Redox chemistry of gold in a Au/FeOx/CeO2 CO oxidation catalyst

Calcination and evacuation of a Au/FeOx/CeO2 catalyst at 573 K leads to reduction of the deposited gold to metal. This metal state is stable under oxygen and only at 573 K some metal atoms are oxidized to Auδ+ sites (Au+ cations situated on metal gold particles). However, even at room temperature, gold is readily oxidized in a CO + O2 mixture producing, in addition to the Auδ+ sites, some isolated Au+ cations.Proyecto bilateral España - Bulgaria CSIC/BAS (2004BG001)Apoyo de la Junta de Andalucía al grupo TEP106Bulgarian Scientific Foundation - Project VUX-303Ministerio de Educación y Ciencia a través del contrato Juan de la Cierva de Anna Dimitrova Penkov

Effect of noble metal addition over active Ru/TiO2 catalyst for CO selective methanation from H2 rich-streams

Financial support for this work has been obtained from the Spanish Ministerio de Ciencia, Innovacion y Universidades (Grant: RTI2018-096294-B-C33) and Junta de Andalucia project with reference US-1263288, both programs being co-funded by the European Union FEDER.Selective CO methanation from H2-rich stream has been regarded as a promising route for deep removal of low CO concentration and catalytic hydrogen purification processes. This work is focused on the development of more efficient catalysts applied in practical conditions. For this purpose, we prepared a series of catalysts based on Ru supported over titania and promoted with small amounts of Rh and Pt. Characterization details revealed that Rh and Pt modify the electronic properties of Ru. The results of catalytic activity showed that Pt has a negative effect since it promotes the reverse water gas shift reaction decreasing the selectivity of methanation but Rh increases remarkably the activity and selectivity of CO methanation. The obtained results suggest that RuRh-based catalyst could become important for the treatment of industrial-volume streams.Spanish Government RTI2018-096294-B-C33European Union (EU)Junta de Andalucia US-126328

Structural and catalytic properties of lanthanide (La, Eu, Gd) doped ceria

Este documento es la última versión enviada a la revista con los ajustes finales después de la revisión de los evaluadores.In this work, Ce0.9M0.1O2−δ mixed oxides (M=La, Eu and Gd) were synthesized by coprecipitation. Independent of the dopant cation, the obtained solids maintain the F-type crystalline structure, characteristic of CeO2 (fluorite structure) without phase segregation. The ceria lattice expands depending on the ionic radii of the dopant cation, as indicated by X-ray diffraction studies. This effect also agrees with the observed shift of the F2g Raman vibrational mode. The presence of the dopant cations in the ceria lattice increases the concentration of structural oxygen vacancies and the reducibility of the redox pair Ce4+/Ce3+. All synthesized materials show higher catalytic activity for the CO oxidation reaction than that of bare CeO2, being Eu-doped solid the one with the best catalytic performances despite of its lower surface area.Junta de Andalucía con su apoyo a la unidad TEP106Ministerio de Ciencia e Innovación mediante la subvención del proyecto: ENE2009-14522-C05-01 cofinanciado con fondos FEDER de la Unión EuropeaPrograma Alban a través de la beca predoctoral de W.Y. Hernández: (E06D101739CO

Policies and Motivations for the CO2 Valorization through the Sabatier Reaction Using Structured Catalysts. A Review of the Most Recent Advances

The current scenario where the effects of global warming are more and more evident, has motivated different initiatives for facing this, such as the creation of global policies with a clear environmental guideline. Within these policies, the control of Greenhouse Gase (GHG) emissions has been defined as mandatory, but for carrying out this, a smart strategy is proposed. This is the application of a circular economy model, which seeks to minimize the generation of waste and maximize the efficient use of resources. From this point of view, CO2 recycling is an alternative to reduce emissions to the atmosphere, and we need to look for new business models which valorization this compound which now must be considered as a renewable carbon source. This has renewed the interest in known processes for the chemical transformation of CO2 but that have not been applied at industrial level because they do not offer evident profitability. For example, the methane produced in the Sabatier reaction has a great potential for application, but this depends on the existence of a sustainable supply of hydrogen and a greater efficiency during the process that allows maximizing energy efficiency and thermal control to maximize the methane yield. Regarding energy efficiency and thermal control of the process, the use of structured reactors is an appropriate strategy. The evolution of new technologies, such as 3D printing, and the consolidation of knowledge in the structing of catalysts has enabled the use of these reactors to develop a wide range of possibilities in the field. In this sense, the present review presents a brief description of the main policies that have motivated the transition to a circular economy model and within this, to CO2 recycling. This allows understanding, why efforts are being focused on the development of different reactions for CO2 valorization. Special attention to the case of the Sabatier reaction and in the application of structured reactors for such process is paid

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

Microreactors technology for hydrogen purification: Effect of the catalytic layer thickness on CuOx/CeO2-coated microchannel reactors for the PROX reaction

Two blocks of microreactors composed by 100 microchannels and coated, respectively, with 150 and 300 mg of a CuOx/CeO2 catalyst, were prepared and tested in the preferential oxidation of CO in presence of H2 (PROX). The deposition of different amount of catalyst resulted in different catalytic layer thicknesses thus modifying the catalytic performances of the microreactor. The evaluation of the main reaction variables (the space velocity, the O2-to-CO ratio and the presence of H2O and/or CO2 in the stream) was performed over both microreactors and compared to that of the parent powder catalyst. The least loaded microreactor, with a coating thickness around 10 μm, presented the highest CO conversion and selectivity levels at temperatures below 160 ºC. This result evidences i) the improvement of the catalytic performances got by the structuration of the powder catalyst and ii) the importance of the selection of the adequate thickness of the catalytic layer on the microreactor, which have not to exceed and optimal value. An adequate coating thickness allows minimizing the mass and heat transport limitations, thus resulting in the enhancement of the catalytic performance during the PROX reactionEspana Mineco ENE2012-374301-C03-01 ENE2013-47880-C3-2- RFEDER Junta de Andalucia Unión Europea TEP-819

Oxidation of CO over gold supported on Zn-modified ceria catalysts

A series of Zn-modified ceria solids were prepared by thermal decomposition of the corresponding metal propionates. The formation of segregated ZnO particles on the ceria surface is evidenced for these solids using X-ray diffraction; in addition to this the characterization data may allow discarding the formation of a ZnO¿CeO2 solid solution. On modifying with Zn, the reducibility of the ceria support is enhanced, being the highest reducibility the one obtained for the ZnO¿CeO2 solid having a 1:9 Zn:Ce atomic ratio (CeZn10). The activity of this solid in the CO oxidation reaction was the highest among the tested Zn-modified ceria solids. Therefore, catalysts containing 1 wt.% gold, supported on pure ceria and CeZn solids, were prepared, characterized and their catalytic activities tested. The Zn-modified gold catalyst is more active than the un-modified Au/CeO2 catalyst in the oxidation of CO; this behavior is related to the higher metallic dispersion of gold on the CeZn support surface. However, the number of oxygen vacancies acting as nucleation sites for gold, is hardly modified in the Zn-modified ceria support and, therefore, the higher gold dispersion must be related to high electron density sites on the catalyst surface as a result of Au-Ce-Zn interaction, this improved gold dispersion results in higher activities for CO oxidation.Ministerio de Ciencia e Innovación ENE2009-14522-C05-01Junta de Andalucía P09-TEP-545

A review on additive manufacturing and materials for catalytic applications: Milestones, key concepts, advances and perspectives

Catalysis, a driving force of the chemical industry is increasingly being influenced by additive manufacturing. The link between them is based on the need to intensify catalytic processes in order to make them more efficient and sustainable. Additive manufacturing can satisfy such a need, generating devices with an advanced design, easy production, and great adaptation, in addition to their catalytic functionality. The exponential growth of examples reported on the application of 3D-printing in catalysis has led to the need to compile and analyse these cases and thus establish, through this review, the most in-depth analysis done to date. The manuscript includes a brief background of the history of additive manufacturing and the classification of the different printing techniques. Subsequently, it identifies the intensification of processes, among other aspects, as the key for understanding the union of additive manufacturing and catalysis. Then, it explores in detail how such a combination occurs, establishing the most comprehensive classification to date between the two large groups of printable devices with catalytic properties. Finally, a series of perspectives are proposed in which the most probable courses of new advances in this field of research are identified.O.H. Laguna agradece a la Universidad de Jaén por el apoyo el contrato postdoctoral a través de la ‘‘Acción 6 del Plan de Apoyo a la Investigación de la Universidad de Jaén (2017-2019).

Gold supported on metal-doped ceria catalysts (M = Zr, Zn and Fe) for the preferential oxidation of CO (PROX)

A series of ceria oxides doped with 10 mol.% of Zr, Zn and Fe have been prepared by a pseudo sol-gel method throughout the thermal decomposition of the corresponding metallic propionates. With these supports, 1 wt.% gold catalysts were prepared by the deposition-precipitation method. All the solids were characterized by means of XRF, N2 adsorption, XRD, Raman spectroscopy and SEM techniques, and their catalytic activity toward preferential oxidation of CO (PROX) reaction tested. The results showed solid solution when doping with Zr and Fe and ZnO surface segregation in the case of Zn. We demonstrate that gold dispersion depends on not only the oxygen vacancy concentration but also the nature of the doping agent. Finally, the catalytic activity was highly promoted by gold in all cases, being the doped gold catalysts more active than Au/CeO2 at low temperature.Ministerio de Ciencia e Innovación ENE2009-14522-C05-01Junta de Andalucía P09- TEP-545