Ligand‐Free Pt‐Ln Nanoclusters Synthesized by Femtosecond Lasers for Electrocatalytic Methanol Oxidation

Abstract

Methanol oxidation reaction (MOR) is critical for direct methanol fuel cells (DMFCs), but designing cost‐effective Pt‐based catalysts with high catalytic activity remains challenging. The study synthesizes lanthanide‐doped Pt nanoclusters via femtosecond laser ablation, with PtLa clusters achieving a mass activity of up to 17.50 A mgPt−1. Characterization shows these metastable PtLa nanoclusters feature clean surfaces and uniform La distribution within Pt nanocrystal frameworks. Comprehensive in situ/operando techniques, including attenuated total reflectance‐surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS), ambient pressure X‐ray photoelectron spectroscopy (APXPS), and X‐ray absorption spectroscopy (XAS), demonstrate that La incorporation markedly enhances both OH− adsorption and the central role of HCOO− as the primary reaction intermediate during MOR. Ultraviolet photoelectron spectroscopy (UPS) and density functional theory (DFT) calculations indicate La doping elevates the Pt d‐band center, strengthening intermediate adsorption and reducing kinetic barriers. The oxygenophilic nature of La enhances local OH− coverage near active sites, facilitating the activation of reaction intermediates and accelerating the turnover rate at electrolyte/electrode interface. The study provides a facile and effective strategy for synthesizing conventionally difficult‐to‐synthesize catalysts using femtosecond laser technology, paving the way for the controlled preparation of rare earth alloys and applications in large‐scale deployment of DMFCs and beyond.