Volume 198, 2017

Temperature dependence of photocatalytic CO2 reduction by trans(Cl)–Ru(bpy)(CO)2Cl2: activation energy difference between CO and formate production

Abstract

The temperature dependence of photocatalytic CO2 reduction by trans(Cl)–Ru(bpy)(CO)2Cl2 (bpy: 2,2′-bipyridine) has been researched in ethanol (EtOH)/N,N-dimethylacetamide (DMA) solutions containing [Ru(bpy)3]2+ (a photosensitizer) and 1-benzyl-1,4-dihydronicotinamide (BNAH, an electron donor). The catalytic system efficiently reduces CO2 to carbon monoxide (CO) with formate (HCOO) as a minor product. The mechanism of the catalysis consists of the electron-relay cycle and the catalytic cycle: in the former cycle the photochemically generated reduced species of the photosensitizer injects an electron to the catalyst, and in the latter the catalyst reduces CO2. At a low concentration of the catalyst (5.0 μM), where the catalytic cycle is rate-determining, the temperature dependence of CO/HCOO is also dependent on the EtOH contents: the selectivity of CO/HCOO decreases in 20% and 40%-EtOH/DMA with increasing temperature, while it increases in 60%-EtOH/DMA. The temperature dependence of the CO/HCOO selectivity indicates that the difference in activation energy (ΔΔG) between CO and HCOO production is estimated as ca. 3.06 kJ mol−1 in 40%-EtOH/DMA at 298 K.

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
26 nov 2016
Accepted
12 dec 2016
First published
15 mar 2017

Faraday Discuss., 2017,198, 263-277

Temperature dependence of photocatalytic CO2 reduction by trans(Cl)–Ru(bpy)(CO)2Cl2: activation energy difference between CO and formate production

H. Ishida and A. Sakaba, Faraday Discuss., 2017, 198, 263 DOI: 10.1039/C6FD00242K

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