Molten salt assistant synthesis of three-dimensional cobalt doped graphitic carbon nitride for photocatalytic N2 fixation: Experiment and DFT simulation analysis

Abstract In this work, three-dimensional cobalt doped graphitic carbon nitride was synthesized by molten salt assistant method. XRD, N2 adsorption, SEM, XPS, UV–Vis spectroscopy, N2-TPD and Photoluminescence were used to characterize the prepared catalysts. The result shows that the addition of molten salt remarkably changes the morphology of as-prepared catalyst. Cobalt exists as coordinative Co-N bond, which can chemisorb and activate N2 molecules, and promote the electron transfer from catalyst to the nitrogen molecules. The as-prepared cobalt doped g-C3N4 displays the NH4+ production rate of 5.8 mg·L−1·h−1·gcat−1, which is 24 times of bulk g-C3N4. Density functional theory (DFT) simulations show that cobalt doping can not only prolong N N bond which activate N2 molecules, but promote the electrons-holes separation efficiency of g-C3N4. The d orbit of cobalt easily acts as a channel for transferring electrons from the transition metal to the N2 molecule, which enhances the N2 photofixation ability.