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Impact of hydronium ions on the Pd-catalyzed furfural hydrogenation

Author

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  • Iris K. M. Yu

    (Technische Universität München
    The Hong Kong Polytechnic University, Hung Hom, Kowloon)

  • Fuli Deng

    (Technische Universität München)

  • Xi Chen

    (Technische Universität München)

  • Guanhua Cheng

    (Technische Universität München
    Shandong University)

  • Yue Liu

    (Technische Universität München
    East China Normal University)

  • Wei Zhang

    (Technische Universität München
    East China Normal University)

  • Johannes A. Lercher

    (Technische Universität München
    Pacific Northwest National Laboratory)

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.

Suggested Citation

  • Iris K. M. Yu & Fuli Deng & Xi Chen & Guanhua Cheng & Yue Liu & Wei Zhang & Johannes A. Lercher, 2022. "Impact of hydronium ions on the Pd-catalyzed furfural hydrogenation," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
  • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-34608-8
    DOI: 10.1038/s41467-022-34608-8
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    References listed on IDEAS

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    1. Long Kuai & Zheng Chen & Shoujie Liu & Erjie Kan & Nan Yu & Yiming Ren & Caihong Fang & Xingyang Li & Yadong Li & Baoyou Geng, 2020. "Titania supported synergistic palladium single atoms and nanoparticles for room temperature ketone and aldehydes hydrogenation," Nature Communications, Nature, vol. 11(1), pages 1-9, December.
    2. Wenchao Sheng & Zhongbin Zhuang & Minrui Gao & Jie Zheng & Jingguang G. Chen & Yushan Yan, 2015. "Correlating hydrogen oxidation and evolution activity on platinum at different pH with measured hydrogen binding energy," Nature Communications, Nature, vol. 6(1), pages 1-6, May.
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