Abstract
The electroreduction of CO2 has recently achieved notable progress in the formation of C2 products such as ethylene and ethanol. However, the direct synthesis of C3 products is considerably limited by the C2–C1 coupling reaction and the faradaic efficiency has remained low. Here we present a supersaturation strategy for the electrosynthesis of 2-propanol from CO2 in highly carbonated electrolytes. By controlling the CO2 concentration above the saturation limit, we have developed a co-electrodeposition method with suppressed galvanic replacement to obtain a CuAg alloy catalyst. In supersaturated conditions, the alloy achieved high performance for the production of 2-propanol with a faradaic efficiency of 56.7% and at a specific current density of 59.3 mA cm−2. Our investigations revealed that the presence of dispersed Ag atoms in Cu weakens the surface binding of intermediates in the middle position of the alkyl chain and strengthens the C–O bonds, which favours the formation of 2-propanol over 1-propanol.
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All data are available in the public Figshare repository (https://doi.org/10.6084/m9.figshare.22002014.v1) or from the corresponding author upon reasonable request. Source data are provided with this paper.
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All code used within the Article is available in the public Figshare repository (https://doi.org/10.6084/m9.figshare.22083551.v1) or from the corresponding author upon reasonable request.
References
Qiao, J. L., Liu, Y. Y., Hong, F. & Zhang, J. J. A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels. Chem. Soc. Rev. 43, 631–675 (2014).
Wang, M. et al. CO2 electrochemical catalytic reduction with a highly active cobalt phthalocyanine. Nat. Commun. 10, 3602 (2019).
Wang, Z. Y., Li, Y. G., Boes, J., Wang, Y. & Sargent, E. H. CO2 electrocatalyst design using graph theory. Preprint at https://doi.org/10.21203/rs.3.rs-66715/v1, (2020).
Raaijman, S. J., Schellekens, M. P., Corbett, P. J. & Koper, M. T. M. High-pressure CO electroreduction at silver produces ethanol and propanol. Angew. Chem. Int. Ed. 60, 21732–21736 (2021).
Xiao, H., Cheng, T. & Goddard, W. A. III Atomistic mechanisms underlying selectivities in C1 and C2 products from electrochemical reduction of CO on Cu(111). J. Am. Chem. Soc. 139, 130–136 (2017).
Peng, C. et al. Double sulfur vacancies by lithium tuning enhance CO2 electroreduction to n-propanol. Nat. Commun. 12, 1580 (2021).
Wang, X. et al. Efficient electrosynthesis of n-propanol from carbon monoxide using a Ag–Ru–Cu catalyst. Nat. Energy 7, 170–176 (2022).
Yang, P. P. et al. Protecting copper oxidation state via intermediate confinement for selective CO2 electroreduction to C2+ fuels. J. Am. Chem. Soc. 142, 6400–6408 (2020).
Zhuang, T. T. et al. Copper nanocavities confine intermediates for efficient electrosynthesis of C3 alcohol fuels from carbon monoxide. Nat. Catal. 1, 946–951 (2018).
Gunathunge, C. M., Ovalle, V. J., Li, Y. W., Janik, M. J. & Waegele, M. M. Existence of an electrochemically inert CO population on Cu electrodes in alkaline pH. ACS Catal. 8, 7507–7516 (2018).
Chang, C. J. et al. Quantitatively unraveling the redox shuttle of spontaneous oxidation/electroreduction of CuOx on silver nanowires using in situ X-ray absorption spectroscopy. ACS Cent. Sci. 5, 1998–2009 (2019).
Vasileff, A., Xu, C. C., Jiao, Y., Zheng, Y. & Qiao, S. Z. Surface and interface engineering in copper-based bimetallic materials for selective CO2 electroreduction. Chem 4, 1809–1831 (2018).
Ting, L. R. L. et al. Enhancing CO2 electroreduction to ethanol on copper–silver composites by opening an alternative catalytic pathway. ACS Catal. 10, 4059–4069 (2020).
Wang, Y. H. et al. Catalyst synthesis under CO2 electroreduction favours faceting and promotes renewable fuels electrosynthesis. Nat. Catal. 3, 98–106 (2020).
Ye, Y. F. et al. Dramatic differences in carbon dioxide adsorption and initial steps of reduction between silver and copper. Nat. Commun. 10, 1875 (2019).
Yang, C. P. et al. Overcoming immiscibility toward bimetallic catalyst library. Sci. Adv. 6, eaaz6844 (2020).
Lv, X. M. et al. Electron-deficient Cu sites on Cu3Ag1 catalyst promoting CO2 electroreduction to alcohols. Adv. Energy Mater. 10, 2001987 (2020).
Zhou, B. W. et al. Highly efficient binary copper–iron catalyst for photoelectrochemical carbon dioxide reduction toward methane. Proc. Natl Acad. Sci. USA 117, 1330–1338 (2020).
Liu, J. J., Zou, S. H., Xiao, L. P. & Fan, J. Well-dispersed bimetallic nanoparticles confined in mesoporous metal oxides and their optimized catalytic activity for nitrobenzene hydrogenation. Catal. Sci. Technol. 4, 441–446 (2014).
Gibbons, B. M. et al. In situ X-ray absorption spectroscopy disentangles the roles of copper and silver in a bimetallic catalyst for the oxygen reduction reaction. Chem. Mater. 32, 1819–1827 (2020).
de Arquer, F. P. G. et al. CO2 electrolysis to multicarbon products at activities greater than 1 A cm−2. Science 367, 661–666 (2020).
Lin, S. C. et al. Operando time-resolved X-ray absorption spectroscopy reveals the chemical nature enabling highly selective CO2 reduction. Nat. Commun. 11, 3525 (2020).
Gu, Z. X. et al. Efficient electrocatalytic CO2 reduction to C2+ alcohols at defect-site-rich Cu surface. Joule 5, 429–440 (2021).
Herzog, A. et al. Operando investigation of Ag-decorated Cu2O nanocube catalysts with enhanced CO2 electroreduction toward liquid products. Angew. Chem. Int. Ed. 60, 7426–7435 (2021).
Qi, K. et al. Enhancing the CO2-to-CO conversion from 2D silver nanoprisms via superstructure assembly. ACS Nano 15, 7682–7693 (2021).
Li, J. C., Guo, J. Y. & Dai, H. J. Probing dissolved CO2(aq) in aqueous solutions for CO2 electroreduction and storage. Sci. Adv. 8, eabo0399 (2022).
Dutta, A. et al. Activation of bimetallic AgCu foam electrocatalysts for ethanol formation from CO2 by selective Cu oxidation/reduction. Nano Energy 68, 12 (2020).
Rayer, A. V. et al. Electrochemical carbon dioxide reduction to isopropanol using novel carbonized copper metal organic framework derived electrodes. J. CO2 Util. 39, 101159 (2020).
Munir, S., Varzeghani, A. R. & Kaya, S. Electrocatalytic reduction of CO2 to produce higher alcohols. Sustain. Energy Fuels 2, 2532–2541 (2018).
Kim, D. Y., Kley, C. S., Li, Y. F. & Yang, P. D. Copper nanoparticle ensembles for selective electroreduction of CO2 to C2–C3 products. Proc. Nat. Acad. Sci. USA 114, 10560–10565 (2017).
Jiang, K. et al. Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO2 reduction. Nat. Catal. 1, 111–119 (2018).
Zhuang, T. T. et al. Steering post-C–C coupling selectivity enables high efficiency electroreduction of carbon dioxide to multi-carbon alcohols. Nat. Catal. 1, 421–428 (2018).
Ren, D., Fong, J. H. & Yeo, B. S. The effects of currents and potentials on the selectivities of copper toward carbon dioxide electroreduction. Nat. Commun. 9, 925 (2018).
Liu, H., Liu, J. & Yang, B. Promotional role of a cation intermediate complex in C2 formation from electrochemical reduction of CO2 over Cu. ACS Catal. 11, 12336–12343 (2021).
Gabardo, C. M. et al. Continuous carbon dioxide electroreduction to concentrated multi-carbon products using a membrane electrode assembly. Joule 3, 2777–2791 (2019).
Burdyny, T. & Smith, W. A. CO2 reduction on gas-diffusion electrodes and why catalytic performance must be assessed at commercially-relevant conditions. Energy Environ. Sci. 12, 1442–1453 (2019).
Chang, X. X., Malkani, A., Yang, X. & Xu, B. J. Mechanistic insights into electroreductive C–C coupling between CO and acetaldehyde into multicarbon products. J. Am. Chem. Soc. 142, 2975–2983 (2020).
Li, J. et al. Constraining CO coverage on copper promotes high-efficiency ethylene electroproduction. Nat. Catal. 2, 1124–1131 (2019).
Blyholder, G. Molecular orbital view of chemisorbed carbon monoxide. J. Phys. Chem. 68, 2772–2777 (1964).
Li, Y. G. C. et al. Binding site diversity promotes CO2 electroreduction to ethanol. J. Am. Chem. Soc. 141, 8584–8591 (2019).
Gao, J. et al. Selective C–C coupling in carbon dioxide electroreduction via efficient spillover of intermediates as supported by operando Raman spectroscopy. J. Am. Chem. Soc. 141, 18704–18714 (2019).
Li, F. W. et al. Molecular tuning of CO2-to-ethylene conversion. Nature 577, 509–513 (2020).
Wang, X. et al. Gold-in-copper at low *CO coverage enables efficient electromethanation of CO2. Nat. Commun. 12, 3387 (2021).
Schah-Mohammedi, P. et al. Hydrogen/deuterium-isotope effects on NMR chemical shifts and symmetry of homoconjugated hydrogen-bonded ions in polar solution. J. Am. Chem. Soc. 122, 12878–12879 (2000).
Yang, B. P. et al. Accelerating CO2 electroreduction to multicarbon products via synergistic electric-thermal field on copper nanoneedles. J. Am. Chem. Soc. 144, 3039–3049 (2022).
Cao, X. Y. et al. In situ characterization for boosting electrocatalytic carbon dioxide reduction. Small Methods 5, 2100700 (2021).
Zheng, Y. et al. Understanding the roadmap for electrochemical reduction of CO2 to multi-carbon oxygenates and hydrocarbons on copper-based catalysts. J. Am. Chem. Soc. 141, 7646–7659 (2019).
Pablo-García, S. et al. Mechanistic routes toward C3 products in copper-catalysed CO2 electroreduction. Catal. Sci. Technol. 12, 409–417 (2022).
Santatiwongchai, J., Faungnawakij, K. & Hirunsit, P. Comprehensive mechanism of CO2 electroreduction toward ethylene and ethanol: the solvent effect from explicit water–Cu(100) interface models. ACS Catal. 11, 9688–9701 (2021).
Gabardo, C. M. et al. Combined high alkalinity and pressurization enable efficient CO2 electroreduction to CO. Energy Environ. Sci. 11, 2531–2539 (2018).
Vavra, J., Shen, T. H., Stoian, D., Tileli, V. & Buonsanti, R. Real-time monitoring reveals dissolution/redeposition mechanism in copper nanocatalysts during the initial stages of the CO2 reduction reaction. Angew. Chem. Int. Ed. 60, 1347–1354 (2020).
Ramdin, M. et al. High pressure electrochemical reduction of CO2 to formic acid/formate: a comparison between bipolar membranes and cation exchange membranes. Ind. Eng. Chem. Res. 58, 1834–1847 (2019).
Edwards, J. P. et al. Efficient electrocatalytic conversion of carbon dioxide in a low-resistance pressurized alkaline electrolyzer. Appl. Energy 261, 114305 (2020).
Shaughnessy, C. I. et al. Intensified electrocatalytic CO2 conversion in pressure-tunable CO2-expanded electrolytes. ChemSusChem 12, 3761–3768 (2019).
Rahaman, M., Dutta, A., Zanetti, A. & Broekmann, P. Electrochemical reduction of CO2 into multicarbon alcohols on activated Cu mesh catalysts: an identical location (IL) study. ACS Catal. 7, 7946–7956 (2017).
Li, J. et al. Copper adparticle enabled selective electrosynthesis of n-propanol. Nat. Commun. 9, 4614 (2018).
Qi, K. et al. Single-atom cobalt array bound to distorted 1T MoS2 with ensemble effect for hydrogen evolution catalysis. Nat. Commun. 10, 5231 (2019).
Akemann, W. & Otto, A. Vibrational modes of CO adsorbed on disordered copper films. J. Raman Spectrosc. 22, 797–803 (1991).
Acknowledgements
D.V., K.Q. and H.W. acknowledge funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant no. 804320). This work was also supported by the Laboratoire d’Excellence sur la Chimie des Systèmes Moléculaires et Interfaciaux (LabEx CheMISyst). K.Q. and Y.Z. acknowledge financial support from the China Postdoctoral Science Foundation (2018M633127) and the Natural Science Foundation of Guangdong Province (2018A030310602). L.L. acknowledges funding from the Andalusian regional government (FEDER-UCA-18-106613), the European Union’s Horizon 2020 research and innovation programme (823717-ESTEEM3) and the Spanish Ministerio de Economia y Competitividad (PID2019-107578GA-I00). X.C. acknowledges funding from the National Natural Science Foundation of China (grant nos. 12034002 and 22279044). We thank the SOLEIL Synchrotron and A. Zitolo for allocating beamtime at beamline Samba within proposal number 20200732. We thank E. Oliviero and F. Godiard from the University of Montpellier for their help with the TEM analysis. P. Montels and D. Valenza are acknowledged for their technical support. We thank X. Tao from the University of Extremadura for the MATLAB coding. Part of the S/TEM investigations was performed at the National Facility ELECMI ICTS (‘Division de Microscopia Electronica’, Universidad de Cadiz, DME-UCA). This work was granted access to the HPC resources of IDRIS under the allocation 2021-2022-A0110913046 made by GENCI.
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D.V. and K.Q. designed and directed the research. K.Q., Y.Z., H.W. and Y.Z. synthesized the materials and performed the materials property characterization. N.O., W.W. and J.L. carried out and analysed the DFT calculations. E.P. and C.S. carried out the liquid NMR spectroscopy measurements. L.L., X.C. and Y.W. performed the TEM characterization and analysed the data. K.Q. and D.V. wrote the manuscript. K.Q., J.L., G.J., J.W., J.M. and J.F. performed the hXAS measurements and fitting. D.V. supervised the project and established the final version of the paper. All authors contributed to the manuscript and have approved the final version of the manuscript.
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Qi, K., Zhang, Y., Onofrio, N. et al. Unlocking direct CO2 electrolysis to C3 products via electrolyte supersaturation. Nat Catal 6, 319–331 (2023). https://doi.org/10.1038/s41929-023-00938-z
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DOI: https://doi.org/10.1038/s41929-023-00938-z
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