Quantitative, Spectro-kinetic Analysis of Oxygen in Electron-Beam Sensitive, Multimetallic Oxide Nanostructures

The oxygen stoichiometry of hollandite, KxMnO2-δ, nanorods has been accurately determined from a quantitative analysis of scanning-transmission electron microscopy (STEM) X-Ray Energy Dispersive Spectroscopy (XEDS) experiments carried out in chrono-spectroscopy mode. A methodology combining 3D reconstructions of high-angle annular dark field electron tomography experiments, using compressed-sensing algorithms, and quantification through the so-called ζ-factors method of XEDS spectra recorded on a high-sensitivity detector has been devised to determine the time evolution of the oxygen content o... Mehr ...

Verfasser: López Haro, Miguel
Gómez-Recio, Isabel
Pan, Huiyan
Delgado Jaén, Juan José
Chen, Xiaowei
Cauqui López, Miguel Ángel
Pérez Omil, José Antonio
Ruiz-González, María Luisa
Hernando, María
Parras, Marina
González-Calbet, José M.
Calvino Gámez, José Juan
Dokumenttyp: journal article
Erscheinungsdatum: 2024
Verlag/Hrsg.: Oxford University Press
Schlagwörter: chrono-spectroscopy-electron tomographycombination / electron-beam sensitive materials / oxygen stoichiometry / potassium-manganese hollandites / quantitative XEDS at nanoscale
Sprache: Englisch
Permalink: https://search.fid-benelux.de/Record/base-28675690
Datenquelle: BASE; Originalkatalog
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Link(s) : http://hdl.handle.net/10498/32577

The oxygen stoichiometry of hollandite, KxMnO2-δ, nanorods has been accurately determined from a quantitative analysis of scanning-transmission electron microscopy (STEM) X-Ray Energy Dispersive Spectroscopy (XEDS) experiments carried out in chrono-spectroscopy mode. A methodology combining 3D reconstructions of high-angle annular dark field electron tomography experiments, using compressed-sensing algorithms, and quantification through the so-called ζ-factors method of XEDS spectra recorded on a high-sensitivity detector has been devised to determine the time evolution of the oxygen content of nanostructures of electron-beam sensitive oxides. Kinetic modeling of O-stoichiometry data provided K0.13MnO1.98 as overall composition for nanorods of the hollandite. The quantitative agreement, within a 1% mol error, observed with results obtained by macroscopic techniques (temperature-programmed reduction and neutron diffraction) validate the proposed methodology for the quantitative analysis, at the nanoscale, of light elements, as it is the case of oxygen, in the presence of heavy ones (K, Mn) in the highly compromised case of nanostructured materials which are prone to electron-beam reduction. Moreover, quantitative comparison of oxygen evolution data measured at macroscopic and nanoscopic levels allowed us to rationalize beam damage effects in structural terms and clarify the exact nature of the different steps involved in the reduction of these oxides with hydrogen.