Artículos SCI
2021
2021
Química de Superficies y Catálisis
Biogas Conversion to Syngas Using Advanced Ni-Promoted Pyrochlore Catalysts: Effect of the CH4/CO2 Ratio
le Sache, E; Moreno, AA; Reina, TRFrontiers in Chemistry, 9 (2021) 672419 DOI: 10.3389/fchem.2021.672419
Abstract
Biogas is defined as the mixture of CH4 and CO2 produced by the anaerobic digestion of biomass. This particular mixture can be transformed in high valuable intermediates such as syngas through a process known as dry reforming (DRM). The reaction involved is highly endothermic, and catalysts capable to endure carbon deposition and metal particle sintering are required. Ni-pyrochlore catalysts have shown outstanding results in the DRM. However, most reported data deals with CH4/CO2 stoichiometric ratios resulting is a very narrow picture of the overall biogas upgrading via DRM. Therefore, this study explores the performance of an optimized Ni-doped pyrochlore, and Ni-impregnated pyrochlore catalysts in the dry reforming of methane, under different CH4/CO2 ratios, in order to simulate various representatives waste biomass feedstocks. Long-term stability tests showed that the ratio CH4/CO2 in the feed gas stream has an important influence in the catalysts' deactivation. Ni doped pyrochlore catalyst, presents less deactivation than the Ni-impregnated pyrochlore. However, biogas mixtures with a CH4 content higher than 60%, lead to a stronger deactivation in both Ni-catalysts. These results were in agreement with the thermogravimetric analysis (TGA) of the post reacted samples that showed a very limited carbon formation when using biogas mixtures with CH4 content <60%, but CH4/CO2 ratios higher than 1.25 lead to an evident carbon deposition. TGA analysis of the post reacted Ni impregnated pyrochlore, showed the highest amount of carbon deposited, even with lower stoichiometric CH4/CO2 ratios. The later result indicates that stabilization of Ni in the pyrochlore structure is vital, in order to enhance the coke resistance of this type of catalysts.
Abril, 2021 | DOI: 10.3389/fchem.2021.672419
Reactividad de Sólidos
Enhancing the electrical conductivity of in-situ reduced graphene oxide-zirconia composites through the control of the processing routine
Lopez-Pernia, C; Morales-Rodriguez, A; Gallardo-Lopez, A; Poyato, RCeramics International, 47 (2021) 9382-9391 DOI: 10.1016/j.ceramint.2020.12.069
Abstract
Graphene oxide (GO) was mixed with 3 mol% yttria tetragonal zirconia polycrystal (3YTZP) using two powder processing routines: a colloidal method in an aqueous solution and a combination of ultrasonication with highenergy planetary ball milling in wet conditions. Highly densified 3YTZP composites with reduced GO (rGO) were consolidated by Spark Plasma Sintering. The in-situ reduction of GO was successfully achieved during the high temperature sintering process and a detailed study of the restoration of the graphene structure in the sintered composites has been made by Raman spectroscopy. Although no differences between the composites prepared by the two processing methods were found in the distribution of the rGO throughout the 3YTZP matrix for high rGO contents (i.e. the composites with 5 and 10 vol% rGO), a better distribution of the graphene phase was found in the composites with 1 and 2.5 vol% rGO prepared by planetary ball milling. This result, together with a better reduction of the GO in these composites, led to the obtaining of rGO/3YTZP composites with a better behavior in terms of electrical conductivity: an electrical percolation threshold below 2.5 vol% rGO and a high electrical conductivity value (-610 S/m for 10 vol% rGO).
Abril, 2021 | DOI: 10.1016/j.ceramint.2020.12.069
Nanotecnología en Superficies y Plasma
Form Birefringence in Resonant Transducers for the Selective Monitoring of VOCs under Ambient Conditions
Oliva-Ramirez, Manuel; Lopez-Santos, Carmen; Berthon, Hermine; Goven, Mathilde; Portoles, Jose; Gil-Rostra, Jorge; Gonzalez-Elipe, Agustin R.; Yubero, FranciscoACS Applied Materials & Interfaces, 13 (2021) 19148-19158 DOI: 10.1021/acsami.1c02499
Abstract
In this work, we have developed a new kind of nanocolumnar birefringent Bragg microcavity (BBM) that, tailored by oblique angle deposition, behaves as a selective transducer of volatile organic compounds (VOCs). Unlike the atomic lattice origin of birefringence in anisotropic single crystals, in the BBM, it stems from an anisotropic self-organization at the nanoscale of the voids and structural elements of the layers. The optical adsorption isotherms recorded upon exposure of these nanostructured systems to water vapor and VOCs have revealed a rich yet unexplored phenomenology linked to their optical activity that provides both capacity for vapor identification and partial pressure determination. This photonic response has been reproduced with a theoretical model accounting for the evolution of the form birefringence of the individual layers upon vapor condensation in nanopores and internanocolumnar voids. BBMs that repel water vapor but are accessible to VOCs have been also developed through grafting of their internal surfaces with perfluorooctyltriethoxysilane molecules. These nanostructured photonic systems are proposed for the development of transducers that, operating under environmental conditions, may respond specifically to VOCs without any influence by the degree of humidity of the medium.
Abril, 2021 | DOI: 10.1021/acsami.1c02499
Materiales de Diseño para la Energía y Medioambiente
Organophilization of acid and thermal treated sepiolite for its application in BTEX adsorption from aqueous solutions
Varela, CF; Pazos, MC; Alba, MDJournal of Water Process Engineering, 40 (2021) 101949 DOI: 10.1016/j.jwpe.2021.101949
Abstract
Acid and thermal treated sepiolite was organophilized by cationic exchange with several alkylammonium cations (octylammonium, hexadecylammonium, tetradecyltrimethylammonium, and hexadecyltrimethylammonium). The adsorption capacity of BTEX from aqueous solutions was evaluated through the adsorption isotherms performed in batch. The results were analysed using three isotherm models: Freundlich, Langmuir and Dubinin-Radushkevich (D-R model). The behaviour of adsorption isotherm suggested the multilayer coverage on a heterogeneous surface, which is according to the Freundlich isotherm model. The thermodynamic analyse using the D-R model show that physical mechanisms govern the process. The maximum adsorption capacity of BTEX on the obtained materials was in the range values of 81.19 mg g(-1) - 1448.42 mg g(-)(1), which are higher than those reported up to now. The organo-sepiolite materials exhibit a high potential in the adsorption of BTEX compounds from aqueous solutions.
Abril, 2021 | DOI: 10.1016/j.jwpe.2021.101949
Nanotecnología en Superficies y Plasma
Rietveld Refinement, mu-Raman, X-ray Photoelectron, and Mossbauer Studies of Metal Oxide-Nanoparticles Growth on Multiwall Carbon Nanotubes and Graphene Oxide
Ramos-Guivar, JA; Gonzalez-Gonzalez, JC; Litterst, FJ; Passamani, ECCrystal Growth & Design, 21 (2021) 2128-2141 DOI: 10.1021/acs.cgd.0c01551
Abstract
Applying a modified coprecipitation method, maghemite and anatase nanoparticles embedded in graphene oxide and multiwall carbon nanotube frameworks were prepared, and a detailed structural characterization is presented. Transmission electron images have revealed that the multiwall carbon nanotubes and graphene oxide act as substrates to reduce the nanoparticle agglomeration with narrow sizes of ca. 9-20 nm, in agreement with the results of the Rietveld refinement, which have also indicated their crystallite apparent size and shapes using the spherical harmonics approach. In structural studies of maghemite nanoparticles by Raman spectroscopy, it was found that the effect of optical density and laser power intensity plays a significant role. When no optical filter was located between the powder sample and the laser source, a transformation from the gamma-Fe2O3 to the alpha-Fe2O3 phase was observed, as demonstrated by the disappearance of the characteristic broad Raman peak (A(1g)) of the gamma-Fe2O3 phase when increasing the laser power. X-ray photoelectron spectroscopy has also brought insights into the functionalization mechanism, suggesting that the one-pot reduction of the graphene oxide is favored by the alkaline gamma-Fe2O3 nanoparticle growth. The temperature dependence of the Fe-57 Mossbauer spectra has indicated that the effective anisotropy constant of Fe oxide-based nanoparticles is similar to that of bulk maghemite, and magnetic relaxation of Fe3+ spins depends on particle sizes.
Abril, 2021 | DOI: 10.1021/acs.cgd.0c01551
Nanotecnología en Superficies y Plasma
New Insights on the Conversion Reaction Mechanism in Metal Oxide Electrodes for Sodium-Ion Batteries
Mosa, J; Garcia-Garcia, FJ; Gonzalez-Elipe, AR; Aparicio, MNanomaterials, 11 (2021) 966 DOI: 10.3390/nano11040966
Abstract
Due to the abundance and low cost of exchanged metal, sodium-ion batteries have attracted increasing research attention for the massive energy storage associated with renewable energy sources. Nickel oxide (NiO) thin films have been prepared by magnetron sputtering (MS) deposition under an oblique angle configuration (OAD) and used as electrodes for Na-ion batteries. A systematic chemical, structural and electrochemical analysis of this electrode has been carried out. The electrochemical characterization by galvanostatic charge-discharge cycling and cyclic voltammetry has revealed a certain loss of performance after the initial cycling of the battery. The conversion reaction of NiO with sodium ions during the discharge process to generate sodium oxide and Ni metal has been confirmed by X-ray photoelectron spectra (XPS) and micro-Raman analysis. Likewise, it has been determined that the charging process is not totally reversible, causing a reduction in battery capacity.
Abril, 2021 | DOI: 10.3390/nano11040966
Nanotecnología en Superficies y Plasma
Novel procedure for studying laser-surface material interactions during scanning laser ablation cleaning processes on Cu-based alloys
Di Francia, E; Lahoz, R; Neff, D; Rico, V; Nuns, N; Angelini, E; Grassini, SApplied Surface Science, 544 (2021) art. 178820 DOI: 10.1016/j.apsusc.2020.148820
Abstract
Laser ablation is an effective method to clean Cu-based alloys. A novel procedure of characterisation was developed involving O-18 isotopes evaluated by ToF-SIMS spectroscopy to assess the driving mechanisms of laser-surface interactions. The presence of re-oxidised compounds was detected, discerning between the oxygen from the corrosion layer and the one introduced by the interaction with the laser (that was generated in a controlled atmosphere of O-18 diluted in N-2). A set of samples treated with different laser conditions were characterised by FESEM and mu Raman. The results have shown that re-oxidation phenomenon can occur and its selectivity depends on the laser conditions.
Abril, 2021 | DOI: 10.1016/j.apsusc.2020.148820
Fotocatálisis Heterogénea: Aplicaciones
Fluorinated and platinized Titania for Glycerol oxidation
Murcia, J.J.; Bautista, E; Ávila Martínez, E.G.; Rangel R.N.; Romero, R.; Cubillos Lobo, J.A.; Rojas Sarmiento, H.A.; Hernández, J.S.; Cárdenas, O.; Hidalgo, M.C.; Navío, J.A.; Baeza, R.Materials Proceedings, 4 (2021) 37 DOI: 10.3390/IOCN2020-07792
Abstract
In this research, photocatalysts based on TiO2 modified by fluorination and platinum addition were evaluated in the glycerol oxidation. These materials were characterized by different instrumental analysis techniques to determine the physicochemical properties. It was found that the surface modification lead to improve the materials absorption in the Visible region of the electromagnetic spectra and to increase the surface area of TiO2. By HPLC analysis was possible to observed that the photocatalysts 0.5% Pt-F-TiO2 showed the highest yield and selectivity towards glyceraldehyde (GAL). It was also observed that the increase in the platinum content until values of 2% had a negative effect in the effectiveness of fluorinated Titania in the glycerol photo-oxidation. The fluorination and platinum addition modify some physicochemical properties of TiO2, leading also to modify the reaction mechanism and selectivity during glycerol partial photo-oxidation and the dose of photocatalysts is an important reaction condition to obtain GAL and Dyhidroxyacetone (DHA) with yields above to 70%.
Abril, 2021 | DOI: 10.3390/IOCN2020-07792
Materiales Coloidales
Holmium phosphate nanoparticles as negative contrast agents for high-field magnetic resonance imaging: Synthesis, magnetic relaxivity study and in vivo evaluation
Gomez-Gonzalez, E; Caro, C; Martinez-Gutierrez, D; Garcia-Martin, ML; Ocana, M; Becerro, AIJournal of Colloid and Interface Science, 587 (2021) 131-140 DOI: 10.1016/j.jcis.2020.11.119
Abstract
The increasing use of high magnetic fields in magnetic resonance imaging (MRI) scanners demands new contrast agents, since those used in low field instruments are not effective at high fields. In this paper, we report the synthesis of a negative MRI contrast agent consisting of HoPO4 nanoparticles (NPs). Three different sizes (27 nm, 48 nm and 80 nm) of cube-shaped NPs were obtained by homogeneous precipitation in polyol medium and then coated with poly(acrylic) acid (PAA) to obtain stable colloidal suspensions of HoPO4@PAA NPs in physiological medium (PBS). The transverse relaxivity (r2) of aqueous suspensions of the resulting NPs was evaluated at both 1.44 T and 9.4 T. A positive correlation between r2 values and field strength as well as between r2 values and particle size at both magnetic field strengths was found although this correlation failed for the biggest NPs at 9.4 T, likely due to certain particles aggregation inside the magnet. The highest r2 value (489.91 mM-1s−1) was found for the 48 nm NPs at 9.4 T. Toxicity studies demonstrated that the latter NPs exhibited low toxicity to living systems. Finally, in vivo studies demonstrated that HoPO4@PAA NPs could be a great platform for next-generation T2-weighted MRI contrast agents at high magnetic field.
Abril, 2021 | DOI: 10.1016/j.jcis.2020.11.119
Materiales de Diseño para la Energía y Medioambiente
Pb2+, Cd2+ and Hg2+ removal by designed functionalized swelling high-charged micas
Osuna, FJ; Pavon, E; Alba, MDScience of The Total Environment, 764 (2021) 142811 DOI: 10.1016/j.scitotenv.2020.142811
Abstract
The increasing accumulation of toxic heavy metals in the environment has generated the need of efficient removal systems, being the adsorption method the most popular one applied in aqueous solutions. Of particular concern is the case of Pb2+, Cd2+ and Hg2+ due to their high potential hazard. In this paper, we describe the feasibility of a new family of nanomaterials, swelling high charge micas, in the removal of these cations from aqueous solutions. Batch adsorption experiments were carried out in the as-made micas, NaMn, and after functionalization with ethylammonium, EA-Mn, and mercaptoethylammonium, MEA-Mn. The results have demonstrated that all of them are efficient heavy metal adsorbents, being Na-M2 the best adsorbent for Pb2+ and Cd2+, and, MEA-M2 for Hg2+.
Abril, 2021 | DOI: 10.1016/j.scitotenv.2020.142811
Materiales y Procesos Catalíticos de Interés Ambiental y Energético
Elucidating the nature of Mo species on ZSM-5 and its role in the methane aromatization reaction
Lopez-Martin, A.; Platero, F; Colon, G.; Caballero, A.Reaction Chemistry & Engineering DOI: 10.1039/d1re00044f
Abstract
The valorization of methane is one of the most important goals during the transition period to the general use of renewable energies. Its transformation into a valuable chemical like benzene by direct aromatization of methane (DAM) reaction has been extensively studied in the past years, mainly using Mo/ZSM-5 catalytic systems. Although viable, this DAM reaction poses a number of issues mainly derived from poor conversion and deactivation processes. Therefore, a deeper knowledge of these systems is needed. Herein, by combining chemical (TPR), spectroscopic (XPS), HAADF and other techniques, we have identified the different Mo precursors stabilized in the calcined ZSM-5 support, their nature (monomers, dimers and bulk Mo oxides), location in the zeolite framework (external surface or micropores), and the partial segregation of aluminum during the preparation of catalysts. The role of each Mo phase promoting or hindering the transformation of methane in aromatics has been also clarified.
Abril, 2021 | DOI: 10.1039/d1re00044f
Materiales y Procesos Catalíticos de Interés Ambiental y Energético
LED-driven controlled deposition of Ni onto TiO2 for visible-light expanded conversion of carbon dioxide into C-1-C-2 alkanes
Sanz-Marco, A; Hueso, JL; Sebastian, V; Nielsen, D; Mossin, S; Holgado, JP; Bueno-Alejo, CJ; Balas, F; Santamaria, JNanoscale Advances DOI: 10.1039/d1na00021g
Abstract
Photocatalytic gas-phase hydrogenation of CO2 into alkanes was achieved over TiO2-supported Ni nanoparticles under LED irradiation at 365 nm, 460 nm and white light. The photocatalysts were prepared using photo-assisted deposition of Ni salts under LED irradiation at 365 nm onto TiO2 P25 nanoparticles in methanol as a hole scavenger. This procedure yielded 2 nm Ni particles decorating the surface of TiO2 with a nickel mass content of about 2%. Before the photocatalytic runs, Ni/TiO2 was submitted to thermal reduction at 400 °C in a 10% H2 atmosphere which induced O-defective TiO2−x substrates. The formation of oxygen vacancies, Ti3+ centers and metallic Ni sites upon photocatalytic CO2 hydrogenation was confirmed by operando EPR analysis. In situ XPS under reaction conditions suggested a strong metal–support interaction and the co-existence of zero and divalent Ni states. These photoactive species enhanced the photo-assisted reduction of CO2 below 300 °C to yield CO, CH4 and C2H6 as final products.
Abril, 2021 | DOI: 10.1039/d1na00021g
Nanotecnología en Superficies y Plasma
Electrochromic response and porous structure of WO3 cathode layers
Louloudakis, D; Mouratis, K; Gil-Rostra, J; Koudoumas, E; Alvarez, R; Palmero, A; Gonzalez-Elipe, ARElectrochimica Acta, 376 (2021) 138049 DOI: 10.1016/j.electacta.2021.138049
Abstract
Maximizing the electrochromic response of tungsten oxide-based systems demands highly porous electrode layers that facilitate the incorporation of electrolyte cations during the reduction process. In this work, amorphous and porous WO3 thin films were grown on indium tin dioxide glass substrates by magnetron sputtering at oblique angles at two different plasma gas pressures. Remarkably, the film that showed higher porosity presented a worse electrochromic response in terms of durability, time response and charge density capacity. This result is analyzed and explained on the basis of the features of the porous structure of the films: While the typical nanostructure developed at low pressures possesses large and connected pore voids with few ramifications, the nanostructure generated at a higher pressure presents a rather sponge-like porous structure with numerous and small well-connected voids. A general discussion on the role of the porous structure and, particularly, on the accessible pore volume and area is carried out. It is concluded that not only the accessible pore volume, defining the volume of electrolyte that stays inside the layer, but also the accessible pore area, which defines the efficiency of the incorporation/release of Li+ cations within the electrode material, determine the efficiency and reversibility of the electrochromic response.
Abril, 2021 | DOI: 10.1016/j.electacta.2021.138049
Química de Superficies y Catálisis
Cu supported Fe-SiO2 nanocomposites for reverse water gas shift reaction
Gonzalez-Castano, M; de Miguel, JCN; Sinha, F; Wabo, SG; Klepel, O; Arellano-Garcia, HJournal of CO2 Utilization, 46 (2021) 101493 DOI: 10.1016/j.jcou.2021.101493
Abstract
This work analyses the catalytic activity displayed by Cu/SiO2, Cu-Fe/SiO2 and Cu/FSN (Fe-SiO2 nanocomposite) catalysts for the Reverse Water Gas Shift reaction. Compared to Cu/SiO2 catalyst, the presence of Fe resulted on higher CO?s selectivity and boosted resistances against the constitution of the deactivation carbonaceous species. Regarding the catalytic performance however, the extent of improvement attained through incorporation Fe species strongly relied on the catalysts' configuration. At 30 L/gh and H-2:CO2 ratios = 3, the performance of the catalysts? series increased according to the sequence: Cu/SiO2 < Cu-Fe/SiO2 << Cu/FSN. The remarkable catalytic enhancements provided by Fe-SiO2 nanocomposites under different RWGS reaction atmospheres were associated to enhanced catalyst surface basicity's and stronger Cu-support interactions. The catalytic promotion achieved by Fe-SiO2 nanocomposites argue an optimistic prospective for nanocomposite catalysts within future CO2-valorising technologies.
Abril, 2021 | DOI: 10.1016/j.jcou.2021.101493
Química de Superficies y Catálisis
Zr and Fe on Pt/CeO2-MOx/Al2O3 catalysts for WGS reaction
Gonzalez-Castano, M; Ivanova, S; Centeno, MA; Ioanides, T; Arellano-Garcia, H; Odriozola, JAInternational Journal of Hydrogen Energy, (2021) DOI: 10.1002/er.6646
Abstract
By evaluating the functional modifications induced by Zr and Fe as dopants in Pt/CeO2‐MOx/Al2O3 catalysts (M = Fe and Zr), the key features for improving water gas shift (WGS) performance for these systems have been addressed. Pt/ceria intrinsic WGS activity is often related to improved H2 surface dynamics, H2O absorption, retentions and dissociation capacities which are influenced greatly by the support nature. Two metals, iron and zirconia, were chosen as ceria dopants in this work, either in separate manner or combined. Iron incorporation resulted in CO‐redox properties and oxygen storage capacities (OSC) improvement but the formation of Ce‐Fe solid solutions did not offer any catalytic benefit, while the Zr incorporation influenced in a great manner surface electron densities and shows higher catalytic activity. When combined both metals showed an important synergy evidenced by 30% higher CO conversions and attributed to greater surface electron densities population and therefore absorption and activity. This work demonstrates that for Pt/ceria catalysts OSC enhancement does not necessarily imply a catalytic promotion.
Marzo, 2021 | DOI: 10.1002/er.6646
Fotocatálisis Heterogénea: Aplicaciones
Facile synthesis and characterization of a novel 1,2,4,5-benzene tetracarboxylic acid doped polyaniline@zinc phosphate nanocomposite for highly efficient removal of hazardous hexavalent chromium ions from water
Abdelghani Hsini, Yassine Naciri, Mohamed Benafqir, Zeeshan Ajmal, Nouh Aarab, Mohamed Laabd, J.A. Navío, F. Puga, Rabah Boukherroub, Bahcine Bakiz, Abdallah AlbourineJournal of Colloid and Interface Science, 585 (2021) 560-573 DOI: 10.1016/j.jcis.2020.10.036
Abstract
The present study describes the preparation of a novel 1,2,4,5-benzene tetracarboxylic acid doped polyaniline@zinc phosphate (BTCA-PANI@ZnP) nanocomposite via a facile two-step procedure. Thereafter, the as-prepared composite material adsorption characteristics for Cr(VI) ions removal were evaluated under batch adsorption. Kinetic approach studies for Cr(VI) removal, clearly demonstrated that the results of the adsorption process followed the pseudo second order and Langmuir models. The thermodynamic study indicated a spontaneous and endothermic process. Furthermore, higher monolayer adsorption was determined to be 933.88 mg g1 . In addition, the capability study regarding Cr(VI) ions adsorption over BTCA-PANI@ZnP nanocomposite clearly revealed that our method is suitable for large scale application. X-ray photoelectron spectroscopy (XPS) analysis confirmed Cr(VI) adsorption on the BTCA-PANI@ZnP surface, followed by its subsequent reduction to Cr(III). Thus, the occurrence of external mass transfer, electrostatic attraction and reduction phenomenon were considered as main mechanistic pathways of Cr(VI) ions removal. The superior adsorption performance of the material, the multidimensional characteristics of the surface and the involvement of multiple removal mechanisms clearly demonstrated the potential applicability of the BTCA-PANI@ZnP material as an effective alternative for the removal of Cr(VI) ions from wastewater.
Marzo, 2021 | DOI: 10.1016/j.jcis.2020.10.036
Materiales Ópticos Multifuncionales
The Complex Interplay of Lead Halide Perovskites with Their Surroundings
Galisteo-Lopez, JF; Calvo, ME; Miguez, HAdvanced Optical Materials, (2021) 2100133 DOI: 10.1002/adom.202100133
Abstract
Photoexcitation of lead halide perovskites induces a restructuration of the material that simultaneously enhances its emission properties and triggers its degradation. These concomitant processes are strongly dependent on the surroundings of the perovskite, both while and after being processed, underlining the relevance the environment and the interfacial design have in the stability and performance of these materials and the devices based on them. This shocking observation reveals that when subjected to external illumination, lead halide perovskites undergo a number of photophysical processes that strongly modify their structure and thus their optoelectronic properties. Such photoinduced instability stems from a defective structure directly linked to the low-temperature and solution-processed fabrication routes generally employed to build perovskite solar cells with efficiencies comparable to state-of-the-art values. On the other hand, these same inexpensive and unsophisticated procedures make this material a promising component in energy conversion devices. Here, an analysis is provided regarding the different impact on the perovskite structure, hence on its optoelectronic performance, that the interaction with its surroundings has, providing specific examples that highlight this interplay, describing the kind of modification it induces, and listing the related effects on the optoelectronic properties that should be accounted for when characterizing them.
Marzo, 2021 | DOI: 10.1002/adom.202100133
Materiales Ópticos Multifuncionales - Materiales Coloidales
Persistent luminescence of transparent ZnGa2O4:Cr3+ thin films from colloidal nanoparticles of tunable size
Arroyo, E; Medran, B; Castaing, V; Lozano, G; Ocana, M; Becerro, AIJournal of Materials Chemistry C, 9 (2021) 4474-4485 DOI: 10.1039/d1tc00258a
Abstract
We report on the fabrication of ZnGa2O4:Cr3+ transparent thin films and the evaluation, for the first time in the literature, of their persistent red to NIR emission. For this purpose, we have used a simple and economic global strategy based on wet processing methods from colloidal nanospheres with uniform size. A microwave-assisted hydrothermal method was first developed for the synthesis of precursor particles, which allows size tuning from 300 nm to 30 nm through simple modification of the Zn2+ precursor and the Cr3+ content of the starting solutions. ZnGa2O4:Cr3+ transparent thin films over quartz substrates were then easily fabricated by spin coating, and their structural and optical characteristics were analyzed in detail after annealing at high temperature to elucidate the effect of processing temperature and particle size on the properties of the films. Indeed, our results indicate that high temperature annealing does not compromise the transparency of the films but improves their photoluminescence. In addition, the analysis reveals that persistence luminescence in our films is rather independent of the size of the precursor nanoparticles. Due to their transparency and persistent emission properties, films fabricated from colloidal suspensions of ZnGa2O4:Cr3+ nanoparticles show great potential for application in the fields of chemical sensing, information storage, labelling, and anti-counterfeiting technology.
Marzo, 2021 | DOI: 10.1039/d1tc00258a
Química de Superficies y Catálisis
Functionalized biochars as supports for Pd/C catalysts for efficient hydrogen production from formic acid
Santos, JL; Megias-Sayago, C; Ivanova, S; Centeno, MA; Odriozola, JAApplied Catalysis B-Environmental, 282 (2021) 119615 DOI: 10.1016/j.apcatb.2020.119615
Abstract
Biomass waste product was used to generate biochars as catalytic supports for selective hydrogen production from formic acid. The supports were obtained after pyrolysis in CO2 atmosphere of non-pretreated and che-mically ZnCl2 activated raw materials (vine shoot and crystalline cellulose). The support series includes materials with different textural properties and surface chemistry. The support nature and especially textural properties firstly affects significantly Pd size and dispersion and its interaction with the support and secondly influence in a great extent the catalytic behavior of the final material. The presence of prevailing mesoporous character appeared to be the most important parameter influencing formic acid dehydrogenation and overall hydrogen production.
Marzo, 2021 | DOI: 10.1016/j.apcatb.2020.119615
Nanotecnología en Superficies y Plasma
Solid-State Dewetting of Gold on Stochastically Periodic SiO2 Nanocolumns Prepared by Oblique Angle Deposition
Oliva-Ramirez, M; Wang, D; Flock, D; Rico, V; Gonzalez-Elipe, AR; Schaaf, PACS Applied Materials & Interfaces, 13 (2021) 11385-11395 DOI: 10.1021/acsami.0c19327
Abstract
Solid-state dewetting (SSD) on patterned substrates is a straightforward method for fabricating ordered arrays of metallic nanoparticles on surfaces. However, a drawback of this procedure is that the patterning of substrates usually requires time-consuming and expensive two-dimensional (2D) fabrication methods. Nanostructured thin films deposited by oblique angle deposition (OAD) present at the surface a form of stochastically arranged periodic bundles of nanocolumns that might act as a patterned template for fabricating arrays of nanoparticles by SSD. In this work, we explore this concept and investigate the effect of three different types of OAD SiO2 thin films on the SSD of Au deposited on their surface. We demonstrate that the size and spatial distribution of the particles can be tailored through the surface morphology of these OAD film substrates. It has been found that the SSD of the evaporated Au layer gives rise to a bimodal size distribution of particles. A majority of them appeared as mesoparticles with sizes.100 nm and the rest as nanoparticles with similar to 10 nm, respectively, located either on top of the nanocolumns following their lateral distribution (i.e., resulting from a patterning effect) or incorporated inside the open mesopores existing among them. Moreover, on the SiO2-OAD thin films where interconnected nanocolumnar bundles arrange in the form of discrete motifs, the patterning effect gave rise to the formation of approximately one Au mesoparticle per motif, which is one of the assets of patterned SSD. The morphological, optical (i.e., plasmon resonance), and crystalline structural characteristics of Au mesoparticles suggest that the interplay between a discontinuous nanocolumnar surface acting as a template and the poor adhesion of Au onto SiO2 are key factors for the observed template effect controlling the SSD on the surface of OAD thin films.
Marzo, 2021 | DOI: 10.1021/acsami.0c19327
Materiales de Diseño para la Energía y Medioambiente
Zirconium retention for minimizing environmental risk: Role of counterion and clay mineral
Montes, L; Pavon, E; Cota, A; AlbaChemosphere, 267 (2021) 128914 DOI: 10.1016/j.chemosphere.2020.128914
Abstract
Zr(IV) together with U(IV) are the major components of high-level radionuclide waste (HLRW) and spent nuclear fuel (SNF) from nuclear power plants. Thus, their retention in the waste disposal is of great importance for the environmental risk control. Here, the influence of clay minerals on the retention of Zr(IV), as component of the nuclear waste and as chemical analogues of U(IV), has been evaluated. Three clay minerals, two bentonites and one saponite, were hydrothermally treated with three zirconium salts. A structural study at long-range order by X-ray diffraction and short-range order by NMR was performed to evaluate the generation of new zirconium phases and degradation of the clay minerals. Three immobilization mechanisms were observed: i) cation exchange of ZrO2+ or Zr4+ by clay minerals, ii) the precipitation/crystallization of ZrO2, and, iii) the chemical interaction of zirconium with the clay minerals, with the formation of zirconium silicates.
Marzo, 2021 | DOI: 10.1016/j.chemosphere.2020.128914
Materiales y Procesos Catalíticos de Interés Ambiental y Energético
Overcoming Pd-TiO2 Deactivation during H-2 Production from Photoreforming Using Cu@Pd Nanoparticles Supported on TiO2
Platero, F; Lopez-Martin, A; Caballero, A; Rojas, TC; Nolan, M; Colon, GACS Applied Nano Materials, 4 (2021) 3204-3219 DOI: 10.1021/acsanm.1c00345
Abstract
Different Cu@Pd-TiO2 systems have been prepared by a two-step synthesis to obtain a bimetallic co-catalyst for the H-2 photoreforming reaction. We find that the tailored deposition of Pd covering the Cu nanoclusters by a galvanic replacement process results in the formation of a core@shell structure. The photocatalytic H-2 production after 18 h is 350 mmol/g on the Cu@Pd-1.0-TiO2 bimetallic system, which is higher than that on the monometallic ones with a H-2 production of 250 mmol/g on Pd-supported TiO2. Surface characterization by highangle annular dark-field scanning transmission electron microscopy, H-2-temperatureprogramed reduction, CO-FTIR spectroscopy, and XPS gives clear evidence of the formation of a core@shell structure. With a Pd loading of 0.2-0.3 at. %, we propose a full coverage of the Cu nanoparticles with Pd. Long-time photoreforming runs show the enhanced performance of supported Cu@Pd with respect to bare palladium leading to a more stable catalyst and ultimately higher H-2 production.
Marzo, 2021 | DOI: 10.1021/acsanm.1c00345
Reactividad de Sólidos
A first insight into the microstructure and crack propagation in novel boron nitride nanosheet/3YTZP composites
Munoz-Ferreiro, C; Morales-Rodriguez, A; Gallardo-Lopez, A; Poyato, RBoletin de la Sociedad Española de Cerámica y Vidrio, 60 (2021) 128-136 DOI: 10.1016/j.bsecv.2020.02.003
Abstract
In this work, novel 3 mol% yttria tetragonal zirconia polycristalline (3YTZP) ceramic composites with boron nitride nanosheets (BNNS) are investigated for the first time. Highly densified composites with 1 and 4 vol% BNNS were obtained by spark plasma sintering (SPS) after BNNS synthesis using a solution exfoliation method and BNNS dispersion into the ceramic powder by ultrasonication. The BNNS presented homogeneous distribution throughout the ceramic matrix and preferential alignment in the plane perpendicular to the pressing axis during SPS. The BNNS incorporation had practically no effect on the Vickers hardness of the material nor on the Young's modulus. Anisotropy in crack development was found in the composite with 4% vol BNNS, together with a mechanism of extensive microcracking. Several energy-absorbing mechanisms during crack propagation, such as crack deflection, crack bridging, crack branching, BNNS pull-out and BNNS debonding, were identified in the composites by a close observation of the indentation-induced fracture paths.
Marzo, 2021 | DOI: 10.1016/j.bsecv.2020.02.003
Reactividad de Sólidos
EGFR-targeting antitumor therapy: Neuregulins or antibodies?
de Lavera, I; Merkling, PJ; Oliva, JM; Sayagues, MJ; Cotan, D; Sanchez-Alcazar, JA; Infante, JJ; Zaderenko, A.P.European Journal of Pharmaceutical Sciences, 158 (2021) 105678 DOI: 10.1016/j.ejps.2020.105678
Abstract
Malignancies such as lung, breast and pancreatic carcinomas are associated with increased expression of the epidermal growth factor receptor, EGFR, and its role in the pathogenesis and progression of tumors has made this receptor a prime target in the development of antitumor therapies. In therapies targeting EGFR, the development of resistance owing to mutations and single nucleotide polymorphisms, and the expression of the receptor ligands themselves are very serious issues. In this work, both the ligand neuregulin and a bispecific antibody fragment to EGFR are conjugated separately or together to the same drug-delivery system to find the most promising candidate. Camptothecin is used as a model chemotherapeutic drug and superparamagnetic iron oxide nanoparticles as a delivery system. Results show that the lowest LD50 is achieved by formulations conjugated to both the antibody and the ligand, demonstrating a synergy. Additionally, the ligand location in the nucleus favors the antitumor activity of Camptothecin. The high loading capacity and efficiency convert these systems into a good alternative for administering Camptothecin, a drug whose use is otherwise severely limited by its chemical instability and poor solubility. Our choice of targeting agents allows treating tumors that express ErbB2 (Her2+ tumors) as well as Her2- tumors expressing EGFR.
Marzo, 2021 | DOI: 10.1016/j.ejps.2020.105678
Propiedades mecánicas, modelización y caracterización de cerámicos avanzados
Cation-driven electrical conductivity in Ta-doped orthorhombic zirconia ceramics
Moshtaghioun, BM; Laguna-Bercero, MA; Pena, JI; Gomez-Garcia, D; Dominguez-Rodriguez, ACeramics International, 47 (2021) 7248-7522 DOI: 10.1016/j.ceramint.2020.10.227
Abstract
This paper is devoted to the study of the electrical conductivity of tantalum-doped zirconia ceramics prepared by spark plasma sintering. In this study, the temperature dependence of conductivity in as-prepared specimens and in those previously annealed in air is determined and compared. A semi-empirical model, which is based on the oxidation states of the cations, has been developed and successfully assessed. According to this, the conductivity is basically controlled by the diffusion of tetravalent zirconium cations in both cases, although the concentration of these species varies drastically with the amount of induced oxygen vacancies. This is a quite unexpected fact, since conductivity is normally controlled by anionic diffusion in zirconia ceramics. This option is forbidden here due to the presence of substitutional pentavalent cations. Therefore, conductivity values are much lower than those reported in trivalent or divalent substitutional cation doped zirconia ceramics.
Marzo, 2021 | DOI: 10.1016/j.ceramint.2020.10.227
Materiales para Bioingeniería y Regeneración Tisular
Nanofibrous Gelatin-Based Biomaterial with Improved Biomimicry Using D-Periodic Self-Assembled Atelocollagen
Borrego-Gonzalez, S; Dalby, MJ; Diaz-Cuenca, ABiomimetics, 6 (2001) 20 DOI: 10.3390/biomimetics6010020
Abstract
Design of bioinspired materials that mimic the extracellular matrix (ECM) at the nanoscale is a challenge in tissue engineering. While nanofibrillar gelatin materials mimic chemical composition and nano-architecture of natural ECM collagen components, it lacks the characteristic D-staggered array (D-periodicity) of 67 nm, which is an important cue in terms of cell recognition and adhesion properties. In this study, a nanofibrous gelatin matrix with improved biomimicry is achieved using a formulation including a minimal content of D-periodic self-assembled atelocollagen. We suggest a processing route approach consisting of the thermally induced phase separation of the gelatin based biopolymeric mixture precursor followed by chemical-free material cross-linking. The matrix nanostructure is characterized using field emission gun scanning electron microscopy (FEG-SEM), transmission electron microscopy (TEM), wide angle X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FT-IR). The cell culture assays indicate that incorporation of 2.6 wt.% content of D-periodic atelocollagen to the gelatin material, produces a significant increase of MC3T3-E1 mouse preosteoblast cells attachment and human mesenchymal stem cells (hMSCs) proliferation, in comparison with related bare gelatin matrices. The presented results demonstrate the achievement of an efficient route to produce a cost-effective, compositionally defined and low immunogenic “collagen-like” instructive biomaterial, based on gelatin.
Marzo, 2021 | DOI: 10.3390/biomimetics6010020
Nanotecnología en Superficies y Plasma
Electrical and reaction performances of packed-bed plasma reactors moderated with ferroelectric or dielectric materials
Gomez-Ramirez, A; Alvarez, R; Navascues, P; Garcia-Garcia, FJ; Palmero, A; Cotrino, J; Gonzalez-Elipe, ARPlasma Processes and Polymers, (2021) e2000193 DOI: 10.1002/ppap.202000193
Abstract
The operational behavior of packed-bed plasma reactors depends on the dimension, shape, and chemical properties of the pellets used as moderators, but little information exists about the influence of their specific dielectric properties. Herein, we comparatively study the electrical behavior of a packed-bed reactor filled with pellets of either dielectric (Al2O3 and glass) or ferroelectric (BaTiO3 and lead zirconate titanate) materials. We found that plasma current was higher for ferroelectrics and presented a nonlineal dependence on voltage. Moreover, for BaTiO3, we found a drastic decrease at around its relatively low Curie temperature. Differences in electrical behavior have a direct effect on the reactor performance, as illustrated for the ammonia synthesis, demonstrating the importance of moderator material dielectric properties and their dependence on temperature.
Marzo, 2021 | DOI: 10.1002/ppap.202000193
Química de Superficies y Catálisis
Synergizing carbon capture and utilization in a biogas upgrading plant based on calcium chloride: Scaling-up and profitability analysis
Baena-Moreno, FM; Reina, TR; Rodriguez-Galan, M; Navarrete, B; Vilches, LFScience of The Total Environment, 758 (2021) 143645 DOI: 10.1016/j.scitotenv.2020.143645
Abstract
Herein we analyze the profitability of a novel regenerative process to synergize biogas upgrading and carbon dioxide utilization. Our proposal is a promising alternative which allows to obtain calcium carbonate as added value product while going beyond traditional biogas upgrading methods with high thermal energy consumption. Recently we have demonstrated the experimental viability of this route. In this work, both the scale-up and the profitability of the process are presented. Furthermore, we analyze three representative scenarios to undertake a techno-economic study of the proposed circular economy process. The scale-up results demonstrate the technical viability of our proposal. The precipitation efficiency and the product quality are still remarkable with the increase of the reactor size. The techno-economic analysis reveals that the implementation of this circular economy strategy is unprofitable without subsidies. Nonetheless, the results are somehow encouraging as the subsides needed to reach profitability are lower than in other biogas upgrading and carbon dioxide utilization proposals. Indeed, for the best-case scenario, a feed-in tariff incentive of 4.3 (sic)/MWh makes the approach profitable. A sensitivity study through tornado analysis is also presented, revealing the importance of reducing bipolar membrane electrodialysis energy consumption. Overall our study envisages the big challenge that the EU faces during the forthcoming years. The evolution towards bio-based and circular economies requires the availability of economic resources and progress on engineering technologies.
Marzo, 2021 | DOI: 10.1016/j.scitotenv.2020.143645
Materiales Avanzados
Mining Wastes of an Albite Deposit as Raw Materials for Vitrified Mullite Ceramics
Sanchez-Soto, PJ; Garzon, E; Perez-Villarejo, L; Angelopoulos, GN; Eliche-Quesada, DMinerals, 11 (2021) 232 DOI: 10.3390/min11030232
Abstract
In this work, an examination of mining wastes of an albite deposit in south Spain was carried out using X-ray Fluorescence (XRF), X-ray diffraction (XRD), particle size analysis, thermodilatometry and Differential Thermal Analysis (DTA) and Thermogravimetric (TG) analysis, followed by the determination of the main ceramic properties. The albite content in two selected samples was high (65-40 wt. %), accompanied by quartz (25-40 wt. %) and other minor minerals identified by XRD, mainly kaolinite, in agreement with the high content of silica and alumina determined by XRF. The content of Na2O was in the range 5.44-3.09 wt. %, being associated with albite. The iron content was very low (<0.75 wt. %). The kaolinite content in the waste was estimated from similar to 8 to 32 wt. %. The particle size analysis indicated values of 11-31 wt. % of particles <63 mu m. The ceramic properties of fired samples (1000-1350 degrees C) showed progressive shrinkage by the thermal effect, with water absorption and open porosity almost at zero at 1200-1250 degrees C. At 1200 ffiC, the bulk density reached a maximum value of 2.38 g/cm(3). An abrupt change in the phase evolution by XRD was found from 1150 to 1200 degrees C, with the disappearance of albite by melting in accordance with the predictions of the phase diagram SiO2-Al2O3-Na2O and the system albite-quartz. These fired materials contained as main crystalline phases quartz and mullite. Quartz was present in the raw samples and mullite was formed by decomposition of kaolinite. The observation of mullite forming needle-shape crystals was revealed by Scanning Electron Microscopy (SEM). The formation of fully densified and vitrified mullite materials by firing treatments was demonstrated.
Marzo, 2021 | DOI: 10.3390/min11030232
Química de Superficies y Catálisis
Guaiacol hydrodeoxygenation in hydrothermal conditions using N-doped reduced graphene oxide (RGO) supported Pt and Ni catalysts: Seeking for economically viable biomass upgrading alternatives
Parrilla-Lahoz, S; Jin, W; Pastor-Perez, L; Carrales-Alvarado, D; Odriozola, JA; Dongil, AB; Reina, TRApplied Catalysis A-General, 611 (2021) 117977 DOI: 10.1016/j.apcata.2020.117977
Abstract
Herein we present an innovative route for model biomass compounds upgrading via “H2-free” hydrodeoxygenation (HDO) reactions. The underlaying idea is to implement a multifunctional catalyst able to activate water and subsequently use in-situ generated hydrogen for the HDO process. In this sense we have developed a series of effective Ni and Pt based catalysts supported on N-promoted graphene decorated with ceria. The catalyst reached commendable conversion levels and selectivity to mono-oxygenated compounds considering the very challenging reaction conditions. Pt outperforms Ni when the samples are tested as-prepared. However, Ni performance is remarkably boosted upon applying a pre-conditioning reductive treatment. Indeed, our NiCeO2/GOr-N present the best activity/selectivity balance and it is deemed as a promising catalyst to conduct the H2-free HDO reaction. Overall, this “proof-concept” showcases an economically appealing route for bio-compounds upgrading evidencing the key role of advanced catalysts for a low carbon future.
Febrero, 2021 | DOI: 10.1016/j.apcata.2020.117977
Collagen Type I Biomaterials as Scaffolds for Bone Tissue Engineering
Rico-Llanos, GA; Borrego-Gonzalez, S; Moncayo-Donoso, M; Becerra, J; Visser, RPolymers, 13 (2021) art599 DOI: 10.3390/polym13040599
Abstract
Collagen type I is the main organic constituent of the bone extracellular matrix and has been used for decades as scaffolding material in bone tissue engineering approaches when autografts are not feasible. Polymeric collagen can be easily isolated from various animal sources and can be processed in a great number of ways to manufacture biomaterials in the form of sponges, particles, or hydrogels, among others, for different applications. Despite its great biocompatibility and osteoconductivity, collagen type I also has some drawbacks, such as its high biodegradability, low mechanical strength, and lack of osteoinductive activity. Therefore, many attempts have been made to improve the collagen type I-based implants for bone tissue engineering. This review aims to summarize the current status of collagen type I as a biomaterial for bone tissue engineering, as well as to highlight some of the main efforts that have been made recently towards designing and producing collagen implants to improve bone regeneration.
Febrero, 2021 | DOI: 10.3390/polym13040599
Nanotecnología en Superficies y Plasma - Tribología y Protección de Superficies
Patterning and control of the nanostructure in plasma thin films with acoustic waves: mechanical vs. electrical polarization effects
García-Valenzuela, A.; Fakhouri, A.; Oliva-Ramírez, M.; Rico-Gavira, V.; Rojas, T.C.; Alvarez, R.; Menzel, S.B.; Palmero, A.; Winkler, A.; González-Elipe, A.R.Materials Horizons, 8 (2021) 515-524 DOI: 10.1039/D0MH01540G
Abstract
Nanostructuration and 2D patterning of thin films are common strategies to fabricate biomimetic surfaces and components for microfluidic, microelectronic or photonic applications. This work presents the fundamentals of a surface nanotechnology procedure for laterally tailoring the nanostructure and crystalline structure of thin films that are plasma deposited onto acoustically excited piezoelectric substrates. Using magnetron sputtering as plasma technique and TiO2 as case example, it is demonstrated that the deposited films depict a sub-millimetre 2D pattern that, characterized by large lateral differences in nanostructure, density (up to 50%), thickness, and physical properties between porous and dense zones, reproduces the wave features distribution of the generated acoustic waves (AW). Simulation modelling of the AW propagation and deposition experiments carried out without plasma and under alternative experimental conditions reveal that patterning is not driven by the collision of ad-species with mechanically excited lattice atoms of the substrate, but emerges from their interaction with plasma sheath ions locally accelerated by the AW-induced electrical polarization field developed at the substrate surface and growing film. The possibilities of the AW activation as a general approach for the tailored control of nanostructure, pattern size, and properties of thin films are demonstrated through the systematic variation of deposition conditions and the adjustment of AW operating parameters.
Febrero, 2021 | DOI: 10.1039/D0MH01540G
Tribología y Protección de Superficies
Long-term low friction maintenance and wear reduction on the ventral scales in snakes
Sanchez-Lopez, JC; Schaber, CF; Gorb, SNMaterials Letters, 285 (2021) 129011 DOI: 10.1016/j.matlet.2020.129011
Abstract
Snake skins evolved to withstand permanent friction and wear during sliding. Here, the microstructure of ventral scales of the snake Lampropeltis getula californiae was analyzed using scanning electron microscopy, and the long-term dynamic friction behavior was investigated by reciprocating sliding friction tests. A smooth epoxy resin with similar elasticity modulus and hardness was used for comparison purposes. Strong differences in frictional and wear mechanisms between the two materials were revealed in spite of similar mechanical properties. Snake skin showed a considerably lower frictional coefficient that kept stable over several thousands of sliding cycles. A reduction of the stick-slip behavior was also denoted by analyzing the variation of the friction coefficient in the forward and reverse motion influencing the wear mechanism. This frictional behavior can be explained by three different but complementary mechanisms: fibrous layered composite material of the skin with a gradient of material properties, surface microstructure, and the presence of ordered layers of lipid molecules at the skin surface.
Febrero, 2021 | DOI: 10.1016/j.matlet.2020.129011
Materiales Ópticos Multifuncionales
Impact of Tb4+ and morphology on the thermal evolution of Tb-doped TiO2 nanostructured hollow spheres and nanoparticles
Colomer, MT; Rodriguez, E; Moran-Pedroso, M; Vattier, F; de Andres, AJournal of Alloys and Compounds, 853 (2021) 156973 DOI: 10.1016/j.jallcom.2020.156973
Abstract
Tb-doped TiO2 hollow spheres (HSs) in the range 0.0-2.0 at.% have been synthesized by the first time to the best of our knowledge. The HSs are compared with nanoparticles (NPs) to evaluate the impact of morphology on their physicochemical and photoluminescence (PL) behavior upon increasing calcination temperature. After calcination at 550 degrees C, the particles are anatase with a primary average size of 10.0 +/- 0.2 nm for the NPs and 12.0 +/- 0.2 nm for those that form the micron sized hollow spheres of 1.8 +/- 0.2 mu m diameter and ca. 64 nm shell thickness. The temperature of the anataseerutile transition is found to be strongly dependent on the presence of Tb as well as on morphology. Contrarily to the usual stabilization of anatase when doping with trivalent rare-earth ions, the transition temperature is reduced when doping with Tb. The rutile phase is further favored for the HSs compared to the NPs probably related to the low density of the HSs and/or a more efficient packing density and/or a bigger crystal size of the nanoparticles that form those spheres with respect to the packing and the size of the NPs and/or the crystal size of the nanoparticles of the HSs with respect to the size of the NPs. Only a slight unit-cell volume increase for the anatase structure is observed upon Tb doping, in both the NPs and in the HSs, contrary to the expected increment due to the larger ionic radius of Tb3+ compared to Ti4+. In addition, the intensity of the characteristic f-f Tb3+ emission bands is extremely weak both in the anatase and rutile phases. The transition is accompanied with the emergence of an infrared emission band centered at 810 nm related to the formation of defects during the structural transformation providing deep levels in the gap that partly quench the f-f emissions in the rutile phase. The results are consistent with the presence of Tb in both +3 and +4 valence states. XPS measurements confirmed the presence of Tb3+ as well as of Tb4+ in both HSs and NPs. The large fraction of Tb4+ present in the samples originates the weak f-f emission intensity, an only slight increase of the cell parameters and the destabilization of the anatase phase.
Febrero, 2021 | DOI: 10.1016/j.jallcom.2020.156973
Tribología y Protección de Superficies
Insights into the role of the layer architecture of Cr-Ti-N based coatings in long-term high temperature oxidation experiments in steam atmosphere
Mato, S; Sanchez-Lopez, JC; Barriga, J; Perez, FJ; Alcala, GCeramics International, 47 (2021) 4257-4266 DOI: 10.1016/j.ceramint.2020.10.003
Abstract
Knowledge on hard coatings has been applied in the energy field extending their use as protecting coatings of steam power generation plants components. The role of the layer architecture of Cr-Ti-N based coatings deposited by reactive cathodic arc evaporation on P92 steel substrates was studied with the focus on their oxidation resistance at 650 degrees C in 100% steam atmosphere up to 2000 h. Characterization of the coatings was performed by gravimetry, scanning electron microscopy, electron probe microanalysis, glow discharge optical emission spectroscopy, X-ray diffraction, thermodynamic simulations using the CALPHAD method, Rockwell C indentation and nanoindentation. The layered arrangement improves the oxidation resistance of TiN under the working conditions of steam power plants, as well as the mechanical properties of CrN. The produced architectures performance under the described working conditions boosts the understanding of the processes taking place at high temperature, making possible the design of optimal coatings combining the best behavior of both nitrides for each specific application, reaching a corrosion protection at high temperature in water vapor comparable to that of CrN and a hardness and Young's modulus as high as those of TiN.
Febrero, 2021 | DOI: 10.1016/j.ceramint.2020.10.003
Nanotecnología en Superficies y Plasma
Active sites and optimization of mixed copper-cobalt oxide anodes for anion exchange membrane water electrolysis
Lopez-Fernandez, E; Gil-Rostra, J; Escudero, C; Villar-Garcia, IJ; Yubero, F; Consuegra, AD; Gonzalez-Elipe, ARJournal of Power Sources, 485 (2021) 229217 DOI: 10.1016/j.jpowsour.2020.229217
Abstract
The optimization of the catalysts incorporated to the electrodes for anion exchange membrane water electmlysers is a key issue to maximize their performance through the improvement of the oxygen evolution reaction (OER) yield. In this work, we show that the modification of the microstructure and the chemical properties of a mixed copper-cobalt oxide anode may contribute to increase the activity of this reaction. For this purpose, the OER has been systematically studied, either in a half cell or in a membrane electrode assembly configuration, as a function of the load and agglomeration degree of the catalysts used as electrodes, as prepared on a carbon paper support by magnetron sputtering deposition in an oblique angle configuration. Chemical analysis by X-ray absorption spectroscopy and electrochemical analysis by cyclic voltammetry and impedance spectroscopy have shown that cobalt-copper mixed oxide catalysts with a 1.8 Co/Cu atomic ratio and about one micron equivalent thickness maximizes the cell performance. The chemical, structural and microstructural factors controlling the final behaviour of these anodes and accounting for this maximization of the reaction yield are discussed on the basis of these characterization results and as a function of preparation variables of the electrodes and operating conditions of the cell.
Febrero, 2021 | DOI: 10.1016/j.jpowsour.2020.229217
Propiedades mecánicas, modelización y caracterización de cerámicos avanzados
The Possible Detriment of Oxygen in Creep of Alumina and Zirconia Ceramic Composites Reinforced with Graphene
Cano-Crespo, R; Rivero-Antunez, P; Gomez-Garcia, D; Moreno, R; Dominguez-Rodriguez, AMaterials, 14 (2021) 984 DOI: 10.3390/ma14040984
Abstract
This paper aims to give an answer to the following question: is the oxidation of graphene a critical issue for high-temperature plasticity in graphene-reinforced ceramics? To give a convincing reply, we will focus on two very different graphene-based ceramic composites: reduced graphene oxide (rGO)-reinforced alumina (alpha-Al2O3) and reduced graphene oxide (rGO)-reinforced yttria tetragonal zirconia (t-ZrO2). The processing of the powders has been made using a colloidal route, and after that, a spark plasma sintering process was performed in order to densify the samples. Creep tests were performed at temperatures between 1200-1250 degrees C in an argon atmosphere. The microstructure obtained by SEM of the sintered and tested specimens was characterized quantitatively to elucidate the deformation mechanism. Raman spectroscopy was carried out to check the integrity of the graphene. The average grain size was in the order of 1 mu m and the shape factor was 0.7 for all the studied materials. The integrity of the graphene was checked before and after the creep experiments. The careful analysis of the creep tests shows that graphene oxide or its reduced version are not efficient phases for creep resistance improvement in general, contrary to what is reported elsewhere. However, the results permit the suggestion of a creep improvement in nanocomposites at a very high temperature regime due to an enhanced reactivity of oxygen between carbon and alumina interfaces. In the case of zirconia, the results give us the conclusion that the oxidation of graphene is a highly detrimental issue regarding the improvement of high-temperature plasticity.
Febrero, 2021 | DOI: 10.3390/ma14040984
Reactividad de Sólidos
A Novel, Simple and Highly Efficient Route to Obtain PrBaMn2O5+δ Double Perovskite: Mechanochemical Synthesis
Garcia-Garcia, FJ; Sayagues, MJ; Gotor, FJNanomaterials, 11 (2021) 380 DOI: 10.3390/nano11020380
Abstract
In this work, a mechanochemical route was proposed for the synthesis of the PrBaMn2O5+δ (PMBO) double layered perovskite phase. The mechanochemical reaction between Pr6O11, BaO2, and MnO powders with cationic stoichiometric ratios of 1/1/2 for Pr/Ba/Mn was performed using high-energy milling conditions in air. After 150 min of milling, a new phase with perovskite structure and cubic symmetry consistent with the A-site disordered Pr0.5Ba0.5MnO3 phase was formed. When this new phase was subsequently annealed at a high temperature in an inert Ar atmosphere, the layered PrBaMn2O5+δ phase was obtained without needing to use a reducing atmosphere. At 1100 °C, the fully reduced layered PrBaMn2O5 phase was achieved. A weight gain was observed in the 200–300 °C temperature range when this fully reduced phase was annealed in air, which was consistent with the transformation into the fully oxidized PrBaMn2O6 phase. The microstructural characterization by SEM, TEM, and HRTEM ascertained the formation of the intended PrBaMn2O5+δ phase. Electrical characterization shows very high electrical conductivity of layered PBMO in a reducing atmosphere and suitable in an oxidizing atmosphere, becoming, therefore, excellent candidates as solid oxide fuel cell (SOFC electrodes).
Febrero, 2021 | DOI: 10.3390/nano11020380
Reactividad de Sólidos
Influence of Successive Chemical and Thermochemical Treatments on Surface Features of Ti6Al4V Samples Manufactured by SLM
Gonzalez, JE; de Armas, G; Negrin, J; Beltran, AM; Trueba, P; Gotor, FJ; Peon, E; Torres, YMetals, 11 (2021) 313 DOI: 10.3390/met11020313
Abstract
Ti6Al4V samples, obtained by selective laser melting (SLM), were subjected to successive treatments: acid etching, chemical oxidation in hydrogen peroxide solution and thermochemical processing. The effect of temperature and time of acid etching on the surface roughness, morphology, topography and chemical and phase composition after the thermochemical treatment was studied. The surfaces were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction and contact profilometry. The temperature used in the acid etching had a greater influence on the surface features of the samples than the time. Acid etching provided the original SLM surface with a new topography prior to oxidation and thermochemical treatments. A nanostructure was observed on the surfaces after the full process, both on their protrusions and pores previously formed during the acid etching. After the thermochemical treatment, the samples etched at 40 °C showed macrostructures with additional submicro and nanoscale topographies. When a temperature of 80 °C was used, the presence of micropores and a thicker anatase layer, detectable by X-ray diffraction, were also observed. These surfaces are expected to generate greater levels of bioactivity and high biomechanics fixation of implants as well as better resistance to fatigue.
Febrero, 2021 | DOI: 10.3390/met11020313
Fotocatálisis Heterogénea: Aplicaciones
Enhanced UV and visible light photocatalytic properties of synthesized AgBr/SnO2 composites
Puga, F.; Navío, J.A.; Hidalgo, M.C.Separation and Purification Tecnology, 257 (2021) 117948 DOI: 10.1016/j.seppur.2020.117948
Abstract
Composites (AgBr/SnO2) comprised of AgBr and SnO2 with different molar % of bare SnO2, have been synthesized by simple precipitation methods; the bare SnO2 used, was synthesized by hydrothermal procedure. Samples have been characterized by X-ray diffraction (XRD), N2-adsorption, UV–vis diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of the as-prepared photocatalysts was evaluated through photocatalytic degradation of rhodamine B (RhB) and caffeic acid (CAFA) under UV and Visible illumination. In photocatalytic degradation studies, for both substrates, conversion rates of around 95% were found in 45 min of both UV-illumination and 85% under visible lighting. These conversion rates were superior than the conversion rates of pure parental components, AgBr and SnO2 under the same experimental conditions. At least, for RhB no loss of photocatalytic activity has been observed after five recycles although the mineralization degree progressively diminished along the recycles. The enhanced photocatalytic degradation of AgBr/SnO2 compounds was attributed, in part, to a synergistic increase in adsorption viability, as well as to the effective separation of photoinduced load carriers that resulted from the formation of a heterojunction according to the type II junction. Radical scavengers’ experiments indicated that active oxidant species as O2.−, ·OH and h+ all are involved in this photocatalytic system, although it seems that O2.− played the major role in the photocatalytic degrading of RhB by AgBr/SnO2 composites. In summary, coupling AgBr with SnO2 remarkably improves the photocatalytic activity under both UV and visible-illumination with respect to the parental components. These features open the route to future applications of this material in the field of environmental remediation.
Febrero, 2021 | DOI: 10.1016/j.seppur.2020.117948
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