Interfacial Charge Transfer Controls Plasmon-Enhanced Catalysis in DNA-Coated Gold Nanorods.

The ultrafast recombination of plasmon-generated hot carriers (within ∼100 fs) has long prevented their productive use in catalysis. Here, we show that a DNA corona coated on gold nanorods (AuNRs) overcomes this barrier through chemical interface damping (CID): hot electrons generated by longitudinal plasmon excitation transfer directly into the DNA layer, creating charge-separated states that drive long-range catalysis within the corona phase. Using three complementary single-particle techniques, single-particle force spectroscopy, single-particle scattering spectroscopy, and single-particle fluorescence microscopy, we establish the first quantitative, sample-level correlation between population-averaged interfacial charge transfer efficiency (ηCT) and enzyme-like catalytic activity. As the DNA:AuNR feed ratio increases, ηCT rises from 20% to 32%, and the plasmon-enhanced turnover rate increases proportionally. Photothermal effects are rigorously excluded by control experiments. These results reveal that the DNA corona simultaneously serves as a substrate-binding scaffold and stabilizes interfacial charge-separated states, establishing CID engineering as a design principle for next-generation plasmonic photocatalysts.