Study of CoxPt1−x nanoalloy formation mechanism via single-source precursors

Abstract

This paper is devoted to the study of formation mechanism of metal solid solutions during the thermolysis of single-source precursors in Co–Pt systems with a wide range of superstructural ordering. It is shown that the thermal decomposition of [Pt(NH3)4][Co(C2O4)2(H2O)2]·2H2O salt in helium is critically different from that under hydrogen atmospheres. Thermal degradation under the helium atmosphere is followed by a gradual reduction of platinum and cobalt, and at each thermolysis temperature only one phase is present. At 380 °C an equiatomic Co0.50Pt0.50 solid solution is formed (a = 3.749 (4) Å, Fm−3m space group, V/Z = 13.17 Å3, crystallite size: 5–7 nm). When the precursor is decomposed under a hydrogen atmosphere, the process proceeds mainly through the simultaneous reduction of the platinum and cobalt atoms, and at each temperature section two metal phases are present. The formation of the close to equiatomic Co0.50Pt0.50 solid solution (a = 3.782 (4) Å, Fm−3m space group, V/Z = 13.52 Å3, crystallite size: 7–9 nm) occurs at 450 °C. The calculations of crystallite sizes are confirmed by transmission electron microscopy data.