Design of AIEgen‐based porphyrin for efficient heterogeneous photocatalytic hydrogen evolution

Abstract

Abstract Tetraphenylethylene (TPE)‐conjugated porphyrin TPE‐ZnPF is synthesized in high yield and characterized by single‐crystal X‐ray diffraction. The propeller‐shaped TPE groups not only enable exceptional aggregation‐induced emission (AIE) in the solid state but also abolish the strong π‐π stacking of porphyrin moieties and thus prohibit aggregation‐caused quenching (ACQ). TPE‐ZnPF aggregates feature long‐lived photoexcited states, which subsequently suppress non‐radiative decay channels and enhance emission intensity. Moreover, its aggregates show more efficient light‐harvesting ability due to the Förster resonance energy transfer from the TPE energy donor to the porphyrin core energy acceptor, well‐defined nanosphere morphology, and more efficient photoinduced charge separation than the porphyrin Ph‐ZnPF, which possesses ACQ and agglomerated morphology. As a result, an excellent photocatalytic hydrogen evolution rate ( η H 2 ) of 56.20 mmol g ‒1 h ‒1 is recorded for TPE‐ZnPF aggregates, which is 94‐fold higher than that of the aggregates of Ph‐ZnPF (0.60 mmol g ‒1 h ‒1 ) without the TPE groups.