Highly efficient photocatalytic hydrogen production via porphyrin-fullerene supramolecular photocatalyst with donor-acceptor structure

A novel tetraphenylporphyrin-C60 supramolecular photocatalyst (SA-TPP-C60) with donor–acceptor (D-A) structure is successfully constructed. Self-assembly of covalently-linked D-A molecule TPP-C60 gives rise to SA-TPP-C60 with highly-ordered layered D-A structure. TPP-C60 molecule is characterized with strong D-A interaction, inducing a significantly larger molecular dipole moment (ca. 4.86 D) than the referential TPP molecule (only 0.04 D). In consequence, robust internal electric field (IEF) with 4.7 times enhancement is built up in SA-TPP-C60, contributing to ultrafast photogenerated charge separation (∼0.5 ps) and enhanced charge transport. Notably, unprecedented long-lived photogenerated charge separation (τ = 26.3 ns) was observed in SA-TPP-C60. Thus, the photocatalytic hydrogen evolution performance of SA-TPP-C60 reached 10.69 mmol g-1h−1, which is about 80 times higher than SA-TPP. Briefly, this study sheds light on D-A structure engineering of supramolecular photocatalysts for high-performance photocatalytic applications.