Particle-size effect of nanoscale platinum catalysts in oxygen reduction reaction: an electrochemical and 195Pt EC-NMR study.
Oxygen reduction reaction (ORR) measurements and (195)Pt electrochemical nuclear magnetic resonance (EC-NMR) spectroscopy were combined to study a series of carbon-supported platinum nanoparticle electrocatalysts (Pt/CB) with average diameters in the range of roughly 1-5 nm. ORR rate constants and H(2)O(2) yields evaluated from hydrodynamic voltammograms did not show any particle size dependency. The apparent activation energy of 37 kJ mol(-1), obtained for the ORR rate constant, was identical to that obtained for bulk platinum electrodes. Pt/CB catalysts on Nafion produced only 0.7-1% of H(2)O(2), confirming that the direct four-electron reduction of O(2) to H(2)O is the predominant reaction. NMR spectral features showed characteristic size dependence, and the line shapes were reproduced by using the layer-deconvolution model. Namely, the variations in the NMR spectra with particle size can be explained as due to the combined effect of the layer-by-layer variation of the s-type and d-type local density of states. However, the surface peak position of (195)Pt NMR spectra and the spin-lattice relaxation time of surface platinum atoms showed practically no change with the particle size variation. We conclude that there is a negligible difference in the surface electronic properties of these Pt/CB catalysts due to size variations and therefore, the ORR activities are not affected by the differences in the particle size.
Yano
Hiroshi
H
Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi, Clean Energy Research Center, Takeda 4, Kofu 400-8511, Japan.
Inukai
Junji
J
Uchida
Hiroyuki
H
Watanabe
Masahiro
M
Babu
Panakkattu K
PK
Kobayashi
Takeshi
T
Chung
Jong Ho
JH
Oldfield
Eric
E
Wieckowski
Andrzej
A
D002384:Catalysis; D004563:Electrochemistry; D007554:Isotopes; D009682:Magnetic Resonance Spectroscopy; D046529:Microscopy, Electron, Transmission; D036103:Nanotechnology; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010316:Particle Size; D010984:Platinum / Q000737:chemistry*; D013696:Temperature
D007554:Isotopes; D010984:Platinum; D010100:Oxygen