Revisiting structural and photocatalytic properties of g-C3N4/TiO2: Is surface modification of TiO2 by calcination with urea an effective route to “solar” photocatalyst?

Abstract

g-C3N4/TiO2 derived from the surface modification of TiO2 by calcination with urea has been widely studied as a “visible-light-active” photocatalyst for environmental remediation. However, few attentions have been paid to the structure characterization and the photocatalytic properties of the resultant nanocomposite photocatalysts under a practical sunlight irradiation. Here we employ various characterization techniques, including TGA, XRD, TEM, XPS, UV–vis spectrum, and N2-sorption analysis to characterize the evolutions in phase crystal structure, microstructure and optical properties of g-C3N4/TiO2 nanohybrids synthesized through calcining a mechanical mixture of urea and Evonik Aeroxide P-25 TiO2 (P25) at 350–500 °C. The thermal pyrolysis of urea leads to the surface decoration of TiO2 with graphitic carbon nitrate (g-C3N4) at temperatures above 400 °C. The photocatalytic properties of the resultant g-C3N4/TiO2 nanoparticles are evaluated through photocatalytic decoloration of methylene blue (MB) and reduction of Cr (VI) to Cr (III) under visible (420 nm), UV (365 nm), and simulated solar light irradiations. The nanohybrid photocatalysts, as most previous studies reported, show much higher photocatalytic activity under visible light irradiation than the single-component counterparts, i.e. P25 or g-C3N4. However, under solar and UV irradiation, no considerable improvements are found, which is caused by the decrease in redox potential upon interfacial charge carrier transfer between g-C3N4 and TiO2. Moreover, g-C3N4/TiO2 shows an ultralow photocatalytic activity in Cr (VI) reduction. The surface modification with organic g-C3N4 is assumed to tune the surface properties (e.g. hydrophilicity) of TiO2. Our results demonstrate that photocatalytic activity in UV range is as important as that in visible range, and developing efficient “solar” photocatalysts should balance the photocatalytic activities at both ranges since they might be incompatible with each other.