The effect of valence state and site geometry on Cr L3,2 electron energy-loss spectra of Cr-bearing oxidic compounds

Chromium L-3,L-2 energy loss near-edge structures (ELNES) of nine chromium compounds were measured in a transmission electron microscope to study the effect of valence state and site geometry of chromium on spectral features. The compounds studied represent a set of standards with given valence state and coordination. The chromium coordination is either octahedral or tetrahedral with different degree of distortion. The distortion of polyhedra results in a loss of the fine detail of spectral features in Cr L-3,L-2 ELNES spectra. The effect of valence state manifests in a systematic chemical shift of the ELNES spectra by about 2 eV per oxidation state for octahedrally coordinated Cr and 0.4-1.4 eV per oxidation state for tetrahedrally coordinated Cr. On the basis of collected Cr L-3,L-2 ELNES spectra we propose a simple quantification technique for the determination of chromium oxidation state in oxidic compounds which is independent of the coordination. (C) 2014 Elsevier GmbH. All rights reserved.