Scientific Papers in SCI
2020
2020
Propiedades mecánicas, modelización y caracterización de cerámicos avanzados
Disclination dipoles are the Holy Grail for high temperature superplasticity in ceramics
Moshtaghioun, BM; Bejarano-Palma, JA; Garcia, DGScripta Materialia, 185 (2020) 21-24
A model for high-temperature plasticity of polycrystals controlled by disclination dipoles is proposed that predict a parabolic dependence of the strain rate versus the applied stress. The presence of a precise stationary disclination density explains the origin of plasticity without microstructural invariance, commonly known as superplasticity. The disclination mechanism is universal, although other processes, such as dislocation glide, are superposed to this one in many systems such as metals or metallic alloys. While, in ceramics it is likely to be the only operative mechanism. Activation of disclination dipoles is a necessary condition for plasticity and sufficient one for superplastic yielding.
August, 2020 | DOI: 10.1016/j.scriptamat.2020.03.049
Materiales y Procesos Catalíticos de Interés Ambiental y Energético
Thermo-Photocatalytic Methanol Reforming for Hydrogen Production over a CuPd-TiO2 Catalyst
Lopez-Martin, A; Platero, F; Caballero, A; Colon, GChemPhotoChem, 4 (2020) 630-637
A bimetallic CuPd/TiO2 system has been prepared by a two-step synthesis and was used for a methanol steam photoreforming reaction. By sequential deposition, palladium is deposited over copper nanoclusters through a galvanic replacement process. Hydrogen production by steam reforming from methanol was achieved by both thermo-photocatalytic and photocatalytic processes. It appears that H-2 production on the bimetallic system is notably higher than the Pd monometallic reference. Moreover this difference in the catalytic performance could be related to the higher CO evolution observed for the monometallic Pd-1.0 TiO2 system which is partially inhibited in the bimetallic catalyst. In addition, an important thermal effect can be envisaged in all cases. Nevertheless, this improved effect in the thermo-photocatalytic process is accompanied by a remarkable CO evolution and SMSI effect (important strong metal-support interactions) that hindered the efficiency as temperature increases. On this basis, optimal operational conditions for H-2 production are obtained for thermo-photocatalytic reforming at 100 degrees C, for which the synergetic effect is higher with lower CO production (H-2/CO=4)
August, 2020 | DOI: 10.1002/cptc.202000010
Química de Superficies y Catálisis
Elucidation of Water Promoter Effect of Proton Conductor in WGS Reaction over Pt-Based Catalyst: An Operando DRIFTS Study
Jurado, L; Garcia-Moncada, N; Bobadilla, LF; Romero-Sarria, F; Odriozola, JACatalysts, 10 (2020) 841
A conventional Pt/CeO2/Al(2)O(3)catalyst physically mixed with an ionic conductor (Mo- or Eu-doped ZrO2) was tested at high space velocity (20,000 h(-1)and 80 L h(-1)g(cat)(-1)) under model conditions (only with CO and H2O) and industrial conditions, with a realistic feed. The promoted system with the ionic conductor physically mixed showed better catalytic activity associated with better water dissociation and mobility, considered as a rate-determining step. The water activation was assessed by operando diffuse reflectance infrared fourier transformed spectroscopy (DRIFTS) studies under reaction conditions and the Mo-containing ionic conductor exhibited the presence of both dissociated (3724 cm(-1)) and physisorbed (5239 cm(-1)) water on the Eu-doped ZrO(2)solid solution, which supports the appearance of proton conductivity by Grotthuss mechanism. Moreover, the band at 3633 cm(-1)ascribed to hydrated Mo oxide, which increases with the temperature, explains the increase of catalytic activity when the physical mixture was used in a water gas shift (WGS) reaction.
August, 2020 | DOI: 10.3390/catal10080841
Materiales Coloidales
Design of a nanoprobe for high field magnetic resonance imaging, dual energy X-ray computed tomography and luminescent imaging
Gonzalez-Mancebo, D; Becerro, AI; Corral, A; Garcia-Embid, S; Balcerzyk, M; Garcia-Martin, ML; de la Fuente, JM; Ocana, MJournal of Colloid and Interface Science, 573 (2020) 278-286
The combination of different bioimaging techniques, mainly in the field of oncology, allows circumventing the defects associated with the individual imaging modalities, thus providing a more reliable diagnosis. The development of multimodal endogenous probes that are simultaneously suitable for various imaging modalities, such as magnetic resonance imaging (MRI), X-ray computed tomography (CT) and luminescent imaging (LI) is, therefore, highly recommended. Such probes should operate in the conditions imposed by the newest imaging equipment, such as MRI operating at high magnetic fields and dual-energy CT. They should show, as well, high photoluminescence emission intensity for their use in optical imaging and present good biocompatibility. In this context, we have designed a single nanoprobe, based on a core-shell architecture, composed of a luminescent Eu3+:Ba0.3Lu0.7F2.7 core surrounded by an external HoF3 shell that confers the probe with very high magnetic transverse relaxivity at high field. An intermediate, optically inert Ba0.3Lu0.7F2.7 layer was interposed between the core and the shell to hinder Eu3+-Ho3+ cross-relaxation and avoid luminescence quenching. The presence of Ba and Lu, with different K-edges, allows for good X-ray attenuation at high and low voltages. The core-shell nanoparticles synthesized are good potential candidates as trimodal bioprobes for MRI at high field, dual-energy CT and luminescent imaging.
August, 2020 | DOI: 10.1016/j.jcis.2020.03.101
Química de Superficies y Catálisis
Evaluation of the Oxygen Mobility in CePO4-Supported Catalysts: Mechanistic Implications on the Water-Gas Shift Reaction
Navarro-Jaen, S; Bobadilla, LF; Romero-Sarria, F; Laguna, OH; Bion, N; Odriozola, JAJournal of Physical Chemistry C, 124 (2020) 16391-16401
The hexagonal and monoclinic phases of CePO4 have been demonstrated to be excellent catalytic supports for Pt-based water-gas shift (WGS) catalysts. Consequently, the elucidation of the WGS reaction mechanism in these materials constitutes a fundamental aspect in order to explain their catalytic behavior. Because the observed WGS reaction path is closely related to the absence or presence of oxygen vacancies in the support, the study of the oxygen mobility in these solids constitutes a key factor for the understanding of the structure of the materials and its influence on the reaction mechanism. In this study, the oxygen mobility in CePO4 supports and the corresponding Pt catalysts has been evaluated by means of isotopic exchange experiments using O-18(2) and (CO2)-O-18 as probe molecules. Results demonstrate that the evaluated solids present a low exchange activity when O-18(2) is used, indicating the absence of oxygen vacancies in these solids, thus suggesting a poor influence of the WGS redox mechanism. On the contrary, a high oxygen exchange activity is observed using (CO2)-O-18, demonstrating that the exchange in these materials takes place through the formation of carbonate-like intermediates, thus suggesting the associative mechanism of the WGS reaction as the preferred path in these solids. Operando diffuse reflectance infrared spectroscopy experiments under WGS reaction conditions confirm these results, proving that the WGS reaction in the studied materials takes place through a formate-mediated associative mechanism.
July, 2020 | DOI: 10.1021/acs.jpcc.0c03649
Química de Superficies y Catálisis
Metal catalysts supported on biochars: Part I synthesis and characterization
Santos, JL; Maki-Arvela, P; Monzon, A; Murzin, DY; Centeno, MAApplied Catalysis B-Environmental, 268 (2020) 118423
In the current study, synthesis and detailed characterization of cellulose biochars as a waste biomass model component and vine shoot biochars as a real waste biomass catalyst was performed. Although initially biochars exhibit poor textural properties, a simple activation process can make them much more suitable as a catalyst supports. A combination of physical (CO2) and chemical activation (ZnCl2) was evaluated. The characterization results indicated that the surface area and pore volume of the biochars have increased significantly by chemical activation treatment with ZnCl2. A series of metal catalysts (Pd, Au and Ru) supported on biochars was prepared and characterized. The prepared materials represent a set of noble metal catalysts supported on biochars with different textural and surface properties, which can be used to evaluate the catalytic role of the active phase and carbon support nature in catalytic reactions of interest, such as hydrodeoxygenation, described in the part II.
July, 2020 | DOI: 10.1016/j.apcatb.2019.118423
Química de Superficies y Catálisis
Hydrodeoxygenation of vanillin over noble metal catalyst supported on biochars: Part II: Catalytic behaviour
Santos, JL; Maki-Arvela, P; Warna, J; Monzon, A; Centeno, MA; Murzin, DYApplied Catalysis B-Environmental, 268 (2020) 118425
Vanillin hydrodeoxygenation was investigated using noble metal (Pd, Au, Ru) supported on active carbon prepared from waste derived biochars, which were produced via pyrolysis in CO2 atmosphere. Chemical activation with ZnCl2 and HNO3 was also used in the preparation of active carbon to enhance the specific surface area and demineralize material, respectively. Both fresh and spent catalysts were characterized with X-ray diffraction, DRIFTS, zeta potential measurement and HR-TEM. The highest selectivity to p-creosol, 92 % selectivity at complete vanillin conversion after 3 h was obtained in vanillin hydrodeoxygenation at 100 degrees C under 30 bar in hydrogen in water with Pd/C catalyst prepared via pyrolysis under CO2 from wine waste and using ZnCl2 as a chemical activation agent. Hydrodeoxygenation activity increased with increasing metal dispersion. A kinetic model including adsorption of vanillin described well the experimental data.
July, 2020 | DOI: 10.1016/j.apcatb.2019.118425
Materiales de Diseño para la Energía y Medioambiente
Performance trends in wall-flow diesel particulate filters: Comparative analysis of their filtration efficiency and pressure drop
Orihuela, MP; Chacartegui, R; Gomez-Martin, A; Ramirez-Rico, J; Villanueva, JABJournal of Cleaner Production, 60 (2020) 12063
Soot and particulate emissions from the transport sector are a major concern worldwide, given their harmful effects on public health and the environment. On-road vehicles are the main contributing source to this kind of pollution. They are strictly regulated in many countries, with limitations on the number and concentration of released particles, and they must be equipped with particle abatement systems. Wall-flow particulate filters are the most popular and effective devices to reduce particulate emissions from diesel and gasoline vehicles. Diesel Particulate Filters (DPFs) have been a recurrent research topic since the last century. There are different research studies analysing different aspects of these systems, at different levels, using different methodologies and different approaches. Their results are not always comparable. This work analyses the latest advances and trends in this technology by comparing two relevant performance parameters: their filtration efficiency and pressure drop. The findings of this study suggest that, in order to be competitive, upcoming DPFs should have filtration efficiencies above 80%, and pressure drops below 10 kPa, for space velocities of 1.5.10(5) h(-1) or more at the clean state. They should reach similar to 100% efficiency after a short operation period, before the soot load reaches 0.2 g/L. Later, they should keep a low pressure drop for a longer time, with a reference of no more than 13 kPa for 6 g/L of soot load. Based on this analysis, this work proposes some test criteria and suggestions for the main parameters.
July, 2020 | DOI: 10.1016/j.jclepro.2020.120863
Reactividad de Sólidos
Calcium-Looping Performance of Biomineralized CaCO3 for CO2 Capture and Thermochemical Energy Storage
Arcenegui-Troya, J; Sanchez-Jimenez, PE; Perejon, A; Valverde, JM; Chacartegui, R; Perez-Maqueda, LAIndustrial & Engineering Chemistry Research, 59 (2020) 12924-12933
The commercial deployment of calcium-looping (CaL)-based technologies relies on the availability of nontoxic, widely available and cheap CaCO3 rich materials. Biomineralized CaCO3 from waste amply fulfills the aforementioned requirements. In the present work, we study the performance of eggshell and snail shell from food waste as CaO precursors for CaL applications. The results obtained suggest the feasible use of these waste materials. The multicyclic conversion exhibited by biomineralized CaCO3 was comparable to that demonstrated by limestone, which is a commonly proposed material for CaL applications. In addition, the temperature needed to completely calcine biomineralized CaCO3 in short residence times is lower than that required to fully calcine limestone. This would mitigate the energy cost of the technology.
July, 2020 | DOI: 10.1021/acs.iecr.9b05997
Reactividad de Sólidos
ICTAC Kinetics Committee recommendations for analysis of multi-step kinetics
Vyazovkin, S; Burnham, AK; Favergeon, L; Koga, N; Moukhina, E; Perez-Maqueda, LA; Sbirrazzuoli, NThermochimica Acta, 689 (2020) 178597
The present recommendations have been developed by the Kinetics Committee of the International Confederation for Thermal Analysis and Calorimetry (ICTAC). The recommendations provide guidance on kinetic analysis of multi-step processes as measured by thermal analysis methods such as thermogravimetry (TGA) and differential scanning calorimetry (DSC). Ways of detecting the multi-step kinetics are discussed first. Then, four different approaches to evaluation of kinetic parameters (the activation energy, the pre-exponential factor, and the reaction model) for individual steps are considered. The approaches considered include multi-step model-fitting as well as distributed reactivity, isoconversional, and deconvolution analyses. For each approach practical advice is offered on its effective usage. Due attention is also paid to the typical problems encountered and to the ways of resolving them. The objective of these recommendations is to help a non-expert with efficiently performing multi-step kinetic analysis and interpreting its results.
July, 2020 | DOI: 10.1016/j.tca.2020.178597
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