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

Fundamental photocatalytic limitations of solar CO 2 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‐C 3 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‐C 3 N 4 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‐C 3 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‐C 3 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‐C 3 N 4 . This work presents the role of defects in modulating light absorption and charge separation, which opens an avenue to robust solar‐energy conversion performance.