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Scientific Papers in SCI

2018


New concept for old reaction: Novel WGS catalyst design


Garcia-Moncada, N; Gonzalez-Castano, M; Ivanova, S; Centeno, MA; Romero-Sarria, F; Odriozola, JA
Applied Catalysis A-General, 238 (2018) 1-5

ABSTRACT

The viability of water gas shift catalytic system for mobile application passes through obligatory reactor volume reduction, achieved normally by using less charge of more efficient catalyst. Completely new concept for catalyst design is proposed: a catalytic system including classically reported WGS catalysts of different nature or active phase (Cu, Pt or Au) mechanically mixed with an ionic conductor. The influence of the later on catalyst activity is studied and discussed, more precisely its effect on the rate of the reaction-limiting step and catalysts' efficiency. It is demonstrated with this study, that the presence of an ionic conductor in contact with a WGS catalyst is essential for the water supply (dissociation and transport), thereby potentiating the water activation step, whatever the mechanism and catalyst overall performance.


December, 2018 | DOI: 10.1016/j.apcatb.2018.06.068

CO/H-2 adsorption on a Ru/Al2O3 model catalyst for Fischer Trospch: Effect of water concentration on the surface species


Jimenez-Barrera, E; Bazin, P; Lopez-Cartes, C; Romero-Sarria, F; Daturi, M; Odriozola, JA
Applied Catalysis B-Environmental, 237 (2018) 986-995

ABSTRACT

Water presence and concentration strongly influence CO conversion and CS+ selectivity in the Fischer Tropsch reaction. In this work, the influence of the water concentration was investigated using a model Ru/Al2O3 (5 wt. %) catalyst. The surface species formed after CO and H-2 adsorption in dry and wet (different water concentrations) conditions were analyzed by FTIR. Firstly, water adsorption was carried out up to complete filling of the pores and then CO was put in contact with the catalyst. The absence of adsorbed CO species in these conditions evidences that CO diffusion in water controls the access of the gas to the active sites and explains the negative effect of high water concentrations reported by some authors. Moreover, the adsorption of a mixture of CO + H-2 + H2O, being the water concentration close to that needed to have a monolayer, and a dry mixture of CO + H-2 were carried out and compared. Results evidence that water in this low concentration, is able to gasify the surface carbon species formed by CO dissociation on the metallic sites. This cleaning effect is related to the positive effect of water on CO conversion detected by some authors.


December, 2018 | DOI: 10.1016/j.apcatb.2018.06.053

Selective CO methanation with structured RuO2/Al2O3 catalysts


Munoz-Murillo, A; Martinez, LM; Dominguez, MI; Odriozola, JA; Centeno, MA
Applied Catalysis B-Environmental, 236 (2018) 420-427

ABSTRACT

Active and selective structured RuO2/Al2O3 catalysts for CO methanation using a flow simulating CO2-rich reformate gases from WGS and PROX units (H-2 excess, CO2 presence and 300 ppm CO concentration) were prepared. Both, the RuO2/Al2O3 powder and the slurry prepared from it for its structuration by washcoating of the metallic micromonolithic structure, were also active and selective. Both the slurry (S-RuAl) and micro monoliths (M-RuAl) were able to completely and selectively methanate CO at much lower temperatures than the parent RuAI powder. The optimal working temperature in which the CO conversion is maximum and the CO2 conversion is minimized was determined to be from 149 degrees C to 239 degrees C for S-RuAl and from 165 degrees C to 232 degrees C for M-RuAl, whilst it was from 217 degrees C to 226 degrees C for RuAI powder. TPR, XRD and TEM measurements confirmed that the changes in the activity and selectivity for CO methanation among the considered catalysts can be related with modifications in the surface particle size of ruthenium and its reducibility. These were ascribed to the metallic substrate, the presence of PVA and colloidal alumina in the slurry preparation, the aqueous and acidic media and the thermal treatment used, resulting in a more active and selective catalysts than the parent powder.


November, 2018 | DOI: 10.1016/j.apcatb.2018.05.020

Exotic grain growth law in twinned boron carbide under electric fields


Moshtaghioun, BM; Gomez-Garcia, D; Rodriguez, AD
Journal of the European Ceramic Society, 38 (2018) 4590-4596

ABSTRACT

Grain growth is a ubiquitous phenomenon in all materials, and it affects both structural and functional properties. Despite its intrinsic importance, a full comprehension of grain growth from a fundamental point of view-i.e., from the nanoscale to the macroscale-is still a pending issue. In practical terms, our knowledge relies on the classical kinetic laws reported sixty years ago. 

This paper reports the violation of such classical laws in boron carbide ceramics consolidated by spark plasma sintering. The conjunction of high temperature gradients with large compressive stress when a pulse electric current passes through the ceramic powders gives rise to an intense twinning-detwinning formation. These forming steps at the grain boundaries change the grain mobility drastically. Therefore, a new 'exotic' law for grain-growth kinetics is found and validated at different temperatures and dwell times.


November, 2018 | DOI: 10.1016/j.jeurceramsoc.2018.06.029

Mechanically induced combustion synthesis of niobium carbonitride nanoparticles


Jalaly, M; Gotor, FJ; Sayagues, MJ
Journal of Solid State Chemistry, 267 (2018) 106-112

ABSTRACT

Niobium carbonitride [Nb(C,N)] nanoparticles were synthesized by a combustive mechanochemical reaction in the Mg/Nb2O5/C3H6N6 system. High-energy ball milling was used to promote a mechanically induced self-sustaining reaction (MSR). Combustion occurred after a very short milling period of 5 min. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS) and electron energy loss spectroscopy (EELS) analyses revealed that the nature of the product is an intermixed carbonitride material. The formation mechanism of Nb(C,N) resulted from the magnesiothermic reduction of niobium oxide to generate elemental Nb, which then reacted with the species generated from the melamine decomposition.


November, 2018 | DOI: 10.1016/j.jssc.2018.08.027

Behavior of High-Strength Polypropylene Fiber-Reinforced Self-Compacting Concrete Exposed to High Temperatures


Rios, JD; Cifuentes, H; Leiva, C; Garcia, C; Alba, MD
Journal of Materials in Civil Engineering, 30 (2018) 04018271

ABSTRACT

In this study we analyzed the use of high-performance structural concrete reinforced with polypropylene fibers in applications requiring long exposure times to high temperatures, such as thermal energy storage systems. We analyzed the behavior of the concrete at different temperatures (hot tests: 100 degrees C, 300 degrees C, 500 degrees C and 700 degrees C), cooled-down states (cold tests) and exposure times (6, 24, and 48h). We also experimentally determined the thermogravimetric analysis, fracture behavior, compressive strength, Young's modulus, and tensile strength of concrete. Subsequently, we performed a comprehensive analysis of the thermal and mechanical behavior of high-performance concrete under different thermal conditions. We applied longer exposure times to broaden the available results on the behavior of high-performance fiber-reinforced concrete when subjected to high temperatures. Results show that, once thermal and moisture equilibriums are reached, exposure time does not have any influence on mechanical properties. They also provide useful information about the influence of high temperatures on the different parameters of fiber-reinforced concrete and its application for thermal energy storage structures.


November, 2018 | DOI: 10.1061/(ASCE)MT.1943-5533.0002491

Photocatalytic H2 production from glycerol aqueous solutions over fluorinated Pt-TiO2 with high {001} facet exposure


V. Vaiano; M.A. Lara; G. Iervolino; M. Matarangolo; J.A. Navío; M.C. Hidalgo
Journal of Photochemistry and Photobiology A-Chemistry, 365 (2018) 52-59

ABSTRACT

An optimized fluorinated TiO2 catalyst with high {001} facet exposure loaded with platinum (TiO2-PtFAC) was tested in the photocatalytic hydrogen production from glycerol solution under UV light irradiation. The samples were synthesized by direct hydrothermal treatment starting from two different types of precursors that are titanium tetraisopropoxide (I) or titanium butoxide (B), while platinisation was performed by photodeposition method. The obtained catalysts were characterised by different techniques (XRD, FESEM, TEM, BET, UV–vis DRS, XRF and XPS) and the results evidenced that anatase is the only crystalline phase present in all TiO2 samples. The morphology of the samples was seen as rectangular platelets particles where Pt particles were was observed all over the surface. The presence of Pt and F in the platinised samples was also confirmed by XRF and XPS analysis. The photocatalytic results have shown that the presence of Pt on TiO2{001}facet surface remarkably enhanced the hydrogen production from aqueous solution at 5 wt % of glycerol. Comparing the results obtained from the photocatalysts prepared by the two different precursors, it was found that the best performances in terms of H2 production was achieved with TiO2-PtFAC(I) (about 13 mmol L−1 after 4 h of irradiation time), while the H2 production was lower for TiO2-PtFAC(B) (about 9 mmol L−1 after 4 h of irradiation time). The effect of the operating conditions using TiO2-PtFAC(I) evidenced that the highest H2 production was obtained with a photocatalyst dosage equal to 1.5 g L−1, initial glycerol concentration at 5 wt% and a pH value equal to 7. Finally, a photocatalytic test was also performed on glycerol solution prepared with a real water matrix. Despite the presence of ions scavengers (chlorides and carbonates) in solution, TiO2-PtFAC(I) was able to reach a photocatalytic H2production of about 6 mmol L−1 after 4 h of UV light irradiation.


October, 2018 | DOI: 10.1016/j.jphotochem.2018.07.032

Biomass fly ash and aluminium industry slags-based geopolymers


Perez-Villarejo, L; Bonet-Martinez, E; Eliche-Quesada, D; Sanchez-Soto, PJ; Rincon-Lopez, JM; Castro-Galiano, E
Materials Letters, 229 (2018) 6-12

ABSTRACT

Geopolymers are a new class of non-Portland cements produced using an alumino-silicate material and an activating solution, which is mainly composed of sodium or potassium and waterglass to be subsequently cured at relatively low temperatures. Those can be formulated by adding natural minerals, waste and/or industrial by-products. The study investigates the microstructural properties of geopolymers synthesized from metakaolin (MK) and the admixture of fly ash (FBA) and aluminium industry slags (AIS) at different ages of curing. Five different geopolymer compositions were prepared and characterized by XRD, ATR-FTIR and SEM/EDS. The study revealed that geopolymeric gels are identified, which show mainly glassy microstructures, in agreement with the X-ray amorphous diffraction patterns, broad FTIR features and confirmed by SEM/EDS, with promising results prior to an industrial scale.


October, 2018 | DOI: 10.1016/j.matlet.2018.06.100

Manufacture of sustainable clay ceramic composite with composition SiO2-Al2O3-CaO-K2O materials valuing biomass ash from olive pomace


Bonet-Martinez, E; Perez-Villarejo, L; Eliche-Quesada, D; Sanchez-Soto, PJ; Carrasco-Hurtado, B; Castro-Galiano, E
Materials Letters, 229 (2018) 21-25

ABSTRACT

Fly ash is a biomass combustion by-product produced by dragging ash from the base of the furnace. Disposing of ash is a growing economic and environmental burden. Based on physical and chemical properties, fly ash could be used in the manufacture of construction materials. This paper investigates the influence of biomass fly ash from olive pomace as additive to manufacture of clay ceramic composite materials. Fired clay brick at 950 degrees C were prepared containing between 0 and 25 wt% fly ash. Final products are studied by water absorption, bulk density, loss of ignition, linear shrinkage, compressive strength and physisorption N-2. The results reveal that the porosity of the materials increases with the level of fly ash replacement (10% up to 25 wt%) resulting in to increased water absorption and decreased compressive strength. Fired clay brick developed in this study can be used for construction materials based on criteria of the current regulations. 


October, 2018 | DOI: 10.1016/j.matlet.2018.06.105

Study of the thermal decomposition of historical metal threads


Perez-Rodriguez, JL; Perez-Maqueda, R; Franquelo, ML; Duran, A
Journal of Thermal Analysis and Calorimetry, 134 (2018) 15-22

ABSTRACT

In this work, it is reported that thermal analysis techniques such as differential thermal analysis and thermogravimetric analysis are very useful for evaluating metals threads and fibres used in the manufacture of historical artifacts. Thermal analysis has been used to characterize the silk, cotton and linen employed as supports and the copper, silver and aluminium as the metallic components in the studied threads. Other organic compounds, mainly added for the conservation of the threads, have also been characterized.


October, 2018 | DOI: 10.1007/s10973-017-6924-x

Pt/CePO4 catalysts for the WGS reaction: influence of the water-supplier role of the support on the catalytic performance


Navarro-Jaen, S; Centeno, MA; Laguna, OH; Odriozola, JA
Journal of Materials Chemistry A, 6 (2018) 17001-17010

ABSTRACT

For Pt catalysts which have demonstrated great activity for the WGS reaction, the activation of water is described as the rate-limiting step. Such limitation could be overcome through the design of supports able to supply water. In this study, the hexagonal and monoclinic phases of CePO4 have been evaluated as supports for Pt WGS catalysts. The hexagonal structure presents channels containing water, absent in the monoclinic structure. The presence of these channels in the hexagonal phase increases the interaction with the water molecules, leading to an enhancement of the WGS catalytic performance. DRIFTS results showed that dissociation of water does not occur on these supports, while calculated apparent activation energies present values similar to those reported in the literature for the dissociation of water in Pt (111). These results suggest that cerium phosphates act as water suppliers, increasing the number of available species to be dissociated on the Pt surface.


September, 2018 | DOI: 10.1039/c8ta04603d

A direct in situ observation of water-enhanced proton conductivity of Eu-doped ZrO2: Effect on WGS reaction


Garcia-Moncada, N; Bobadilla, LF; Poyato, R; Lopez-Cartes, C; Romero-Sarria, F; Centeno, MA; Odriozola, JA
Applied Catalysis B-Environmental, 231 (2018) 343-356

ABSTRACT

Eu-doped ZrO2 solid solutions have been synthesized in order to prepare proton conductors as water-enhancer additives for the WGS reaction. Elemental characterization has been carried out revealing homogeneous dopant distribution resulting in fluorite-type solid solutions for Eu2O3 contents up to similar to 9 mol.%. Representative samples of the Eu-doped ZrO2 series have been analysed by Impedance Spectroscopy (IS) in inert, oxygen and wet conditions. The solid solution with 5 mol.% of Eu2O3 has presented the highest conductivity values for all tested conditions indicating an optimal amount of dopant. Moreover, the presence of vapour pressure results in an increment of the conductivity at temperatures lower than 300 degrees C, meanwhile at higher temperatures the conductivity is the same than that in inert conditions. To elucidate these results, in situ DRIFTS studies were carried out. These experiments evidenced the existence of water dissociation at oxygen vacancies (band at 3724 cm(-1)) as well as the presence of physisorbed water at temperatures up to similar to 300 degrees C where the band at 5248 cm(-1) characteristic of these species disappeared. These results points to a layer model where the physisorbed water interacts with surface hydroxyls generated by dissociated water that improves the proton conductivity through Grotthuss' mechanism in the RT-300 degrees C temperature range. These samples were successfully tested in WGS reaction as additive to a typical Pt-based catalyst. The presence of the mixed oxide reveals an increase of the catalyst' activity assisted by the proton conductor, since improves the water activation step.


September, 2018 | DOI: 10.1016/j.apcatb.2018.03.001

A comprehensive and in-depth analysis of the synthesis of advanced adsorbent materials


Osuna, FJ; Cota, A; Pavon, E; Alba, MD
Journal of Cleaner Production, 194 (2018) 665-672

ABSTRACT

Na-Mica-4, a synthetic fluorophlogopite, is an attractive adsorbent. However, the synthesis at large scale demands an economically prized, feasible scalable and sustainable synthesis method, which requires a deep knowledge of the influence of each synthesis step. A set of Na-Mica-4 were synthesized by methods that had one synthesis parameter as variable. The purity, crystallinity and heteroatoms distribution were analysed thorough X-ray diffraction and nuclear magnetic resonance. The results shed a light on the main factors for the design of the final product and indicated that an environmental friendship synthesis could be possible. 


September, 2018 | DOI: 10.1016/j.jclepro.2018.05.179

Performance improvement in olive stone's combustion from a previous carbonization transformation


Gomez-Martin, A; Chacartegui, R; Ramirez-Rico, J; Martinez-Fernandez, J
Fuel, 228 (2018) 254-262

ABSTRACT

Under the framework of circular economy, agricultural wastes are an interesting carbon-based feedstock for thermal energy and power generation. Their use could extend the availability of biomass-based fuel and, at the same time, would reduce negative environmental effects. However, depending on the residues' characteristics, their direct combustion in boilers presents some challenges which could be overcome with a carbonization pretreatment. In this paper, the main mechanisms of thermochemical transformation of an abundant agricultural waste, olive stone, into biochar products via slow carbonization are analyzed, with emphasis on the effect of peak carbonization temperature. Thermogravimetric and differential scanning calorimetry analysis are used to evaluate the performance of the resulting biochars compared to raw olive stone in combustion processes and to assess the correlation between the peak carbonization temperature and compositional and fuel properties. Results show that with a prior treatment up to an optimum temperature of 800 degrees C the energy density is increased up to three times compared to the raw material. These findings suggest that carbonization of olive stones reduces the barriers to their direct use in current biomass boiler technology.


September, 2018 | DOI: 10.1016/j.fuel.2018.04.127

Nanostructural Analysis of Porous Oblique Angle Deposited (OAD) Multilayer Systems by Grazing-Incidence Small-Angle X-Ray Scattering


Oliva-Ramirez, M; Lopez-Santos, C; Yubero, F; Gonzalez-Elipe, AR
Advanced Optical Materials, 5 (2018) 1800530

ABSTRACT

This work reports a thorough characterization analysis of various porous thin film multilayers by means of grazing-incidence small-angle X-ray scattering (GISAXS). Alternated TiO2/SiO2 nanocolumnar layers deposited at oblique angles are fabricated in slanted, chiral, and zig-zag configurations by rotating azimuthally the substrate from one layer to the next. Multilayer systems formed by the stacking of 3 and 15 alternant thin films of these two oxides are morphologically characterized by scanning electron microscopy (SEM) and structurally by GISAXS. This technique has provided a means to determine various vertical and lateral correlation lengths and to assess the anisotropic electron density distribution along the structural elements existing in the multilayers. This information can be systematically used to account for the actual arrangement of nanostructural elements in multilayer systems.


September, 2018 | DOI: 10.1002/admi.201800530

Sensing and biosensing with screen printed electrodes modified with nanostructured nickel oxide thin films prepared by magnetron sputtering at oblique angles


Salazar, P; Garcia-Garcia, FJ; Gonzalez-Elipe, AR
Electrochemistry Communications, 94 (2018) 5-8

ABSTRACT

This work reports about the sensing and biosensing applications of a novel screen printed electrode (SPE) modified by nanostructured nickel oxide thin films obtained by reactive magnetron sputtering under an oblique angle configuration. Using these films as electrodes we demonstrate their ability to detect hydrogen peroxide under neutral pH conditions. Furthermore, as a proof-of-concept, NiO-modified SPEs have been developed and their cholesterol biosensing properties determined by cyclic voltammetry and chronoamperometry.


September, 2018 | DOI: 10.1016/j.elecom.2018.07.020

ZnO and Pt-ZnO photocatalysts: Characterization and photocatalytic activity assessing by means of three substrates


Jaramillo, C; Navio, J.A.; Hidalgo, M.C.; Macías, M.
Catalysis Today, 313 (2018) 12-19

ABSTRACT

ZnO nanoparticles have been previously synthesized by a facile precipitation procedure by mixing aqueous solutions of Zn(II) acetate and dissolved Na2CO3 at pH ca. 7.0 without the addition of a template. The as-prepared ZnO material was anealed at 400 °C in air for 2 h. The Pt-ZnO catalysts (0.5 or 1.0 Pt wt.%) were obtained by photochemical deposition method on the surface of the prepared ZnO sample, using hexachloroplatinic acid (H2PtCl6). It has been shown that Zn2+ is lost from the photocatalyst to the medium and a replacement of the cationic vacancies of Zn2+ by Pt4+ cations occurs during the platinization process of the ZnO samples, regardless of whether the platinum metal photodeposition process. The as-prepared catalysts were characterized by XRD, BET, FE-SEM, TEM, XPS and diffuse reflectance spectroscopy (DRS). Three different probe molecules were used to evaluate the photocatalytic properties under UV-illumination: Methyl Orange and Rhodamine B were chosen as dye substrates and Phenol as a transparent substrate. High conversion values (ca. 100%) and a total organic carbon (TOC) removal of 90–96%, were obtained over these photocatalysts after 160 min of UV illumination. In general, it was observed that the presence of Pt on ZnO affects the lattice parameters and the crystallite size. Although ZnO can completely degrade RhB, MO and Phenol totally in ca. 60 min, the process is more efficient for Pt–ZnO photocatalysts.


September, 2018 | DOI: 10.1016/j.cattod.2017.12.009

Graphene or carbon nanofiber-reinforced zirconia composites: Are they really worthwhile for structural applications?


Cano-Crespo, R; Moshtaghioun, BM; Gomez-Garcia, D; Moreno, R; Dominguez-Rodriguez, A
Journal of the European Ceramic Society, 38 (2018) 3994-4002

ABSTRACT

The use of allotropic phases of carbon (i.e. nanotubes, graphene or carbon nanofibers) as second phases to design ceramic composites is a hot topic at present. Researchers try to provide a remarkable improvement of the parent ceramic assuming that some of the outstanding mechanical properties of these phases migrate to the resultant composite. This reasonable idea has been questioned severely in the case of nanotubes addition but there is not any analysis for the other two phases cited previously. To elucidate this question, zirconia was selected as a model ceramic. This paper reports the mechanical properties of zirconia composites reinforced either with graphene or carbon nanofibers, with special emphasis on the high-temperature plasticity.


September, 2018 | DOI: 10.1016/j.jeurceramsoc.2018.04.045

Mechanosynthesis of Sr1-xLaxTiO3 anodes for SOFCs: Structure and electrical conductivity


Sayagues, MJ; Gotor, J; Pueyo, M; Poyato, R; Garcia-Garcia, FJ
Journal of Alloys and Compounds, 763 (2018) 679-686

ABSTRACT

Sr1-xLaxTiO3 (SLT; 0 <= x <= 0.5) powder samples were synthesised at room temperature by a mechanochemical method from SrO, La2O3 and TiO2 mixtures in 90 min. The obtained SLT samples as potential anode materials in solid oxide fuel cells (SOFCs) were investigated. The microstructure, electrical conductivity and chemical compatibility with yttria-stabilised zirconia (YSZ) were studied. The powder samples had a nanometric character after milling. After a subsequently heating at 900 degrees C, the particle size slightly increased, but still remained nanometric. At this high temperature, a good chemical compatibility with YSZ was found. The x = 0.2 sample gave the best electrical conductivity values, i.e. 0.23 W cm(-2). These features make such as-obtained samples good candidates to be used as anodes in SOFCs.


September, 2018 | DOI: 10.1016/j.jallcom.2018.05.243

Nanostructured vanadium carbonitride prepared by combustion synthesis during mechanical milling


Jalaly, M; Gotor, FJ; Sayagues, MJ
Journal of Alloys and Compounds, 763 (2018) 18-24

ABSTRACT

Vanadium carbonitride (VCN) nanoparticles were synthesized by a mechanically induced magnesiothermic combustion in a Mg/V2O5/C3H6N6 system. Initial materials ignited after a short milling time of 6 min. Various characterizations such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDX), high-resolution transmission electron microscopy (HRTEM) and elemental mapping confirmed that the product of the combustion was a mixed carbonitride. In this process, magnesium reduces vanadium oxide to generate elemental V and a great amount of heat. Melamine decomposes due to the temperature rise, and its decomposed species form the carbonitride compound. The chemical composition of the synthesized product was estimated to be VC0.26N0.36.


September, 2018 | DOI: 10.1016/j.jallcom.2018.05.352

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