Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Designing materials for electrochemical carbon dioxide recycling

Abstract

Electrochemical carbon dioxide recycling provides an attractive approach to synthesizing fuels and chemical feedstocks using renewable energy. On the path to deploying this technology, basic and applied scientific hurdles remain. Integrating catalytic design with mechanistic understanding yields scientific insights and progresses the technology towards industrial relevance. Catalysts must be able to generate valuable carbon-based products with better selectivity, lower overpotentials and improved current densities with extended operation. Here, we describe progress and identify mechanistic questions and performance metrics for catalysts that can enable carbon-neutral renewable energy storage and utilization.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: Electrochemical CO2 reduction.
Fig. 2: The path from gaseous CO2 to valuable products.
Fig. 3: Example of linear scaling relations.
Fig. 4: Solution dynamics in CO2 reduction.
Fig. 5: Designing materials to activate CO2.
Fig. 6: Motifs on Cu that may influence dimerization.
Fig. 7

References

  1. 1.

    Smil, V. Energy Transitions: History, Requirements, Prospects (Praeger, Santa Barbara, 2010).

    Google Scholar 

  2. 2.

    Chu, S. & Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 488, 294–303 (2012).

    CAS  Article  Google Scholar 

  3. 3.

    Chu, S., Cui, Y. & Liu, N. The path towards sustainable energy. Nat. Mater. 16, 16–22 (2016).

    PubMed  Google Scholar 

  4. 4.

    Obama, B. The irreversible momentum of clean energy. Science 355, 126–129 (2017).

    CAS  PubMed  Google Scholar 

  5. 5.

    Gao, D., Arán-Ais, R. M., Jeon, H. S. & Roldán Cuenya, B. Rational catalyst and electrolyte design for CO2 electroreduction towards multicarbon products. Nat. Catal. 2, 198–210 (2019).

    CAS  Google Scholar 

  6. 6.

    Handoko, A. D., Wei, F., Jenndy, Yeo, B. S. & Seh, Z. W. Understanding heterogeneous electrocatalytic carbon dioxide reduction through operando techniques. Nat. Catal. 1, 922–934 (2018). A comprehensive review of state-of-the-art characterization of CO 2 RR electrocatalysts under working conditions.

  7. 7.

    Kim, D., Sakimoto, K. K., Hong, D. & Yang, P. Artificial photosynthesis for sustainable fuel and chemical production. Angew. Chem. Int. Ed. 54, 3259–3266 (2015).

    CAS  Google Scholar 

  8. 8.

    Hori, Y. in Modern Aspects of Electrochemistry (Springer, 2008). This chapter provides a comprehensive summary of CO 2 RR electrochemistry on a variety of metal surfaces.

  9. 9.

    Seh, Z. W. et al. Combining theory and experiment in electrocatalysis: insights into materials design. Science 355, eaad4998 (2017). This review describes the interplay between experiment and theory in electrocatalysis for a variety of reactions, as well as introducing intermediate binding strength and scaling relations as frameworks for understanding catalytic activity.

    PubMed  Google Scholar 

  10. 10.

    Göttle, A. J. & Koper, M. T. M. Proton-coupled electron transfer in the electrocatalysis of CO2 reduction: prediction of sequential vs. concerted pathways using DFT. Chem. Sci. 8, 458–465 (2017).

    PubMed  Google Scholar 

  11. 11.

    Singh, M. R., Clark, E. L. & Bell, A. T. Effects of electrolyte, catalyst, and membrane composition and operating conditions on the performance of solar-driven electrochemical reduction of carbon dioxide. Phys. Chem. Chem. Phys. 17, 18924–18936 (2015).

    CAS  PubMed  Google Scholar 

  12. 12.

    Weiss, R. F. Carbon dioxide in water and seawater: the solubility of a non-ideal gas. Mar. Chem. 2, 203–215 (1974).

    CAS  Google Scholar 

  13. 13.

    Singh, M. R., Kwon, Y., Lum, Y., Ager, J. W. & Bell, A. T. Hydrolysis of electrolyte cations enhances the electrochemical reduction of CO2 over Ag and Cu. J. Am. Chem. Soc. 138, 13006–13012 (2016).

    CAS  PubMed  Google Scholar 

  14. 14.

    Wuttig, A., Yaguchi, M., Motobayashi, K., Osawa, M. & Surendranath, Y. Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity. Proc. Natl Acad. Sci. 113, E4585–E4593 (2016).

    CAS  PubMed  Google Scholar 

  15. 15.

    Lee, C. W., Cho, N. H., Yang, K. D. & Nam, K. T. Reaction mechanisms of the electrochemical conversion of carbon dioxide to formic acid on tin oxide electrodes. ChemElectroChem 4, 2130–2136 (2017).

    CAS  Google Scholar 

  16. 16.

    Hansen, H. A., Varley, J. B., Peterson, A. A. & Nørskov, J. K. Understanding trends in the electrocatalytic activity of metals and enzymes for CO2 reduction to CO. J. Phys. Chem. Lett. 4, 388–392 (2013).

    CAS  PubMed  Google Scholar 

  17. 17.

    Feaster, J. T. et al. Understanding selectivity for the electrochemical reduction of carbon dioxide to formic acid and carbon monoxide on metal electrodes. ACS Catal. 7, 4822–4827 (2017).

    CAS  Google Scholar 

  18. 18.

    Baruch, M. F., Pander, J. E., White, J. L. & Bocarsly, A. B. Mechanistic insights into the reduction of CO2 on tin electrodes using in situ ATR-IR spectroscopy. ACS Catal. 5, 3148–3156 (2015).

    CAS  Google Scholar 

  19. 19.

    Kuhl, K. P., Cave, E. R., Abram, D. N. & Jaramillo, T. F. New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces. Energy Environ. Sci. 5, 7050–7059 (2012). Sixteen distinct products are accounted for from CO 2 RR on a polycrystalline Cu surface, providing insight into the competing reaction pathways for multi-carbon product formation on Cu surfaces.

    CAS  Google Scholar 

  20. 20.

    Hori, Y., Takahashi, R., Yoshinami, Y. & Murata, A. Electrochemical reduction of CO at a copper electrode. J. Phys. Chem. B 101, 7075–7081 (1997).

    CAS  Google Scholar 

  21. 21.

    Schmid, B. et al. Reactivity of copper electrodes towards functional groups and small molecules in the context of CO2 electro-reductions. Catalysts 7, 161 (2017).

    Google Scholar 

  22. 22.

    Kortlever, R., Shen, J., Schouten, K. J. P., Calle-Vallejo, F. & Koper, M. T. M. Catalysts and reaction pathways for the electrochemical reduction of carbon dioxide. J. Phys. Chem. Lett. 6, 4073–4082 (2015).

    CAS  PubMed  PubMed Central  Google Scholar 

  23. 23.

    Goodpaster, J. D., Bell, A. T. & Head-Gordon, M. Identification of possible pathways for C–C bond formation during electrochemical reduction of CO2: new theoretical insights from an improved electrochemical model. J. Phys. Chem. Lett. 7, 1471–1477 (2016).

    CAS  PubMed  Google Scholar 

  24. 24.

    Liu, X. et al. Understanding trends in electrochemical carbon dioxide reduction rates. Nat. Commun. 8, 15438 (2017).

    CAS  PubMed  PubMed Central  Google Scholar 

  25. 25.

    Hall, A. S., Yoon, Y., Wuttig, A. & Surendranath, Y. Mesostructure-induced selectivity in CO2 reduction catalysis. J. Am. Chem. Soc. 137, 14834–14837 (2015).

    CAS  Google Scholar 

  26. 26.

    Zhang, Y. J., Sethuraman, V., Michalsky, R. & Peterson, A. A. Competition between CO2 reduction and H2 evolution on transition-metal electrocatalysts. ACS Catal. 4, 3742–3748 (2014).

    CAS  Google Scholar 

  27. 27.

    Cave, E. R. et al. Trends in the catalytic activity of hydrogen evolution during CO2 electroreduction on transition metals. ACS Catal. 8, 3035–3040 (2018).

    CAS  Google Scholar 

  28. 28.

    Ross, M. B. et al. Electrocatalytic rate alignment enhances syngas generation. Joule 3, 257–264 (2019).

    CAS  Google Scholar 

  29. 29.

    Liu, M. et al. Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration. Nature 537, 382–386 (2016).

    CAS  Google Scholar 

  30. 30.

    Chen, L. D., Urushihara, M., Chan, K. & Nørskov, J. K. Electric field effects in electrochemical CO2 reduction. ACS Catal. 6, 7133–7139 (2016).

    CAS  Google Scholar 

  31. 31.

    Pérez-Gallent, E., Marcandalli, G., Figueiredo, M. C., Calle-Vallejo, F. & Koper, M. T. M. Structure- and potential-dependent cation effects on CO reduction at copper single-crystal electrodes. J. Am. Chem. Soc. 139, 16412–16419 (2017).

    PubMed  PubMed Central  Google Scholar 

  32. 32.

    Perez-Gallent, E., Figueiredo, M. C., Calle-Vallejo, F. & Koper, M. T. M. Spectroscopic observation of a hydrogenated CO dimer intermediate during CO reduction on Cu(100) electrodes. Angew. Chem. Int. Ed. 129, 3675–3678 (2017).

    Google Scholar 

  33. 33.

    Rosen, B. A. et al. Ionic liquid-mediated selective conversion of CO2 to CO at low overpotentials. Science 334, 643–644 (2011).

    CAS  PubMed  Google Scholar 

  34. 34.

    Urushihara, M., Chan, K., Shi, C. & Nørskov, J. K. Theoretical Study of EMIM+ Adsorption on Silver Electrode Surfaces. J. Phys. Chem. C. 119, 20023–20029 (2015).

    CAS  Google Scholar 

  35. 35.

    Han, Z., Kortlever, R., Chen, H.-Y., Peters, J. C. & Agapie, T. CO2 reduction selective for C2+ products on polycrystalline copper with N-substituted pyridinium additives. ACS Cent. Sci. 3, 853–859 (2017).

    CAS  PubMed  PubMed Central  Google Scholar 

  36. 36.

    Verma, S., Kim, B., Jhong, H. R. M., Ma, S. & Kenis, P. J. A. A gross-margin model for defining technoeconomic benchmarks in the electroreduction of CO2. ChemSusChem 9, 1972–1979 (2016). This work presents a thorough technoeconomic analysis of CO 2 reduction at the device level, explicitly describing how to treat capital costs, catalyst durability and electricity prices.

    CAS  PubMed  Google Scholar 

  37. 37.

    Jouny, M., Luc, W. W. & Jiao, F. A general techno-economic analysis of CO2 electrolysis systems. Ind. Eng. Chem. Res. 57, 2165–2177 (2018).

    CAS  Google Scholar 

  38. 38.

    Bushuyev, O. S. et al. What should we make with CO2 and how can we make it? Joule 2, 825–832 (2018).

    CAS  Google Scholar 

  39. 39.

    Hoang, T. T. H. et al. Nano porous copper-silver alloys by additive-controlled electro-deposition for the selective electroreduction of CO2 to ethylene and ethanol. J. Am. Chem. Soc. 140, 5791–5797 (2018).

    CAS  PubMed  Google Scholar 

  40. 40.

    Verma, S. et al. Insights into the low overpotential electroreduction of CO2 to CO on a supported gold catalyst in an alkaline flow electrolyzer. ACS Energy Lett. 3, 193–198 (2018).

    CAS  Google Scholar 

  41. 41.

    Ma, S. et al. One-step electrosynthesis of ethylene and ethanol from CO2 in an alkaline electrolyzer. J. Power Sources 301, 219–228 (2016).

    CAS  Google Scholar 

  42. 42.

    Dinh, C. et al. Sustained high-selectivity CO2 electroreduction to ethylene via hydroxide-mediated catalysis at an abrupt reaction interface. Science 360, 783–787 (2018). This work illustrates how the design of an electrolyser system can dramatically improve performance, here, particularly for the synthesis of ethylene.

    CAS  PubMed  PubMed Central  Google Scholar 

  43. 43.

    Jhong, H. R. M., Ma, S. & Kenis, P. J. Electrochemical conversion of CO2 to useful chemicals: current status, remaining challenges, and future opportunities. Curr. Opin. Chem. Eng. 2, 191–199 (2013).

    Google Scholar 

  44. 44.

    Ripatti, D. S., Veltman, T. R. & Kanan, M. W. Carbon monoxide gas diffusion electrolysis that produces concentrated C2 products with high single-pass conversion. Joule 3, 240–256 (2019).

    CAS  Google Scholar 

  45. 45.

    Yang, H., Kaczur, J. J., Sajjad, S. D. & Masel, R. I. Electrochemical conversion of CO2 to formic acid utilizing SustainionTM membranes. J. CO2 Util. 20, 208–217 (2017).

    CAS  Google Scholar 

  46. 46.

    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).

    CAS  Google Scholar 

  47. 47.

    Chen, Y. & Kanan, M. W. Tin oxide dependence of the CO2 reduction efficiency on tin electrodes and enhanced activity for tin/tin oxide thin-film catalysts. J. Am. Chem. Soc. 134, 1986–1989 (2012). The first demonstration of the oxide-derived approach in CO 2 RR electrocatalysis that has consistently been shown to improve activity and selectivity.

    CAS  PubMed  Google Scholar 

  48. 48.

    Luc, W. et al. Ag-Sn bimetallic catalyst with a core-shell structure for CO2 reduction. J. Am. Chem. Soc. 139, 1885–1893 (2017).

    CAS  PubMed  Google Scholar 

  49. 49.

    Kim, D., Resasco, J., Yu, Y., Asiri, A. M. & Yang, P. Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold-copper bimetallic nanoparticles. Nat. Commun. 5, 4948 (2014).

    CAS  PubMed  Google Scholar 

  50. 50.

    Christophe, J., Doneux, T. & Buess-Herman, C. Electroreduction of carbon dioxide on copper-based electrodes: activity of copper single crystals and copper-gold alloys. Electrocatalysis 3, 139–146 (2012).

    CAS  Google Scholar 

  51. 51.

    Kim, D. et al. Electrochemical activation of CO2 through atomic ordering transformations of AuCu nanoparticles. J. Am. Chem. Soc. 139, 8329–8336 (2017).

    CAS  PubMed  Google Scholar 

  52. 52.

    Ross, M. B. et al. Tunable Cu enrichment enables designer syngas electrosynthesis from CO2. J. Am. Chem. Soc. 139, 9359–9363 (2017).

    CAS  PubMed  Google Scholar 

  53. 53.

    Durand, W. J., Peterson, A. A., Studt, F., Abild-Pedersen, F. & Nørskov, J. K. Structure effects on the energetics of the electrochemical reduction of CO2 by copper surfaces. Surf. Sci. 605, 1354–1359 (2011).

    CAS  Google Scholar 

  54. 54.

    Zhu, W. et al. Active and selective conversion of CO2 to CO on ultrathin Au nanowires. J. Am. Chem. Soc. 136, 16132–16135 (2014).

    CAS  PubMed  Google Scholar 

  55. 55.

    Hong, X., Chan, K., Tsai, C. & Norskov, J. K. How doped MoS2 breaks transition-metal scaling relations for CO2 electrochemical reduction. ACS Catal. 6, 4428–4437 (2016).

    CAS  Google Scholar 

  56. 56.

    Handoko, A. D., Khoo, K. H., Tan, T. L., Jin, H. & Seh, Z. W. Establishing new scaling relations on two-dimensional MXenes for CO2 electroreduction. J. Mater. Chem. A 6, 21885–21890 (2018).

    CAS  Google Scholar 

  57. 57.

    Hori, Y., Wakebe, H., Tsukamoto, T. & Koga, O. Electrocatalytic process of CO selectivity in electrochemical reduction of CO2 at metal electrodes in aqueous media. Electrochim. Acta 39, 1833–1839 (1994).

    CAS  Google Scholar 

  58. 58.

    Hori, Y., Takahashi, I., Koga, O. & Hoshi, N. Selective formation of C2 compounds from electrochemical reduction of CO2 at a series of copper single crystal electrodes. J. Phys. Chem. B 106, 15–17 (2002).

    CAS  Google Scholar 

  59. 59.

    Calle-Vallejo, F. & Koper, M. T. M. Theoretical considerations on the electroreduction of CO to C2 Species on Cu(100) electrodes. Angew. Chem. Int. Ed. 52, 7282–7285 (2013).

    CAS  Google Scholar 

  60. 60.

    Schouten, K. J. P., Qin, Z., Gallent, E. P. & Koper, M. T. M. Two pathways for the formation of ethylene in CO reduction on single-crystal copper electrodes. J. Am. Chem. Soc. 134, 9864–9867 (2012).

    CAS  PubMed  PubMed Central  Google Scholar 

  61. 61.

    Montoya, J. H., Shi, C., Chan, K. & Nørskov, J. K. Theoretical Insights into a CO dimerization mechanism in CO2 electroreduction. J. Phys. Chem. Lett. 6, 2032–2037 (2015).

    CAS  PubMed  Google Scholar 

  62. 62.

    Sandberg, R. B., Montoya, J. H., Chan, K. & Nørskov, J. K. CO-CO coupling on Cu facets: coverage, strain and field effects. Surf. Sci. 654, 56–62 (2016).

    CAS  Google Scholar 

  63. 63.

    Huang, Y., Handoko, A. D., Hirunsit, P. & Yeo, B. S. Electrochemical reduction of CO2 using copper single-crystal surfaces: effects of CO* coverage on the selective formation of ethylene. ACS Catal. 7, 1749–1756 (2017).

    CAS  Google Scholar 

  64. 64.

    Roberts, F. S., Kuhl, K. P. & Nilsson, A. High selectivity for ethylene from carbon dioxide reduction over copper nanocube electrocatalysts. Angew. Chem. Int. Ed. 54, 5179–5182 (2015).

    CAS  Google Scholar 

  65. 65.

    Gao, D. et al. Plasma-activated copper nanocube catalysts for efficient carbon dioxide electroreduction to hydrocarbons and alcohols. ACS Nano 11, 4825–4831 (2017).

    CAS  PubMed  Google Scholar 

  66. 66.

    Loiudice, A. et al. Tailoring copper nanocrystals towards C2 products in electrochemical CO2 reduction. Angew. Chem. Int. Ed. 55, 5789–5792 (2016).

    CAS  Google Scholar 

  67. 67.

    Grosse, P. et al. Dynamic changes in the structure, chemical state and catalytic selectivity of Cu nanocubes during CO2 electroreduction: size and support effects. Angew. Chem. Int. Ed. 130, 6300–6305 (2018).

    Google Scholar 

  68. 68.

    Li, C. W. & Kanan, M. W. CO2 reduction at low overpotential on Cu electrodes resulting from the reduction of thick Cu2O films. J. Am. Chem. Soc. 134, 7231–7234 (2012).

    CAS  PubMed  Google Scholar 

  69. 69.

    Li, C. W., Ciston, J. & Kanan, M. W. Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper. Nature 508, 504–507 (2014).

    CAS  Google Scholar 

  70. 70.

    Verdaguer-Casadevall, A. et al. Probing the active surface sites for CO reduction on oxide-derived copper electrocatalysts. J. Am. Chem. Soc. 137, 9808–9811 (2015).

    CAS  PubMed  Google Scholar 

  71. 71.

    Kas, R. et al. Electrochemical CO2 reduction on Cu2O-derived copper nanoparticles: controlling the catalytic selectivity of hydrocarbons. Phys. Chem. Chem. Phys. 16, 12194–12201 (2014).

    CAS  PubMed  Google Scholar 

  72. 72.

    Ren, D. et al. Selective electrochemical reduction of carbon dioxide to ethylene and ethanol on copper(I) oxide catalysts. ACS Catal. 5, 2814–2821 (2015).

    CAS  Google Scholar 

  73. 73.

    Mistry, H. et al. Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene. Nat. Commun. 7, 12123 (2016).

    PubMed  PubMed Central  Google Scholar 

  74. 74.

    Kas, R., Kortlever, R., Yilmaz, H., Koper, M. T. M. & Mul, G. Manipulating the hydrocarbon selectivity of copper nanoparticles in CO2 electroreduction by process conditions. ChemElectroChem 2, 354–358 (2015).

    CAS  Google Scholar 

  75. 75.

    Lum, Y., Yue, B., Lobaccaro, P., Bell, A. T. & Ager, J. W. Optimizing C–C coupling on oxide-derived copper catalysts for electrochemical CO2 reduction. J. Phys. Chem. C. 121, 14191–4203 (2017).

    CAS  Google Scholar 

  76. 76.

    Ren, D., Fong, J. & Yeo, B. S. The effects of currents and potentials on the selectivities of copper toward carbon dioxide electroreduction. Nat. Commun. 9, 925 (2018).

    PubMed  PubMed Central  Google Scholar 

  77. 77.

    Bertheussen, E. et al. Electroreduction of CO on polycrystalline copper at low overpotentials. ACS Energy Lett. 3, 634–640 (2018).

    CAS  Google Scholar 

  78. 78.

    Dutta, A., Rahaman, M., Luedi, N. C., Mohos, M. & Broekmann, P. Morphology matters: tuning the product distribution of CO2 electroreduction on oxide-derived Cu foam catalysts. ACS Catal. 6, 3804–3814 (2016).

    CAS  Google Scholar 

  79. 79.

    Kim, D., Kley, C. S., Li, Y. & Yang, P. Copper nanoparticle ensembles for selective electroreduction of CO2 to C2-C3 products. Proc. Natl Acad. Sci. 114, 10560–10565 (2017). This work demonstrates the importance of Cu structural dynamics in electrolytic conditions that produce multi -carbon products.

    CAS  PubMed  Google Scholar 

  80. 80.

    Feng, X., Jiang, K., Fan, S. & Kanan, M. W. A direct grain-boundary-activity correlation for CO electroreduction on Cu nanoparticles. ACS Cent. Sci. 2, 169–174 (2016).

    CAS  PubMed  PubMed Central  Google Scholar 

  81. 81.

    Li, Y. et al. Structure-sensitive CO2 electroreduction to hydrocarbons on ultrathin five-fold twinned copper nanowires. Nano Lett. 17, 1312–1317 (2017).

    CAS  PubMed  Google Scholar 

  82. 82.

    De Luna, P. et al. Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction. Nat. Catal. 1, 103–110 (2018).

    Google Scholar 

  83. 83.

    Kim, Y. G., Baricuatro, J. H., Javier, A., Gregoire, J. M. & Soriaga, M. P. The evolution of the polycrystalline copper surface, first to Cu(111) and then to Cu(100), at a fixed CO2RR potential: a study by operando EC-STM. Langmuir 30, 15053–15056 (2014).

    CAS  PubMed  PubMed Central  Google Scholar 

  84. 84.

    Gunathunge, C. M. et al. Spectroscopic observation of reversible surface reconstruction of copper electrodes under CO2 reduction. J. Phys. Chem. C. 121, 12337–12344 (2017).

    CAS  Google Scholar 

  85. 85.

    Weng, Z. et al. Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction. Nat. Commun. 9, 415 (2018).

    PubMed  PubMed Central  Google Scholar 

  86. 86.

    Xiao, H., Cheng, T. & Goddard, W. A. 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).

    CAS  PubMed  Google Scholar 

  87. 87.

    Bertheussen, E. et al. Acetaldehyde as an intermediate in the electroreduction of carbon monoxide to ethanol on oxide-derived copper. Angew. Chem. Int. Ed. 55, 1450–1454 (2016).

    CAS  Google Scholar 

  88. 88.

    Lum, Y. & Ager, J. W. Evidence for product-specific active sites on oxide-derived Cu catalysts for electrochemical CO2 reduction. Nat. Catal. 2, 86–93 (2019).

    CAS  Google Scholar 

  89. 89.

    Lum, Y., Cheng, T., Goddard, W. A. & Ager, J. W. Electrochemical CO reduction builds solvent water into oxygenate products. J. Am. Chem. Soc. 140, 9337–9340 (2018).

    CAS  PubMed  Google Scholar 

  90. 90.

    Jouny, M., Luc, W. & Jiao, F. High-rate electroreduction of carbon monoxide to multi-carbon products. Nat. Catal. 1, 748–755 (2018).

    CAS  Google Scholar 

  91. 91.

    Clark, E. L. et al. Explaining the Incorporation of oxygen derived from solvent water into the oxygenated products of CO reduction over Cu. J. Am. Chem. Soc. 141, 4191–4193 (2019).

    CAS  PubMed  Google Scholar 

  92. 92.

    Hahn, C. et al. Engineering Cu surfaces for the electrocatalytic conversion of CO2: Controlling selectivity toward oxygenates and hydrocarbons. Proc. Natl Acad. Sci. 114, 5918–5923 (2017).

    CAS  PubMed  Google Scholar 

  93. 93.

    Ren, D., Ang, B. S. H. & Yeo, B. S. Tuning the selectivity of carbon dioxide electroreduction toward ethanol on oxide-derived CuxZn catalysts. ACS Catal. 6, 8239–8247 (2016).

    CAS  Google Scholar 

  94. 94.

    Clark, E. L., Hahn, C., Jaramillo, T. F. & Bell, A. T. Electrochemical CO2 reduction over compressively strained CuAg surface alloys with enhanced multi-carbon oxygenate selectivity. J. Am. Chem. Soc. 139, 15848–15857 (2017).

    CAS  PubMed  Google Scholar 

  95. 95.

    Ren, D., Wong, N. T., Handoko, A. D., Huang, Y. & Yeo, B. S. Mechanistic insights into the enhanced activity and stability of agglomerated Cu nanocrystals for the electrochemical reduction of carbon dioxide to n-propanol. J. Phys. Chem. Lett. 7, 20–24 (2016).

    CAS  PubMed  Google Scholar 

  96. 96.

    Chen, C. S., Wan, J. H. & Yeo, B. S. Electrochemical reduction of carbon dioxide to ethane using nanostructured Cu2O-derived copper catalyst and palladium(II) chloride. J. Phys. Chem. C. 119, 26875–26882 (2015).

    CAS  Google Scholar 

  97. 97.

    Jensen, M. T. et al. Scalable carbon dioxide electroreduction coupled to carbonylation chemistry. Nat. Commun. 8, 489 (2017).

    PubMed  PubMed Central  Google Scholar 

  98. 98.

    Ostapowicz, T. G., Schmitz, M., Krystof, M., Klankermayer, J. & Leitner, W. Carbon dioxide as a C1 building block for the formation of carboxylic acids by formal catalytic hydrocarboxylation. Angew. Chem. Int. Ed. 52, 12119–12123 (2013).

    CAS  Google Scholar 

  99. 99.

    Klankermayer, J., Wesselbaum, S., Beydoun, K. & Leitner, W. Selective catalytic synthesis using the combination of carbon dioxide and hydrogen: catalytic chess at the interface of energy and chemistry. Angew. Chem. Int. Ed. 55, 7296–7343 (2016).

    CAS  Google Scholar 

  100. 100.

    Haas, T., Krause, R., Weber, R., Demler, M. & Schmid, G. Technical photosynthesis involving CO2 electrolysis and fermentation. Nat. Catal. 1, 32–39 (2018).

    CAS  Google Scholar 

  101. 101.

    Zhao, C. et al. Ionic exchange of metal-organic frameworks to access single nickel sites for efficient electroreduction of CO2. J. Am. Chem. Soc. 139, 8078–081 (2017).

    CAS  PubMed  Google Scholar 

  102. 102.

    Yang, H. Bin et al. Atomically dispersed Ni(I) as the active site for electrochemical CO2 reduction. Nat. Energy 3, 140–147 (2018).

    CAS  Google Scholar 

  103. 103.

    Wang, X. et al. Regulation of coordination number over single Co sites: triggering the efficient electroreduction of CO2. Angew. Chem. Int. Ed. 57, 1944–1948 (2018).

    CAS  Google Scholar 

  104. 104.

    Jiang, K. et al. Isolated Ni single atoms in graphene nanosheets for high-performance CO2 reduction. Energy Environ. Sci. 11, 893–903 (2018).

    CAS  Google Scholar 

  105. 105.

    Ju, W. et al. Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO2. Nat. Commun. 8, 944 (2017).

    PubMed  PubMed Central  Google Scholar 

  106. 106.

    Zhang, X. et al. Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures. Nat. Commun. 8, 14675 (2017).

    PubMed  PubMed Central  Google Scholar 

  107. 107.

    Jackson, M. N. et al. Strong electronic coupling of molecular sites to graphitic electrodes via pyrazine conjugation. J. Am. Chem. Soc. 140, 1004–1010 (2018).

    CAS  PubMed  Google Scholar 

  108. 108.

    Deng, Y. et al. On the role of sulfur for the selective electrochemical reduction of CO2 to formate on CuSx catalysts. ACS Appl. Mater. Interfaces 10, 28572–28581 (2018).

    CAS  PubMed  Google Scholar 

  109. 109.

    Zheng, X. et al. Sulfur-modulated tin sites enable highly selective electrochemical reduction of CO2 to formate. Joule 1, 794–805 (2017).

    CAS  Google Scholar 

  110. 110.

    Jain, A. et al. Commentary: the materials project: a materials genome approach to accelerating materials innovation. APL Mater. 1, 011002 (2013).

    Google Scholar 

  111. 111.

    Bligaard, T. et al. The Brønsted-evans-polanyi relation and the volcano curve in heterogeneous catalysis. J. Catal. 224, 206–217 (2004).

    CAS  Google Scholar 

  112. 112.

    Aspuru-Guzik, A., Lindh, R. & Reiher, M. The matter simulation (R)evolution. ACS Cent. Sci. 4, 144–152 (2018).

    CAS  PubMed  PubMed Central  Google Scholar 

  113. 113.

    Ulissi, Z. W. et al. Machine-learning methods enable exhaustive searches for active bimetallic facets and reveal active site motifs for CO2 reduction. ACS Catal. 7, 6600–6608 (2017).

    CAS  Google Scholar 

  114. 114.

    Ma, X., Li, Z., Achenie, L. E. K. & Xin, H. Machine-learning-augmented chemisorption model for CO2 electroreduction catalyst screening. J. Phys. Chem. Lett. 6, 3528–3533 (2015).

    CAS  PubMed  Google Scholar 

  115. 115.

    Tran, K. & Ulissi, Z. W. Active learning across intermetallics to guide discovery of electrocatalysts for CO2 reduction and H2 evolution. Nat. Catal. 1, 696–703 (2018).

    CAS  Google Scholar 

  116. 116.

    Singh, A. K., Montoya, J. H., Gregoire, J. M. & Persson, K. A. Robust and synthesizable photocatalysts for CO2 reduction: a data-driven materials discovery. Nat. Commun. 10, 443 (2019).

    PubMed  PubMed Central  Google Scholar 

  117. 117.

    Huang, L. et al. Catalyst design by scanning probe block copolymer lithography. Proc. Natl Acad. Sci. 115, 3764–3769 (2018).

    CAS  PubMed  Google Scholar 

  118. 118.

    Nikolaev, P. et al. Autonomy in materials research: a case study in carbon nanotube growth. npj Comput. Mater. 2, 16031 (2016).

    Google Scholar 

  119. 119.

    Gromski, P. S., Henson, A. B., Granda, J. M. & Cronin, L. How to explore chemical space using algorithms and automation. Nat. Rev. Chem. 3, 119–128 (2019).

    Google Scholar 

  120. 120.

    Nie, X., Esopi, M. R., Janik, M. J. & Asthagiri, A. Selectivity of CO2 reduction on copper electrodes: the role of the kinetics of elementary steps. Angew. Chem. Int. Ed. 52, 2459–462 (2013).

    CAS  Google Scholar 

  121. 121.

    Liu, X. et al. pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper. Nat. Commun. 10, 32 (2019).

    PubMed  PubMed Central  Google Scholar 

  122. 122.

    Cheng, T., Fortunelli, A. & Goddard, W. A. III. Reaction intermediates during operando electrocatalysis identified from full solvent quantum mechanics molecular dynamics. Proc. Natl Acad. Sci. 116, 7718–7722 (2019).

    CAS  PubMed  Google Scholar 

  123. 123.

    Wheeldon, I. et al. Substrate channeling as an approach to cascade reactions. Nat. Chem. 8, 299–309 (2016).

    CAS  PubMed  Google Scholar 

  124. 124.

    Ye, R., Hurlburt, T. J.,Sabyrov, K., Alayoglu, S. & Somorjai, G. A. Molecular catalysis science: perspective on unifying the fields of catalysis. Proc. Natl Acad. Sci. 113, 5159–5166 (2016).

    CAS  PubMed  Google Scholar 

  125. 125.

    Irvine, J. T. S. et al. Evolution of the electrochemical interface in high-temperature fuel cells and electrolysers. Nat. Energy 1, 15014 (2016).

    CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the CIFAR Bio-Inspired Solar Energy program; by the Ontario Research Fund—Research Excellence Program; by the Director, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, & Biosciences Division, of the US Department of Energy under Contract No. DE-AC02-05CH11231, FWP No. CH030201; and by the Director, Office of Science, Office of Basic Energy Sciences, Materials Science and Engineering Division, of the US Department of Energy under Contract No. DE-AC02-05CH11231. M.B.R. gratefully acknowledges support from the CIFAR Bio-Inspired Solar Energy Program. PDL wishes to thank the Natural Sciences and Engineering Research Council (NSERC) of Canada for support in the form of the Canadian Graduate Scholarship – Doctoral award. D.K. acknowledges support from Samsung Scholarship.

Author information

Affiliations

Authors

Contributions

All authors contributed to the conception and writing of this manuscript.

Corresponding authors

Correspondence to Peidong Yang or Edward H. Sargent.

Ethics declarations

Competing interests

The authors claim no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Ross, M.B., De Luna, P., Li, Y. et al. Designing materials for electrochemical carbon dioxide recycling. Nat Catal 2, 648–658 (2019). https://doi.org/10.1038/s41929-019-0306-7

Download citation

Further reading

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing