Aerogel
BioMOF
Gas adsorption
Green chemistry
Hydrophobicity
topic Aerogel
BioMOF
Gas adsorption
Green chemistry
Hydrophobicity
description The preparation of highly porous metal organic frameworks (MOFs) chemically resistant to water is essential for the forthcoming use of these materials as adsorbents in applications of gas separation under moisture or for wastewater remediation. However, most of the synthesized MOFs have a framework with low thermodynamic stability against water. MOFs modification performed in this work aims to modify the water behavior by addressing kinetic factors affecting the dissolution reaction rate. For this purpose, a post-synthetic process is designed to functionalize MOF particles on the surface with a hydrophobic compound, particularly, stearic acid. The microporous bioMOF CaSyr-1, recently synthesized in our laboratories, was selected as a case study. Pristine CaSyr-1 transforms in water into a second crystalline phase, CaSyr-2 with a non-porous structure resolved in this work. An external surface coating method was chosen to prevent the bioMOF from water-induced degradation, while preserving the internal empty volume to a large extent, thus almost not affecting the adsorption capacity. The developed synthetic method allows the straightforward assembly of the composite CaSyr-1/stearate into a monolithic aerogel with a multimodal porosity. The significant enhancement of the kinetic stability of the hydrophobized CaSyr-1 with respect to the parent bioMOF was demonstrated by structural and morphological analysis. Textural properties and adsorption capacities of CaSyr-1/stearate were evaluated with different adsorbates, including N<inf>2,</inf> CO<inf>2</inf> and H<inf>2</inf>O. In particular, significant water adsorption was attained in the coated MOF without affecting the integrity of the framework. Besides, water adsorption works as an effective activation method for the composite by displacing stearic acid adsorbed inside CaSyr-1 pores. As a consequence, CO<inf>2</inf> adsorption at room temperature in the water-activated sample was enhanced by a factor of two with respect to the vacuum-activated sample, reaching and uptake of 31 cm<sup>3</sup> of CO<inf>2</inf> per gram of adsorbent.
publishDate 2025
dc.date.none.fl_str_mv 2025
2025
2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/392319
https://api.elsevier.com/content/abstract/scopus_id/85214335193
url http://hdl.handle.net/10261/392319
https://api.elsevier.com/content/abstract/scopus_id/85214335193
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
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info:eu-repo/grantAgreement/MICINN/Plan Estatal de investigación Científica y Técnica y de Innovación 2021-2023/TED2021-1298378-C41
Applied Materials Today
http://doi.org/10.1016/j.apmt.2024.102573
Sí
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dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
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spelling Hydrophobic post-functionalization of a water instable bioMOF: Effect on CO2 and water adsorptionRosado, AlbertBorrás, AlejandroSuárez García, FabiánVallcorba, OriolLópez Periago, Ana M.Ayllón, José A.Domingo Pascual, M. ConcepciónAerogelBioMOFGas adsorptionGreen chemistryHydrophobicityThe preparation of highly porous metal organic frameworks (MOFs) chemically resistant to water is essential for the forthcoming use of these materials as adsorbents in applications of gas separation under moisture or for wastewater remediation. However, most of the synthesized MOFs have a framework with low thermodynamic stability against water. MOFs modification performed in this work aims to modify the water behavior by addressing kinetic factors affecting the dissolution reaction rate. For this purpose, a post-synthetic process is designed to functionalize MOF particles on the surface with a hydrophobic compound, particularly, stearic acid. The microporous bioMOF CaSyr-1, recently synthesized in our laboratories, was selected as a case study. Pristine CaSyr-1 transforms in water into a second crystalline phase, CaSyr-2 with a non-porous structure resolved in this work. An external surface coating method was chosen to prevent the bioMOF from water-induced degradation, while preserving the internal empty volume to a large extent, thus almost not affecting the adsorption capacity. The developed synthetic method allows the straightforward assembly of the composite CaSyr-1/stearate into a monolithic aerogel with a multimodal porosity. The significant enhancement of the kinetic stability of the hydrophobized CaSyr-1 with respect to the parent bioMOF was demonstrated by structural and morphological analysis. Textural properties and adsorption capacities of CaSyr-1/stearate were evaluated with different adsorbates, including N<inf>2,</inf> CO<inf>2</inf> and H<inf>2</inf>O. In particular, significant water adsorption was attained in the coated MOF without affecting the integrity of the framework. Besides, water adsorption works as an effective activation method for the composite by displacing stearic acid adsorbed inside CaSyr-1 pores. As a consequence, CO<inf>2</inf> adsorption at room temperature in the water-activated sample was enhanced by a factor of two with respect to the vacuum-activated sample, reaching and uptake of 31 cm<sup>3</sup> of CO<inf>2</inf> per gram of adsorbent.This work was supported by the Spanish Ministry of Science and Innovation through the Severo Ochoa Program for Centers of Excellence (CEX2023–001263-S), the Spanish National Plan of Research with project PID2020-115631GB-I00 and Ecological Transition and Digital Transition Project TED2021-1298378-C41. This work has been performed in the framework of the doctoral program “Chemistry” of the UAB by A.R. that acknowledges the financial support of an FPI 2019 grant. We acknowledge the thorough language and text revision performed by Rosy Sunday.With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2023-001263-S).Peer reviewedElsevierMinisterio de Ciencia, Innovación y Universidades (España)Ministerio de Ciencia e Innovación (España)Agencia Estatal de Investigación (España)Rosado, Albert [0000-0003-3222-9566]Borrás, Alejandro [0000-0002-0725-421X]Vallcorba, Oriol [0000-0001-6499-7688]Ayllón, José A. [0000-0001-7965-7424]Domingo Pascual, M. Concepción [0000-0002-6976-8283]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202520252025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/392319https://api.elsevier.com/content/abstract/scopus_id/85214335193reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de investigación Científica y Técnica y de Innovación 2021-2023/CEX2023-001263-Sinfo:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-115631GB-I00info:eu-repo/grantAgreement/MICINN/Plan Estatal de investigación Científica y Técnica y de Innovación 2021-2023/TED2021-1298378-C41Applied Materials Todayhttp://doi.org/10.1016/j.apmt.2024.102573Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3923192026-05-22T06:33:51Z
score 15,812429

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