Mechanism of CO{sub 2} and H{sup +} reduction by Ni(cyclam){sup +} in aqueous solution. A pulse and continuous radiolysis study

Journal Article · Mon Apr 05 00:00:00 EDT 1999 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic980902p· OSTI ID:343691

Kelly, C A; Blinn, E L ^[1]; Camaioni, N; D`Angelantonio, M; Mulazzani, Q G ^[2]

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1. Bowling Green State Univ., OH (United States). Dept. of Chemistry
2. Ist. di Fotochimica e Radiazioni d`Alta Energia del CNR, Bologna (Italy)

The reduction of CO{sub 2} and H{sup +} by Ni(cyclam){sup +} in aqueous solution was found to proceed by the reduction of Ni(cyclam)(CO{sub 2}){sup +} or Ni(cyclam)(H){sup 2}{sup +} by Ni(cyclam){sup +}. At ambient temperature the rate constants for the bimolecular reactions are 1.6 {times} 10{sup 8} and 7.2 {times} 10{sup 7} M{sup {minus}1} s{sup {minus}1}, respectively. Continuous {gamma}-radiolysis studies have demonstrated nearly quantitative formation of CO from two Ni(cyclam){sup +} at pH 5.2 under 1 atm of CO{sub 2} and in the presence of formate. Under the same conditions, but at low CO{sub 2} concentration, the reduction of protons was found to compete with CO{sub 2} reduction.

• OSTI ID: 343691
• Journal Information: Inorganic Chemistry, Vol. 38, Issue 7; Other Information: PBD: 5 Apr 1999
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
CARBON DIOXIDE
REDUCTION
NICKEL COMPOUNDS
HYDROGEN
AQUEOUS SOLUTIONS
CHEMICAL REACTION KINETICS
CARBON MONOXIDE