Electrochemical reduction of carbon dioxide

The electrochemical reduction of carbon dioxide is the conversion of carbon dioxide to more reduced chemical species using electrical energy. It is one possible step in the broad scheme of carbon capture and utilization. The first examples of electrochemical reduction of carbon dioxide are from the 19th century, when carbon dioxide was reduced to carbon monoxide using a zinc cathode. Research in this field intensified in the 1980s following the oil embargoes of the 1970s. Electrochemical reduction of carbon dioxide represents a possible means of producing chemicals or fuels, converting carbon dioxide (CO
2) to organic feedstocks such as formic acid (HCOOH),[1] carbon monoxide (CO), ethylene (C2H4), ethanol (C2H5OH) and methane (CH4).[2][3][4] Among the more selective metallic catalysts in this field are tin for formic acid, silver for carbon monoxide and copper for ethylene, ethanol or methane. Propanol and 1-butanol have also been produced via CO2 electrochemical reduction, albeit in small quantities. [5]

This article is about the electrochemical system. For related systems, see Photoelectrochemical reduction of carbon dioxide and Photochemical reduction of carbon dioxide.

Chemicals from carbon dioxide

In carbon fixation, plants convert carbon dioxide into sugars, from which many biosynthetic pathways originate. The catalyst responsible for this conversion, RuBisCo, is the most common protein on earth. Some anaerobic organisms employ enzymes to convert CO2 to carbon monoxide, from which fatty acids can be made.[6]

In industry, a few products are made from CO2, including urea, salicylic acid, methanol, and certain inorganic and organic carbonates.[7] In the laboratory, carbon dioxide is sometimes used to prepare carboxylic acids. No electrochemical CO2 electrolyzer that operates at room temperature has been commercialized. Elevated temperature solid oxide electrolyzer cells (SOEC) for CO2 reduction to CO are commercially available. For example, Haldor Topsoe offers SOECs for CO2 reduction with a reported 6-8 kWh per Nm3 CO produced and purity up to 99.999% CO.[8]

Electrocatalysis

The electrochemical reduction of carbon dioxide to CO is usually described as:

CO2 + 2 H+ + 2 e− → CO + H2O

The redox potential for this reaction is similar to that for hydrogen evolution in aqueous electrolytes, thus electrochemical reduction of CO2 is usually competitive with hydrogen evolution reaction.[4]

Electrochemical methods have gained significant attention: 1) at ambient pressure and room temperature; 2) in connection with renewable energy sources (see also solar fuel) 3) competitive controllability, modularity and scale-up are relatively simple.[9] The electrochemical reduction or electrocatalytic conversion of CO2 can produce value-added chemicals such methane, ethylene, ethane, etc., and the products are mainly dependent on the selected catalysts and operating potentials (applying reduction voltage).[10][11][12]

A variety of homogeneous and heterogeneous catalysts[13] have been evaluated.[4][2] Many such processes are assumed to operate via the intermediacy of metal carbon dioxide complexes.[14] Many processes suffer from high overpotential, low current efficiency, low selectivity, slow kinetics, and/or poor catalyst stability.[15]

The composition of the electrolyte can be decisive.[16][17] Gas-diffusion electrodes are beneficial.[18][19][20]

See also

References
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  2. Centi, Gabriele; Perathoner, Siglinda (2009). "Opportunities and prospects in the chemical recycling of carbon dioxide to fuels". Catalysis Today. 148 (3–4): 191–205. doi:10.1016/j.cattod.2009.07.075.
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  5. https://onlinelibrary.wiley.com/doi/full/10.1002/anie.202008289
  6. Fontecilla-Camps, J. C.; Amara, P.; Cavazza, C.; Nicolet, Y.; Volbeda, A. (2009). "Structure-function relationships of anaerobic gas-processing metalloenzymes". Nature. 460 (7257): 814–822. Bibcode:2009Natur.460..814F. doi:10.1038/nature08299. PMID 19675641.
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  8. https://www.topsoe.com/processes/carbon-monoxide. Missing or empty |title= (help)
  9. Lee, S.; et al. (2016). "Electrode Build-Up of Reducible Metal Composites toward Achievable Electrochemical Conversion of Carbon Dioxide". ChemSusChem. 9 (4): 333–344. doi:10.1002/cssc.201501112. PMID 26610065.
  10. Lee, S.; et al. (2015). "Sustainable production of formic acid by electrolytic reduction of gaseous carbon dioxide". J. Mater. Chem. A. 3 (6): 3029–3034. doi:10.1039/C4TA03893B.
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    2     Utilization via Direct Heterogeneous Electrochemical Reduction". J. Phys. Chem. Lett. 1 (24): 3451–3458. doi:10.1021/jz1012627.
  12. Machundaa, R.L.; et al. (2011). "Electrocatalytic reduction of CO
    2     gas at Sn-based gas diffusion electrode". Current Applied Physics. 11: 986–988. doi:10.1016/j.cap.2011.01.003.
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  14. Benson, Eric E.; Kubiak, Clifford P.; Sathrum, Aaron J.; Smieja, Jonathan M. (2009). "Electrocatalytic and homogeneous approaches to conversion of CO
    2     to liquid fuels". Chem. Soc. Rev. 38 (1): 89–99. doi:10.1039/b804323j. PMID 19088968. S2CID 20705539.
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  17. R.F. Service, Two new ways to turn 'garbage’ carbon dioxide into fuel www.sciencemag.org/news/2017/09/two-new-ways-turn-garbage-carbon-dioxide-fuel
  18. Thorson, Michael R.; Siil, Karl I.; Kenis, Paul J. A. (2013). "Effect of Cations on the Electrochemical Conversion of CO 2 to CO". Journal of the Electrochemical Society. 160 (1): F69–F74. doi:10.1149/2.052301jes. ISSN 0013-4651. S2CID 95111100.
  19. Lv, Jing-Jing; Jouny, Matthew; Luc, Wesley; Zhu, Wenlei; Zhu, Jun-Jie; Jiao, Feng (December 2018). "A Highly Porous Copper Electrocatalyst for Carbon Dioxide Reduction". Advanced Materials. 30 (49): 1803111. doi:10.1002/adma.201803111. PMID 30368917.
  20. Dinh, Cao-Thang; Burdyny, Thomas; Kibria, Md Golam; Seifitokaldani, Ali; Gabardo, Christine M.; García de Arquer, F. Pelayo; Kiani, Amirreza; Edwards, Jonathan P.; De Luna, Phil (2018-05-18). "CO 2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface". Science. 360 (6390): 783–787. doi:10.1126/science.aas9100. ISSN 0036-8075. PMID 29773749.
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