Synthesis of Dimethyl Carbonate by Transesterification of Propylene Carbonate with Methanol on CeO2-La2O3 Oxides Prepared by the Soft Template Method.

In this study, CeO2, La2O3, and CeO2-La2O3 mixed oxide catalysts with different Ce/La molar ratios were prepared by the soft template method and characterized by different techniques, including inductively coupled plasma atomic emission spectrometry, X-ray diffraction, N2 physisorption, thermogravimetric analysis, and Raman and Fourier transform infrared spectroscopies. NH3 and CO2 adsorption microcalorimetry was also used for assessing the acid and base surface properties, respectively. The behavior of the oxides as catalysts for the dimethyl carbonate synthesis by the transesterification of propylene carbonate with methanol, at 160 °C under autogenic pressure, was studied in a stainless-steel batch reactor. The activity of the catalysts was found to increase with an increase in the basic sites density. The formation of dimethyl carbonate was favored on medium-strength and weak basic sites, while it underwent decomposition on the strong ones. Several parasitic reactions occurred during the transformation of propylene carbonate, depending on the basic and acidic features of the catalysts. A reaction pathway has been proposed on the basis of the components identified in the reaction mixture.

Sub-Micrometric MCM-41 Particles as Support to Design Efficient and Regenerable Maghemite-Based Sorbent for H2S Removal.

In this work, highly dispersed maghemite (λ-Fe2O3) in form of ultrasmall nanoparticles (about 2 nm) was embedded into a mesostructured silica MCM-41 (about 600 nm) featuring regular submicrometric hexagonal shaped particles via the two-solvent incipient wetness impregnation strategy. The obtained nanocomposite was then tested as H2S sorbent in the mid-temperature range. When compared with a commercial sorbent (KatalkoJM 32-5), it showed superior performances after the first sulfidation which remained steady over three repeated sulfidation cycles, highlighting the regenerability properties of the composite. In order to evaluate the effect of the length of the pore channels on the accessibility of H2S to the active phase, an analogous micrometric λ-Fe2O3@MCM-41, featuring micrometric channels and particles of irregular shape was used as reference.

Nanostructured Ni/CeO2-ZrO2 Catalysts for CO2 Conversion into Synthetic Natural Gas.

NiO-CeO2-ZrO2 mixed oxides, with Ni/(Ce + Zr) = 1 mol/mol and different Ce/Zr molar ratios, were prepared by the soft-template method. The chemical composition, texture, structure, and redox features of the synthesized systems were investigated by different techniques. All samples were nanocrystalline (NiO nanocrystal average size 4 nm) and had high surface area and quite an ordered mesoporous system. The catalytic performances in the CO2 conversion into methane were studied at atmospheric pressure, 300 °C, and stoichiometric H2/CO2 molar ratio. Prior to reaction the catalysts were submitted to a mild reduction pretreatment (H2 at 400 °C for 1 h). XRD analysis of the samples after pretreatment showed the presence of small Ni crystals (4-7 nm) on all the samples as well as of some unreduced NiO nanocrystals on the systems with high Zr content, in accordance with H2-TPR experiments, which indicated that NiO reduction is promoted by CeO2 but hindered by ZrO2. The catalytic tests were performed at two different space velocities (72000 and 900000 cm³ h-1 g-1cat) on a series of Ni-based catalysts supported on CeO2-ZrO2 systems with different Ce/Zr ratios, including the two pure oxides. CO2 conversion and selectivity to CH4 (which was always close to 100 mol%) were constant throughout the 6-hour runs. CO2 conversion resulted to increase with CeO2 content in the catalyst, thus indicating the role of the CeO2 component of the support in activating CO2, whereas H2 is activated on the Ni nanoparticles.

Modifications induced by pretreatments on Au/SBA-15 and their influence on the catalytic activity for low temperature CO oxidation.

SBA-15 functionalization with mercaptopropyltrimethoxysilane has been used to prepare supported gold catalysts for the low temperature CO oxidation reaction. Supports and catalysts have been characterized by chemical analysis, CHS analysis, XRD, TGA, nitrogen adsorption-desorption at 77 K, TEM, CPMAS NMR, XPS and EPR. Catalytic runs have been carried out at atmospheric pressure and 313-623 K and the influence of diverse thermal treatments of the samples prior to reaction has been investigated. The presence of organic residues and the size of the gold nanoparticles strongly affect catalytic activity. Only high-temperature calcination in air followed by treatment under H2 atmosphere leads to active catalysts. After complete elimination of the functionalizing agent, caused by the calcination step, a gold-mediated "activation" process of the silica support takes place during the hydrogen treatment. As a consequence, active catalysts for the low temperature CO oxidation are obtained, even though the size of the Au particles is too large for establishing direct Au-oxygen interactions, usually assumed to be essential for the reaction over silica-supported gold catalysts.