Role of dopants and defects on the photocatalytic performance of g-C3N4 under visible light and sub-band gap excitation

Abstract Here, we report the photocatalytic (PC) activity of graphitic carbon nitride (g-C 3 N 4 ) doped with potassium (K), magnesium (Mg), and boron (B) under visible (>390 nm), green (532 nm), and red (660 nm) light. Doped g-C 3 N 4 has an improved band structure, high carrier density, and tunable band-edge absorption as compared to pure g-C 3 N 4 . An atomic force microscope shows a decrease in layer thickness that follows the order: g-C 3 N 4 > K/g-C 3 N 4 > Mg/g-C 3 N 4 > B/g-C 3 N 4 . The evolution of nitrogen vacancies in doped g-C 3 N 4 was identified via x-ray photoelectron spectroscopy (XPS) and CHNS/O analyses. The red-shift in the absorption spectrum of K/g-C 3 N 4 and the emission spectrum of B/g-C 3 N 4 is caused by the band gap renormalization (BGR) effect. Quantum confinement and a possible Burstein–Moss (BM) effect both contribute to the spectral blue shift in the absorption spectra of Mg/g-C 3 N 4 and B/g-C 3 N 4 . The BM effect, quantum confinement, and dopant-induced lattice strain might all alter the band structure and move the conduction band edge away from the valence band zone centre, causing an above band gap emission in K/g-C 3 N 4 and Mg/g-C 3 N 4 . All samples degraded methylene blue (MB) under visible light with outstanding results, but they responded poorly to methyl orange (MO) and rhodamine B (RhB). With 83.59% MB degradation at a rate constant of 1.1 × 10 −2 min −1 , Mg/g-C 3 N 4 recorded the best PC, which was three times quicker than g-C 3 N 4 (3.7 × 10 −3 min −1 ). When compared to g-C 3 N 4 , the doped samples’ current density (both anodic and cathodic) and carrier density were almost two times greater. The mechanism demonstrated how active edge sites, defects, and dopants contributed to the remarkable PC activity in the doped samples.