A novel method to introduce acidic and basic bi-functional sites in graphitic carbon nitride for sustainable catalysis: cycloaddition, esterification, and transesterification reactions

Abstract

Graphitic carbon nitride was prepared using urea, thiourea, and a mixture of urea–thiourea. Functional carbon nitride was prepared by reacting g-C3N4 with aqueous H2SO4. Characterizations revealed that bifunctional acidic (–SO3H) and basic (–NH2) sites were introduced after the aqueous H2SO4 treatment. The characterizations also revealed that the surface acidity and basicity were influenced by the concentration of aqueous H2SO4 solution. A detailed characterization of the catalyst was made using a complementary combination of powder X-ray diffraction, N2 adsorption–desorption, scanning/ transmission electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, elemental analysis, and X-ray photoelectron spectroscopy. Furthermore, the bi-functional nature (acidity/basicity) of the catalyst was investigated with NH3 and CO2 temperature-programmed desorption techniques. The activation and utilization of CO2 in the synthesis of cyclic carbonates and quinazoline-2,4(1H,3H)-dione over bi-functional graphitic carbon nitride was investigated. Kinetic and thermodynamic parameters (such as k, Ea, DH, DG, and DS) were calculated for the cycloaddition reaction of CO2 to epichlorohydrin by varying the reaction parameters. Graphitic carbon nitride (prepared with urea–thiourea) treated with 60 wt% aqueous H2SO4 exhibited the highest catalytic activity and selectivity in the synthesis of cyclic carbonates and quinazoline-2,4(1H,3H)-dione. The catalyst was easily recovered and recycled with negligible loss of activity. In addition, the catalyst exhibited significantly high activity in the transesterification reaction of cyclic carbonate with methanol and the esterification reaction of oleic acid with methanol. The uniqueness of this study is the introduction of bifunctional (acid–base) sites by treating g-C3N4 with aqueous sulfuric acid, which was confirmed using NH3 and CO2 temperature-programmed desorption techniques and the various other physico-chemical characterization techniques mentioned above. Due to its simple and economical synthesis procedure, tuneable functional sites, efficient recyclability, and diverse catalytic activity, this catalyst is highly attractive for sustainable catalysis