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A new and reliable method to obtain micropore volume in nanoporous solids by gas adsorption based on Dubinin works and the thickness of the adsorbed layer

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Abstract

It is known that the use of the Dubinin–Radushkevich method in micro-mesoporous samples does not give adequate values of micropore volumes, unlike when the samples contain only microporous. Based on that, in this work, we propose an easy method to calculate a reliable micropore volume (VμP) of micro-mesoporous (nanopores) samples, separating the microporous region from the experimental isotherm. For this, the original isotherm is modified, estimating the thickness of the adsorbed layer (t) as a function of relative pressure and changing the external surface area (Sext) to obtain a Type I adsorption isotherm in the microporous region; then, the DR method can be applied to the modified isotherm. This proposal, named the DR_t method, allows the calculation of a reliable VμP of any nanoporous material using different adsorbates. Using this method, we analyzed adsorbents of distinct nature (i.e., carbons and silicas) with different adsorbates as N2 and O2 at 77 K, Ar at 87 K, and CO2 at 273 K. We used this method to calculate VμP in different samples and compare them with those obtained with the traditional DR method, highlighting that unlike the latter the DR_t method showed similar and consistent results with the different adsorbates. Therefore, the values of micropore volume calculated using the DR_t method demonstrate consistency across various adsorbates, not only for N2 but especially for CO2, which is suggested to analyze narrow micropore volumes.

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Acknowledgements

The authors wish to thank UNSL, ANPCyT and CONICET for the financial support of this work. The authors also thank Dr. Jacek Jagiello from Micromeritics Instrument Corporation for providing the reference isotherm data of CABOT BP280 for CO2 and O2 at 273 and 77 K, respectively.

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Authors and Affiliations

  1. Laboratorio de Sólidos Porosos (LabSoP), Instituto de Física Aplicada (INFAP-CONICET), Universidad Nacional de San Luis, Av. Ejército de los Andes 950, 5700, San Luis, Argentina

    Jhonny Villarroel-Rocha, José J. Arroyo-Gómez, Deicy Barrera & Karim Sapag

  2. Departamento de Almacenamiento y Conversión de La Energía, Subgerencia Operativa de Energía y Movilidad, Instituto Nacional de Tecnología Industrial (INTI), Av. General Paz 5445, San Martín, Buenos Aires, Argentina

    José J. Arroyo-Gómez

  3. Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Buenos Aires, Argentina

    José J. Arroyo-Gómez

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  1. Jhonny Villarroel-Rocha
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Contributions

J.V.R and K.S.: conceptualization; J.V.R: methodology; J.V.R, J.J.A.G., and D.B.: formal analysis; K.S.: resources; J.V.R, J.J.A.G., and D.B.: data curation; J.V.R, J.J.A.G., and D.B.: writing original draft; J.V.R, J.J.A.G., D.B., and K.S.: writing‒review & editing. All authors have read and agreed to the published version of the manuscript.

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Correspondence to Jhonny Villarroel-Rocha or Karim Sapag.

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Villarroel-Rocha, J., Arroyo-Gómez, J.J., Barrera, D. et al. A new and reliable method to obtain micropore volume in nanoporous solids by gas adsorption based on Dubinin works and the thickness of the adsorbed layer. J Porous Mater (2024). https://doi.org/10.1007/s10934-024-01573-0

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