A Full‐Spectrum Porphyrin–Fullerene D–A Supramolecular Photocatalyst with Giant Built‐In Electric Field for Efficient Hydrogen Production

A full-spectrum (300-850 nm) responsive donor-acceptor (D-A) supramolecular photocatalyst tetraphenylporphinesulfonate/fullerene (TPPS/C₆₀ ) is successfully constructed. The theoretical spectral efficiency of TPPS/C₆₀ is as high as 70%, offering the possibility of full-solar-spectrum light harvesting. The TPPS/C₆₀ performs a highly efficient photocatalytic H₂ evolution rate of 276.55 µmol h^-1 (34.57 mmol g^-1 h^-1 ), surpassing many reported organic photocatalysts. The D-A structure effectively promotes electron transfer from TPPS to C₆₀ , which is beneficial to the photocatalytic reaction. Specifically, a giant internal electric field in the D-A structure is built via the enhanced molecular dipole, which dramatically promotes the charge separation (CS) efficiency by 2.35 times. Transient absorption spectra results show a long-lived CS state TPPS^•+ -C₆₀ ^•- in the D-A structure, which effectively promotes participation of photogenerated electrons in the reduction reaction. Briefly, this work provides a novel approach for designing high-performance photocatalytic materials via enhancing the interfacial electric field.