Mechanistic and kinetic studies of cobalt macrocycles in a photochemical CO2 reduction system

Evidence of Co-CO2 adducts as intermediates

Tomoyuki Ogata, Shozo Yanagida, Etsuko Fujita, Etsuko Fujita

Research output: Contribution to journalArticle

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Abstract

Cobalt macrocycles mediate electron transfer in the photoreduction of CO2 with p-terphenyl as a photosensitizer and a tertiary amine as a sacrificial electron donor in a 5:1 acetonitrile/methanol mixture. The mechanism and kinetics of this system have been studied by continuous and flash photolysis techniques. Transient spectra provide evidence for the sequential formation of the p-terphenyl radical anion, the CoIL+ complex, the [CoIL-CO2]+ complex, and the [S-CoIIIL-(CO2 2-)]+ complex (L = HMD = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene; S = solvent) in the catalytic system. The electron-transfer rate constant for the reaction of p-terphenyl radical anion with CoIIL2+ is 1.1 × 1010 M-1 s-1 and probably diffusion controlled because of the large driving force (∼+1.1 V). Flash photolysis studies yield a rate constant 1.7 × 108 M-1 s-1 and an equilibrium constant 1.1 × 104 M-1 for the binding of CO2 to CoIL+ in the catalytic system. These are consistent with those previously obtained by conventional methods in acetonitrile. Studies of catalytic systems with varying cobalt macrocycles highlight some of the factors controlling the kinetics of the photoreduction of CO2. Steric hindrance and reduction potentials are important factors in the catalytic activity for photochemical CO2 reduction.

Original languageEnglish
Pages (from-to)6708-6716
Number of pages9
JournalJournal of the American Chemical Society
Volume117
Issue number25
Publication statusPublished - Jun 28 1995

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Cobalt
Photolysis
Electrons
Acetonitrile
Kinetics
Anions
Rate constants
Negative ions
Helmet mounted displays
Photosensitizing Agents
Photosensitizers
Equilibrium constants
Amines
Methanol
Catalyst activity
acetonitrile

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Mechanistic and kinetic studies of cobalt macrocycles in a photochemical CO2 reduction system : Evidence of Co-CO2 adducts as intermediates. / Ogata, Tomoyuki; Yanagida, Shozo; Fujita, Etsuko; Fujita, Etsuko.

In: Journal of the American Chemical Society, Vol. 117, No. 25, 28.06.1995, p. 6708-6716.

Research output: Contribution to journalArticle

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abstract = "Cobalt macrocycles mediate electron transfer in the photoreduction of CO2 with p-terphenyl as a photosensitizer and a tertiary amine as a sacrificial electron donor in a 5:1 acetonitrile/methanol mixture. The mechanism and kinetics of this system have been studied by continuous and flash photolysis techniques. Transient spectra provide evidence for the sequential formation of the p-terphenyl radical anion, the CoIL+ complex, the [CoIL-CO2]+ complex, and the [S-CoIIIL-(CO2 2-)]+ complex (L = HMD = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene; S = solvent) in the catalytic system. The electron-transfer rate constant for the reaction of p-terphenyl radical anion with CoIIL2+ is 1.1 × 1010 M-1 s-1 and probably diffusion controlled because of the large driving force (∼+1.1 V). Flash photolysis studies yield a rate constant 1.7 × 108 M-1 s-1 and an equilibrium constant 1.1 × 104 M-1 for the binding of CO2 to CoIL+ in the catalytic system. These are consistent with those previously obtained by conventional methods in acetonitrile. Studies of catalytic systems with varying cobalt macrocycles highlight some of the factors controlling the kinetics of the photoreduction of CO2. Steric hindrance and reduction potentials are important factors in the catalytic activity for photochemical CO2 reduction.",
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