Synthesis and evaluation of PtNi electrocatalysts for CO and methanol oxidation in low temperature fuel cells

Pt(Ni)/C and PtRu(Ni)/C catalysts were synthesized by electroless deposition of Ni on a carbon dispersion followed by sequenced Pt deposition and spontaneous deposition of Ru species. The structural analyses of the catalysts with 88:12 and 98:2 Pt:Ni atomic ratios pointed out to the formation of small hexagonal Ni crystallites covered by thin cubic Pt surface structures with no evidence about PtNi alloy formation. The onset potentials for CO oxidation on Pt(Ni)/C and PtRu(Ni)/C were about 0.10 and 0.24 V more negative than those of Pt/C, thus indicating their better CO tolerance. The surface Ru species appeared to have the major effect by facilitating the CO removal by the bifunctional mechanism. The onset potential for the methanol oxidation reaction (MOR) of Pt(Ni)/C was about 0.15 V lower than that of Pt/C. The mass and specific activities together with the exchange current densities of the Pt(Ni)/C catalysts were also higher than those of Pt/C, making in evidence their higher activity in front of the MOR. The Tafel slopes for the MOR on Pt(Ni)/C suggested different reaction mechanism than on Pt/C. The electronic (ligand) effect of Ni on Pt was considered the main reason to explain the higher activity of Pt(Ni)/C in front of the CO oxidation and the MOR.