Impact of hydronium ions on the Pd-catalyzed furfural hydrogenation

Iris K. M. Yu, Fuli Deng, Xi Chen, Guanhua Cheng, Yue Liu, Wei Zhang () and Johannes A. Lercher ()
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Iris K. M. Yu: Technische Universität München
Fuli Deng: Technische Universität München
Xi Chen: Technische Universität München
Guanhua Cheng: Technische Universität München
Yue Liu: Technische Universität München
Wei Zhang: Technische Universität München
Johannes A. Lercher: Technische Universität München

Nature Communications, 2022, vol. 13, issue 1, 1-9

Abstract: Abstract In aqueous mediums, the chemical environment for catalytic reactions is not only comprised of water molecules but also of corresponding ionized species, i.e., hydronium ions, which can impact the mechanism and kinetics of a reaction. Here we show that in aqueous-phase hydrogenation of furfural on Pd/C, increasing the hydronium ion activities by five orders of magnitude (from pH 7 to pH 1.6) leads to an increase of less than one order of magnitude in the reaction rate. Instead of a proton-coupled electron transfer pathway, our results show that a Langmuir-Hinshelwood mechanism describes the rate-limiting hydrogen addition step, where hydrogen atom adsorbed on Pd is transferred to the carbonyl C atom of the reactant. As such, the strength of hydrogen binding on Pd, which decreases with increasing hydronium ion concentration (i.e., 2 kJ molH2−1 per unit pH), is a decisive factor in hydrogenation kinetics (rate constant +270%). In comparison, furfural adsorption on Pd is pH-independent, maintaining a tilted geometry that favors hydrogen attack at the carbonyl group over the furan ring.

Date: 2022
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DOI: 10.1038/s41467-022-34608-8

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