Multi‐Layered PtAu Nanoframes and Their Light‐Enhanced Electrocatalytic Activity via Plasmonic Hot Spots

Here, the rational design of complex PtAu double nanoframes (DNFs) for plasmon‐enhanced electrocatalytic activity toward the methanol oxidation reaction (MOR) is reported. The synthetic strategy for the DNFs consists of on‐demand multiple synthetic chemical toolkits, including well‐faceted Au growth, rim‐on selective Pt deposition, and selective Au etching steps. DNFs are synthesized by utilizing Au truncated octahedrons (TOh) as a starting template. The outer octahedral (Oh) nanoframes (NFs) nest the inner TOh NFs, eventually forming DNFs with a tunable intra‐nanogap distance. Residual Au adatoms on Pt skeletons act as light entrappers and produce plasmonic hot spots between inner and outer frames through localized surface plasmon resonance (LSPR) coupling, which promotes enhanced electrocatalytic activity for the MOR. Importantly, the correlation between the gap‐induced hot carriers and electrocatalytic activity is evaluated. The highest catalytic activity is achieved when the gap is the narrowest. To further harness their light‐trapping capability, hierarchically structured triple NFs (TNFs) are synthesized, wherein three NFs are entangled in a single entity with a high density of hot regions, exhibiting superior electrocatalytic activity toward the MOR with a sixfold larger current density under light irradiation compared to the dark conditions. Herein, the rationale design of multi‐layered PtAu double nanoframes is presented via multiple synthetic pathways for plasmon‐enhanced electrocatalytic activity. Plasmonic hot spots formed between the inner and outer frames promote light‐induced electrocatalytic enhancement toward the methanol oxidation reaction. Notably, the correlation of hot spots with plasmon‐enhanced electrocatalytic efficiency is demonstrated by precisely tuning the number and distance of nanogaps.