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Selective CO-to-acetate electroreduction via intermediate adsorption tuning on ordered Cu–Pd sites

Nature Catalysis volume 5, pages 251–258 (2022)Cite this article

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Abstract

Electrochemical reduction of carbon monoxide (CO) has recently emerged as a potential approach for obtaining high-value, multicarbon products such as acetate, while the activity and selectivity for prodution of acetate have remained low. Herein, we develop an atomically ordered copper–palladium intermetallic compound (CuPd) composed of a high density of Cu–Pd pairs that feature as catalytic sites to enrich surface *CO coverage, stabilize ethenone as a key acetate path intermediate and inhibit the hydrogen evolution reaction, thus substantially promoting acetate formation. The CuPd electrocatalyst enables a high Faradaic efficiency of 70 ± 5% for CO-to-acetate electroreduction and a high acetate partial current density of 425 mA cm−2. Under membrane electrode assembly conditions, the CuPd electrocatalyst demonstrated a 500 h CO-to-acetate conversion at 500 mA cm−2 with a stable acetate Faradaic efficiency of ~50%.

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Fig. 1: Structural characterization.
Fig. 2: X-ray absorption spectroscopy analysis of Cu–Pd alloys.
Fig. 3: CO electroreduction performance.
Fig. 4: DFT calculations.

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Data availability

The atomic coordinates of the optimized computational models are provided as Supplementary Data 1 with this paper. The source data of XRD (Fig. 1a) and the electrochemical stability plot (Fig. 3f) are provided with this paper. Other data that support the findings of this study are available from the corresponding author upon request.

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Acknowledgements

We thank the following funding agencies for supporting this work: the National Key Research and Development Programme of China (nos. 2018YFA0209401 to G.Z. and 2018YFA0208600 to X.X.); the Natural Science Foundation of China (nos. 22025502 and 21975051 to G.Z. and 21688102 to X.X.); the Science and Technology Commission of Shanghai Municipality (nos. 21DZ1206800 and 19XD1420400 to G.Z.); and the Shanghai Municipal Education Commission (no. 2019-01-07-00-07-E00045 to G.Z.). This research used the synchrotron resources of Canadian Light Source.

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Author notes

  1. These authors contributed equally: Yali Ji, Zheng Chen

Authors and Affiliations

  1. Department of Chemistry, Laboratory of Advanced Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, China

    Yali Ji, Zheng Chen, Chao Yang, Anxiang Guan, Xin Xu & Gengfeng Zheng

  2. School of Chemistry and Environment, Southwest Minzu University, Chengdu, China

    Ruilin Wei & Yaoyue Yang

  3. Institute of Functional Nano & Soft Materials, Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Soochow University, Suzhou, China

    Yuhang Wang & Jie Xu

  4. Institute for New Energy Materials & Low-Carbon Technologies and Tianjin Key Lab of Photoelectric Materials & Devices, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, China

    Hao Zhang & Jun Luo

  5. Department of Chemistry, University of Western Ontario, London, Ontario, Canada

    Jiatang Chen & Tsun-Kong Sham

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Contributions

G.Z. and X.X. proposed, designed and supervised the project. G.Z., X.X., Y.J., Z.C. and Y.W. wrote the manuscript. Y.J. synthesized catalysts and performed electrochemistry experiments. Y.J., C.Y. and A.G. analysed electrochemical data. Z.C. and X.X. performed theoretical calculations. R.W. and Y.Y. conducted ATR–SEIRAS measurements. J.X., H.Z. and J.L. performed aberration-corrected HAADF–STEM characterizations. J.C. and T.-K.S. performed X-ray absorption spectroscopy characterizations. All authors contributed to discussion of the results and manuscript preparation.

Corresponding authors

Correspondence to Xin Xu or Gengfeng Zheng.

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Nature Catalysis thanks Yijin Kang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary methods, Figs. 1–46, Tables 1–21 and references.

Supplementary Data

A compressed zip file containing all optimized DFT structures (in Vienna ab initio simulation package CONTCAR format).

Source data

Source Data Fig. 1

Source data of XRD for CuPd (Fig. 1a).

Source Data Fig. 3

Source data of the stability plot (Fig. 3f).

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Ji, Y., Chen, Z., Wei, R. et al. Selective CO-to-acetate electroreduction via intermediate adsorption tuning on ordered Cu–Pd sites. Nat Catal 5, 251–258 (2022). https://doi.org/10.1038/s41929-022-00757-8

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