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Theory-guided Sn/Cu alloying for efficient CO2 electroreduction at low overpotentials

Nature Catalysisvolume 2pages5561 (2019) | Download Citation

Abstract

Electrochemical CO2 reduction to formate provides an avenue to reduce globally accelerating CO2 emissions and produce value-added products. Unfortunately, high selectivity in formate electrosynthesis has thus far only been achieved at highly cathodic potentials. Here we use density functional theory to investigate the effect of alloying Cu and Sn on the activity and selectivity towards formate. A theoretical thermodynamic analysis of the reaction energetics suggests that the incorporation of copper into tin could suppress hydrogen evolution and CO production, thus favouring formate generation. Consistent with theoretical trends, the designed CuSn3 catalysts by co-electrodeposition exhibit a Faradaic efficiency of 95% towards formate generation at −0.5 V versus RHE. Furthermore, the catalysts show no degradation over 50 h of operation. In situ Sn L3-edge and Cu K-edge X-ray absorption spectroscopy indicate electron donation from Sn to Cu, which indicates positive oxidation states of Sn in CuSn3 under operating conditions.

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Acknowledgements

This work was supported by the Department of Energy (DOE), Office of Basic Energy Sciences, Division of Materials Sciences and Engineering (contract no. DE-AC02-76SF00515). Theoretical calculations were based on work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the US Department of Energy under award no. DE-SC0004993. Theoretical calculations used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the US Department of Energy under contract no. DE-AC02- 05CH11231. The authors thank S. Fakra and acknowledge use of Beamline 10.3.2 at the Advanced Light Source for collection of XAS data. The Advanced Light Source and Molecular Foundry are supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231. The authors thank R. Davis and E. Jonathan from SSRL for XAS measurements. Use of the Stanford Synchrotron Radiation Lightsource (SLAC National Accelerator Laboratory) is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02-06CH11357. The authors acknowledge support with electron microscopy from the Stanford Nano Shared Facilities. Y.J. thanks the Knut & Alice Wallenberg Foundation for financial support through the ‘Wallenberg Postdoctoral Scholarship Program’ at Stanford.

Author information

Affiliations

  1. Department of Material Science and Engineering, Stanford University, Stanford, CA, USA

    • Xueli Zheng
    • , Jing Tang
    • , Jiangyan Wang
    • , Bofei Liu
    • , Kipil Lim
    • , Yuzhang Li
    •  & Yi Cui
  2. SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford, CA, USA

    • Yongfei Ji
  3. SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    • Yongfei Ji
    •  & Karen Chan
  4. Stanford Synchrotron Radiation Light source, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    • Hans-Georg Steinrück
    • , Kipil Lim
    •  & Michael F. Toney
  5. Stanford Institute for Materials and Energy Science, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    • Yi Cui

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Contributions

X.Z. and Y.C. conceived the research and designed the experiments. X.Z., J.T., J.W. and B.L. performed electrochemical measurements. Y.J. and K.C. carried out simulation parts. M.F.T. supervised and designed X-ray absorption and XRD experiments. X.Z., K.L. and H.-G.S. performed the X-ray absorption measurements. H.-G.S. carried out XRD measurements. Y.L. performed TEM measurements. All authors discussed the results and assisted during manuscript preparation.

Competing interests

The authors declare no competing interests.

Corresponding author

Correspondence to Yi Cui.

Supplementary information

  1. Supplementary Information

    Supplementary Methods, Supplementary Figures 1–19, Supplementary Tables 1–3 and Supplementary References

  2. Supplementary Data

    Optimized Cartesian coordinates of the CuSn and CuSn3 models

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DOI

https://doi.org/10.1038/s41929-018-0200-8