Simultaneous layer exfoliation and defect activation in g-C3N4 nanosheets with air-water interfacial plasma: spectroscopic defect probing with tailored optical properties

Defect-activated ultrathin graphitic carbon nitride nanosheets (g-C3N4) show an enhanced visible light absorption, better charge-separation, and facile charge transport properties. These are requisites for the designing of an active photocatalyst. Conventional methods used for layer exfoliation and defect activation require strong acids, reducing agents, or ultrasonic treatment for a sufficiently long duration. Furthermore, single-step approaches for layer exfoliation and defect incorporation have hardly been reported. Herein, we have shown atmospheric plasma enabled fabrication of g-C3N4 nanosheets. This approach is simple, low-cost, less time-consuming, and a green approach to exfoliate layers and activate multiple defects concurrently. The protocol involves plasma discharging at an air-water interface at 5 kV for 30-150 min. Atomic force microscopy (AFM) reveals a layer thickness of 96.27 nm in bulk g-C3N4. The thickness becomes 3.78 nm after 150 min of plasma treatment. The exfoliated layers emerge with nitrogen-vacancy sites and self-incorporated defects as probed by positron annihilation spectroscopy (PAS) and X-ray photoelectron spectroscopy (XPS). The defect activated layers show visible light absorption extended up to 600 nm. It is demonstrated that a non-uniform change in the band gap with the plasma treatment time results from quantum confinement in thin layers and Urbach tailing due to defects acting in opposition. Further, steady-state and time-resolved spectroscopy shows the contribution of multiple defect sites for a prolonged lifetime of photoinduced carriers. These defect-activated ultrathin nanosheets of CN serve as an active photocatalyst in the degradation of rhodamine B (RhB) under white LED illumination.