Effect of electron-vibration interactions on the thermoelectric efficiency of molecular junctions.

From first-principles approaches, we investigate the thermoelectric efficiency of a molecular junction where a benzene molecule is connected directly to the platinum electrodes. We calculate the thermoelectric figure of merit ZT in the presence of electron-vibration interactions with and without local heating under two scenarios: linear response and finite bias regimes. In the linear response regime, ZT saturates around the electrode temperature T(e) = 25 K in the elastic case, while in the inelastic case we observe a non-saturated and a much larger ZT beyond T(e) = 25 K attributed to the tail of the Fermi-Dirac distribution. In the finite bias regime, the inelastic effects reveal the signatures of the molecular vibrations in the low-temperature regime. The normal modes exhibiting structures in the inelastic profile are characterized by large components of atomic vibrations along the current density direction on top of each individual atom. In all cases, the inclusion of local heating leads to a higher wire temperature T(w) and thus magnifies further the influence of the electron-vibration interactions due to the increased number of local phonons.

Real-time monitoring of benzene, toluene, and p-xylene in a photoreaction chamber with a tunable mid-infrared laser and ultraviolet differential optical absorption spectroscopy.

We describe the implementation of a mid-infrared laser-based trace gas sensor with a photoreaction chamber, used for reproducing chemical transformations of benzene, toluene, and p-xylene (BTX) gases that may occur in the atmosphere. The system performance was assessed in the presence of photoreaction products including aerosol particles. A mid-infrared external cavity quantum cascade laser (EC-QCL)-tunable from 9.41-9.88 µm (1012-1063 cm(-1))-was used to monitor gas phase concentrations of BTX simultaneously and in real time during chemical processing of these compounds with hydroxyl radicals in a photoreaction chamber. Results are compared to concurrent measurements using ultraviolet differential optical absorption spectroscopy (UV DOAS). The EC-QCL based system provides quantitation limits of approximately 200, 200, and 600 parts in 10(9) (ppb) for benzene, toluene, and p-xylene, respectively, which represents a significant improvement over our previous work with this laser system. Correspondingly, we observe the best agreement between the EC-QCL measurements and the UV DOAS measurements with benzene, followed by toluene, then p-xylene. Although BTX gas-detection limits are not as low for the EC-QCL system as for UV DOAS, an unidentified by-product of the photoreactions was observed with the EC-QCL, but not with the UV DOAS system.

A model for prediction of product distributions for the reactions of phenol derivatives with hydroxyl radicals.

In this study, with the intention of estimating the photocatalytic or photodegradation rates and finding certain predictors to be used for the determination of the most probable reaction path and the primary intermediate, the reactions of (*)OH radicals with 11 phenol derivatives including benzene were modeled. For 43 possible reaction routes, calculations of the geometric parameters, the electronic and thermodynamic properties of the reactants, the product radicals and the transition state complexes were performed with the semiempirical PM3 and DFT/B3LYP/6-31G(*) methods. The solvation effects were computed using COSMO as the solvation model. Based on the results of quantum mechanical calculations, the rate constants, the branching ratios and the product distributions of all the possible reaction paths were calculated by means of the transition state theory. Three predictors were determined for the prediction of the most probable transition state and the reaction path. The differences in the reaction rates were explained in terms of the presence of hydrogen bonds in the transition state complexes and the entropy effects. Finally the results obtained were compared with the available experimental data in order to assess the reliability of the proposed model.

Decomposition of benzene and toluene in air streams in fixed-film photoreactors coated with TiO2 catalyst.

The decomposition of benzene and toluene in air streams by UV/TiO2 process was studied in different annular photoreactors under various operating conditions. The shells of reactors used in this research are made of stainless steel, Pyrex glass, or titanium. The TiO2 film was coated to the inner surface of the reactors by either rotating coating or sol-gel techniques. The TiO2 films coated by sol-gel technique were found to be smoother and more uniform than those coated by rotating coating. However, experimental results indicated that the photocatalysis of benzene or toluene in a glass reactor with rotating-coated TiO2 film delivered higher decompositions in air streams than that with sol-gel coated reactors. Benzene and toluene were decomposed more effectively in a coated glass reactor than in a coated stainless steel reactor under the same operating conditions. The presence of water vapor in air-stream plays an important role in the decomposition of benzene and toluene, and a relative humidity of approximately 5-6% was found to be adequate. The presence of excessive amounts of humidity retarded the decomposition to certain extents possibly results from the competitive adsorption of water molecules on the active sites of TiO2.

Kinetics of photocatalytic VOCs abatement in a standardized reactor.

A standardized micro-pilot scale continuous flow apparatus has been built up, using two types of differential photoreactors, and equipped with a refined control of the working conditions in order to study the photocatalytic degradation as a way to abate VOCs in air. Kinetic measurements have been carried out on trichloroethylene (TCE), methanol and benzene as model pollutants. The absence of diffusional limitation and of reaction product effect on the kinetics have both been demonstrated under our working conditions. The influences of concentration, light flux and temperature on the initial degradation rate have been studied. A simple Langmuir-Hinshelwood kinetic model has been verified for TCE and methanol, whereas benzene degradation was more complex and did not follow this simple mechanism. The determined experimental data aim at being useful in the scaling-up of photocatalytic reactors.

Benzene formation during aquasonolysis of selected cyclic C6Hx hydrocarbons.

Yield and selectivity of benzene produced from aquasonolysis of the selected cyclic C6Hx hydrocarbons, i.e., 1,4-cyclohexadiene, 1,3-cyclohexadiene, cyclohexene, cyclohexane, and methylcyclopentane, have been investigated in this work. Benzene cannot be detected during the aquasonolysis of cyclohexane and methylcyclopentane. The order of yield and selectivity of benzene was as follows: 1,4-cyclohexadiene>>1,3-cyclohexadiene>>cyclohexene. The initial concentrations of substrates can affect the yield of benzene. During the aquasonolysis of 1,3-cyclohexadiene and cyclohexene, other C6 species except benzene were also found. It was suggested that benzene could directly be generated by formal dehydrogenation of cyclic C6Hx hydrocarbons.

Towards the enhancement of the photon/neutron discrimination of C6D6 detectors in the range from 1 to 10 MeV using liquid scintillator materials doped with high-Z elements.

The study on the behaviour of deuterated benzene detectors in the energy range from 1 to 10 MeV has been carried out. It is shown that the photon-to-neutron discrimination, attained with standard detectors, can be improved by doping the C6D6 liquid scintillator with high-Z elements. The motivation for doping the organic scintillator stems from the fact that they should increase the gamma detection efficiencies with no significant changes in the abilities to detect neutrons. The results obtained using the MCNP and EGS4 codes show that increasing the fraction of high-Z elements: (a) the energy deposited in the medium by photons increases, (b) the energy deposited by neutrons decreases and (c) the rate of detection of photon/neutron is enhanced. Owing to their low sensitivity to neutrons and the enhanced gamma detection efficiency, these detectors could be ideally used to carry out studies in mixed neutron-photon fields in the energy range considered and to assess the gamma backgrounds in noisy neutron environments.

Enhanced visible-light induced degradation of benzene on Mg-ferrite/hematite/PANI nanospheres: in situ FTIR investigation.

The dramatic enhanced visible-light photocatalytic activity of Mg-ferrite/hematite nanospheres photocatalysts on benzene were obtained after hybridized by polyaniline (PANI) using the chemisorption method. The samples were characterized by scanning electron microscope, transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectra and UV-Vis diffuse reflectance spectroscopy. The enhancement of photocatalytic degradation of benzene under visible-light irradiation was mainly ascribed to the high efficiency of charge separation induced by the hybrid effect of PANI and Mg-ferrite/hematite. By using the in situ FTIR technique, ethyl acetate, carboxylic acid and aldehyde could be regarded as the intermediate products, and CO(2) is determined as the final product during the reaction process.

Efficient removal of toluene and benzene in gas phase by the TiO2/Y-zeolite hybrid photocatalyst.

Efficient removal of toluene or benzene molecules thinly diffused in gas phase was achieved by using TiO(2)/Y-zeolite hybrid photocatalysts. TiO(2) of 10 wt% hybridized with a hydrophobic USY zeolite showed higher photocatalytic reactivity as compared to TiO(2) hybridized with hydrophilic H-Y or Na-Y zeolites. This phenomenon can be explained by the fact that the hydrophobic USY zeolite efficiently adsorbs the organic compounds and smoothly supplies them onto the TiO(2) photocatalyst surface. However, the toluene or benzene molecules, which are strongly trapped on the hydrophilic H(+) or Na(+) sites of zeolite, cannot diffuse onto the TiO(2) surfaces, resulting in lower photocatalytic reactivity. Although the adsorption capacity of the pure TiO(2) sample rapidly deteriorated, the TiO(2)/Y-zeolite hybrid system maintained a high adsorption efficiency to remove such aromatic compounds for a long period.

Sunlight-induced efficient and selective photocatalytic benzene oxidation on TiO2-supported gold nanoparticles under CO2 atmosphere.

The sunlight-induced photocatalytic oxidation of aqueous benzene on TiO(2)-supported gold nanoparticles was considerably improved when the reaction was conducted under a CO(2) atmosphere. 13% yield and 89% selectivity of phenol was obtained on P25-supported gold nanoparticles under 230 kPa of CO(2).

Degradation of benzene over a zinc germanate photocatalyst under ambient conditions.

A rod-shaped Zn2GeO4 photocatalyst has been successfully prepared by a surfactant-assisted hydrothermal method. The photocatalyst was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, UV/vis, N2 adsorption-desorption, and FTIR techniques. The photocatalytic activity of the sample was evaluated by the decomposition of benzene in the gas phase under UV light illumination and was compared with that of bulk Zn2GeO4, commercial titania (Degussa P25), and Pt/P25. The results revealed that the Zn2GeO4 nanorods had the best photocatalytic activity for mineralizing benzene to CO2 among the catalysts examined. No obvious deactivation of Zn2GeO4 nanorods was observed during the prolonged operation of 140 h. It was found that the Zn2GeO4 was also more active and stable than TiO2-based catalysts toward photocatalytic decomposition of other volatile aromatic pollutants (e.g., toluene and ethylbenzene).

Generation and detection of the cyclohexadienyl radical in phosphonium ionic liquids.

The formation of the cyclohexadienyl radical, C(6)H(6)Mu, in ionic and molecular solvents has been compared. This is the first time that a muoniated free radical is reported in an ionic liquid. In marked contrast to molecular liquids, free radical generation in ionic liquids is significantly enhanced. Comparison of the hyperfine interactions in the ionic liquid and in molecular solvents and with theoretical calculations, suggests significant and unforeseen solvent interaction with the cyclohexadienyl radical.

The potential and realistic hazards after a solar-driven chemical treatment of benzene using a health risk assessment at a gas station site in Korea.

In order to evaluate the potential use for ex situ remediation, a solar-driven, photocatalyzed reactor system was constructed and applied for the treatment of groundwater contaminated with benzene using selected advanced oxidation processes (AOP) processes, such as H(2)O(2)/solar light, TiO(2) slurry/solar light and immobilized TiO(2)/solar light. However; to date, there have been few attempts to characterize the potential impact of residual levels of benzene on human health after treatment. Some papers have focused on the application of treatment methods of benzene, but most have not considered the effects of realistic hazards and human health. Therefore, potential and realistic hazards of benzene to human health were investigated at a gas station site using a risk-based assessment approach. Among the different remediation actions, the solar light/TiO(2) slurry/H(2)O(2) system (Action 5) showed higher removal efficiency than the solar light/TiO(2) slurry (Action 3) and the solar light/immobilized TiO(2) (Action 2) systems for the treatment of benzene. The Action 5 remediation method achieved 98% degradation, and lead to a substantial increase in the removal of benzene due to the synergetic effect of TiO(2) with the oxidant, H(2)O(2). Also, using the realistic and potential hazard assessment instead of the point estimation of concentration after benzene treatment, the total health risk exceeded the target risk value (1 x 10(-6)). However, the 95th percentile target cancer risk, found using a probabilistic analysis (Monte Carlo method), was around 1 x 10(-6), indicating a low potential carcinogenic risk. Therefore, it was concluded that no adverse health risk was unlikely to be posed if the Action 5 system, which included the addition of TiO(2) and H(2)O(2), or if an increased reaction time was applied. In addition, continuous efforts and proper actions must be taken on the "Soil and Groundwater Remediation Action" based on the risk assessment in Korea.

Basic studies on the treatment of volatile organic pollutant in sand by microwave radiation.

The heating characteristics of water and sand were investigated to understand the basic features of a microwave soil pollution treatment system and the reasonableness of this method was examined. The evaporation and temperature change of water by microwave irradiation were dependent on its volume and sand showed a three-fold temperature change compared with water. When microwave energy was applied, water showed an even variation in temperature on the whole, however, there was approximately 30 square difference according to the location inside the sand. Sand temperature was observed to show a larger difference as it was horizontally and vertically closer to the microwave irradiation point and horizontal temperature variations were more evenly distributed than vertical variations. Heating characteristics according to the particle size of sand showed that the temperature change was larger when the particle size became smaller and the moisture content of sand was found to influence its heating behavior. In the conditions of experiment, about 50% of the benzene in sand was volatized after 23 minutes of heating and 85% of the total benzene was removed from the sand after 60 minutes of microwave irradiation. For real soil test, more than 70% of BTEX was successfully removed from the soil after 120 minutes of heating.

Photoreaction of a 2,11-diaza[3.3]paracyclophane derivative: formation of octahedrane by photochemical dimerization of benzene.

Upon photoirradiation at 300 nm, the title diazaparacyclophane (R = COCF3) provided an octahedrane by the photodimerization of its benzene chromophores. This is the first photochemical formation of octahedrane, namely, via the dimerization of benzene. No octahedrane formation was observed for the photolysis of corresponding carbon-bridged paracyclophane. Thus the nitrogen bridges play an important role in the excited state to afford the octahedrane.

Products of the triplet excited state produced in the radiolysis of liquid benzene.

The radiation chemical yields of the products derived from the triplet excited state produced in the radiolysis of liquid benzene with gamma-rays, 10 MeV 4He ions, and 10 MeV 12C ions have been determined. Iodine scavenging techniques have been used to examine the formation and role of radicals, especially the H atom and phenyl radical. For all irradiation types examined here, the increase in hydrogen iodide yields with increasing iodine concentration matches the increase in iodobenzene yields. This agreement suggests that the benzene triplet excited state is the common precursor for the H atom and the phenyl radical. Pulse radiolysis studies in liquid benzene have determined the rate coefficients for the reactions of phenyl radicals with iodine and with the solvent benzene to be 9.3 x 10(9) M(-1) s(-1) and 3.1 x 10(5) M(-1) s(-1), respectively. Direct measurements of polymer formation, which refers to trimers (C18) and higher order compounds (>C18), in liquid benzene radiolysis using gamma-rays, 4He ions, and 12C ions at relatively high doses have been performed using gel permeation chromatography. The yields of trimers increase from gamma-rays to 12C ions due to the increased importance of intratrack radical-radical reactions that can be scavenged by the radical scavenging reactions of iodine. On the other hand, the >C18 product yields decrease from gamma-rays to 12C ions. The structure of the polymer consists of a partly saturated ring as determined by infrared and gas chromatography/mass spectrometry studies. A schematic representation for the radiolytic decomposition of the benzene triplet excited state is presented.

Synthesis and characterization of nano titania powder with high photoactivity for gas-phase photo-oxidation of benzene from TiOCl(2) aqueous solution at low temperatures.

Nano rutile, anatase, and bicrystalline (anatase + brookite) titania powders with an average crystal size of below 10 nm are prepared from aqueous TiOCl(2) solution at low temperatures by adjusting pH values of the starting solution and adding different additives. Adding a small amount of octyl phenol poly(ethylene oxide) into aqueous TiOCl(2) solution leads to the change of particle morphologies of obtained nano titania from needlelike to nano spherical rutile crystals. Amorphous-anatase transformation of titania could proceed in liquid-solid reaction at low temperatures, even at room temperature. A formation mechanism of rutile, anatase, and brookite titania was proposed. It is found that H(+) or H(3)O(+) plays a catalytic role in the phase transformation from amorphous to anatase titania and that the presence of a small amount of SO(4)(2)(-) ion is unfavorable to the formation of both rutile and brookite. By carefully adjusting preparation conditions, nano pure anatase with higher surface area, good crystallinity, and a lower recombination rate of photoexcited electrons and holes was obtained. This nano pure anatase showed a very good photocatalytic activity for gas-phase photo-oxidation of benzene.

Single photon infrared emission spectroscopy: a study of IR emission from UV laser excited PAHs between 3 and 15 micrometers.

Single-photon infrared emission spectroscopy (SPIRES) has been used to measure emission spectra from polycyclic aromatic hydrocarbons (PAHs). A supersonic free-jet expansion has been used to provide emission spectra of rotationally cold and vibrationally excited naphthalene and benzene. Under these conditions, the observed width of the 3.3-micrometers (C-H stretch) band resembles the bandwidths observed in experiments in which emission is observed from naphthalene with higher rotational energy. To obtain complete coverage of IR wavelengths relevant to the unidentified infrared bands (UIRs), UV laser-induced desorption was used to generate gas-phase highly excited PAHs. Lorentzian band shapes were convoluted with the monochromator-slit function in order to determine the widths of PAH emission bands under astrophysically relevant conditions. Bandwidths were also extracted from bands consisting of multiple normal modes blended together. These parameters are grouped according to the functional groups mostly involved in the vibration, and mean bandwidths are obtained. These bandwidths are larger than the widths of the corresponding UIR bands. However, when the comparison is limited to the largest PAHs studied, the bandwidths are slightly smaller than the corresponding UIR bands. These parameters can be used to model emission spectra from PAH cations and cations of larger PAHs, which are better candidate carriers of the UIRs.