Bulk‐ and Surface‐Engineered Carbon Nitride with Promoted Electron Transfer for NADH Regeneration and Artificial Photosynthesis

Abstract Carbon nitride (CN), a well‐known photocatalyst, has been extensively utilized in light‐driven redox reactions, including NADH regeneration. However, its catalytic efficiency is hindered by rapid charge recombination due to obstructed electron transfer. Herein, we developed a highly porous CN coated with a thin layer of rhodium complex (Rh*‐PCN) through a combination of bulk and surface engineering for enhanced NADH regeneration. The bulk‐engineered porous network of PCN facilitates oriented electron transfer in Rh*‐PCN, while the surface‐engineered Rh layer minimizes the electron transfer distance between PCN and the rhodium complex. Rh*‐PCN achieves an initial NADH regeneration rate of 16.80 mmol g⁻¹ h⁻¹. Moreover, Rh*‐PCN suppresses enzyme deactivation by compartmentalizing the enzyme from the photogenerated holes on PCN and the rhodium complex. When integrated with glutamate dehydrogenase, the Rh*‐PCN/enzyme coupled system produces L‐glutamic acid.