PtCu nanoparticles were synthesized with different pH and support conditions using radiochemical process. The nanoparticle structures were characterized by transmission electron microscopy, inductively coupled plasma atomic emission spectrometry, X-ray absorption spectroscopy, and X-ray diffraction techniques. The nanoparticle structure was relevant to the pH of the precursor solutions. The lattice parameter of PtCu alloy increased in high pH samples, which indicates the critical effect of metal ion adsorption in precursor solution on nanoparticle structure.

Electrode catalysts composed of carbon supported PtRu nanoparticles (PtRu/C) synthesized by radiochemical process were annealed to control the PtRu substructure to enhance catalytic activity. The substructure of the PtRu nanoparticles synthesized by using high-energy electron beam under acidic condition was Pt-rich core/Ru-rich shell type, reflecting the redox potentials of each precursor ions. The material characterization techniques revealed that the reductive annealing led to the mixing of PtRu both in the core and on the surface. The sample with annealing temperature of 300°C for 5 hour showed the highest methanol oxidation current, 2.3 times higher than that obtained with before annealing.

A nanoparticle catalyst of PtRuAu/C was synthesized by including an Au precursor in the radiolytic process for preparing a PtRu/C catalyst. Their methanol oxidation activity and electrochemical durability were measured by linear sweep voltammetry before and after potential cycling treatment. PtRuAu/C had a significantly higher durability than PtRu/C while maintaining a comparable high activity. The morphology and substructure of the nanoparticles were investigated by energy-dispersive x-ray spectroscopy, x-ray diffraction, and x-ray absorption fine structure spectroscopy. Metallic nanoparticles with diameters of about 2 nm were obtained; they probably had Pt-core/PtRu-shell structures. Transmission electron microscopy observations after potential cycling revealed that 2-nm-diameter nanoparticles containing Au did not coarsen, whereas nanoparticles without Au coarsened significantly to 3.7 nm. Some crystal defaults were observed in the coarsened particles, implying that the coarsening was caused by Ostwald ripening. The Au addition to catalyst particles consisting of PtRu inhibits coarsening and consequently improves the electrochemical durability.