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Title: Enhanced activity of clays and its crucial role for the activity in ethylene polymerization
Author(s): Camejo-Abreu, C; Tabernero, V; Alba, MD; Cuenca, T; Terreros, P
Source: Journal of Molecular Catalysis A-Chemical, 393 (2014) 96-104
abstract | fulltext

This paper presents a study of the effects of different treatments on the polymerization activity of modified clays as cocatalysts. To achieve this goal, an intercalating cation was introduced into two smectites and these clays were then modified with trimethyl aluminium. The results for ethylene polymerization, when a zirconocene complex was used as catalyst, and the structure analysis, allow us to obtain interesting deductions about the generation mode of the active species. All active materials employed as support activators presented aluminium in a pentahedral environment together with acidic hydrogen atoms. These two features were detected only after TMA treatment and they seem to be crucial elements in active cocatalyst generation. Moreover, a material without structural aluminium displayed the best activity pointing to the new aluminium species generated in the solid matrix as the determining factor for the activity. We proposed a synergic effect between Lewis acid aluminium centres and acidic Bronsted protons that generate the SiOHAl groups that activate the zirconium compound.

October, 2014 | DOI: 10.1016/j.molcata.2014.05.030

Title: Quantification and comparison of the reaction properties of FEBEX and MX-80 clays with saponite: Europium immobilisers under subcritical conditions
Author(s): Villa-Alfageme, M; Hurtado, S; Castro, MA; El Mrabet, S; Orta, MM; Pazos, MC; Alba, MD
Source: Applied Clay Science, 101 (2014) 10-15
abstract | fulltext

The evaluation of the retention mechanisms in FEBEX and MX-80 bentonites, selected as reference materials to construct engineered barriers, carries major implications in the safe storage of immobilisation capacity through a recently discovered chemical retention mechanism and the structural analysis of the reaction products. Hydrothermal treatments were accomplished with immobilisation capacity through a recently discovered chemical retention mechanism and the structural analysis of the reaction products. Hydrothermal treatments were accomplished with Eu(NO3)3 (151Eu and 153Eu, with 52.2% 153Eu) and spiked with radioactive 152Eu for the quantification of the reactions. Results were compared with saponite as the reference smectite. The strong dependence of the reaction parameters with temperature and time was quantified and the reaction velocity was evaluated. The velocity follows these trends: 240 days are needed for the total retention of europium for temperatures over 200 °C; below 150 °C, significantly longer reaction times, on the order of three years, are required to complete the reaction. Clays do not influence velocity rates, but the retention capacity of bentonites remains lower than for saponite. At 300 °C, the milliequivalents retained by the three clays are consistently over CEC. The structural analyses reveal not only adsorption of europium but also the presence of Eu(OH)3 precipitation and Eu2SiO3 confirming the existence of a chemical reaction.

October, 2014 | DOI: 10.1016/j.clay.2014.08.012

Title: Characterization of porous graphitic monoliths from pyrolyzed wood
Author(s): Gutierrez-Pardo, A; Ramirez-Rico, J; de Arellano-Lopez, AR; Martinez-Fernandez, J
Source: Journal of Materials Science, 49 (2014) 7688-7696
abstract | fulltext

Porous graphitic carbons were obtained from wood precursors using Ni as a graphitization catalyst during pyrolysis. The structure of the resulting material retains that of the original wood precursors with highly aligned, hierarchical porosity. Thermal characterization was performed by means of thermogravimetry and differential scanning calorimetry, and the onset temperature for graphitization was determined to be similar to 900 A degrees C. Structural and microstructural characterization was performed by means of electron microscopy, electron and x-ray diffraction, and Raman spectroscopy. The effect of maximum pyrolysis temperature on the degree of graphitization was assessed. No significant temperature effect was detected by means of Raman scattering in the range of 1000-1400 A degrees C, but at temperatures over the melting point of the catalyst, the formation of graphite grains with long-range order was detected.

October, 2014 | DOI: 0.1007/s10853-014-8477-8

Title: Properties of mechanochemically synthesized nanocrystalline Bi2S3 particles
Author(s): Dutkova, E; Sayagues, MJ; Zorkovska, A; Real, C; Balaz, P; Satka, A; Kovac, J
Source: Materials Science in Semiconductor Processing, 27 (2014) 267-272
abstract | fulltext

Nanocrystalline Bi2S3 particles have been synthesized from Bi and S powders by high-energy milling in a planetary mill. Structural and microstructural characterization of the prepared particles, including phase identification, specific surface area measurement and particle size analysis has been carried out. The optical properties were measured by spectroscopic methods and the structural stability up to 500 °C was studied by thermal analysis. The production of orthorhombic Bi2S3 with crystallite size of about 26 nm was confirmed by X-ray diffraction. The nanocrystals tend to agglomerate due to their large specific surface area. Accordingly, the average hydrodynamic diameter of the mechanochemically synthesized particles is 198 nm. EDS analysis shows that the synthesized material is pure Bi2S3. The band gap of the Bi2S3 nanoparticles is 4.5 eV which is wider than that in bulk materials. The nanoparticles exhibit good luminescent properties with a peak centered at 490 and 390 nm. Differential scanning calorimetry curves exhibit a broad exothermic peak between 200 and 300 °C, suggesting recovery processes. This interpretation is supported by X-ray diffraction measurements that indicate a 10-fold increase of the crystallite size to about 230 nm. The controlled mechanochemical synthesis of Bi2S3 nanoparticles at ambient temperature and atmospheric pressure remains a great challenge.

October, 2014 | DOI: 10.1016/j.mssp.2014.05.057

Title: Active Site Considerations on the Photocatalytic H-2 Evolution Performance of Cu-Doped TiO2 Obtained by Different Doping Methods
Author(s): Valero, JM; Obregon, S; Colon, G
Source: ACS Catalysis, 4 (2014) 3320-3329
abstract | fulltext

A photocatalytic H2 evolution reaction was performed over copper doped TiO2. The influence of sulfate pretreatment over fresh TiO2 support and the Cu doping method has been evaluated. Wide structural and surface characterization of catalysts was carried out in order to establish a correlation between the effect of sulfuric acid treatment and the further Cu-TiO2photocatalytic properties. Notably a different copper dispersion and oxidation state is obtained by different metal decoration methods. From the structural and surface analysis of the catalysts we have stated that the occurrence of highly disperse and reducible Cu2+ species is directly related to the photocatalytic activity for the H2 production reaction. Highly active materials have been obtained from a chemical reduction method leading to 18 mmol·h–1·g–1for 3 mol % copper loading.

September, 2014 | DOI: 10.1021/cs500865y

Title: Heterostructured Er3+ doped BiVO4 with exceptional photocatalytic performance by cooperative electronic and luminescence sensitization mechanism
Author(s): Obregon, S; Colon, G
Source: Applied Catalysis B: Environmental, 158-159 (2014) 242-249
abstract | fulltext

Er-BiVO4 has been synthesized by means of mw-assisted hydrothermal method having good photoactivity under sun-like excitation. It is stated that the precursor addition sequence plays a critical role which determine the further structural feature of BiVO4. From the structural and morphological characterization, it can be demonstrated that the presence of Er3+ would induce the stabilization of the tetragonal phase probably due to the formation of tetragonal-ErVO4 seeds previous to BiVO4 formation. The best photocatalytic performance is attained for the sample with 0.75 at% Er3+ content. At this dopant loading a mixture of tetragonal and monoclinic phase (70% tetragonal) is obtained. The dramatic increase in the photocatalytic activity for 0.75 at% Er-BiVO4 is related to the occurrence of such heterostructure. For this system, the MB degradation rate constant appears drastically higher as bare m-BiVO4. Furthermore, activities of photocatalysts for visible-light-driven O2 evolution have been evaluated, demonstrating that the photocatalytic activity of this Er-doped system (O2 evolution rate, 1014 μmol g−1 h−1) is 20 times as that of undoped m-BiVO4 (O2 evolution rate, 54 μmol g−1 h−1). From the obtained results, the cooperative conjunction of electronic and luminescence mechanism involved in the reaction is proposed to be the origin of the enhanced photocatalytic efficiencies of such systems.

September, 2014 | DOI: 10.1016/j.apcatb.2014.04.029

Title: Supported Co catalysts prepared as thin films by magnetron sputtering for sodium borohydride and ammonia borane hydrolysis
Author(s): Paladini, M; Arzac, GM; Godinho, V; De Haro, MCJ; Fernandez, A
Source: Applied Catalysis B: Environmental, 158-159 (2014) 400-409
abstract | fulltext

Supported Co catalysts were prepared for sodium borohydride and ammonia borane hydrolysis by magnetron sputtering for the first time under different conditions. Ni foam was selected as support. Deposition conditions (time, pressure, and power) were varied to improve catalytic activity. A decrease in deposition power from 200 to 50 W, leads to a decrease in crystallite and column size and a higher activity of catalysts. The increase in deposition pressure from 1.5 × 10−2 to 4.5 × 10−2 mbar produces same effect but in this case the enhancement in activity is higher because amorphous materials were obtained. The highest activity for SB hydrolysis was 2650 ml min−1 gcat−1 for the 50 W Co 4.5 (4 h) sample (Ea = 60 ± 2 kJ mol−1). For AB hydrolysis activity for the 50 W Co 3.2 (4 h) sample was similar. Durability of the thin films was tested for both reactions upon cycling (14 cycles). Diluted acid washing was effective to recover the activity for sodium borohydride reaction but not for ammonia borane hydrolysis. The strong Co–NH3 interactions explain the non-efficiency of the acid washing.

September, 2014 | DOI: 10.1016/j.apcatb.2014.04.047

Title: Shape-defined nanodimers by tailored heterometallic epitaxy
Author(s): Garcia-Negrete, Carlos A; Rojas, Teresa C; Knappett, Benjamin R; Jefferson, David A; Wheatley, Andrew E H; Fernandez, Asuncion
Source: Nanoscale, 6 (2014) 11090-11097
abstract | fulltext

The systematic construction of heterogeneous nanoparticles composed of two distinct metal domains (Au and Pt) and exhibiting a broad range of morphologically defined shapes is reported. It is demonstrated that careful Au overgrowth on Pt nanocrystal seeds with shapes mainly corresponding to cubeoctahedra, octahedra and octapods can lead to heterometallic systems whose intrinsic structures result from specific epitaxial relationships such as {111} + {111}, {200} + {200} and {220} + {220}. Comprehensive analysis shows also that nanoparticles grown from octahedral seeds can be seen as comprising of four Au tetrahedral subunits and one Pt octahedral unit in a cyclic arrangement that is similar to the corresponding one in decahedral gold nanoparticles. However, in the present case, the multi-component system is characterized by a broken five-fold rotational symmetry about the [011] axis. This set of bimetallic dimers could provide new platforms for fuel cell catalysts and plasmonic devices.

September, 2014 | DOI: 10.1039/C4NR01815J

Title: The Mitigation Effect of Synthetic Polymers on Initiation Reactivity of CL-20: Physical Models and Chemical Pathways of Thermolysis
Author(s): Yan, QL; Zeman, S; Jimenez, PES; Zhang, TL; Perez-Maqueda, LA; Elbeih, A
Source: Journal of Physical Chemistry C, 118 (2014) 22881-22895
abstract | fulltext

In this paper, the thermal decomposition physical models of different CL-20 polymorph crystals and their polymer bonded explosives (PBXs) bonded by polymeric matrices using polyisobutylene (PIB), acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), Viton A, and Fluorel binders are obtained and used to predict the temperature profiles of constant rate decomposition. The physical models are further supported by the detailed decomposition pathways simulated by a reactive molecular dynamics (ReaxFF-lg) code. It has been shown that both ε-CL-20 and α-CL-20 decompose in the form of γ-CL-20, resulting in close activation energy (169 kJ mol–1) and physical model (first-order autoaccelerated model, AC1). Fluoropolymers could change the decomposition mechanism of ε-CL-20 from the “first-order autocatalytic” model to a “three-dimensional nucleation and growth” model (A3), while the polymer matrices of Formex P1, Semtex, and C4 could change ε-CL-20 decomposition from a single-step process to a multistep one with different activation energies and physical models. Compared to fluoropolymers, PIB, SBR and NBR may make ε-CL-20 undergo more complete N–NO2 scission before collapse of the cage structure. This is likely the main reason why those polymer bases could greatly mitigate the decomposition process of ε-CL-20 from a single step to a multistep, resulting in lower impact sensitivity, whereas fluoropolymers have only a little effect on that. For ε-CL-20 and its PBXs, the impact sensitivity depends not only on the heat built-up period of their decomposition, but also on the probability of hotspot generation (defects in solid crystals and interfaces) especially when it decomposes in a solid state.

September, 2014 | DOI: 10.1021/jp505955n

Title: Single phase, electrically insulating, multiferroic La-substituted BiFeO3 prepared by mechanosynthesis
Author(s): Perejon, A; Sanchez-Jimenez, PE; Perez-Maqueda, LA; Criado, JM; de Paz, JR; Saez-Puche, R; Maso, N; West, AR
Source: Journal of Materials Chemistry C, 2 (2014) 8398-8411
abstract | fulltext

Single phase, electrically insulating samples of Bi1−xLaxFeO3 solid solutions have been prepared by mechanosynthesis over the whole compositional range for the first time. Lanthanum substitution influenced the kinetics of the mechanochemical reaction and crystallite size of the products. For 0 ≤ x ≤ 0.15, an increase in the La content produced a significant decrease in the weight-normalized cumulative kinetic energy required to obtain the final product and an increase in the resulting crystallite size. Larger La contents did not affect either the reactivity or the crystallite size. The effect of x on the structure has been identified. Samples in the ranges x ≤ 0.15 and x ≥ 0.45 gave single phase solid solutions with R3c and Pnma space groups, respectively, while for the intermediate range, a non-centrosymetric Pn21a(00γ)s00 super structure was obtained. For 0 ≤ x ≤ 0.30, differential scanning calorimetry showed two endothermic effects corresponding to the Néel temperature (TN, antiferromagnetic–paramagnetic transition) and the Curie temperature (TC, ferroelectric–paraelectric transition), demonstrating their multiferroic character. Compositions with a larger La content only showedTN. Dilatometric and permittivity measurements confirmed the results obtained by DSC for the ferroelectric–paraelectric transition. The composition dependence of TN and TC showed that, at low x, TN < TC, but a cross-over, or isoferroic transition occurred at x [[similar]] 0.28, when TN = TC = 386 °C. Ceramics with 0 ≤ x ≤ 0.15 were highly insulating at room temperature with a resistivity, extrapolated from the Arrhenius plots, of [[similar]] 7 × 1016 to 8 × 1014 Ω cm and an activation energy [[similar]] 1.14–1.20 eV. Magnetization of the samples improved with La substitution.

September, 2014 | DOI: 10.1039/C4TC01426J