Constructing a Supramolecular THPP/C ₆₀ ‐NH ₂ Donor–Acceptor System via Strong Electrostatic Interaction for Efficient Photocatalytic Hydrogen Evolution

The rational design and construction of efficient donor–acceptor (D–A) architectures represent a pivotal strategy for enhancing photocatalytic activity, particularly toward boosting solar‐driven hydrogen evolution performance. To further modulate the electron transfer pathway at the donor–acceptor (D–A) interface, a supramolecular composite (THPP/C 60 ‐NH 2 ) is rationally designed and synthesized using tetrahydroxyphenylporphyrin (THPP) and amino‐functionalized fullerene (C 60 ‐NH 2 ) as building blocks. Benefiting from the strong electron‐donating characteristic of THPP and the excellent electron‐accepting capability of C 60 ‐NH 2 , as well as the directional hydrogen bonding interaction between amino groups and porphyrin hydroxyl groups, this system realizes efficient and precise intermolecular electron transfer. The long‐lived charge‐separated state generated in the composite effectively suppresses carrier recombination and enhances photogenerated carrier separation efficiency. The obtained THPP/C 60 ‐NH 2 exhibits a high photocatalytic H 2 production activity of 15.86 mmol g −1 h −1 , approximately 2.7 times that of pure THPP, providing a new route to regulate D–A interfacial kinetics through polar group modification.