Reversible Transformation of Pt Nanoparticles into Single Atoms inside High-Silica Chabazite Zeolite

摘要

We report the encapsulation of platinum species in highly siliceous chabazite (CHA) crystallized in the presence of N,N,N-trimethyl-1-adamantammonium and a thiol-stabilized Pt complex. When compared to Pt/SiO_2 or Pt-containing Al-rich zeolites, the materials in this work show enhanced stability toward metal sintering in a variety of industrial conditions, including H_2, O_2, and H_2O. Remarkably, temperatures in the range 650-750 ℃ can be reached without significant sintering of the noble metal. Detailed structural determinations by X-ray absorption spectroscopy and aberration-corrected high-angle annular dark-field scanning transmission electron microscopy demonstrate subtle control of the supported metal structures from ～1 nm nanoparticles to site-isolated single Pt atoms via reversible interconversion of one species into another in reducing and oxidizing atmospheres. The combined used of microscopy and spectroscopy is critical to understand these surface-mediated transformations. When tested in hydrogenation reactions, Pt/CHA converts ethylene (～80%) but not propylene under identical conditions, in contrast to Pt/SiO_2, which converts both at similar rates. These differences are attributed to the negligible diffusivity of propylene through the small-pore zeolite and provide final evidence of the metal encapsulation.