Electrochemical conversion of carbon dioxide to methane in aqueous NaHCO3 solution at less than 273 K

The electrochemical reduction of CO₂ on a Cu electrode was investigated in aqueous NaHCO₃ solution, at low temperature. A divided H-type cell was employed, the catholyte was 0.65 mol dm⁻³ NaHCO₃ aqueous solution and the anolyte was 1.1 mol dm⁻³ KHCO₃ aqueous solution. The temperature during the electrolysis of CO₂ was decreased stepwise to 271 K. Methane and formic acid were obtained as the main products. The maximum Faradaic efficiency of methane was 46% at −2.0 V and 271 K. The efficiency of hydrogen formation, a competing reaction of CO₂ reduction, was significantly depressed with decreasing temperature. Based on the results of this work, the proposed electrochemical method appears to be a viable means for removing CO₂ from the atmosphere and converting it into more valuable chemicals. The synthesis of methane by the electrochemical method might be of practical interest for fuel production and the storage of solar energy.     

Conversion of methane to syngas in a solid oxide fuel cell with Ni-SDC anode and LSGM electrolyte

A solid oxide fuel cell constructed from Ni-SDC anode and LSGM electrolyte was applied to the partial oxidation of methane to syngas (CO+H₂) at 700-800 °C with the merits of co-generation of electricity and controllable O₂ supply. It was found that the co-generated syngas at H₂/CO ratio of 1.4-2.0 varied with applied current densities, CH₄ flow rates and operating temperatures. The cell voltage at 100 mA cm⁻² and 800 °C was 0.90 V, i.e. about 90 mW cm⁻² power density could be obtained. The cell operating at 50 mA cm⁻² for 24 h almost showed no degradation of the cell performance. The observed carbon deposition seemed mainly taking place by CH₄ cracking reaction.     

Size dependence of crystallization within spherical microdomain structures

We have investigated the size dependence of crystallization within spherical microdomains formed in various poly(ε-caprolactone)-block-polybutadiene diblock copolymers (PCL-b-PB). The crystallinity (χ) and melting temperature (T_m) of the PCL block are considerably lower than those of PCL homopolymer, and χ decreases steadily and T_m decreases only slightly with decreasing radius of PCL spheres (R) for a series of PCL-b-PB with a same molecular weight (M_n). When PCL-b-PB is compared with the similar R but different M_n, χ is significantly different, suggesting that the sphere size is not the unique factor to control crystallization within spherical microdomains.     

Marked particle size and support effect of Pd catalysts upon the direct decomposition of nitric oxide

The catalytic behavior of beryllia-supported Pd catalyst for the direct decomposition of NO was compared with that of silica supported one. The TOF of NO decomposition was one order of magnitude larger in the case of Pd/BeO. Over Pd/SiO₂, the TOF was increased with the increase of the Pd particle size. On the contrary, over Pd/BeO smaller Pd particles exhibited higher TOF for NO decomposition suggesting some strong electronic or structural interaction between Pd and beryllia. TPD spectra of NO(a) over reduced catalysts indicated that NO was adsorbed on Pd/SiO₂ more strongly than on Pd/BeO, and dissociation of NO(a) was easier on the former catalyst. FT-IR spectra of adsorbed NO at room temperature followed by the evacuation at elevated temperatures confirmed this. TPD spectra of O₂ desorbed from oxidized surface indicated that adsorption strength of O(a) is one of the most important factors to determine the catalytic activity of NO decomposition over supported Pd catalysts.     

Intrinsic Elastic, Dielectric, and Piezoelectric Losses in Lead Zirconate Titanate Ceramics Determined by an Immittance-Fitting Method

The material coefficients of "soft" and "hard" lead zirconate titanate (PZT) ceramics were determined as complex values by the nonlinear least-squares-fitting of immittance data measured for length-extensional bar resonators. The piezoelectric d -constant should be a complex value to obtain a best fitting between observed and calculated results. Because the elastic, dielectric, and piezoelectric losses determined in this process were not "intrinsic" losses, a calculation process to evaluate the "intrinsic" losses was proposed. It was confirmed that the intrinsic losses were smaller than the corresponding extrinsic losses. The intrinsic piezoelectric loss existed in both soft and hard PZTs; ∼50% of the loss of piezoelectric d -constant was derived from the elastic and dielectric losses. The most notable difference between the soft and hard PZTs was observed in their elastic losses.     

Structure of microporous polypropylene sheets containing CaCO3 filler

The microporous polypropylene sheets were prepared by biaxially stretching polypropylene sheets containing CaCO₃ filler (particle size, 0.08–3.0 μm), when the CaCO₃ filler content was 59% by weight and the stretching ratio was 2.8 × 1.8. The microstructure of the sheets were investigated in relation to the CaCO₃ particle size by a N₂ gas permeation method. (1) Effective porosity increases with decreasing mean particle size of filler. (2) The tortuosity factor of the pore is in the range of 25–40 and becomes relatively smaller with decreasing mean particle size of filler. (3) The equivalent pore size becomes relatively smaller with decreasing mean particle size of filler.     

Catalytic performance of K-promoted Rh/USY catalysts in preferential oxidation of CO in rich hydrogen

K-promoted Rh/USY (molar ratio: K/Rh=3) catalyst was found to exhibit high performance in preferential oxidation of CO in rich hydrogen. Such high performance was maintained in the presence of steam and CO₂. The CO oxidation activity of the K-Rh/USY catalyst was independent of the partial pressure of H₂, while the activity of the unpromoted Rh/USY catalyst was decreased significantly in hydrogen-rich stream. The effect of potassium addition on the catalyst structure was investigated and is discussed in terms of the differences in the catalytic performance.     

Fabrication of three‐dimensionally ordered microporous membrane by wet phase separation

We report a novel porous fluorinated polyimide membrane with a cylinder structure fabricated by a wet phase inversion process, which is formed by a ternary system, polyimide/solvent/water. The porous polyimide membranes consisted of a thin top porous layer and three‐dimensionally ordered cylinder micropores. The porous membrane‐forming solvents were N‐methylpyrrolidone containing nonsolvent additives such as alcohol, and the height and width of the cylinder structure were controlled by the solvents. Water fluxes through the porous polyimide membranes were measured using a stirred dead‐end filtration cell, and the fluxes of the porous membrane with the cylinder‐type structure were approximately three times greater than those of the membrane with the finger‐type structure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3016–3021, 2004     

Design of new catalysts for ecological high-quality transportation fuels by combinatorial computational chemistry and tight-binding quantum chemical molecular dynamics approaches

Recently, we introduced a concept of combinatorial chemistry to computational chemistry and proposed a new method called “combinatorial computational chemistry”, which enables us to perform a theoretical high-throughput screening of catalysts. In the present paper, we reviewed our recent application of our combinatorial computational chemistry approach to the design of new catalysts for high-quality transportation fuels. By using our combinatorial computational chemistry techniques, we succeeded to predict new catalysts for methanol synthesis and Fischer–Tropsch synthesis. Moreover, we have succeeded in the development of chemical reaction dynamics simulator based on our original tight-binding quantum chemical molecular dynamics method. This program realizes more than 5000 times acceleration compared to the regular first-principles molecular dynamics method. Electronic- and atomic-level information on the catalytic reaction dynamics at reaction temperatures significantly contributes the catalyst design and development. Hence, we also summarized our recent applications of the above quantum chemical molecular dynamics method to the clarification of the methanol synthesis dynamics in this review.     

NiZnCu Ferrite Thick Film with Nano Scale Crystallites Formed by the Aerosol Deposition Method

This paper describes the magnetic properties of NiZnCu ferrite film deposited at room temperature by an aerosol deposition method (ADM). The thickness of the film was 6 μm and the deposition rate was estimated as 2 μm/min. The microstructure of as-deposited at room temperature films consists of randomly oriented nanocrystallites with a size of 20 nm. As-deposited and annealed films exhibited the following magnetic properties: intensity of magnetization M _s= 0.147 T (117 emu/cm³), coercivity H _c= 40.58 kA/m (510 Oe); and M _s= 0.3 T (250 emu/cm³), H _c= 14.95 kA/m (188 Oe), respectively.