Surface electric dipole and coordinate microenvironment mediated charge separation and transfer for patterned carbon nitride photocatalysis

The manipulation of charge separation and transfer during microscopic processes in semiconductors and correlation of interfacial catalysis is significant to improve photocatalysis efficiency. Here, we develop holey nanoridge patterns (HnRP) in carbon nitride to investigate the mediation of surface electric dipole and coordinate bonding microenvironment on the charge separation and transfer. The unique structural of HnRP with nanoscale hole defects and Turing-like spatial heterogeneity, create a vertical electric dipole and charge accumulation around the tip of the nanoridge and the hole on the surface. The regulation of hole domain size, defect holey edge, surface non-stoichiometry, and terminating bonds at HnRP provides electronic band structure with more photophysical and photoelectrical advantages for charge separation and transfer, driving the photocatalytic hydrogen evolution. The optimal HnRP gives patterned carbon nitride a hydrogen yield of 1.11 mmol·g−1·h−1 under simulated solar light irradiation. The HnRP can also modulate electron transfer across interface from suppressing the deactivation to accelerating the regeneration, evidenced by an electrochemical analysis with the triethanolamine as a probe molecule. Furthermore, we reveal the terminating amino and nitrile bonds facilitate the coordinate bonding and electron loss at platinum (Pt) site, elucidating the active origin of HnRP at atomic and molecular scale.