Lanthanide-Induced Ligand Effect to Regulate the Electronic Structure of Platinum−Lanthanide Nanoalloys for Efficient Methanol Oxidation

The ligand effect in alloy catalysts is one of the decisive parameters of the catalytic performance. However, the strong interrelation between the ligand effect and the geometric effect of the active atom and its neighbors as well as the systematic alteration of the microenvironment of the active site makes the active mechanism unclear. Herein, Pt₃Tm, Pt₃Yb, and Pt₃Lu with a cubic crystal system (<i>Pm</i>-3<i>m</i>) were selected. With the difference of Pt-Pt interatomic distance within 0.02 Å, we minimize the geometric effect to realize the disentanglement of the system. Through precise characterization, due to the low electronegativity of Ln (Ln = Tm, Yb, and Lu) and the ligand effect in the alloy, the electronic structure of Pt is continuously optimized, which improves the electrochemical methanol oxidation reaction (MOR) performance. The Ln electronegativity has a linear relationship with the MOR performance, and Pt₃Yb/C achieves a high mass activity of up to 11.61 A mg_Pt^-1, which is the highest value reported so far in Pt-based electrocatalysts. The results obtained in this study provide fundamental insights into the mechanism of ligand effects on the enhancement of electrochemical activity in rare-earth nanoalloys.