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Scientific Papers in SCI


Title: Sonogashira Cross-Coupling and Homocoupling on a Silver Surface: Chlorobenzene and Phenylacetylene on Ag(100)
Author(s): Sanchez-Sanchez, C; Orozco, N; Holgado, JP; Beaumont, SK; Kyriakou, G; Watson, DJ; Gonzalez-Elipe, AR; Feria, L; Sanz, JF; Lambert, RM
Source: Journal of the American Chemical Society, 137 (2015) 940-947
abstract | fulltext

Scanning tunneling microscopy, temperature-programmed reaction, near-edge X-ray absorption fine structure spectroscopy, and density functional theory calculations were used to study the adsorption and reactions of phenylacetylene and chlorobenzene on Ag(100). In the absence of solvent molecules and additives, these molecules underwent homocoupling and Sonogashira cross-coupling in an unambiguously heterogeneous mode. Of particular interest is the use of silver, previously unexplored, and chlorobenzene—normally regarded as relatively inert in such reactions. Both molecules adopt an essentially flat-lying conformation for which the observed and calculated adsorption energies are in reasonable agreement. Their magnitudes indicate that in both cases adsorption is predominantly due to dispersion forces for which interaction nevertheless leads to chemical activation and reaction. Both adsorbates exhibited pronounced island formation, thought to limit chemical activity under the conditions used and posited to occur at island boundaries, as was indeed observed in the case of phenylacetylene. The implications of these findings for the development of practical catalytic systems are considered.

December, 2014 | DOI: 10.1021/ja5115584

Title: Optical Description of Mesostructured Organic-Inorganic Halide Perovskite Solar Cells
Author(s): Anaya, M; Lozano, G; Calvo, ME; Zhang, W; Johnston, MB; Snaith, HJ; Miguez, H
Source: Journal of Physical Chemistry Letters, 6 (2015) 48-53
abstract | fulltext

Herein we describe both theoretically and experimentally the optical response of solution-processed organic–inorganic halide perovskite solar cells based on mesostructured scaffolds. We develop a rigorous theoretical model using a method based on the propagation of waves in layered media, which allows visualizing the way in which light is spatially distributed across the device and serves to quantify the fraction of light absorbed by each medium comprising the cell. The discrimination between productive and parasitic absorption yields an accurate determination of the internal quantum efficiency. State-of-the-art devices integrating mesoporous scaffolds infiltrated with perovskite are manufactured and characterized to support the calculations. This combined experimental and theoretical analysis provides a rational understanding of the optical behavior of perovskite cells and can be beneficial for the judicious design of devices with improved performance. Notably, our model justifies the presence of a solid perovskite capping layer in all of the highest efficiency perovskite solar cells based on thinner mesoporous scaffolds.

December, 2014 | DOI: 10.1021/jz502351s

Title: Ca-looping for postcombustion CO2 capture: A comparative analysis on the performances of dolomite and limestone
Author(s): Valverde, JM; Sanchez-Jimenez, PE; Perez-Maqueda, LA
Source: Applied Energy, 138 (2015) 202-215
abstract | fulltext

The low cost and wide availability of natural limestone (CaCO3) is at the basis of the industrial competitiveness of the Ca-looping (CaL) technology for postcombustion CO2 capture as already demonstrated by similar to 1 Mw(t) scale pilot projects. A major focus of studies oriented towards further improving the efficiency of the CaL technology is how to prevent the gradual loss of capture capacity of limestone derived CaO as the number of carbonation/calcination cycles is increased. Natural dolomite (MgCa(CO3)(2)) has been proposed as an alternative sorbent precursor to limestone. Yet, carbonation of MgO is not thermodynamically favorable at CaL conditions, which may hinder the capture performance of dolomite. In the work described in this paper we carried out a thermogravimetric analysis on the multicyclic capture performance of natural dolomite under realistic regeneration conditions necessarily implying high calcination temperature, high CO2 concentration and fast transitions between the carbonation and calcination stages. Our study demonstrates that the sorbent derived from dolomite has a greater capture capacity as compared to limestone. SEM analysis shows that MgO grains in the decomposed dolomite are resistant to sintering under severe calcination conditions and segregate from CaO acting as a thermally stable support which mitigates the multicyclic loss of CaO conversion. Moreover, full decomposition of dolomite is achieved at significantly lower calcination temperatures as compared to limestone, which would help improving further the industrial competitiveness of the technology. 

December, 2014 | DOI: 10.1016/j.apenergy.2014.10.087

Title: "In Operando" X-ray Absorption Spectroscopy Analysis of Structural Changes During Electrochemical Cycling of WO3 and WxSiyOz Amorphous Electrochromic Thin Film Cathodes
Author(s): Garcia-Garcia, FJ; Gil-Rostra, J; Yubero, F; Espinos, JP; Gonzalez-Elipe, AR; Chaboy, J
Source: Journal of Physical Chemistry C, 119 (2015) 644-652
abstract | fulltext

This work reports a X-ray absorption spectroscopy (XAS) study under in operando conditions of the structural and chemical changes undergone by WO3 and WxSiyOz thin films used as electrochromic cathodes. The electrochromic films were prepared by magnetron sputtering deposition at oblique angles and then characterized by a large variety of techniques. The voltammograms and chronoamperometric diagrams in both aqueous and organic electrolyte media revealed a total reversibility of the electrochromic behavior, a low response time, and a high coloration efficiency for the two types of thin films. The in operando X-ray absorption study of the films working in aqueous solutions revealed that when they were electrochemically cycled the average WO distances reversibly varied by a Delta d of 0.06 and 0.08 angstrom for, respectively, WO3 and WxSiyOz. These changes are discussed by assuming the reduction of W6+ cations and the transformation of W-O double bonds into single WO bond structures during the electrochemical cycling of the films.

December, 2014 | DOI: 10.1021/jp508377v

Title: Limestone Calcination Nearby Equilibrium: Kinetics, CaO Crystal Structure, Sintering and Reactivity
Author(s): Valverde, JM; Sanchez-Jimenez, PE; Perez-Maqueda, LA
Source: Journal of Physical Chemistry C, 119 (2015) 1523-1541
abstract | fulltext

In this work, we analyze limestone calcination kinetics at environmental conditions involving a CO2 partial pressure P close to the equilibrium pressure Peq by means of in situ X-ray diffraction (XRD) and thermogravimetric (TG) analyses. In contrast with previous empirical observations carried out mostly at conditions far from equilibrium (P/Peq ≪ 1), our results show that the decarbonation rate decreases as the temperature in increased while P/Peq is kept constant, which is explained from a reaction mechanism including desorption of CO2 and the exothermic structural transformation from metastable CaO* nanocrystals to the stable CaO form. The crystal structure and sintering of nascent CaO during calcination has been investigated from in situ XRD analysis, physisorption analysis, and scanning electron microscopy (SEM), which shows that the ratio of the size of polycrystalline CaO grains to crystallite size increases linearly with the CO2 partial pressure in the calcination atmosphere. For high CO2 partial pressures, the size of CaO grains reaches a maximum value of around 1 μm, which leads to a residual surface area of about 1 m2/g, whereas in the limit P → 0 grain size and crystallite size (of the order of 10 nm) would coincide. Accordingly, sintering in the presence of CO2 would be triggered by the agglomeration of CaO crystals enhanced by CO2adsorption, which increases the surface energy. The carbonation reactivity of CaO resulting from calcination scales proportionally to its surface area and is not determined by a growth of the CaO exposed surface along a preferred crystallographic direction wherein carbonation would be unfavorable as suggested in recent works.

December, 2014 | DOI: 10.1021/jp508745u

Title: Quick synthesis, functionalization and properties of uniform, luminescent LuPO4-based nanoparticles
Author(s): Becerro, AI; Ocana, M
Source: RSC Advances, 44 (2015) 34517-34524
abstract | fulltext

The aim of this study was to find a surfactant-free method for the synthesis of uniform Eu:LuPO4nanophosphors which are able to form stable colloidal suspensions in aqueous media. Uniform, ovoid Eu-doped LuPO4 fluorescent nanoparticles were obtained after aging for 30 minutes at 180 °C a butylene glycol solution containing, exclusively, lutetium acetate, europium acetate and H3PO4. XRD and digital diffraction patterns of HRTEM images suggested that the particles were single crystalline in nature with the c-axis of the unit cell parallel to the long particle axis. The luminescence study revealed that the optimum doping level was 5 molar%. The latter particles (85 nm × 40 nm dimensions) were functionalized with polyacrylic acid and their colloidal stability in two different biological buffers was demonstrated to persist for at least 15 days.

December, 2014 | DOI: 10.1039/C5RA05305F

Title: Catalytic screening of Au/CeO2-MOx/Al2O3 catalysts (M = La, Ni, Cu, Fe, Cr, Y) in the CO-PrOx reaction
Author(s): Reina, TR; Ivanova, S; Centeno, MA; Odriozola, JA
Source: International Journal of Hydrogen Energy, 40 (2015) 1782-1788
abstract | fulltext

In this work, a series of Au/CeO2-MOx/Al2O3 catalysts has been prepared and evaluated in the PrOx reaction. Within the series of dopants Fe and Cu containing samples enhanced the catalytic performance of the parent Au/CeO2/Al2O3 catalyst being copper the most efficient promoter. For both samples an enhanced oxygen storage capacity (OSC) is registered and accounts for the high CO oxidation activity. More particularly, the Au/CeO2-CuOx/Al2O3 catalyst successfully withstands the inclusion of water in the PrOx stream and presents good results in terms of CO elimination. However to achieve a good selectivity toward, CO2 formation properly adjusting of the reaction parameters, such as oxygen concentration and space velocity is needed. Within the whole screened series the Cu-containing catalyst can be considered as the most interesting alternative for H-2 clean-up applications.

December, 2014 | DOI: 10.1016/j.ijhydene.2014.11.141

Title: Template-free synthesis and luminescent properties of hollow Ln:YOF (Ln = Eu or Er plus Yb) microspheres
Author(s): Martinez-Castro, E; Garcia-Sevillano, J; Cusso, F; Ocana, M
Source: Journal of Alloys and Compounds, 619 (2015) 44-51
abstract | fulltext

A method for the synthesis of hollow lanthanide doped yttrium oxyfluoride (YOF) spheres in the micrometer size range with cubic structure based on the pyrolysis at 600 degrees C of liquid aerosols generated from aqueous solutions containing the corresponding rare earth chlorides and trifluoroacetic acid has been developed. This procedure, which has been used for the first time for the synthesis of YFO based materials, is simpler and advantageous when compared with other methods usually employed for the production of hollow spheres since it does not require the use of sacrificial templates. In addition, it is continuous, which is desirable because of practical reasons. The procedure is also suitable for doping the YOF spheres with europium cations resulting in down converting red phosphors when activated with UV light, or for co-doping with both Er3+ and Yb3+ giving rise to up-converting phosphors, which emit intense red light under near infrared (NIR) irradiation. Because of their optical properties and hollow architecture, the developed materials may find applications in optoelectronic devices and biotechnology. 

December, 2014 | DOI: 10.1016/j.jallcom.2014.09.023

Title: Biotribological behavior of Ag–ZrCxN1−x coatings against UHMWPE for joint prostheses devices
Author(s): Calderon, SV; Sanchez-Lopez, JC; Cavaleiro, A; Carvalho, S
Source: Journal of the Mechanical Behavior of Biomedical Materials, 41 (2015) 83-91
abstract | fulltext

This study aims to evaluate the structural, mechanical and tribological properties of zirconium carbonitrides (ZrCxN1−x) coatings with embedded silver nanoparticles, produced with the intention of achieving a material with enhanced multi-functional properties, including mechanical strength, corrosion resistance, tribological performance and antibacterial behavior suitable for their use in joint prostheses. The coatings were deposited by direct current (DC) reactive magnetron sputtering onto 316 L stainless steel, changing the silver content from 0 to 20 at% by modifying the current density applied to the targets. Different nitrogen and acetylene gas fluxes were used as reactive gases. The coatings revealed different mixtures of crystalline ZrCxN1−x, silver nanoparticles and amorphous carbon phases. The hardness of the films was found to be mainly controlled by the ratio between the hard (ZrCxN1−x) and soft (Ag and amorphous carbon) phases in the films, fluctuating between 7.4 and 20.4 GPa. The coefficient of friction, measured against ultra-high molecular weight polyethylene (UHMWPE) in Hank’s balanced salt solution with 10 g L−1albumin, is governed by the surface roughness and hardness. The UHMWPE wear rates were in the same order of magnitude (between 1.4 and 2.0×10−6 mm3 N−1 m−1), justified by the effect of the protective layer of albumin formed during the tests. The small differences were due to the hydrophobic/hydrophilic character of the surface, as well as to the silver content.

December, 2014 | DOI: 10.1016/j.jmbbm.2014.09.028

Title: New Insights on the Kinetic Analysis of Isothermal Data: The Independence of the Activation Energy from the Assumed Kinetic Model
Author(s): Sanchez-Jimenez, PE; Perejon, A; Perez-Maqueda, LA; Criado, JM
Source: Energy & Fuels, 29 (2015) 392-397
abstract | fulltext

Isothermal experiments are widely employed to study the kinetics of solid-state reactions or processes to extract essential kinetic information needed for modeling the processes at an industrial scale. The kinetic analysis of isothermal data requires finding or assuming a kinetic function that can properly fit the evolution of the reaction rate with time, so that the resulting parameters, i.e., the activation energy and pre-exponential factor, can be considered reliable. In the present work, we demonstrate using both simulated and experimental data that the kinetic analysis of a set of isothermal plots obtained at different temperatures, considering a single-step solid-state reaction, necessarily leads to the real activation energy, regardless the mathematical function selected for performing the kinetic analysis. This makes irrelevant the election of the kinetic function used to fit the experimental data and greatly facilitates the estimation of the activation energy for any single process.

December, 2014 | DOI: 10.1021/ef502269r