Formation of Catalytically Active Nanoparticles under Thermolysis of Silver Chloroplatinate(II) and...

The thermal behaviour of Ag₂[PtCl₄] and Ag₂[PtCl₆] complex salts in inert and reducing atmospheres has been studied. The thermolysis of compounds in a helium atmosphere is shown to occur in two stages. At the first stage, the complexes decompose in the temperature range of 350-500 °C with the formation of platinum and silver chloride and the release of chlorine gas. At the second stage, silver chloride is sublimated in the temperature range of 700-900 °C, while metallic platinum remains in the solid phase. In contrast to the thermolysis of Ag₂[PtCl₆], the thermal decomposition of Ag₂[PtCl₄] at 350 °C is accompanied by significant heat release, which is associated with disproportionation of the initial salt to Ag₂[PtCl₆], silver chloride, and platinum metal. It is confirmed by DSC measurements, DFT calculations of a suggested reaction, and XRD. The thermolysis of Ag₂[PtCl₄] and Ag₂[PtCl₆] compounds is shown to occur in a hydrogen atmosphere in two poorly separable steps. The compounds are decomposed within 170-350 °C, and silver and platinum are reduced to a metallic state, while a metastable single-phase solid solution of Ag_0.67Pt_0.33 is formed. The catalytic activity of the resulting nanoalloy Ag_0.67Pt_0.33 is studied in the reaction of CO total (TOX) and preferential (PROX) oxidation. Ag_0.67Pt_0.33 enhanced Pt nano-powder activity in CO TOX, but was not selective in CO PROX.