Synergistic adsorption and kinetic studies of heterostructured g-C3N4/TiO2 nano-photocatalyst under visible light for enhanced CO2 reduction.

Abstract

Graphitic carbon nitride (g-C3N4) and titanium dioxide (TiO2) were synthesized using sol-gel and ultrasonic impregnation technique followed by calcination for photocatalytic CO2 reduction. The nano-photocatalysts were analyzed for their morphological, structural, and optical characteristics. Scanning electron microscopy (SEM) revealed the presence of spherical and layered sheet-like nanoparticles, as well as the occurrence of minor aggregations. The ultraviolet-visible spectroscopy (UV-vis) revealed that g-C3N4 has good photocatalytic properties with a medium band gap (2.7eV), and TiO2 has high charge transfer potentials, robust oxidation properties, and high band gap (3.20eV). However, the larger band gap makes it unresponsive in the visible light spectrum. In order to circumvent this constraint, a hybrid heterostructured g-C3N4/TiO2 catalyst with different compositions, viz., 1:1, 1:2, and 2:1, were fabricated using the ultrasonic impregnation technique followed by calcination process. The optical band gap of g-C3N4/TiO2 nanocomposite shows a red shift towards 2.85eV from 3.20eV for bare TiO2, inferring enhanced absorption in the visible light region. Further, the photocatalytic experiments were performed using visible light sources for all the catalysts. The g-C3N4/TiO2 (2:1) reported higher photocatalytic activity due to its reduced crystallite size of 12.94nm which were investigated using X-ray diffraction analysis (XRD) and lower band gap of 2.85eV. The study infers that hybrid photocatalyst enhances the visible light absorption, electron-hole (e - /h +) pair separation rate, and photocatalytic reduction of CO2. In addition, two adsorption models Langmuir and Freundlich were used and adsorption kinetic data were fitted to pseudo-first-orderreaction for all thefive catalysts. The adsorption isotherm of CO2 by g-C3N4/TiO2 (2:1) wellfitted by the Freundlich adsorption equation. On the basis of adsorption magnitude (n) values (1.74), it was found that the interaction between CO2 molecules and g-C3N4/TiO2 occurs according to the chemisorption mechanism. The kinetic study infers that the highest value of apparent rate constant (kapp) was exhibited by g-C3N4/TiO2 (2:1), which indicates that the products predominate at equilibrium.