Electrochemical reduction of carbon dioxide

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The electrochemical reduction of carbon dioxide, also known as CO2RR, is the conversion of carbon dioxide (CO2) to more reduced chemical species using electrical energy. It represents one potential step in the broad scheme of carbon capture and utilization. [1]

Contents

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 and demonstration cale carbon dioxide electrochemical reduction is being developed by several companies, including Siemens, [3] Dioxide Materials, [4] [5] Twelve, GIGKarasek, and OCOchem. 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]

CO2RR electrolyzers have been developed to reduce other forms of CO2 including [bi]carbonates sourced from CO2 captured directly from the air using strong alkalis like KOH [8] or carbamates sourced from flue gas effluents using alkali or amine-based absorbents like MEA or DEA. [9] While the techno-economics of these systems are not yet feasible, they provide a near net carbon neutral pathway to produce commodity chemicals like ethylene at industrially relavant scales. [10]

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. [11]

In industry, a few products are made from CO2, including urea, salicylic acid, methanol, and certain inorganic and organic carbonates. [12] 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 at an industrial scale cell size (15,000cm2) was announced by OCOchem in April 2024 as part of an R&D contract issued by the US Army.  The CO2 electrolyzer was reported as the largest in the world with a cathode surface area of 15,000cm2, 650% larger than nearest alternative, and achieving a sustained 85% Faradaic efficiency [13] . 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 [note 1] CO produced and purity up to 99.999% CO. [14]

Electrocatalysis

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

ReactionReduction potential Eo (V) at pH = 7 vs SHE [15]
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. [16]

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 [17] have been evaluated. [18] [2]

Many such processes are assumed to operate via the intermediacy of metal carbon dioxide complexes. [19] Many processes suffer from high overpotential, low current efficiency, low selectivity, slow kinetics, and/or poor catalyst stability. [20]

The composition of the electrolyte can be decisive. [21] [22] [23] Gas-diffusion electrodes are beneficial. [24] [25] [26]

Catalysts

Catalysts can be grouped by their primary products. [18] [27] [28] Several metal are unfit for CO2RR because they promote to perform hydrogen evolution instead. [29] 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. [30]

Three common products are carbon monoxide, formate, or higher order carbon products (two or more carbons). [31]

Carbon monoxide-producing

Carbon monoxide can be produced from CO2RR over various precious metal catalysts. [32] Steel has proven to be one such catalyst., [33] or hydrogen. [34]

Mechanistically, carbon monoxide arises from the metal bonded to the carbon of CO2 (see metallacarboxylic acid). Oxygen is lost as water. [35]

Formate/formic acid-producing

Formic acid is produced as a primary product from CO2RR over diverse catalysts. [36]

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. [35] Indium catalysts promote formate production because the Indium-Oxygen binding energy is stronger than the Indium-Carbon binding energy. [37] 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.) [38] These products are more valuable than C1 products, but the current efficiencies are low. [39]

See also

Notes

  1. ↑ Normal Cubic Meter - the quantity of gas that occupies one cubic meter at standard temperature and pressure.

References

  1. ↑ "Dream or Reality? Electrification of the Chemical Process Industries". www.aiche-cep.com. Retrieved 2021-08-22.
  2. 1 2 3 Appel AM, Bercaw JE, Bocarsly AB, Dobbek H, DuBois DL, Dupuis M, et al. (August 2013). "Frontiers, opportunities, and challenges in biochemical and chemical catalysis of CO2 fixation". Chemical Reviews. 113 (8): 6621–58. doi:10.1021/cr300463y. PMC   3895110 . PMID   23767781.
  3. ↑ "CO2 is turned into feedstock". siemens-energy.com Global Website. Archived from the original on 2021-07-09. Retrieved 2021-07-04.
  4. ↑ "CO2 Electrolyzers With Record Performance". Dioxide Materials. Retrieved 2021-07-04.
  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. 16 (2): 118–128. Bibcode:2021NatNa..16..118M. doi:10.1038/s41565-020-00823-x. ISSN   1748-3395. OSTI   1756565. PMID   33432206. S2CID   231580446.
  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. doi:10.1021/acs.iecr.7b03514. ISSN   0888-5885. OSTI   1712664.
  7. ↑ Shin, Haeun; Hansen, Kentaro U.; Jiao, Feng (October 2021). "Techno-economic assessment of low-temperature carbon dioxide electrolysis". Nature Sustainability. 4 (10): 911–919. Bibcode:2021NatSu...4..911S. doi:10.1038/s41893-021-00739-x. ISSN   2398-9629. S2CID   235801320.
  8. ↑ Li, Tengfei; Lees, Eric W.; Goldman, Maxwell; Salvatore, Danielle A.; Weekes, David M.; Berlinguette, Curtis P. (2019-06-19). "Electrolytic Conversion of Bicarbonate into CO in a Flow Cell". Joule. 3 (6): 1487–1497. arXiv: 1905.04580 . doi:10.1016/j.joule.2019.05.021. ISSN   2542-4785.
  9. ↑ Lee, Geonhui; Li, Yuguang C.; Kim, Ji-Yong; Peng, Tao; Nam, Dae-Hyun; Sedighian Rasouli, Armin; Li, Fengwang; Luo, Mingchuan; Ip, Alexander H.; Joo, Young-Chang; Sargent, Edward H. (January 2021). "Electrochemical upgrade of CO2 from amine capture solution". Nature Energy. 6 (1): 46–53. doi:10.1038/s41560-020-00735-z. ISSN   2058-7546.
  10. ↑ Venkataraman, Anush; Song, Hakhyeon; Brandão, Victor D.; Ma, Chen; Casajus, Magdalena Salazar; Fernandez Otero, Carlos A.; Sievers, Carsten; Hatzell, Marta C.; Bhargava, Saket S.; Arora, Sukaran S.; Villa, Carlos; Dhingra, Sandeep; Nair, Sankar (November 2024). "Process and techno-economic analyses of ethylene production by electrochemical reduction of aqueous alkaline carbonates". Nature Chemical Engineering. 1 (11): 710–723. doi: 10.1038/s44286-024-00137-y . ISSN   2948-1198.
  11. ↑ Fontecilla-Camps JC, Amara P, Cavazza C, Nicolet Y, Volbeda A (August 2009). "Structure-function relationships of anaerobic gas-processing metalloenzymes". Nature. 460 (7257): 814–22. Bibcode:2009Natur.460..814F. doi:10.1038/nature08299. PMID   19675641. S2CID   4421420.
  12. ↑ Susan Topham, "Carbon Dioxide" in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim. doi : 10.1002/14356007.a05_165
  13. ↑ Yahoo News (April 25, 2024). "OCOchem Advances Hydrogen Formate Electrolyzer Process By 10x To Create World's Largest Industrial Scale CO2 Electrolyzer Cell". Yahoo Finance.{{cite news}}: CS1 maint: url-status (link)
  14. ↑ "Produce Your Own Carbon Monoxide - on-site and on-demand". www.topsoe.com. Haldor Topsoe. Archived from the original on 28 February 2021.
  15. ↑ Zhu D, Liu J, Qiao S (2016). "Recent Advances in Inorganic Heterogeneous Electrocatalysts for Reduction of Carbon Dioxide". Advanced Materials. 28 (18): 3423–3452. Bibcode:2016AdM....28.3423Z. doi: 10.1002/adma.201504766 . PMID   26996295.
  16. ↑ Lee S, Lee J (February 2016). "Electrode Build-Up of Reducible Metal Composites toward Achievable Electrochemical Conversion of Carbon Dioxide". ChemSusChem. 9 (4): 333–44. Bibcode:2016ChSCh...9..333L. doi:10.1002/cssc.201501112. PMID   26610065.
  17. ↑ Hori Y (2008). "Electrochemical CO2 Reduction on Metal Electrodes". Modern Aspects of Electrochemistry. Vol. 42. pp. 89–80. doi:10.1007/978-0-387-49489-0_3. ISBN   978-0-387-49488-3.
  18. 1 2 Centi G, Perathoner S (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.
  19. ↑ Benson EE, Kubiak CP, Sathrum AJ, Smieja JM (January 2009). "Electrocatalytic and homogeneous approaches to conversion of CO2 to liquid fuels". Chemical Society Reviews. 38 (1): 89–99. doi:10.1039/b804323j. PMID   19088968. S2CID   20705539.
  20. ↑ Halmann MM, Steinberg M (May 1998). Greenhouse gas carbon dioxide mitigation: science and technology. CRC press. ISBN   1-56670-284-4.
  21. ↑ Li, Fengwang; et al. (2020). "Molecular tuning of CO2-to-ethylene conversion". Nature. 577 (7791): 509–513. doi:10.1038/s41586-019-1782-2. PMID   31747679. S2CID   208217415.
  22. ↑ Rosen BA, Salehi-Khojin A, Thorson MR, Zhu W, Whipple DT, Kenis PJ, Masel RI (November 2011). "Ionic liquid-mediated selective conversion of CO₂ to CO at low overpotentials". Science. 334 (6056): 643–4. Bibcode:2011Sci...334..643R. doi: 10.1126/science.1209786 . PMID   21960532. S2CID   31774347.
  23. ↑ Service RF (1 September 2017). "Two new ways to turn 'garbage' carbon dioxide into fuel". Science Magazine. doi:10.1126/science.aap8497.
  24. ↑ Thorson MR, Siil KI, Kenis PJ (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.
  25. ↑ Lv JJ, Jouny M, Luc W, Zhu W, Zhu JJ, Jiao F (December 2018). "A Highly Porous Copper Electrocatalyst for Carbon Dioxide Reduction". Advanced Materials. 30 (49): e1803111. Bibcode:2018AdM....3003111L. doi:10.1002/adma.201803111. OSTI   1712663. PMID   30368917. S2CID   53093014.
  26. ↑ Dinh CT, Burdyny T, Kibria MG, Seifitokaldani A, Gabardo CM, García de Arquer FP, et al. (May 2018). "CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface". Science. 360 (6390): 783–787. doi: 10.1126/science.aas9100 . PMID   29773749.
  27. ↑ Qiao J, Liu Y, Hong F, Zhang J (January 2014). "A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels". Chemical Society Reviews. 43 (2): 631–75. doi:10.1039/c3cs60323g. PMID   24186433.
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  29. ↑ Lin, Jiayi; Zhang, Yixiao; Xu, Pengtao; Chen, Liwei (2023-05-01). "CO2 electrolysis: Advances and challenges in electrocatalyst engineering and reactor design". Materials Reports: Energy. CO2 Reductions to Fuels and Carbon Feedstocks (Part 2). 3 (2): 100194. doi: 10.1016/j.matre.2023.100194 . ISSN   2666-9358.
  30. ↑ Ting LR, García-Muelas R, Martín AJ, Veenstra FL, Chen ST, Peng Y, et al. (November 2020). "Electrochemical Reduction of Carbon Dioxide to 1-Butanol on Oxide-Derived Copper". Angewandte Chemie. 59 (47): 21072–21079. doi:10.1002/anie.202008289. PMC   7693243 . PMID   32706141.
  31. ↑ Mok, Dong Hyeon; Li, Hong; Zhang, Guiru; Lee, Chaehyeon; Jiang, Kun; Back, Seoin (2023-11-11). "Data-driven discovery of electrocatalysts for CO2 reduction using active motifs-based machine learning". Nature Communications. 14 (1): 7303. doi: 10.1038/s41467-023-43118-0 . ISSN   2041-1723. PMC   10640609 . PMID   37952012.
  32. ↑ Marcandalli, Giulia; Monteiro, Mariana C. O.; Goyal, Akansha; Koper, Marc T. M. (2022-07-19). "Electrolyte Effects on CO 2 Electrochemical Reduction to CO". Accounts of Chemical Research. 55 (14): 1900–1911. doi:10.1021/acs.accounts.2c00080. ISSN   0001-4842. PMC   9301915 . PMID   35772054.
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  35. 1 2 Feaster, Jeremy T.; Shi, Chuan; Cave, Etosha R.; Hatsukade, Toru; Abram, David N.; Kuhl, Kendra P.; Hahn, Christopher; Nørskov, Jens K.; Jaramillo, Thomas F. (2017-07-07). "Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes". ACS Catalysis. 7 (7): 4822–4827. doi:10.1021/acscatal.7b00687. ISSN   2155-5435. OSTI   1390311.
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  37. ↑ Guo, Weiwei; Tan, Xingxing; Bi, Jiahui; Xu, Liang; Yang, Dexin; Chen, Chunjun; Zhu, Qinggong; Ma, Jun; Tayal, Akhil; Ma, Jingyuan; Huang, Yuying; Sun, Xiaofu; Liu, Shoujie; Han, Buxing (2021-05-12). "Atomic Indium Catalysts for Switching CO 2 Electroreduction Products from Formate to CO". Journal of the American Chemical Society. 143 (18): 6877–6885. doi:10.1021/jacs.1c00151. ISSN   0002-7863. PMID   33856799. S2CID   233257736.
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  39. ↑ Kong, Qingquan; An, Xuguang; Liu, Qian; Xie, Lisi; Zhang, Jing; Li, Qinye; Yao, Weitang; Yu, Aimin; Jiao, Yan; Sun, Chenghua (2023-03-06). "Copper-based catalysts for the electrochemical reduction of carbon dioxide: progress and future prospects". Materials Horizons. 10 (3): 698–721. doi: 10.1039/D2MH01218A . ISSN   2051-6355. PMID   36601800.

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