In Situ ATR-FTIR Investigation of Photodegradation of 3,4-Dihydroxybenzoic Acid on TiO2

The catalytic photo-oxidation of 3,4-dihydroxybenzoic acid on TiO2 has been studied by in situ ATR-FTIR in flowing water and in flowing wet air/nitrogen gas. In flowing water it was difficult to observe photodegradation intermediates despite photocatalytic action during UV illumination. In the flowing wet air/nitrogen system carboxylic acids and carbonates were observed. It was shown that water plays an important role in the formation of oxidation active species. Oxygen shows a prominent role for carboxylic acid degradation, but the photogenerated hole plays the important role for the 3,4-dihydroxybenzoic acid ring cleavage

Structural, Vibrational and Electronic-properties of A Crystalline Hydrate From Ab-initio Periodic Hartree-fock Calculations

The hydrate crystal lithium hydroxide monohydrate LiOH.H2O has been studied by ab initio periodic Hartree-Fock calculations. The influence of the crystalline environment on the local molecular properties (molecular geometry, atomic charges, electron density, molecular vibrations and deuterium quadrupole coupling constants) of the water molecule, the lithium and hydroxide ions has been calculated. A number of crystalline bulk properties are also presented, optimized crystalline structure, lattice energy and electronic band structure. The optimized cell parameters from calculations with a large basis set of triple-zeta quality differ by only 1-3% from the experimental neutron-determined cell, whereas the STO-3g basis set performs poorly (differences of 5-10%). With the triple-zeta basis also the atomic positions and intermolecular distances agree very well with the experiment. The lattice energy differs by approximately 8% from the experimental value, and by at most 3% when a density-functional electron correlation correction is applied. Large electron-density rearrangements occur in the water molecule and in the hydrogen bond and are in qualitative and quantitative agreement with experimental X-ray diffraction results. The quadrupole-coupling constants of the water and hydroxide deuterium atoms are found to be very sensitive to the O-H bond length and are in good agreement with experimental values when the calculation is based on the experimental structure. The anharmonic O-H stretching vibrations in the crystal are presented and found to be very close to results from calculations on molecular clusters. The electronic band and density-of-states spectra are discussed. Model calculations on a hydrogen fluoride chain were used to rationalize the results

Metal oxide nanoparticles as novel gate materials for field-effect gas sensors

Oxide nanoparticle layers have shown interesting behavior as gate materials for high temperature (typically at 300-400°C) metal-insulator-silicon carbide (MISiC) capacitive sensors. Distinct shifts in the depletion region of the C-V (capacitance-voltage) characteristics could be observed while switching between different oxidizing and reducing gas ambients (air, O2, H2, NH3, CO, NOx, C3H6). Shifts were also noticed in the accumulation region of the C-V curves, which can be attributed to the change in resistivity of the gate material. Sensor response patterns have been found to depend on operating temperature

Nanoparticles for long-term stable, more selective MISiCFET gas sensors

Synthesis of metal-oxide nanoparticles and utilization of these particles as gate materials for field-effect sensor devices is reported. Improved selectivity to specific gases is expected by modulating the size of the oxide nanoparticles or impregnating them with catalytic metals. Another objective is to improve the long-term thermal stability of the sensors, since the metal loaded nanoparticles may prevent thermally induced restructuring of the gate layer, which is often a problematic issue for the catalytic metal layers. Because of its reasonably high electrical conductivity, which is especially important for the capacitive gas sensors, ruthenium dioxide has been identified to be one of the potential candidates as gate material for the field-effect sensor devices. Interestingly, this material has been found to change its resistivity in different gaseous ambients. When used as a gate material, sensitivity to reducing gases has been observed for the RuO2/SiO2/4H-SiC capacitors. Changes in the resistivity of the films due to various gas exposures have also been recorded. Morphological studies of nanoparticles (SiO2 and Al2O3), loaded or impregnated with catalytic metals (e.g. Pt), have been performed

The electronic structure of free water clusters probed by Auger electron spectroscopy

(H2O)(N) clusters generated in a supersonic expansion source with N similar to 1000 were core ionized by synchrotron radiation, giving rise to core-level photoelectron and Auger electron spectra (AES), free from charging effects. The AES is interpreted as being intermediate between the molecular and solid water spectra showing broadened bands as well as a significant shoulder at high kinetic energy. Qualitative considerations as well as ab initio calculations explain this shoulder to be due to delocalized final states in which the two valence holes are mostly located at different water molecules. The ab initio calculations show that valence hole configurations with both valence holes at the core-ionized water molecule are admixed to these final states and give rise to their intensity in the AES. Density-functional investigations of model systems for the doubly ionized final states-the water dimer and a 20-molecule water cluster-were performed to analyze the localization of the two valence holes in the electronic ground states. Whereas these holes are preferentially located at the same water molecule in the dimer, they are delocalized in the cluster showing a preference of the holes for surface molecules. The calculated double-ionization potential of the cluster (22.1 eV) is in reasonable agreement with the low-energy limit of the delocalized hole shoulder in the AES

The inhomogeneous structure of water at ambient conditions

Small-angle X-ray scattering (SAXS) is used to demonstrate the presence of density fluctuations in ambient water on a physical length-scale of ≈1 nm; this is retained with decreasing temperature while the magnitude is enhanced. In contrast, the magnitude of fluctuations in a normal liquid, such as CCl4, exhibits no enhancement with decreasing temperature, as is also the case for water from molecular dynamics simulations under ambient conditions. Based on X-ray emission spectroscopy and X-ray Raman scattering data we propose that the density difference contrast in SAXS is due to fluctuations between tetrahedral-like and hydrogen-bond distorted structures related to, respectively, low and high density water. We combine our experimental observations to propose a model of water as a temperature-dependent, fluctuating equilibrium between the two types of local structures driven by incommensurate requirements for minimizing enthalpy (strong near-tetrahedral hydrogen-bonds) and maximizing entropy (nondirectional H-bonds and disorder). The present results provide experimental evidence that the extreme differences anticipated in the hydrogen-bonding environment in the deeply supercooled regime surprisingly remain in bulk water even at conditions ranging from ambient up to close to the boiling point