Chemically and electrochemically catalysed conversion of CO2 to CO with follow-up utilization to value-added chemicals

A Publisher Correction to this article was published on 11 December 2018

This article has been updated

Abstract

Carbon dioxide is ubiquitous and a vital molecule for maintaining life on our planet. However, the ever-increasing emission of anthropogenic CO2 into our atmosphere has provoked dramatic climate changes. In principle, CO2 could represent an important one-carbon building block for the chemical industry, yet its high thermodynamic and kinetic stability has limited its applicability to only a handful of industrial applications. On the other hand, carbon monoxide represents a more versatile reagent applied in many industrial transformations. Here we review the different methods for converting CO2 to CO with specific focus on the reverse water gas shift reaction, main element reductants, and electrochemical protocols applying homogeneous and heterogeneous catalysts. Particular emphasis is given to synthetic methods that couple the deoxygenation step with a follow-up carbonylation step for the synthesis of carbonyl-containing molecules, thus avoiding the need to handle or store this toxic but highly synthetically useful diatomic gas.

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Fig. 1: Transformation of CO2 to value-added chemicals.
Fig. 2: Application of CO produced from the RWGSR into a variety of chemical transformations.
Fig. 3: Boron and silicon based reductants for CO2 conversion.
Fig. 4: Electrocatalysts exhibiting a FEmax ≥ 90% for CO2-to-CO conversion.
Fig. 5: Electrochemical CO2-to-CO conversion coupled with CO utilization for carbonylation reactions.
Fig. 6: Future challenges.

Change history

  • 11 December 2018

    In the version of this Review Article originally published, the received and accepted dates were missing, and the published online date of 10 April 2018 was incorrect; they should have read ‘Received: 24 December 2017; Accepted: 28 February 2018; Published online: 16 April 2018’. This has now been corrected.

References

  1. 1.

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

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  2. 2.

    D’Alessandro, D. M., Smit, B. & Long, J. R. Carbon dioxide capture: Prospects for new materials. Angew. Chem. Int. Ed. 49, 6058–6082 (2010).

    Google Scholar 

  3. 3.

    Kondratenko, E. V., Mul, G., Baltrusaitis, J., Larrazabal, G. O. & Perez-Ramirez, J. Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes. Energy Environ. Sci. 6, 3112–3135 (2013).

    CAS  Google Scholar 

  4. 4.

    Liu, Q., Wu, L., Jackstell, R. & Beller, M. Using carbon dioxide as a building block in organic synthesis. Nat. Commun. 6, 5933 (2015).

    PubMed  Google Scholar 

  5. 5.

    Cokoja, M., Bruckmeier, C., Rieger, B., Herrmann, W. A. & Kühn, F. E. Transformation of carbon dioxide with homogeneous transition-metal catalysts: a molecular solution to a global challenge? Angew. Chem. Int. Ed. 50, 8510–8537 (2011).

    CAS  Google Scholar 

  6. 6.

    Goeppert, A., Czaun, M., Jones, J.-P., Surya Prakash, G. K. & Olah, G. A. Recycling of carbon dioxide to methanol and derived products — closing the loop. Chem. Soc. Rev. 43, 7995–8048 (2014).

    CAS  Google Scholar 

  7. 7.

    Bernskoetter, W. H. & Hazari, N. Reversible hydrogenation of carbon dioxide to formic acid and methanol: Lewis acid enhancement of base metal catalysts. Acc. Chem. Res. 50, 1049–1058 (2017).

    CAS  PubMed  Google Scholar 

  8. 8.

    Beuls, A. et al. Methanation of CO2: further insight into the mechanism over Rh/γ-Al2O3 catalyst. Appl. Catal. B 113−114, 2–10 (2012).

    Google Scholar 

  9. 9.

    Barnard, C. F. J. Palladium-catalyzed carbonylation — a reaction come of age. Organometallics 27, 5402–5422 (2008).

    CAS  Google Scholar 

  10. 10.

    Brennführer, A., Neumann, H. & Beller, M. Palladium-catalyzed carbonylation reactions of aryl halides and related compounds. Angew. Chem. Int. Ed. 48, 4114–4133 (2009).

    Google Scholar 

  11. 11.

    Wu, X.-F., Neumann, H. & Beller, M. Palladium-catalyzed carbonylative coupling reactions between Ar–X and carbon nucleophiles. Chem. Soc. Rev. 40, 4986–5009 (2011).

    CAS  PubMed  Google Scholar 

  12. 12.

    Dry, M. E. The Fischer–Tropsch process: 1950–2000 Catal. Today 71, 227–241 (2002).

    CAS  Google Scholar 

  13. 13.

    Maitlis, P. M., Haynes, A., Sunley, G. J. & Howard, M. J. Methanol carbonylation revisited: thirty years on. J. Chem. Soc. Dalton Trans. 2187–2196 (1996).

  14. 14.

    Jones, J. H. The Cativa process for the manufacture of acetic acid. Iridium catalyst improves productivity in an established industrial process. Platin. Met. Rev. 44, 94–105 (2000).

    CAS  Google Scholar 

  15. 15.

    Morimoto, T. & Kakiuchi, K. Evolution of carbonylation catalysis: no need for carbon monoxide. Angew. Chem. Int. Ed. 43, 5580–5588 (2004).

    CAS  Google Scholar 

  16. 16.

    Wu, L., Liu, Q., Jackstell, R. & Beller, M. Carbonylations of alkenes with CO surrogates. Angew. Chem. Int. Ed. 53, 6310–6320 (2014).

    CAS  Google Scholar 

  17. 17.

    Friis, S. D., Lindhardt, A. T. & Skrydstrup, T. The development and application of two-chamber reactors and carbon monoxide precursors for safe carbonylation reactions. Acc. Chem. Res. 49, 594–605 (2016).

    CAS  PubMed  Google Scholar 

  18. 18.

    Lehn, J. -M. & Ziessel, R. Photochemical generation of carbon monoxide and hydrogen by reduction of carbon dioxide and water under visible light irradiation. Proc. Natl Acad. Sci. USA 79, 701–704 (1982).

    CAS  PubMed  Google Scholar 

  19. 19.

    Rosas-Hernandez, A., Steinlechner, C., Junge, H. & Beller, M. Earth-abundant photocatalytic systems for the visible-light-driven reduction of CO2 to CO. Green Chem. 19, 2356–2360 (2017).

    CAS  Google Scholar 

  20. 20.

    Daza, Y. A. & Kuhn, J. N. CO2 conversion by reverse water gas shift catalysis: comparison of catalysts, mechanisms and their consequences for CO2 conversion to liquid fuels. RSC Adv. 6, 49675–49691 (2016).

    CAS  Google Scholar 

  21. 21.

    Erisman, J. W., Sutton, M. A., Galloway, J., Klimont, Z. & Winiwarter, W. How a century of ammonia synthesis changed the world. Nat. Geosci. 1, 636 (2008).

    CAS  Google Scholar 

  22. 22.

    Baker, E. C., Hendriksen, D. E. & Eisenberg, R. Mechanistic studies of the homogeneous catalysis of the water gas shift reaction by rhodium carbonyl iodide. J. Am. Chem. Soc. 102, 1020–1027 (1980).

    CAS  Google Scholar 

  23. 23.

    Kattel, S., Liu, P. & Chen, J. G. Tuning selectivity of CO2 hydrogenation reactions at the metal/oxide interface. J. Am. Chem. Soc. 139, 9739–9754 (2017). An excellent overview of heterogenous catalysts available for the reduction of CO 2 using the reverse water gas shift reaction.

    CAS  PubMed  Google Scholar 

  24. 24.

    Choi, S. et al. Catalytic behavior of metal catalysts in high-temperature RWGS reaction: in-situ FT-IR experiments and first-principles calculations. Sci. Rep. 7, 41207 (2017).

    CAS  PubMed  PubMed Central  Google Scholar 

  25. 25.

    Fujitani, T. et al. Development of an active Ga2O3 supported palladium catalyst for the synthesis of methanol from carbon dioxide and hydrogen. Appl. Catal. A 125, L199–L202 (1995).

    CAS  Google Scholar 

  26. 26.

    Kattel, S., Yan, B., Chen, J. G. & Liu, P. CO2 hydrogenation on Pt, Pt/SiO2 and Pt/TiO2: importance of synergy between Pt and oxide support. J. Catal. 343, 115–126 (2016).

    CAS  Google Scholar 

  27. 27.

    Kattel, S. et al. CO2 hydrogenation over oxide-supported PtCo catalysts: the role of the oxide support in determining the product selectivity. Angew. Chem. Int. Ed. 55, 7968–7973 (2016).

    CAS  Google Scholar 

  28. 28.

    da Silva, D. C. D., Letichevsky, S., Borges, L. E. P. & Appel, L. G. The Ni/ZrO2 catalyst and the methanation of CO and CO2. Int. J. Hydrog. Energy 37, 8923–8928 (2012).

    Google Scholar 

  29. 29.

    Razzaq, R., Li, C., Usman, M., Suzuki, K. & Zhang, S. A highly active and stable Co4N/γ-Al2O3 catalyst for CO and CO2 methanation to produce synthetic natural gas (SNG). Chem. Eng. J. 262, 1090–1098 (2015).

    CAS  Google Scholar 

  30. 30.

    Kharaji, A. G., Shariati, A. & Ostadi, M. Development of Ni-Mo/Al2O3 catalyst for reverse water gas shift (RWGS) reaction. J. Nanosci. Nanotechnol. 14, 6841–6847 (2014).

    CAS  PubMed  Google Scholar 

  31. 31.

    Kharaji, A. G., Shariati, A. & Takassi, M. A. A novel γ-alumina supported Fe–Mo bimetallic catalyst for reverse water gas shift reaction. Chin. J. Chem. Eng. 21, 1007–1014 (2013).

    CAS  Google Scholar 

  32. 32.

    Fujita, S.-I., Usui, M. & Takezawa, N. Mechanism of the reverse water gas shift reaction over Cu/ZnO catalyst. J. Catal. 134, 220–225 (1992).

    CAS  Google Scholar 

  33. 33.

    Tominaga, K.-i. & Sasaki, Y. Ruthenium complex-catalyzed hydroformylation of alkenes with carbon dioxide. Catal. Commun. 1, 1–3 (2000).The first example of using CO 2 for the hydroformylation of alkenes.

    CAS  Google Scholar 

  34. 34.

    Tominaga, K.-i & Sasaki, Y. Ruthenium-catalyzed one-pot hydroformylation of alkenes using carbon dioxide as a reactant. J. Mol. Catal. A 220, 159–165 (2004).

    CAS  Google Scholar 

  35. 35.

    Franke, R., Selent, D. & Börner, A. Applied hydroformylation. Chem. Rev. 112, 5675–5732 (2012).

    CAS  PubMed  Google Scholar 

  36. 36.

    Jääskeläinen, S. & Haukka, M. The use of carbon dioxide in ruthenium carbonyl catalyzed 1-hexene hydroformylation promoted by alkali metal and alkaline earth salts. Appl. Catal. A 247, 95–100 (2003).

    Google Scholar 

  37. 37.

    Kontkanen, M.-L. et al. One-dimensional metal atom chain [Ru(CO)4]n as a catalyst precursor — hydroformylation of 1-hexene using carbon dioxide as a reactant. Appl. Catal. A 365, 130–134 (2009).

    CAS  Google Scholar 

  38. 38.

    Tsuchiya, K., Huang, J.-D. & Tominaga, K.-i Reverse water-gas shift reaction catalyzed by mononuclear Ru complexes. ACS Catal. 3, 2865–2868 (2013).

    CAS  Google Scholar 

  39. 39.

    Fujita, S. I., Okamura, S., Akiyama, Y. & Arai, M. Hydroformylation of cyclohexene with carbon dioxide and hydrogen using ruthenium carbonyl catalyst: influence of pressures of gaseous components. Int. J. Mol. Sci. 8, 749–759 (2007).

    CAS  PubMed Central  Google Scholar 

  40. 40.

    Ali, M., Gual, A., Ebeling, G. & Dupont, J. Ruthenium-catalyzed hydroformylation of alkenes by using carbon dioxide as the carbon monoxide source in the presence of ionic liquids. ChemCatChem 6, 2224–2228 (2014).

    CAS  Google Scholar 

  41. 41.

    Liu, Q. et al. Development of a ruthenium/phosphite catalyst system for domino hydroformylation — reduction of olefins with carbon dioxide. Chem. Eur. J. 20, 6888–6894 (2014).

    CAS  PubMed  Google Scholar 

  42. 42.

    Fleischer, I. et al. Towards the development of a selective ruthenium-catalyzed hydroformylation of olefins. Chem. Eur. J. 19, 10589–10594 (2013).

    CAS  PubMed  Google Scholar 

  43. 43.

    Srivastava, V. K. & Eilbracht, P. Ruthenium carbonyl-complex catalyzed hydroaminomethylation of olefins with carbon dioxide and amines. Catal. Commun. 10, 1791–1795 (2009).

    CAS  Google Scholar 

  44. 44.

    Ren, X. et al. Rhodium-complex-catalyzed hydroformylation of olefins with CO2 and hydrosilane. Angew. Chem. Int. Ed. 56, 310–313 (2017).

    CAS  Google Scholar 

  45. 45.

    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 

  46. 46.

    Wu, L., Liu, Q., Fleischer, I., Jackstell, R. & Beller, M. Ruthenium-catalysed alkoxycarbonylation of alkenes with carbon dioxide. Nat. Commun. 5, 3091 (2014). The first example of reducing CO 2 to CO using alcohols instead of dihydrogen as the reductant coupled to alkoxycarbonylation of alkenes.

    PubMed  Google Scholar 

  47. 47.

    Clegg, W. et al. Highly active and selective catalysts for the production of methyl propanoate via the methoxycarbonylation of ethene. Chem. Commun. 1877−1878 (1999).

  48. 48.

    Stouten, S. C., Noel, T., Wang, Q., Beller, M. & Hessel, V. Continuous ruthenium-catalyzed methoxycarbonylation with supercritical carbon dioxide. Catal. Sci. Technol. 6, 4712–4717 (2016).

    CAS  Google Scholar 

  49. 49.

    Laitar, D. S., Müller, P. & Sadighi, J. P. Efficient homogeneous catalysis in the reduction of CO2 to CO. J. Am. Chem. Soc. 127, 17196–17197 (2005). The first example of reducing CO 2 to CO using alcohols instead of dihydrogen as the reductant coupled to alkoxycarbonylation of alkenes.

    CAS  PubMed  Google Scholar 

  50. 50.

    Zhao, H., Lin, Z. & Marder, T. B. Density functional theory studies on the mechanism of the reduction of CO2 to CO catalyzed by copper(I) boryl complexes. J. Am. Chem. Soc. 128, 15637–15643 (2006).

    CAS  PubMed  Google Scholar 

  51. 51.

    Kleeberg, C., Cheung, M. S., Lin, Z. & Marder, T. B. Copper-mediated reduction of CO2 with pinB-SiMe2Ph via CO2 insertion into a copper–silicon bond. J. Am. Chem. Soc. 133, 19060–19063 (2011).

    CAS  PubMed  Google Scholar 

  52. 52.

    Lescot, C. et al. Efficient fluoride-catalyzed conversion of CO2 to CO at room temperature. J. Am. Chem. Soc. 136, 6142–6147 (2014). A metal-free reduction of CO 2 to CO coupled to ensuing amino- and alkoxycarbonylation reaction.

    CAS  PubMed  Google Scholar 

  53. 53.

    Hermange, P. et al. Ex situ generation of stoichiometric and substoichiometric 12CO and 13CO and its efficient incorporation in palladium catalyzed aminocarbonylations. J. Am. Chem. Soc. 133, 6061–6071 (2011).

    CAS  PubMed  Google Scholar 

  54. 54.

    Flinker, M. et al. Experimental and theoretical studies on the reduction of CO2 to CO with chloro(methyl)disilane components from the direct process. Synlett 28, 2439–2444 (2017).

    CAS  Google Scholar 

  55. 55.

    Ma, G., Song, G. & Li, Z. H. Theoretical design and mechanistic study of the metal-free reduction of CO2 to CO. Phys. Chem. Chem. Phys. 19, 28313–28322 (2017).

    CAS  PubMed  Google Scholar 

  56. 56.

    Lian, Z., Nielsen, D. U., Lindhardt, A. T., Daasbjerg, K. & Skrydstrup, T. Cooperative redox activation for carbon dioxide conversion. Nat. Commun. 7, 13782 (2016).

    PubMed  PubMed Central  Google Scholar 

  57. 57.

    Lu, Q., Rosen, J. & Jiao, F. Nanostructured metallic electrocatalysts for carbon dioxide reduction. ChemCatChem 7, 38–47 (2015).

    Google Scholar 

  58. 58.

    Schreier, M. et al. Solar conversion of CO2 to CO using earth-abundant electrocatalysts prepared by atomic layer modification of CuO. Nat. Energy 2, 17087 (2017).

    CAS  Google Scholar 

  59. 59.

    Benson, E. E., Kubiak, C. P., Sathrum, A. J. & Smieja, J. M. Electrocatalytic and homogeneous approaches to conversion of CO2 to liquid fuels. Chem. Soc. Rev. 38, 89–99 (2009).

    CAS  PubMed  Google Scholar 

  60. 60.

    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 

  61. 61.

    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 

  62. 62.

    Francke, R., Schille, B. & Roemelt, M. Homogeneously catalyzed electroreduction of carbon dioxide — methods, mechanisms, and catalysts. Chem. Rev. https://doi.org/10.1021/acs.chemrev.7b00459 (2018).

  63. 63.

    Bhugun, I., Lexa, D. & Savéant, J.-M. Catalysis of the electrochemical reduction of carbon dioxide by iron(0) porphyrinÿs: synergystic effect of weak Bronsted acids. J. Am. Chem. Soc. 118, 1769–1776 (1996).

    CAS  Google Scholar 

  64. 64.

    Costentin, C., Drouet, S., Robert, M. & Savéant, J. -M. A local proton source enhances CO2 electroreduction to CO by a molecular Fe catalyst. Science 338, 90–94 (2012).

    CAS  PubMed  Google Scholar 

  65. 65.

    Costentin, C., Passard, G., Robert, M. & Savéant, J. -M. Ultraefficient homogeneous catalyst for the CO2-to-CO electrochemical conversion. Proc. Natl Acad. Sci. USA 111, 14990–14994 (2014).

    CAS  PubMed  Google Scholar 

  66. 66.

    Azcarate, I., Costentin, C., Robert, M. & Sav‚ant, J. -M. Through-space charge interaction substituent effects in molecular catalysis leading to the design of the most efficient catalyst of CO2-to-CO electrochemical conversion. J. Am. Chem. Soc. 138, 16639–16644 (2016). Positively charged iron porphyrin represents the most efficient electrocatalysts for homogeneous CO 2 -to-CO conversion benefiting from through space charge interaction substituent effects.

    CAS  PubMed  Google Scholar 

  67. 67.

    Costentin, C., Drouet, S., Passard, G., Robert, M. & Savéant, J. -M. Proton-coupled electron transfer cleavage of heavy-atom bonds in electrocatalytic processes. Cleavage of a C–O bond in the catalyzed electrochemical reduction of CO2. J. Am. Chem. Soc. 135, 9023–9031 (2013).

    CAS  PubMed  Google Scholar 

  68. 68.

    Beley, M., Collin, J. P., Ruppert, R. & Sauvage, J. P. Electrocatalytic reduction of carbon dioxide by nickel cyclam2+ in water: study of the factors affecting the efficiency and the selectivity of the process. J. Am. Chem. Soc. 108, 7461–7467 (1986).

    CAS  PubMed  Google Scholar 

  69. 69.

    Costentin, C., Robert, M., Savéant, J. -M. & Tatin, A. Efficient and selective molecular catalyst for the CO2-to-CO electrochemical conversion in water. Proc. Natl Acad. Sci. USA 112, 6882–6886 (2015).

    CAS  PubMed  Google Scholar 

  70. 70.

    Hawecker, J., Lehn, J. -M. & Ziessel, R. Electrocatalytic reduction of carbon dioxide mediated by Re(bipy)(CO)3Cl (bipy = 2,2'-bipyridine). J. Chem. Soc. Chem. Commun. 328–330 (1984).

  71. 71.

    Bourrez, M., Molton, F., Chardon-Noblat, S. & Deronzier, A. Mn(bipyridyl)(CO)3Br: an abundant metal carbonyl complex as efficient electrocatalyst for CO2 reduction. Angew. Chem. Int. Ed. 50, 9903–9906 (2011).

    CAS  Google Scholar 

  72. 72.

    Chen, L. et al. Molecular catalysis of the electrochemical and photochemical reduction of CO2 with Earth-abundant metal complexes. Selective production of CO vs HCOOH by switching of the metal center. J. Am. Chem. Soc. 137, 10918–10921 (2015).

    CAS  PubMed  Google Scholar 

  73. 73.

    Chapovetsky, A., Do, T. H., Haiges, R., Takase, M. K. & Marinescu, S. C. Proton-assisted reduction of CO2 by cobalt aminopyridine macrocycles. J. Am. Chem. Soc. 138, 5765–5768 (2016).

    CAS  PubMed  Google Scholar 

  74. 74.

    Rosas-Hernandez, A., Junge, H., Beller, M., Roemelt, M. & Francke, R. Cyclopentadienone iron complexes as efficient and selective catalysts for the electroreduction of CO2 to CO. Catal. Sci. Technol. 7, 459–465 (2017).

    CAS  Google Scholar 

  75. 75.

    Zhang, L., Zhao, Z. J. & Gong, J. L. Nanostructured materials for heterogeneous electrocatalytic CO2 reduction and their related reaction mechanisms. Angew. Chem. Int. Ed. 56, 11326–11353 (2017).

    CAS  Google Scholar 

  76. 76.

    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).

    PubMed  Google Scholar 

  77. 77.

    Lin, S. et al. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water. Science 349, 1208–1213 (2015). The first report incorporating metal complexes into porous frameworks to achieve high activity for CO 2 -to-CO conversion in water.

    CAS  PubMed  Google Scholar 

  78. 78.

    Kornienko, N. et al. Metal–organic frameworks for electrocatalytic reduction of carbon dioxide. J. Am. Chem. Soc. 137, 14129–14135 (2015).

    CAS  PubMed  Google Scholar 

  79. 79.

    Maurin, A. & Robert, M. Noncovalent immobilization of a molecular iron-based electrocatalyst on carbon electrodes for selective, efficient CO2-to-CO conversion in water. J. Am. Chem. Soc. 138, 2492–2495 (2016).

    CAS  PubMed  Google Scholar 

  80. 80.

    Morlanés, N., Takanabe, K. & Rodionov, V. Simultaneous reduction of CO2 and splitting of H2O by a single immobilized cobalt phthalocyanine electrocatalyst. ACS Catal. 6, 3092–3095 (2016).

    Google Scholar 

  81. 81.

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

    PubMed  PubMed Central  Google Scholar 

  82. 82.

    Hu, X.-M., Rønne, M. H., Pedersen, S. U., Skrydstrup, T. & Daasbjerg, K. Enhanced catalytic activity of cobalt porphyrin in CO2 electroreduction upon immobilization on carbon materials. Angew. Chem. Int. Ed. 56, 6468–6472 (2017).

    CAS  Google Scholar 

  83. 83.

    Zhu, W. et al. Monodisperse Au nanoparticles for selective electrocatalytic reduction of CO2 to CO. J. Am. Chem. Soc. 135, 16833–16836 (2013).

    CAS  PubMed  Google Scholar 

  84. 84.

    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 

  85. 85.

    Liu, M. et al. Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration. Nature 537, 382–386 (2016). This paper demonstrates the enhanced electrocatalytic CO 2 reduction due to the electric field induced high local concentration of electrolyte cations and CO 2 close to the active sites.

    CAS  PubMed  Google Scholar 

  86. 86.

    Lu, Q. et al. A selective and efficient electrocatalyst for carbon dioxide reduction. Nat. Commun. 5, 3242 (2014).

    PubMed  Google Scholar 

  87. 87.

    Gao, D. et al. Size-dependent electrocatalytic reduction of CO2 over Pd nanoparticles. J. Am. Chem. Soc. 137, 4288–4291 (2015).

    CAS  PubMed  Google Scholar 

  88. 88.

    Quan, F. J., Zhong, D., Song, H. C., Jia, F. L. & Zhang, L. Z. A highly efficient zinc catalyst for selective electroreduction of carbon dioxide in aqueous NaCl solution. J. Mater. Chem. A 3, 16409–16413 (2015).

    CAS  Google Scholar 

  89. 89.

    DiMeglio, J. L. & Rosenthal, J. Selective conversion of CO2 to CO with high efficiency using an inexpensive bismuth-based electrocatalyst. J. Am. Chem. Soc. 135, 8798–8801 (2013).

    CAS  PubMed  PubMed Central  Google Scholar 

  90. 90.

    Asadi, M. et al. Robust carbon dioxide reduction on molybdenum disulphide edges. Nat. Commun. 5, 4470 (2014).

    CAS  PubMed  Google Scholar 

  91. 91.

    Asadi, M. et al. Nanostructured transition metal dichalcogenide electrocatalysts for CO2 reduction in ionic liquid. Science 353, 467–470 (2016). Nanostructured transition metal dichalcogenides represent the most efficient electrocatalysts for heterogeneous CO 2 -to-CO conversion in aqueous media.

    CAS  PubMed  Google Scholar 

  92. 92.

    Xu, J. et al. Revealing the origin of activity in nitrogen-doped nanocarbons towards electrocatalytic reduction of carbon dioxide. ChemSusChem 9, 1085–1089 (2016).

    CAS  PubMed  Google Scholar 

  93. 93.

    Huan, T. N. et al. Electrochemical reduction of CO2 catalyzed by Fe-N-C materials: a structure–selectivity study. ACS Catal. 7, 1520–1525 (2017).

    CAS  Google Scholar 

  94. 94.

    Li, X. et al. Exclusive Ni–N4 sites realize near-unity CO selectivity for electrochemical CO2 reduction. J. Am. Chem. Soc. 139, 14889–14892 (2017). Single nickel atoms embedded in a carbon matrix exhibits near-unity selectivity for electrochemical CO 2 -to-CO conversion in water.

    CAS  PubMed  Google Scholar 

  95. 95.

    Jensen, M. T. et al. Scalable carbon dioxide electroreduction coupled to carbonylation chemistry. Nat. Commun. 8, 489 (2017). The first example of applying electrochemistry for a scalable reduction of CO 2 to CO coupled to ensuing carbonylative transformations.

    PubMed  PubMed Central  Google Scholar 

  96. 96.

    Nielsen, D. U. et al. Palladium-catalyzed double carbonylation using near stoichiometric carbon monoxide: Expedient access to substituted 13C2-labeled phenethylamines. J. Org. Chem. 77, 6155–6165 (2012).

    CAS  PubMed  Google Scholar 

  97. 97.

    Gøgsig, T. M., Nielsen, D. U., Lindhardt, A. T. & Skrydstrup, T. Palladium catalyzed carbonylative Heck reaction affording monoprotected 1,3-ketoaldehydes. Org. Lett. 14, 2536–2539 (2012).

    PubMed  Google Scholar 

  98. 98.

    Prat, D., Hayler, J. & Wells, A. A survey of solvent selection guides. Green Chem. 16, 4546–4551 (2014).

    CAS  Google Scholar 

  99. 99.

    Tahir, M. et al. Electrocatalytic oxygen evolution reaction for energy conversion and storage: a comprehensive review. Nano Energy 37, 136–157 (2017).

    CAS  Google Scholar 

  100. 100.

    Tatin, A. et al. Efficient electrolyzer for CO2 splitting in neutral water using earth-abundant materials. Proc. Natl Acad. Sci. USA 113, 5526–5529 (2016).

    CAS  PubMed  Google Scholar 

  101. 101.

    Ren, L., Li, X. & Jiao, N. Dioxygen-promoted Pd-catalyzed aminocarbonylation of organoboronic acids with amines and CO: a direct approach to tertiary amides. Org. Lett. 18, 5852–5855 (2016).

    CAS  PubMed  Google Scholar 

  102. 102.

    Sheng, W. et al. Electrochemical reduction of CO2 to synthesis gas with controlled CO/H2 ratios. Energy Environ. Sci. 10, 1180–1185 (2017).

    CAS  Google Scholar 

  103. 103.

    Pumera, M. & Loo, A. H. Layered transition-metal dichalcogenides (MoS2 and WS2) for sensing and biosensing. Trac-Trends Anal. Chem. 61, 49–53 (2014).

    CAS  Google Scholar 

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Acknowledgements

We thank the Danish National Research Foundation (grant no. DNRF118) and Aarhus University for financial support.

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Correspondence to Kim Daasbjerg or Troels Skrydstrup.

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T.S. is co-owner of SyTracks a/s, which commercializes the two-chamber system, COware.

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Nielsen, D.U., Hu, XM., Daasbjerg, K. et al. Chemically and electrochemically catalysed conversion of CO2 to CO with follow-up utilization to value-added chemicals. Nat Catal 1, 244–254 (2018). https://doi.org/10.1038/s41929-018-0051-3

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