Hydrophobic post-functionalization of a water instable bioMOF : Effect on CO2 and water adsorption
Rosado, Albert (Institut de Ciència de Materials de Barcelona)
Borrás, Alejandro (Institut de Ciència de Materials de Barcelona)
Suárez-García, Fabián (Consejo Superior de Investigaciones Científicas (Espanya). Instituto de Ciencia y Tecnología del Carbono)
Vallcorba Valls, Oriol (ALBA Laboratori de Llum de Sincrotró)
Lopez-Periago, Ana M. (Institut de Ciència de Materials de Barcelona)
Ayllon, Jose Antonio (Universitat Autònoma de Barcelona. Departament de Química)
Domingo, Concepción (Institut de Ciència de Materials de Barcelona)

Data:	2025
Resum:	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 CO and HO. 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 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 of CO per gram of adsorbent.
Ajuts:	Ministerio de Ciencia, Innovación y Universidades CEX2023-001263-S Agencia Estatal de Investigación TED2021-1298378-C41 Agencia Estatal de Investigación PID2020-115631GB-I00
Nota:	Altres ajuts: 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.
Drets:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.
Llengua:	Anglès
Document:	Article ; recerca ; Versió publicada
Matèria:	BioMOF ; Hydrophobicity ; Aerogel ; Gas adsorption ; Green chemistry
Publicat a:	Applied Materials Today, Vol. 42 (February 2025) , art. 102573, ISSN 2352-9415

DOI: 10.1016/j.apmt.2024.102573

11 p, 8.7 MB

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