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Monolithic resorcinol–formaldehyde alcogels and their corresponding nitrogen-doped activated carbons

  • Review Paper: Nano- and macroporous materials (aerogels, xerogels, cryogels, etc.)
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Abstract

Here we report the adaptation of formaldehyde crosslinked phenolic resin-based aerogel and xerogel synthesis to ethanol-based solvent systems. Three specific formulations, namely one resorcinol–formaldehyde (RF) and two resorcinol–melamine–formaldehyde (RMF) systems were studied. As-prepared resins were characterized in terms of envelope and skeletal density. Furthermore, resin samples were pyrolyzed and activated in a CO2 gas atmosphere using a single-step protocol. The corresponding carbon materials featured high surface areas, moderate water uptake capacity and thermal conductivities in the 0.1 W.m−1K−1 range, in line with comparable activated carbons. The amount of formaldehyde in the synthesis of the RMF derived carbons proved to be a critical parameter in terms of both structural features and amount of N dopant in the carbonaceous matrix. Furthermore, a high formaldehyde concentration also has a drastic effect on the pore structure of the corresponding RMF carbons, leading primarily to mesopore formation without almost any macropore formation. Perhaps more importantly, the effect of the ammonia curing catalyst concentration on the material microstructure showed the opposite effect as observed in classical, water-based phenolic resin preparations. The ethanol-based synthesis clearly affects the pore structure of the resulting materials but also opens up the possibility to create inorganic/organic hybrid materials by simple combination with classical alkoxide-based silica sol–gel chemistry.

Highlights

  • Transposition of a porous phenolic resin recipe from an aqueous to an ethanolic environment.

  • Improvement of Nitrogen retention rate through pyrolysis and activation.

  • One-step combined heat treatment to create microporosity.

  • Compatibilization with inorganic systems such as alkoxysilanes.

  • Results differ from current literature in some way.

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Acknowledgements

The authors would like to thank the Laboratory for Organic Chemistry at ETH Zürich for the elemental analysis, Dr Arndt Remhof at Empa for allowing us to use his X-ray diffractometer, and the Cellulose & Wood Materials laboratory at Empa for the measuring time on their DVS apparatus.

Funding

MMK gratefully acknowledges financial support from the Swiss National Science Foundation (Grant number IZLRZ2_164058).

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Authors and Affiliations

  1. Empa, Swiss Federal Laboratories for Materials Science and Technology, Ueberlandstrasse 129, 8600, Duebendorf, Switzerland

    Romain Civioc, Matthias M. Koebel & Sandra Galmarini

  2. Department of Chemistry, University of Fribourg, Chemin du Musée 9, 1700, Fribourg, Switzerland

    Marco Lattuada

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  1. Romain Civioc
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Correspondence to Romain Civioc.

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Civioc, R., Lattuada, M., Koebel, M.M. et al. Monolithic resorcinol–formaldehyde alcogels and their corresponding nitrogen-doped activated carbons. J Sol-Gel Sci Technol 95, 719–732 (2020). https://doi.org/10.1007/s10971-020-05288-x

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