Electrocatalytic Reduction of CO2 to Ethylene by Molecular Cu‐Complex Immobilized on Graphitized Mesoporous Carbon

The electrochemical reduction of carbon dioxide (CO₂) to hydrocarbons is a challenging task because of the issues in controlling the efficiency and selectivity of the products. Among the various transition metals, copper has attracted attention as it yields more reduced and C2 products even while using mononuclear copper center as catalysts. In addition, it is found that reversible formation of copper nanoparticle acts as the real catalytically active site for the conversion of CO₂ to reduced products. Here, it is demonstrated that the dinuclear molecular copper complex immobilized over graphitized mesoporous carbon can act as catalysts for the conversion of CO₂ to hydrocarbons (methane and ethylene) up to 60%. Interestingly, high selectivity toward C2 product (40% faradaic efficiency) is achieved by a molecular complex based hybrid material from CO₂ in 0.1 m KCl. In addition, the role of local pH, porous structure, and carbon support in limiting the mass transport to achieve the highly reduced products is demonstrated. Although the spectroscopic analysis of the catalysts exhibits molecular nature of the complex after 2 h bulk electrolysis, morphological study reveals that the newly generated copper cluster is the real active site during the catalytic reactions.     

A simple mathematical analysis on the effect of sand in Cr(VI) reduction using zero valent iron

A simple mathematical model was proposed to analyze the enhancement of Cr(VI) reduction when sand materials are added to the zero valent iron (ZVI). Natural decay of Cr(VI) in a control experiment was analyzed by using a zero-order decay reaction. Adsorption kinetics of Cr(VI) to sand was modeled as a first-order reversible process, and the reduction rate by ZVI was treated as a first-order reaction. Natural decay of Cr(VI) was also included in other experiments, i.e., the adsorption to sand, the reduction by ZVI, and both adsorption and reduction when sand and ZVI are present together. The model parameters were estimated by fitting the solution of each model to the corresponding experimental data. To observe the effect of sand addition to ZVI, both adsorption and reduction rate models were considered simultaneously including the natural decay. The solution of the combined model was fitted to the experimental data to determine the first-order adsorption and reduction rate constants when sand as well as ZVI is present. The first-order reduction rate constant in the presence of sand was about 35 times higher than that with ZVI only.     

Facile synthesis of nanocrystalline zinc ferrite via a self-propagating combustion method

Macroporous nanocrystalline zinc ferrite with single spinel-phase was prepared by a facile self-propagating combustion method using zinc nitrate, iron nitrate and glycine. The as-prepared ZnFe₂O₄ were characterized by X-ray diffraction (XRD) analysis, N₂ adsorption, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and energy dispersive X-ray spectrum (EDS). The magnetic properties of the prepared ZnFe₂O₄ were also studied.     

Structure and processability of iodinated poly(vinyl alcohol). IV. Drawability of the films iodinated at solution before casting

The drawability of iodinated at solution before casting (IBC) polyvinyl alcohol films prepared by casting aqueous solutions of 10 wt % PVA containing 15.2, 39.8, 83.2, 117.0, and 140.1% was examined with a tensile tester at 20–60°C. The tensile behavior of IBC films showed that the yield and breaking loads were much lower, and the breaking elongation was even higher than those of the unoriented iodinated after casting (IAC) films as well as the untreated PVA films. The maximum draw ratios of the films with the weight gain of 15.2, 39.8, 83.2, 117, and 140.1% were 4.5, 5.5, 8.5, 8.0, and 7.5, respectively, which were achieved at 20°C in all. The crystallinity of all films increased by the maximum draw, regardless of crystallinity before drawing. The crystalline structure was recovered to the original PVA crystalline lattice by deiodination. Amorphous orientation and initial moduli increased with the maximum draw ratio, while the orientation of crystals was constant. The orientation and moduli increased up to the weight gain of 83.2%, whose highest draw ratio and initial modulus were 8.5 and of 7.1 GPa, respectively, and then decreased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Complications following major abdominal surgery in cirrhotic patients

The morbidity and mortality associated with major abdominal surgical interventions in 34 histologically proven cirrhotic patients are analyzed by the authors. The surgical interventions were carried out as urgent, absolute and elective indications. Thirty-seven general and surgical complications were observed following major abdominal surgery in 34 cirrhotics. Seven out of 34 patients died, giving a mortality rate of 21%. Suture-line insufficiency, peritonitis, sepsis and other inflammatory processes turned out to be the most common complications. Statistical analysis showed that the Child criteria, prothrombin level and white blood cell count were useful prognostic factors.     

Effect of reactive diluents on properties of unsaturated polyester/montmorillonite nanocomposites

Unsaturated polyester (UP)/montmorillonite (MMT) nanocomposite was prepared by using hydroxypropylacrylate (HPA) as a reactive diluent instead of conventional styrene monomer and the effect of polarity of reactive diluent on properties of nanocomposite was investigated. X‐ray and mechanical test data indicated that mixing for an extended period of time is essential to enhance the physical properties of nanocomposites in the UP/Cloisite 6A system. This was attributed to the high polarity of HPA that may disturb the preintercalation of UP resin into the galleries of MMT. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 238–242, 2004     

Measurement and modeling solubility of bioactive coumarin and its derivatives in supercritical carbon dioxide

To design a supercritical fluid extraction process for the separation of bioactive substances from natural products, a quantitative knowledge of phase equilibria between target biosolutes and solvent is necessary. How-ever, mostly no such information is available in literature to date. Thus in the present study, illustratively the solubility of bioactive coumarin and its various derivatives (i.e., hydroxy-, methyl-, and methoxy-derivatives) in supercritical CO₂ were measured at 308.15–328.15 K and 10–30 MPa. Also, the pure physical properties such as normal boiling point, critical constants, acentric factor, molar volume and standard vapor pressure for coumarin and its derivatives were estimated. By these estimated information, the measured solubilities were quantitatively correlated by an approximate lattice equation of state proposed recently by the present authors.     

Changes in pore properties of phenol formaldehyde-based carbon with carbonization and oxidation conditions

Porous carbon beads were prepared by carbonizing at 700 and 1000 °C under N₂ (NN-series) or CO₂ atmospheres (CO-series) and a subsequent oxidization with boiling nitric acid solution (13%, v/v) for 3 h (ANN- and ACO-series). BET surface area of both CO- and NN-series samples tends to increase with increasing carbonization temperature, but CO-series samples show higher BET surface areas (700 °C: 610 m²/g, 1000 °C: 780 m²/g) compared with those of NN-series samples (700 °C: 380 m²/g, 1000 °C: 580 m²/g). After acid oxidation, BET surface areas of NN-series samples increased from 580 to 650 m²/g, whereas those of CO-series samples decreased from 780 to 600 m²/g. On subsequent acid oxidation, acidic surface functional groups increased in both CO- and NN-series samples, but the CO-series samples tend to have much more acidic surface functional groups. Adsorption of halogenated methanes, such as tetra-, tri- and dichloromethanes, onto the samples of CO-, NN-, ACO- and ANN-series was thought to be driven initially by the basicity, but the acidic functional groups that could attract adsorbates via dipole-dipole interaction might hinder the adsorption of subsequently incoming adsorbates.