Atomic Resolution Electron Microscopy: A Key Tool for Understanding the Activity of Nano-Oxides for Biomedical Applications.

Transition metal oxides constitute one of the most fruitful sources of materials with continuously increasing potential applications prompted by the expectations derived from the reduction of the particle size. The recent advances in transmission electron microscopy, because of the development of lenses, have made it possible to reach atomic resolution, which can provide answers regarding the performance of the transition metal nano-oxides. This critical information is related not only to the ability to study their microstructural characteristics but also their local composition and the oxidation state of the transition metal. Exploring these features is a well-known task in nano-oxides for energy and electronic technologies, but they are not so commonly used for elucidating the activity of these oxides for biomedical applications. Nevertheless, the identification at the atomic level of a certain dopant or the unambiguous determination of the oxidation state of a transition metal in a nano-oxide can be important questions to be answered in a certain biomedical application. In this work, we provide several examples in transition metal nano-oxides to show how atomic-resolution electron microscopy can be a key tool for its understanding.

Exceptional Low-Temperature CO Oxidation over Noble-Metal-Free Iron-Doped Hollandites: An In-Depth Analysis of the Influence of the Defect Structure on Catalytic Performance.

A family of iron-doped manganese-related hollandites, K x Mn1-y Fe y O2-δ (0 ≤ y ≤ 0.15), with high performance in CO oxidation have been prepared. Among them, the most active catalyst, K0.11Mn0.876Fe0.123O1.80(OH)0.09, is able to oxidize more than 50% of CO at room temperature. Detailed compositional and structural characterization studies, using a wide battery of thermogravimetric, spectroscopic, and diffractometric techniques, both at macroscopic and microscopic levels, have provided essential information about this never-reported behavior, which relates to the oxidation state of manganese. Neutron diffraction studies evidence that the above compound stabilizes hydroxyl groups at the midpoints of the tunnel edges as in isostructural ß-FeOOH. The presence of oxygen and hydroxyl species at the anion sublattice and Mn3+, confirmed by electron energy loss spectroscopy, appears to play a key role in the catalytic activity of this doped hollandite oxide. The analysis of these detailed structural features has allowed us to point out the key role of both OH groups and Mn3+ content in these materials, which are able to effectively transform CO without involving any critical, noble metal in the catalyst formulation.

Unambiguous localization of titanium and iron cations in doped manganese hollandite nanowires.

New insights into the chemical and structural features of iron or titanium-doped KxMnO2 hollandites are reported. Neutron diffraction and atomically resolved transmission electron microscopy elucidate the localization of the dopant cations that could be one of the key factors governing the functional activity of these nanomaterials.