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

Author

Listed:
  • Guanhua Cheng

    (Technische Universität München, Department of Chemistry and Catalysis Research Center
    Shandong University)

  • Wei Zhang

    (Technische Universität München, Department of Chemistry and Catalysis Research Center
    East China Normal University)

  • 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
    East China Normal University)

  • Johannes A. Lercher

    (Technische Universität München, Department of Chemistry and Catalysis Research Center
    Pacific Northwest National Laboratory)

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.

Suggested Citation

  • Guanhua Cheng & Wei Zhang & Andreas Jentys & Erika E. Ember & Oliver Y. Gutiérrez & Yue Liu & Johannes A. Lercher, 2022. "Importance of interface open circuit potential on aqueous hydrogenolytic reduction of benzyl alcohol over Pd/C," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-35554-1
    DOI: 10.1038/s41467-022-35554-1
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    Cited by:

    1. Xianxian Qin & Jiejie Li & Tian-Wen Jiang & Xian-Yin Ma & Kun Jiang & Bo Yang & Shengli Chen & Wen-Bin Cai, 2024. "Disentangling heterogeneous thermocatalytic formic acid dehydrogenation from an electrochemical perspective," Nature Communications, Nature, vol. 15(1), pages 1-14, December.

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