Authors
Christian Heinekamp, C Tufan Cakir, Ana Guilherme Buzanich, Konstantin Klementiev, Michael Roemelt, Thomas Braun, Franziska Emmerling
Published in
Physical chemistry chemical physics : PCCP. Oct 20, 2026. Epub Oct 20, 2026.
Abstract
Valence-to-core (VtC) X-ray emission spectroscopy (XES) is a powerful probe for the local electronic structure in transition-metal materials, but its potential for 4d metals such as zirconium remains largely unexplored. Here, we demonstrate that non-resonant Zr Kβ VtC XES provides quantitative descriptors that are sensitive to ligand chemistry, by probing fluorine- and oxygen-based coordination environments in well-defined and catalytically relevant Zr compounds. High-resolution X-ray emission spectra containing Zr-Kβ2 and -Kβ4 are recorded for a series of reference systems (ZrO2, ZrF4, ZrF4·H2O, ZrCl4, Zr(acac)4, Zr metal) and for Zr fluoride materials, and are analysed using quantitative line-shape parameters. Projected densities of states (PDOS) obtained from FDMNES calculations reveal that fluorine coordination enhances the Kβ″ contribution and induces characteristic changes in Kβ2 intensity and asymmetry compared to oxygen and chlorine ligands. These ligand-specific spectral signatures enable a systematic discrimination between F- and O-containing coordination spheres, even when conventional X-ray absorption or diffraction techniques provide limited contrast. This combined experimental-computational framework demonstrates that Zr Kβ VtC XES can resolve subtle ligand-dependent coordination changes in Zr-based materials, offering a general route to identify active structures in C-F bond activation and oxygen-evolution catalysis.
PMID:
42898037
Bibliographic data and abstract were imported from PubMed on 20 Oct 2026.
Read full publication at:
Please sign in
to see all details.
Advertisement
Stats
- Recommendations n/a n/a positive of 0 vote(s)
- Views 13
- Comments 0