期刊
CHEMICAL ENGINEERING SCIENCE
卷 264, 期 -, 页码 -出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.ces.2022.118143
关键词
Three-phase liquid-liquid-gas reactions; Polyoxometalates; Density -functional calculations; Spectroscopic investigations; Catalyst activation; deactivation
资金
- German Science Foundation (DFG)
- DFG
- [AL 2130/3-2]
- [SFB 1452]
- [431781331]
Three-phase liquid-liquid gas reactions are promising strategies that combine highly active and selective homogeneous-catalysed oxidation reactions with in-situ product isolation. This article focuses on the interaction between polyoxometalate (POM) catalysts and carboxylic acids, and explains their effects on the catalytic performance.
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 polyox-ometalate (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 perfor-mance while acetic and especially formic acid form stable complexes with the active centres and there-fore inhibit the oxidation activity. These findings greatly improve the understanding of POM-acid complexes and their effect on the catalytic performance. (c) 2022 Elsevier Ltd. All rights reserved.
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