Surface-Specific Modification of Graphitic Carbon Nitride by Plasma for Enhanced Durability and Selectivity of Photocatalytic CO2 Reduction with a Supramolecular Photocatalyst

Photocatalytic CO₂ reduction is in high demand for sustainable energy management. Hybrid photocatalysts combining semiconductors with supramolecular photocatalysts represent a powerful strategy for constructing visible-light-driven CO₂ reduction systems with strong oxidation power. Here, we demonstrate the novel effects of plasma surface modification of graphitic carbon nitride (C₃N₄), which is an organic semiconductor, to achieve better affinity and electron transfer at the interface of a hybrid photocatalyst consisting of C₃N₄ and a Ru(II)-Ru(II) binuclear complex (RuRu'). This plasma treatment enabled the "surface-specific" introduction of oxygen functional groups via the formation of a carbon layer, which worked as active sites for adsorbing metal-complex molecules with methyl phosphonic-acid anchoring groups onto the plasma-modified surface of C₃N₄. Upon photocatalytic CO₂ reduction with the hybrid under visible-light irradiation, the plasma-surface-modified C₃N₄ with RuRu' enhanced the durability of HCOOH production by three times compared to that achieved when using a nonmodified system. The high selectivity of HCOOH production against byproduct evolution (H₂ and CO) was improved, and the turnover number of HCOOH production based on the RuRu' used reached 50 000, which is the highest among the metal-complex/semiconductor hybrid systems reported thus far. The improved activity is mainly attributed to the promotion of electron transfer from C₃N₄ to RuRu' under light irradiation via the accumulation of electrons trapped in deep defect sites on the plasma-modified surface of C₃N₄.