Synergistically enhanced photocatalytic properties of Co3O4-G/GO nanocomposites: unravelling their interactions and charge-transfer dynamics using XAS.

Metal oxide composites with graphene/graphene oxide have increasingly gained popularity in enhancing the photocatalytic degradation of several existing harmful dyes. Moreover, identifying the role of carbon networks and their interactions in composite formation would assist in the design and development of photocatalysts. In the present study, we investigated the role of carbon networks in improving photocatalytic properties. Electronic structure analysis of cobalt oxide-graphene (C2)/graphene oxide (C3) nanocomposites using XAS suggested possible charge transfer from cobalt oxide nanoparticles to the carbon network during composite formation. The photocatalytic degradation of C3 towards phenol dye (1 × 10-3 M) was >50% and improved the degradation rate with k = 0.231 h-1.In the quest to understand the mechanism unfolding on its surface, in situ XAS under UV-visible irradiation was performed, which shed light on delayed excitonic recombination in the synthesized nanocomposites. This enabled hydroxy radicals (˙OH) to play a preeminent role in the cleavage of the phenol ring and its intermediaries. Based on these observations, a detailed mechanism for charge transfer occurring during nanocomposite formation and the mechanism involved in the enhanced photocatalytic activity of the nanocomposite photocatalyst towards phenol degradation under the influence of UV-visible irradiation are discussed.

Probing size-dependent defects in zinc oxide using synchrotron techniques: impact on photocatalytic efficiency.

In the present study, synchrotron-based X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS) and X-ray excited optical luminescence (XEOL) have been used to investigate the induced defect states in metal oxide nanomaterials. Specifically, two synthesis approaches have been followed to develop unique nano-sized peanut-shaped (N-ZnO) nanostructures and micron-sized hexagonal rods (M-ZnO). XANES analysis at the Zn K-edge revealed the presence of defect states with a divalent oxidation state of zinc (Zn2+) in a tetrahedral structure. Furthermore, XAS measurements performed at the Zn L3,2-edge and O K-edge confirm higher oxygen-related defects in M-ZnO, while N-ZnO appeared to have a higher concentration of surface defects due to size confinement. Moreover, the in-line XEOL and time dependent-XEOL measurements exposed the radiative excitonic recombination phenomena occurring in the band-tailing region as a function of absorption length, X-ray energy excitation, and time. Based on the chronology developed in the defect state improvement, a possible energy band diagram is proposed to accurately locate the defect states in the two systems. Furthermore, the increased absorption intensity at the Zn L3,2-edge and the O K-edge under the UV lamp suggests delayed recombination of electrons and holes, highlighting their potential use as photo catalysts. The photocatalytic activity degrading the rhodamine B dye established M-ZnO as a superior catalyst with a rapid degradation rate and significant mineralization. Overall, this work provides valuable insights into ZnO defect states and provides a foundation for efficient advanced materials for environmental or other optoelectronic applications.