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Nano Research 2024, 17(5): 3863-3871 https://doi.org/10.1007/s12274-023-6368-5
Research Article | Issue | Published: 29 December 2023

OH regulator of highly dispersed Ru sites on host Pd nanocrystals for selective ethanol electro-oxidation

Show Author's Information Zhihe Xiao1,  Yueguang Chen1( ),  Renjie Wu1,  Yuwei He1,  Chunfeng Shi2( ),  Leyu Wang1( )
State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China
Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China
Keywords:
atomic sites, host–guest interaction, OH regulator, ethanol electro-oxidation
Topics:
Catalytic oxidation Structural optimization
Cite this article:
Xiao Z, Chen Y, Wu R, et al. OH regulator of highly dispersed Ru sites on host Pd nanocrystals for selective ethanol electro-oxidation. Nano Research, 2024, 17(5): 3863-3871. https://doi.org/10.1007/s12274-023-6368-5
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Abstract Full text Electronic supplementary material About this article

The ethanol oxidation reaction (EOR) is crucial in direct alcohol fuel cells and chemical production. However, the electro-oxidation of ethanol molecules to produce acetaldehyde and carbon monoxide can poison the active sites of nanocatalysts, resulting in reduced performance and posing challenges in achieving high activity and selectivity for ethanol oxidation. In this study, we employed a dynamic seed-mediated method to precisely modify highly dispersed Ru sites onto well-defined Pd nanocrystals. The oxyphilic Ru sites serve as "OH valves", regulating water dissociation, while the surrounding Pd atomic arrangements control electronic states for the oxidation dehydrogenation of carbonaceous intermediates. Specifically, Ru0.040@Pd nanocubes (Ru:Pd = 0.04 at.%), featuring (100) facets in Ru-Pd4 configurations, demonstrate an outstanding mass activity of 6.53 A·mgPd−1 in EOR under alkaline conditions, which is 6.05 times higher than that of the commercial Pd/C catalyst (1.08 A·mgPd−1). Through in-situ experiments and theoretical investigations, we elucidate that the hydrophilic Ru atoms significantly promote the dynamic evolution of H2O dissociation into OHads species, while the electron redistribution from Ru to adjacent Pd concurrently adjusts the selective oxidation of C2 intermediates. This host–guest interaction accelerates the subsequent oxidation of carbonaceous intermediates (CH3COads) to acetate, while preventing the formation of toxic *CHx and *CO species, which constitutes the rate-determining step.


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Electronic supplementary material
About this article

OH regulator of highly dispersed Ru sites on host Pd nanocrystals for selective ethanol electro-oxidation

Show Author's information Zhihe Xiao1, Yueguang Chen1( ), Renjie Wu1, Yuwei He1, Chunfeng Shi2( ), Leyu Wang1( )
State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China
Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China

Abstract

The ethanol oxidation reaction (EOR) is crucial in direct alcohol fuel cells and chemical production. However, the electro-oxidation of ethanol molecules to produce acetaldehyde and carbon monoxide can poison the active sites of nanocatalysts, resulting in reduced performance and posing challenges in achieving high activity and selectivity for ethanol oxidation. In this study, we employed a dynamic seed-mediated method to precisely modify highly dispersed Ru sites onto well-defined Pd nanocrystals. The oxyphilic Ru sites serve as "OH valves", regulating water dissociation, while the surrounding Pd atomic arrangements control electronic states for the oxidation dehydrogenation of carbonaceous intermediates. Specifically, Ru0.040@Pd nanocubes (Ru:Pd = 0.04 at.%), featuring (100) facets in Ru-Pd4 configurations, demonstrate an outstanding mass activity of 6.53 A·mgPd−1 in EOR under alkaline conditions, which is 6.05 times higher than that of the commercial Pd/C catalyst (1.08 A·mgPd−1). Through in-situ experiments and theoretical investigations, we elucidate that the hydrophilic Ru atoms significantly promote the dynamic evolution of H2O dissociation into OHads species, while the electron redistribution from Ru to adjacent Pd concurrently adjusts the selective oxidation of C2 intermediates. This host–guest interaction accelerates the subsequent oxidation of carbonaceous intermediates (CH3COads) to acetate, while preventing the formation of toxic *CHx and *CO species, which constitutes the rate-determining step.

Keywords: atomic sites, host–guest interaction, OH regulator, ethanol electro-oxidation

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Publication history
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Acknowledgements

Publication history

Received: 13 November 2023
Revised: 23 November 2023
Accepted: 23 November 2023
Published: 29 December 2023
Issue date: May 2024

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This research was supported by the National Natural Science Foundation of China (No. 22275009), SINOPEC (Contact No. 421028), and Fundamental Research Funds for the Central Universities (No. XK2020-02). We thank the BL14W1 station in Shanghai Synchrotron Radiation Facility (SSRF).

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