Effects of p-substituents on electrochemical CO oxidation by Rh porphyrin-based catalysts.
Electrochemical CO oxidation by several carbon-supported rhodium tetraphenylporphyrins with systematically varied meso-substituents was investigated. A quantitative analysis revealed that the p-substituents on the meso-phenyl groups significantly affected CO oxidation activity. The electrocatalytic reaction was characterized in detail based on the spectroscopic and X-ray structural results as well as electrochemical analyses. The difference in the activity among Rh porphyrins is discussed in terms of the properties of p-substituents along with a proposed reaction mechanism. Rhodium tetrakis(4-carboxyphenyl)porphyrin (Rh(TCPP)), which exhibited the highest activity among the porphyrins tested, oxidized CO at a high rate at much lower potentials (<0.1 V vs. a reversible hydrogen electrode, at 60 degrees C) than the present PtRu catalysts. This means that CO is electrochemically oxidized by this catalyst when a slight overpotential is applied during the operation of a proton exchange membrane fuel cell. This catalyst exhibited little H(2) oxidation activity, in contrast to Pt-based catalysts.
Yamazaki
Shin-ichi
S
Research Institute for Ubiquitous Energy Device, National Institute of Advanced Industrial Science and Technology, 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577, Japan. s-yamazaki@aist.go.jp
Yamada
Yusuke
Y
Takeda
Sahori
S
Goto
Midori
M
Ioroi
Tsutomu
T
Siroma
Zyun
Z
Yasuda
Kazuaki
K