Oxidation State and Local Structure of Chromium Ions in LaOCl

Materials (Basel). 2021 Jun 25;14(13):3539. doi: 10.3390/ma14133539.

Abstract

LaOCl doped with 0-10 mol% Cr was synthesized by thermal decomposition of chlorides. X-ray diffraction (XRD) analysis revealed that incorporation of chromium results in a decrease of the lattice parameter a and a simultaneous increase of the lattice parameter c. The local structure of chromium ions was studied with X-ray photoelectron (XPS), X-ray absorption (XANES), multifrequency electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy techniques. It was determined that synthesis in oxidizing atmosphere promotes the incorporation of chromium ions predominantly in the 5+ oxidation state. Changes of chromium oxidation state and local environment occur after a subsequent treatment in reducing atmosphere. Spin-Hamiltonian (SH) parameters for a Cr5+ and two types of Cr3+ centers in LaOCl were determined from the EPR spectra simulations.

Keywords: LaOCl; X-ray absorption spectroscopy; X-ray photoelectron spectroscopy (XPS); chromium; electron paramagnetic resonance (EPR); electron-nuclear double resonance (ENDOR).