Structuring Cu/ZnO/Al2O3 catalyst for methanol synthesis: Slurry additive effect in the washcoating method

The best slurry formulation to prepare a structured catalyst for methanol synthesis reaction by washcoating method was investigated. The effect of different inorganic oxide colloids in the slurry preparation of Cu/ZnO/Al2O3 catalyst was studied: colloidal ZnO, SiO2, and Al2O3. The addition of all these colloids showed an improvement in adherence obtained on Fecralloy® monoliths, but Al2O3 exhibited the best performance. Adherence >80% was obtained with a lower amount of Al2O3 than with the other colloids. Nevertheless, the addition of these additives changes the catalytic properties of the parent catalyst. Adding a high amount of colloids decreases the copper metallic surface area which is the active phase of the methanol synthesis reaction. Moreover, the addition of Al2O3 gave rise to the dehydration of methanol to dimethyl ether (DME) due to the high acidity that Al2O3 presents. Something similar happens but to a less extent with SiO2, which present weak acidity. In contrast, the basic character of ZnO neutralizes the parent catalyst's low acidity reducing the selectivity to DME. Finally, the slurry formulation containing 10% Al2O3 exhibited the best methanol yield. Hence, a methanol synthesis structured catalyst was successfully prepared with similar activity to the powder catalyst.The authors acknowledge the Basque Government (IT1069-16), the Spanish MINECO/FEDER (RTI2018-096294-B-C32 and CTQ2015-73901-JIN) and The University of the Basque Country (GIU21/033) for the financial support. I. Pérez-Miqueo also acknowledges the Basque Government for the PhD scholarship (PRE_2014_1_141)

Experimental and theoretical study of the effect of different functionalities of graphene oxide/polymer composites on selective CO2 capture

There is a constant need for versatile technologies to reduce the continuously increasing concentration of CO2 in the atmosphere, able to provide effective solutions under different conditions (temperature, pressure) and composition of the flue gas. In this work, a combination of graphene oxide (GO) and functionalized waterborne polymer particles was investigated, as versatile and promising candidates for CO2 capture application, with the aim to develop an easily scalable, inexpensive, and environmentally friendly CO2 capture technology. There are huge possibilities of different functional monomers that can be selected to functionalize the polymer particles and to provide CO2-philicity to the composite nanostructures. Density functional theory (DFT) was employed to gain a deeper understanding of the interactions of these complex composite materials with CO2 and N-2 molecules, and to build a basis for efficient screening for functional monomers. Estimation of the binding energy between CO2 and a set of GO/polymer composites, comprising copolymers of methyl methacrylate, n-butyl acrylate, and different functional monomers, shows that it depends strongly on the polymer functionalities. In some cases, there is a lack of cooperative effect of GO. It is explained by a remarkably strong GO-polymer binding, which induced less effective CO2-polymer interactions. When compared with experimental results, in the cases when the nanocomposite structures presented similar textural properties, the same trends for selective CO2 capture over N-2 were attained. Besides novel functional materials for CO2 capture and a deeper understanding of the interactions between CO2 molecules with various materials, this study additionally demonstrates that DFT calculations can be a shorter route toward the efficient selection of the best functionalization of the composite materials for selective CO2 capture.Spanish Government (BES-2017-080221) is gratefully acknowledged for its financial support. The authors would like to acknowledge the contribution of the COST Action CA 15107. The authors thank SGIker (UPV/EHU, ERDF, EU) for technical and human support

Fischer-Tropsch synthesis in microchannels

Different metallic supports (aluminum foams of 40ppi, honeycomb monolith and micromonolith of 350 and 1180cpsi, respectively) have been loaded with a 20%Co-0.5%Re/γ-Al2O3 catalyst by the washcoating method. Layers of different thicknesses have been deposited onto the metallic supports. The catalytic coatings were characterized measuring their textural properties, adhesion and morphology. These structured catalysts have been tested in the Fischer-Tropsch synthesis (FTS) and compared with a microchannel block presenting perpendicular channels for reaction and cooling. The selectivity depends on the type of support used and mainly on the thickness of the layer deposited. In general, the C5+ selectivity decreased at increasing CO conversion for all of the systems (powder, monoliths, foams and microchannels block). On the other hand, the selectivity to methane increased with the thickness of the catalytic layer due to the higher effective H2/CO ratio over the active sites resulting from the higher diffusivity of H2 compared with CO in the liquid products filling the pores. The C5+ selectivity of the microchannels reactor is higher than that of the structured supports and the powder catalyst.Ministerio de Ciencia e Innovación MAT2006-12386-C05, ENE2009-14522-C0

Recent advances and future perspectives on porous materials for biomedical applications

Unformatted postprint version of the accepted articleThe authors gratefully acknowledge financial support from MCIN/AEI/10.13039/501100011033 and FEDER (RTI2018-098951- B-I00, RTI2018-096294-B-C32), IKERBASQUE-Basque Foundation for Science, Basque Government (Elkartek projects KK- 2019/00086 and KK-2020/00010; proyectos de investigacio´ n ba´ sica/aplicada PIBA 2020 1 0056, IT1069-16), Gipuzkoa Provincial Council (2019-CIEN-000075-01). MSO and S.C-E acknowledge support by the Marie-Slodowska-Curie Action under the H2020 framework program, with the projects ‘THERMUCNA’ [896775] and ‘PRIUS-TE’ [845488], respectively. A.B. thanks to the Spanish Research Agency (AEI) for the financial support (PID2019-110239RB-I00 from I+D call and RYC2018-025923-I from RyC program), including FEDER funds; and BBVA foundation (Leonardo Fellowships, IN [21] CBB QUI 0086). The authors have no other relevant affiliations or financial involvement with any organization or entity with a financial interest in or financial conflict with the subject matter or materials discussed in the manuscript apart from those disclosed

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

Design and Test of a Miniature Hydrogen Production Integrated Reactor

A detailed study of the experimental issues involved in the design and operation of a methanol steam microreformer is presented in this paper. Micromachining technology was utilized to fabricate a metallic microchannel block coupling the exothermic and endothermic process. The microchannel block was coated with a Pd/ZnO catalyst in the reforming channels and with Pd/Al2O3 in the combustion channels by washcoating. An experimental system had been designed and fine-tuned allowing estimation of the heat losses of the system and to compensate for them by means of electric heating cartridges. In this way, the heat necessary for the reforming reaction is provided by methanol combustion, thanks to the temperature and flow cascade controller we developed. Thus, the coupling of both reactions in a block of microchannels without the interference caused by significant heat loss due to the small size of the laboratory microreactor could be studied. Runs of this microreformer device were carried out, varying the deposited catalyst amount, methanol steam reforming temperature and space velocity. When the reforming reaction was compensated by the combustion reaction and the heat losses by the electric heating, an almost isothermal behavior of the microchannel reactor was observed. In the less favorable case, with a 460 mg catalyst load, ΔTMSR was about 8 K and ΔTCOMB was about 16 K. This confirmed good coupling of the methanol steam reforming and the methanol combustion.This research was funded by MICINN/FEDER grant numbers RTI2018-096294-B-C32 and CTQ2015-73901-JIN and by the Basque Government grant number IT1069-16

Tailoring of Textural Properties of 3D Reduced Graphene Oxide Composite Monoliths by Using Highly Crosslinked Polymer Particles toward Improved CO2 Sorption

The main constraint on developing a full potential for CO2 adsorption of 3D composite monoliths made of reduced graphene oxide (rGO) and polymer materials is the lack of control of their textural properties, along with the diffusional limitation to the CO2 adsorption due to the pronounced polymers' microporosity. In this work, the textural properties of the composites were altered by employing highly crosslinked polymer particles, synthesized by emulsion polymerization in aqueous media. For that aim, waterborne methyl methacrylate (MMA) particles were prepared, in which the crosslinking was induced by using different quantities of divinyl benzene (DVB). Afterward, these particles were combined with rGO platelets and subjected to the reduction-induced self assembly process. The resulting 3D monolithic porous materials certainly presented improved textural properties, in which the porosity and BET surface area were increased up to 100% with respect to noncrosslinked composites. The crosslinked density of MMA polymer particles was a key parameter controlling the porous properties of the composites. Consequently, higher CO2 uptake than that of neat GO structures and composites made of noncrosslinked MMA polymer particles was attained. This work demonstrates that a proper control of the microstructure of the polymer particles and their facile introduction within rGO self assembly 3D structures is a powerful tool to tailor the textural properties of the composites toward improved CO2 capture performance.I.B. gratefully acknowledges the financial support of the Spanish Government (BES-2017-080221). L.S. thank s the grant P20_00328 funded by the Consejeria de Transformacion Economica, Industria, Conocimiento y Universidades of the Junta de Andalucia and by the EU FEDER funds. The authors thank the technical and human support provided by SGIker (UPV/EHU/ERDF, EU)

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.Ministerio de Economía y Competitividad ENE2012- 37431-C03-03Junta de Andalucía TEP-819

Stacked wire mesh monoliths for the simultaneous abatement of VOCs and diesel soot

Structured catalysts based on Pt,CeO2 deposited on stainless steel wire meshes were developed to build catalytic cartridges for the treatment of diesel exhaust gases. The cartridges were tested for the simultaneous combustion of volatile organic compounds (VOCs) and soot. To this end, n-hexane, acetyl acetate, and toluene were selected as probe molecules. Each of them were loaded together with real soot into the cartridges showing that while VOCs abatement takes place between 200 °C and 350 °C, soot combustion occurs in the 300-500 °C temperature range with an average maximum combustion rate at 420 °C. The catalytic cartridges were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and Brunauer-Emmett-Teller (BET) techniques. The mechanical stability of the coatings was confirmed by the ultrasound method. Air permeability of the cartridges prepared with different mesh sizes was also measured and the results were correlated using the Payri equation.Fil: Godoy, Maria Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Banus, Ezequiel David. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Sanz, Oihane. Universidad del País Vasco; EspañaFil: Montes Ramirez, Mario. Universidad del País Vasco; EspañaFil: Miro, Eduardo Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Milt, Viviana Guadalupe. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentin

Toward enhanced catalytic activity of magnetic nanoparticles integrated into 3D reduced graphene oxide for heterogeneous Fenton organic dye degradation

Composite Fenton nanocatalyst was prepared by water-based in situ creation of Fe3O4 nanoparticles integrated within the self-assembly 3D reduced graphene oxide (rGO) aerogel. The hybrid applied for the degradation of Acid Green 25 (AG-25) organic dye in an aqueous solution, in the presence of H2O2. By investigating the conditions that maximize the dye adsorption by the 3D composite, it was found that the pH of the solution should be adjusted between the pKa of the functional groups present on the rGO surface (carboxylic acid) and that of the dye (sulfonic acid) to promote electrostatic interactions dye-3D structure. Performed under these conditions, Fenton degradation of AG-25 in presence of H2O2 was completed in less than 30 min, including all the intermediate products, as demonstrated by MALDI-TOF-MS analysis of the aqueous solution after discoloration. Moreover, this was achieved in a solution with as high a dye concentration of 0.5 mg/mL, with only 10 mg of 3D composite catalyst, at room temperature and without additional energy input. The high performance was attributed to the creation of charge-transfer complex between rGO and Fe3O4 nanoparticles throughout covalent bond C-O-Fe, the formation of which was promoted by the in situ synthesis procedure. For the first time, up to the authors' knowledge, AG-25 degradation mechanism was proposed.The authors gratefully acknowledge the financial support of the Basque Government (GV IT999-16 and GV IT1069-16)