Minimizing electron-hole pair recombination through band-gap engineering in novel ZnO-CeO-rGO ternary nanocomposite for photoelectrochemical and photocatalytic applications.

A novel ZnO-CeO-rGO (ZCG) ternary nanocomposite with varying ZnO/CeO weight proportions was synthesized by a hydrothermal process for photoelectrochemical water splitting and photocatalytic application. XRD diffraction peaks of ZCG nanocomposites displayed the patterns of ZnO and CeO nanoparticles, and SEM revealed irregular flake-like particles, which were uniformly decorated on the rGO matrix. Increase in the intensity ratio of D and G bands from Raman spectra revealed changes in oxygen bonding in the ZnO-rGO (ZG) and ZCG nanocomposites. The shift in the band edge positions and the decrease in the band gap with increase in the cerium oxide content in ZCG composites were observed from UV-Vis and Mott-Schottky plots. XPS results showed that Ce fraction increased with an increase in the cerium oxide content in ZCG nanocomposites. The ZCG3 (85:15) nanocomposite exhibited decreased electron-hole recombination rate as evidenced from the photoluminescence and electrochemical impedance spectroscopy Nyquist plots. The characteristic frequency in Bode's plot shifted to a lower frequency for the ZCG3 electrode demonstrating low interfacial charge transfer resistance, and ZCG3 photoelectrode displayed a higher photocurrent density of 0.69 mA/cm at 1.5 V compared with other photoelectrode. The optimized and highly efficient ZCG3 nanocomposite exhibited improved photocatalytic degradation of methylene blue (MB) with a reaction rate constant of 0.0201 min. Combination of defects in the form of Ce ion and surface oxygen vacancies coupled with rGO as the electron acceptor improved the charge carrier density and carrier transport in addition to the formation Schottky-type junction and the presence of an internal electric field.