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Directing CO2 electroreduction pathways for selective C2 product formation using single-site doped copper catalysts

Nature Chemical Engineering volume 1, pages 159–169 (2024)Cite this article

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Abstract

Manipulating the selectivity-determining step in post-C–C coupling is crucial for enhancing C2 product specificity during electrocatalytic CO2 reduction, complementing efforts to boost rate-determining step kinetics. Here we highlight the role of single-site noble metal dopants on Cu surfaces in influencing C–O bond dissociation in an oxygen-bound selectivity-determining intermediate, steering post-C–C coupling toward ethylene versus ethanol. Integrating theoretical and experimental analyses, we demonstrate that the oxygen binding strength of the Cu surface controls the favorability of C–O bond scission, thus tuning the selectivity ratio of ethylene-to-ethanol. The Rh-doped Cu catalyst with optimal oxygen binding energy achieves a Faradaic efficiency toward ethylene of 61.2% and an ethylene-to-ethanol Faradaic efficiency ratio of 4.51 at –0.66 V versus RHE (reversible hydrogen electrode). Integrating control of both rate-determining and selectivity-determining steps further raises ethylene Faradaic efficiency to 68.8% at 1.47 A cm−2 in a tandem electrode. Our insights guide the rational design of Cu-based catalysts for selective CO2 electroreduction to a single C2 product.

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Fig. 1: DFT calculations of post-C–C coupling steps on MCu catalysts.
Fig. 2: Structural characterization of RhCuO and RhCu catalyst.
Fig. 3: Electrocatalytic CO2RR performance.
Fig. 4: Correlations between theoretical descriptors and experimental reactivities at –0.65 ± 0.01 V.
Fig. 5: CO2RR performance of the ZnO/RhCu cs-GDE in an MEA cell.

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Data availability

All the data that support the findings of this study are available in the main text and the Supplementary Information. The atomic coordinates of the optimized computational models are available in the Materials Cloud repository (https://doi.org/10.24435/materialscloud:4b-cf). Source data are provided with this paper.

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Acknowledgements

This work is supported by the Department of Energy (DOE) Office of Energy Efficiency and Renewable Energy under IEDO contract DE-EE0010836 and partly supported by the National Science Foundation (NSF) grant CBET-2033343. P.W. and T.P.S. acknowledge funding support from a Rice University Interdisciplinary Excellence Award and NSF grant CBET-2143941. S.Y. acknowledges the use of facilities within the Eyring Materials Center at Arizona State University, supported in part by NNCI-ECCS-1542160. Z.L. acknowledges URC Graduate Student Stipend awarded by the Office of Research at University of Cincinnati. Z.L. thanks X. Shang for discussing catalyst synthesis and reaction mechanisms. V.S., V.K.R.K., and Y.F. acknowledge the funding from the UC CEAS Pilot Program NOEMA. A.I.F. and S.X. acknowledge support by the NSF grant CHE 2102299. S.D.S. is supported by a US DOE Early Career Award. J.D.J. is supported by the Brookhaven National Laboratory Goldhaber Distinguished Fellowship. The work carried out at Brookhaven National Laboratory was supported by the DOE under contract DE-SC0012704. The XAS measurements used resources 7-BM and 8-ID of the National Synchrotron Light Source II, a DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract DE-SC0012704. The 7-BM beamline operations were supported in part by the Synchrotron Catalysis Consortium (DOE Office of Basic Energy Sciences grant DE-SC0012335). We would like to thank E. Stavitski, S. Ehrlich, and N. Marinkovic for help with XAFS data collection.

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Author notes

  1. These authors contributed equally: Zhengyuan Li, Peng Wang.

Authors and Affiliations

  1. Department of Chemical and Environmental Engineering, University of Cincinnati, Cincinnati, OH, USA

    Zhengyuan Li, Takeshi Ito, Tianyu Zhang, Jithu Raj, Vesselin Shanov & Jingjie Wu

  2. Department of Chemical and Biomolecular Engineering, Rice University, Houston, TX, USA

    Peng Wang & Thomas P. Senftle

  3. Electrification and Energy Infrastructures Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Xiang Lyu, Yaocai Bai, Jianlin Li & Alexey Serov

  4. Department of Mechanical and Materials Engineering, University of Cincinnati, Cincinnati, OH, USA

    Vamsi Krishna Reddy Kondapalli, Yanbo Fang & Vesselin Shanov

  5. Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, NY, USA

    Shuting Xiang & Anatoly I. Frenkel

  6. Chemistry Division, Brookhaven National Laboratory, Upton, NY, USA

    Juan D. Jimenez, Anatoly I. Frenkel & Sanjaya D. Senanayake

  7. National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY, USA

    Lu Ma

  8. Eyring Materials Center, Arizona State University, Tempe, AZ, USA

    Shize Yang

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  1. Zhengyuan Li
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Contributions

Z.L. and P.W. conceptualized the project under the supervision of T.P.S. and J.W.; Z.L. synthesized catalysts, performed the electrochemical tests, and analyzed experimental data with the help of T.I. and T.Z.; P.W. performed DFT simulation; S.Y., X.L. and Z.L. conducted the catalyst characterization with the help of Y.B., J.L. and A.S.; Z.L. and V.K.R.K. carried out in situ Raman measurements with the assistance of Y.F. and V.S.; S.X., J.D.J., L.M., A.I.F. and S.D.S. carried out XAS measurements and analyses. Z.L., P.W., J.R., S.Y., T.P.S. and J.W. wrote the paper. All authors discussed the results and commented on the paper.

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Correspondence to Shize Yang, Thomas P. Senftle or Jingjie Wu.

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Li, Z., Wang, P., Lyu, X. et al. Directing CO2 electroreduction pathways for selective C2 product formation using single-site doped copper catalysts. Nat Chem Eng 1, 159–169 (2024). https://doi.org/10.1038/s44286-023-00018-w

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