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.     

Probing stress effects in HfO2 gate stacks with time dependent measurements

Effects of constant voltage stress (CVS) on gate stacks consisting of an ALD HfO₂ dielectric with various interfacial layers were studied with time dependent sensing measurements: DC I–V, pulse I–V, and charge pumping (CP) at different frequencies. The process of injected electron trapping/de-trapping on pre-existing defects in the bulk of the high-κ film was found to constitute the major contribution to the time dependence of the threshold voltage (V_t) shift during stress. The trap generation observed with the low frequency CP measurements is suggested to occur within the interfacial oxide layer or the interfacial layer/high-κ interface, with only a minor effect on V_t.     

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.     

Microstructure and fatigue characteristics of direct chill cast and electromagnetic cast 2024 Al alloy ingots

The distinct advantages of the electromagnetic casting (EMC) process consist in the presence of stirring motions in the melt, which lead to significant grain size reduction in solidified ingot. Furthermore, surface and subsurface qualities are improved due to the absence of ingot mold. However, it is impossible to achieve the aforementioned advantages in conventional direct chill casting (DCC). In order to contrast the before and after heat treatments of the microstructural and mechanical characteristics of EMC and DCC 2024 aluminium alloys, optical microscopy, scanning electron microscopy, transmission electron microscopy (TEM), X-ray diffractions (XRD), differential scanning calorimetry (DSC), etc. were carried out. Compared with the DCC ingot, the EMC ingot has better mechanical properties not only in the ascast condition but also in the as-aged condition. The DSC curves show that the EMC specimens have high enthalpy, i.e., the thermal kinetic energy to form precipitates during the aging treatment process. Despite heat treatments applied to the DCC ingot, it fails to attain the same mechanical properties as the EMC ingot. Moreover, considering the expernsive scalping operation for DCC ingots, the EMC technique, which offers a lower manufacturing cost, is one of the best manufacturing methods used in obtaining the ingots of wrought aluminum alloys.     

An Area Optimization Method for Digital Filter Design

In this paper, we propose an efficient design method for area optimization in a digital filter. The conventional methods to reduce the number of adders in a filter have the problem of a long critical path delay caused by the deep logic depth of the filter due to adder sharing. Furthermore, there is such a disadvantage that they use the transposed direct form (TDF) filter which needs more registers than those of the direct form (DF) filter. In this paper, we present a hybrid structure of a TDF and DF based on the flattened coefficients method so that it can reduce the number of flip‐flops and full‐adders without additional critical path delay. We also propose a resource sharing method and sharing‐pattern searching algorithm to reduce the number of adders without deepening the logic depth. Simulation results show that the proposed structure can save the number of adders and registers by 22 and 26%, respectively, compared to the best one used in the past.     

Extraction of halide quaternary salts in an organic solvent/water system: Hydrodynamics and mass transfer

The hydrodynamic characteristics and mass transfers of halide quaternary salts between two immiscible phases in a stirred membrane permeation cell were investigated. The concentration of quaternary salt, temperature, solvent and the four kinds of halide quaternary salts were evaluated to achieve the extractive optimum condition. The diffusivity, overall mass‐transfer coefficients and individual mass‐transfer coefficients were determined and correlated in terms of the conventional Sh‐Re‐Sc relationship. The transfer time of quaternary salts across the membrane and the thickness of the hydrodynamic diffusion boundary layer were determined as well, so as to characterize the extractive phenomenon of quaternary salts between the two phases that is useful in phase‐transfer catalysis.     

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