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Micro to mesoporous SiO2xerogels: the effect of acid catalyst type in sol–gel process

  • Original Paper: Fundamentals of sol–gel and hybrid materials processing
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Abstract

Silicon dioxide (SiO2) obtained by Sol–Gel methods is widely used as adsorbents, catalytic supports, filter membranes and in drugs delivery, among others. For most of the applications, surface area and porosity are key parameters that should be controlled, depending on the purpose of the material. These characteristics depend on the chemistry of the precursors in solution. Silicon alkoxides are commonly used as precursors, where the chemical pathway to produce sols and then gels depends on several factors such as water/alcohol ratio, pH, type of catalyst, temperature, etc. In order to control the microstructural characteristics of SiO2, it is necessary to understand the effect of the different chemical components on the hydrolysis-condensation reactions. In this work, we explored the acid-catalyzed hydrolysis and condensation reactions of silicon tetra-ethyl-alkoxide (TEOS) employing three common acids: HF, HCl, and HNO3. Gel formation kinetics was studied by low field nuclear magnetic resonance. Structural evolution of gels and xerogels at the nanoscale was determined by small angle X-ray scattering (SAXS). The microstructure of xerogels was determined by nitrogen adsorption (BET method), and by scanning and transmission electron microscopy (SEM and TEM, respectively). The final SiO2 products revealed different porosity type and texture depending on the acid employed, which are related to the chemical pathway during the sol–gel transition.

Highlights

  • SiO2 gelation time determined by LF-1H-NMR decreases with nucleophilicity of acid catalyst anion.

  • SiO2 gels microstructure change slightly with aging for HF catalyst but quite remarkably with HNO3/HCl.

  • SiO2 xerogel microstructure is defined during drying for HF catalyst but during aging for HNO3/HCl.

  • HF as catalyst lead to mesoporous xerogels, while HNO3/HCl lead to microporous ones.

  • Catalyst selection allows tailoring SiO2 morphologies and microstructure for different applications.

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Funding

This work was supported through the University of Buenos Aires (project UBACyT 20020090100297), through the National Agency for the Promotion of Science and Technology (ANPCyT, projects PICT 2016-2940 and PICT 2017-3150). The authors wish to thank the National Laboratory of Synchrotron Radiation (LNLS) for the support through project SAXS1 11755. Cristián Huck-Iriart, María Lidia Herrera and Roberto Jorge Candal are members of the Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET).

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  1. Noé J. Morales

    Present address: Yacimientos Petrolíferos Fiscales (YPF), Macacha Güemes 515, C1107 CABA, Buenos Aires, Argentina

Authors and Affiliations

  1. Laboratorio de Cristalografía Aplicada, ECyT, Universidad Nacional de San Martín, Campus Miguelete, 1650, San Martín, Provincia de Buenos Aires, Argentina

    Cristián Huck-Iriart

  2. Instituto de Química Física de los Materiales, Medio Ambiente y Energía (INQUIMAE), Universidad de Buenos Aires, CONICET, Facultad de Ciencias Exactas y Naturales, Pabellón II, Ciudad Universitaria, C1428EHA, Buenos Aires, Argentina

    Noé J. Morales

  3. Instituto de Tecnología de Polímeros y Nanotecnología (ITPN), Universidad de Buenos Aires, CONICET, Facultad de Arquitectura, Pabellón III, Ciudad Universitaria, C1428EHA, Buenos Aires, Argentina

    María Lidia Herrera

  4. Instituto de Investigación e Ingeniería Ambiental (IIIA), Universidad Nacional de San Martín, CONICET, 3iA, Campus Miguelete, 1650, San Martín, Provincia de Buenos Aires, Argentina

    Roberto J. Candal

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  1. Cristián Huck-Iriart
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Huck-Iriart, C., Morales, N.J., Herrera, M.L. et al. Micro to mesoporous SiO2xerogels: the effect of acid catalyst type in sol–gel process. J Sol-Gel Sci Technol 102, 197–207 (2022). https://doi.org/10.1007/s10971-021-05601-2

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