Boosting the Quantum Efficiency of Ionic Carbon Nitrides in Photocatalytic H 2 O 2 Evolution via Controllable n → π* Electronic Transition Activation

Abstract Hydrogen peroxide (H 2 O 2 ) is a crucial chemical used in numerous industrial applications, yet its manufacturing relies on the energy‐demanding anthraquinone process. Solar‐driven synthesis of H 2 O 2 is gaining traction as a promising research area, providing a sustainable method for its production. Herein, a controllable activation of n → π* electronic transition is presented to boost the photocatalytic H 2 O 2 evolution in ionic carbon nitrides. This enhancement is achieved through the simultaneous introduction of structural distortions and defect sites (─C ≡ N groups and N vacancies) into the KPHI framework. The optimal catalyst ( 2%Ox‐ KPHI) reached an apparent quantum yield of 41% at 410 nm without the need for any cocatalysts, outperforming most previously reported carbon nitride‐based photocatalysts. Extensive experimental characterizations and theoretical calculations confirm that a corrugated configuration and the presence of defects significantly broaden the light absorption profile, improve carrier separation and migration, promote O 2 adsorption, and lower the energy barriers for H 2 O 2 desorption. Transient absorption spectroscopy indicates that the enhanced photocatalytic performance of 2%Ox ‐KPHI is largely attributed to the preferential migration of electrons at defect sites over extended timescales, following the diffusion of geminate carriers across the PHI sheets.