Novel nitrogen plasma doping on CdS/GO compounds and their photocatalytic assessment.

Nitrogen-doping of cadmium sulfide nanostructured compounds was carried out under a nitrogen plasma source to produce CdS-N compounds. Once prepared, it was supported on graphene oxide sheets for producing CdS-N/GO photocatalysts, which were tested in the degradation of lignin and methylene blue (MB) molecules. Photocatalytic reactions were carried out under UV and visible (vis) energy irradiation. To provide insight on the catalytic behavior the CdS, CdS-N, GO, and CdS-N/GO compounds were characterized using different techniques including x-ray diffraction, scanning electron microscopy, Raman, and UV-vis diffuse reflectance spectroscopy. X-ray photoelectron spectroscopy allowed determining the chemical composition in samples. It was observed an outstanding performance in photocatalytic activity tests, attributed to the extended response towards the visible light regime, and the synergistic effect between CdS-N and GO particles. The catalytic activity tests, reveal that the CdS-N/GO compound achieved over 90% lignin degradation and 100% of MB degradation. In addition, a remarkable performance is observed in the CdS-N/GO compound which exhibited stability after performing several reaction cycles.

Columnar nitrogen-doped ZnO nanostructured thin films obtained through atomic layer deposition.

The present study was aimed to develop nitrogen-doped nanostructured ZnO thin films. These films were produced in a sequential procedure involving the atomic layer deposition technique, and a hydrothermal process supported by microwave heating. Employing the atomic layer deposition technique, through self-limited reactions of diethylzinc (DEZn) and H2O, carried out at 3.29 × 10-4atm and 190 °C, a high-quality ZnO seed was grown on a Si (100) substrate, producing a textured film. In a second stage, columnar ZnO nanostructures were grown perpendicularly oriented to the silicon substrate on those films, using a solvothermal process in a microwave heating facility, employing Zn(NO3)2as zinc precursor, while hexamethylenetetramine (HMTA) was used to produce the bridging of Zn2+ions. The consequence of N-doping concentration on the physicochemical properties of ZnO thin films was studied. The manufactured films were structurally analyzed by scanning electron microscopy and x-ray diffraction. Also, x-ray photoelectron spectroscopy, Raman, and UV-vis spectroscopies were used to provide further insight on the effect of nitrogen doping. The N-doped films displayed textured wurtzite-like structures that changes their preferential growth from the (002) to the (100) crystallographic plane, apparently promoted by the increase of nitrogen precursor. It is also shown that nitrogen-doped films undergo a reduction in their bandgap, compared to ZnO. The methodology presented here provides a viable way to perform high-quality N-ZnO nanostructured thin films.

Ce, Eu incorporation through doping of ALD-ZnO thin films for enhancing their photoluminescent properties.

Nanostructured ZnO nanoarrays deposited on silicon oriented substrates is a very promising area in the study of the control of physicochemical properties, in which photoluminescence plays a crucial role. This optical property inherent to ZnO, can be favorably modified through the inclusion of doping elements, with the purpose of appropriately modifying their optical absorption and luminescence. Following this objective, in the present work we present the development of Zn(1-x-y)Ce(x)Eu(y)O nanostructured thin films. The samples were produced in two steps process by atomic layer deposition technique followed by a solvothermal synthesis. The purpose of Cerium and Europium incorporation into the ZnO compound is to enhance the photoluminescence in ZnO thin films. In a first stage textured thin films were obtained from diethylzinc at a temperature of 190 °C and a pressure of 3.29 × 10-4 atm, on silicon substrates (111). Subsequently, the perpendicular growth of nanostructures was induced under a solvothermal process, where Zn(NO3)2 was used as Zn precursor and hexamethylene-tetramine operating as a dual-ligand to promote the linking of Zn2+ ions. The growth of cerium-europium ZnO nanostructures was promoted with Ce(C2H3O2)3·H2O and Eu(NO3)3·5H2O. The obtained Zn(1-x-y)Ce(x)Eu(y)O nanostructured thin films, were examined through SEM-microscopy, x-ray diffraction, x-ray photoelectron spectroscopy and photoluminescence studies. The attained results show that it is feasible to produce Ce-Eu-doped ZnO nanostructures with tailored photoluminescence and crystal size. Interestingly the Ce-Eu doping induces a strong shift in comparison to the typical UV emission of ZnO; an effect that can be related with the increase of lattice defects in ZnO.

"Tailoring the TiO2 phases through microwave-assisted hydrothermal synthesis: Comparative assessment of bactericidal activity".

Nanocrystalline titania (TiO2) is one of the most investigated crystalline nanostructured systems in the field of materials science. The technological applications of this material are related to its optoelectronic and photocatalytic properties, which in turn are strongly dependent on the crystal phase (i.e., anatase, brookite, and rutile), particle size, and surface structure. However, systematic comparative studies of all its crystal phases are scarce in literature due to difficulties in providing a controlled synthesis, which is primarily important in obtaining the brookite phase. In this report, the synthesis of TiO2 nanoparticles in the anatase, brookite, and rutile structures was explored, using amorphous TiO2 as a common precursor under microwave-assisted hydrothermal conditions. The influence of parameters such as temperature, acidity, and precursor concentration on phase crystallization were investigated. The TiO2 materials (amorphous and crystalline phases as well as commercial Degussa P25) were systematically characterized using Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, UV-visible reflectance spectroscopy, and dynamic and electrophoretic light scattering. The bactericidal activity and photocatalytic antibacterial effectiveness of each material were evaluated through the determination of the minimum inhibitory and bactericidal concentrations, and via the mortality kinetic method under ultraviolet (UV) illumination under similar conditions with two bacterial groups of unique cellular structures: Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus). The results are discussed with particular emphasis on the relationship between the synthesis parameters (acidity, precursor concentration, temperature and reaction time) and the bactericidal properties.

Determination of the nonradiative conversion efficiency of lead mixed-halide perovskites using optical and photothermal spectroscopy.

Mixed-halide organic-inorganic hybrid perovskites are considered promising light-absorbing materials in the development of solar cells related to the obtained high-power conversion efficiency. Current efforts are focused on the study of the energy-conversion mechanisms, where the nonradiative recombination pathway is the least explored. In this work, a combination of optical and photoacoustic spectroscopies is used to determine the visible spectral light-into-heat conversion efficiency of lead-based mixed-halide organic-inorganic hybrid perovskites in a semicomplete n-i-p mesoscopic perovskite solar cell (PSC). A remarkable average conversion efficiency of about 87% has been found for the nonradiative combination in the perovskite, with the estimated composition ${{\rm FA}_{0.71}}{{\rm MA}_{0.29}}{{\rm PbI}_{2.9}}{{\rm Br}_{0.1}}$FA0.71MA0.29PbI2.9Br0.1 in the wavelength range of 400 to 800 nm. As a result, 13% of the incident light is transformed in radiative recombination processes and/or photodegradation of the material. Furthermore, the extinction coefficient and refractive index of the material are reported, and it was found that the optical constants and the optical absorption in the short-wavelength range are significantly smaller than previously reported for${{\rm MAPbI}_3}$MAPbI3.

Measurement of the hysteretic thermal properties of W-doped and undoped nanocrystalline powders of VO2.

Hysteresis loops exhibited by the thermal properties of undoped and 0.8 at.% W-doped nanocrystalline powders of VO2 synthesized by means of the solution combustion method and compacted in pellets, are experimentally measured by photothermal radiometry. It is shown that: (i) the W doping reduces both the hysteresis loops of VO2 and its transition temperature up to 15 °C. (ii) The thermal diffusivity decreases (increases) until (after) the metallic domains become dominant in the VO2 insulating matrix, such that its variation across the metal-insulation transition is enhanced by 23.5% with W-0.8 at.% doping. By contrast, thermal conductivity (thermal effusivity) increases up to 45% (40%) as the metallic phase emerges in the VO2 structure due to the insulator-to-metal transition, and it enhances up to 11% (25%) in the insulator state when the local rutile phase is induced by the tungsten doping. (iii) The characteristic peak of the VO2 specific heat capacity is observed in both heating and cooling processes, such that the phase transition of the 0.8 at.% W-doped sample requires about 24% less thermal energy than the undoped one. (iv) The impact of the W doping on the four above-mentioned thermal properties of VO2 mainly shows up in its insulator phase, as a result of the distortion of the local lattice induced by the electrons of tungsten. W doping at 0.8 at.% thus enhances the VO2 capability to transport heat but diminishes its thermal switching efficiency.

Photocatalytic performance of nitrogen doped ZnO structures supported on graphene oxide for MB degradation.

In the present work, the photocatalytic efficiency of a novel system based on ZnO doped with nitrogen (ZT) and supported on graphene oxide (GO) is investigated. ZnO synthesis and their N doping were carried out in a microwave reactor using thiourea as nitrogen source, while the GO was prepared through a variation of the Hummers' method. Structural, morphological and photochemical characterization of the developed material was performed by X-ray diffraction (XRD), UV-Vis spectroscopy, energy dispersive spectroscopy (EDS), scanning electron microscopy (SEM), analysis by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The compounds were used to photodegrade the methylene blue molecule, which confirms the efficiency of nitrogen doped supported system compared to pristine ZnO. The degradation percentage of MB under UV energy using nitrogen-doped ZnO/GO, in a time of 35 min, reached 98% degradation; while using visible light 93% of degradation was reached.

Thermal hysteresis measurement of the VO2 emissivity and its application in thermal rectification.

Hysteresis loops in the emissivity of VO2 thin films grown on sapphire and silicon substrates by a pulsed laser deposition process are experimentally measured through the thermal-wave resonant cavity technique. Remarkable variations of about 43% are observed in the emissivity of both VO2 films, within their insulator-to-metal and metal-to-insulator transitions. It is shown that: i) The principal hysteresis width (maximum slope) in the VO2 emissivity of the VO2 + silicon sample is around 3 times higher (lower) than the corresponding one of the VO2 + sapphire sample. VO2 synthesized on silicon thus exhibits a wider principal hysteresis loop with slower MIT than VO2 on sapphire, as a result of the significant differences on the VO2 film microstructures induced by the silicon or sapphire substrates. ii) The hysteresis width along with the rate of change of the VO2 emissivity in a VO2 + substrate sample can be tuned with its secondary hysteresis loop. iii) VO2 samples can be used to build a radiative thermal diode able to operate with a rectification factor as high as 87%, when the temperature difference of its two terminals is around 17 °C. This record-breaking rectification constitutes the highest one reported in literature, for a relatively small temperature change of diode terminals.

Laser-induced transient grating setup with continuously tunable period.

We present a modification of the laser-induced transient grating setup enabling continuous tuning of the transient grating period. The fine control of the period is accomplished by varying the angle of the diffraction grating used to split excitation and probe beams. The setup has been tested by measuring dispersion of bulk and surface acoustic waves in both transmission and reflection geometries. The presented modification is fully compatible with optical heterodyne detection and can be easily implemented in any transient grating setup.

Thermal characterization of magnetically aligned carbonyl iron/agar composites.

Composites of magnetic particles into polymeric matrices have received increasing research interest due to their capacity to respond to external magnetic or electromagnetic fields. In this study, agar from Gelidium robustum has been chosen as natural biocompatible polymer to build the matrix of the magnetic carbonyl iron particles (CIP) for their uses in biomedical fields. Heat transfer behavior of the CIP-agar composites containing different concentrations (5, 10, 15, 20, 25 and 30% w/w) of magnetically aligned and non-aligned CIP in the agar matrix was studied using photothermal radiometry (PTR) in the back-propagation emission configuration. The morphology of the CIP-agar composites with aligned and non-aligned CIP under magnetic field was also evaluated by scanning electron microscopy (SEM). The results revealed a dominant effect of CIP concentration over the alignment patterns induced by the magnetic field, which agrees with the behavior of the thermal diffusivity and thermal conductivity. Agar served as a perfect matrix to be used with CIP, and CIP-agar composites magnetically aligned at 20% CIP concentration can be considered as promising 'smart' material for hyperthermia treatments in the biomedical field.

Photothermal model fitting in the complex plane for thermal properties determination in solids.

Thermal properties of solids are obtained by fitting the exact complex photothermal model to the normalized photoacoustic (PA) signal in the front configuration. Simple closed-form expressions for the amplitude and phase are presented in all frequency ranges. In photoacoustic it has been common practice to assume that all the absorptions of radiation take place in the sample. However, in order to obtain the accurate thermal properties it is necessary to consider the PA signal contributions produced at the cell walls. Such contributions were considered in our study. To demonstrate the usefulness of the proposed methodology, commercial stainless steel layers AISI 302 were analyzed. It is shown that using our approach the obtained thermal diffusivity and effusivity were in good agreement with those reported in the literature. Also, a detailed procedure for the calculation of the standard error in the thermal properties is discussed.

Nanoindentation characterization of the micro-lamellar arrangement of black coral skeleton.

Black corals (antipatharians) are colonial cnidarians whose branched tree-like skeleton is mostly constituted of chitin fibrils inside a lipoproteic matrix. The skeleton exhibits growth rings formed by chitin layers (micro-lamellae). In order to know the effect of the arrangement microlamellae of chitin of black corals and to improve the understanding of the role of chitin structure in the antipatharian skeleton, the mechanical properties of the skeleton of two black corals, Antipathes caribbeana and Antipathes pennacea, were examined using nanoindentation tests. Measurements of reduced elastic modulus, nanohardness and the viscoelastic behavior were measured with a spheroconical indenter. The results indicate variations in the values of the mechanical properties clearly associated with different structures present in the skeletons, the core being the one that invariably shows the maximum values. The solid multilamellar arrangement of black coral chitin, its viscoelastic behavior, and the anisotropic mechanical response, are relevant factors contributing to the successful adaptation of black coral colonies to shallow as well as to very deep waters.