Au and Pt Remain Unoxidized on a CeO2-Based Catalyst during the Water-Gas Shift Reaction.

The active forms of Au and Pt in CeO2-based catalysts for the water-gas shift (WGS) reaction are an issue that remains unclear, although it has been widely studied. On one hand, ionic species might be responsible for weakening the Ce-O bonds, thus increasing the oxygen mobility and WGS activity. On the other hand, the close contact of Au or Pt atoms with CeO2 oxygen vacancies at the metal-CeO2 interface might provide the active sites for an efficient reaction. In this work, using in situ X-ray absorption spectroscopy, we demonstrate that both Au and Pt remain unoxidized during the reaction. Remarkable differences involving the dynamics established by both species under WGS atmospheres were recognized. For the prereduced Pt catalyst, the increase of the conversion coincided with a restructuration of the Pt atoms into cuboctahedrical metallic particles without significant variations on the overall particle size. Contrary to the relatively static behavior of Pt0, Au0 nanoparticles exhibited a sequence of particle splitting and agglomeration while maintaining a zero oxidation state despite not being located in a metallic environment during the process. High WGS activity was obtained when Au atoms were surrounded by oxygen. The fact that Au preserves its unoxidized state indicates that the chemical interaction between Au and oxygen must be necessarily electrostatic and that such an electrostatic interaction is fundamental for a top performance in the WGS process.

Highly Effective Non-Noble MnO2 Catalysts for 5-Hydroxymethylfurfural Oxidation to 2,5-Furandicarboxylic Acid.

Noble metal-free catalyst or catalytic oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid are proposed in this study as a proposal to solve one of the great disadvantages of this reaction of using preferably noble metal-based catalysts. The catalytic activity of six MnO2 crystal structures is studied as alternative. The obtained results showed a strong connection between catalytic activity the type of MnO2 structure organization and redox behavior. Among all tested catalysts, ϵ-MnO2 showed the best performance with an excellent yield of 74 % of 2,5-furandicarboxylic acid at full -hydroxymethylfurfural conversion.

Finely Tunable Carbon Nanofiber Catalysts for the Efficient Production of HMF in Biphasic MIBK/H2O Systems.

This work proposes catalytic systems for fructose dehydration to 5-hydroxymethylfurfural using a series of functionalized carbon nanofibers. The catalysts were synthesized via finely selected covalent grafting in order to include a variety of functionalities like pure Bronsted acid, tandem Brønsted/Lewis acid, and tandem Lewis acid/Lewis base catalysts. After the characterization and evaluation of acidity strength and the amount of acid centers, the catalyst series was screened and related to the product distribution. The best-performing catalyst was also used to optimize the reaction parameters in order to achieve 5-hydroxymethylfurfural yields rounding at 60% without significant humin formation.

Multiple zeolite structures from one ionic liquid template.

This study reports the use of 1-butyl-3-methyl imidazolium methanesulfonate ionic liquid as a template in the synthesis of zeolites. It is found that the silicon source determines the formation of beta (BEA), mordenite framework inverted (MFI), or analcime (ANA) zeolites. Depending on this source, different preorganized complexes are obtained that drive the formation of the different zeolite structures. In the presence of ethanol, the ionic liquid form preorganized complexes that drive the formation of MFI. In its absence, BEA is obtained. Whereas, the large amount of sodium present when using sodium metasilicate leads to ANA formation. A molecular simulation study of the relative stability of the template-framework system and location of the template provides further insight into the mechanism of synthesis.

Formic Acid Dehydrogenation over Ru- and Pd-Based Catalysts: Gas- vs. Liquid-Phase Reactions.

Formic acid has recently been revealed to be an excellent hydrogen carrier, and interest in the development of efficient and selective catalysts towards its dehydrogenation has grown. This reaction has been widely explored using homogeneous catalysts; however, from a practical and scalable point of view, heterogeneous catalysts are usually preferred in industry. In this work, formic acid dehydrogenation reactions in both liquid- and vapor-phase conditions have been investigated using heterogeneous catalysts based on mono- or bimetallic Pd/Ru. In all of the explored conditions, the catalysts showed good catalytic activity and selectivity towards the dehydrogenation reaction, avoiding the formation of undesired CO.

Functionalized Biochars as Supports for Ru/C Catalysts: Tunable and Efficient Materials for γ-Valerolactone Production.

Cotton stalks-based biochars were prepared and used to synthetize Ru-supported catalysts for selective production of γ-valerolactone from levulinic acid in aqueous media. Different biochars' pre-treatments (HNO3, ZnCl2, CO2 or a combination of them) were carried out to activate the final carbonaceous support. Nitric acid treatment resulted in microporous biochars with high surface area, whereas the chemical activation with ZnCl2 substantially increases the mesoporous surface. The combination of both treatments led to a support with exceptional textural properties allowing the preparation of Ru/C catalyst with 1422 m2/g surface area, 1210 m2/g of it being a mesoporous surface. The impact of the biochars' pre-treatments on the catalytic performance of Ru-based catalysts is fully discussed.

Bimetallic Ni-Ru and Ni-Re Catalysts for Dry Reforming of Methane: Understanding the Synergies of the Selected Promoters.

Designing an economically viable catalyst that maintains high catalytic activity and stability is the key to unlock dry reforming of methane (DRM) as a primary strategy for biogas valorization. Ni/Al2O3 catalysts have been widely used for this purpose; however, several modifications have been reported in the last years in order to prevent coke deposition and deactivation of the samples. Modification of the acidity of the support and the addition of noble metal promoters are between the most reported strategies. Nevertheless, in the task of designing an active and stable catalyst for DRM, the selection of an appropriate noble metal promoter is turning more challenging owing to the lack of homogeneity of the different studies. Therefore, this research aims to compare Ru (0.50 and 2.0%) and Re (0.50 and 2.0%) as noble metal promoters for a Ni/MgAl2O4 catalyst under the same synthesis and reaction conditions. Catalysts were characterized by XRF, BET, XRD, TPR, hydrogen chemisorption (H2-TPD), and dry reforming reaction tests. Results show that both promoters increase Ni reducibility and dispersion. However, Ru seems a better promoter for DRM since 0.50% of Ru increases the catalytic activity in 10% and leads to less coke deposition.

Wall paintings studied using Raman spectroscopy: a comparative study between various assays of cross sections and external layers.

This work describes a comparative study between in situ applications of portable Raman spectroscopy and direct laboratory measurements using micro-Raman spectroscopy on the surface of small samples and of cross sections. The study was performed using wall paintings from different sites of the Alcazar of Seville. Little information was obtained using a portable Raman spectrometer due to the presence of an acrylic polymer, calcium oxalate, calcite and gypsum that was formed or deposited on the surface. The pigments responsible for different colours, except cinnabar, were not detected by the micro-Raman spectroscopy study of the surface of small samples taken from the wall paintings due to the presence of surface contaminants. The pigments and plaster were characterised using cross sections. The black colour consisted of carbon black. The red layers were formed by cinnabar and white lead or by iron oxides. The green and white colours were composed of green emerald or atacamite and calcite, respectively. Pb3O4 has also been characterised. The white layers (plaster) located under the colour layers consisted of calcite, quartz and feldspars. The fresco technique was used to create the wall paintings. A wall painting located on a gypsum layer was also studied. The Naples yellow in this wall painting was not characterised due to the presence of glue and oils. This study showed the advantage of studying cross sections to completely characterise the pigments and plaster in the studied wall paintings.

Modificaciones ee las propiedades texturales y structurales de una zeolita usyy y de sus mezclas con "caolín clay" y clorhidrol como consecuencia del tratamiento hidrotérmico / Modifications of the textural and structural proprties of zeolite usy and its miixture with kaolin clay and chlorhydrol as consequence of the hydrothermal treatment

El catalizador de FCC está constituido por partículas de composición compleja donde el componente activo es una zeolita Y. En este trabajo se presentan los resultados texturales y estructurales de una zeolita USY comercial lixiviada, de una serie de catalizadores con 7, 15, 25, 35 y 45% de material activo y los de estos materiales desactivados hidrotérmicamente. Las muestras se caracterizaron por fluorescencia de rayos X (FRX), difracción de rayos X (DRX), resonancia magnética nuclear de silicio (29Si RMN) y fisiadsorción de nitrógeno a 77 K. A partir de estos resultados se hallaron correlaciones entre el volumen de microporo y el contenido de zeolita y entre el grado de cristalinidad y el porcentaje de zeolita. Además, se encontró que un tratamiento con sólo 20% de vapor de agua a 1033 K durante 16 horas destruye los grupos estructurales Si(2Al) y Si(3Al) como reflejo de la dealuminización drástica que sufre el material.

FCC catalyst is made up of particles of complex composition where the main active component is a Y zeolite. This work presents the textural and structural results of a commercial USY zeolite which had been previously prepared from a set of catalysts with 7, 15, 25, 35 y 45% of active material and of the hydrothermally deactivated materials zeolite. The samples have been characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), 29Si NMR spectroscopy and nitrogen adsorption at 77K. From these results was found correlations between micropore volume and zeolite content and degree crystallinity and %zeolite. Also, it was found that an hydrothermal treatment at 1033 K with only 20% steam during 16 hours destroys the structural groups Si(2Al) and Si(3Al) as a reflection of the strongly dealumination of the zeolite component of the catalyst.

Mediastinitis necrotizante descendente / Descending necrotizing mediasstinitis

Se presenta un niño de 3 años que a consecuencia de una herida punzante en la pared posterior de la faringe, desarrolló un absceso retrofaríngeo, el cual por vía descendente invadió mediatino y ambas cavidades pleurales. A pesar de la antibioticoterapia agresiva, drenaje toráxico bilateral, y drenaje del espacio retrovisceral, el paciente falleció. La mediastinitis Necrotizante Descendente (MND) ocurre como complicacion de un proceso infeccioso localizado en orofaringe, y en esta presentación se discuten problemas etiológicos, fisiopatológicos y terapeúticos (AU)

Mediastinitis necrotizante descendente / Descending necrotizing mediasstinitis

Se presenta un niño de 3 años que a consecuencia de una herida punzante en la pared posterior de la faringe, desarrolló un absceso retrofaríngeo, el cual por vía descendente invadió mediatino y ambas cavidades pleurales. A pesar de la antibioticoterapia agresiva, drenaje toráxico bilateral, y drenaje del espacio retrovisceral, el paciente falleció. La mediastinitis Necrotizante Descendente (MND) ocurre como complicacion de un proceso infeccioso localizado en orofaringe, y en esta presentación se discuten problemas etiológicos, fisiopatológicos y terapeúticos