Electrochemical reduction of carbon dioxide

The electrochemical reduction of carbon dioxide (ERC) is the conversion of carbon dioxide to more reduced chemical species using electrical energy. 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 (CO2) to organic feedstocks such as formic acid (HCOOH), methanol (CH3OH), ethylene (C2H4), methane (CH4), and carbon monoxide (CO).[1][2][3]

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.[4]

In industry, a few products are made from CO2, including urea, salicylic acid, methanol, and certain inorganic and organic carbonates.[5] In the laboratory, carbon dioxide is sometimes used to prepare carboxylic acids. No electrochemical process involving CO2 has been commercialized.

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.[3]

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 is relatively simple.[6] 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).[7][8][9]

Although an electrochemical route to CO (or other chemicals) has not been commercialized, a variety of homogeneous and heterogeneous catalysts[10] have been evaluated.[3][1] Many such processes are assumed to operate via the intermediacy of metal carbon dioxide complexes.[11] Generally speaking, the processes developed up to 2010 either had poor thermodynamic efficiency (high overpotential), low current efficiency, low selectivity, slow kinetics, and/or poor stability.[12] In 2011, workers from Dioxide Materials and University of Illinois showed that the combination of two catalysts could eliminate the high overpotential [13] More recently, the same group showed that the process was stable for 6 months at over 90% selectivity.[14]

See also

References

  1. 1 2 Gabriele Centi, Siglinda Perathoner "Opportunities and prospects in the chemical recycling of carbon dioxide to fuels" Catalysis Today 148 (2009) 191–205.doi:10.1016/j.cattod.2009.07.075
  2. ↑ J. Qiao, et al., A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels, Chem.Soc.Rev., 2014, 43 , 631-675.
  3. 1 2 3 Appel, A. M. et al. "Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO2 Fixation", Chem. Rev. 2013, vol. 113, 6621-6658. doi:10.1021/cr300463y
  4. ↑ 1. J. C. Fontecilla-Camps, P. Amara, C. Cavazza, Y. Nicolet and A. Volbeda, "Structure-function relationships of anaerobic gas-processing metalloenzymes", Nature 2009, volume 460, p. 814-822.doi:10.1038/nature08299
  5. ↑ Susan Topham, "Carbon Dioxide" in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim. doi:10.1002/14356007.a05_165
  6. ↑ S. Lee et al., ChemSusChem 9 (2016) 333-344, Electrode Build-Up of Reducible Metal Composites toward Achievable Electrochemical Conversion of Carbon Dioxidedoi:10.1002/cssc.201501112
  7. ↑ S. Lee et al., Sustainable production of formic acid by electrolytic reduction of gaseous carbon dioxide, J. Mater. Chem. A, 2015,3, 3029-3034 doi:10.1039/C4TA03893B
  8. ↑ D.T. Whipple et al., Prospects of CO2 Utilization via Direct Heterogeneous Electrochemical Reduction J. Phys. Chem. Lett., 2010, 1 (24), pp 3451–3458 doi:10.1021/jz1012627
  9. ↑ R.L. Machundaa et al., Electrocatalytic reduction of CO2 gas at Sn based gas diffusion electrode, Current Applied Physics 11 (2011) 986. doi:10.1016/j.cap.2011.01.003
  10. ↑ Hori, Y. (2008). "Electrochemical CO2 Reduction on Metal Electrodes". Modern Aspects of Electrochemistry. Modern Aspects of Electrochemistry. 42. pp. 89–80. doi:10.1007/978-0-387-49489-0_3. ISBN 978-0-387-49488-3.
  11. ↑ Eric E. Benson, Clifford P. Kubiak,* Aaron J. Sathrum and Jonathan M. Smieja "Electrocatalytic and homogeneous approaches to conversion of CO2 to liquid fuels" Chem. Soc. Rev., 2009, vol. 38, pp. 89–99.doi:10.1039/b804323j
  12. ↑ Halmann and Steinberg, "Greenhouse Gas Carbon Dioxide Mitigation," Lewis Publishers, 1999. ISBN 1-56670-284-4
  13. ↑ Brian A. Rosen, Amin Salehi-Khojin, Michael R. Thorson, W. Zhu, Devin T. Whipple, Paul J. A. Kenis, Richard I Masel * , Ionic Liquid-Mediated Selective Conversion of CO2 to CO at Low Overpotentials, Science Vol. 334 no. 6056 pp. 643-644 (2011) doi:10.1126/science.1209786
  14. ↑ 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
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