Low-Temperature Catalytic Synthesis of Graphite Aerogels from Polyacrylonitrile-Crosslinked Iron Oxide and Cobalt Oxide Xerogel Powders
Abstract
We demonstrate the Fe- or Co-catalyzed preparation of graphitic carbon aerogels that bypasses the typical use of supercritical fluid drying, and takes place at much lower temperatures (800–1500 °C) than conventional graphitization (2500–3300 °C). The process starts with preparation of polyacrylonitrile (PAN)-crosslinked iron and cobalt oxide xerogel powders via surface-initiated free-radical polymerization of acrylonitrile on the porous solid networks of sol-gel-derived particle suspensions of the oxides. The resulting wet-gel oxide/polymer composite powders were dried under vacuum at 50 °C to xerogel powders, which were compressed into desirable form factors, e.g., discs or cylinders. These compacts were then aromatized (300 °C, O2), and subsequently carbonized in the range of 800 °C to 1500 °C under Ar. In situ carbothermal reduction of the oxide networks by the newly produced carbon yielded catalytic-toward-graphitization Fe(0) or Co(0) nanoparticles embedded within the carbons. Post-pyrolysis, those metallic nanoparticles were removed with aqua regia leaving behind pure graphitic carbon aerogels. Chemical characterization of materials up to aromatization was carried out with solid-state 13C NMR; characterization of the terminal graphite aerogels was based on powder-XRD, Raman, TEM, SEM, XPS and N2-sorption. Porosities in the range of 63%–78% v/v were created during aromatization, and mainly during pyrolytic carbonization. The best quality graphite aerogels were obtained with iron at 1500 °C. These materials consisted of 99.8% w/w graphitic carbon, the crystallite domain size along the (002) plane reached 170 Å, and the crystallite width along the a-axis was 70 nm.
Recommended Citation
R. U. Soni et al., "Low-Temperature Catalytic Synthesis of Graphite Aerogels from Polyacrylonitrile-Crosslinked Iron Oxide and Cobalt Oxide Xerogel Powders," Carbon, vol. 193, pp. 107 - 127, Elsevier, Jun 2022.
The definitive version is available at https://doi.org/10.1016/j.carbon.2022.02.080
Department(s)
Chemistry
Keywords and Phrases
Aerogels; Carbon; Catalyst; Cobalt; Graphite; Iron
International Standard Serial Number (ISSN)
0008-6223
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2023 Elsevier, All rights reserved.
Publication Date
30 Jun 2022
Comments
National Science Foundation, Grant 101