Empirical and Theoretical Investigations into the Mechanism of Wireless CO₂ Reduction over Modified g-C₃N₄ Photocatalyst

The light-driven reduction of carbon dioxide holds promise for CO₂ mitigation and the conversion of CO₂ into valuable fuels and chemicals. While extensive efforts have been dedicated to elucidating the mechanistic aspects of photocatalytic CO2RR, the majority of reported studies have primarily focused on liquid-phase reactions using metal-based photocatalysts. In this investigation, we systematically explore the water-vapor assisted CO2RR employing a modified, metal-free g-C₃N₄-based photocatalyst without the incorporation of any cocatalyst, photosensitizer, or sacrificial reagent. Our approach utilizes In-Situ FTIR, DFT calculations, and operando XAS to deepen our understanding of the reaction mechanism. Furthermore, this study yields significant insights into the dynamics of charge carriers and the identification of active sites, thereby advancing our comprehension of the entire photocatalytic process.