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.

Rational catalyst and electrolyte design for CO2 electroreduction towards multicarbon products

Abstract

The CO2 electroreduction reaction (CO2RR) to fuels and feedstocks is an attractive route to close the anthropogenic carbon cycle and store renewable energy. The generation of more reduced chemicals, especially multicarbon oxygenate and hydrocarbon products (C2+) with higher energy densities, is highly desirable for industrial applications. However, selective conversion of CO2 to C2+ suffers from a high overpotential, a low reaction rate and low selectivity, and the process is extremely sensitive to the catalyst structure and electrolyte. Here we discuss strategies to achieve high C2+ selectivity through rational design of the catalyst and electrolyte. Current state-of-the-art catalysts, including Cu and Cu–bimetallic catalysts, as well as some alternative materials, are considered. The importance of taking into consideration the dynamic evolution of the catalyst structure and composition are highlighted, focusing on findings extracted from in situ and operando characterizations. Additional theoretical insight into the reaction mechanisms underlying the improved C2+ selectivity of specific catalyst geometries and compositions in synergy with a well-chosen electrolyte are also provided.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

All prices are NET prices.

Fig. 1: NP size and loading effects.
Fig. 2: Real time characterization of Cu-based catalysts.
Fig. 3: Various parameters affecting the CO2RR selectivity of Cu-based bimetallic catalysts.
Fig. 4: Non-Cu catalysts for the production of hydrocarbons and oxygenates.
Fig. 5: Electrolyte effect on catalyst structure.
Fig. 6: Electrolyte effect on CO2RR reactivity.

References

  1. Montoya, J. H. et al. Materials for solar fuels and chemicals. Nat. Mater. 16, 70–81 (2017).

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

  3. Nielsen, D. U., Hu, X.-M., Daasbjerg, K. & Skrydstrup, T. Chemically and electrochemically catalysed conversion of CO2 to CO with follow-up utilization to value-added chemicals. Nat. Catal. 1, 244–254 (2018).

    Article  Google Scholar 

  4. Whipple, D. T. & Kenis, P. J. A. Prospects of CO2 utilization via direct heterogeneous electrochemical reduction. J. Phys. Chem. Lett. 1, 3451–3458 (2010).

    Article  CAS  Google Scholar 

  5. Gao, D., Cai, F., Wang, G. & Bao, X. Nanostructured heterogeneous catalysts for electrochemical reduction of CO2. Curr. Opin. Green Sustain. Chem. 3, 39–44 (2017).

    Article  Google Scholar 

  6. 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).

    Article  CAS  PubMed  Google Scholar 

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

    Article  Google Scholar 

  8. 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).

    Article  CAS  PubMed  Google Scholar 

  9. 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).

    Article  CAS  PubMed  Google Scholar 

  10. 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. 56, 3621–3624 (2017). The first spectroscopic observation of a hydrogenated CO dimer Intermediate (*OCCOH) on Cu(100) during CO reduction using operando IR spectroscopy.

    Article  CAS  Google Scholar 

  11. Clark, E. L. & Bell, A. T. Direct observation of the local reaction environment during the electrochemical reduction of CO2. J. Am. Chem. Soc. 140, 7012–7020 (2018).

    Article  CAS  PubMed  Google Scholar 

  12. 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).

    Article  CAS  Google Scholar 

  13. Arán-Ais, R. M., Gao, D. & Roldan Cuenya, B. Structure- and electrolyte-sensitivity in CO2 electroreduction. Acc. Chem. Res. 51, 2906–2917 (2018).

    Article  PubMed  CAS  Google Scholar 

  14. Larrazábal, G. O., Martín, A. J. & Pérez-Ramírez, J. Building blocks for high performance in electrocatalytic CO2 reduction: materials, optimization strategies, and device engineering. J. Phys. Chem. Lett. 8, 3933–3944 (2017).

    Article  PubMed  CAS  Google Scholar 

  15. Zhu, D. D., Liu, J. L. & Qiao, S. Z. Recent advances in inorganic heterogeneous electrocatalysts for reduction of carbon dioxide. Adv. Mater. 28, 3423–3452 (2016).

    Article  CAS  PubMed  Google Scholar 

  16. 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).

    Article  Google Scholar 

  17. Choi, Y. W., Mistry, H. & Roldan Cuenya, B. New insights into working nanostructured electrocatalysts through operando spectroscopy and microscopy. Curr. Opin. Electrochem. 1, 95–103 (2017).

    Article  CAS  Google Scholar 

  18. Weekes, D. M., Salvatore, D. A., Reyes, A., Huang, A. & Berlinguette, C. P. Electrolytic CO2 reduction in a flow cell. Acc. Chem. Res. 51, 910–918 (2018).

    Article  CAS  PubMed  Google Scholar 

  19. Dinh, C. T. et al. CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface. Science 360, 783–787 (2018). Ethylene was selectively produced with 70% FE at −0.55 V versus RHE in a flow cell with GDE configuration and highly alkaline electrolyte.

    Article  CAS  PubMed  Google Scholar 

  20. Reske, R., Mistry, H., Behafarid, F., Roldan Cuenya, B. & Strasser, P. Particle size effects in the catalytic electroreduction of CO2 on Cu nanoparticles. J. Am. Chem. Soc. 136, 6978–6986 (2014).

    Article  CAS  PubMed  Google Scholar 

  21. Mistry, H. et al. Exceptional size-dependent activity enhancement in the electroreduction of CO2 over Au nanoparticles. J. Am. Chem. Soc. 136, 16473–16476 (2014).

    Article  CAS  PubMed  Google Scholar 

  22. Mistry, H., Reske, R., Strasser, P. & Roldan Cuenya, B. Size-dependent reactivity of gold-copper bimetallic nanoparticles during CO2 electroreduction. Catal. Today 288, 30–36 (2017).

    Article  CAS  Google Scholar 

  23. Jeon, H. S. et al. Operando evolution of the structure and oxidation state of size-controlled Zn nanoparticles during CO2 electroreduction. J. Am. Chem. Soc. 140, 9383–9386 (2018).

    Article  CAS  PubMed  Google Scholar 

  24. Merino-Garcia, I., Albo, J. & Irabien, A. Tailoring gas-phase CO2 electroreduction selectivity to hydrocarbons at Cu nanoparticles. Nanotechnology 29, 014001 (2018).

    Article  CAS  PubMed  Google Scholar 

  25. Ampelli, C. et al. Electrocatalytic conversion of CO2 to produce solar fuels in electrolyte or electrolyte-less configurations of PEC cells. Faraday Discuss. 183, 125–145 (2015).

    Article  CAS  PubMed  Google Scholar 

  26. Roth, C. et al. Determination of O[H] and CO coverage and adsorption sites on PtRu electrodes in an operating PEM fuel cell. J. Am. Chem. Soc. 127, 14607–14615 (2005).

    Article  CAS  PubMed  Google Scholar 

  27. Velasco-Vélez, J.-J. et al. The role of the copper oxidation state in the electrocatalytic reduction of CO2 into valuable hydrocarbons. ACS Sustain. Chem. Eng. 7, 1485–1492 (2019).

    Article  CAS  Google Scholar 

  28. Saveleva, V. A. et al. Operando evidence for a universal oxygen evolution mechanism on thermal and electrochemical iridium oxides. J. Phys. Chem. Lett. 9, 3154–3160 (2018).

    Article  CAS  PubMed  Google Scholar 

  29. Wiltshire, R. J. K. et al. A PEM fuel cell for in situ XAS studies. Electrochim. Acta 50, 5208–5217 (2005).

    Article  CAS  Google Scholar 

  30. Mistry, H. et al. Tuning catalytic selectivity at the mesoscale via interparticle interactions. ACS Catal. 6, 1075–1080 (2016).

    Article  CAS  Google Scholar 

  31. 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. USA 114, 10560–10565 (2017).

    Article  CAS  PubMed  Google Scholar 

  32. Wang, X., Varela, A. S., Bergmann, A., Kühl, S. & Strasser, P. Catalyst particle density controls hydrocarbon product selectivity in CO2 electroreduction on CuOx. ChemSusChem 10, 4642–4649 (2017).

    Article  CAS  PubMed  Google Scholar 

  33. 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).

    Article  CAS  Google Scholar 

  34. 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).

    Article  CAS  Google Scholar 

  35. 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).

    Article  CAS  Google Scholar 

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

    Article  CAS  PubMed  Google Scholar 

  37. Peterson, A. A., Abild-Pedersen, F., Studt, F., Rossmeisl, J. & Nørskov, J. K. How copper catalyzes the electroreduction of CO2 into hydrocarbon fuels. Energy Environ. Sci. 3, 1311 (2010).

    Article  CAS  Google Scholar 

  38. 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).

    Article  CAS  Google Scholar 

  39. Kim, Y. G., Javier, A., Baricuatro, J. H. & Soriaga, M. P. Regulating the product distribution of CO reduction by the atomic-level structural modification of the Cu electrode surface. Electrocatalysis 7, 391–399 (2016).

    Article  CAS  Google Scholar 

  40. Schouten, K. J. P., Pérez Gallent, E. & Koper, M. T. M. Structure sensitivity of the electrochemical reduction of carbon monoxide on copper single crystals. ACS Catal. 3, 1292–1295 (2013).

    Article  CAS  Google Scholar 

  41. Chen, C. S. et al. Stable and selective electrochemical reduction of carbon dioxide to ethylene on copper mesocrystals. Catal. Sci. Technol. 5, 161–168 (2015).

    Article  CAS  Google Scholar 

  42. Roberts, F. S., Kuhl, K. P. & Nilsson, A. High selectivity for ethylene from CO2 reduction over copper nanocube electrocatalysts. Angew. Chem. Int. Ed. 54, 5179–5182 (2015).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  PubMed  Google Scholar 

  45. 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. 6192–6197 (2018).Dynamic changes of morphological and chemical states of Cu nanocubes during CO 2 RR were monitored using operando EC-AFM and EXAFS and correlated to the activity and selectivity.

  46. 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).

    Article  CAS  Google Scholar 

  47. Dutta, A., Rahaman, M., Mohos, M., Zanetti, A. & Broekmann, P. Electrochemical CO2 conversion using skeleton (sponge) type of Cu catalysts. ACS Catal. 7, 5431–5437 (2017).

    Article  CAS  Google Scholar 

  48. Reller, C. et al. Selective electroreduction of CO2 toward ethylene on nano dendritic copper catalysts at high current density. Adv. Energy Mater. 7, 1602114 (2017).

    Article  CAS  Google Scholar 

  49. Klingan, K. et al. Reactivity determinants in electrodeposited Cu foams for electrochemical CO2 reduction. ChemSusChem 11, 3449–3459 (2018).

    Article  CAS  PubMed  Google Scholar 

  50. Jeon, H. S., Kunze, S., Scholten, F. & Roldan Cuenya, B. Prism-shaped Cu nanocatalysts for electrochemical CO2 reduction to ethylene. ACS Catal. 8, 531–535 (2018).

    Article  CAS  Google Scholar 

  51. Mariano, R. G., McKelvey, K., White, H. S. & Kanan, M. W. Selective increase in CO2 electroreduction activity at grain-boundary surface terminations. Science 358, 1187–1192 (2017).

    Article  CAS  PubMed  Google Scholar 

  52. Tang, W. et al. The importance of surface morphology in controlling the selectivity of polycrystalline copper for CO2 electroreduction. Phys. Chem. Chem. Phys. 14, 76–81 (2012).

    Article  CAS  PubMed  Google Scholar 

  53. Gupta, N., Gattrell, M. & MacDougall, B. Calculation for the cathode surface concentrations in the electrochemical reduction of CO2 in KHCO3 solutions. J. Appl. Electrochem. 36, 161–172 (2006).

    Article  CAS  Google Scholar 

  54. Pander, J. E. et al. Understanding the heterogeneous electrocatalytic reduction of CO2 on oxide-derived catalysts. ChemElectroChem 5, 219–237 (2018).

    Article  CAS  Google Scholar 

  55. Mandal, L. et al. Investigating the role of copper oxide in electrochemical CO2 reduction in real time. ACS Appl. Mater. Interfaces 10, 8574–8584 (2018).

    Article  CAS  PubMed  Google Scholar 

  56. Lum, Y. & Ager, J. W. Stability of residual oxides in oxide-derived copper catalysts for electrochemical CO2 reduction investigated with 18O labeling. Angew. Chem. Int. Ed. 57, 551–554 (2018).

    Article  CAS  Google Scholar 

  57. Mistry, H. et al. Highly selective plasma-activated copper catalysts for CO2 reduction to ethylene. Nat. Commun. 7, 12123 (2016).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  58. Favaro, M. et al. Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2. Proc. Natl Acad. Sci. USA 114, 6706–6711 (2017).

    CAS  PubMed  Google Scholar 

  59. Xiao, H., Goddard, W., Cheng, T. & Liu, Y. Cu metal embedded in oxidized matrix catalyst to promote CO2 activation and CO dimerization for electrochemical reduction of CO2. Proc. Natl Acad. Sci. USA 114, 6685–6688 (2017). The interface between Cu + and Cu 0 species significantly improves the kinetics and thermodynamics of both CO 2 activation, and CO dimerization.

    Article  CAS  PubMed  Google Scholar 

  60. Zhou, Y. et al. Dopant-induced electron localization drives CO2 reduction to C2 hydrocarbons. Nat. Chem. 10, 947–980 (2018).

    Article  CAS  Google Scholar 

  61. Gao, D., Scholten, F. & Roldan Cuenya, B. Improved CO2 electroreduction performance on plasma-activated Cu catalysts via electrolyte design: Halide effect. ACS Catal. 7, 5112–5120 (2017).

    Article  CAS  Google Scholar 

  62. Gao, D. et al. Activity and selectivity control in CO2 electroreduction to multicarbon products over CuOx catalysts via electrolyte design. ACS Catal. 8, 10012–10020 (2018). By combining experiment and DFT calculations, a synergistic effect of the electrolyte (larger cations, halides) and the presence of subsurface oxygen species was found to stabilize Cu + species during CO 2 RR and improve the C 2+ production and stability of CuO x catalysts.

    Article  CAS  Google Scholar 

  63. Wang, L. et al. Electrochemical carbon monoxide reduction on polycrystalline copper: Effects of potential, pressure, and pH on selectivity toward multicarbon and oxygenated products. ACS Catal. 8, 7445–7454 (2018).

    Article  CAS  Google Scholar 

  64. Clark, E. L. et al. Standards and protocols for data acquisition and reporting for studies of the electrochemical reduction of carbon dioxide. ACS Catal. 8, 6560–6570 (2018).

    Article  CAS  Google Scholar 

  65. Schlögl, R. Heterogeneous catalysis. Angew. Chem. Int. Ed. 54, 3465–3520 (2015).

    Article  CAS  Google Scholar 

  66. Garza, A. J., Bell, A. T. & Head-Gordon, M. Is subsurface oxygen necessary for the electrochemical reduction of CO2 on copper? J. Phys. Chem. Lett. 9, 601–606 (2018).

    Article  CAS  PubMed  Google Scholar 

  67. Yin, Z. et al. Highly selective palladium-copper bimetallic electrocatalysts for the electrochemical reduction of CO2 to CO. Nano Energy 27, 35–43 (2016).

    Article  CAS  Google Scholar 

  68. Ma, S. et al. Electroreduction of CO2 to hydrocarbons using bimetallic Cu–Pd catalysts with different mixing patterns. J. Am. Chem. Soc. 139, 47–50 (2017). Phase-separated Cu–Pd bimetallic NPs achieved higher selectivity (>60%) for C 2 chemicals than ordered and disordered ones. Geometric effects rather than electronic effects seem to be key in determining the selectivity of bimetallic Cu–Pd catalysts.

    Article  CAS  PubMed  Google Scholar 

  69. Chen, D. et al. Tailoring the selectivity of bimetallic copper-palladium nanoalloys for electrocatalytic reduction of CO2 to CO. ACS Appl. Energy Mater. 1, 883–890 (2018).

    Article  CAS  Google Scholar 

  70. Li, M. et al. Mesoporous palladium-copper bimetallic electrodes for selective electrocatalytic reduction of aqueous CO2 to CO. J. Mater. Chem. A 4, 4776–4782 (2016).

    Article  CAS  Google Scholar 

  71. Mavrikakis, M., Hammer, B. & Nørskov, J. K. Effect of strain on the reactivity of metal surfaces. Phys. Rev. Lett. 81, 2819–2822 (1998).

    Article  Google Scholar 

  72. Bligaard, T. & Nørskov, J. K. Ligand effects in heterogeneous catalysis and electrochemistry. Electrochim. Acta 52, 5512–5516 (2007).

    Article  CAS  Google Scholar 

  73. Reske, R. et al. Controlling catalytic selectivities during CO2 electroreduction on thin Cu metal overlayers. J. Phys. Chem. Lett. 4, 2410–2413 (2013).

    Article  CAS  Google Scholar 

  74. Bernal, M. et al. CO2 electroreduction on copper-cobalt nanoparticles: Size and composition effect. Nano Energy 53, 27–36 (2018).

    Article  CAS  Google Scholar 

  75. 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).

    Article  CAS  PubMed  Google Scholar 

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

    Article  CAS  PubMed  Google Scholar 

  77. 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). The CO spillover effect was observed and applied to facilitate selective CO2 RR to ethanol on oxide-derived Cu x Zn catalysts.

    Article  CAS  Google Scholar 

  78. Lee, S., Park, G. & Lee, J. Importance of Ag–Cu biphasic boundaries for selective electrochemical reduction of CO2 to ethanol. ACS Catal. 7, 8594–8604 (2017).

    Article  CAS  Google Scholar 

  79. 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).

    Article  CAS  PubMed  Google Scholar 

  80. He, J., Johnson, N. J. J., Huang, A. & Berlinguette, C. P. Electrocatalytic alloys for CO2 reduction. ChemSusChem 11, 48–57 (2018).

    Article  CAS  PubMed  Google Scholar 

  81. Lum, Y. & Ager, J. W. Sequential catalysis controls selectivity in electrochemical CO2 reduction on Cu. Energy Environ. Sci. 11, 2935–2944 (2018).

    Article  CAS  Google Scholar 

  82. Morales-Guio, C. G. et al. Improved CO2 reduction activity towards C2+ alcohols on a tandem gold on copper electrocatalyst. Nat. Catal. 1, 764–771 (2018).

    Article  Google Scholar 

  83. Jovanov, Z. P. et al. Opportunities and challenges in the electrocatalysis of CO2 and CO reduction using bifunctional surfaces: a theoretical and experimental study of Au–Cd alloys. J. Catal. 343, 215–231 (2016).

    Article  CAS  Google Scholar 

  84. Kortlever, R. et al. Palladium–gold catalyst for the electrochemical reduction of CO2 to C1–C5 hydrocarbons. Chem. Commun. 52, 10229–10232 (2016).

    Article  CAS  Google Scholar 

  85. Torelli, D. A. et al. Nickel–gallium-catalyzed electrochemical reduction of CO2 to highly reduced products at low overpotentials. ACS Catal. 6, 2100–2104 (2016).

    Article  CAS  Google Scholar 

  86. Paris, A. R. & Bocarsly, A. B. Ni–Al films on glassy carbon electrodes generate an array of oxygenated organics from CO2. ACS Catal. 7, 6815–6820 (2017).

    Article  CAS  Google Scholar 

  87. 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).

    Article  CAS  PubMed  Google Scholar 

  88. Dutta, A., Morstein, C. E., Rahaman, M., Cedeño López, A. & Broekmann, P. Beyond copper in CO2 electrolysis: effective hydrocarbon production on silver nano-foam catalysts. ACS Catal. 8, 8357–8368 (2018). By creating high density of defects and lower-coordinated sites, one could transform a CO-producing catalyst (with weak CO binding) into a hydrocarbon- and alcohol-producing catalyst.

    Article  CAS  Google Scholar 

  89. Mistry, H. et al. Enhanced CO2 electroreduction to CO over defect-rich plasma-activated silver catalysts. Angew. Chem. Int. Ed. 56, 11394–11398 (2017).

    Article  CAS  Google Scholar 

  90. Michalsky, R., Zhang, Y. J., Medford, A. J. & Peterson, A. A. Departures from the adsorption energy scaling relations for metal carbide catalysts. J. Phys. Chem. C 118, 13026–13034 (2014).

    Article  CAS  Google Scholar 

  91. Kim, S. K., Zhang, Y. J., Bergstrom, H., Michalsky, R. & Peterson, A. Understanding the low-overpotential production of CH4 from CO2 on Mo2C catalysts. ACS Catal. 6, 2003–2013 (2016).

    Article  CAS  Google Scholar 

  92. Chan, K., Tsai, C., Hansen, H. A. & Nørskov, J. K. Molybdenum sulfides and selenides as possible electrocatalysts for CO2 reduction. ChemCatChem 6, 1899–1905 (2014).

    Article  CAS  Google Scholar 

  93. Francis, S. A. et al. Reduction of aqueous CO2 to 1-propanol at MoS2 electrodes. Chem. Mater. 30, 4902–4908 (2018).

    Article  CAS  Google Scholar 

  94. Calvinho, K. U. D. et al. Selective CO2 reduction to C3 and C4 oxyhydrocarbons on nickel phosphides at overpotentials as low as 10 mV. Energy Environ. Sci. 11, 2550–2559 (2018).

    Article  CAS  Google Scholar 

  95. Back, S. & Jung, Y. TiC- and TiN-supported single-atom catalysts for dramatic improvements in CO2 electrochemical reduction to CH4. ACS Energy Lett. 2, 969–975 (2017).

    Article  CAS  Google Scholar 

  96. Cheng, M. J., Clark, E. L., Pham, H. H., Bell, A. T. & Head-Gordon, M. Quantum mechanical screening of single-atom bimetallic alloys for the selective reduction of CO2 to C1 hydrocarbons. ACS Catal. 6, 7769–7777 (2016).

    Article  CAS  Google Scholar 

  97. Back, S., Lim, J., Kim, N. Y., Kim, Y. H. & Jung, Y. Single-atom catalysts for CO2 electroreduction with significant activity and selectivity improvements. Chem. Sci. 8, 1090–1096 (2017).

    Article  CAS  PubMed  Google Scholar 

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

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  99. Bagger, A., Ju, W., Varela, A. S., Strasser, P. & Rossmeisl, J. Single site porphyrine-like structures advantages over metals for selective electrochemical CO2 reduction. Catal. Today 288, 74–78 (2017).

    Article  CAS  Google Scholar 

  100. Genovese, C. et al. Operando spectroscopy study of the carbon dioxide electro-reduction by iron species on nitrogen-doped carbon. Nat. Commun. 9, 935 (2018).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  101. Wu, J. et al. A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates. Nat. Commun. 7, 13869 (2016). The N-doped graphene quantum dots showed a high total CO 2 RR FE of up to 90%, with the C 2 and C 3 product distribution and production rate comparable to those obtained with copper nanoparticle-based electrocatalysts.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  102. Liu, Y., Chen, S., Quan, X. & Yu, H. Efficient electrochemical reduction of carbon dioxide to acetate on nitrogen-doped nanodiamond. J. Am. Chem. Soc. 137, 11631–11636 (2015).

    Article  CAS  PubMed  Google Scholar 

  103. Liu, Y. et al. Selective electrochemical reduction of carbon dioxide to ethanol on a boron- and nitrogen-co-doped nanodiamond. Angew. Chem. Int. Ed. 56, 15607–15611 (2017).

    Article  CAS  Google Scholar 

  104. Nakata, K., Ozaki, T., Terashima, C., Fujishima, A. & Einaga, Y. High-yield electrochemical production of formaldehyde from CO2 and seawater. Angew. Chem. Int. Ed. 53, 871–874 (2014).

    Article  CAS  Google Scholar 

  105. Song, Y. et al. Metal-free nitrogen-doped mesoporous carbon for electroreduction of CO2 to ethanol. Angew. Chem. Int. Ed. 56, 10840–10844 (2017).

    Article  CAS  Google Scholar 

  106. Huang, J. et al. Potential-induced nanoclustering of metallic catalysts during electrochemical CO2 reduction. Nat. Commun. 9, 3117 (2018).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  107. Kim, Y.-G., Baricuatro, J. H. & Soriaga, M. P. Surface reconstruction of polycrystalline Cu electrodes in aqueous KHCO3 electrolyte at potentials in the early stages of CO2 reduction. Electrocatalysis 9, 526–530 (2018).

    Article  CAS  Google Scholar 

  108. 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). An operando EC-STM study showed the surface reconstruction from a polycrystalline Cu electrode first to Cu(111), and then to Cu(100) under CO 2 RR conditions.

    Article  CAS  PubMed  Google Scholar 

  109. 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).

    Article  Google Scholar 

  110. Lee, S. Y. et al. Mixed copper states in anodized Cu electrocatalyst for stable and selective ethylene production from CO2 reduction. J. Am. Chem. Soc. 140, 8681–8689 (2018).

    Article  CAS  PubMed  Google Scholar 

  111. 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).

    Article  CAS  PubMed  Google Scholar 

  112. Resasco, J. et al. Promoter effects of alkali metal cations on the electrochemical reduction of carbon dioxide. J. Am. Chem. Soc. 139, 11277–11287 (2017).

    Article  CAS  PubMed  Google Scholar 

  113. 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).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  114. Ayemoba, O. & Cuesta, A. Spectroscopic evidence of size-dependent buffering of interfacial pH by cation hydrolysis during CO2 electroreduction. ACS Appl. Mater. Interfaces 9, 27377–27382 (2017).

    Article  CAS  PubMed  Google Scholar 

  115. Schizodimou, A. & Kyriacou, G. Acceleration of the reduction of carbon dioxide in the presence of multivalent cations. Electrochim. Acta 78, 171–176 (2012).

    Article  CAS  Google Scholar 

  116. Dunwell, M. et al. The central role of bicarbonate in the electrochemical reduction of CO2 on gold. J. Am. Chem. Soc. 139, 3774–3783 (2017).

    Article  CAS  PubMed  Google Scholar 

  117. Zhu, S., Jiang, B., Cai, W. & Shao, M. Direct observation on reaction intermediates and the role of bicarbonate anions in CO2 electrochemical reduction reaction on Cu surfaces. J. Am. Chem. Soc. 139, 15664–15667 (2017).

    Article  CAS  PubMed  Google Scholar 

  118. Wuttig, A., Yoon, Y., Ryu, J. & Surendranath, Y. Bicarbonate is not a general acid in Au-catalyzed CO2 electroreduction. J. Am. Chem. Soc. 139, 17109–17113 (2017).

    Article  CAS  PubMed  Google Scholar 

  119. Huang, Y., Ong, C. W. & Yeo, B. S. Effects of electrolyte anions on the reduction of carbon dioxide to ethylene and ethanol on copper (100) and (111) surfaces. ChemSusChem 11, 3299–3306 (2018).

    Article  CAS  PubMed  Google Scholar 

  120. McCrum, I. T., Akhade, S. A. & Janik, M. J. Electrochemical specific adsorption of halides on Cu 111,100, and 211: A density functional theory study. Electrochim. Acta 173, 302–309 (2015).

    Article  CAS  Google Scholar 

  121. Varela, A. S., Ju, W., Reier, T. & Strasser, P. Tuning the catalytic activity and selectivity of Cu for CO2 electroreduction in the presence of halides. ACS Catal. 6, 2136–2144 (2016).

    Article  CAS  Google Scholar 

  122. Schouten, K. J. P., Pérez Gallent, E. & Koper, M. T. M. The influence of pH on the reduction of CO and CO2 to hydrocarbons on copper electrodes. J. Electroanal. Chem. 716, 53–57 (2014).

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

  124. Todoroki, M., Hara, K., Kudo, A. & Sakata, T. Electrochemical reduction of high pressure CO2 at Pb, Hg and In electrodes in an aqueous KHCO3 solution. J. Electroanal. Chem. 394, 199–203 (1995).

    Article  Google Scholar 

  125. Melchaeva, O. et al. Electrochemical reduction of protic supercritical CO2 on copper electrodes. ChemSusChem 10, 3660–3670 (2017).

    Article  CAS  PubMed  Google Scholar 

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

    Article  CAS  PubMed  Google Scholar 

  127. Sun, X. et al. Design of a Cu(i)/C-doped boron nitride electrocatalyst for efficient conversion of CO2 into acetic acid. Green Chem. 19, 2086–2091 (2017).

    Article  CAS  Google Scholar 

  128. Pătru, A., Binninger, T., Pribyl, B. & Schmidt, T. J. Design principles of bipolar electrochemical co-electrolysis cells for efficient reduction of carbon dioxide from gas phase at low temperature. J. Electrochem. Soc. 166, F34–F43 (2019).

    Article  Google Scholar 

  129. Gao, D. et al. Gas-phase electrocatalytic reduction of carbon dioxide using electrolytic cell based on phosphoric acid-doped polybenzimidazole membrane. J. Energy Chem. 23, 694–700 (2014).

    Article  Google Scholar 

  130. 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).

    Article  CAS  PubMed  Google Scholar 

  131. Mills, J. N., McCrum, I. T. & Janik, M. J. Alkali cation specific adsorption onto fcc(111) transition metal electrodes. Phys. Chem. Chem. Phys. 16, 13699–13707 (2014).

    Article  CAS  PubMed  Google Scholar 

  132. Deng, Y. & Yeo, B. S. Characterization of electrocatalytic water splitting and CO2 reduction reactions using in situ/operando Raman spectroscopy. ACS Catal. 7, 7873–7889 (2017).

    Article  CAS  Google Scholar 

  133. Dutta, A., Kuzume, A., Rahaman, M., Vesztergom, S. & Broekmann, P. Monitoring the chemical state of catalysts for CO2 electroreduction: an in operando study. ACS Catal. 5, 7498–7502 (2015).

    Article  CAS  Google Scholar 

  134. Zhu, C. et al. In-situ liquid cell transmission electron microscopy investigation on oriented attachment of gold nanoparticles. Nat. Commun. 9, 421 (2018).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the European Research Council under grant ERC-OPERANDOCAT (ERC-725915) and the German Federal Ministry of Education and Research (BMBF) under grants #03SF0523C-’CO2EKAT’ and #033RCOO4D-’e-Ethylene’, as well as the German Research Foundation (DFG) - SFB 1316, subproject B1.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Beatriz Roldan Cuenya.

Ethics declarations

Competing interests

The authors declare 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

Gao, D., Arán-Ais, R.M., Jeon, H.S. et al. Rational catalyst and electrolyte design for CO2 electroreduction towards multicarbon products. Nat Catal 2, 198–210 (2019). https://doi.org/10.1038/s41929-019-0235-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41929-019-0235-5

This article is cited by

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