On the Mechanism of Catalytic Decarboxylation of Carboxylic Acids on Carbon-Supported Palladium Hydride

Deng, Fuli; Huang, Juanjuan; Ember, Erika E.; Achterhold, Klaus; Dierolf, Martin; Jentys, Andreas; Liu, Yue; Pfeiffer, Franz; Lercher, Johannes A.

doi:10.1021/acscatal.1c03869

On the Mechanism of Catalytic Decarboxylation of Carboxylic Acids on Carbon-Supported Palladium Hydride

Journal Article · 03 December 2021 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.1c03869· OSTI ID:1835715

Deng, Fuli ^[1]; Huang, Juanjuan ^[1]; Ember, Erika E. ^[1]; Achterhold, Klaus ^[1]; Dierolf, Martin ^[1]; Jentys, Andreas ^[1]; Liu, Yue ^[2]; Pfeiffer, Franz ^[1]; ^[3]

Technische Universitat Munchen
East China Normal University
BATTELLE (PACIFIC NW LAB)

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 a-phase palladium hydride (a-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 a-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 a-C- H position.

Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1835715

Report Number(s):: PNNL-SA-168730

Journal Information:: ACS Catalysis, Vol. 11, Issue 23

Country of Publication:: United States

Language:: English

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