Boosting Built‐In Electric Field via Asymmetric Architecture for Synergistic Production of H 2 O 2 and Benzaldehyde

ABSTRACT Photocatalytic concurrent valorization of photogenerated electrons and holes for co‐production of high‐value chemicals is an emerging strategy to maximize solar energy utilization, but its application is hindered by severe charge carrier recombination and low half‐reaction selectivity of conventional photocatalysts. Herein, we develop an asymmetric organic photocatalyst denoted as AT‐PDI, synthesized via condensation of perylene‐3,4,9,10‐tetracarboxylic dianhydride (PTCDA) with 2‐aminothiazole (2‐AT). The asymmetric molecular structure induces intrinsic electron polarization—yielding a larger dipole moment, extended electron‐hole centroid distance, and significantly enhanced built‐in electric field—which effectively facilitates charge separation and migration. Meanwhile, AT‐PDI exhibits higher 2‐electron oxygen reduction selectivity than pristine PTCDA, enabling efficient H 2 O 2 production via the electron‐driven half reaction, whereas photogenerated holes simultaneously oxidize benzyl alcohol to benzaldehyde. Under AM 1.5 G irradiation at pH = 2, the optimal AT‐PDI delivers H 2 O 2 and benzaldehyde production rates of 33.4 and 40.0 mmol·g −1 h −1 , respectively, realizing full synergistic utilization of photogenerated charge carriers. This work provides a facile asymmetric structure engineering strategy for the design of high‐performance bifunctional photocatalysts for co‐production systems.