Displacement Reaction in Pulse Current Deposition of PtRu for Methanol Electro-Oxidation

Galvanostatic depositions in rectangular pulses and nitrosol precursors were employed to prepare PtRu nanoparticles on carbon clothes in various sizes and compositions. Variables including current on-time (T-on), current off-time (T-off), and current density were explored to identify the optimized catalytic performances for methanol electro-oxidation. Electrochemical characterizations including cyclic voltammetry and hydrogen desorption were carried out. Images from a transmission electron microscope on the PtRu nanoparticles revealed a moderate size distribution. Signals from X-ray patterns indicated a slight shift of diffraction peaks, suggesting that the Ru was alloyed successfully in the Pt lattice. In addition, the amount of alloyed Ru was found to decrease with reduced duty cycles. Composition determinations from inductively coupled plasma mass spectrometry and analysis on the oxidation states from X-ray photoelectron spectroscopy suggested a displacement reaction in which the Ru was alternately deposited and dissolved during T-on and T-off, while the Pt was deposited continuously. As a result, we observed substantial enrichment of Pt in the PtRu nanoparticles when the duty cycle was shortened.