The Interfacial Interpenetration Effect for Controlled Reaction Stability of Palladium Catalysts

Tailoring well-defined interfacial structures of heterogeneous metal catalysts has become an effective strategy for identifying the interface relationships and facilitating the reactions involving multiple intermediates. Here, a particle-particle heterostructure catalyst consisting of Pd and copper oxide nanoparticles is designed to achieve high-performance alkaline methanol oxidation electrocatalysis. The strong coupling particle-particle heterostructure catalyst induced a unique interfacial interpenetration effect to improve the interfacial charge redistribution and regulate the <i>d</i>-band structure for optimizing the adsorption of CO intermediates on the catalyst. The resulting catalyst shows impressive mass activity (4.0 A mg_Pd^-1) and current density (215.8 mA cm^-2) for the methanol oxidation reaction (MOR) in alkaline media, which is 80.0 and 154.1 times higher than 10% Pd/C. The catalyst also exhibited outstanding stability for the MOR without obvious mass activity decay after 30,000 cycles. Experimental results and theoretical simulation (DFT) studies show that the chemical bond of the Cu-O-Pd interface can be regulated by the Pd penetration effect, greatly improving the activity and stability of the MOR. The present work exhibits the superiority of the metal particle-metal oxide heterostructure interface toward the rational design of advanced electrocatalysts.