Enhanced Electrochemical Hydrogenation of Benzaldehyde to Benzyl Alcohol on Pd@Ni-MOF by Modifying the Adsorption Configuration

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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
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Date

2024-02-14

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en

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10

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ACS Applied Materials and Interfaces, Volume 16, issue 6, pp. 6948-6957

Abstract

Electrocatalytic hydrogenation (ECH) approaches under ambient temperature and pressure offer significant potential advantages over thermal hydrogenation processes but require highly active and efficient hydrogenation electrocatalysts. The performance of such hydrogenation electrocatalysts strongly depends not only on the active phase but also on the architecture and surface chemistry of the support material. Herein, Pd nanoparticles supported on a nickel metal-organic framework (MOF), Ni-MOF-74, are prepared, and their activity toward the ECH of benzaldehyde (BZH) in a 3 M acetate (pH 5.2) aqueous electrolyte is explored. An outstanding ECH rate up to 283 μmol cm-2 h-1 with a Faradaic efficiency (FE) of 76% is reached. Besides, higher FEs of up to 96% are achieved using a step-function voltage. Materials Studio and density functional theory calculations show these outstanding performances to be associated with the Ni-MOF support that promotes H-bond formation, facilitates water desorption, and induces favorable tilted BZH adsorption on the surface of the Pd nanoparticles. In this configuration, BZH is bonded to the Pd surface by the carbonyl group rather than through the aromatic ring, thus reducing the energy barriers of the elemental reaction steps and increasing the overall reaction efficiency.

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Publisher Copyright: © 2024 American Chemical Society.

Keywords

benzaldehyde, benzyl alcohol, electrochemical hydrogenation, metal−organic-framework-supported palladium, tilted adsorption configuration

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Citation

Gong, L, Zhang, C Y, Li, J, Montaña-Mora, G, Botifoll, M, Guo, T, Arbiol, J, Zhou, J Y, Kallio, T, Martínez-Alanis, P R & Cabot, A 2024, ' Enhanced Electrochemical Hydrogenation of Benzaldehyde to Benzyl Alcohol on Pd@Ni-MOF by Modifying the Adsorption Configuration ', ACS Applied Materials and Interfaces, vol. 16, no. 6, pp. 6948-6957 . https://doi.org/10.1021/acsami.3c13920