The High-Temperature Acidity Paradox of Oxidized Carbon: An in situ DRIFTS Study

Herold F, Oefner N, Zakgeym D, Drochner A, Qi W, Etzold BJ (2022)

Publication Type: Journal article

Publication year: 2022

Journal

ChemCatChem Wiley-VCH Verlag

Book Volume: 14

Article Number: e202101586

Journal Issue: 4

DOI: 10.1002/cctc.202101586

Abstract

Until now, oxygen functionalized carbon materials were not considered to exhibit significant acidity at high temperatures, since carboxylic acids, the most prominent acidic functionality, are prone to decarboxylation at temperatures exceeding 250 °C. Paradoxically, we could show that oxidized carbon materials can act as highly active high-temperature solid acid catalysts in the dehydration of methanol at 300 °C, showing an attractive selectivity to dimethyl ether (DME) of up to 92 % at a conversion of 47 %. Building on a tailor-made carbon model material, we developed a strategy to utilize in situ DRIFT spectroscopy for the analysis of carbon surface species under process conditions, which until now proofed to be highly challenging due to the high intrinsic absorbance of carbon. By correlating the catalytic behavior with a comprehensive in situ DRIFTS study and extensive post mortem analysis we could attribute the high-temperature acidity of oxidized carbons to the interaction of thermally stable carboxylic anhydrides and lactones with nucleophilic constituents of the reaction atmosphere e. g. methanol and H2O. Dynamic equilibria of surface oxides depending on reaction atmosphere and temperature were observed, and a methyl ester, formed by methanolysis of anhydrides and lactones, was identified as key intermediate for DME generation on oxidized carbon catalysts.

Authors with CRIS profile

Bastian Etzold

Involved external institutions

Technische Universität Darmstadt

Germany (DE) Forschungszentrum Jülich / Research Centre Jülich (FZJ)

Germany (DE) Chinese Academy of Sciences (CAS) / 中国科学院

China (CN)

How to cite

APA:

Herold, F., Oefner, N., Zakgeym, D., Drochner, A., Qi, W., & Etzold, B.J. (2022). The High-Temperature Acidity Paradox of Oxidized Carbon: An in situ DRIFTS Study. ChemCatChem, 14(4). https://doi.org/10.1002/cctc.202101586

MLA:

Herold, Felix, et al. "The High-Temperature Acidity Paradox of Oxidized Carbon: An in situ DRIFTS Study." ChemCatChem 14.4 (2022).

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