Cr- and Ga-Modified ZSM-5 Catalyst for the Production of Renewable BTX from Bioethanol.

Light aromatics (benzene, toluene, and xylene, collectively known as BTX) are essential commodity chemicals in the petrochemical industry. The present study examines the aromatization of bioethanol with Cr- and Ga-modified ZSM-5. Both Cr and Ga were incorporated by the ion-exchange method. Cr-modified ZSM-5 outperforms the Ga-modified ZSM-5 and H-ZSM-5 catalysts. Cr-H-ZSM-5 almost doubled the carbon yield of aromatics compared to H-ZSM-5 at an optimum reaction temperature of 450 °C. Cr-H-ZSM-5 produced aromatics with a yield of ~40 %. The effect of dilution in feed on BTX production is also studied. Cr-H-ZSM-5 was found to be more active than H-ZSM-5. Complete ethanol conversion was obtained with both pure and dilute bioethanol. The Bronsted-Lewis acid (BLA) pair formed after metal incorporation is responsible for dehydrogenation followed by aromatization, leading to increased aromatic production.

DFT Study on the Stability and the Acid Strength of Brønsted Acid Sites in Zeolite ß.

Acid sites are studied computationally for zeolite ß. Different deprotonated and protonated models are used. The issue of difference in the stability of acid sites is addressed. Separate and paired acid sites are created, and their stability and acidity are estimated. The sites in the 6-membered rings have a favorable position; however, the study does not exclude the diversity of sites in other positions. The zeolite module and model chemistry have an influence on the computational results. The influence of the mutual arrangement of two acid sites in a single model is studied. Hydrogen bonding influences the stability and acidity in this case. Four and six acid sites are created that possess hydrogen bonding in the same model. The distance and mutual orientation of the sites affect their stability. Thus, the dipole-dipole interactions, structure deformations, and inductive effect all play their roles in the chemistry of the acid sites. Both thermodynamics and chemical kinetics of the zeolite can influence Al locations in zeolites, and their influence should be concerted according to the linear relation of the free energies.

The Course of the Angular Artery in the Midface: Implications for Surgical and Minimally Invasive Procedures.

BACKGROUND: Previous anatomic studies have provided valuable information on the 2-dimensional course of the angular segment of the facial artery in the midface and its arterial connections. The third dimension (ie, the depth of the artery) is less well characterized. OBJECTIVES: The objective of the present study was to describe the 3-dimensional pathway of the angular segment of the facial artery and its relationship to the muscles of facial expression. METHODS: The bilateral location and the depth of the midfacial segment of the facial artery was measured utilizing multi-planar computed tomographic image analyses obtained from contrast agent-enhanced cranial computed tomographic scans of 156 Caucasians aged a of 45.19 ± 18.7 years and with a mean body mass index of 25.05 ± 4.9 kg/m2. RESULTS: At the nasal ala, the mean depth of the main arterial trunk was 13.7 ± 3.7 mm (range, 2.7-25.0 mm), whereas at the medial canthus it was 1.02 ± 0.62 mm (range, 1.0-3.0 mm). This was reflected by the arteries' relationship to the midfacial muscles: at the nasal ala superficial to levator anguli oris in 62.0% but deep to the levator labii superioris alaeque nasi in 53.6%; at the medial canthus superficial to the levator labii superioris alaeque nasi in 83.1% and superficial to the orbicularis oculi in 82.7%. CONCLUSIONS: The results presented herein confirm the high variability in the course of the angular segment of the facial artery. Various arterial pathways have been identified providing evidence that, in the midface, there is no guaranteed safe location for minimally invasive procedures.

Advancing Fenton and photo-Fenton water treatment through the catalyst design.

The review is devoted to modern Fenton, photo-Fenton, as well as Fenton-like and photo-Fenton-like reactions with participation of iron species in liquid phase and as heterogeneous catalysts. Mechanisms of these reactions were considered that include hydroxyl radical and oxoferryl species as the reactive intermediates. The barriers in the way of application of these reactions to wastewater treatment were discussed. The following fundamental problems need further research efforts: inclusion of more mechanism steps and quantum calculations of all rate constants lacking in the literature, checking the outer sphere electron transfer contribution, determination of the causes for the key changes in the homogeneous Fenton reaction mechanism with a change in the reagents concentration. The key advances for Fenton reactions implementation for the water treatment are related to tremendous hydrodynamical effects on the catalytic activity, design of ligands for high rate and completeness of mineralization in short time, and design of highly active heterogeneous catalysts. While both homogeneous and heterogeneous Fenton and photo-Fenton systems are open for further improvements, heterogeneous photo-Fenton systems are most promising for practical applications because of the inherent higher catalyst stability. Modern methods of quantum chemistry are expected to play a continuously increasing role in development of such catalysts.

Determination of graphene's edge energy using hexagonal graphene quantum dots and PM7 method.

Graphene quantum dots (GQDs) are important for a variety of applications and designs, and the shapes of GQDs rely on the energy of their boundaries. Presently, many methods have been developed for the preparation of GQDs with the required boundaries, shapes and edge terminations. However, research on the properties of GQDs and their applications is limited due to the unavailability of these compounds in pure form. In the present computational study, the standard enthalpy of formation, the standard enthalpy of formation of edges and the standard enthalpy of hydrogenation are studied for hexagonal GQDs with purely zigzag and armchair edges in non-passivated and H-passivated forms using the semiempirical quantum chemistry method pm7. The standard enthalpy of formation of the edge is found to remain constant for GQDs studied in the range of 1 to 6 nm, and the enthalpies of edge C atoms are 32.4 and 35.5 kcal mol-1 for armchair and zigzag edges, respectively. In contrast to some literature data, the standard enthalpy of formation of hydrogenated edges is far from zero, and the values are 7.3 and 8.0 kcal mol-1 C for armchair and zigzag edges, respectively. The standard enthalpy of hydrogenation is found to be -10.2 and -9.72 eV nm-1 for the armchair and zigzag edges, respectively.

Benchmarking semiempirical and DFT methods for the interaction of thiophene and diethyl sulfide molecules with a Ti(OH)4(H2O) cluster.

Semiempirical methods pm6 and pm7 as well as density functional theory functionals exchange LSDA, exchange-correlation PW91 and PBE, hybrid B3LYP1 and PBE0 were compared for energy and geometry of thiophene, diethyl sulfide (DES) molecules and their binding to a frozen Ti(OH)4(H2O) complex having one coordinatively unsaturated Ti5C site representing small fragment of TiO2 anatase (001) surface. PBE0/6-31G(d) with DFT-D3 dispersion correction was the best method for description of thiophene and DES molecules geometries as comparison with experimental data demonstrated. Semiempirical methods pm6 and pm7 resulted in only three of four possible binding configurations of thiophene with the Ti(OH)4(H2O) complex while pm7 described correctly the enthalpy and all configurations of DES binding with the Ti(OH)4(H2O) complex. SBKJC pseudopotential and LSDA with and without dispersion correction produced flawed results for many configurations. PBE0 and PBE with and without dispersion correction and PW91 with 6-31G(d) basis set systematically produced dependable results for thiophene and DES binding to the Ti(OH)4(H2O) complex. PBE0-D3/6-31G(d), B3LYP1-D3/6-31G(d), and PBE-D3/6-31G(d) gave best match of binding energy for thiophene while PBE0/6-31G(d) gave best match of DES binding energy as comparison with CCSD(T) energy demonstrated. On the basis of the superior results obtained with PBE0/6-31G(d), it is the recommended method for modeling of adsorption over TiO2 surfaces. Such a conclusion is in agreement with recent literature.

Paramagnetic properties of carbon-doped titanium dioxide.

This paper reports the experimental results on paramagnetic properties of carbon-doped titanium dioxide. The electron paramagnetic resonance study of the samples has been carried out both in dark and under illumination. The nature of defects and their dynamics under illumination of carbon-doped TiO_2 samples are discussed.

Parametric studies of diethyl phosphoramidate photocatalytic decomposition over TiO2.

The present study is focused on influences of parameters including pH, temperature, TiO(2) catalyst concentration, and reactant concentration on the rate of photocatalytic diethyl phosphoramidate (DEPA) decomposition with Hombikat UV 100 (HK) and Degussa P25 (P25) TiO(2). Total mineralization of DEPA is observed. Two regimes of pH, namely in acid and near-neutral environments were found where maximum total carbon (TC) decomposition was observed. The electrostatic effects on adsorption over the TiO(2) surface explain the above phenomena. The maximum rate is observed for P25 at DEPA concentration 1.3 mM whereas the rate grows continuously with DEPA concentration rise for HK. The temperature dependence of TC decomposition rate in the range of 15-63°C with both HK and P25 follows the Arrhenius equation. The activation energy for total carbon decomposition with HK and P25 are 29.5±1.0 and 24.3±3.1 kJ/mol, respectively. The decomposition rate of DEPA is larger over P25 than over HK. The rate over P25 increases faster than that with HK for each unit of the titania added when the TiO(2) concentration is less than 375 mg/l. The higher light absorption and particles aggregation of P25 are responsible for the decrease of reaction rate we observed at catalyst concentration above a certain level. In contrast, the rate over HK increases monotonically with the concentration of the photocatalyst used.

Experimental study of dimethyl methylphosphonate decomposition over anatase TiO2.

Removal from air and decomposition of dimethyl methylphosphonate (DMMP) over high surface area anatase TiO(2) at ambient temperature have been quantitatively studied by employing Fourier transform infrared (FTIR) technique under static conditions. In the first scenario of air purification, DMMP underwent reactive adsorption that upon completion was followed by photocatalytic oxidation. DMMP was captured over the TiO(2) surface at the speed of external diffusion. Hydrolysis of adsorbed DMMP led to methanol and methyl methylphosphonate (MMP). At low DMMP coverage quantity, it hydrolyzed completely with the formation of completely surface-bound methanol at 1% relative humidity (RH) and mostly gaseous methanol at 50% RH. Photocatalytic oxidation generated CO(2) as the only carbonaceous gaseous product and bidentate formates as the intermediate surface product. At high DMMP coverage quantity, it was captured incompletely and hydrolyzed partially with CH(3)OH in the gas phase only, 50% RH enhancing both processes. Photocatalytic oxidation generated gaseous HCOOH, CO, and CO(2) and was incomplete due to catalyst deactivation by nonvolatile products. In the second scenario of air purification, DMMP underwent adsorption, hydrolysis, and photooxidation at the same time. It resulted in the quickest removal of DMMP from the gas phase and completion of oxidation in 30 min, suggesting this process for practical air decontamination. At least 0.8 nm(2) of TiO(2) surface per each DMMP molecule should be available for complete purification of air.