14337-01-0Relevant articles and documents
Cobalt porphyrin catalyzed reduction of CO2. Radiation chemical, photochemical, and electrochemical studies
Behar,Dhanasekaran,Neta,Hosten,Ejeh,Hambright,Fujita, Etsuko
, p. 2870 - 2877 (2007/10/03)
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.
Formation of Ozone in the Reaction of OH with O3- and the Decay of the Ozonide Ion Radical at pH 10-13
Sehested, K.,Holcman, J.,Bjergbakke, E.,Hart, Edwin J.
, p. 269 - 273 (2007/10/02)
Ozone forms in aqueous alkaline solutions, pH 10-13, by a reaction between OH and O3- radicals.The reaction, OH + O3- -> O3 + OH-, is about 30percent of the total reaction.A second reaction is OH + O3- + OH- -> 2O2- + H2O.The ozone formation is demonstrated by a high-pressure pulse radiolysis technique using a 4-μs, 40-krd pulse.The ozone rapidly disappears in a reaction with the simultaneously formed O2- re-forming O3-.The product resulting from the O3- decay is the peroxy radical, O2-.The overall rate constant, k(OH + O3-), is (8.5 +/- 1.0) x 1E9 dm3 mol-1 s-1.Computer simulations of the high-pressure system as well as a of the atmospheric-pressure oxygenated system with high and low pulse intensity support a mechanism for the O3- decay based on the above-mentioned reactions.The protonation rate constant of the O3- radical ion, k(O3- + H+), is (9.0 +/- 1.0) x 1E10 dm3 s-1.
