Two-dimensional copper nanosheets for electrochemical reduction of carbon monoxide to acetate

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Abstract

Upgrading carbon dioxide to high-value multicarbon (C2+) products is one promising avenue for fuel and chemical production. Among all the monometallic catalysts, copper has attracted much attention because of its unique ability to convert CO2 or CO into C2+ products with an appreciable selectivity. Although numerous attempts have been made to synthesize Cu materials that expose the desired facets, it still remains a challenge to obtain high-quality nanostructured Cu catalysts for the electroreduction of CO2/CO. Here we report a facile synthesis of freestanding triangular-shaped two-dimensional Cu nanosheets that selectively expose the (111) surface. In a 2 M KOH electrolyte, the Cu nanosheets exhibit an acetate Faradaic efficiency of 48% with an acetate partial current density up to 131 mA cm−2 in electrochemical CO reduction. Further analysis suggest that the high acetate selectivity is attributed to the suppression of ethylene and ethanol formation, probably due to the reduction of exposed (100) and (110) surfaces.

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Fig. 1: Characterization of Cu nanosheets and Cu nanocubes.
Fig. 2: CO electroreduction performance of Cu nanosheets.
Fig. 3: Comparison of Cu nanosheets with commercial Cu particles in 1 M KOH.
Fig. 4: DFT calculations.

Data availability

The data sets generated during and/or analysed during the current study are available from the corresponding authors on reasonable request.

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Acknowledgements

The work is supported by the Department of Energy (USA) under Award no. DE-FE0029868 and the National Natural Science Foundation of China under Award nos 51601030 and 21773023. F.J., W.L., J.-J.L., M.J. and B.H.K. also thank the National Science Foundation Faculty Early Career Development program (Award no. CBET-1350911). Y.K. and X.F. acknowledge the support from International Institute for Nanotechnology (IIN) and Institute for Sustainability and Energy (ISEN) at Northwestern University. The theoretical calculation is supported by the Welch Foundation (Grant no. F-1959-20180324) and the startup grant from UT Austin, and used computational resources sponsored by the DOE’s Office of Energy Efficiency and Renewable Energy and located at the National Renewable Energy Laboratory, and the Texas Advanced Computing Center (TACC) at UT Austin. This work made use of the Electron Probe Instrumentation Center (EPIC) facility of Northwestern University’s Atomic and Nanoscale Characterization Experimental Center (NUANCE), which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the Materials Research Science and Engineering Centers (MRSEC) program (NSF DMR-1121262) at the Materials Research Center; the IIN. This work made use of the J.B. Cohen X-Ray Diffraction Facility supported by MRSEC and SHyNE. The authors acknowledge D. Su (Brookhaven National Laboratory), X. Ye (Indiana University) and A. Petford-Long (Northwestern University) for help in the discussion. This research used resources at the 8-ID Beamline of the National Synchrotron Light Source II, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract no. DE-SC0012704. The authors acknowledge E. Stavitski (8-ID Beamline, NSLS-II, Brookhaven National Laboratory) for assistance in the XAS measurements.

Author information

Y.K. and F.J. conceived the idea and supervised the project. X.F. designed the catalyst and synthesized the Cu nanomaterials. W.L. performed the electrocatalytic studies. Y.K., X.F., W.L., Y.L. and F.J. analysed the data and drafted the manuscript. J.-J.L. and M.J, performed the electrocatalytic study on the Cu nanoparticles and micrometre-sized particles. M.J. designed the operando XAS flow-cell electrolyser, and M.J., B.H.K. and W.L. performed the XAS study. Y.X., X.H. and J.W. facilitated the electron microscopic work. Q.T. assisted the AFM measurement. J.S. and Y.L. performed the computational modelling studies. All the authors contributed to the discussion of the results and manuscript preparation. W.L. and X.F. contributed equally to this work.

Correspondence to Feng Jiao or Yijin Kang.

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Supplementary Information

Supplementary Figures 1–24 and Supplementary Table 1.

Supplementary Data 1

Atomic coordinates of the optimized computational models.

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Luc, W., Fu, X., Shi, J. et al. Two-dimensional copper nanosheets for electrochemical reduction of carbon monoxide to acetate. Nat Catal 2, 423–430 (2019) doi:10.1038/s41929-019-0269-8

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