Manipulating selective amine transformation pathways via cocatalyst-modified monolayer ZnIn2S4 photocatalysts

Semiconductor-based artificial photoredox-catalyzed organic synthesis offers a promising and green opportunity to harness solar energy for green organic chemistry. However, the precise manipulation of product selectivity over semiconductor-based photocatalysts for selective organic synthesis remains challenging. In this work, we report the rational preparation and application of two kinds of cocatalyst, (RuS2 or Cu2S)-decorated monolayer ZnIn2S4, for the selective dehydrocoupling of aromatic amines into tunable C=N coupled imines or C-N coupled secondary amines, respectively, under visible light irradiation. The presence of the RuS2 or Cu2S cocatalyst not only facilitates the charge carrier separation and migration owing to the well-matched energy band structure, but also maneuvers the interfacial charge transfer routes for the selectivity switching between C=N and C-N product formation. This work would inspire the rational design of ingenious semiconductor-based composites toward selective modulation in heterogeneous photocatalytic organic synthesis.

Automated summary

This study reports the rational preparation and application of two types of cocatalysts, (RuS2 or Cu2S)-decorated monolayer ZnIn2S4, for the selective dehydrocoupling of aromatic amines into tunable C=N coupled imines or C-N coupled secondary amines. The presence of the RuS2 or Cu2S cocatalyst facilitates charge carrier separation, migration, and maneuvers interfacial charge transfer routes for the selectivity switching between C=N and C-N product formation. This work inspires the rational design of ingenious semiconductor-based composites for selective modulation in heterogeneous photocatalytic organic synthesis.