William Larsson

Nitrogen-Doped Anatase Nanofibers Decorated with Noble Metal Nanoparticles for Photocatalytic Production of Hydrogen

We report the synthesis of N-doped TiO(2) nanofibers and high photocatalytic efficiency in generating hydrogen from ethanol-water mixtures under UV-A and UV-B irradiation. Titanate nanofibers synthesized by hydrothermal method are annealed in air and/or ammonia to achieve N-doped anatase fibers. Depending on the synthesis route, either interstitial N atoms or new N-Ti bonds appear in the lattice, resulting in slight lattice expansion as shown by XPS and HR-TEM analysis, respectively. These nanofibers were then used as support for Pd and Pt nanoparticles deposited with wet impregnation followed by calcination and reduction. In the hydrogen generation tests, the N-doped samples were clearly outperforming their undoped counterparts, showing remarkable efficiency not only under UV-B but also with UV-A illumination. When 100 mg of catalyst (N-doped TiO(2) nanofiber decorated with Pt nanoparticles) was applied to 1 L of water-ethanol mixture, the H(2) evolution rates were as high as 700 μmol/h (UV-A) and 2250 μmol/h (UV-B) corresponding to photo energy conversion percentages of ∼3.6 and ∼12.3%, respectively.

Alkaline modified oil shale fly ash: optimal synthesis conditions and preliminary tests on CO2 adsorption.

Environmentally friendly product, calcium-silica-aluminum hydrate, was synthesized from oil shale fly ash, which is rendered so far partly as an industrial waste. Reaction conditions were: temperature 130 and 160°C, NaOH concentrations 1, 3, 5 and 8M and synthesis time 24h. Optimal conditions were found to be 5M at 130°C at given parameter range. Original and activated ash samples were characterized by XRD, XRF, SEM, EFTEM, (29)Si MAS-NMR, BET and TGA. Semi-quantitative XRD and MAS-NMR showed that mainly tobermorites and katoite are formed during alkaline hydrothermal treatment. Physical adsorption of CO(2) on the surface of the original and activated ash samples was measured with thermo-gravimetric analysis. TGA showed that the physical adsorption of CO(2) on the oil shale fly ash sample increases from 0.06 to 3-4 mass% after alkaline hydrothermal activation with NaOH. The activated product has a potential to be used in industrial processes for physical adsorption of CO(2) emissions.

Photocatalytic activity of nitrogen-doped TiO2-based nanowires: a photo-assisted Kelvin probe force microscopy study

In this study, a set of nitrogen-doped TiO2-based nanomaterials demonstrating photocatalytic activity was developed by combining the efforts of lattice doping and metal nanoparticle decoration and tested for photo-degradation of methylene blue dye by applying solar simulator irradiation. The surface potential shifts of these TiO2-based photocatalytic nanomaterials measured by Kelvin probe force microscope have been used to study the degree of electron generation of the photocatalysts after irradiation and were well correlated with the photocatalytic activity. The nitrogen-doped TiO2 nanowires decorated with Pt nanoparticles can induce obvious electron accumulation and result in a large shift of surface potential. The analysis shows a clear correlation between the surface potential shift and the photodegradation activity. Furthermore, a thorough comparative photocatalytic activity study combined with X-ray photoelectron spectroscopy analysis of the materials—doped with nitrogen under various conditions—reveals that the photocatalytic efficiency of the catalysts is maintained even if the lattice doping is leached e.g., by thermal treatments after doping.Graphical AbstractBy monitoring the surface potential shifts of various TiO2-based photocatalysts by photo-assisted Kelvin probe force microscopy, we obtain a useful tool for developing novel materials with high photocatalytic activity.

In vivo skin measurements with a novel probe head for simultaneous skin impedance and near-infrared spectroscopy

Background/purpose: Near‐infrared (NIR) spectroscopy and skin impedance (IMP) measurements are useful techniques for objective diagnostics of various skin diseases. Here, we present a combined probe head for simultaneous, time‐saving NIR spectroscopy and skin impedance measurements. The probe also ensures that both measurements are performed under equal conditions and at the same skin location.

Interference-free coulometric titration of water in lithium bis(oxalato)borate using Karl Fischer reagents based on N-methylformamide

A non-alcoholic coulometric reagent based on N-methylformamide (NMF) was shown to eliminate the severe interference effect caused by the alcohol component of the conventional Karl Fischer (KF) reagent on the battery electrolyte lithium bis(oxalato)borate (LiBOB). For sample amounts up to 240 microg of water, the stoichiometry of the KF reaction deviated only slightly from the ideal 1:1 ratio for the best reagent composition. Both solid and dissolved (in acetonitrile, tetrahydrofuran (THF), and ethylene carbonate/ethyl methyl carbonate) LiBOB were titrated successfully using a Metrohm 756 KF Coulometer with a diaphragm cell. The detection limit was estimated to be 0.5-1 microg of water using 100ml of reagent in this system.

Coulometric Karl Fischer titration of trace water in diaphragm-free cells

Factors influencing the accuracy and precision for diaphragm-free Karl Fischer coulometric determinations of low mug-amounts of water have been studied using the Metrohm 756 (pulsed current) coulometer and eight different types of commercial coulometric reagents and some modifications of these. As in the case of diaphragm-free coulometric titration of large amounts of water, the positive errors, due to the formation of oxidizable reduction products (of sulfur dioxide) in the cathode reaction (besides hydrogen), were found to be minimized by the use of highest possible pulse current (in the range 100-400mA) in combination with the fastest possible titration rate. Most accurate (102-103%) and precise results (typical relative standard deviation 1.8%) were obtained for reagents containing very large concentrations of imidazole in combination with the presence of modifiers like hexanol, chloroform and propylene glycol (i.e. the HYDRA-POINT reagents). Similar results were obtained when this type of reagent was mixed 60/40 with xylene according to the ASTM recommendation for water determinations in petroleum products like crude and lubricating oils. Addition of decanol to this type of reagent mixture was found to reduce the influence from the oxidative reduction products significantly. A reduction of the error from 3.6% relative to 1.6% was achieved by addition of 9% (v/v) of decanol to a 60/40 reagent mixture of HYDRA-POINT Coulometric Gen (containing hexanol as modifier) and xylene. For larger concentrations of decanol the pulse current had to be lowered to 100mA and this might explain why no further improvement was observed. An additional attempt to minimize the interference by lowering the concentration of sulfur dioxide in the reagents gave no significant effect. However, by means of a home-built computer-controlled coulometric instrumentation based on continuous instead of pulsed current (including a large cathodic current density) it was possible to achieve recovery rates close to 100% for the best reagents investigated. The reason for this improvement is discussed.

Studies on sodium lignosulfonate depolymerization over Al2O3 supported catalysts loaded with metals and metal oxides in a continuous flow reactor

The aim of this work was to study the how various heterogeneous catalysts perform upon lignosulfonate decomposition reactions. The main target of the study was to obtain extractable phenolic compounds as potential renewable chemicals for the production of fuel components and chemicals. The nature of the heterogeneous catalyst was found to have a great impact on the obtained product yields and the composition of the product mixture. Initially, a nickel–tungsten on alumina (NiW/Al2O3) reference catalyst was applied upon screening the influence of catalyst particle size and various reaction parameters. Significantly increasing product yields with decreasing catalyst particle size indicated that the lignosulfonate transformation takes place on the external catalyst surface due to large macromolecular structure of the feedstock. The contact time (space time velocity) and catalyst particle size were the most important factors influencing the selectivity profiles towards various products as well as the yields observed. The highest conversion to phenolics was obtained over in-house-prepared NiO/Al2O3 and NiMo/Al2O3 catalysts with various NiO and MoO3 loadings.

Investigation of Amine-Buffered Amide Reagents for Coulometric Karl Fischer Titration

Formamide (FA), N-methylformamide (NMF), and dimethylformamide (DMF), were evaluated as solvents for coulometric Karl Fischer (KF) reagents in combination with several amine bases. Except for the effect of the iodine species (iodine or triiodide), the pH of the reagent and the position of the sulfur dioxide/hydrogen sulfite equilibrium were found to be the main factors explaining the large difference in the observed reaction rates between water and the KF reagent in these solvents. Acid-base titrations showed that hydrogen sulfite is the main sulfur reactant in these media. The results will be of great importance in finding suitable combinations of base and solvent with respect to stoichiometry, side reactions caused by active carbonyl compounds, and reagent stability.

Reaction Network upon One-pot Catalytic Conversion of Pulp

Nordic sulphite and sulphate (Kraft) cellulose originating from Nordic pulp mills were used as raw materials in the catalytic synthesis of green platform chemicals, levulinic and formic acids, resp ...