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/C 60 ) is successfully constructed. The theoretical spectral efficiency of TPPS/C 60 is as high as 70%, offering the possibility of full‐solar‐spectrum light harvesting. The TPPS/C 60 performs a highly efficient photocatalytic H 2 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 C 60 , 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 •+ –C 60 •− 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.