A jade pished hand-axe from Tubino's Cection (Valencina de la Concepción Local Museum, Sevilla, Spain)

A pished axe donated to the Valencina de la Concepción Museum (Seville, Spain) in November 2010, and that had belonged to Francisco María Tubino y Oliva's (1833-1888) personal clection, is studied. Although the exact provenance of this object is unknown, there are reasons to think that it might have been found on some archaẽogical site of the Seville province. Through the application of two different analytical techniques (XRD, DCμRS), this axe is identified as a jade-jadeite of purity above 95 ml%, which necessarily implies it came from the Alps. In the conclusions a discussion of this artifact is made in terms of long distance contact in Iberian Late Prehistory.Peer Reviewe

Au-supported on Fe-doped ceria solids prepared in water-in-oil microemulsions: Catalysts for CO oxidation

Gold catalysts were synthesized by deposition-precipitation employing Fe-doped ceria systems, previously obtained by means of the water-in-oil microemulsions methodology with different iron contents (10, 25 and 50 Fe at.%). The final catalysts were tested in the CO oxidation reaction in presence of H2. After gold deposition the crystalline structure of the supports was not altered. Moreover no XRD lines associated to gold were detected, indicating its high dispersion. Solid solution was generated in all samples, although the segregation of iron oxide was detected for the material with the highest iron loading. This phenomenon was then enhanced for the corresponding gold catalyst that also presented sintering of the gold nanoparticles. Strong interaction between gold and the oxygen vacancies of the supports was demonstrated, as well as the promotion of the reducibility of surface Ce4+ and Fe3+ species at low temperatures. A remarkable promotion of the CO conversion at lower temperatures respect to that of the supports was observed for the gold catalysts. Below 120 °C, lower the amount of iron incorporated, higher the catalytic performance of the catalyst. This behaviour is closely related not only to a high gold dispersion but also to the ability for creating additional oxygen vacancies in the support, required for the CO oxidation reaction

Fe-doped ceria solids synthesized by the microemulsion method for CO oxidation reactions

A series of Ce-Fe mixed oxides as well as the pure oxides were synthesized by the microemulsions method. The solid solution formation was established for all the Fe-doped systems and only a hardly noticeable segregation of α-Fe2O3 was appreciated for the solid with the maximum iron content (50at.% Fe). The oxygen exchange is improved for all the Fe-doped systems; however the 10at.% Fe appears as the optimal iron content for achieving the maximum oxygen vacancies concentration and the higher reducibility efficiency. The CO oxidation (TOX, PROX) is especially achieved for the solids with the lower iron contents but with a superior oxygen vacancies proportion. These Ce-Fe systems prepared from microemulsions are very attractive to be considered as supports for depositing active phases capable of enhancing oxygen exchange ability of the whole system, allowing higher CO oxidation abilities.Ministerio de Ciencia e Innovación ENE2009-14522-C05-01Junta de Andalucía P09-TEP-545

Au/CeO2 metallic monolith catalysts: Influence of the metallic substrate

Ceria-based gold catalysts were successfully deposited on ferritic stainless steel (Fecralloy) and aluminium monoliths. The prepared monolithic and reference powder catalysts were characterized by means of S BET, X-ray diffraction, glow discharge optical emission spectroscopy and scanning electron microscopy-energy dispersive X-ray analysis techniques and tested in the CO oxidation reaction. Characterization results put in evidence the diffusion of cations from the catalytic layer on the surface of the monoliths to the metallic oxide scale and inversely, from the oxide scale to the catalysts, thus altering the catalytic formulation and affecting the CO oxidation properties of the catalytic device. The extension and nature of the modifications produced depend on the nature of the catalysts and the metallic substrate, as well as the reaction conditions applied. These facts must be considered when gold catalysts are supported on metallic-structured devices. © 2013 The Author(s).Peer Reviewe

Preferential oxidation of CO over Au/CuOx-CeO2 catalyst in microstructured reactors studied through CFD simulations

A computational fluid dynamics (CFD) simulation study of the preferential oxidation of CO (CO-PROX) in microstructured reactors consisting in square and semicircular microchannels coated with anAu/CuOx¿CeO2catalyst is presented. The CO content of the feed stream was set at 1 vol.%. A parametricsensitivity analysis has been performed under isothermal conditions revealing that an optimal reactiontemperature exists that leads to a minimum CO content at the microreactor exit. The influence of thespace velocity, CO2concentration and oxygen-to-CO molar ratio in the feed stream (), catalyst loading,and microchannel characteristic dimension (d) on the microreactor performance has been investigated.Under suitable conditions, the CO concentration can be reduced below 10 ppm at relatively low tem-peratures within the 155¿175¿C range. A negative effect of the increase of d from 0.35 mm to 2.8 mmon the CO removal efficiency has been found and attributed to a more detrimental effect of the masstransport limitations on the oxidation of CO than that of H2. Non-isothermal CFD simulations have beenperformed to investigate the cooling of the CO-PROX reactor with air or a fuel cell anode off gas surrogatein parallel microchannels. Due to the very rapid heat transfer allowed by the microreactor and the stronginfluence of the reaction temperature on the exit CO concentration, a careful control of the coolant flowrate and inlet temperature is required for proper reactor operation. The microreactor behavior is virtuallyisothermal.Peer Reviewe

Preferential oxidation of CO over Au/CuOx-CeO2 catalyst in microstructured reactors studied through CFD simulations

A computational fluid dynamics (CFD) simulation study of the preferential oxidation of CO (CO-PROX) in microstructured reactors consisting in square and semicircular microchannels coated with anAu/CuOx¿CeO2catalyst is presented. The CO content of the feed stream was set at 1 vol.%. A parametricsensitivity analysis has been performed under isothermal conditions revealing that an optimal reactiontemperature exists that leads to a minimum CO content at the microreactor exit. The influence of thespace velocity, CO2concentration and oxygen-to-CO molar ratio in the feed stream (), catalyst loading,and microchannel characteristic dimension (d) on the microreactor performance has been investigated.Under suitable conditions, the CO concentration can be reduced below 10 ppm at relatively low tem-peratures within the 155¿175¿C range. A negative effect of the increase of d from 0.35 mm to 2.8 mmon the CO removal efficiency has been found and attributed to a more detrimental effect of the masstransport limitations on the oxidation of CO than that of H2. Non-isothermal CFD simulations have beenperformed to investigate the cooling of the CO-PROX reactor with air or a fuel cell anode off gas surrogatein parallel microchannels. Due to the very rapid heat transfer allowed by the microreactor and the stronginfluence of the reaction temperature on the exit CO concentration, a careful control of the coolant flowrate and inlet temperature is required for proper reactor operation. The microreactor behavior is virtuallyisothermal.Ministerio de Ciencia e Innovación ENE2009-14522-C04Ministerio de Economía y Competitividad ENE2012-37431-C0

Organocatalytic Michael Addition of Unactivated α-Branched Nitroalkanes to Afford Optically Active Tertiary Nitrocompounds

The direct, asymmetric conjugate addition of unactivated α-branched nitroalkanes is developed based on the combined use of chiral amine/ureidoaminal bifunctional catalysts and a tunable acrylate template to provide tertiary nitrocompounds in 55–80% isolated yields and high enantioselectivity (e.r. up to 96:4). Elaboration of the ketol moiety in thus obtained adducts allows a fast entry to not only carboxylic and aldehyde derivatives but also nitrile compounds and enantioenriched 5,5-disubstituted γ-lactams.We thank the Basque Government (EJ, grant IT1583-22) and Agencia Estatal de Investigación (grants PID2019-109633GB and PID2022-137153NB-C21/AEI/10.13039/501100011033) for financial support. A.G.-U. thanks EJ; B.L. thanks the Navarra Government, and M.E.-V. thanks UPNA (PJUPNA18-2022). Authors also thank SGIker (UPV/EHU/ERDF, EU) for providing NMR, HRMS, and X-ray resources

Preferential oxidation of CO (CO-PROX) over CuOx/CeO2 coated microchannel reactor

The general aspects of the synthesis and characterization results of a CuOx/CeO2 catalyst were presented. In addition the principal steps for manufacturing a microchannel reactor and for the coating of the CuOx/CeO2 catalyst onto the microchannels walls, were also summarized. The catalytic activity of this microchannel reactor during the preferential oxidation of CO (CO-PROX) was evaluated employing a feed-stream that simulates a reformate off-gas after the WGS unit. Two activation atmospheres were studied (H2/N2 and O2/N 2). The reducing pretreatment improved the resistance to deactivation by formation of carbonaceous species over the catalyst surface at high temperatures. The presence of H2O and CO2 in the feed-stream was also analyzed indicating that the adsorption of CO2 inhibited the conversion of CO at lower temperatures because these compounds modified the active sites through the formation of carbonaceous species on the catalyst surface. Finally, the experimental results of the microreactor performance were compared with CFD simulations that were carried out using a kinetic for the CuOx/CeO2 powder catalyst. The experimental results were reasonably well described by the model, thus confirming its validity.Peer Reviewe

Selective CO removal over Au/CeFe and CeCu catalysts in microreactors studied through kinetic analysis and CFD simulations

A kinetic study of the preferential oxidation of CO in H2 rich streams (CO-PrOx) over a cerium-copper oxide (CeCu) and a gold catalyst supported on cerium-iron oxide (Au/CeFe) is presented. The gold catalyst is very active but the CeCu oxide is more selective. A kinetic model describing the CO-PrOx system with CO2 and H2O in the feed has been formulated considering the oxidation of CO and H2 and the reverse water-gas shift reaction. The rate equations have been implemented in computational fluid dynamics codes to study the influence of the operating variables on the CO-PrOx in microchannels and microslits. The CeCu catalyst is the only one capable of achieving final CO contents below 10-100ppmv. Due to the opposite effect of temperature on activity and selectivity there is an optimal temperature at which the CO content is minimal over CeCu. This temperature varies between 170 and 200°C as the GHSV increases from 10,000 to 50,000h-1. Simulations have evidenced the very good heat transfer performance of the microdevices showing that the CO-PrOx temperature can be controlled using air as cooling fluid although the inlet temperature and flow rate should be carefully controlled to avoid reaction extinction. Both microchannels and microslits behaved similarly. The fact that the microslits are much easier to fabricate may be an interesting advantage in favour of that geometry in this case.Ministerio de Ciencia e Innovación MAT2006-12386-C05, ENE2009-14522-C0

Influence of the O2/CO ratio and the presence of H2O and CO2 in the feed-stream during the preferential oxidation of CO (PROX) over a CuOx/CeO2-coated microchannel reactor

The catalytic performance of a CuOx/CeO2 powder catalyst and that of a microchannel reactor or microreactor (MR) coated with the same solid was determined and compared. The catalytic activity measurements were carried out with varying O2/CO molar ratios in the feed-stream. In addition, the influence of the presence of CO2 and H2O in the reaction mixture was studied. Some discrepancies were observed between the performances of the powder catalyst and the MR depending on the O2/CO ratio. The MR presented a very good performance with a superior selectivity for CO conversion. This behaviour was due to a more efficient heat removal in the case of the MR that inhibited the H2 oxidation reaction and the r-WGS. The isothermicity of the microreactor during the process was demonstrated through the monitoring of the MR inlet and outlet temperatures. Concerning the presence of CO2 or H2O in the feed-stream, both compounds gave rise to a decrease of the CO conversion. The negative effect on the catalytic performance was more marked when both compounds were fed together, although the principal inhibitor effect was associated to the CO2. This seems to be related with the formation of stable carbonates at the catalyst surface.Ministerio de Ciencia e Innovación ENE2009-14522-C05-01Junta de Andalucía P09-TEP-545