ABSTRACT The spin‐dependent recombination behavior of photogenerated charges has long been overlooked in the study of photocatalytic hydrogen (H 2 ) evolution over covalent organic frameworks (COFs). Moreover, correlating the structure of COFs with the spin states of photogenerated charges to enhance photocatalytic H 2 evolution performance remains a significant challenge. Herein, we present a chiral amino acid functionalization strategy to engineer chiral TpPa‐1 COF for boosted photocatalytic H 2 evolution. Following systematic optimization, the chiral TpPa‐1 COFs showcased a ∼5‐fold enhancement in photocatalytic performance, achieving a record TOF of 9867 h −1 , alongside the second‐highest reported AQY of 66% at 475 nm and HER of 2.54 mmol h −1 among the reported state‐of‐the‐art COF‐based photocatalysts for H 2 evolution. Mechanism studies revealed that the synergistic effect between the chirality and the directional charge transfer allows efficient photo‐generated charge separation. Furthermore, Chiral TpPa‐1 assembled with polymeric carbon nitride (g‐C 3 N 4 ) in an S‐scheme heterojunction can overcome the bottleneck in photocatalytic overall water splitting on g‐C 3 N 4 without oxygen evolution co‐catalysts. In this work, we present a universal design strategy from a charge spin perspective to synthesize chiral photocatalysts for efficient photocatalytic performance.
Li et al. (Thu,) studied this question.