Anchoring Positively Charged Pd Single Atoms in Ordered Porous Ceria to Boost Catalytic Activity and Stability in Suzuki Coupling Reactions

Abstract

Single-atom (SA) catalysis bridging homogeneous and heterogeneous catalysis offers new opportunities for organic synthesis, but developing SA catalysts with high activity and stability is still a great challenge. Herein, a heterogeneous catalyst of Pd SAs anchored in 3D ordered macroporous ceria (Pd-SAs/3DOM-CeO₂ ) is developed through a facile template-assisted pyrolysis method. The high specific surface area of 3DOM CeO₂ facilitates the heavily anchoring of Pd SAs, while the introduction of Pd atoms induces the generation of surface oxygen vacancies and prevents the grain growth of CeO₂ support. The Pd-SAs/3DOM-CeO₂ catalyst exhibits excellent activity toward Suzuki coupling reactions for a broad scope of substrates under ambient conditions, and the Pd SAs can be stabilized in CeO₂ in long-term catalytic cycles without leaching or aggregating. Theoretical calculations indicate that the CeO₂ supported Pd SAs can remarkably reduce the energy barriers of both transmetalation and reductive elimination steps for Suzuki coupling reactions. The strong metal-support interaction contributes to modulating the electronic state and maintaining the stability of Pd SA sites. This work demonstrates an effective strategy to design and synthesize stable single-atom catalysts as well as sheds new light on the origin for enhanced catalysis based on the strong metal-support interactions.