Constructing a Supramolecular THPP/C60-NH2 Donor–Acceptor System via Strong Electrostatic Interaction for Efficient Photocatalytic Hydrogen Evolution

Abstract

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/C₆₀-NH₂) is rationally designed and synthesized using tetrahydroxyphenylporphyrin (THPP) and amino-functionalized fullerene (C₆₀-NH₂) as building blocks. Benefiting from the strong electron-donating characteristic of THPP and the excellent electron-accepting capability of C₆₀-NH₂, 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/C₆₀-NH₂ exhibits a high photocatalytic H₂ 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.