Abstract
This paper reviews the most common reaction pathways for CO2 electroreduction proposed by various workers in recent years. Each pathway involves certain intermediate compounds and certain end products and thus the pathways promoted, within a specific process, can be deduced from which of these have been detected. There are considered to be four principal pathways, each based on one of the following reactions: (1) CO(g) formation via disproportionation, (2) •CO2 − radical formation, (3) COOH(ad) formation and (4) the formation of reduced CO x y−(ad) species giving a range of reduced CO2 end products. This paper places particular emphasis on the formation of HCOOH. The effects of electrocatalyst and process conditions on reaction pathways is also reviewed.
References
M.M. Halmann and M. Steinberg, 'Greenhouse Gas Carbon Dioxide Mitigation Science and Technology' (Lewis Publishers, Boca Raton, FL, 1999).
J. Houghton, 'Global Warming' (CUP, Cambridge, UK, 1997), p. 251.
R.P.S. Chaplin, The Reduction of Carbon Dioxide to Formate in a Solid Polymer Electrolyte Reactor, PhD thesis, (Exeter University, Exeter, UK, 2001).
B.I. Podlovchenko, E.A. Kolyadko and Sh. Lu, Electrokhimiya 30 (1994) 670.
Ch. Furuya, Chem. Abstr. 121 (1994) 21038a and 124 (1996) 17519c. Japanese patents JP 06 93 485 (1994) and JP 07 258 877 (1994).
N. Furuya, T. Yamazaki and M. Shibata, J. Electroanal. Chem. 431 (1997) 39.
M. Jitaru, D.A. Lowy, M. Toma, B.C. Toma and L. Oniciu, J. Appl. Electrochem. 27 (1997) 875.
K. Ikeue, S. Nozaki, M. Ogawa and M. Anpo, Catal. Lett. 80 (2002) 11.
K. Ohta, Y. Ohguchi, S. Kaneco and T. Mizuno, Energy Sources 21 (1999) 467.
K. Hirota, D.A. Tryk, K. Hashimoto, M. Okawa and A. Fujishima, J. Electrochem. Soc. 145 (1998) L82.
R. Hinogami, Y. Nakamura, S. Yae and Y. Nakato, J. Phys. Chem. B 102 (1998) 974.
R. Hinogami, Y. Nakamura, S. Yae and Y. Nakato, Appl. Surf. Sci. 121-122 (1997) 301.
B.P. Sullivan, S.K. Krist and H.E. Guard (Eds), 'Electrochemical and Electrocatalytic Reduction of Carbon Dioxide' (Elsevier, Amsterdam, 1993).
B.I. Podlovchenko, E.A. Kolyadko and Sh. Lu, J. Electroanal. Chem. 373 (1994) 185.
Ch. Caix, S. Chardon-Noblat and A. Deronzier, J. Electroanal. Chem. 434 (1997) 163.
A.W.B. Aylmer-Kelly, A. Bewick, P.R. Cantrill and A.M. Tuxford, Faraday Discussion, Chem. Soc. 56 (1973) 96.
W.M. Ayers, Special Pub. Royal Society of Chemistry (1994) 365.
K.S. Udupa, G.S. Subramanian and H.V.K. Udupa, Electrochim. Acta 16 (1971) 1593.
T. Mizuno, K. Ohta, A. Sasaki, T. Akai, M. Hirano and A. Kawabe, Energy Sources 17 (1995) 503.
B.R. Eggins, C. Ennis, R. McConnell and M. Spence, J. Appl. Electrochem. 27 (1997) 706.
Yu B. Vassiliev, V.S. Bagotzky, N.V. Osetpova, O.A. Khazova and N. Mayorova, J. Electroanal. Chem. 189 (1985) 271.
A. Kudo, Sh. Nakagawa, A. Tsuneto and T. Sakata, J. Electrochem. Soc. 140 (1993) 1541.
O. Koga and Y. Hori, Denki Kagaku 61 (1993) 812.
Y. Hori, A. Murata, R. Takahashi and Sh. Suzuki, J. Am. Chem. Soc. 109 (1987) 5022.
S. Komatsu, M. Tanaka, A. Okumura and A. Kungi, Electrochim. Acta 40 (1995) 745.
K. Hara, A. Kudo and T. Sakata, J. Electroanal. Chem. 391 (1995) 141.
H. Noda, Sh. Ikeda, Y. Oda and K. Ito, Chem. Lett. (1989) 289.
H. De Jesus-Cardona, C. Del Moral and C.R. Cabrera, J. Electroanal. Chem. 513 (2001) 45.
D.P. Summers and K.W. Frese Jr., J. Electrochem. Soc. 135 (1988) 264.
G.Z. Kyriacou and A.K. Anagnostopoulos, J. Appl. Electrochem. 23 (1993) 483.
J. Lee and Y. Tak, Electrochim. Acta 46 (2001) 3015.
R.M. Hernandez, J. Marquez, O.P. Marquez, M. Choy, C. Ovalles, J.J. Garcia and B. Scharifker, J. Electrochem. Soc. 146 (1999) 4131.
K. Ito and S. Ikeda, Bull. Chem. Soc. Japan 60 (1987) 2517.
C. Amatore and J. Saveant, J. Am. Chem. Soc. 103 (1981) 5021.
K. Hirota, D.A. Tryk, T. Yamamoto, K. Hashimoto, M. Okawa and A. Fujishima, J. Phys. Chem. B. 102 (1998) 9834.
G.B. Stevens, T. Reda and B. Raguse, J. Electroanal. Chem. 526 (2002) 125.
Y. Hori, K. Kikuchi and S. Suzuki, Chem. Lett. (1985) 1695.
S. Kaneco, R. Iwao, K. Iiba, S. Itoh, K. Ohta and T. Mizuno, Environ. Eng. Sci. 16 (1999) 131.
Y. Terunuma, A. Saitoh and Y. Momose, J. Electroanal. Chem. 434 (1997) 69.
N. Hoshi and Y. Hori, Electrochim. Acta 45 (2000) 4263.
N. Hoshi, S. Kawatani, M. Kudo and Y. Hori, J. Electroanal. Chem. 467 (1999) 67.
N. Hoshi, M. Kato and Y. Hori, J. Electroanal. Chem. 440 (1997) 283.
N. Hoshi, T. Suzuki and Y. Hori, J. Phys. Chem. B 101 (1997) 8520.
N. Hoshi, M. Noma, T. Suzuki and Y. Hori, J. Electroanal. Chem. 421 (1997) 15.
M.N. Mahmood, D. Masheder and C.J. Harty, J. Appl. Electrochem. 17 (1987) 1159.
Yu.B. Vassiliev, V.S. Bogotzky, N.V. Osetpova, O.A. Khazova and N. Mayorova, J. Electroanal. Chem. 189 (1985) 295.
M. Todoroki, K. Hara, A. Kudo and T. Sakata, J. Electroanal. Chem. 394 (1995) 199.
M. Spichiger-Ulmann and J. Augustynski, J. Chem. Soc. Faraday Trans. 181 (1985) 713.
F. Ko00leli, T. Ro00pke and C. Hamann, Synthe. Met. In press (2003).
F. Ko00leli, T. Ro00pke and C. Hamann, Electrochim. Acta 48 (2003) 1595.
R. Aydin and F. Ko00leli, J. Electroanal. Chem. 535 (2003) 107.
H.A. Schwarz and R.W. Dodson, J. Phys. Chem. 93 (1989) 409.
S.C. Yeo and A. Eisenberg, J. Appl. Polym. Sci. 21 (1977) 875.
V.S. Bagotsky and Yu.B. Vassiliev, J. Electroanal. Chem. 271 (1985) 189.
H. Noda, Sh. Ikeda, Y. Oda, K. Imai, M. Maeda and K. Ito, Bull. Chem. Soc. Japan 63 (1990) 2459.
K. Ito and T. Murata, Bull. Nagoya Ind. Technol. 271 (1975) 369.
H.E. Ulery, J. Electrochem. Soc. 112 (1969) 1201.
M. Azuma, K. Hashimoto, M. Watanabe and T. Sakata, J. Electroanal. Chem. 260 (1989) 441.
K. Kara, A. Tsuneto, A. Kudo and T. Sakata, J. Electroanal. Chem. 434 (1997) 239.
H. Yano, F. Shirai, M. Nakayama and K.J. Ogura, J. Electroanal. Chem. 519 (2002) 93.
S. Kaneco, K. liba, K. Ohta and T. Mizuno, Energy Sources 22 (2000) 127.
K. Ohta, K. Suda, S. Kaneco and T. Mizuno, J. Electrochem. Soc. 147 (2000) 233.
S. Komatsu, T. Yanagihara, Y. Hiraga, M. Tanaka and A. Kunugi, Denki Kagaku 63 (1995) 217.
S. Ikeda, A. Hattori, M. Maeda, K. Ito and H. Noda, Electrochemistry 68 (2000) 257.
B.R. Eggins, E.M. Brown, C.A. McNeiu and Y. Grimshaw, Tetrahedron Lett. 29 (1988) 945.
S. Kaneco, R. Iwao, K. Iiba, K. Ohta and T. Mizuno, Energy 23 (1998) 1107.
T. Yamamoto, D.A. Tryk, A. Fujishima and H. Ohta, Electrochim. Acta 47 (2002) 3327.
S. Taguchi and A. Aramata, Electrochim. Acta 39 (1994) 2533.
Y. Tomita, S. Teruya, O. Koga and Y. Hori, J. Electrochem. Soc. 147 (2000) 4164.
K. Hara, A. Tsuneto, A. Kudo and T. Sakata, Shokubai 35 (1993) 513; Chem. Abstr. 120 (1994) 120149u.
K. Ito, Sh. Ikeda and M. Okabe, Denki Kagaku 48 (1980) 247.
K. Ito, Sh. Ikeda, T. lida and H. Niwa, Denki Kagaku 49 (1981) 106.
Y. Hori, O. Koga, A. Aramata and M. Enyo, Bull. Chem. Soc. Japan 65 (1992) 3008.
H.J. Freund and R.P. Messmer, Surf. Sci. 172 (1986) 1.
T. Mizuno, M. Kawamoto, S. Kaneco and K. Ohta, Electrochim. Acta 43 (1998) 899.
T.V. Magdesieva, T. Yamamoto, D.A. Tryk and A.J. Fujishima, J. Electrochem. Soc. 149 (2002) D89.
T. Yamamoto, D.A. Tryk, K. Hashimoto, A. Fujishima and M. Okawa, J. Electrochem. Soc. 147 (2000) 3393.
S. Chardon-Noblat, P. Da Costa, A. Deronzier, S. Maniguet and R. Ziessel, J. Electroanal. Chem. 529 (2002) 135.
F. Ko00leli, T. Atilan, N. Palamut, A.M. Gizir, R. Aydin and C.H. Hamann, J. Appl. Electrochem. 33 (2003) 447.
K. Ohta, M. Kawamoto, T. Mizuno and D.A. Lowy, J. Appl. Electrochem. 28 (1998) 717.
S. Kaneco, K. Iiba, N. Hiei, K. Ohta, T. Mizuno and T. Suzuki, Electrochim. Acta 44 (1999) 4701.
S. Kaneco, K. Iiba, K. Ohta and T. Mizuno, Energy Sources 21 (1999) 643.
J. Li and G. Prentice, J. Electrochem. Soc. 144 (1997) 4284.
R. Schrebler, P. Cury, F. Herrera, H. Gomez and R. Cordova, J. Electroanal. Chem. 516 (2001) 23.
T. Ohmori, A. Nakayama, H. Mametsuka and E. Suzuki, J. Electroanal. Chem. 514 (2001) 51.
S. Kaneco, K. Iiba, K. Ohta, T. Mizuno and A. Saji, Electrochim. Acta 44 (1998) 573.
Engineering and Physical Sciences Research Council (UK); Final Report (2002), Award number GR/L57777.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Chaplin, R., Wragg, A. Effects of process conditions and electrode material on reaction pathways for carbon dioxide electroreduction with particular reference to formate formation. Journal of Applied Electrochemistry 33, 1107–1123 (2003). https://doi.org/10.1023/B:JACH.0000004018.57792.b8
Issue Date:
DOI: https://doi.org/10.1023/B:JACH.0000004018.57792.b8