γ-Fe2O3-supported Pt-Cu nanoparticles synthesized by radiolytic process for catalytic CO preferential oxidation

Pt-Cu bimetallic nanoparticles immobilized on gamma-Fe2O3 support were synthesized by a unique radiolytic process and their physical properties and catalytic activity for CO preferential oxidation were investigated for various Pt/Cu atomic ratios. The chemical composition of the catalysts measured by inductively coupled plasma revealed most of the platinum and copper aqueous precursors were deposited on to the gamma-Fe2O3 support after irradiation with electron beam. Crystallographic analysis of the catalysts by X-ray diffraction showed Pt-Cu alloy is formed for wide range of Pt/Cu ratio. From the lattice parameter of this Pt-Cu alloy, it was found that Cu can be incorporated into Pt lattice up to 30 at% with the present irradiation condition. The rest of Cu for high-Cu (low-Pt) samples was identified as divalent oxide with poor crystallinity by XANES spectrum. Detailed STEM-EDX analyses further confirmed that Pt-Cu alloy exists as nanoparticles with a few nanometers in diameter and CuO with low crystallinity distributes on entire surface of the gamma-Fe2O3 support. The PROX activity showed different trends between high-Pt and high-Cu samples. The CO conversion decreased as the Pt loading was decreased to 50 at%, and it monotonically decreased with increasing temperature. However, as the Pt loading was further decreased, the activity increased with temperature by contraries, and reached the maximum conversion at 100 degrees C. Regardless of the low Pt loading, the sample with 10 at% Pt and 90 at% Cu exhibited the highest activity at 100 degrees C, which is preferable for low temperature fuel cell applications. This enhanced activity was attributed to oxygen supply via the copper of low crystallinity from the O-2-poor atmosphere to Pt-Cu alloy particles that chemisorbs CO molecules. (C) 2011 Elsevier B.V. All rights reserved.