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•Valence-band hybridization in AgPd nanoalloys upshifts the d-band center.•Intraband and interband transitions are synchronized and enhanced by the LSPR of Ag.•Multi-electron transfer facilitates the O2 activation and atomic oxygen generation.•AgPd0.6 performs the best activity and selectivity of direct oxidative esterification.•Visible illumination alters the reaction pathway of benzyl alcohol oxidation.
To achieve green, economic, and selective catalytic oxidation processes for pathway-controllable chemical synthesis, the activation of molecular oxygen is a crucial requirement but faces thermodynamic challenges. Here we show that the synergy of the plasmon resonance and valence-band hybridization exciting both interband and intraband transitions in nanoalloys is a promising strategy for O2 dissociation and reaction pathway alteration at mild conditions. For the oxidation of benzyl alcohol over AgPd nanoalloys, at compositions with Ag content around the Golden Ratio and under visible illumination we observe >95 % selectivity to esters, which is superior to that at other compositions or in the dark. The plasmon-coupled valence-band hybridization promotes the generation of atomic oxygen species at near room temperature, driving the direct oxidative esterification and reducing the aldehyde formation. These results exemplify a predictable design for the electronic structure regulation in plasmonic nanoalloys to develop new reaction pathways via photoactivation of reactants.