Photoactive Zr-aromatic hybrid thin films made by molecular layer deposition.

The principle of antimicrobial photodynamic therapy (PDT) is appealing because it can be controlled by an external light source and possibly the use of durable materials. However, to utilise such surfaces requires a process for their production that allows for coating on even complex geometries. We have therefore explored the ability of the emerging molecular layer deposition (MLD) technique to produce and tune PDT active materials. This study demonstrates how the type of aromatic ligand influences the optical and antimicrobial properties of photoactive Zr-organic hybrid thin films made by MLD. The three aromatic dicarboxylic acids: 2,5-dihydroxy-1,4-benzenedicarboxylic acid, 2-amino-1,4-benzenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid have been combined with ZrCl4 to produce hybrid coatings. The first system has not been previously described by MLD and is therefore more thoroughly investigated using in situ quartz crystal microbalance (QCM), Fourier transform infrared (FTIR) and UV-Vis spectroscopy. The antibacterial phototoxic effects of Zr-organic hybrids have been explored in the Staphylococcus aureus bacteria model using a UVA/blue light source. Films based on the 2,6-naphthalenedicarboxylic acid linker significantly reduced the number of viable bacteria by 99.9%, while no apparent activity was observed for the two other photoactive systems. Our work thus provides evidence that the MLD technique is a suitable tool to produce high-quality novel materials for possible applications in antimicrobial PDT, however it requires a careful selection of aromatic ligands used to construct photoactive materials.

Molecular layer deposition of photoactive metal-naphthalene hybrid thin films.

We here report on photoactive organic-inorganic hybrid thin films prepared by the molecular layer deposition (MLD) method. The new series of hybrid films deposited using 2,6-naphthalenedicarboxylic acid (2,6-NDC) and either hafnium chloride (HfCl4), yttrium tetramethylheptanedionate (Y(thd)3) or titanium chloride (TiCl4) were compared with the known zirconium chloride (ZrCl4) based system. All metal-naphthalene films are amorphous as-deposited and show self-saturating growth as expected for an ideal MLD process with varied growth rates depending on the choice of metal precursor. The growth was studied in situ using quartz crystal microbalance (QCM) and the films were further characterised using spectroscopic ellipsometry (SE), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and UV-Vis and photoluminescence (PL) spectroscopy to obtain information on their physicochemical properties. The hybrid thin films display intense blue photoluminescence, except for the Ti-organic complex in which titanium clusters were found to be an effective PL quencher for the organic linker. We demonstrate how the optical properties of the films depend on the choice of metal component to make a foundation for further studies on these types of organic-inorganic hybrid materials for applications as photoactive agents.

Real Time 3D Observations of Portland Cement Carbonation at CO2 Storage Conditions.

Depleted oil reservoirs are considered a viable solution to the global challenge of CO2 storage. A key concern is whether the wells can be suitably sealed with cement to hinder the escape of CO2. Under reservoir conditions, CO2 is in its supercritical state, and the high pressures and temperatures involved make real-time microscopic observations of cement degradation experimentally challenging. Here, we present an in situ 3D dynamic X-ray micro computed tomography (µ-CT) study of well cement carbonation at realistic reservoir stress, pore-pressure, and temperature conditions. The high-resolution time-lapse 3D images allow monitoring the progress of reaction fronts in Portland cement, including density changes, sample deformation, and mineral precipitation and dissolution. By switching between flow and nonflow conditions of CO2-saturated water through cement, we were able to delineate regimes dominated by calcium carbonate precipitation and dissolution. For the first time, we demonstrate experimentally the impact of the flow history on CO2 leakage risk for cement plugging. In-situ µ-CT experiments combined with geochemical modeling provide unique insight into the interactions between CO2 and cement, potentially helping in assessing the risks of CO2 storage in geological reservoirs.

Novel Montmorillonite/TiO2/MnAl-Mixed Oxide Composites Prepared from Inverse Microemulsions as Combustion Catalysts.

A novel design of combustion catalysts is proposed, in which clay/TiO2/MnAl-mixed oxide composites are formed by intermixing exfoliated organo-montmorillonite with oxide precursors (hydrotalcite-like in the case of Mn-Al oxide) obtained by an inverse microemulsion method. In order to assess the catalysts' thermal stability, two calcination temperatures were employed: 450 and 600 °C. The composites were characterized with XRF (X-ray fluorescence), XRD (X-ray diffraction), HR SEM (high resolution scanning electron microscopy, N2 adsorption/desorption at -196 °C, and H2 TPR (temperature programmed reduction). Profound differences in structural, textural and redox properties of the materials were observed, depending on the presence of the TiO2 component, the type of neutralization agent used in the titania nanoparticles preparation (NaOH or NH3 (aq)), and the temperature of calcination. Catalytic tests of toluene combustion revealed that the clay/TiO2/MnAl-mixed oxide composites prepared with the use of ammonia showed excellent activity, the composites obtained from MnAl hydrotalcite nanoparticles trapped between the organoclay layers were less active, but displayed spectacular thermal stability, while the clay/TiO2/MnAl-mixed oxide materials obtained with the aid of NaOH were least active. The observed patterns of catalytic activity bear a direct relation to the materials' composition and their structural, textural, and redox properties.