High electrocatalytic activity of RRSS-[Ni{sup II}HTIM](ClO{sub 4}){sub 2} and [Ni{sup II}DMC](ClO{sub 4}){sub 2} for carbon dioxide reduction (HTIM = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradecane, DMC = C-meso-5,12-dimethyl-1,4,8,11-tetraazacyclotetradecane)
- Brookhaven National Lab., Upton, NY (United States)
- Technische Hochschule Darmstadt (Germany); and others
Ni(cyclam){sup 2+} (cyclam = 1,4,8,11-tetraazacyclotetradecane) is a very effective and selective catalyst for the electrochemical reduction of CO{sub 2} to CO relative to the reduction of water to H{sub 2} in aqueous solution. However, photochemical reduction of CO{sub 2} using a photosensitizer, a sacrificial electron donor, and Ni(cyclam){sup 2+} as the catalyst has been only moderately successful. In order to understand the factors responsible for the superior electrocatalytic activity of Ni(cyclam){sup 2+} extensive studies have been carried out. While Ni(cyclam){sup +} adsorbed on the surface of a mercury electrode in an active species, other aspects of the catalytic mechanism have remained unclear. Here the authors report the catalytic activity in aqueous solution and the CO{sub 2} binding in acetonitrile of RRSS- and RSSR-NiHTIM(ClO{sub 4}){sub 2} (HTIM = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and NiDMC(ClO{sub 4}{sub 4}){sub 2} (DMC = C-meso-5,12-dimethyl-1,4,8,11-tetraazacyclotetradecane) compared to those of Ni(cyclam){sup 2+}.
- Research Organization:
- Brookhaven National Laboratory (BNL), Upton, NY
- DOE Contract Number:
- AC02-76CH00016
- OSTI ID:
- 421003
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 21 Vol. 33; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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