On the Mechanism of Catalytic Decarboxylation of Carboxylic Acids on Carbon-Supported Palladium Hydride
Deng F, Huang J, Ember EE, Achterhold K, Dierolf M, Jentys A, Liu Y, Pfeiffer F, Lercher JA (2021)
Publication Type: Journal article
Publication year: 2021
Journal
Book Volume: 11
Pages Range: 14625-14634
Journal Issue: 23
Abstract
The high chemical stability of aliphatic carboxylic acid makes catalytic decarboxylation at low temperatures challenging. We show that arylaliphatic acids (Ar-CnH2n-COOH, n ≥ 1) decarboxylate on carbon-supported Pd nanoparticles (Pd/C) at 90 °C with 100% selectivity. In situ XANES during decarboxylation of preadsorbed substrates indicates that the active phase is α-phase palladium hydride (α-PdHx). The reaction rate is enhanced by one order of magnitude when hydrogen is preadsorbed. Tracing deuterium labeling positions, it is concluded that carboxylic acid (Ar-CnH2n-COOH) undergoes an α-C-H bond dissociation on the Pd surface to the Ar-(CH2)n-1-CH*-COO∗ intermediate in the first step, followed by the C-COO scission, and finally, Ar-(CH2)n-1-CH∗ reacts with two sorbed H to produce Ar-(CH2)n-1-CH3. The high rates are related to the concentration of hydride present on the catalyst particles to complete the catalytic cycle in a Mars-van Krevelen-type mechanism and the rate of H/D exchange at the α-C-H position.
Involved external institutions
Germany (DE)How to cite
APA:
Deng, F., Huang, J., Ember, E.E., Achterhold, K., Dierolf, M., Jentys, A.,... Lercher, J.A. (2021). On the Mechanism of Catalytic Decarboxylation of Carboxylic Acids on Carbon-Supported Palladium Hydride. ACS Catalysis, 11(23), 14625-14634. https://doi.org/10.1021/acscatal.1c03869
MLA:
Deng, Fuli, et al. "On the Mechanism of Catalytic Decarboxylation of Carboxylic Acids on Carbon-Supported Palladium Hydride." ACS Catalysis 11.23 (2021): 14625-14634.
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