Excess-Methane CO2 Reforming over Reduced KIT-6-Ni-Y Mesoporous Silicas Monitored by In Situ XAS-XRD.

Making Europe less dependent on imported fuels requires a long-term strategy. Low-quality natural gas and biogas could be used to mitigate the energy crisis, and excess-methane dry reforming has the potential to upgrade a mixture of CH4 and CO2. Herein, nickel-based KIT-6-supported catalysts (KIT-6-Ni) were modified with 3, 6, and 8 wt % of yttrium (Y/Ni molar ratio of 0.5, 1.07, and 1.5) to investigate the influence of this element on catalytic performance. Yttrium was well dispersed, preserving the mesopore structure of KIT-6. The yttrium addition increased the total basicity, contributing to a lower deactivation factor and remarkably stable syngas production compared to the catalyst containing only Ni. In situ XAS-XRD showed that Y allowed for the reduction of Ni2+ to Ni0 at significantly lower temperatures. A significant difference in the rate of reduction was observed for the studied samples. The analysis showed that the data of linear combination fitting of XANES can demonstrate linear fits with the reduction rate of NiO. The reduction rate of bulk and weakly interacting NiO increased for Y-promoted samples, while a decrease in the rate was registered for species strongly interacting with the support. The latter decreased more with increasing yttrium content. EXAFS analysis showed that Ni is completely reduced in the samples. Under excess-methane dry reforming conditions, the studied catalysts remained fully reduced and showed resistance to sintering of Ni particles. HRTEM results of KIT-6-Ni5-Y8 indicated that metallic Ni particles were decorated by Y2O3 and/or NiYO3. The dominant deactivation mechanism was the carbon encapsulation of Ni particles and the growth of filaments.

Co-Precipitated Ni-Mg-Al Hydrotalcite-Derived Catalyst Promoted with Vanadium for CO2 Methanation.

Co-precipitated Ni-Mg-Al hydrotalcite-derived catalyst promoted with vanadium were synthesized with different V loadings (0-4 wt%) and studied in CO2 methanation. The promotion with V significantly changes textural properties (specific surface area and mesoporosity) and improves the dispersion of nickel. Moreover, the vanadium promotion strongly influences the surface basicity by increasing the total number of basic sites. An optimal loading of 2 wt% leads to the highest activity in CO2 methanation, which is directly correlated with specific surface area, as well as the basic properties of the studied catalysts.

Syngas Production via CO2 Reforming of Methane over Aluminum-Promoted NiO-10Al2O3-ZrO2 Catalyst.

CO2 reforming of methane was studied at medium temperature (700 °C) using a GSHV of 48,000 h-1 over nickel catalysts supported on ZrO2 promoted by alumina. The catalysts were prepared by a one-step synthesis method and characterized by BET, H2-TPR, XRD, XPS, TEM, Raman spectroscopy, and TGA. The NiO-10Al2O3-ZrO2 catalyst exhibited higher catalytic performance in comparison with the NiO-ZrO2 catalyst. The enhancement of catalytic activity in dry reforming could be associated with the alterations in surface properties due to Al promotion. First, the Al promoter could modify the structure of ZrO2, leading to an increase of its pore volume and pore diameter. Second, the NiO-10Al2O3-ZrO2 catalyst exhibited high resistance to sintering. Third, the NiO-10Al2O3-ZrO2 catalyst showed high suppression to the loss of nickel during a long-term catalytic test. Finally, the addition of Al could inhibit the reduction of ZrO2 during the reduction and reaction, endowing further the stability.

High Performance Tunable Catalysts Prepared by Using 3D Printing.

Honeycomb monoliths are the preferred supports in many industrial heterogeneous catalysis reactions, but current extrusion synthesis only allows obtaining parallel channels. Here, we demonstrate that 3D printing opens new design possibilities that outperform conventional catalysts. High performance carbon integral monoliths have been prepared with a complex network of interconnected channels and have been tested for carbon dioxide hydrogenation to methane after loading a Ni/CeO2 active phase. CO2 methanation rate is enhanced by 25% at 300 °C because the novel design forces turbulent flow into the channels network. The methodology and monoliths developed can be applied to other heterogeneous catalysis reactions, and open new synthesis options based on 3D printing to manufacture tailored heterogeneous catalysts.

Physical and chemical characterization of shock-induced cavitation.

A strong impact on a water surface induces a shock wave propagation with a significant pressure variation leading to cavitation bubble formation. A new shock induced cavitation reactor described in this work was characterized by physical and chemical techniques. Water hammer model verification with Joukowsky approach allowed to determine the wave speed propagation and gas fraction in water submitted to shock. These values were used for frequency analysis and compared with direct bubble visualization in order to estimate the influence of the experimental parameters on the shock-induced cavitation. Thereby, the shock wave contains a broad spectrum as decomposed into frequencies. This multi-frequency nature induces heterogeneous bubbles with calculated radii of 0.01 to 3.5 mm and observed radii of 0.01 to 2.8 mm depending on experimental conditions (initial pressure, impact height, gas atmosphere). For the first time, the formation of hydroxyl radicals was proven under impact-induced cavitation. The concentration of radicals increases with increasing number of successive impacts, reaching ca. 1.3 µmol.L-1 after 500 impacts in the presence of 20% O2-Ar as saturating gas. Radical generation seems to be relatively independent of the impact height but strongly depend on the type of gas saturating water, being substantially lower in the presence of air. Moreover, radical generation increases when decreasing the initial pressure and depends on the frequency at which water is impacted by the piston. Nevertheless, yield of OH radicals during shock-induced cavitation remains much lower than that produced by power ultrasound.

New Approach for Understanding the Oxidation Stability of Neopolyol Ester Lubricants Using a Small-Scale Oxidation Test Method.

This work presents, for the first time, the evaluation on the oxidation stability of synthetic oils for an aircraft engine using the rapid small-scale oxidation test (RSSOT) method. Polyol ester lubricants with and without additives were oxidized at 423 K and 7 bar. The pressure drop plots show that during the first period of thermal degradation, the consumption of oxygen is similar for both samples. This part corresponds to the initiation steps of the mechanism of oxidation. Then, the curve of the oil without additives reveals an increase in the depletion of oxygen, corresponding to the kinetic propagation step. Because of the presence of antioxidants, this phase is not observed for oil-containing additives. The RSSOT method also allows us to quantify the time needed for the ester base to produce enough free radicals in order to propagate the mechanism of oxidation. A methodic comparison with other samples containing the raw oil and one additive is also proposed.

Histopathologic and Ultrastructural Features of Gold Thread Implanted in the Skin for Facial Rejuvenation.

The authors report the histopathologic and ultrastructural features of gold threads, which were implanted in the cheek subcutis of a 77-year-old woman 10 years ago. These particles did not give rise to any adverse reactions and were fortuitously discovered by the surgeon during a facelift. Histopathology showed a nonpolarizing exogenous material consisting of black oval structures surrounded by a capsule of fibrosis and by a discrete inflammatory reaction with a few giant cells. In some cases, only a long fibrous tract surrounded by a moderate mononucleate infiltrate was observed. The wires were characterized with scanning electron microscopy, and X-ray microanalysis revealed a specific peak at 2.2 keV representative of gold that was absent in the control skin sample. As this value is specific for gold, it confirms the presence of the metal in the patient's skin. The histopathologic appearance of gold threads is particularly distinctive and easily recognizable by dermatopathologists.

A molecular approach for unraveling surface phase transitions: sulfation of BaO as a model NO(x) trap.

SO(3) -induced surface reconstruction: The SO(3) molecule as a multidentate ligand induces remarkable surface reconstruction phenomena on alkaline earth oxide surface. By using ab initio computations, adsorption properties are derived to elucidate the thermodynamics of the SO(3) -BaO system.