The Pivotal Role of Hot Carriers in Plasmonic Catalysis of C-N Bond Forming Reaction of Amines

Here, we demonstrate the simultaneous utilization of both the hot carriers (electrons and holes) in the photocatalytic transformation of benzylamine to N-benzylidenebenzylamine and the scope of reaction has also been successfully demonstrated with catalytic oxidation of 4-methoxybenzylamine. The wavelength-dependent excitation of AuNP allows us to tune the potential energy of charge carriers relative to the redox potential of the reactants which leads to energetically favorable product formation on the nanoparticle surface. We capture the formation of reaction intermediates and products by using in situ Raman spectroscopy, complemented by NMR spectroscopy and GC-MS. Based on the experimental substantiations, a plausible reaction mechanism has been proposed.

Automated summary

The study demonstrates the simultaneous utilization of hot carriers in the photocatalytic transformation of benzylamine and the catalytic oxidation of 4-methoxybenzylamine using gold nanoparticles. Excitation of AuNP allows tuning of charge carrier potential energy relative to reactants' redox potential, leading to energetically favorable product formation. The reaction mechanism is proposed based on in situ Raman spectroscopy, NMR spectroscopy, and GC-MS analysis of reaction intermediates and products.