The implementation of plasmonic materials in heterogeneous catalysis was limited due to the lack of experimental access in managing the plasmonic hot carriers. Herein, we propose a liquid-state surface-enhanced Raman scattering (SERS) technique to manipulate and visualize heterogeneous photocatalysis with transparent plasmonic chips. The liquid-state measurement conquers the difficulties that arise from the plasmon-induced thermal effects, and thus the plasmon based strategies can be extended to investigate a wider range of catalytic reactions. We demonstrated the selection of reaction products by modulating the plasmonic hot carriers and explored the mechanisms in several typical C-C coupling reactions with 4-bromothiophenol (4-BTP) as reactants. The real-time experimental results suggest brand new mechanisms of the formation of C-C bonds on plasmonic metal nanoparticles (NPs): the residue of 4-BTP, but not thiophenol (TP), is responsible for the C-C coupling. Furthermore, this technique was extended to study the evolution of the Suzuki-Miyaura reaction on nonplasmonic palladium metals by establishing the charge transfer channels between palladium and Au NPs. The cleavage and formation of chemical bonds in each individual reaction step were discerned, and the corresponding working mechanisms were clarified.
Keywords: C−C coupling reaction; heterogeneous catalysis; hot carriers; liquid-state SERS; plasmon.