Importance of interface open circuit potential on aqueous hydrogenolytic reduction of benzyl alcohol over Pd/C

Guanhua Cheng, Wei Zhang, Andreas Jentys, Erika E. Ember, Oliver Y. Gutiérrez, Yue Liu () and Johannes A. Lercher ()
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Guanhua Cheng: Technische Universität München, Department of Chemistry and Catalysis Research Center
Wei Zhang: Technische Universität München, Department of Chemistry and Catalysis Research Center
Andreas Jentys: Technische Universität München, Department of Chemistry and Catalysis Research Center
Erika E. Ember: Technische Universität München, Department of Chemistry and Catalysis Research Center
Oliver Y. Gutiérrez: Pacific Northwest National Laboratory
Yue Liu: Technische Universität München, Department of Chemistry and Catalysis Research Center
Johannes A. Lercher: Technische Universität München, Department of Chemistry and Catalysis Research Center

Nature Communications, 2022, vol. 13, issue 1, 1-8

Abstract: Abstract The open circuit potential (OCP) established by the quasi-equilibrated electrode reaction of H2 and H3O+(hydr.), complicates catalytic reactions significantly. The hydrogenolysis rate of benzylic alcohol on Pd/C increases 2-3 orders of magnitude with the pH decreasing from 7 to 0.6. The reaction follows a pathway of protonated benzyl alcohol dehydration to a benzylic carbenium ion, followed by a hydride addition to form toluene. The dehydration of protonated benzyl alcohol is kinetic relevent, thus, being enhanced at lower pH. The OCP stabilizes all cationic species in the elementary steps. Particularly, the initial state (benzyl alcohol oxonium ion) is less stabilized than the dehydration transition state and the product (benzylic carbenium), thus, lowering the free energy barrier of the rate-determining step. In accordance, the rate increased with increasingly negative OCP. Beside OCP, an external negative electric potential in an electrocatlaytic system was also demonstrated to enhance the rate in the same way.

Date: 2022
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DOI: 10.1038/s41467-022-35554-1

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