Anisotropic Dual S‐Scheme Heterojunctions Mimic Natural Photosynthetic System for Boosting Photoelectric Response

The design of heterojunctions that mimic natural photosynthetic systems holds great promise for enhancing photoelectric response. However, the limited interfacial space charge layer (SCL) often fails to provide sufficient driving force for the directional migration of inner charge carriers. Drawing inspiration from the electron transport chain (ETC) in natural photosynthesis system, we developed a novel anisotropic dual S‐scheme heterojunction artificial photosynthetic system composed of Bi2O3−BiOBr−AgI for the first time, with Bi2O3 and AgI selectively distributed along the bicrystal facets of BiOBr. Compared to traditional semiconductors, the anisotropic carrier migration in BiOBr overcomes the recombination resulting from thermodynamic diffusion, thereby establishing a potential ETC for the directional migration of inner charge carriers. Importantly, this pioneering bioinspired design overcomes the limitations imposed by the limited distribution of SCL in heterojunctions, resulting in a remarkable 55‐fold enhancement in photoelectric performance. Leveraging the etching of thiols on Ag‐based materials, this dual S‐scheme heterojunction is further employed in the construction of photoelectrochemical sensors for the detection of acetylcholinesterase and organophosphorus pesticides. We propose an innovative biomimetic artificial photosynthetic system for the first time. The anisotropic migration of BiOBr carriers demonstrates exceptional charge pre‐separation properties, effectively mimicking the role of electron transport chain observed in natural photosynthesis. The incorporation of a stepped dual S‐Scheme band structure ensures the optimal simulation of the photosystem (PSII/PSI).