Porphyrin‐Regulated Bimetallic Sulfide With Ultrafast Interfacial Charge Transfer for Boosted Photocatalytic Hydrogen Evolution

ABSTRACT The interaction between different components in the hybrid photocatalytic material system may modulate the interfacial charge transfer behaviors and thus exerts an influence on the overall photocatalytic performance. However, developing effective strategies to enhance interfacial charge transfer in hybrid material systems for improved photocatalytic performance remains a challenging topic. Herein, a proof‐of‐concept photocatalytic hydrogen evolution system has been fabricated by the hybridization of platinum tetracaboxyporphyrin (PtTCPP), as photosensitizer and electron‐transporting carrier, and the ternary bimetallic sulfide nanodot Cd 0.5 Zn 0.5 S (nCZS), as catalytic center. The strong coupled interfacial molecule/inorganic semiconductor heterostructure establishes molecular‐level electron transfer channels and accelerates charge migration. By virtue of the coordination bonds between nCZS and PtTCPP, a substantial electrostatic potential difference is set‐up and helps to form a 3.48 times higher interfacial electric field than that in pristine nCZS, which promotes the rapid transfer of electrons to nCZS. Resultantly, the nCZS/PtTCPP shows an extremely high hydrogen production rate of 86.7 mmol·g −1 ·h −1 , surprising all the related hybrid photocatalysts. Notably, an outstanding apparent quantum yield (AQY) up to 82.63% and excellent long‐term photocatalytic stability are also achieved in this hybrid system. The work provides a new insight on design of interfacial molecule/inorganic semiconductor heterostructures for efficient solar‐to‐chemical energy conversion.