Intrinsic Insight on Localized Surface Plasmon Resonance Enhanced Methanol Electro-oxidation over Au@AgPt Hollow Urchin-like Nanostructure

Plasmon effect on the catalytic performances of metal nanoparticles (NPs) has shown great potential in designing the novel catalytic reaction. However, the intrinsic mechanisms underlying the catalysis triggered by localized surface plasmon resonance (LSPR) are still ambiguous. In this work, we construct an Au@AgPt hollow urchin-like structures (Au@AgPt HUSs) with an ultra-thin Pt shell for electrocatalytic methanol oxidation reaction (MOR) in an alkaline solution under irradiation (200 mW cm-2). A superior MOR mass activity (3.26 A mg-1 Pt) is achieved on Au@AgPt HUSs, which is 5.43 times of commercial Pt black catalysts (0.6 A mg-1 Pt) under irradiation. It is found that the localized heating, which is resulted from the photothermal effect under irradiation, can accelerate the reaction kinetics of MOR over Au@AgPt HUSs. And our theoretical calculations demonstrate that the reduction in the lowest unoccupied molecular orbital (LUMO) energy level of CO induced by the localized electric field can accelerate the rate-determining step of *CO to *COOH, and the energetic hot carriers promote the *CO transferring from the hollow site to top site of Pt. Thus, the hollow Pt active sites poisoned by *CO can be reactivated due to the *CO transferring mechanism, leading to more available active sites for MOR process. This work reveals the intrinsic effect of the LSPR on catalysis and paves the way to boost conventional catalytic reactions by introducing solar energy flow.