Defects Promote Ultrafast Charge Separation in Graphitic Carbon Nitride for Enhanced Visible‐Light‐Driven CO₂ Reduction Activity

Abstract

Fundamental photocatalytic limitations of solar CO₂ reduction remain due to low efficiency, serious charge recombination, and short lifetime of catalysts. Herein, two-dimensional graphitic carbon nitride nanosheets with nitrogen vacancies (g-C₃ N_x ) located at both three-coordinate N atoms and uncondensed terminal NH_x species were prepared by one-step tartaric acid-assistant thermal polymerization of dicyandiamide. Transient absorption spectra revealed that the defects in g-C₃ N₄ act as trapped states of charges to result in prolonged lifetimes of photoexcited charge carriers. Time-resolved photoluminescence spectroscopy revealed that the faster decay of charges is due to the decreased interlayer stacking distance in g-C₃ N_x in favor of hopping transition and mobility of charge carriers to the surface of the material. Owing to the synergic virtues of strong visible-light absorption, large surface area, and efficient charge separation, the g-C₃ N_x nanosheets with negligible loss after 15 h of photocatalysis exhibited a CO evolution rate of 56.9 μmol g^-1 h^-1 under visible-light irradiation, which is roughly eight times higher than that of pristine g-C₃ N₄ . This work presents the role of defects in modulating light absorption and charge separation, which opens an avenue to robust solar-energy conversion performance.