TY - JOUR A1 - Kraffert, K. A1 - Kabelitz, Anke A1 - Siemensmeyer, K. A1 - Schmack, R. A1 - Bernsmeier, D. A1 - Emmerling, Franziska A1 - Kraehnert, R. T1 - Nanocasting of superparamagnetic iron oxide films with ordered mesoporosity N2 - Maghemite and magnetite show superparamagnetic behavior when synthesized in a nanostructured form. The material’s inducible magnetization enables applications ranging from contrast enhancing agents for magnetic resonance imaging to drug delivery systems, magnetic hyperthermia, and separation. Superparamagnetic iron oxides with templated porosity have been synthesized so far only in the form of hard-templated powders, where silicon retained from the template severely degrades the material’s magnetic properties. Here, for the first time, the synthesis of superparamagnetic iron oxides with soft-templated mesopore structure is reported. The synthesis of nanostructured maghemite and magnetite films succeeds using micelles of amphiphilic block-copolymers as templates. A thermal treatment of the initially formed mesoporous ferrihydrite in nitrogen produces maghemite, which can be partly reduced to magnetite via thermal treatment in hydrogen while retaining the templated mesopore structure. The resulting materials feature a unique combination of high surface area, controlled pore diameter, and tunable magnetic properties. KW - Iron oxide films KW - Mesoporosity KW - Soft-templated PY - 2018 U6 - https://doi.org/10.1002/admi.201700960 SN - 2196-7350 VL - 5 IS - 3 SP - 1700960, 1 EP - 1700960, 7 PB - Wiley-VCH CY - Weinheim AN - OPUS4-43560 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Seidel, R. A1 - Kraffert, K. A1 - Kabelitz, Anke A1 - Pohl, M.N. A1 - Kraehnert, R. A1 - Emmerling, Franziska A1 - Winter, B. T1 - Detection of the electronic structure of iron-(III)-oxo oligomers forming in aqueous solutions N2 - The nature of the small iron-oxo oligomers in iron-(III) aqueous solutions has a determining effect on the chemical processes that govern the formation of nanoparticles in aqueous phase. Here we report on a liquid-Jet photoelectron-spectroscopy experiment for the investigation of the electronic structure of the occurring iron-oxo oligomers in FeCl3 aqueous solutions. The only iron species in the as-prepared 0.75 M solution are Fe3+ monomers. Addition of NaOH initiates Fe3+ hydrolysis which is followed by the formation of iron-oxo oligomers. At small enough NaOH concentrations, corresponding to approximately [OH]/[Fe] = 0.2–0.25 ratio, the iron oligomers can be stabilized for several hours without engaging in further aggregation. Here, we apply a combination of non-resonant as well as iron 2p and Oxygen 1s resonant photoelectron spectroscopy from a liquid microjet to detect the electronic structure of the occurring species. Specifically, the oxygen 1s partial electron yield X-ray absorption (PEY-XA) spectra are found to exhibit a peak well below the onset of liquid water and OH (aq) absorption. The iron 2p absorption gives rise to signal centered between the main absorption bands typical for aqueous Fe3+. Absorption bands in both PEY-XA spectra are found to correlate with an enhanced photoelectron Peak near 20 eV binding energy, which demonstrates the sensitivity of resonant photoelectron (RPE) spectroscopy to mixing between iron and ligand orbitals. These various signals from the iron-oxo oligomers exhibit Maximum intensity at [OH]/[Fe] = 0.25 ratio. For the same ratio, we observe changes in the pH as well as in complementary Raman spectra, which can be assigned to the Transition from monomeric to oligomeric species. At approximately [OH]/[Fe] = 0.3 we begin to observe particles larger than 1 nm in radius, detected by small-angle X-ray scattering. KW - Iron-oxo oligomers KW - XPS KW - Electronic structure PY - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-433468 SN - 1463-9076 SN - 1463-9084 VL - 19 IS - 48 SP - 32226 EP - 32234 AN - OPUS4-43346 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -