Reactivity and stability of platinum and platinum alloy catalysts toward the oxygen reduction reaction

Density functional theory (DFT) is used to study the reactivity of Pt and Pt-M\n(M: Pd, Co, Ni, V, and Rh) alloy catalysts towards the oxygen reduction reaction (ORR)\nas a function of the alloy overall composition and surface atomic distribution and\ncompared to that on pure Pt surfaces. Reactivity is evaluated on the basis of the\nadsorption strength of oxygenated compounds which are intermediate species of the\nfour-electron oxygen reduction reaction, separating the effect of the first electron-proton\ntransfer from that of the three last electron-proton transfer steps.\nIt is found that most homogeneous distribution PtxM catalysts\nthermodynamically favor the dissociation of adsorbed OOH in comparison with pure\nPlatinum and adsorb strongly O and OH due to the strong oxyphilicity of the M\nelements. On the other hand, in all cases skin Platinum surfaces catalysts do not favor\nthe dissociation of adsorbed OOH and do favor the reduction of M-O and M-OH with\nrespect to Platinum. Considering the overall pathway of the reactions to catalyze the\nORR most of the skin Platinum monolayer catalysts provide more negative free energy\nchanges and should behave at least in a similar way than Platinum in following order:\nPt3V (skin Pt) > Pt3Co (skin Pt) > Pt3Ni (skin Pt) > Pt > PtPd (skin) > Pt4Rh (skin Pt) >\nPtPd3 (skin ). In all cases, the reactivity is shown to be not only sensitive to the overall\ncomposition of the catalyst, but most importantly to the surface atomic distribution.\nProposed electrochemical dissolution reactions of the catalyst atoms are also\nanalyzed for the ORR catalysts, by computing the free energy changes of Platinum and\nbimetallic Pt-X (X: Co, Pd, Ni, and Rh) catalysts. It is found that Platinum is\nthermodynamically more stable than Pt-alloys in Pt3Co, Pt3Pd, Pt3Ni and Pt4Rh.