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Critical Role of Oxygen in Silver-Catalyzed Glaser-Hay Coupling on Ag(100) under Vacuum and in Solution on Ag Particles

Orozco, N; Kyriakou, G; Beaumont, SK; Sanz, JF; Holgado, JP; Taylor, MJ; Espinos, JP; Marquez, AM; Watson, DJ; Gonzalez-Elipe, AR; Lambert, RM
ACS Catalysis, 7 (2017) 3113-3120


The essential role of oxygen in enabling heterogeneously catalyzed Glaser–Hay coupling of phenylacetylene on Ag(100) was elucidated by STM, laboratory and synchrotron photoemission, and DFT calculations. In the absence of coadsorbed oxygen, phenylacetylene formed well-ordered dense overlayers which, with increasing temperature, desorbed without reaction. In striking contrast, even at 120 K, the presence of oxygen led to immediate and complete disruption of the organic layer due to abstraction of acetylenic hydrogen with formation of a disordered mixed layer containing immobile adsorbed phenylacetylide. At higher temperatures phenylacetylide underwent Glaser–Hay coupling to form highly ordered domains of diphenyldiacetylene that eventually desorbed without decomposition, leaving the bare metal surface. DFT calculations showed that, while acetylenic H abstraction was otherwise an endothermic process, oxygen adatoms triggered a reaction-initiating exothermic pathway leading to OH(a) + phenylacetylide, consistent with the experimental observations. Moreover, it was found that, with a solution of phenylacetylene in nonane and in the presence of O2, Ag particles catalyzed Glaser–Hay coupling with high selectivity. Rigorous exclusion of oxygen from the reactor strongly suppressed the catalytic reaction. Interestingly, too much oxygen lowers the selectivity toward diphenyldiacetylene. Thus, vacuum studies and theoretical calculations revealed the key role of oxygen in the reaction mechanism, subsequently borne out by catalytic studies with Ag particles that confirmed the presence of oxygen as a necessary and sufficient condition for the coupling reaction to occur. The direct relevance of model studies to a mechanistic understanding of coupling reactions under conditions of practical catalysis was reaffirmed.

Mayo, 2017 | DOI: 10.1021/acscatal.7b00431

NO photooxidation with TiO2 photocatalysts modified with gold and platinum

Rodriguez, MJH; Melian, EP; Santiago, DG; Diaz, OG; Navio, JA; Rodriguez, JMD
Applied Catalysis B-Environmental, 205 (2017) 148-157


In this study, a comparative analysis is made of TiO2 modified with Pt or Au in NO photoxidation under different radiation and humidity conditions. The metals were deposited on the TiO2 surface using two methods, photodeposition and chemical reduction. All catalysts were supported on borosilicate 3.3 plates using a dip-coating technique. These modified photocatalysts were characterized by X-ray diffraction analysis (XRD), UV-vis diffuse reflectance spectra (DRS), Brunauer-Emmett-Teller measurements (BET), transmission electron microscopy (TEM) and X-ray photoelectron spectrum analysis (XPS). It was found from the XPS results that Pt and oxidized Pt species coexist on the samples obtained by photodeposition and chemical reduction. In the case of Au, though other oxidation states were also detected the dominant oxidation state for both catalysts is Au. TEM results showed most Au-C particles are below 5 nm, whereas for Au-P the nanoparticles are slightly bigger. With UV irradiation, the Pt modified catalysts do not show any significant improvement in NO photocatalytic oxidation in comparison with the unmodified P25. For Au, both modified photocatalysts (Au-P and Au-C) exceed the photocatalytic efficiency of the unmodified P25, with Au-C giving slightly better results. The incorporation of metals on the TiO2 increases its activity in the visible region. 

Mayo, 2017 | DOI: 10.10161/j.apcatb.2016.12.006

Energy-Sensitive Ion- and Cathode-Luminescent Radiation-Beam Monitors Based on Multilayer Thin-Film Designs

Gil-Rostra, Jorge; Ferrer, Francisco J.; Pedro Espinos, Juan; Gonzalez-Elipe, Agustin R.; Yubero, Francisco
ACS Applied Materials & Interfaces, 9 (2017) 16313-16320


A multilayer luminescent design concept is presented to develop energy sensitive radiation-beam monitors on the basis of colorimetric analysis. Each luminescent layer within the stack consists of rare-earth-doped transparent oxides of optical quality and a characteristic luminescent emission under excitation with electron or ion beams. For a given type of particle beam (electron, protons, alpha particles, etc.), its penetration depth and therefore its energy loss at a particular buried layer within the multilayer stack depend on the energy of the initial beam. The intensity of the luminescent response of each layer is proportional to the energy deposited by the radiation beam within the layer, so characteristic color emission will be achieved if different phosphors are considered in the layers of the luminescent stack. Phosphor doping, emission efficiency, layer thickness, and multilayer structure design are key parameters relevant to achieving a broad colorimetric response. Two case examples are designed and fabricated to illustrate the capabilities of these new types of detector to evaluate the kinetic energy of either electron beams of a few kilo-electron volts or a particles of alpha few mega-electron volts.

Mayo, 2017 | DOI: 10.1021/acsami.7b01175

Design and Realization of a Novel Optically Disordered Material: A Demonstration of a Mie Glass

Miranda-Munoz, Jose M.; Lozano, Gabriel; Miguez, Hernan
Advanced Optical Materials, 5 (2017) art. 1700025


Herein, a diffusive material presenting optical disorder is introduced, which represents an example of a Mie glass. Comprising spherical crystalline TiO2 nanoparticles randomly dispersed in a mesoporous TiO2 matrix, it is proved that the scattering of light in this inhomogeneous solid can be predicted in an unprecedented manner from single-particle considerations employing Mie theory. To that aim, a study of the dependence of the key parameters employed is performed to describe light propagation in random media, i.e., the scattering mean free path and the transport mean free path, as a function of the size and concentration of the spherical inclusions based on a comparison between experimental results and analytical calculations. It is also demonstrated that Mie glasses enable enhanced fluorescence intensity due to a combined absorptance enhancement of the excitation light combined with an improved outcoupling of the emitted light. The method offers the possibility to perform a deterministic design for the realization of a light diffuser with tailor-made scattering properties.

Mayo, 2017 | DOI: 10.1002/adom.201700025

Non-enzymatic hydrogen peroxide detection at NiO nanoporous thin film-electrodes prepared by physical vapor deposition at oblique angles

Salazar, Pedro; Rico, Victor; Gonzalez-Elipe, Agustin R.
Electrochimica Acta, 235 (2017) 534-542


In this work we report a non-enzymatic sensor for hydrogen peroxide (H2O2) detection based on nanostructured nickel thin films prepared by physical vapor deposition at oblique angles. Porous thin films deposited on ITO substrates were characterized by X-ray diffraction analysis, scanning electron microcopy (SEMs), X-ray photoelectron spectroscopy (XPS) and electrochemical techniques such as Cyclic Voltammetry (CV) and Constant Potential Amperometry (CPA). The microstructure of the thin films consisted of inclined and separated Ni nanocolumns forming a porous thin layer of about 500 nm thickness. Prior to their use, the films surface was electrochemically modified and the chemical state studied by CV and XPS analysis. These techniques also showed that Ni2+/Ni3+ species were involved in the electrochemical oxidation and detection of H2O2 in alkaline medium. Main analytical parameters such as sensitivity (807 mA M(-1)cm(-2)), limit of detection (3.22 mu M) and linear range (0.011-2.4 mM) were obtained under optimal operation conditions. Sensors depicted an outstanding selectivity and a high stability and they were successfully used to determine H2O2 concentration in commercial antiseptic solutions.

Mayo, 2017 | DOI: 10.1016/j.electacta.2017.03.087

CO2 capture performance of Ca-Mg acetates at realistic Calcium Looping conditions

Miranda-Pizarro, J; Perejon, A; Valverde, JM; Perez-Maqueda, LA; Sanchez-Jimenez, PE
Fuel, 196 (2017) 497-507


The Calcium Looping (CaL) process, based on the cyclic carbonation/calcination of CaO, has emerged in the last years as a potentially low cost technique for CO2 capture at reduced energy penalty. In the present work, natural limestone and dolomite have been pretreated with diluted acetic acid to obtain Ca and Ca-Mg mixed acetates, whose CO2 capture performance has been tested at CaL conditions that necessarily imply sorbent regeneration under high CO2 partial pressure. The CaL multicycle capture performance of these sorbents has been compared with that of CaO directly derived from limestone and dolomite calcination. Results show that acetic acid pretreatment of limestone does not lead to an improvement of its capture capacity, although it allows for a higher calcination efficiency to regenerate CaO at reduced temperatures (similar to 900 degrees C) as compared to natural limestone (>similar to 930 degrees C). On the other hand, if a recarbonation stage is introduced before calcination to reactivate the sorbent, a significantly higher residual capture capacity is obtained for the Ca -Mg mixed acetate derived from dolomite as compared to either natural dolomite or limestone. The main reason for this behavior is the enhancement of carbonation in the solid-state diffusion controlled phase. It is argued that the presence of inert MgO grains in the mixed acetate with reduced segregation notably promotes solid state diffusion of ions across the porous structure created after recarbonation.

Mayo, 2017 | DOI: 10.1016/j.fuel.2017.01.119

Structure evolution in the LaMn1 − xFexO3 + δ system by Rietveld analysis

Cordoba, J. M.; Ponce, M.; Sayagues, M. J.
Solis State Ionics, 303 (2017) 132-137


The synthesis of LaMn1 − xFexO3 + δ (0 ≤ x ≤ 1) solid solutions perovskite powder was carried out using high-energy milling from the constituent oxides, and further crystallization by high temperature treatment. The compositions of the crystalline phases as a function of x were determined by X-ray powder diffraction using a Rietveld refinement. The relationship between composition and structure was covered. This showed that LaMn1 − xFexO3 + δ exists with the rhombohedral structure (R-3c, 167) only below x = 0.3 and with the orthorhombic structure (Pnma, 62) over x = 0.7. The rhombohedral phase coexists with the orthorhombic phase between 0.4 < x < 0.6.

Mayo, 2017 | DOI: 10.1016/j.ssi.2017.02.020

New findings on thermal degradation properties of fluoropolymers

Liu, SE; Zhou, WL; Yan, QL; Qi, XF; An, T; Perez-Maqueda, LA; Zhao, FQ
Journal of Thermal Analysis and Calorimetry, 128 (2017) 675-685


In this paper, the thermal degradation properties of Viton A and Fluorel are investigated by both isoconversional and combined kinetic analysis methods using non-isothermal thermogravimetry technique. It has been found that the heating rate has little affect on the degradation residue of Fluorel and Viton A, where around 1.3% char was formed for Fluorel and 3.5% for Viton A. Different from the literature, the decomposition of Viton A should be considered as an overlapped dehydrofluorination and carbon chain scission process, with activation energy of 214 +/- 11 and 268 +/- 13 kJ mol(-1), respectively. The effect of dehydrofluorination on degradation of Fluorel is not so significant due to low content of H, and hence, it could be considered as a single-step mechanism with average activation energy of 264 +/- 14 kJ mol(-1). The thermal stability of Fluorel is much better than that of Viton A, and the predicted half-life is around 218 min for Fluorel and 49 min for Viton A at 420 A degrees C, which are consistent with experimental values. If using a single-step model as in the literature for Viton A, its half-life at 420 A degrees C would be underestimated for > 20%.

Mayo, 2017 | DOI: 10.1007/s10973-016-5963-z

Synthesis, Characterisation, and Photocatalytic Behaviour of Mesoporous ZnS Nanoparticles Prepared Using By-Product Templating

Emrooz, HBM; Rahmani, AR; Gotor, FJ
Australian Journal of Chemistry, 70 (2017) 1099-1105


High surface area mesoporous ZnS nanoparticles (MZN) were obtained with the aid of the by-product of the synthesising reaction. This by-product, namely NaNO3, can be considered as a soft template responsible for the formation of pores. Ethanol and water were chosen as the synthesis media. Ultrasonic waves were used as an accelerator for the synthesis of MZNs. Photocatalytic activities of the synthesised samples for the degradation of methylene blue (MB) were investigated under ultraviolet irradiation. Synthesised specimens were characterised using field emission scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, diffuse reflectance spectroscopy, N-2-physisorption, and FT-IR spectroscopy. Results indicated that the synthesis media has a pronounced effect on the surface properties of the final porous particles by several mechanisms. The specific surface area of the MZN samples synthesised in water and ethanol were determined to be 53 and 201m(2)g(-1), respectively. The difference in the specific surface area was attributed to the weak solvation of S2- ions (Na(2)S5H(2)O in ethanol) and also to the by-product of the synthesis reaction. The photocatalytic behaviour of the mesoporous ZnS nanoparticles synthesised in these two media were investigated and the results have been interpreted with the aid of effective surface area, pore volume, and bandgap energy of the specimens.

Mayo, 2017 | DOI: 10.1071/CH17192

Improving the pollutant removal efficiency of packed-bed plasma reactors incorporating ferroelectric components

Gomez-Ramirez, Ana; Montoro-Damas, Antonio M.; Rodriguez, Miguel A.; Gonzalez-Elipe, Agustin R.; Cotrino, Jose
Chemical Engineering Journal, 314 (2017) 311-319


In this work we have studied the plasma removal of air contaminants such as methane, chloroform, toluene and acetone in two parallel plate packed-bed dielectric barrier discharge (DBD) reactors of different sizes. Removal and energy efficiencies have been determined as a function of the residence time of the contaminated air within the reactor, the kind of packed-bed material (ferroelectrics or classical dielectric materials), the frequency and the incorporation of a ferroelectric plate onto the active electrode together with the inter-electrode ferroelectric pellets filling the gap. Results at low frequency with the small reactor and the ferroelectric plate showed an enhancement in energy efficiency (e.g., it was multiplied by a factor of six and three for toluene and chloroform, respectively) and in removal yield (e.g., it increased from 22% to 52% for chloroform and from 15% to 21% for methane). Such enhancements have been attributed to the higher energy of plasma electrons and a lower reactor capacitance found for this plate-modified configuration. A careful analysis of reaction efficiencies and electron energy distributions for the different investigated conditions and the simulation of the electric field at the necks between ferroelectric/dielectric pellets complete the present study. Overall, the obtained results prove the critical role of the barrier architecture and operating conditions for an enhanced performance of pollution removal processes using DBD systems.

Abril, 2017 | DOI: 10.1016/j.cej.2016.11.065

Deep insight into Zr/Fe combination for successful Pt/CeO2/Al2O3 WGS catalyst doping

Gonzalez-Castano, M; Ivanova, S; Ioannides, T; Centeno, MA; Odriozola, JA
Catalysis Science & Technology, 7 (2017) 1556-1564


Efficient promotion of the Pt/CeO2/Al2O3 catalytic system was achieved by the addition of two different ceria promoters, Zr and Fe. From the exhaustive data analysis, the key features for enhanced catalytic performance and the roles of each doping metal are established. The combination of both doping agents manifests a synergistic effect reflected in noteworthy improvements in H2 reducibility. In addition, the catalyst's doping influences its chemisorptive properties, which is reflected in an increase of the easiness of carbonaceous species desorption, thus leading to superior catalyst resistance toward deactivation.

Abril, 2017 | DOI: 10.1039/c6cy02551j

High UV-photocatalytic activity of ZnO and Ag/ZnO synthesized by a facile method

C. Jaramillo-Páez; J.A. Navío; M.C. Hidalgo; M. Macías
Catalysis Today, 284 (2017) 121-128


ZnO nanoparticles have been successfully synthesized by a facile precipitation procedure by mixing aqueous solutions of Zn(II) acetate and dissolved Na2CO3 at pH ca. 7.0 without template addition. We have investigated the effect of annealing temperature in the final surface and structural properties. Photocatalytic studies were performed using two selected substrates, Methyl Orange and Phenol, both as single model substrates and in mixtures of them.

It has been stated that calcination treatments lead to a significant improvement in the photocatalytic properties of the studied samples, even better than TiO2(P25). As expected, the addition of Ag+ during the photocatalytic degradation of MO increases the reaction rate of the degradation of MO, giving a resultant Ag/ZnO photocatalyst which, after recovery, can be reused at least 18 times for the MO degradation tests, being even more photoactive than ZnO.

Abril, 2017 | DOI: 10.1016/j.cattod.2016.11.021

Formation of nitrile species on Ag nanostructures supported on a-Al2O3: a new corrosion route for silver exposed to the atmosphere

Pelaez, RJ; Espinos, JP; Afonso, CN
Nanotechnology, 28 (2017) 175709


The aging of supported Ag nanostructures upon storage in ambient conditions (air and room temperature) for 20 months has been studied. The samples are produced on glass substrates by pulsed laser deposition (PLD); first a 15 nm thick buffer layer of amorphous aluminum oxide (a-Al2O3) is deposited, followed by PLD of Ag. The amount of deposited Ag ranges from that leading to a discontinuous layer up to an almost-percolated layer with a thickness of <6 nm. Some regions of the as-grown silver layers are converted, by laser induced dewetting, into round isolated nanoparticles (NPs) with diameters of up to ~25 nm. The plasmonic, structural and chemical properties of both as-grown and laser exposed regions upon aging have been followed using extinction spectroscopy, scanning electron microscopy and x-ray photoelectron spectroscopy, respectively. The results show that the discontinuous as-grown regions are optically and chemically unstable and that the metal becomes oxidized faster, the smaller the amount of Ag. The corrosion leads to the formation of nitrile species due to the reaction between NO x species from the atmosphere adsorbed at the surface of Ag, and hydrocarbons adsorbed in defects at the surface of the a-Al2O3 layer during the deposition of the Ag nanostructures by PLD that migrate to the surface of the metal with time. The nitrile formation thus results in the main oxidation mechanism and inhibits almost completely the formation of sulphate/sulphide. Finally, the optical changes upon aging offer an easy-to-use tool for following the aging process. They are dominated by an enhanced absorption in the UV side of the spectrum and a blue-shift of the surface plasmon resonance that are, respectively, related to the formation of a dielectric overlayer on the Ag nanostructure and changes in the dimensions/features of the nanostructures, both due to the oxidation process.

Abril, 2017 | DOI: 10.1088/1361-6528/aa65c0

Effect of Thermal Pretreatment and Nanosilica Addition on Limestone Performance at Calcium-Looping Conditions for Thermochemical Energy Storage of Concentrated Solar Power

Valverde, Jose Manuel; Barea-Lopez, Manuel; Perejon, Antonio; Sanchez-Jimenez, Pedro E.; Perez-Maqueda, Luis A.
Enery & Fuels, 31 (2017) 4226-4236


The share of renewable energies is growing rapidly, partly in response to the urgent need for mitigating CO2 emissions from fossil fuel power plants. However, cheap and efficient large-scale energy storage technologies are not yet available to allow for a significant penetration of renewable energies into the grid. Recently, a potentially low-cost and efficient thermochemical energy storage (TCES) system has been proposed, based on the integration of the calcium-looping (CaL) process into concentrated solar power plants (CSPs). The CaL process relies on the multicycle carbonation/calcination of CaO, which can be derived from calcination of widely available, cheap, and nontoxic natural limestone (CaCO3). This work explores the effect on the multicycle activity of limestone-derived CaO of thermal pretreatment under diverse atmospheres and the addition of nanosilica, which would be expected to hinder CaO grain sintering. Importantly, optimum CaL conditions for CSP energy storage differ radically from those used in the application of the CaL process for CO2 capture. Thus, calcination should be ideally carried out under low CO2 partial pressure at moderate temperature (below 750 degrees C), whereas CO2 concentration and temperature should be high for carbonation in order to maximize thermoelectric efficiency. When limestone is subjected to carbonation/calcination cycles at these conditions, its performance is critically dependent on the type of pretreatment. Our results indicate that the multicycle CaO activity is correlated with the size of the particles and the CaO pore size distribution. Thus, CaO activity is impaired as particle size is increased and/or CaO pore size is decreased. These observations suggest that pore plugging poses a main limitation to the multicycle performance of limestone-derived CaO at the optimum CaL conditions for TCES in CSPs, which is supported by scanning electron microscopy analysis. Strategies to enhance the performance of natural limestone at these conditions should be therefore oriented toward minimizing pore plugging rather than CaO grain sintering, which stands as the main limitation at CaL conditions for CO2 capture.

Abril, 2017 | DOI: 10.1021/acs.energyfuels.6b03364

Mechanochemical Solvent-Free Synthesis of Quaternary Semiconductor Cu-Fe-Sn-S Nanocrystals

Balaz, Peter; Balaz, Matej; Sayagues, Maria J.; Skorvanek, Ivan; Zorkovska, Anna; Dutkova, Erika; Briancin, Jaroslav; Kovac, Jaroslav; Kovac, Jaroslav, Jr.; Shpotyuk, Yaroslav
Nanoscale Research Letters, 12 (2017) art. 256


In this study, we demonstrate a one-pot mechanochemical synthesis of the nanocomposite composed of stannite Cu2FeSnS4 and rhodostannite Cu2FeSn3S8 nanocrystals using a planetary ball mill and elemental precursors (Cu, Fe, Sn, S). By this approach, unique nanostructures with interesting properties can be obtained. Methods of XRD, Raman spectroscopy, UV-Vis, nitrogen adsorption, SEM, EDX, HRTEM, STEM, and SQUID magnetometry were applied. Quaternary tetragonal phases of stannite and rhodostannite with crystallite sizes 18-19 nm were obtained. The dominant Raman peaks corresponding to the tetragonal stannite structure corresponding to A-symmetry optical modes were identified in the spectra. The bandgap 1.25 eV calculated from UV-Vis absorption spectrum is very well-acceptable value for the application of the synthesized material. The SEM micrographs illustrate the clusters of particles in micron and submicron range. The formation of agglomerates is also illustrated on the TEM micrographs. Weak ferromagnetic properties of the synthesized nanocrystals were documented.

Abril, 2017 | DOI: 10.1186/s11671-017-2029-5

Structural and catalytic properties of Au/MgO-type catalysts prepared in aqueous or methanol phase: application in the CO oxidation reaction

Hernandez, Willinton Y.; Alic, Funda; Navarro-Jaen, Sara; Centeno, Miguel A.; Vermeir, Pieter; Van der Voort, Pascal; Verberckmoes, An
Journal of Materials Science, 52 (2017) 4727-4741


Au/MgO and Au/Mg(OH)(2)-type catalysts for CO oxidation reaction were prepared by using two different synthesis methods in presence of either an aqueous or methanol phase. The influence of the porous and morphological properties of the starting magnesium oxide supports was analyzed and correlated with the catalytic performances of the final gold-supported catalysts. It was found that the deposition of gold in the presence of methanol as a solvent avoids the total rehydration of the MgO support and maintains the textural and morphological properties of the starting oxides. The support synthesized by a surfactant-assisted hydrothermal route, having a combined meso-macroporous structure (i.e., MgO-P) showed a positive influence on the CO oxidation reaction as it favored the dispersion of gold and the surface-to-gas phase interaction during the catalytic process.

Abril, 2017 | DOI: 10.1007/s10853-016-0715-9

Features of electrical properties of BE-C(Fe) biocarbons carbonized in the presence of an Fe-containing catalyst

Popov, VV; Orlova, TS; Gutierrez-Pardo, A; Ramirez-Rico, J
Physics of the Solid State


The effect of partial graphitization on electrical and galvanomagnetic properties of BE-C(Fe) biomorphic carbons produced by beech wood carbonization at temperatures of 850-1600A degrees C in the presence of an iron-containing catalyst is studied. The use of an Fe catalyst at D cent (carb) ae<yen> 1000A degrees C leads to the formation of nanoscale graphite-phase inclusions; its total volume and nanocrystallite sizes increase with D cent (carb). The data on the carrier concentration and mobility are obtained. It was shown that partially graphitized BE-C(Fe) carbons with D cent (carb) ae<yen> 1000A degrees C in the conductivity type and magnetoresistance features relate to highly disordered metal systems whose conductivity can be described taking into account the contribution of quantum corrections, mainly the correction caused by the electron-electron interaction. It is shown that nonmonotonic dependences of the Hall constant R on the magnetic field are characteristic of BE-C(Fe) samples with 1000 ae<currency> D cent (carb) < 1600A degrees C, which is most probably caused by the contribution of various carrier groups, i.e., electrons and holes. In BE-C(Fe) samples with D cent (carb) = 1600A degrees C, the Hall coefficient corresponds to the metal state, which is associated with conducting medium homogenization resulting from the formation of a significant graphite phase volume.

Abril, 2017 | DOI: 10.1134/S1063783417040205

Mechanochemically Synthesized CuFeSe2 Nanoparticles and Their Properties

Dutkova, E; Skorvanek, I; Sayagues, MJ; Zorkovska, A; Kovac, J; Balaz, P
Acta Physica Polonica A, 131 (2017) 1156-1158


The mechanochemical synthesis of nanocrystalline CuFeSe2 particles prepared by high-energy milling in a planetary mill in an argon atmosphere from copper, iron, and selenium for 60 min is reported for the first time. The CuFeSe2 nanoparticles crystallize in tetragonal structure with mean crystallite size of about 32 +/- 1 nm. High resolution transmission electron microscopy measurements confirmed the presence of agglomerates which are formed by small nanocrystalline domains (5-40 nm). The magnetic data revealed that paramagnetic CuFeSe2 nanoparticles coexist with a small amount of ferromagnetic impurities at room temperature. The magnetic transition towards a weak ferromagnetic or ferrimagnetic behavior occurs in CuFeSe2 at approximately 79 K. The band gap of the CuFeSe2 particles is 0.95 eV which is wider than the band gap in bulk materials (0.16 eV), which could be in many aspects of application more beneficial.

Abril, 2017 | DOI: 10.12693/APhysPolA.131.1156

Diverse Applications of Nanomedicine

Pelaz, Beatriz; Alexiou, Christoph; Alvarez -Puebla, Ramon A.; Alves, Frauke; Andrews, Anne M.; Ashraf, Sumaira; Balogh, Lajos P.; Ballerini, Laura; Bestetti, Alessandra; Brendel, Cornelia; Bosi, Susanna; Carril, Monica; Chan, Warren C. W.; Chen, Chunying
ACS Nano, 11 (2017) 2312-2381


The design and use of materials in the nanoscale size range for addressing medical and health-related issues continues to receive increasing interest. Research in nanomedicine spans a multitude of areas, including drug delivery, vaccine development, antibacterial, diagnosis and imaging tools, wearable devices, implants, high-throughput screening platforms, etc. using biological, nonbiological, biomimetic, or hybrid materials. Many of these developments are starting to be translated into viable clinical products. Here, we provide an overview of recent developments in nanomedicine and highlight the current challenges and upcoming opportunities for the field and translation to the clinic.

Marzo, 2017 | DOI: 10.1021/acsnano.6b06040

Multicolored Emission and Lasing in DCM-Adamantane Plasma Nanocomposite Optical Films

Alcaire, M; Cerdan, L; Zamarro, FL; Aparicio, FJ; Gonzalez, JC; Ferrer, FJ; Borras, A; Espinos, JP; Barranco, A
ACS Applied Materials & Interfaces, 9 (2017) 8948-8959


We present a low-temperature versatile protocol for the fabrication of plasma nanocomposite thin films to act as tunable emitters and optical gain media. The films are obtained by the remote plasma-assisted deposition of a 4-(dicyano-methylene)-2-methy1-6-(4-dimethylamino-styry1)-4Hpyran (DCM) laser dye alongside adamantane. The experimental parameters that determine the concentration of the dye in the films and their optical properties, including light absorption, the refractive index, and luminescence, are evaluated. Amplified spontaneous emission experiments in the DCM/adamantane nano composite waveguides show the improvement of the copolymerized nano composites' properties compared to films that were deposited with DCM as the sole precursor. Moreover, one-dimensional distributed feed-back laser emission is demonstrated and characterized in some of the nanocomposite films that are studied. These results open new paths for the optimization of the optical and lasing properties of plasma nanocomposite polymers, which can be straightforwardly integrated as active components in optoelectronic devices.

Marzo, 2017 | DOI: 10.1021/acsami.7b01534