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Nickel dual-atom sites for electrochemical carbon dioxide reduction

Nature Synthesis volume 1, pages 719–728 (2022)Cite this article

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Abstract

Dual-atom catalysts, combining single-atom catalysts and metal alloys, are promising electrocatalysts for CO2 reduction but are limited by sluggish CO2 reduction kinetics and ill-defined dual-atom sites. Here, we develop a catalyst of Ni dual-atom sites via in situ conversion of nanoparticles into dual atoms. We achieve efficient electrocatalytic CO2 reduction on Ni dual-atom catalysts with a CO partial current density up to ~1 A cm−2 and turnover frequency of 77,500 h−1 at >99% Faradaic efficiency. In situ X-ray absorption and theoretical calculations reveal that during the catalytic process the Ni dual-atom sites trigger the adsorption of hydroxyl (OHad), forming electron-rich active centres that endow a moderate reaction kinetic barrier of *COOH formation and *CO desorption. The resultant catalytic microenvironment enables expedited kinetics compared with either the kinetics of bare dual-atom sites or OHad regulated single-atom sites.

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Fig. 1: Morphology of Ni2NC.
Fig. 2: Structural characterizations of Ni2NC and Ni1NC.
Fig. 3: Electrocatalytic CO2 activity using flow cell with 1 M KOH electrolyte.
Fig. 4: In situ XAFS analysis.
Fig. 5: DFT calculations.
Fig. 6: Characterizations of other M2NC catalysts.

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Data availability

Data supporting the findings of this study are available in the article and Supplementary Information. Source data are provided with this paper.

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Acknowledgements

H.X.Z. acknowledges funding from the Alexander von Humboldt Foundation. This work was supported by the National Natural Science Foundation of China (21725103, 51925102), National Key R&D Program of China (2020YFB1505603, 2019YFA0705704), Jilin Province Science and Technology Development Plan Funding Project (20200201079JC) and Youth Innovation Promotion Association CAS (2021223).

Author information

Author notes

  1. These authors contributed equally: Qi Hao, Hai-xia Zhong, Jia-zhi Wang, Kai-hua Liu.

Authors and Affiliations

  1. State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, P. R. China

    Qi Hao, Hai-xia Zhong, Jia-zhi Wang, Kai-hua Liu, Na Zhou & Xin-bo Zhang

  2. Key Laboratory of Automobile Materials Ministry of Education and College of Materials Science and Engineering, Jilin University, Changchun, P. R. China

    Qi Hao, Jun-min Yan, Xiao Zhao & Dong-xue Liu

  3. Center for Advancing Electronics Dresden (CFAED) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Dresden, Germany

    Hai-xia Zhong

  4. University of Science and Technology of China, Hefei, P. R. China

    Jia-zhi Wang, Na Zhou & Xin-bo Zhang

  5. School of Chemistry and Chemical Engineering, In-situ Center for Physical Sciences, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai, P. R. China

    Zhou-hong Ren, Xi Liu & Li-wei Chen

  6. School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, P. R. China

    Hao Zhang & Jun Luo

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Contributions

X.B.Z. conceived and designed the project. Q.H. synthesized the materials. Q.H. and K.H.L. carried out the electrochemical testing. H.X.Z., Q.H., K.H.L. and D.X.L. contributed to the characterization and related discussion. Q.H. and N.Z. performed in situ ATR-IR measurements. J.Z.W. contributed to the theoretical calculations. Z.H.R., X.L. and L.W.C. contributed to the in situ ESTEM measurements. X.Z. contributed to the XANES simulations. H.Z. and J.L. contributed to the STEM simulation. Q.H., H.X.Z., K.H.L., J.Z.W., J.M.Y. and X.B.Z. co-wrote the paper. All the authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Xin-bo Zhang.

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Nature Synthesis thanks Shaojun Guo and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Hao, Q., Zhong, Hx., Wang, Jz. et al. Nickel dual-atom sites for electrochemical carbon dioxide reduction. Nat. Synth 1, 719–728 (2022). https://doi.org/10.1038/s44160-022-00138-w

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