The “Particle Proximity Effect” in Three Dimensions: a Case Study on Vulcan XC 72R
Abstract
The “particle proximity effect” is a hypothesis claiming that Pt nanoparticles have higher ORR activity when they get closer to one another. In order to put this hypothesis under scrutiny, the “tool-box” approach was investigated in each process step by electron microscopy, ICP, and surface science methods. It is shown that particle size stability is brought about by a NaCl shell which can effectively be removed by washing with water. I.e., the “tool-box” synthesis with an additional washing step produces clean, closely spaced, and well-separated particles with interparticle distances necessary for the effect to occur. Despite this powerful synthesis route, a conclusive proof of the “proximity effect” could not be obtained. This is due to difficulties with catalyst film formation at higher platinum loadings on Vulcan XC 72R, suggesting that film deposition and drying methods have to be optimized for each catalyst loading separately and that a holistic approach is not very realistic.
Sometimes less is more: Oxygen reduction catalysts on Vulcan XC 72R with high Pt loading (> 10 %) show unfavorable film qualities on glassy carbon tips and cannot be evaluated for their kinetic current and specitic activities (extensive coffee ring formation) while for lower loadings reliable values can be obtained.
Keywords
Oxygen reduction reaction (ORR) “Particle proximity effect” Colloidal “tool-box” approach Thin-film rotating disk electrode (TF-RDE) Electron microscopy, X-ray photoemission spectroscopy (XPS)Notes
Acknowledgments
TEM micrographs recorded by Yusuke Akimoto, ICP-OES analysis by Satoru Kosaka, and HR-SEM images taken by Juntaro Seki are gratefully acknowledged.
Supplementary material
References
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