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

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.

Weiwei Zhang, Miaojie Yu, Tao Liu, Muyu Cong, Xueyan Liu, Haofan Yang, Yang Bai, Qiang Zhu, Shuo Zhang, Hongxu Gu, Xiaofeng Wu, Zhiyun Zhang, Yongzhen Wu, He Tian, Xiaobo Li, Wei-Hong Zhu, Andrew I. Cooper