Electric‐Field‐Mediated Electron Tunneling of Supramolecular Naphthalimide Nanostructures for Biomimetic H2 Production

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AbstractThe design and synthesis of two semiconducting bis (4‐ethynyl‐bridging 1, 8‐naphthalimide) bolaamphiphiles (BENI‐COO− and BENI‐NH3+) to fabricate supramolecular metal–insulator–semiconductor (MIS) nanostructures for biomimetic hydrogen evolution under visible light irradiation is presented. A H2 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−‐NH3+‐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 6.10×108 s−1, which is five times larger than the BENI‐NH3+ nanoribbons (1.17×108 s−1). The electric field benefited significantly the electron tunneling dynamics and compensated the charge‐separated states insufficient in the BENI‐COO− nanofibers.