Difference in reaction mechanism between ZnZrOx and InZrOx for CO2 hydrogenation.

Oxide solid-solution catalysts, such as Zn-doped ZrO2 (ZnZrOx) and In-doped ZrO2 (InZrOx), exhibit distinctive catalytic capabilities for CH3OH synthesis via CO2 hydrogenation. We investigated the active site structures of these catalysts and their associated reaction mechanisms using both experimental and computational approaches. Electron microscopy and X-ray absorption spectroscopy reveal that the primary active sites are isolated cations, such as Zn2+ and In3+, dissolved in tetragonal ZrO2. Notably, for Zn2+, decomposition of the methoxy group, which is an essential intermediate in CH4 synthesis, is partially suppressed because of the relatively high stability of the methoxy group. Conversely, the methyl group strongly adsorbs on In3+, facilitating the conversion of the methoxy species into methyl groups. The decomposition of CH3OH is also suggested to contribute to CH4 synthesis. These results highlight the generation of CH4 as a byproduct of the InZrOx catalyst. Understanding the active site structure and elucidating the reaction mechanism at the atomic level are anticipated to contribute significantly to the future development of oxide solid-solution catalysts.

Direct conversion of carbon dioxide and steam into hydrocarbons and oxygenates using solid acid electrolysis cells.

Electrolysis at intermediate temperatures (100-600°C) is promising because high reaction rates and high product selectivity can be achieved simultaneously during CO2 reduction. However, intermediate temperature electrolysis has rarely been reported owing to electrolyte limitations. Here, solid acid electrolysis cells (SAECs) were adopted for electrochemically reducing CO2. Carbon monoxide, methane, methanol, ethane, ethylene, ethanol, acetaldehyde and propylene were produced from CO2 and steam, using Cu-containing composite cathodes at 220°C and atmospheric pressure. The results demonstrate the potential of SAECs for producing valuable chemical feedstocks. At the SAEC cathode, CO2 was electrochemically reduced by protons and electrons. The product selectivity and reaction rate were considerably different from those of thermochemical reactions with gaseous hydrogen. Based on the differences, plausible reaction pathways were proposed.

An in situ DRIFTS study on nitrogen electrochemical reduction over an Fe/BaZr0.8Y0.2O3-δ -Ru catalyst at 220 °C in an electrolysis cell using a CsH2PO4/SiP2O7 electrolyte.

In situ DRIFTS measurements of an Fe/BZY-Ru cathode catalyst in an electrolysis cell using a CsH2PO4/SiP2O7 electrolyte were carried out in a mixed N2-H2 gas flow under polarization. The formation of N2H x species was confirmed under polarization, and an associative mechanism in the electrochemical NRR process was verified.

Porous intermetallic Ni2XAl (X = Ti or Zr) nanoparticles prepared from oxide precursors.

Porous intermetallic Ni2XAl (X = Ti or Zr) nanoparticles with small crystallite sizes (24-34 nm) and high Brunauer-Emmett-Teller (BET) surface areas (10-71 m2 g-1) were prepared from oxide precursors by a chemical route. CaH2 acted as a template to form the porous morphologies and assisted the reduction.

Hydrogen Production by Steam Electrolysis in Solid Acid Electrolysis Cells.

Hydrogen production by steam electrolysis at intermediate temperatures has potential for both the high energy conversion efficiency and the flexible operability suitable for the utilization of renewable energy resources. Employment of proton-conducting solid acid electrolytes at around 200 °C is considered promising but has rarely been investigated. Here, steam electrolysis was performed at 160-220 °C using a solid acid electrolysis cell (SAEC) composed of a CsH2 PO4 /SiP2 O7 composite electrolyte and Pt/C electrodes. Hydrogen production was successfully demonstrated with Faraday efficiencies around 80 %. Key factors affecting the SAEC stability were investigated in detail for the first time. It was revealed that a certain part of the electrolyte migrated into the porous anode structure during the operation. The migrated electrolyte prevented the gas diffusion and flooded the Pt/C catalyst layer. It was also found that carbonaceous materials in the anode was oxidized, leading to the decrease in the number of electrochemically active sites. Based on the findings, Pt mesh was employed as an alternative anode. The SAEC with the Pt mesh anode showed superior stability, demonstrating the importance of the anode design. The present work provides a comprehensive view of the stability issues, which is essential for the development of durable and practical SAECs.

Direct electrochemical synthesis of oxygenates from ethane using phosphate-based electrolysis cells.

Ethane was converted directly to acetaldehyde and ethanol by partial oxidation at 220 °C and ambient pressure using an electrolysis cell with a proton-conducting electrolyte, CsH2PO4/SiP2O7, and Pt/C electrodes. The ethane conversion and the selectivity to the products increased with the voltage applied to the cell. It was found that O species generated by water electrolysis functioned as a favorable oxidant for partial oxidation of ethane on the Pt/C anode at intermediate temperatures. The production rates of acetaldehyde and ethanol recorded in this study were significantly higher than those in preceding reports.

Synthesis of Silica Membranes by Chemical Vapor Deposition Using a Dimethyldimethoxysilane Precursor.

Silica-based membranes prepared by chemical vapor deposition of tetraethylorthosilicate (TEOS) on γ-alumina overlayers are known to be effective for hydrogen separation and are attractive for membrane reactor applications for hydrogen-producing reactions. In this study, the synthesis of the membranes was improved by simplifying the deposition of the intermediate γ-alumina layers and by using the precursor, dimethyldimethoxysilane (DMDMOS). In the placement of the γ-alumina layers, earlier work in our laboratory employed four to five dipping-calcining cycles of boehmite sol precursors to produce high H2 selectivities, but this took considerable time. In the present study, only two cycles were needed, even for a macro-porous support, through the use of finer boehmite precursor particle sizes. Using the simplified fabrication process, silica-alumina composite membranes with H2 permeance > 10-7 mol m-2 s-1 Pa-1 and H2/N2 selectivity >100 were successfully synthesized. In addition, the use of the silica precursor, DMDMOS, further improved the H2 permeance without compromising the H2/N2 selectivity. Pure DMDMOS membranes proved to be unstable against hydrothermal conditions, but the addition of aluminum tri-sec-butoxide (ATSB) improved the stability just like for conventional TEOS membranes.

Gas Separation Silica Membranes Prepared by Chemical Vapor Deposition of Methyl-Substituted Silanes.

The effect on the gas permeance properties and structural morphology of the presence of methyl functional groups in a silica membrane was studied. Membranes were synthesized via chemical vapor deposition (CVD) at 650 °C and atmospheric pressure using three silicon compounds with differing numbers of methyl- and methoxy-functional groups: tetramethyl orthosilicate (TMOS), methyltrimethoxysilane (MTMOS), and dimethyldimethoxysilane (DMDMOS). The residence time of the silica precursors in the CVD process was adjusted for each precursor and optimized in terms of gas permeance and ideal gas selectivity criteria. Final H2 permeances at 600 °C for the TMOS-, MTMOS-, and DMDMOS-derived membranes were respectively 1.7 × 10-7, 2.4 × 10-7, and 4.4 × 10-8 mol∙m-2∙s-1∙Pa-1 and H2/N2 selectivities were 990, 740, and 410. The presence of methyl groups in the membranes fabricated with the MTMOS and DMDMOS precursors was confirmed via Fourier-transform infrared (FTIR) spectroscopy. From FTIR analysis, an increasing methyl signal in the silica structure was correlated with both an improvement in the hydrothermal stability and an increase in the apparent activation energy for hydrogen permeation. In addition, the permeation mechanism for several gas species (He, H2, Ne, CO2, N2, and CH4) was determined by fitting the gas permeance temperature dependence to one of three models: solid state, gas-translational, or surface diffusion.

Fabrication and Evaluation of Trimethylmethoxysilane (TMMOS)-Derived Membranes for Gas Separation.

Gas separation membranes were fabricated with varying trimethylmethoxysilane(TMMOS)/tetraethoxy orthosilicate (TEOS) ratios by a chemical vapor deposition (CVD) method at650 °C and atmospheric pressure. The membrane had a high H2 permeance of 8.3 × 10-7 mol m-2 s-1Pa-1 with H2/CH4 selectivity of 140 and H2/C2H6 selectivity of 180 at 300 °C. Fourier transforminfrared (FTIR) measurements indicated existence of methyl groups at high preparationtemperature (650 °C), which led to a higher hydrothermal stability of the TMMOS-derivedmembranes than of a pure TEOS-derived membrane. Temperature-dependence measurements ofthe permeance of various gas species were used to establish a permeation mechanism. It was foundthat smaller species (He, H2, and Ne) followed a solid-state diffusion model while larger species (N2,CO2, and CH4) followed a gas translational diffusion model.

Mechanochemical Decomposition of Crystalline Cellulose in the Presence of Protonated Layered Niobium Molybdate Solid Acid Catalyst.

Direct depolymerization of crystalline cellulose into water-soluble sugars by solvent-free ball milling was examined in the presence of a strongly acidic layered metal oxide, HNbMoO6 , resulting in full conversion with 72 % yield of water-soluble sugars. Measurements by 13 C cross-polarization magic angle spinning NMR spectroscopy and X-ray diffraction revealed that amorphization of cellulose occurred rapidly within 10 min. Scanning electron microscopy equipped with an energy dispersive X-ray indicated that the substrate and the catalyst were well mixed during milling. The time course of the product distribution showed that most of the resultant water-soluble sugars were produced not by successive degradation of oligosaccharides but by direct depolymerization of cellulose chains. The products included glucose, mannose, and cello-oligomers, as well as anhydrosugars. Addition of small amounts of polar solvents increased the sugar yield, whereas further addition of water decreased the selectivity to anhydrosugars. Calculations of the mechanical energy required for the ball-milling process showed that 0.02 % was utilized for the chemical transformation under the conditions examined in this study.

Efficient Epimerization of Aldoses Using Layered Niobium Molybdates.

Both non-acidic LiNbMoO6 and strongly acidic HNbMoO6 efficiently catalyze the epimerization of sugars including glucose, mannose, xylose, and arabinose in water. The reactions over these oxides reached almost equilibrium within a few hours where yields of corresponding epimers from glucose, xylose, and arabinose were 24-29%. The layered mixed oxides functioned as heterogeneous catalysts and could be reused without loss of activity, whereas bulk molybdenum oxide MoO3 was completely dissolved during the reaction. A (13)C substitution experiment showed that the reaction proceeds through a 1,2-rearrangement mechanism. The surface Mo octahedra were responsible for the activity. The layered HNbMoO6 could also afford mannose from cellobiose through hydrolysis and successive epimerization.

Intercalation-controlled cyclodehydration of sorbitol in water over layered-niobium-molybdate solid acid.

Layered niobium molybdate (HNbMoO6 ) was used in the aqueous-phase dehydration of sorbitol and was found to exhibit remarkable selectivity toward its monomolecular-dehydrated intermediate 1,4-sorbitan. This was attributed to the selective intercalation of sorbitol within the interlayers with strong Brønsted acid sites.

Preparation of monodisperse chitosan microcapsules with hollow structures using the SPG membrane emulsification technique.

We describe herein successful preparations of monodisperse chitosan microcapsules with hollow structures using the SPG membrane emulsification technique. Two preparation procedures were examined in this study. In the first method, monodisperse calcium alginate microspheres were prepared and then coated with unmodified chitosan. Subsequently, tripolyphosphate treatment was conducted to physically cross-link chitosan and solubilize the alginate core at the same time. In the second method, photo-cross-linkable chitosan was coated onto the monodisperse calcium alginate microspheres, followed by UV irradiation to chemically cross-link the chitosan shell and tripolyphosphate treatment to solubilize the core. For both methods, it was determined that the average diameters of the chitosan microcapsules depended on those of the calcium alginate microparticles and that the microcapsules have hollow structures. In addition, the first physical cross-linking method using tripolyphosphate was found to be preferable to obtain the hollow structure, compared with the second method using chemical cross-linking by UV irradiation. This was because of the difference in the resistance to permeation of the solubilized alginate through the chitosan shell layers.