Electrochemical decomposition of CO2 and CO gases using porous yttria-stabilized zirconia cell

Electrochemical decomposition of CO₂ and CO gases using a porous cell of Ru-8 mol% yttria-stabilized zirconia (YSZ) anode/porous YSZ electrolyte/Ni–YSZ cathode system at 400–800 °C was studied by analyzing the flow rate and composition of outlet gas, current density, and phases and elementary distribution of the electrodes and electrolyte. A part of CO₂ gas supplied at 50 ml/min was decomposed to solid carbon and O₂ gas through the cell at the electric field strengths of 0.9–1.0 V/cm. The outlet gas at a flow rate of 3 ml/min included 61–63% CO₂ and 37–39% O₂ at 700–800 °C and the outlet gas at a flow rate of 50 ml/min included 73–96% (average 85%) CO₂ and 4–27% (average 15%) O₂ at 800 °C. On the other hand, the supplied CO gas was also decomposed to solid carbon, O₂ and CO₂ gases at 800 °C. The fraction of outlet gas at a flow rate of 50 ml/min during the CO decomposition at 800 °C for 5 h was 11–36% CO, 59–81% O₂ and 2–9% CO₂. The detailed decomposition mechanisms of CO₂ and CO gases are discussed. Both Ni metal in the cathode and porous YSZ grains under the DC electric field have the ability to decompose CO gas into solid carbon and O²⁻ ions or O₂ gas.     

Synthesis of stable and soluble one-handed helical poly(substituted acetylene)s without chiral pendant groups via polymer reaction in membrane state

A soluble and stable one-handed helical conjugated polymer without the coexistence of any other chiral moieties was successfully synthesized by asymmetric-induced polymerization of a chiral monomer having two hydroxyl groups followed by desubstitution of the chiral groups in a solid membrane state. The reason for the success was the polymer reaction was carried out in the membrane state. This is an alternative method to obtain such a unique chiral polymer which was obtained only by the helix-sense-selective polymerization (HSSP) we reported before. In addition the efficiency of the chiral induction was higher than that of the HSSP. It is interesting that the “Membrane state” acted like as if a protecting group.     

Polyhydrides of Sc,Zr and Hf and Their Proposed Formation.

Hydrogenation at 500 psi of (PNP)Sc(CH₃)₂ results in formation of a trinuclear polyhydride complex [(PNP)Sc]₃(μ₂-H)₄(μ₃-H)₂ ( 1 ) in 55 % yield. The solid-state structure shows a non-symmetric trinuclear species resulting from one pincer phosphine arm being demetallated, and where two hydrides bridge all three Sc centers, whereas the other four bridge two. Hydrogenation of (PNP)Zr(CH₃)₃ at 200 psi results instead in formation of a dinclear polyhydride species [(PNP)Zr(H)]₂(μ₂-H)₄ ( 2 ). Conducting the hydrogenation at atmospheric pressure, resulted instead in formation of the bridging methylidene complex [(PNP)Zr(CH₃)]₂(μ₂-H)₂(μ₂-CH₂) ( 3 ), which cleanly converted to 2 , upon hydrogenation at higher pressure. Both 2 and 3 were also structurally characterized. Hydrogenation of (PNP)Hf(CH₃)₃ at 200 psi resulted in incomplete hydrogenation with some formation of dinuclear mono- and dimethyl-polyhydride complexes [(PNP)Hf(CH₃)]₂(μ₂-H)₄ ( 4 ) and [(PNP)Hf(CH₃)][(PNP)Hf(H)](μ₂-H)₄ ( 5 ), which were identified by solid-state X-ray structural studies. Based on these results, we propose a pathway for the complete hydrogenation of (PNP)Zr(CH₃)₃ to 2 .     

Photocatalytic Synthesis of p-Anisaldehyde in a Mini Slurry-Bubble Reactor under Solar Light Irradiation

Dense photocatalyst slurry was employed for the synthesis of p-anisaldehyde under solar light irradiation. An Fe-modified rutile TiO ₂ (Fe-TiO _2, 34.5 m ²/g) photocatalyst was used as a visible-light-responsive photocatalyst. A conventional TiO ₂ (P25, 35 m ²/g) photocatalyst was also examined as a reference catalyst. XRD patterns and diffuse reflectance spectra showed that Fe-TiO ₂ consists of 100 % rutile phase and absorbs more visible light compared to P25, respectively. The catalyst powder was suspended in an ethyl acetate solution of p-methoxytoluene in the mini-reactor, with oxygen bubbling, under a solar simulator, visible light, and UV LEDs. p-anisaldehyde, as a reaction product, was analyzed by sampling using gas-chromatograph. Regardless of the light source, Fe-TiO ₂ always outperformed P25 in terms of both generation rates (GR) of p-anisaldehyde and energy requirements (ER). It was demonstrated that the highly dense Fe-TiO ₂ slurry was efficient for the synthesis under solar light owing to the small size of the reactor. The small amount of Pt and ZrO ₂ cocatalysts significantly enhanced the GR under solar light. By adopting a visible light responsive Fe-TiO ₂ photocatalyst, the mini slurry-bubble reactor under solar light achieved a high GR per catalyst mass (CM), which is one to two orders higher than that reported by most previous studies with high-power lamps.     

Improvement of the surface quality of foam injection molded products from a material property perspective

Microcellular injection molding is an attractive method. However, their surface imperfections have been a major problem hindering wide industrial applications. Several methods have been proposed to improve the surface appearance of foams. In this study, we proposed a method to improve the surface appearance of polypropylene (PP) foams from the material property perspective, especially with regard to crystallization and viscosity. The basic idea of the surface improvement is to reduce the size of bubbles generated at the flow front, delay the solidification behavior of the polymer at the mold interface, squeeze the bubbles existing at the mold–polymer interface, and redissolve the bubbles into the polymer by holding pressure. Blending a low-modulus PP delays the crystallization of the polymers at the skin layer and solidification, taking enough time to squeeze the bubbles smaller. A sorbitol-based gelling agent, bis-O-([4 methylphenyl]methylene)-D-Glucitol, was used to increase the viscosity at a low strain rate to reduce the size of the bubbles generated at the flow front during the filling stage. The foam injection molding experiments demonstrated that the proposed method effectively improved the surface appearance of the foams. In particular, the surface appearance of the foams became almost equivalent to that of solid samples using low-modulus PP.     

Roles of inherent metallic species in secondary reactions of tar and char during rapid pyrolysis of brown coals in a drop-tube reactor

Two pairs of raw and acid-washed coal samples were prepared from Yallourn and Loy Yang brown coals, and subjected to rapid pyrolysis in a drop-tube reactor at 1073-1173 K in a stream of N₂ or H₂O/N₂ mixture. Examinations were made on the roles of the inherent metallic species in the secondary reactions of nascent tar and char that were formed by the intraparticle primary reactions. The experimental results revealed that the inherent metallic species were essential for vary rapid steam reforming/gasification of the nascent tar/char and simultaneous suppression of soot formation. In the absence of the metallic species, the soot formation from the tar accounted as much as 15-19 and 6-13% of the carbon in coal in N₂ and H₂O/N₂, respectively. The metallic species reduced the yield of soot to 6-8% in N₂ by enhancing the reforming of tar by H₂O generated from the pyrolysis of coal. In the H₂O/N₂ stream, instead of soot formation, a net gasification conversion up to 17% within 4.3 s was observed in the presence of the metallic species as a result of catalytic gasification of the nascent char. Moreover, the metallic species catalyzed the steam reforming of the nascent tar, giving its conversion up to 99%. Over the range of the conditions employed, a one-to-one stoichiometry was established between the steam consumption and the yield of carbon oxides formed by the steam reforming/gasification and water-gas-shift reaction.     

Direct Electroplating of Lithium Cobalt Oxide Film on Platinum Substrate in 100°–200°C Aqueous Solution

Well crystallized, shape-formed, and electrochemically active lithium cobalt oxide (LiCoO₂) films are electroplated directly on an electron-conducting substrate in an aqueous solution using a soft solution processing that is economical, consumes less energy consuming, and is environmentally friendly. Although LiCoO₂ films are easily and economically prepared without any post-synthesis heat treatment, the estimated film properties show a possibility of using the deposited films as a cathode film for lithium rechargeable microbatteries. In addition, the soft solution processing reveals that an exact understanding of chemical reactions and the proper combination of the chemical reactions can create an advanced synthetic procedure.     

Preparation, Structure, and Properties of Thermally and Mechanically Improved Aluminum Titanate Ceramics Doped with Alkali Feldspar

Aluminum titanate (AT) ceramic materials doped with alkali feldspar ((Na_0.6K_0.4)AlSi₃O₈) have been prepared. These ceramics exhibited high sinterability, large resistance to thermal decomposition, and large flexure strength. The existence of liquid-phase feldspar at sintering temperatures promoted the formation of AT ceramics as the sintering agent. It was considered that silicon ions substituting for aluminum ions at the surface of AT crystal grains lowered the surface energy and hindered the diffusion of Ti⁴⁺ and Al³⁺, giving rise to the large resistance to thermal decomposition. As a result, doping with alkali feldspar was found to effectively improve the mechanical and thermal properties of AT ceramics.     

Decomposition of Carbon Dioxide to Carbon with Active Wustite at 300°C

Active wustite (FeδO, with a δ value of 0.98) was prepared by keeping normal wustite (δ value of 0.94) in a N₂ atmosphere at 300°C for 10 min. This reaction is given by (4δ₂–3)Fe_δ1O→(4δ₁–3)Fe_δ2O + (δ₂–δ₁)Fe₃O₄ where δ₁= 0.94 and δ₂= 0.98. The equation indicates that the normal wustite undergoes eutectoid decomposition into active wustite and stoichiometric magnetite (Fe₃O₄). Carbon dioxide (1.013 × 10⁵ Pa) was almost completely (100%) decomposed into carbon (zero valence) by the active wustite at the low temperature of 300°C, which was associated with the transformation of the active wustite into the stoichiometric magnetite. The internal pressure of the reaction cell eventually became a vacuum.     

Application of an Ion-Packing Model Based on Defect Clusters to Zirconia Solid Solutions: I, Modeling and Local Structure of Solid Solutions

Oxygen vacancies can be introduced into zirconia solid solution ZrO₂–MO _u ( u = 1 and 1.5) to maintain electroneutrality. Recently, the local structures around Zr⁴⁺ and M^{2 u +} ions in ZrO₂–MO _u solid solutions have been studied through EXAFS spectroscopy, diffuse scattering analysis, and single-crystal structure analysis. The present study constructs an ion-packing model for zirconia solid solutions based on some defect cluster models. The decrease of cell volume with the occurrence of vacancies is assumed to be expressed by decreasing the coordination number (CN) of cations around the vacancy. The distribution of CNs in a solid solution was calculated from a certain defect cluster model. The average interatomic distances, the average CN, and the short-range order parameters were calculated using this distribution of CNs. The local structures calculated from the model were compared with experimental data in the systems ZrO₂–MO_1.5 (M = Y, Gd, Yb, and Ca). In the ZrO₂–YO_1.5 system, the r (s–O) interatomic distance, where s represents Zr⁴⁺ or Y³⁺ and O represents O²⁻, decreased with Y content and therefore vacancy content. The probability of finding Y³⁺ around a vacancy increases with increasing yttria content from a comparison of the calculated results with the ones from recent EXAFS studies. The present model can qualitatively explain compositional and size dependences of the dopant on various local structures.