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

Herold, Felix ; Oefner, Niklas ; Zakgeym, Dina ; Drochner, Alfons ; Qi, Wei ; Etzold, Bastian J. M. (2022):
The High‐Temperature Acidity Paradox of Oxidized Carbon: An in situ DRIFTS Study. (Publisher's Version)
In: ChemCatChem, 14 (4), Wiley-VCH, e-ISSN 1867-3899,
DOI: 10.26083/tuprints-00021534,
[Article]

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.

Item Type: Article
Erschienen: 2022
Creators: Herold, Felix ; Oefner, Niklas ; Zakgeym, Dina ; Drochner, Alfons ; Qi, Wei ; Etzold, Bastian J. M.
Origin: Secondary publication DeepGreen
Status: Publisher's Version
Title: The High‐Temperature Acidity Paradox of Oxidized Carbon: An in situ DRIFTS Study
Language: English
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.

Journal or Publication Title: ChemCatChem
Volume of the journal: 14
Issue Number: 4
Place of Publication: Darmstadt
Publisher: Wiley-VCH
Collation: 12 Seiten
Uncontrolled Keywords: acid/base catalysis, carbon materials, carbon surface chemistry, heterogeneous catalysis, in situ spectroscopy
Divisions: 07 Department of Chemistry
07 Department of Chemistry > Fachgebiet Technische Chemie
Date Deposited: 01 Jul 2022 11:56
DOI: 10.26083/tuprints-00021534
URL / URN: https://tuprints.ulb.tu-darmstadt.de/21534
URN: urn:nbn:de:tuda-tuprints-215343
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