Synthesis of perovskite polyhedron nanocrystals with equivalent facets and the controlled growth of Pt nanoparticles with differing surface concentration of oxidized Pt4+/Pt2+ species

Co-existence of different surfaces in traditional polycrystalline heterogeneous catalysts imposes a challenge to induce different kinds of catalytic species and average reactivity. Supported metal/oxide model catalyst designed with equivalent well-defined surfaces and active species provides an opportunity to control the uniformity, maintain efficient activity, and understand catalytic mechanisms at the atomic and molecular levels. Herein, sub-20 nm perovskite-structure BaTiO 3 polyhedron nanocuboids and Zr-substituted rhombic dodecahedron nanocrystals were synthesized and employed as the oxide support for the subsequent uniform growth of 1–2 nm Pt nanoparticles. These Pt nanoparticles were well dispersed on the 12 equivalent (110) facets of BaTi 0.75 Zr 0.25 O 3 rhombic dodecahedra and on the 6 equivalent (100) facets of BaTiO 3 nanocuboids. The main active centers on the Pt/BaTi 0.75 Zr 0.25 O 3 catalysts in the oxidized surface layer of Pt (111) facets are Pt 4+ versus Pt 2+ , which is in contrast to the oxidized surface layer of the Pt (100) facets on the Pt/BaTiO 3 cuboids where there are a greater number of Pt 2+ species. Compared with Pt/BaTiO 3 nanocuboids, the Pt/BaTi 0.75 Zr 0.25 O 3 catalysts demonstrated higher CO catalytic oxidation activity with a lower apparent Arrhenius activation energy. This work advances our ability to synthesize metal/oxide model catalyst that offer equivalent facets and highly uniform active centers with reasonable surface area in order to gain insight in reaction mechanisms. Two supported Pt model catalysts were fabricated by dispersing 1–2 nm Pt nanoparticles on the 12 equivalent (110) facets of BaTi 0.75 Zr 0.25 O 3 rhombic dodecahedra and on the 6 equivalent (100) facets of BaTiO 3 nanocuboids. Nonmetal active Pt species were identified by in situ DRIFTS and XPS. Different oxide support surface can change the surface Pt 4+ /Pt 2+ ratio and thus optimize CO oxidation. • Synthesis of sub-20 nm perovskite nanocubes and rhombic dodecahedra. • HRTEM/STEM image analysis for perovskite oxide and 1–2 nm Pt nanoparticles. • CO oxidation and DRIFTS characterization on two supported Pt catalysts. • XPS characterization for Pt 4+ and Pt 2+ active species dispersion analysis.