Mechanistic investigations on emission characteristics from g-C3N4, gC3N4@Pt and g-C3N4@Ag nanostructures using X-ray absorption spectroscopy

An improved method for the preparation of g-$C_3N_4$ is described. Currently, heating (> $400^{\circ}C$) of urea is the common method used for preparing the g-$C_3N_4$. We have found that sonication of melamine in $HNO_3$ solution, followed by washing with anhydrous ethanol, not only reduce the crystallite size of g-$C_3N_4$ but also facilitate intriguing electronic structure and photoluminescence (PL) properties. Moreover, loading of metal (Pt and Ag) nanoparticles, by applying the borohydride reduction method, has resulted in multicolor-emission from g-$C_3N_4$. With the help of PL spectra and local electronic structure study, at C K-edge, N K-edge, Pt L-edge and Ag K-edge by X-ray absorption spectroscopy (XAS), a precise mechanism of tunable luminescence is established. The PL mechanism ascribes the amendments in the transitions, via defect and/or metal states assimilation, between the ${\pi}^*$ states of tris-triazine ring of g-$C_3N_4$ and lone pair states of nitride. It is evidenced that interaction between the C/N 2p and metal 4d/5d orbitals of Ag/Pt has manifested a net detraction in the ${\delta}^*{\rightarrow}LP$ transitions and enhancement in the ${\pi}^*{\rightarrow}LP$ and ${\pi}^*{\rightarrow}{\pi}$ transitions, leading to broad PL spectra from g-$C_3N_4$ organic semiconductor compound.