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Additional information
“We have recently found that a large current is produced without formation of adsorbed bridge-bonded formate in the oxidation of methanol with no or little water but with 1 M sulfuric acid [Okamoto et al., Electrochim. Acta 136 (2014) 385-395].”
Journal Reference
Electrochimica Acta, Volume 116, 10 January 2014, Pages 263-270.
Hiroshi Okamoto , Yukimasa Numata, Takeshi Gojuki, Yoshiharu Mukouyama.
Division of Science, School of Science and Engineering, Tokyo Denki University, Hatoyama, Saitama 350–0394, Japan.
Abstract
Clarification has been made whether or not adsorbed bridge-bonded formate (HCOOB) is the reactive intermediate in the direct path during oxidation of formic acid, using surface-enhanced infrared absorption spectroscopy (SEIRAS) simultaneously with electrochemical measurement. With a decrease in the sweep rate of cyclic voltammetry, the potential of the maximum current in the positive-going sweep decreases from 0.9 to 0.6 V, while that of the maximum HCOOB band intensity in the positive-going sweep is almost constant at approximately 0.9 V. When the potential is held at 0.7 V after a potential increase or decrease, the current monotonically decreases, while the HCOOB band intensity keeps constant. In the absence of adsorbed CO, the current presents a maximum at approximately 0.5 V, while the HCOOB band intensity does at approximately 0.9 V. All these results clearly show that HCOOB is not the reactive intermediate. The second order kinetics for the decomposition of HCOOB has also been discussed.
