Plasmonic nanoreactors regulating selective oxidation by energetic electrons and nanoconfined thermal fields.

Optimizing product selectivity and conversion efficiency are primary goals in catalysis. However, efficiency and selectivity are often mutually antagonistic, so that high selectivity is accompanied by low efficiency and vice versa. Also, just increasing the temperature is very unlikely to change the reaction pathway. Here, by constructing hierarchical plasmonic nanoreactors, we show that nanoconfined thermal fields and energetic electrons, a combination of attributes that coexist almost uniquely in plasmonic nanostructures, can overcome the antagonism by regulating selectivity and promoting conversion rate concurrently. For propylene partial oxidation, they drive chemical reactions by not only regulating parallel reaction pathways to selectively produce acrolein but also reducing consecutive process to inhibit the overoxidation to CO, resulting in valuable products different from thermal catalysis. This suggests a strategy to rationally use plasmonic nanostructures to optimize chemical processes, thereby achieving high yield with high selectivity at lower temperature under visible light illumination.