Particle-size effect of nanoscale platinum catalysts in oxygen reduction reaction : an electrochemical and 195Pt EC-NMR study

• Published in: Physical chemistry chemical physics : PCCP 2006-11, Vol.8 (42), p.4932-4939
• Main Authors: YANO, Hiroshi, INUKAI, Junji, UCHIDA, Hiroyuki, WATANABE, Masahiro, BABU, Panakkattu K, KOBAYASHI, Takeshi, JONG HO CHUNG, OLDFIELD, Eric, WIECKOWSKI, Andrzej
• Format: Article
• Language: English
• Subjects: Catalysis; Chemistry; Colloidal state and disperse state; Electrochemistry; Exact sciences and technology; General and physical chemistry; Isotopes; Kinetics and mechanism of reactions; Magnetic Resonance Spectroscopy; Microscopy, Electron, Transmission; Nanotechnology; Oxidation-Reduction; Oxygen - chemistry; Particle Size; Physical and chemical studies. Granulometry. Electrokinetic phenomena; Platinum - chemistry; Temperature; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/b610573d

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.