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Highly selective and productive reduction of carbon dioxide to multicarbon products via in situ CO management using segmented tandem electrodes

Abstract

Electrochemical CO2 reduction provides a promising route to the sustainable generation of valuable chemicals and fuels. Tandem catalysts enable sequential CO2-to-CO and CO-to-multicarbon (C2+) product conversions on complementary active sites, to produce high C2+ Faradaic efficiency (FE). Unfortunately, previous tandem catalysts exhibit poor management of CO intermediates, which diminishes C2+ FE. Here, we design segmented gas-diffusion electrodes (s-GDEs) in which a CO-selective catalyst layer (CL) segment at the inlet prolongs CO residence time in the subsequent C2+-selective segment, enhancing conversion. This phenomenon enables increases in both the CO utilization and C2+ current density for a Cu/Ag s-GDE compared to pure Cu, by increasing the *CO coverage within the Cu CL. Lastly, we develop a Cu/Fe-N-C s-GDE with 90% C2+ FE at C2+ partial current density (jC2+) exceeding 1 A cm−2. These results prove the importance of transport and establish design principles to improve C2+ FE and jC2+ in tandem CO2 reduction.

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Fig. 1: Concept of segmented tandem gas-diffusion electrodes.
Fig. 2: Along-the-channel conversion of generated CO in a s-GDE.
Fig. 3: Effect of Cu:Ag area ratio on the performance of s-GDEs for CO2 reduction.
Fig. 4: Multiphysics model of mass transport and CO adsorption in an s-GDE.
Fig. 5: The compatibility between Cu and CO-selective catalysts.

Data availability

Source data are provided with this paper. All data generated and analysed during the present study are available from the authors upon reasonable request.

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Acknowledgements

This material is based upon work supported by the Office of Fossil Energy and Carbon Management of the US Department of Energy under award number DE-FE0031919 and performed at 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 number DE-SC0004993 and the National Institutes of Health under grant no. S10OD023532. The authors at University of Cincinnati also thank National Science Foundation for financial support (award no. CBET-2033343). J.C.B. acknowledges funding from the National Science Foundation Graduate Research Fellowship under grant no. DGE 1752814. J.C.B. acknowledges funding, in part, by a fellowship award through the National Defense Science and Engineering Graduate (NDSEG) Fellowship Program sponsored by the Army Research Office (ARO). J.C.B. would also like to acknowledge fruitful discussion regarding along-the-channel transport in CO2 electrolysers with E. Lees.

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Contributions

J.W., A.Z.W. and A.T.B. supervised the project. J.W. and T.Z. designed the experiments. T.Z. prepared the electrodes, performed electrochemical experiments and characterizations with the help of Z.L. J.C.B. performed multiphysics simulation. T.Z., Z.L. and J.C.B. performed data interpretation. T.Z., J.C.B., A.T.B., A.Z.W. and J.W. wrote the manuscript. All authors discussed, commented on and revised the manuscript.

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Correspondence to Adam Z. Weber or Jingjie Wu.

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

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Zhang, T., Bui, J.C., Li, Z. et al. Highly selective and productive reduction of carbon dioxide to multicarbon products via in situ CO management using segmented tandem electrodes. Nat Catal 5, 202–211 (2022). https://doi.org/10.1038/s41929-022-00751-0

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