Abstract
Alloying of metals can be used to optimize intermediate binding during electrocatalysis but challenges remain in overcoming thermodynamic atomic miscibility in alloys. Here we report a coordination-controlled metal alloy in which copper clusters are spatially dispersed in a crystalline silver lattice to promote the electrochemical reduction of CO2 to ethanol. The synergistic interactions between Cu–Cu sites and Cu–Ag interfaces achieve highly selective hydrocarbon and oxygenate production by strengthening and diversifying the binding of *CO intermediates on terrace and defect sites. To control atomic coordinates beyond the miscibility limit and optimize the catalyst microstructure, sacrificial elements are incorporated with thermodynamically guided compositions to form intermetallic compounds. The sacrificial elements are then selectively dealloyed. Using a membrane electrode assembly, ethylene-selective production on copper catalysts (Faradaic efficiency, 69.6 ± 1.3%; full cell efficiency, 23.5%) is steered to ethanol-selective production on the supersaturated Ag–Cu solid-solution catalyst (Faradaic efficiency, 40.4 ± 2.4%; full cell efficiency, 14.4%). Metallurgy-designed catalyst fabrication enables the efficient chemical manufacturing of either hydrocarbons or oxygenates and offers guidelines for catalyst design principles.
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Acknowledgements
This research was supported by the Creative Materials Discovery Program through the National Research Foundation of Korea funded by the Ministry of Science, ICT (MSIT) and Future Planning (2017M3D1A1040689 and 2019M3D1A1079215); the program of Carbon to X technology development for the production of useful substances (NRF-2020M3H7A1098376) through the National Research Foundation of Korea (NRF), funded by the Korean government (Ministry of Science and ICT (MSIT)); and a National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIT) (NRF-2018M3A7B8060601 and NRF-2021R1C1C1013784). Material characterization, including X-ray diffraction, SEM and TEM analysis, was supported by the Research Institute of Advanced Materials, Institute of Engineering Research and the National Center for Interuniversity Research Facilities in Seoul National University. ICP-AES and NMR analysis were supported by the National Instrumentation Center for Environmental Management. XPS analysis was supported by the Korea Institute of Ceramic Engineering and Technology. Y.-C.J. acknowledges support from the Supercomputing Center/Korea Institute of Science and Technology Information with supercomputing resources (KSC-2021-RND-0010). Experiments at PLS-II were supported in part by MSIT and POSTECH.
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Contributions
Y.-C.J., E.S.P. and D.-H.N. designed and supervised the overall project. J.-Y.K., H.S.A. and I.K. conceived the idea and carried out the experiments. J.-Y.K. and I.K. conducted the dealloying, characterization and electrochemical experiments. H.S.A. designed and fabricated the alloy. D.H. conducted the DFT calculations. J.J. and H.G.K. carried out the TEM analysis. H.K. and G.K. contributed to the CO2RR performance evaluation and thermodynamic calculation, respectively. M.K.K. and W.H.R. contributed to the alloy fabrication and CCT diagram construction. T.L. and S.G. performed XAS and Raman analysis. G.-D.L. and M.K. supervised the DFT calculations and TEM analysis, respectively. All authors discussed the results and contributed to the paper writing.
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Nature Synthesis thanks Zhiliang Wang 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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Supplementary information
Supplementary Information
Supplementary Figs. 1–74 and Tables 1–3.
Supplementary Data 1
Electrochemical CO2 reduction performance and DFT calculation
Source data
Source Data Fig. 1
Source data for DFT and thermochemical calculations.
Source Data Fig. 2
Source data for thermochemical calculation, CCT diagram and electrochemical CO2 reduction performance.
Source Data Fig. 2
Source data for ternary phase diagrams.
Source Data Fig. 3
Source data for phase fraction and atomic composition.
Source Data Fig. 4
Source data for phase and state analysis.
Source Data Fig. 5
Source data for electrochemical CO2 reduction performance.
Source Data Fig. 6
Source data for Raman analysis and DFT calculation.
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Kim, JY., Ahn, H.S., Kim, I. et al. Selective hydrocarbon or oxygenate production in CO2 electroreduction over metallurgical alloy catalysts. Nat. Synth 3, 452–465 (2024). https://doi.org/10.1038/s44160-023-00449-6
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DOI: https://doi.org/10.1038/s44160-023-00449-6