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Plasmon-induced photocatalysis on noble metal surfaces has attracted broad attention due to its application in sunlight energy conversion, while the selectivity of plasmonic platforms remains unclear. Herein, we present the controlled plasmon-mediated oxidation of para-aminothiophenol (p-ATP) by employing Au@Ag core–shell nanostars with tunable tip plasmons in visible–near-infrared range as reactors. In-situ Raman measurements indicate that Au@Ag core–shell nanostars essentially promote the conversion of p-ATP to 4,4′-dimercaptoazobenzene (DMAB) due to hot carriers excited by localized surface plasmon resonance. Au@Ag nanostars with plasmon modes under resonant light excitation suggested higher catalytic efficiency, as evidenced by the larger intensity ratios between 1440 cm−1 (N=N stretching of DMAB) and 1080 cm−1 shifts (C–S stretching of p-ATP). Importantly, the time-dependent surface-enhanced Raman scattering spectra showed that the conversion efficiency of p-ATP was mainly dictated by the resonance condition between the tip plasmon mode of Au@Ag core–shell nanostars and the excitation light, as well as the choice of excitation wavelength. These results show that plasmon bands of metal nanostructures play an important role in the efficiency of plasmon-driven photocatalysis.

In-Situ Monitoring the SERS Spectra of para-Aminothiophenol Adsorbed on Plasmon-Tunable Au@Ag Core–Shell Nanostars