Abstract
The carbon dioxide and carbon monoxide electroreduction reactions, when powered using low-carbon electricity, offer pathways to the decarbonization of chemical manufacture1,2. Copper (Cu) is relied on today for carbon–carbon coupling, in which it produces mixtures of more than ten C2+ chemicals3,4,5,6: a long-standing challenge lies in achieving selectivity to a single principal C2+ product7,8,9. Acetate is one such C2 compound on the path to the large but fossil-derived acetic acid market. Here we pursued dispersing a low concentration of Cu atoms in a host metal to favour the stabilization of ketenes10—chemical intermediates that are bound in monodentate fashion to the electrocatalyst. We synthesize Cu-in-Ag dilute (about 1 atomic per cent of Cu) alloy materials that we find to be highly selective for acetate electrosynthesis from CO at high *CO coverage, implemented at 10 atm pressure. Operando X-ray absorption spectroscopy indicates in situ-generated Cu clusters consisting of <4 atoms as active sites. We report a 12:1 ratio, an order of magnitude increase compared to the best previous reports, in the selectivity for acetate relative to all other products observed from the carbon monoxide electroreduction reaction. Combining catalyst design and reactor engineering, we achieve a CO-to-acetate Faradaic efficiency of 91% and report a Faradaic efficiency of 85% with an 820-h operating time. High selectivity benefits energy efficiency and downstream separation across all carbon-based electrochemical transformations, highlighting the importance of maximizing the Faradaic efficiency towards a single C2+ product11.
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Acknowledgements
Y.P. acknowledges financial support from the National Key R&D Program of China (grant number 2022YFC2106000), the National Natural Science Foundation of China (grant number 11874164) and the Innovation Fund of Wuhan National Laboratory for Optoelectronics. J.J. acknowledges financial support from the National Natural Science Foundation of China (grant number 52006085) and the China Postdoctoral Science Foundation (grant numbers 2019TQ0104 and 2020M672343). L.M. acknowledges financial support from the National Natural Science Foundation of China (grant numbers 52127816 and 51832004) and the National Key Research and Development Program of China (grant number 2020YFA0715000). J.L. acknowledges financial support from the National Natural Science Foundation of China (grant number BE3250011), the National Key Research and Development Program of China (grant number 2022YFA1505100) and Shanghai Jiao Tong University (grant number WH220432516). E.H.S. acknowledges financial support from the Natural Sciences and Engineering Research Council of Canada (NSERC) Discovery programme (grant number RGPIN-2017-06477) and the Ontario Research Fund (grant number ORF-RE08-034). J.W. acknowledges support from the NSERC Postgraduate Scholarship – Doctoral (PGS-D). Z.W. acknowledges financial support from the Marsden Fund Council for Government funding (grant number 21-UOA-237) and the Catalyst: Seeding General Grant (grant number 22-UOA-031-CGS), managed by the Royal Society Te Apārangi. C.W. acknowledges financial support from the National Natural Science Foundation of China (grant numbers 51972129 and 52272202). Figure 1a was created with BioRender.com. The DFT computations in Fig. 1 exploring reaction pathways were carried out on the Niagara supercomputer at the SciNet HPC Consortium. SciNet is funded by the Canada Foundation for Innovation, the Government of Ontario, the Ontario Research Fund Research Excellence Program and the University of Toronto. This work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (grant number NSF ECCS-2025633), the IIN and Northwestern’s MRSEC programme (grant number NSF DMR-1720139). Part of the research described in this paper was carried out at the Canadian Light Source, a national research facility of the University of Saskatchewan, which is supported by the Canada Foundation for Innovation, NSERC, the National Research Council, the Canadian Institutes of Health Research, the Government of Saskatchewan and the University of Saskatchewan. We thank beamline BL14W1 (X-ray absorption fine structure) at SSRF for providing the beamtime, and also acknowledge the support of the Analytical and Testing Center of Huazhong University of Science and Technology for X-ray diffraction, X-ray photoelectron spectroscopy, inductively coupled plasma optical emission spectroscopy, SEM and TEM measurements.
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Y.P., E.H.S., D.S., Z.W. and L.M. supervised the project. J.J. designed the high-pressure electrocatalytic system and carried out electrochemical experiments. Q.M. completed catalyst synthesis and most of its characterization (TEM, X-ray photoelectron spectroscopy, X-ray diffraction and inductively coupled plasma). J.W. carried out DFT calculations. J.L., P.P., J.W., Y.H., M.S., Q.X., J.M., Y.W., Y.X., Y.P. and Z.J. carried out XAS measurements, and J.L. analysed the XAS data. L.M., R.L., P.Q., Y.P., Z.C., W.Z. and K.Y. carried out Raman characterization, and J.W. analysed the Raman data. R.L. and Y.M. conducted vibrational frequency calculations. J.J., G.S. and Q.M. carried out membrane electrode assembly stability tests. Y.X. and A.O. contributed preliminary stability measurements. J.S. and X.J. carried out NMR measurements. Q.M., Y.L., D.W. and P.Q. carried out SEM measurements. X.H. and V.P.D. carried out the HAADF scanning TEM measurements. Y.-M.Y. and T.-K.S. completed the XANES fitting. J.W. conducted the techno-economic assessment. P.O., X.W., Z.W., C.W., B.Y.X. and D.S. contributed to data analysis. J.J., J.W., Q.M., J.L., Y.P. and E.H.S. co-wrote the manuscript. All authors discussed the results and assisted during manuscript preparation.
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This file contains details regarding the techno-economic analysis, Supplementary Figs. 1–43, Tables 1–31, a Note (Adsorption of C2 intermediates on low Cu concentration surfaces) and References (see contents page for details).
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DFT source data (corresponding to Supplementary Table 31).
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Jin, J., Wicks, J., Min, Q. et al. Constrained C2 adsorbate orientation enables CO-to-acetate electroreduction. Nature 617, 724–729 (2023). https://doi.org/10.1038/s41586-023-05918-8
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DOI: https://doi.org/10.1038/s41586-023-05918-8
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