LAUSR

Summary Plasmon-assisted chemical transformation holds great potential for solar energy conversion. However, simultaneous enhancement of reactivity and selectivity is still challenging and the mechanism remains mysterious. Herein, we elucidate the localized surface plasmon resonance (LSPR)-induced principles underlying the enhanced activity (∼70%) and selectivity of photoelectrocatalytic redox of nitrobenzene (NB) on Au nanoparticles. Hot carriers selectively accelerate the conversion rate from NB to phenylhydroxylamine (PHA) by ∼14% but suppress the transformation rate from PHA to nitrosobenzene (NSB) by ∼13%. By adding an electron accepter, the as-observed suppression ratio is substantially enlarged up to 43%. Our experiments, supported by in situ surface-enhanced Raman spectroscopy and density functional theory simulations, reveal such particular hot-carrier-induced selectivity is conjointly contributed by the accelerated hot electron transfer and the corresponding residual hot holes. This work will help expand the applications of renewable sunlight in the directional production of value-added chemicals under mild conditions.