In situ SERS reveals the route regulation mechanism mediated by bimetallic alloy nanocatalysts for the catalytic hydrogenation reaction

Synthesizing arylamines with high selectivity via hydrogenation of nitroaromatics is a long-standing challenge because of the complex reaction pathways. Revealing the route regulation mechanism is the key to obtain high selectivity of arylamines. However, the underlying reaction mechanism of route regulation is uncertain owing to a lack of direct in situ spectral evidence of the dynamic transformation of intermediate species during the reaction process. In this work, by using in situ surface-enhanced Raman spectroscopy (SERS), we have employed 13 nm Au(100−x)Cu(x) nanoparticles (NPs) deposited on a SERS-active 120 nm Au core to detect and track the dynamic transformation of intermediate species of hydrogenation of para-nitrothiophenol (p-NTP) into para-aminthiophenol (p-ATP). Direct spectroscopic evidence demonstrates that Au(100) NPs exhibited a coupling route with the in situ detection of the Raman signal assigned to coupling product p,p′-dimercaptoazobenzene (p,p′-DMAB). However, Au(67)Cu(33) NPs displayed a direct route without the detection of p,p′-DMAB. The combination of X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations reveals that Cu doping can favor the formation of active Cu–H species owing to the electron transfer from Au to Cu, which can promote the formation of phenylhydroxylamine (PhNHOH*) and favor the occurrence of the direct route on Au(67)Cu(33) NPs. Our study provides direct spectral evidence demonstrating the critical role of Cu in route regulation for the nitroaromatic hydrogenation reaction at a molecular level and clarifies the route regulation mechanism. The results have significant implications for revealing multimetallic alloy nanocatalyst mediated reaction mechanisms and help to guide the rational design of multimetallic alloy catalysts for catalytic hydrogenation reactions.