Electrocatalytic reduction of carbon dioxide

Electrocatalytic reduction of carbon dioxide to Q-C3 hydrocarbons with less than 0.2% electrochemical yield was reported154 at pH 7 in the presence of pyrocatechol, TiCl3, and Na2Mo04 at -1.55 V versus SCE. 

Fisher and Eisenberg (107) have reported on the electrocatalytic reduction of carbon dioxide using macrocycle complexes of nickel and cobalt (e.g., complex 27). An indirect electrochemical reduction of C02 was ac-... 

Regarding suitable cathodes for the electrocatalytic reduction of carbon dioxide to methanol, indium, and tin have good prospects because each has a high overpotential for hydrogen evolution, the chief competitor in aqueous solution for carbon dioxide reduction to methanol ... 

However, Hori (1986) found the electrocatalytic reduction of carbon dioxide to methane on a molybdenum cathode to be electrocatalytic [11]. One hundred percent reduction of carbon dioxide to methanol at 0°C was reported. What remains open to research is the use of nonaqueous solvents, for example, acetonitrile, because there would be then no competition from hydrogen evolution. Carbon dioxide does undergo electrochemical reduction in acetonitrite to glycolic acid. Here is a research topic, which could have world consequences and cost very little (about 105 per year per researcher, even a dozen would make a great difference in five years). 

A number of transition-metal complexes, both in solution and on electrode surfaces, have been shown to be effective in the electrocatalytic reduction of carbon dioxide. All of those complexes significantly decrease the overpotential for reduction of CO2 by up to IV (as compared to a 1-el reduction to the C02 radical), and yield various multielectron reduction products. Known electrocatalysts yield primarily carbon monoxide and formate anion as the major products of the CO2 reduction. Sullivan et al. did detailed mechanistic work on a sales of bipyridine complexes of transition metals, and made several suggestions concerning the design of new electrocatalysts that would be capable of reducing CO2 past the CO and formate step. Their major recommendation is to use as electrocatalysts "electron reservoir" complexes, i.e. compounds capable of storing multiple electrons. 

K. R. Electrochemical and IR Spectroelectrochemical Studies of the Electrocatalytic Reduction of Carbon Dioxide by [Ir2(dimen)4] (dimen = 1,8-Diisocyanomenthane),/norg. Chem. 1996,35,... 

The electrocatalytic reduction of carbon dioxide has recently been reviewed [20]. Work in this area has concentrated on transition meatal complexes such as metal polypyridyl complexes [21], metal macrocycle complexes [22,23] and the use of different metals and alloys [24],... 

In the group IV, macrocyclic complexes containing transition metals have been tested for the electrocatalytic reduction of carbon dioxide. [Ni(cyclam)] ... 

Ogura, K. and H. Uchida (1987). Electrocatalytic reduction of carbon dioxide to methanol. Part 5. Relationship between the ability of metal complexes to engage in homogeneous catalysis and their coordination chemistry. J. Chem. Soc. Dalton Trans. 6, 1377-1380. 

Erese, Jr., K.W. (1993). in B.P. Sullivan, K. Krist, H.E. Guard, (eds). Electrochemical and Electrocatalytic Reduction of Carbon Dioxide. Elsevier, Amsterdam, Chapter 6, and references therein. 

Riquelme, A., M. Isaacs, M. Lucero, E. TroUund, and M. J. Aguirre (2003). Electrocatalytic reduction of carbon dioxide at polymeric cobalt tetra (3-amino (phenyl) porphyrin glassy carbon-moditied electrodes. J. Chil. Chem. Soc. 48(2), 89-92. 

Savinova, E.R., S.A. Yashmk, E.N. Savinov, and VN. Parmon (1992). Gas-phase electrocatalytic reduction of carbon dioxide to carbon monoxide on carbon gas-diffusion electrode promoted by cobalt phthalocyaninre. React. Kinet. Catal. Lett. 46(2), 249-254. 

Fisher BJ, Eisenberg R (1980) Electrocatalytic reduction of carbon dioxide by using macrocycles of nickel and cobalt. J Am Chem Soc. doi 10.1021/ja00544a035... 

Hawecker J, Lehn J-M, Ziessel R (1984) Electrocatalytic reduction of carbon dioxide mediated by Re(bipy)(CO)3Cl (bipy=2,2 -bipyridine). Chem Commun 6 328-330. doi 10.1039/c39840000328... 

Zeng Q, Tory J, Hartl F (2014) Electrocatalytic reduction of carbon dioxide with a manganese (I) tricarbonyl complex containing a nonaromatic a-diimine ligand. Organometallics 33 (18) 5002-5008. doi 10.1021/om500389y... 

C. M. Bolinger, N. Storey, B. P. Sullivan and T. J. Meyer (1988) Electrocatalytic reduction of carbon dioxide by 2,2 -bipyridine complexes of rhodium and iridium , Inow. Chem. 27, 4582-4587. 

Sammels AE, Cook RL (1993) Electrocatalysis and Novel Electrodes for High Rate CO2 reduction under Ambient Conditions. In Sullivan BP, Krist K, Guard HE (eds) Electrochemical and electrocatalytic reduction of carbon dioxide. Elsevier, Amsterdam, p 247... 

Beley M, Collin JP, Rupptat R, Sauvage JP (1986) Electrocatalytic reduction of carbon dioxide by nickel cyclam2-t in water study of the factors affecting the efficiency and the selectivity of the process. J Am Chem Soc 108(24) 7461-7467... 

Metal porphyrins act as catalysts for chain transmission in radical polymerisation [55] and for electrochemical oxidation of sulphur dioxide [64], as well as for oxidation of a wide range of organic substrates [65]. Cobalt and nickel complexes with LI5 are effective in the electrocatalytic reduction of carbon dioxide [66]. Porphyrin complexes of cobalt and tetraazamacrocyclic complexes of nickel catalyse reduction of the proton [67-71]. 

Bruce MRM, Megehee E, Sullivan BP, Thorp H, O Toole TR, Downard A, Meyer TJ (1988) Electrocatalytic reduction of carbon dioxide by associative activation. Organometallics 7 238-240... 

Haines RJ, Wittrig RE, Kubiak CP (1994) Electrocatalytic reduction of carbon dioxide by the binuclear copper complex [Cu2(6-(diphenylphosphino-2,2 -bipyridyl)2(MeCN)2][PF6]2. Inorg Chem 33 4723 728... 

Yan Y, Gu J, Bocarsly AB (2014) Hydrogen bonded pyridine dimer a possible intermediate in the electrocatalytic reduction of carbon dioxide to methanol. Aerosol Air Qual Res 14 515-521... 

Bradley MG, Tysak T, Graves DJ, Viachiopoulos NA (1983) Electrocatalytic reduction of carbon dioxide at illuminated p-type silicon semiconducting electrodes. J Chem Soc Chem Commun 7 349-350... 

Aurian-Blajeni B, Taniguchi I, Bockris JOM (1983) Photoelectrochemical reduction of carbon dioxide using polyaniline-coated silicon. J Electroanal Chem Interf Electrochem 149 291-293 Ogura K, Yoshida I (1987) Electrocatalytic reduction of carbon dioxide to methanol. VI. Use of a solar cell and comparison with that of carbon monoxide. Electrochim Acta 32 1191-1195... 

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