Influence of RE (Pr3+, Er3+, Nd3+) doping on structural, vibrational and enhanced persistent photocatalytic properties of ZnO nanostructures

Spectrochim Acta A Mol Biomol Spectrosc. 2022 Mar 5:268:120679. doi: 10.1016/j.saa.2021.120679. Epub 2021 Nov 30.

Abstract

Rare earth (RE- Pr, Er and Nd) doped ZnO nanostructures were prepared through simple wet chemical precipitation route. The RE doping induced interesting morphological transition from spherical to flower like structures were analyzed. The X-ray diffraction (XRD) measurements revealed that the prepared materials were of highly crystalline in nature and RE dopant ions did not altered the crystal structure of ZnO. The microstrain of ZnO was altered with respect to the nature of dopants. In the case of the Pr doped ZnO, X-ray photoelectron spectroscopy (XPS) analysis confirmed that the dopant (Pr) ions successfully substituted in the ZnO lattice. Raman spectra revealed RE doping induced lower energy side shift and variation in intensity of the peaks related to the characteristic phonon modes of ZnO. In the case of Nd doped ZnO nanostructures, dopant induced suppression in classical Raman modes and evolution of multiphonon related modes were identified. Optical diffuse reflectance spectral (DRS) measurements, along with the characteristic excitonic band of ZnO, other bands associated to the transitions of 4f energy levels related to the RE ions were observed. The partially filled 4f orbitals led to the enhanced photocatalytic activity in RE doped ZnO nanostructures. The observed enhanced photocatalytic activity in RE doped ZnO when compared to bare ZnO was discussed. The decolorization efficiency of MB ensued the following order 96 > 94 > 86 > 78% for ZnErO, ZnNdO, ZnPrO and ZnO, respectively.

Keywords: Methylene blue; Microstructure; Multiphonons; Photocatalysis; RE doped ZnO; Raman spectroscopy.