Controllable Conversion of Platinum Nanoparticles to Single Atoms in Pt/CeO₂ by Laser Ablation for Efficient CO Oxidation

Abstract

Downsizing metal nanoparticles to single atoms (monoatomization of nanoparticles) has been actively pursued to maximize the metal utilization of noble-metal-based catalysts and regenerate the activity of agglomerated metal catalysts. However, precise control of monoatomization to optimize the catalytic performance remains a great challenge. Herein, we developed a laser ablation strategy to achieve the accurate regulation of Pt nanoparticles (Pt_NP) to Pt single atoms (Pt₁) conversion on CeO₂. Owing to the excellent tunability of input laser energy, the proportion of Pt₁ versus total Pt on CeO₂ can be precisely controlled from 0 to 100% by setting different laser powers and irradiation times. The obtained Pt₁Pt_NP/CeO₂ catalyst with approximately 19% Pt₁ and 81% Pt_NP exhibited much-enhanced CO oxidation activity than Pt₁/CeO₂, Pt_NP/CeO₂, and other Pt₁Pt_NP/CeO₂ catalysts. Density functional theory (DFT) calculations showed that Pt_NP was the major active center for CO oxidation, while Pt₁ changed the chemical potential of lattice oxygen on CeO₂, which decreased the energy barrier required for CO oxidation by lattice oxygen and resulted in an overall performance improvement. This work provides a reliable strategy to redisperse metal nanoparticles for designing catalysts with various single-atom/nanoparticle ratios from a top-down path and valuable insights into understanding the synergistic effect of nano-single-atom catalysts.