Electronic Interaction between Pt and Y₂O₃ in Pt-Y₂O₃/C for Enhanced Electrocatalytic Methanol Oxidation.

Rare-earth (RE) elements are often employed to optimize electrocatalytic performance due to their tunable electronic structures and surface properties. Herein, a yttrium oxide-doped Pt-based catalyst (Pt-Y₂O₃/C) is engineered for the electrocatalytic methanol oxidation reaction (MOR), and the surface Y/Pt atomic ratio is precisely modulated to optimize its performance. Pt-Y₂O₃/C-2 (1/0.17 Pt/Y atomic ratio, Pt loading of 4.73 wt %) exhibits optimal mass activity (MA) for MOR, 5.10 A mgPt⁻¹ in 1.0 M KOH with 1.0 M CH₃OH, obviously outperforming commercial 20 wt % Pt/C by a factor of ∼12.8. It also shows superior CO-poisoning tolerance and stability; its MA for the MOR remains at 3.80 A mgPt⁻¹ after the 10 000 s stability test. Integrated characterization results demonstrate that Y₂O₃ doping induces an electronic interaction with Pt, thereby reducing the electron density of Pt and optimizing its electronic structure, attenuating the adsorption of CO* intermediates at the Pt sites. Y₂O₃ doping also decreased the charge transfer resistance (Rct) in the MOR. The superior MOR performance of the Pt-Y₂O₃/C-2 catalyst originates from its uniformly sized Pt-Y₂O₃ nanoparticles and unique electronic effect. This work highlights the regulatory role of the rare-earth metal in Pt-based catalysts for the MOR, offering a general strategy for achieving excellent catalytic performance.