Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 135, Issue 27, Pages 9991-9994Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja403578s
Keywords
-
Categories
Funding
- Japanese Society for the Promotion of Science (JSPS) KAKENHI Grants [24550143, 24750117]
- MEXT Project of Integrated Research on Chemical Synthesis
- Long-Term Fellowship of JSPS [L-11527]
- Northern Advancement Center for Science & Technology of Hokkaido, Japan
- Asian Graduate School, Hokkaido University
- Grants-in-Aid for Scientific Research [24550143, 24750117] Funding Source: KAKEN
Ask authors/readers for more resources
Electro-oxidation of formic acid on Pt in acid is one of the most fundamental model reactions in electrocatalysis. However, its reaction mechanism is still a matter of strong debate. Two different mechanisms, bridge-bonded adsorbed formate mechanism and direct HCOOH oxidation mechanism, have been proposed by assuming a priori that formic acid is the major reactant. Through systematic examination of the reaction over a wide pH range (0-12) by cyclic voltammetry and surface-enhanced infrared spectroscopy, we show that the formate ion is the major reactant over the whole pH range examined, even in strong acid. The performance of the reaction is maximal at a pH close to the pK(a) of formic acid. The experimental results are reasonably explained by a new mechanism in which formate ion is directly oxidized via a weakly adsorbed formate precursor. The reaction serves as a generic example illustrating the importance of pH variation in catalytic proton-coupled electron-transfer reactions.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available