Gadolinium modified g-C3N4 for S-Scheme heterojunction with monoclinic-WO3: Insights from DFT studies and related charge carrier dynamics

Abstract

Modifying the surface structures of g-C3N4 through interfacial coupling with other semiconductors has been spotlighted as an efficient approach for improving photocatalytic efficiency. With the surge of S-scheme heterojunctions, the research is intensified towards designing this kind of composite for energy-environmental-related applications. In this context, a new approach involving surface modifications of g-C3N4 through Gd species and integrating with monoclinic-WO3 via a wet chemical approach to form S-scheme heterojunctions is investigated. The characterization results attested that the adopted protocol promotes the better dispersion of Gd species over the g-C3N4 surface and rigidly integrates with WO3. The optical response of the composite spanned a significant portion of the visible region in the solar spectrum. The computational studies and the findings of the Mott-Schottky plot collectively suggested that the position of band edges qualifies for the formation of S-scheme heterojunction. The results derived from photocurrent response measurements and photoluminescence technique attribute to the effective charge carrier separation in the heterostructure. The rate constant of Gd-g-C3N4/WO3 was 1.48 × 10−2 min−1 which was approximately 4.35 and 2.27 times greater than that of WO3 (0.34 × 10−2 min−1) and g-C3N4/WO3 (0.65 × 10−2 min−1) respectively. Furthermore, RhB degradation in the presence of scavengers validated the participation of superoxide and hydroxyl radicals in the degradation mechanisms. This was possible only when the conduction band electrons of WO3 recombined with the valence band holes of Gd-modified g-C3N4. The present work helps to understand the S-scheme heterojunction formation between surface-modified g-C3N4 and metal oxides and retain the involvement of energetic charge carriers in the desired redox reactions.