Electrochemical reduction of carbon dioxide explained

The electrochemical reduction of carbon dioxide, also known as CO2RR, is the conversion of carbon dioxide to more reduced chemical species using electrical energy. It represents one potential step in the broad scheme of carbon capture and utilization.[1]

CO2RR can produce diverse compounds including formate (HCOO-), carbon monoxide (CO), methane (CH4), ethylene (C2H4), and ethanol (C2H5OH).[2] The main challenges are the relatively high cost of electricity (vs petroleum) and that CO2 is often contaminated with O2 and must be purified before reduction.

The first examples of CO2RR 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. As of 2021, pilot-scale carbon dioxide electrochemical reduction is being developed by several companies, including Siemens,[3] Dioxide Materials,[4] [5] Twelve and GIGKarasek. The techno-economic analysis was recently conducted to assess the key technical gaps and commercial potentials of the carbon dioxide electrolysis technology at near ambient conditions.[6] [7]

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. Some anaerobic organisms employ enzymes to convert CO2 to carbon monoxide, from which fatty acids can be made.[8]

In industry, a few products are made from CO2, including urea, salicylic acid, methanol, and certain inorganic and organic carbonates.[9] In the laboratory, carbon dioxide is sometimes used to prepare carboxylic acids in a process known as carboxylation. An electrochemical CO2 electrolyzer that operates at room temperature has not yet been commercialized. Elevated temperature solid oxide electrolyzer cells (SOECs) 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[10] CO produced and purity up to 99.999% CO.[11]

Electrocatalysis

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

!Reaction!Reduction potential Eo (V) at pH = 7 vs SHE [12]
CO2 + 2 H+ + 2 e− → CO + H2O−0.52
CO2 + 2 H+ + 2 e− → HCOOH−0.61
CO2 + 8 H+ + 8 e− → CH4 + 2 H2O−0.24
2 CO2 + 12 H+ + 12 e− → C2H4 + 4 H2O−0.34

The redox potentials for these reactions are similar to that for hydrogen evolution in aqueous electrolytes, thus electrochemical reduction of CO2 is usually competitive with hydrogen evolution reaction.[2]

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.[13]

The electrochemical reduction or electrocatalytic conversion of CO2 can produce value-added chemicals such methane, ethylene, ethanol, etc., and the products are mainly dependent on the selected catalysts and operating potentials (applying reduction voltage). A variety of homogeneous and heterogeneous catalysts[14] have been evaluated.

Many such processes are assumed to operate via the intermediacy of metal carbon dioxide complexes.[15] Many processes suffer from high overpotential, low current efficiency, low selectivity, slow kinetics, and/or poor catalyst stability.[16]

The composition of the electrolyte can be decisive.[17] [18] [19] Gas-diffusion electrodes are beneficial.[20] [21] [22]

Catalysts

Catalysts can be grouped by their primary products.[23] [24] [25] Several metal are unfit for CO2RR because they promote to perform hydrogen evolution instead.[26] Electrocatalysts selective for one particular organic compound include tin or bismuth for formate and silver or gold for carbon monoxide. Copper produces multiple reduced products such as methane, ethylene or ethanol, while methanol, propanol and 1-butanol have also been produced in minute quantities.[27]

Three common products are carbon monoxide, formate, or higher order carbon products (two or more carbons).[28]

Carbon monoxide-producing

Carbon monoxide can be produced from CO2RR over various precious metal catalysts.[29] Steel has proven to be one such catalyst.,[30] or hydrogen.[31]

Mechanistically, carbon monoxide arises from the metal bonded to the carbon of CO2 (see metallacarboxylic acid). Oxygen is lost as water.[32]

Formate/formic acid-producing

Formic acid is produced as a primary product from CO2RR over diverse catalysts.[33]

Catalysts that promote Formic Acid production from CO2 operate by strongly binding to both oxygen atoms of CO2, allowing protons to attack the central carbon. After attacking the central carbon, one proton attaching to an oxygen results in the creation of formate. Indium catalysts promote formate production because the Indium-Oxygen binding energy is stronger than the Indium-Carbon binding energy.[34] This promotes the production of formate instead of Carbon Monoxide.

C>1-producing catalysts

Copper electrocatalysts produce multicarbon compounds from CO2. These include C2 products (ethylene, ethanol, acetate, etc.) and even C3 products (propanol, acetone, etc.)[35] These products are more valuable than C1 products, but the current efficiencies are low.[36]

See also

Further reading

Notes and References

  1. Web site: Dream or Reality? Electrification of the Chemical Process Industries. 2021-08-22. www.aiche-cep.com. en.
  2. Appel AM, Bercaw JE, Bocarsly AB, Dobbek H, DuBois DL, Dupuis M, Ferry JG, Fujita E, Hille R, Kenis PJ, Kerfeld CA, Morris RH, Peden CH, Portis AR, Ragsdale SW, Rauchfuss TB, Reek JN, Seefeldt LC, Thauer RK, Waldrop GL . 6 . Frontiers, opportunities, and challenges in biochemical and chemical catalysis of CO2 fixation . Chemical Reviews . 113 . 8 . 6621–58 . August 2013 . 23767781 . 3895110 . 10.1021/cr300463y .
  3. Web site: CO2 is turned into feedstock. 2021-07-04. siemens-energy.com Global Website. en. 2021-07-09. https://web.archive.org/web/20210709184434/https://www.siemens-energy.com/global/en/news/magazine/2020/rheticus-worlds-first-automated-co2-electrolyzer.html. dead.
  4. Web site: CO2 Electrolyzers With Record Performance. 2021-07-04. Dioxide Materials. en.
  5. Masel. Richard I.. Liu. Zengcai. Yang. Hongzhou. Kaczur. Jerry J.. Carrillo. Daniel. Ren. Shaoxuan. Salvatore. Danielle. Berlinguette. Curtis P.. 2021. An industrial perspective on catalysts for low-temperature CO 2 electrolysis. Nature Nanotechnology. en. 16. 2. 118–128. 10.1038/s41565-020-00823-x. 33432206. 2021NatNa..16..118M. 1756565. 231580446. 1748-3395.
  6. Jouny. Matthew. Luc. Wesley. Jiao. Feng. 2018-02-14. General Techno-Economic Analysis of CO2 Electrolysis Systems. Industrial & Engineering Chemistry Research. 57. 6. 2165–2177. 10.1021/acs.iecr.7b03514. 1712664. 0888-5885.
  7. Shin. Haeun. Hansen. Kentaro U.. Jiao. Feng. October 2021. Techno-economic assessment of low-temperature carbon dioxide electrolysis. Nature Sustainability. en. 4. 10. 911–919. 10.1038/s41893-021-00739-x. 2021NatSu...4..911S . 235801320. 2398-9629.
  8. Fontecilla-Camps JC, Amara P, Cavazza C, Nicolet Y, Volbeda A . Structure-function relationships of anaerobic gas-processing metalloenzymes . Nature . 460 . 7257 . 814–22 . August 2009 . 19675641 . 10.1038/nature08299 . 2009Natur.460..814F . 4421420 .
  9. Susan Topham, "Carbon Dioxide" in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim.
  10. Normal Cubic Meter - the quantity of gas that occupies one cubic meter at standard temperature and pressure.
  11. Web site: Produce Your Own Carbon Monoxide - on-site and on-demand. Haldor Topsoe. www.topsoe.com. live. https://web.archive.org/web/20210228151311/https://www.topsoe.com/processes/carbon-monoxide. 28 February 2021.
  12. Zhu D, Liu J, Qiao S . 2016 . Recent Advances in Inorganic Heterogeneous Electrocatalysts for Reduction of Carbon Dioxide . Advanced Materials . 28 . 18. 3423–3452 . 10.1002/adma.201504766 . free . 26996295 . 2016AdM....28.3423Z .
  13. Lee S, Lee J . Electrode Build-Up of Reducible Metal Composites toward Achievable Electrochemical Conversion of Carbon Dioxide . ChemSusChem . 9 . 4 . 333–44 . February 2016 . 26610065 . 10.1002/cssc.201501112 . 2016ChSCh...9..333L .
  14. Book: Hori Y . Electrochemical CO2 Reduction on Metal Electrodes . 10.1007/978-0-387-49489-0_3 . Modern Aspects of Electrochemistry . 42 . 89–80 . 2008 . 978-0-387-49488-3 .
  15. Benson EE, Kubiak CP, Sathrum AJ, Smieja JM . Electrocatalytic and homogeneous approaches to conversion of CO2 to liquid fuels . Chemical Society Reviews . 38 . 1 . 89–99 . January 2009 . 19088968 . 10.1039/b804323j . 20705539 .
  16. Book: Halmann MM, Steinberg M . Greenhouse gas carbon dioxide mitigation: science and technology. . CRC press . May 1998 . 1-56670-284-4 .
  17. 10.1038/s41586-019-1782-2 . Molecular tuning of CO2-to-ethylene conversion . 2020 . Li . Fengwang . et al. . Nature . 577 . 7791 . 509–513 . 31747679 . 208217415 .
  18. Rosen BA, Salehi-Khojin A, Thorson MR, Zhu W, Whipple DT, Kenis PJ, Masel RI . Ionic liquid-mediated selective conversion of CO₂ to CO at low overpotentials . Science . 334 . 6056 . 643–4 . November 2011 . 21960532 . 10.1126/science.1209786 . 2011Sci...334..643R . 31774347 . free .
  19. Service RF . Two new ways to turn 'garbage' carbon dioxide into fuel . Science Magazine . 1 September 2017 . 10.1126/science.aap8497 .
  20. Thorson MR, Siil KI, Kenis PJ . 95111100. 2013. Effect of Cations on the Electrochemical Conversion of CO 2 to CO. Journal of the Electrochemical Society. 160. 1. F69–F74. 10.1149/2.052301jes. 0013-4651. free.
  21. Lv JJ, Jouny M, Luc W, Zhu W, Zhu JJ, Jiao F . A Highly Porous Copper Electrocatalyst for Carbon Dioxide Reduction . Advanced Materials . 30 . 49 . e1803111 . December 2018 . 30368917 . 10.1002/adma.201803111 . 2018AdM....3003111L . 1712663 . 53093014 .
  22. Dinh CT, Burdyny T, Kibria MG, Seifitokaldani A, Gabardo CM, García de Arquer FP, Kiani A, Edwards JP, De Luna P, Bushuyev OS, Zou C, Quintero-Bermudez R, Pang Y, Sinton D, Sargent EH . 6 . CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface . Science . 360 . 6390 . 783–787 . May 2018 . 29773749 . 10.1126/science.aas9100 . free .
  23. Centi G, Perathoner S . 2009 . Opportunities and prospects in the chemical recycling of carbon dioxide to fuels . Catalysis Today . 148 . 3–4. 191–205 . 10.1016/j.cattod.2009.07.075 .
  24. Qiao J, Liu Y, Hong F, Zhang J . A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels . Chemical Society Reviews . 43 . 2 . 631–75 . January 2014 . 24186433 . 10.1039/c3cs60323g .
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