Two Tungstates Containing Platinum Nanoparticles Prepared by Air-Calcining Keggin-Type Polyoxotungstate-Coordinated Diplatinum(II) Complexes: Effect on Sintering-Resistance and Photocatalysis

Abstract

Two tungstates containing platinum nanoparticles (Pt Npts) were obtained by air-calcining α-Keggin-type diplatinum(II)-coordinated polyoxotungstates, Cs3[α-PW11O39{cis-Pt(NH3)2}2]⋅8H2O (Cs-P-Pt) and Cs4[α-SiW11O39{cis-Pt(NH3)2}2]⋅11H2O (Cs-Si-Pt), at 700–900 °C for 5 h. The polyoxotungstate Cs-P-Pt was transformed to a mixture of Pt Npts and Cs3PW12O40 upon calcination, while the Cs-Si-Pt structures were transformed to Pt Npts and Cs4W11O35. The Pt Npts generated by air-calcining Cs-P-Pt at 700 °C for 5 h were uniform with an average particle size of 3.6 ± 1.1 nm, which was much smaller than that of the Pt Npts obtained by calcining Cs-Si-Pt (19.9 ± 9.9 nm) under identical conditions. This demonstrated the significant inhibitory effect of Cs-P-Pt on aggregation during high-temperature air-calcination at a high platinum content (10.6 wt.%) and in the absence of a support. During calcination at 700–900 °C, Cs-P-Pt exhibited higher activities than Cs-Si-Pt with respect to hydrogen evolution from aqueous triethanolamine solutions under visible light irradiation in the presence of Eosin Y, α-Keggin-type mono-aluminum-substituted polyoxotungstate, and titanium dioxide. When Cs-P-Pt was calcined at 800 °C for 100 h, no decrease in activity was observed in comparison with that upon calcination for 5 h.Graphical