Cobalt porphyrin catalyzed reduction of CO2. Radiation chemical, photochemical, and electrochemical studies

D. Behar, T. Dhanasekaran, P. Neta, C. M. Hosten, D. Ejeh, P. Hambright, Etsuko Fujita

Research output: Contribution to journalArticle

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Abstract

Several cobalt porphyrins (CoP) have been reduced by radiation chemical, photochemical, and electrochemical methods, in aqueous and organic solvents. In aqueous solutions, the CoIP state is stable at high pH but is shorter lived in neutral and acidic solutions. Stable CoIP is also observed in organic solvents and is unreactive toward CO2. One-electron reduction of CoIP leads to formation of a species that is observed as a transient intermediate by pulse radiolysis in aqueous solutions and as a stable product following reduction by Na in tetrahydrofuran solutions. The spectrum of this species is not the characteristic spectrum of a metalloporphyrin π-radical anion and is ascribed to Co0P. This species binds and reduces CO2. Catalytic formation of CO and HCO2 - is confirmed by photochemical experiments in acetonitrile solutions containing triethylamine as a reductive quencher. Catalytic reduction of CO2 is also confirmed by cyclic voltammetry in acetonitrile and butyronitrile solutions and is shown to occur at the potential at which CoIP is reduced to Co0P. As compared with CoTPP, fluorinated derivatives are reduced, and catalyze CO2 reduction, at less negative potentials.

Original languageEnglish
Pages (from-to)2870-2877
Number of pages8
JournalJournal of Physical Chemistry A
Volume102
Issue number17
Publication statusPublished - Apr 23 1998

Fingerprint

Porphyrins
Cobalt
porphyrins
cobalt
Radiation
radiation
acetonitrile
aqueous solutions
Organic solvents
tetrahydrofuran
radiolysis
Metalloporphyrins
Radiolysis
Carbon Monoxide
anions
Cyclic voltammetry
Anions
products
pulses
Derivatives

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Behar, D., Dhanasekaran, T., Neta, P., Hosten, C. M., Ejeh, D., Hambright, P., & Fujita, E. (1998). Cobalt porphyrin catalyzed reduction of CO2. Radiation chemical, photochemical, and electrochemical studies. Journal of Physical Chemistry A, 102(17), 2870-2877.

Cobalt porphyrin catalyzed reduction of CO2. Radiation chemical, photochemical, and electrochemical studies. / Behar, D.; Dhanasekaran, T.; Neta, P.; Hosten, C. M.; Ejeh, D.; Hambright, P.; Fujita, Etsuko.

In: Journal of Physical Chemistry A, Vol. 102, No. 17, 23.04.1998, p. 2870-2877.

Research output: Contribution to journalArticle

Behar, D, Dhanasekaran, T, Neta, P, Hosten, CM, Ejeh, D, Hambright, P & Fujita, E 1998, 'Cobalt porphyrin catalyzed reduction of CO2. Radiation chemical, photochemical, and electrochemical studies', Journal of Physical Chemistry A, vol. 102, no. 17, pp. 2870-2877.
Behar D, Dhanasekaran T, Neta P, Hosten CM, Ejeh D, Hambright P et al. Cobalt porphyrin catalyzed reduction of CO2. Radiation chemical, photochemical, and electrochemical studies. Journal of Physical Chemistry A. 1998 Apr 23;102(17):2870-2877.
Behar, D. ; Dhanasekaran, T. ; Neta, P. ; Hosten, C. M. ; Ejeh, D. ; Hambright, P. ; Fujita, Etsuko. / Cobalt porphyrin catalyzed reduction of CO2. Radiation chemical, photochemical, and electrochemical studies. In: Journal of Physical Chemistry A. 1998 ; Vol. 102, No. 17. pp. 2870-2877.
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