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Selective hydrocarbon or oxygenate production in CO2 electroreduction over metallurgical alloy catalysts

Nature Synthesis volume 3, pages 452–465 (2024)Cite this article

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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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Fig. 1: Theoretical study on the effect of the atomic arrangement of alloys on CO2 electrocatalysis and the metallurgical design strategy.
Fig. 2: Microstructure optimization of the binary Cu–Al alloy and dealloyed copper catalysts with respect to the composition and cooling rate.
Fig. 3: Design and fabrication of copper-miscible Cu–Zn–Al alloy and dealloyed Cu–Zn catalysts.
Fig. 4: Design and fabrication of copper-immiscible Cu–Ag–Al alloy and dealloyed Cu–Ag catalysts.
Fig. 5: CO2RR performance of dealloyed copper and alloy catalysts.
Fig. 6: In situ Raman and DFT calculation study on the CO2RR of dealloyed copper and supersaturated Ag–Cu.

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All data supporting the findings of this study are available within the articles and its Supplementary Information.

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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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  1. These authors contributed equally: Ji-Yong Kim, Heh Sang Ahn, Intae Kim.

Authors and Affiliations

  1. Department of Materials Science and Engineering, Seoul National University, Seoul, Republic of Korea

    Ji-Yong Kim, Heh Sang Ahn, Intae Kim, Deokgi Hong, Jaeyeon Jo, Hyeontae Kim, Min Kyung Kwak, Hyoung Gyun Kim, Geosan Kang, Wook Ha Ryu, Gun-Do Lee, Miyoung Kim, Eun Soo Park & Young-Chang Joo

  2. Department of Energy Science and Engineering, Daegu Gyeongbuk Institute of Science and Technology (DGIST), Daegu, Republic of Korea

    Taemin Lee, Soohyun Go & Dae-Hyun Nam

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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.

Corresponding authors

Correspondence to Dae-Hyun Nam, Eun Soo Park or Young-Chang Joo.

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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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