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2018


Influence of temperature on the biaxial strength of cemented carbides with different microstructures


Chicardi, E; Bermejo, R; Gotor, FJ; Llanes, L; Torres, Y
International Journal of Refractory Metals & Hard Materials, 71 (2018) 82-91

ABSTRACT

The effect of the temperature on the mechanical strength of WC-Co cemented carbides with different microstructures (grain size and binder content) was evaluated. Biaxial flexural tests were performed on three cemented carbide grades at 600 °C using the ball-on-three-balls (B3B) method. Results were interpreted by Weibull statistics and compared to biaxial strength results at room temperature. A detailed fractographic analysis, supported by Linear Elastic Fracture Mechanics, was performed to differentiate the nature and size of critical defects and the mechanism responsible for the fracture. A significant decrease in the mechanical strength (around 30%) was observed at 600 °C for all grades of cemented carbides. This fact was ascribed to the change in the critical flaw population from sub-surface (at room temperature) to surface defects, associated with the selective oxidation of Co. Additionally, an estimation of the fracture toughness at 600 °C was attempted for the three cemented carbides, based upon the B3B strength results, the corresponding number of the tested specimens fragments and the macroscopic area of the B3B fracture surfaces. The fracture toughness was not affected by the temperature, at least up to 600 °C. In addition, the good agreement with the Single Edge Notch Beam toughness data suggests the possibility of employing this approach for fracture toughness evaluation of brittle materials under different testing conditions.


Febrero, 2018 | DOI: 10.1016/j.ijrmhm.2017.11.003

Experimental measurement of the filtration efficiency and pressure drop of wall-flow diesel particulate filters (DPF) made of biomorphic Silicon Carbide using laboratory generated particles


Orihuela, MP; Gomez-Martin, A; Miceli, P; Becerra, JA; Chacartegui, R; Fino, D
Applied Thermal Engineering, 131 (2018) 41-53

ABSTRACT

Biomorphic Silicon Carbide (bioSiC) has been recently introduced in the scope of porous ceramic substrates for hot gas filtration applications, where it has demonstrated to have good thermal and mechanical properties, and a high potential to meet the requirements for current Diesel Particulate Filters (DPF). In this experimental study, a small wall-flow bioSiC diesel filter was characterized using a soot generator, the particle size distribution of which being similar to the one generated by a diesel engine. The bioSiC samples were manufactured from Medium Density Fiberboard (MDF) following a general manufacturing procedure for bioSiC ceramics, but paying special attention in the mechanizing stage to the geometry and optimal design of the honeycomb structure required for diesel engine applications. The samples had a cell density of 57.59 cell/cm(2) (371.6 cpsi), a square cross section of 9.2 x 9.2 mm, and a length of 31 mm. To generate the particle laden stream and perform the filtration tests, a synthetic Soot Generator (SG) was used. Tests were performed under controlled and reproducible conditions, with a fixed gas flow rate of 5 LPM and a soot mass flow rate of 4 mg/h. The filtration efficiency was determined with the aid of a Scanning Mobility Particle Sizer (SMPS) from the measurements of the particle concentration upstream and downstream the filter samples. During the soot loading process, the pressure drop was also monitored. The results show that, in the initial stage (clean filter), bioSiC wall-flow DPFs may have a filtration efficiency between 0.7 and 0.85 and a pressure drop of around 2 kPa for a normalized wall velocity of 0.01 m/s at ambient temperature. The filtration performance of wall-flow bioSiC particle filters showed in this work can help us to better understand their real potential for automotive applications. 


Febrero, 2018 | DOI: 10.1016/j.applthermaleng.2017.11.149

Effect of Basicity on the Hydrolysis of the Bi(III) Aqua Ion in Solution: An Ab Initio Molecular Dynamics Study


Ayala, R; Martinez, JM; Pappalardo, RR; Refson, K; Marcos, ES
Journal of Physical Chemistry A, 122 (2018) 1905-1915

ABSTRACT

Hydrolysis of the Bi(III) aqua ion under a range of solution conditions has been studied by means of ab initio molecular dynamics simulations. While the Bi(III) aqua ion is stable in pure water, there is an increasing degree of hydrolysis with the number of hydroxide anions in the medium. This is accompanied by a monotonic decrease of the total coordination number to an asymptotic value of similar to 6, reached under extreme basicity conditions. Comparison of the simulated Bi(III) hydrolyzed species with the experimental species distribution at different degrees of basicity suggests that, at the PBE/DFT level of theory here employed, liquid water shows an overly acidic character. Predictions of theoretical EXAFS and XANES spectra were generated from the AIMD trajectories for different Bi hydrolyzed species, [Bi(HO)(m)(H2O)(n)](3-m+), m = 0-3 and n = 7-2. Comparison with available experimental spectra is presented. Spectral features joined to the degree of hydrolysis and hydration are analyzed.


Febrero, 2018 | DOI: 10.1021/acs.jpca.7b12402

High {0 0 1} faceted TiO2 nanoparticles for the valorization of oxygenated compounds present in aqueous biomass-derived feedstocks


Fernández-Arroyo, A.; Lara, M.A.; Domine, M.E.; Sayagués, M.J.; Navío, J.A.; Hidalgo, M.C.
Journal of Catalysts, 358 (2018) 266-276

ABSTRACT

{0 0 1} faceted TiO2 catalysts are hydrothermally synthesized by using titanium(IV) isopropoxide and butoxide precursors (ISO and BUT TiO2samples) together with HF addition. Their activity and stability are evaluated in the catalytic condensation of light oxygenated organic compounds present in an aqueous model mixture simulating a real bio-refinery effluent, under moderate operation conditions. High {0 0 1} faceted TiO2 catalysts show organic products yields superior to those attained with other TiO2 samples (anatase, rutile, and P25). This enhanced catalytic activity relates to their physico-chemical and textural properties, such as high surface area (≈100 m2/g), regular morphology (platelets conformed by partially agglomerated TiO2 nanoparticles), and adequate Lewis acidity. XRD and Raman measurements evidence the unique presence of anatase crystalline phase in both ISO and BUT materials, in which the use of HF during synthesis produces the preferential growth of TiO2 crystals mainly exposing the {0 0 1} plane. This effective {0 0 1} facet exposition directly determines catalytic results. Moreover, TiO2 ISO catalyst shows outstanding stability under reaction conditions, maintaining practically unaltered their activity after several re-uses. In particular, Lewis acid sites present in TiO2 faceted materials are more stable in the presence of organic acids under aqueous environments. This opens new possibilities for the application of these materials in the valorization of light oxygenated compounds present in biomass-derived aqueous effluents.


Febrero, 2018 | DOI: 10.1016/j.jcat.2017.12.018

Self-Assembly of the Nonplanar Fe(III) Phthalocyanine Small-Molecule: Unraveling the Impact on the Magnetic Properties of Organic Nanowires


Filippin, AN; Lopez-Flores, V; Rojas, TC; Saghi, Z; Rico, VJ; Sanchez-Valencia, JR; Espinos, JP; Zitolo, A; Viret, M; Midgley, PA; Barranco, A; Borras, A
Chemistry of Materials, 30 (2018) 879-887

ABSTRACT

In this article we show for the first time the formation of magnetic supported organic nanowires (ONWs) driven by self-assembly of a nonplanar Fe(III) phthalocyanine chloride (FePcCl) molecule. The ONWs grow by a crystallization mechanism on roughness-tailored substrates. The growth methodology consists of a vapor deposition under low vacuum and mild temperature conditions. The structure, microstructure, and chemical composition of the FePcCl NWs are thoroughly elucidated and compared with those of Fe(II) phthalocyanine NWs by a consistent and complementary combination of advanced electron microscopies and X-ray spectroscopies. In a further step, we vertically align the NWs by conformal deposition of a SiO2 shell. Such orientation is critical to analyze the magnetic properties of the FePcCl and FePc supported NWs. A ferromagnetic behavior below 30 K with an easy axis perpendicular to the phthalocyanine plane was observed in the two cases with the FePcCl nanowires presenting a wider hysteresis. These results open the path to the fabrication of nanostructured one-dimensional small-molecule spintronic devices.


Febrero, 2018 | DOI: 10.1021/acs.chemmater.7b04515

In situ monitoring of the phenomenon of electrochemical promotion of catalysis


Espinos, JP; Rico, VJ; Gonzalez-Cobos, J; Sanchez-Valencia, JR; Perez-Dieste, V; Escudero, C; de Lucas-Consuegra, A; Gonzalez-Elipe, AR
Journal of Catalysis, 358 (2018) 27-34

ABSTRACT

In this work we investigate by in-situ near-ambient pressure photoemission (NAPP) spectroscopy the phenomenon of Electrochemical Promotion of Catalysis (EPOC). We studied the reduction and diffusion kinetics of alkaline ions in a solid electrolyte cell formed by a nickel electrode supported on K+-beta-alumina electrolyte. Experiments in ultra-high vacuum and in the presence of steam showed that the amount of potassium atoms supplied to the surface is probably affected by nickel electronic modifications induced by adsorbed OH- groups. It was also deduced that part of the segregated potassium would be adsorbed at inner interfaces where it would be inaccessible to the photoelectron analyzer. A migration mechanism of the promoter is proposed consisting in: (i) the electrochemical reduction of the alkali ions (potassium) at the Ni/solid electrolyte/gas interface; (ii) the spillover of potassium atoms onto the Ni gas-exposed surface; and (iii) the diffusion of potassium atoms to Ni inner grain boundary interfaces.


Febrero, 2018 | DOI: 10.1016/j.jcat.2017.11.027

Calcium-Looping performance of mechanically modified Al2O3-CaO composites for energy storage and CO2 capture


Benitez-Guerrero, M; Valverde, JM; Sanchez-Jimenez, PE; Perejon, A; Perez-Maqueda, LA
Chemical Engineering Journal, 334 (2018) 2343-2355

ABSTRACT

This work reports the Calcium-Looping (CaL) multicycle performance under energy storage and CO2 capture conditions of different Al-composites prepared by milling mixtures of nanoalumina and natural limestone powders. The micro-and nanostructure of the composites have been analyzed by X-ray diffraction, scanning electron microscopy and high-resolution transmission electron microscopy as affected by the type of CaL conditions employed, either for energy storage in Concentrated Solar Power (CSP) plants or for post-combustion CO2 capture. Two types of calcium aluminates are formed under these diverse CaL conditions. A calcium aluminate with ratio Ca/Al < 1 (Ca4Al6O13) is formed under CaL-CSP conditions, which helps stabilize the CaO microstructure and mitigate pore-plugging. On the other hand, a crystalline phase Ca3Al2O6 is formed (Ca/Al > 1) under CaL-CO2 capture conditions presumably due to the higher calcination temperature, which withdraws from the sorbent a relatively higher amount of active Ca. Moreover, the addition of nano-alumina, and the consequent generation of calcium aluminate, affects in a diverse way the microstructure and morphology of the CaO particles as depending on the CaL application, which critically modifies the performance of the composites.


Febrero, 2018 | DOI: 10.1016/j.cej.2017.11.183

Improving the direct synthesis of hydrogen peroxide from hydrogen and oxygen over Au-Pd/SBA-15 catalysts by selective functionalization


Rodriguez-Gomez, A; Platero, F; Caballero, A; Colon, G
Molecular Catalysis, 445 (2018) 142-151

ABSTRACT

A series of gold-palladium catalysts supported in a mesoporous surface functionalized silica SBA-15 was studied for H2O2 direct synthesis. Support functionalization was performed using different organic groups (namely-SO3H, -NH2 and-SH) while metal was then supported by an ion exchanged method. Different Au-Pd/SBA-15 catalysts were tested in the Direct Synthesis of Hydrogen Peroxide (DSHP). Organic functional groups (-SH, -SO3H and-NH2) with acid-base properties acted as anchoring sites controlling both the dispersion of the metallic active phase and the chemical state of gold and palladium species as Au+ and Pd2+, respectively. Compared to a Au-Pd/SBA-15 system prepared by incipient wetness impregnation over non-functionalized SBA-15, catalytic performance is improved upon functionalization, increasing hydrogen peroxide rate in sulfonic-SBA-15 systems and reducing the hydrogenation/decomposition activity by adding amine groups. The occurrence of amine groups clearly suppresses the support microporosity and probably condition the metal cluster size. The analysis of particle size by TEM showed that sulfonated samples lead to a Pd size compromise which improves the H2O2 production hindering the competitive side reactions, particularly suppressed by the presence of amine groups.


Febrero, 2018 | DOI: 10.1016/j.mcat.2017.10.034

High temperature creep of 20 vol%. SiC-HfB2 UHTCs up to 2000 degrees C and the effect of La2O3 addition


Zapata-Solvas, E; Gomez-Garcia, D; Dominguez-Rodriguez, A; Lee, WE
Journal of the European Ceramic Society. 38 (2018) 47-56

ABSTRACT

High temperature compressive creep of SiC-HfB2 UHTCs up to 2000 °C has been studied. Microstructural analysis after deformation reveals formation of new phases in the Hf-B-Si and Hf-B-Si-C systems, which are responsible for the poor creep resistance. RE oxide additions have a negative effect reducing the creep resistance of SiC-HfB2 UHTCs. A simplistic analysis for the required creep resistance is described, indicating that only SiC-HfB2 UHTCs could withstand re-entry conditions for 5 min in a single use. However, RE oxide addition to SiC-HfB2UHTCs does not provide the required creep resistance for them to be candidate materials for hypersonic applications.


Enero, 2018 | DOI: 10.1016/j.jeurceramsoc.2017.08.028

Enhanced photocatalytic removal of phenol from aqueous solutions using ZnO modified with Ag


Vaiano, V.; Matarangolo, M.; Murcia, J.J.; Rojas, H.; Navío, J.A.; Hidalgo, M.C.
Applied Catalysis B-Environmental, 225 (2018) 197-206

ABSTRACT

Different photocatalysts based on commercial ZnO modified by silver photodeposition were prepared in this work. The samples were characterized by X-ray fluorescence spectrometry (XRF), specific surface area (SSA), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and UV–vis diffuse reflectance (UV–vis DRS). XRD and XPS showed that Ag/ZnO samples are composed of metallic Ag (Ag0) and ZnO structure was identified. Furthermore, TEM analysis evidenced that the number of silver particles increased with the Ag content. At last, UV–vis DRS results revealed a reflectance band for Ag/ZnO samples, ascribed to the surface plasmon resonance (SPR) absorption of metal silver particles. Commercial ZnO and Ag/ZnO samples were evaluated in the phenol removal under UV light irradiation. It was observed an enhancement of photocatalytic phenol removal from aqueous solutions by silver addition in comparison to commercial ZnO. In particular, the phenol removal increased with the silver content from 0.14 to 0.88 wt%, after this content (i.e 1.28 wt%) the phenol degradation significantly decreased indicating that the optimal Ag content was equal to 0.88 wt%. The influence of the best photocatalyst dosage and the change of the initial phenol concentration in solution were also investigated in this work and the best photocatalytic performance was obtained by using 50 mg L−1 of phenol initial concentration and 0.15 g L−1 of photocatalyst dosage. Finally, the optimized Ag/ZnO photocatalyst was employed for the treatment of a real drinking wastewater containing phenol in which the almost total phenol removal was achieved after 180 min of UV irradiation time.


Enero, 2018 | DOI: 10.1016/j.apcatb.2017.11.075

Nickel/Copper Bilayer-modified Screen Printed Electrode for Glucose Determination in Flow Injection Analysis


Salazar, P.; Rico, V.; Gonzalez-Elipe, Agustin R.
Electroanalysis, 30 (2018) 187-193

ABSTRACT

This work reports about the performance of a Ni/Cu-modified screen printed electrodes (SPE/Ni/Cu), prepared by physical vapor deposition (PVD) in an oblique angle configuration (OAD), for non-enzymatic glucose sensing applications. SPE/Ni/Cu electrodes showed an excellent reversibility and a catalytic behavior for detection of glucose that were controlled by the diffusion of reactants up to the active sites at the electrode surface. The study with a flow injection analysis (FIA) setup of the main experimental variables affecting the detection process has shown that the developed electrode system had an excellent glucose sensitivity of 1.04AM(-1)cm(-2) (R-2:0.999), a linear response up to 1mM, a limit of detection of 0.33M and a time of analysis of ca. 30s per sample. The selectivity of the sensor was checked against various interferences, including ascorbic acid, uric acid, acetaminophen and other sugars, in all cases with excellent results. The feasibility of using this sensor for practical applications was successfully confirmed by determining the glucose concentration in different commercial beverages.


Enero, 2018 | DOI: 10.1002/elan.201700592

Outstanding performance of rehydrated Mg-Al hydrotalcites as heterogeneous methanolysis catalysts for the synthesis of biodiesel


Navajas, A; Campo, I; Moral, A; Echave, J; Sanz, O; Montes, M; Odriozola, JA; Arzamendi, G; Gandia, LM
Fuel, 211 (2018) 173-181

ABSTRACT

There is still a need for active, selective and stable heterogeneous catalysts for the synthesis of biodiesel. In this work, magnesium-aluminium hydrotalcites with Mg/Al molar ratios within the 1.5-5 range were synthesized by coprecipitation and used as transesterification catalysts for the synthesis of biodiesel. The mixed oxides obtained after calcination recovered the hydrotalcite structure in the form of meixnerite after rehydration in boiling water. The solids were characterized by XRD, TGA, N-2 adsorption-desorption, and SEM. Basic properties were assessed by means of Hammett indicators and CO2-TPD. Rehydrated materials with the highest Mg/Al ratios showed some distinctive features: low surface area, well defined flake-like crystals, high basicity and strong basic sites with H_ values above 11. They were also the most active catalysts allowing to achieve 51-75% sunflower oil methanolysis conversion after 8 h of reaction under mild conditions (60 degrees C, 1 atm), methanol/oil molar ratio of 12 using between 2 and 6 wt% of catalyst. The conversion increased up to 96% (92% fatty acid methyl esters yield) using 2 wt% catalyst and methanol/oil molar ratio of 48. Catalyst leaching was not a serious problem with these solids that could be reutilized maintaining very good activities. A general accordance between solids basic properties and their catalytic performance has been observed. These results are among the best reported in the literature for heterogeneous methanolysis catalysts and have been attributed to the high basicity of the rehydrated solids and the presence of strong and accessible basic sites probably consisting in interlayer hydroxide anions at the edges of the crystals.


Enero, 2018 | DOI: 10.1016/j.fuel.2017.09.061

Core-rim structure formation in TiC-Ni based cermets fabricated by a combined thermal explosion/hot-pressing process


Lemboub, S; Boudebane, S; Gotor, FJ; Haouli, S; Mezrag, S; Bouhedja, S; Hesser, G; Chadli, H; Chouchane, T
International Journal of Refractory Metals & Hard Materials, 70 (2018) 84-92

ABSTRACT

TiC-Ni-based cermets were obtained by thermal explosion from different elemental mixtures (Ti, C, Ni and X, where X = Cr, Mo or W) and subsequently densified by hot-pressing under a cyclic load. The whole process was performed in a single stage in the same experimental device according to the following thermal and pressure procedure: a heating rate ramp up to 1573 K without applying any load followed by an isothermal dwelling under a compressive cyclic load of 32 MPa. The thermal explosion synthesis occurred during the heating ramp at a temperature close to 1273 K that was practically independent of the starting nominal composition. The influence of different refractory elements on the chemical composition and microstructure of cermets was studied. SEM characterization showed that only with Mo and W, the cermets developed the characteristic core-rim structure. A high densification was achieved, but decreased when the refractory elements were added. Nevertheless, in these cases higher hardness values were obtained.


Enero, 2018 | DOI: 10.1016/j.ijrmhm.2017.09.014

A facile shape-controlled synthesis of highly photoactive fluorine containing TiO2 nanosheets with high {001} facet exposure


Lara, M.A.; Sayagués, M.J.; Navío, J.A.; Hidalgo, M.C.
Journal of Materials Science, 53 (2018) 435-446

ABSTRACT

Surface-fluorinated TiO2 materials with high {001} facet exposure were prepared by a simple and high-yield preparation procedure. Faceted/fluorinated samples showed a high photocatalytic performance not only in oxidation processes, tested in phenol and methyl orange degradation, but also in a reduction process as Cr(VI) photoreduction. Reaction rates for these materials greatly exceeded the ones obtained for materials prepared without fluorine addition and for commercial TiO2 Degussa (Evonik) P25 used as reference photocatalyst. A broad characterisation of the samples allowed us to estimate the percentages of different facets and the amount and form in which the fluorine is found on the surfaces. Good photocatalytic behaviour can be ascribed to both high {001} facet exposure and adsorbed fluorine on the photocatalysts surfaces.


Enero, 2018 | DOI: 10.1007/s1085

A new combustion route for synthesis of TaB2 nanoparticles


Jalaly, M; Gotor, FJ
Ceramics International, 44 (2018) 1142-1146

ABSTRACT

Tantalum diboride (TaB2) nanoparticles were synthesized through a mechanically induced self-sustaining reaction (MSR). In this method, the ternary system of Mg/Ta2O5/B was employed in which, magnesium was used as a reducing agent for reduction of tantalum oxides in a combustive regime. The processing route of TaB2 by the solid-state combustion was very short-term and the product purification was extremely easy and rapid. The synthesis mechanism was studied and revealed that magnesiothermic reduction of tantalum oxide is the initiator of the total reaction, while borothermic reduction of the oxide may occur in parallel.


Enero, 2018 | DOI: 10.1016/j.ceramint.2017.10.074

Flexible and Adaptable Light-Emitting Coatings for Arbitrary Metal Surfaces based on Optical Tamm Mode Coupling


Jiménez-Solano, A.; Galisteo-López, J.; Míguez, H.
Advanced Optical Materials, 6 (2018) 1700560

ABSTRACT

This study demonstrates a design that maximizes the power radiated into free space from a monolayer of nanoemitters embedded in a flexible distributed Bragg reflector conformably attached to a metal surface. This is achieved by positioning the light source at the precise depth within the multilayer for which optical Tamm states provide enhanced quantum yield and outcoupling efficiency, which are combined to optimize the luminous power radiated by the surface of the ensemble. This approach, based on the adhesion of flexible multilayer stacks onto metal surfaces with an arbitrary curvature, is versatile and permits the realization of spectrally narrow monodirectional or self-focusing light-emitting surfaces.


Enero, 2018 | DOI: 10.1002/adom.201700560

Nanostructured hybrid device mimicking bone extracellular matrix as local and sustained antibiotic delivery system


Borrego-Gonzalez, S; Romero-Sanchez, LB; Blazquez, J; Diaz-Cuenca, A
Microporous and Mesoporous Materials, 256 (2018) 165-176

ABSTRACT

A fluidic permeable and stable in wet media, MBG-NfGel, device consisting of a mesoporous ceramic embodied in a nanofibrillar biodegradable polymer has been processed using appropriate thermally induced phase separation (TIPS) processing variables of 5.4% (wt/v) gelatin in 50/50 water/ethanol (v/v) ratio. The device comprises high surface area mesoporous bioactive glass (MBG) microparticles within a fibrous matrix of 170 nm average diameter nanofibers gelatin, forming a meshwork of 0.2-1.6 mu m range voids. Gentamicin sulphate (GS) antibiotic high loading capacity and sustained release ability, as well as in vitro bioactivity and osteoprogenitor cells biocompatibility supports long-term antibacterial and bone growth stimulation properties. Antibiotic local delivery functionality in vitro of this device has been analysed and discussed in relation to other systems previously reported. The presented device properties as well as its industrial scalability potential, in terms of process reliability and absence of toxic chemical agents, low raw material biopolymer cost and immunogenicity, are other important advantages. These advantages rank MBG-NfGel device as a potential candidate to further development for application as local antibiotic device in bone surgery and therapy.


Enero, 2018 | DOI: 10.1016/j.micromeso.2017.08.010

Phase-Contact Engineering in Mono- and Bimetallic Cu-Ni Co-catalysts for Hydrogen Photocatalytic Materials


Munoz-Batista, MJ; Meira, DM; Colon, G; Kubacka, A; Fernandez-Garcia, M
Angewandte Chemie-International Edition, 57 (2018) 1199-1203

ABSTRACT

Understanding how a photocatalyst modulates its oxidation state, size, and structure during a photocatalytic reaction under operando conditions is strongly limited by the mismatch between (catalyst) volume sampled by light and, to date, the physicochemical techniques and probes employed to study them. A synchrotron micro-beam X-ray absorption spectroscopy study together with the computational simulation and analysis (at the X-ray cell) of the light-matter interaction occurring in powdered TiO2-based monometallic Cu, Ni and bimetallic CuNi catalysts for hydrogen production from renewables was carried out. The combined information unveils an unexpected key catalytic role involving the phase contact between the reduced and oxidized non-noble metal phases in all catalysts and, additionally, reveals the source of the synergistic Cu-Ni interaction in the bimetallic material. The experimental method is applicable to operando studies of a wide variety of photocatalytic materials.


Enero, 2018 | DOI: 10.1002/anie.201709552

The dizinc bond as a ligand: A computational study of elongated dizinc bonds


Ayala, R; Carmona, E; Galindo, A
Inorganic Chimica Acta, 470 (2018) 197-205

ABSTRACT

Following the synthesis of [Zn-2(eta(2)-C5Me5)(2)] (in short [Zn2Cp*(2)]) many complexes of the directly bonded Zn-Zn unit were prepared and characterized, leading to the recognition of an isolobal analogy between the Zn-Zn bond and the molecule of dihydrogen. Prompted by these results, we have investigated eta(2)-eta(2)-coordination of [Zn2Cp2] and [Zn2Ph2] (Cp = C5H5, Ph = C6H5) to several selected transition metal fragments and report herein the results of a QTAIM study of complexes [(ZnR)(2)Fe(CO)(4)], [(eta(2)-Zn2R2)M(CO)(5)]] and [(eta(2)-Zn2R2)Pd(PR'(3))(2)] (for R = Cp, Ph; M = Cr, Mo, W; and R' = F, H, Me). A decrease of rho(BCP), Delta(2) rho(BCP) and delocalization indexes delta(Zn, Zn), relative to corresponding values in the parent molecules of [Zn2Cp2] and [Zn2Ph2], accompanied dizinc coordination. In most cases the computed d(Zn, Zn) parameters were indicative of significant electron density sharing between the two Zn atoms. Nevertheless, the interaction with [Fe(CO)(4)] resulted in oxidative cleavage of the coordinated Zn-Zn bond, due to high pi backdonation to the sigma* Zn-2 MO as deduced from the delta(M, O-CO) index. The Zn-Zn bond critical points identified in our study are discussed. The computed Zn-Zn contacts concentrate in the range 2.44-2.58 angstrom, and we propose that this interval corresponds to elongated dizinc bonds. 


Enero, 2018 | DOI: 10.1016/j.ica.2017.06.008

Low-cost Ca-based composites synthesized by biotemplate method for thermochemical energy storage of concentrated solar power


Benitez-Guerrero, M; Valverde, JM; Perejon, A; Sanchez-Jimenez, PE; Perez-Maquecla, LA
Applied Energy, 210 (2018) 108-116

ABSTRACT

An ever more environmentally conscious society demands the use of green, sustainable and high-efficiency renewable energy resources. However, large-scale energy storage remains a challenge for a deep penetration of power produced from renewables into the grid. The Calcium-Looping (CaL) process, based on the reversible carbonation/calcination of CaO, is a promising technology for thermochemical energy storage (TCES) in Concentrated Solar Power (CSP) plants. Natural limestone to be used as CaO precursor is cheap, non-toxic and abundant. Nevertheless, recent works have shown that carbonation of CaO derived limestone at optimum conditions for TCES is limited by pore-plugging, which leads to severe deactivation for large enough particles to be employed in practice. In our work, we have synthesized inexpensive CaO/SiO2 composites by means of a biotemplate method using rice husk as support. The morphological and compositional features of the biomorphic materials synthesized help improve the CaO multicycle activity under optimum CSP storage conditions and for particles sufficiently large to be managed in practical processes.


Enero, 2018 | DOI: 10.1016/j.apenergy.2017.10.109

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