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- Atomic layer deposition (1)
- Bimetallic noble metal nanoparticles (1)
- Electrolysis (1)
- Electronic structure (1)
- Ferrihydrite (1)
- Hematite (1)
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Organisationseinheit der BAM
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.
The oxides, hydroxides, and oxo-hydroxides of iron belong to the most abundant materials on earth. They also feature a wide range of practical applications. In many environments, they can undergo facile phase transformations and crystallization processes.
Water appears to play a critical role in many of these processes. Despite numerous attempts, the role of water has not been fully revealed yet. We present a new approach to study the influence of water in the crystallization and phase transformations of iron oxides.
The approach employs model-type iron oxide films that comprise a defined homogeneous nanostructure. The films are exposed to air containing different amounts of water reaching up to pressures of 10 bar. Ex situ analysis via scanning electron microscopy, Transmission electron microscopy, selected area electron diffraction, and X-ray diffraction is combined with operando near-ambient pressure X-ray photoelectron spectroscopy to follow water-induced changes in hematite nd ferrihydrite. Water proves to be critical for the nucleation of ematite domains in ferrihydrite, the resulting crystallite orientation, and the underlying crystallization mechanism.
Hydrogen features a very high specific energy density and is therefore a promising candidate for clean fuel from renewable resources. Water electrolysis can convert electrical energy into storable and transportable hydrogen gas. Under acidic conditions, platinum is the most active and stable monometallic catalyst for the hydrogen evolution reaction (HER). Yet, platinum is rare and needs to be used efficiently. Here, we report a synthesis concept for colloidal bimetallic platinum–ruthenium and rhodium–ruthenium nanoparticles (PtRuNP, RhRuNP) and their incorporation into ordered mesoporous carbon (OMC) films. The films exhibit high surface area, good electrical conductivity and well-dispersed nanoparticles inside the mesopores. The nanoparticles retain their size, crystallinity and composition during carbonization. In the hydrogen evolution reaction (HER), PtRuNP/OMC catalyst films show up to five times higher activity per Pt than Pt/C/Nafion® and PtRu/C/Nafion® reference catalysts.
Detection of the electronic structure of iron-(III)-oxo oligomers forming in aqueous solutions
(2017)
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.
The stabilization of crystal phases and nanostructured morphologies is an essential topic in application-driven design of mesoporous materials. Many applications, e.g. catalysis, require high temperature and humidity. Typical metal oxides transform under such conditions from a metastable, low crystal-line material into a thermodynamically more favorable form, i.e. from ferrihy-drite into hematite in the case of iron oxide. The harsh conditions induce also
a growth of the crystallites constituting pore walls, which results in sintering and finally collapse of the porous network. Herein, a new method to stabi-lize mesoporous templated metal oxides against sintering and pore collapse is reported. The method employs atomic layer deposition (ALD) to coat the internal mesopore surface with thin layers of either alumina or silica. The authors demonstrate that silica exerts a very strong influence: It shifts hematite formation from 400 to 600 °C and sintering of hematite from 600 to 900 °C.
Differences between the stabilization via alumina and silica are rationalized by a different interaction strength between the ALD material and the ferrihydrite film.
The presented approach allows to stabilize mesoporous thin films that require a high crystallization temperature, with submonolayer quantity of an ALD material, and to apply mesoporous materials for high temperature applications.