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

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 degrees 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 degrees 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.

Automated summary

Oxidized carbon materials, contrary to previous beliefs, can act as highly active solid acid catalysts at high temperatures in the dehydration of methanol, with good selectivity and conversion rates. The high-temperature acidity of these materials is attributed to the interaction of thermally stable carboxylic anhydrides and lactones with the reactants. A methyl ester is identified as a key intermediate for DME generation on oxidized carbon catalysts.