Electric‐Field‐Mediated Electron Tunneling of Supramolecular Naphthalimide Nanostructures for Biomimetic H<sub>2</sub> Production
Huan Lin, Zhiyun Ma, Jiwu Zhao, Yang Liu, Jinquan Chen, Junhui Wang, Kaifeng Wu, Huaping Jia, Xuming Zhang, Xinhua Cao, Xuxu Wang, Xianzhi Fu, Jinlin Long
Abstract
Abstract The design and synthesis of two semiconducting bis (4‐ethynyl‐bridging 1, 8‐naphthalimide) bolaamphiphiles (BENI‐COO − and BENI‐NH 3 + ) to fabricate supramolecular metal–insulator–semiconductor (MIS) nanostructures for biomimetic hydrogen evolution under visible light irradiation is presented. A H 2 evolution rate of ca. 3.12 mmol g −1 ⋅h −1 and an apparent quantum efficiency (AQE) of ca. 1.63 % at 400 nm were achieved over the BENI‐COO − ‐NH 3 + ‐Ni MIS photosystem prepared by electrostatic self‐assembly of BENI‐COO − with the opposite‐charged DuBois‐Ni catalysts. The hot electrons of photoexcited BENI‐COO − nanofibers were tunneled to the molecular Ni collectors across a salt bridge and an alkyl region of 2.2–2.5 nm length at a rate of 6.10×10 8 s −1 , which is five times larger than the BENI‐NH 3 + nanoribbons (1.17×10 8 s −1 ). The electric field benefited significantly the electron tunneling dynamics and compensated the charge‐separated states insufficient in the BENI‐COO − nanofibers.