Accelerated discovery of molecular nanojunction photocatalysts for hydrogen evolution by using automated screening and flow synthesis

Abstract Discovering and optimizing multicomponent organic semiconductors is typically a laborious process. High-throughput experimentation can accelerate this, but the results of small-scale screening trials are not always transferable to bulk materials production. Here we report the accelerated discovery of molecular nanojunction photocatalysts based on a combinatorial donor–acceptor molecular library assisted by high-throughput automated screening. The knowledge gained from this high-throughput batch screening is then transferred to a scaled-up, flow-based synthesis process. The scaled-up molecular nanojunction MTPA-CA:CNP147 (3-(4-(bis(4-methoxyphenyl)amino)phenyl)-2-cyanoacrylic acid:2,6-bis(4-cyanophenyl)-4-(4′-fluoro-1,1′-biphenyl-4-yl)pyridine-3,5-dicarbonitrile) exhibits a sacrificial hydrogen evolution rate of 330.3 mmol h −1 g −1 with an external quantum efficiency of 80.3% at 350 nm, which are among the highest reported for an organic photocatalyst. A one-dimensional nanofibre architecture is identified for this molecular nanojunction, which exhibits efficient charge separation. Electronic structure–property correlations across the photocatalyst library show that a moderate binding energy between the donor and the acceptor molecules is a potential factor for efficient molecular nanojunction formation.