Structural and optical properties of ZnS/MgNb2O6 heterostructures

In this letter, we report a simple and efficient synthetic procedure where the first step is a coprecipitation/calcination method used to obtain magnesium niobate MgNb2O6(MN) nanocrystals and in the second stage a microwave assisted hydrothermal method (MAH) is employed to synthesize zinc sulfide (ZnS) nanocrystals and ZnS/MN heterostructures. These heterostructures were characterized by X-ray diffraction (XRD), micro-Raman (MR) spectroscopy, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), high-resolution TEM (HR-TEM), selected area electron diffraction (SAED), energy dispersive X-ray spectrometry (EDX). XRD patterns and MR spectra indicate that MN and ZnS nanocrystals have an orthorhombic and cubic structure, respectively. FE-SEM, TEM and HR-TEM images proved the presence of aggregated MN nanocrystals, ZnS nanocrystals and the presence of ZnS nanocrystals on the surface of MN nanocrystals. Their optical properties were investigated by ultraviolet–visible spectroscopy (UV–vis) and photoluminescence (PL) measurements at room temperature. ZnS/MN heterostructures show a decrease in the values for the optical band gap with respect to both components. The presence of the ZnS nanocrystals in this heterostructure promotes a high intense PL emission

In situ growth of Ag nanoparticles on alpha-Ag2WO4 under electron irradiation: probing the physical principles

Exploiting the plasmonic behavior of Ag nanoparticles grown on α-Ag2WO4 is a widely employed strategy to produce efficient photocatalysts, ozone sensors, and bactericides. However, a description of the atomic and electronic structure of the semiconductor sites irradiated by electrons is still not available. Such a description is of great importance to understand the mechanisms underlying these physical processes and to improve the design of silver nanoparticles to enhance their activities. Motivated by this, we studied the growth of silver nanoparticles to investigate this novel class of phenomena using both transmission electron microscopy and field emission scanning electron microscopy. A theoretical framework based on density functional theory calculations (DFT), together with experimental analysis and measurements, were developed to examine the changes in the local geometrical and electronic structure of the materials. The physical principles for the formation of Ag nanoparticles on α-Ag2WO4 by electron beam irradiation are described. Quantum mechanical calculations based on DFT show that the (001) of α-Ag2WO4 displays Ag atoms with different coordination numbers. Some of them are able to diffuse out of the surface with a very low energy barrier (less than 0.1 eV), thus, initiating the growth of metallic Ag nanostructures and leaving Ag vacancies in the bulk material. These processes increase the structural disorder of α-Ag2WO4 as well as its electrical resistance as observed in the experimental measurements.The authors are grateful to Generalitat Valenciana (Spain) for PrometeoII/2014/022 and ACOMP/2014/270 projects, Ministerio de Economia y Competitividad (Spain), CTQ2012-36253-C03-02, and to the Spanish Brazilian Program (PHB2009-0065-PC), CAPES (203038 009607/2013- 56 088/2013), INCTMN (2008/57872-1), FAPESP (2013/ 07296-2; 2012/14468-1; 2010/16970-0) and CNPq (147001/2013-7; 573636/2008-7) for financially supporting this research. Most of the calculations were performed using IFGW-UNICAMP computer facilities and the National Center for High Performance Computing in São Paulo (CENAPAD- SP)

Identifying and rationalizing the morphological, structural, and optical properties of β-Ag2MoO4 microcrystals, and the formation process of Ag nanoparticles on their surfaces: combining experimental data and first-principles calculations

We present a combined theoretical and experimental study on the morphological, structural, and optical properties of β-Ag2MoO4 microcrystals. β-Ag2MoO4 samples were prepared by a co-precipitation method. The nucleation and formation of Ag nanoparticles on β-Ag2MoO4 during electron beam irradiation were also analyzed as a function of electron beam dose. These events were directly monitored in real-time using in situ field emission scanning electron microscopy (FE-SEM). The thermodynamic equilibrium shape of the β-Ag2MoO4 crystals was built with low-index surfaces (001), (011), and (111) through a Wulff construction. This shape suggests that the (011) face is the dominating surface in the ideal morphology. A significant increase in the values of the surface energy for the (011) face versus those of the other surfaces was observed, which allowed us to find agreement between the experimental and theoretical morphologies. Our investigation of the different morphologies and structures of the β-Ag2MoO4 crystals provided insight into how the crystal morphology can be controlled so that the surface chemistry of β-Ag2MoO4 can be tuned for specific applications. The presence of structural disorder in the tetrahedral [MoO4] and octahedral [AgO6] clusters, the building blocks of β-Ag2MoO4, was used to explain the experimentally measured optical properties

Mn+Sb2O3 thermite/intermetallic delay compositions

The binary Mn + Sb2O3 pyrotechnic composition was investigated for mining detonator time delay applications. EKVI thermodynamic modelling predicted two maxima in the adiabatic reaction temperature. The local maximum, at a manganese fuel content of ca. 36 wt-%, corresponds to a pure thermite-type redox reaction: 3Mn + Sb2O3 3MnO + 2Sb. The overall maximum in the adiabatic reaction temperature (ca. 1640 K), at the fuel-rich composition of 49 wt-% Mn, is consistent with the reaction 5Mn + Sb2O3 3MnO + 2MnSb, i.e. a combination of the standard thermite with an additional exothermic intermetallic reaction. XRD analysis of combustion residues confirmed the formation of MnSb and Mn2Sb for fuel-rich compositions. Burn rates were measured using delay elements assembled into commercial detonators. The d50 particle sizes were 23.4 and 0.92 m for the Mn fuel and Sb2O3 oxidant powders respectively. The delay elements comprised rolled lead tubes with a length of 44 mm and an outer diameter of 6.4 mm. The rolling action compacted the pyrotechnic compositions to 74 2 % theoretical maximum density. The burning rate increased linearly from 4.2 to 9.4 mm s1 over the composition range 25 - 50 wt-% Mn.Financial support from AEL Mining Services and the THRIP programme of the Department of Trade and Industry and the National Research Foundation.http://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1521-40872017-10-31hb2016Chemical Engineerin

Facet-dependent photocatalytic and antibacterial properties of a-Ag2WO4 crystals: combining experimental data and theoretical insights

In this paper, we have combined the various experimental results and first-principles calculations with a new and interesting discussion to explain the photocatalytic and antibacterial activities of α-Ag2WO4 crystals, which were obtained using the microwave-hydrothermal (MH) method with anionic surfactants. The advantages of the insights gained through the present work are two-fold. First, the mechanism and origin of the photocatalytic and antibacterial activities can be rationalized. Second, this facile and controllable synthetic method is expected to encourage the synthesis of complex metal oxides with specific active facets, and these insights can contribute to the rational design of new materials for multifunctional applications. X-ray diffraction and Rietveld refinement analysis confirmed that all the crystals have an orthorhombic structure without deleterious phases. Ultraviolet–visible diffuse reflectance spectroscopy indicated the presence of intermediary energy levels and a variation in the optical band gap values (3.09–3.14 eV) with the crystal growth process. The geometry, electronic properties of the bulk, and surface energies of these crystals were evaluated using first-principles quantum mechanical calculations based on the density functional theory. The crystal shapes was experimentally and theoretically modeled based on Rietveld refinement data, emission scanning electron microscopy images, and Wulff construction. To obtain a wide variety of crystal shapes, the morphologies were gradually varied by tuning the surface chemistry, i.e., the relative stability of the faceted crystals. The growth mechanisms of different α-Ag2WO4 crystals and their facet-dependent photocatalytic and antibacterial performances were explored in details. The combination of experimental and theoretical data revealed the presence of (110) and (011) planes with high surface energies together with the disappearance of faces related to the (010)/(0[1 with combining macron]0) planes in α-Ag2WO4 crystals are key factors that can rationalize both the photocatalytic and antibacterial activities. The different activities may be attributed to the different number of unsaturated superficial Ag and W atoms capable of forming the main active adsorption sites. Finally, we discuss how knowledge of surface-specific properties can be utilized to design a number of crystal morphologies that may offer improved performance in various applications.The authors acknowledge the financial support of the following Brazilian research funding institutions: the Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP; 2012/14004-5 and 2013/07296-2), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq; 479644/2012-8 and 304531/2013-8) and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES). J.A. and L.G. are grateful to Prometeo/2009/053 (GeneralitatValenciana), Ministerio de Economia y Competitividad (Spain; CTQ2012-36253-C03-02), and the Spanish Brazilian program (PHB2009-0065-PC). We also acknowledge the Servei Informática, Universitat Jaume I for the generous allotment of computer time

Intercalibration of the barrel electromagnetic calorimeter of the CMS experiment at start-up

Calibration of the relative response of the individual channels of the barrel electromagnetic calorimeter of the CMS detector was accomplished, before installation, with cosmic ray muons and test beams. One fourth of the calorimeter was exposed to a beam of high energy electrons and the relative calibration of the channels, the intercalibration, was found to be reproducible to a precision of about 0.3%. Additionally, data were collected with cosmic rays for the entire ECAL barrel during the commissioning phase. By comparing the intercalibration constants obtained with the electron beam data with those from the cosmic ray data, it is demonstrated that the latter provide an intercalibration precision of 1.5% over most of the barrel ECAL. The best intercalibration precision is expected to come from the analysis of events collected in situ during the LHC operation. Using data collected with both electrons and pion beams, several aspects of the intercalibration procedures based on electrons or neutral pions were investigated

Allergic conditions and risk of hematological malignancies in adults: a cohort study

BACKGROUND: Two contradictory hypotheses have been proposed to explain the relationship between allergic conditions and malignancies, the immune surveillance hypothesis and the antigenic stimulation hypothesis. The former advocates that allergic conditions may be protective against development of cancer, whereas the latter proposes an increased risk. This relationship has been studied in several case-control studies, but only in a few cohort studies. METHODS: The association between allergic conditions and risk of developing leukemia, Hodgkin's disease, non-Hodgkin's lymphoma and myeloma was investigated in a cohort of 16,539 Swedish twins born 1886–1925. Prospectively collected, self-reported information about allergic conditions such as asthma, hay fever or eczema was obtained through questionnaires administered in 1967. The cohort was followed 1969–99 and cancer incidence was ascertained from the Swedish Cancer Registry. RESULTS: Hives and asthma tended to increase the risk of leukemia (relative risk [RR] = 2.1, 95% Confidence Interval [CI] 1.0–4.5 and RR = 1.6, 95% CI 0.8–3.5, respectively). There was also an indication of an increased risk of non-Hodgkin's lymphoma associated with eczema during childhood (RR = 2.3, 95% CI 1.0–5.3). CONCLUSION: In contrast to most previous studies, our results do not indicate a protective effect of allergic conditions on the risk of developing hematological malignancies. Rather, they suggest that allergic conditions might increase the risk of some hematological malignancies