Elucidating activating and deactivating effects of carboxylic acids on polyoxometalate-catalysed three-phase liquid–liquid-gas reactions
Poller MJ, Bönisch S, Bertleff B, Raabe JC, Görling A, Albert J (2022)
Publication Type: Journal article
Publication year: 2022
Journal
Book Volume: 264
Article Number: 118143
DOI: 10.1016/j.ces.2022.118143
Abstract
Three-phase liquid–liquid gas reactions are promising strategies to combine highly active and selective homogeneous-catalysed oxidation reactions with in-situ product isolation. Several approaches like the three-phasic oxidation of biomass to formic acid (OxFA process) or the three-phasic extraction-coupled oxidative desulfurization (ECODS process) of fuels have been developed. Hereby, an aqueous polyoxometalate (POM) catalyst solution in combination with molecular oxygen as oxidant is used. However, contrary effects on the oxidation performance of the POM-catalyst were observed for different carboxylic acids as reaction products or intermediates. By using model calculations employing Density-Functional Theory (DFT) in combination with magnetic and optical spectroscopy, we could explain the experimental observations that oxalic acid activates the POM catalyst and therefore promotes its oxidation performance while acetic and especially formic acid form stable complexes with the active centres and therefore inhibit the oxidation activity. These findings greatly improve the understanding of POM-acid complexes and their effect on the catalytic performance.
Authors with CRIS profile
Simon Bönisch
Lehrstuhl für Theoretische Chemie
Benjamin Bertleff
Lehrstuhl für Chemische Reaktionstechnik
Andreas Görling
Lehrstuhl für Theoretische Chemie
Involved external institutions
Germany (DE)How to cite
APA:
Poller, M.J., Bönisch, S., Bertleff, B., Raabe, J.C., Görling, A., & Albert, J. (2022). Elucidating activating and deactivating effects of carboxylic acids on polyoxometalate-catalysed three-phase liquid–liquid-gas reactions. Chemical Engineering Science, 264. https://dx.doi.org/10.1016/j.ces.2022.118143
MLA:
Poller, Maximilian J., et al. "Elucidating activating and deactivating effects of carboxylic acids on polyoxometalate-catalysed three-phase liquid–liquid-gas reactions." Chemical Engineering Science 264 (2022).
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