Ion-Exchange Loading Promoted Stability of Platinum Catalysts Supported on Layered Protonated Titanate-Derived Titania Nanoarrays.

Supported metal catalysts are one of the major classes of heterogeneous catalysts, which demand good stability in both the supports and catalysts. Herein, layered protonated titanate-derived TiO2 (LPT-TiO2) nanowire arrays were synthesized to support platinum catalysts using different loading processes. The Pt ion-exchange loading on pristine LPTs followed by thermal annealing resulted in superior Pt catalysts supported on the LPT-TiO2 nanoarrays with excellent hydrothermal stability and catalytic performance toward CO and NO oxidations as compared to the Pt catalysts through wet-impregnation on the anatase TiO2 (ANT-TiO2) nanoarrays resulted from thermal annealing of LPT nanoarrays. Both loading processes resulted in highly dispersed Pt nanoparticles (NPs) with average sizes smaller than 1 nm at their pristine states. However, after hydrothermal aging at 800 °C for 50 h, highly dispersed Pt NPs were only retained on the ion-exchanged LPT-TiO2 nanoarrays with the support structure consisting of a mixture of 74% anatase and 26% rutile TiO2. For the wet-impregnation loading directly on anatase TiO2 nanoarrays derived from LPT, the Pt catalysts experienced severe agglomeration after hydrothermal aging, with the nanoarray supports consisting of 86% anatase and 14% rutile TiO2. Spectroscopy analysis suggested that Pt2+ cations intercalated into the interlayers of the titanate frameworks through ion-exchange impregnation procedure, which altered the chemical and electronic structures of the catalysts, resulting in the shifts of the electronic binding energy, Raman bands, and optical energy bandgap. The ion-exchangeable nature of LPT nanoarrays clearly provides a structural modification in Pt-doped LPT that has resulted in a strong interaction between the Pt catalysts and LPT-TiO2 nanoarray supports, leading to the enhanced hydrothermal stability of the catalysts. Considering the wide applications of the LPT and TiO2 nanomaterials as supports for catalysts, this finding provides a new pathway to design highly stable supported metal catalysts for different reactions.