Presence Of Crystalline Defects Research Articles

Beyond surface: Correlating CuI /CuII and O-vacancy surface sites in CuxO nanocubes with their activities as noble metal-free anodes for fuel cells

Nanocrystals' surface area and shape significantly impact their activities in fuel cells. On the other hand, additional parameters that may affect their activities cannot be neglected. Here, we demonstrate that the presence of crystalline defects (such as oxygen vacancies) and the relative concentration of CuI/CuII may also vary with the decrease of CuxO nanocubes sizes, contributing to the observed activities as noble metal-free anodes for methanol fuel cells. However, such differences did not follow the size as expected, showing that this parameter does not play a critical role in determining materials' properties. To this end, CuxO nanocubes having controllable sizes (50, 65, and 85 nm) were synthesized by a simple and similar protocol, leading to nanocrystals enclosed by {100} surfaces. When the catalytic activity of the different-sized CuxO nanocubes was performed toward the electrooxidation of methanol in alkaline media, the observed performances decreased as follows: 50 nm > 85 nm > 65 nm-CuxO nanocubes, in which 50 nm-CuxO nanocubes led to the best electrocatalytic results. Interestingly, our results showed that the differences in the catalytic activities of CuxO nanocubes displaying different sizes could not only be assigned to a gain of surface area with a decrease in particle size. More specifically, XPS results indicated that the reduction of particle size led to an increase in both Os/OL and Cu(I)/Cu(II) ratios, demonstrating the enrichment of oxygen vacancies at the surface of CuxO nanocubes, which also contributed for the observed catalytic activities.

Systematic Structural and Optical Characterization of TiO2 Nanofibres Synthesised by Electrospinning

TiO2 nanofibres were synthesised by means of the electrospinning technique, which were annealed at high temperatures to achieve the crystalline phase transformation. The chemical stoichiometry of electrospun TiO2 nanofibres was estimated by EDS, finding that at low annealing temperatures excess of oxygen was detected and at high temperatures excess of titanium that originates oxygen vacancies. TEM images show clearly the formation of TiO2 nanofibres that exhibit a homogeneous and continuous aspect without the presence of crystalline defects, whose surface morphology depends strongly on the annealing temperature. The crystalline phase transformation was studied by Raman spectroscopy, which revealed that annealed TiO2 nanofibres showed a crystalline phase transformation from pure anatase to, first a mix of anatase-rutile, then pure rutile as the annealing temperature increased, which was corroborated by X-ray diffraction and high-resolution TEM microscopy. The average grain size, inside the nanofibres, increased with the crystalline phase transformation from 10 to 24 nm for anatase-TiO2 and from 30 to 47 nm for rutile-TiO2, estimated by using the Scherrer-Debye equation. The band gap energy (Eg), obtained from optical absorption spectra, decreases monotonically, where a local minimum is observed at 700 °C, which is ranged in 3.75  Eg  2.42 eV, caused by the anatase → rutile crystalline phase transformation. The photoluminescence shows that radiative bands present a gradual red-shift as the annealing temperature increases due to the continuous change of Eg.

Systematic Structural and Optical Characterization of TiO2 Nanofibers Synthesised by Electrospinning

TiO2 nanofibers were synthesised by means of the electrospinning technique, which were annealed at high temperatures to achieve the crystalline phase transformation. The chemical stoichiometry of electrospun TiO2 nanofibers was estimated by EDS, finding that at low annealing temperatures excess of oxygen was detected and at high temperatures excess of titanium that originates oxygen vacancies. TEM images show clearly the formation of TiO2 nanofibers (NF’s) that exhibit a homogeneous and continuous aspect without the presence of crystalline defects, whose surface morphology depends strongly on the annealing temperature. The crystalline phase transformation was studied by Raman spectroscopy, which revealed that annealed TiO2 NF’s showed a crystalline phase transformation from pure anatase to, first a mix of anatase-rutile, then pure rutile as the annealing temperature increased, which was corroborated by X-ray diffraction and high-resolution TEM diffraction. The average grain size, inside the NF´s, increased with the crystalline phase transformation from 10 to 24 nm for anatase-TiO2 and from 30 to 47 nm for rutile-TiO2, estimated by using the Scherrer-Debye equation. The band gap energy (Eg), obtained from optical absorption spectra, decreases monotonically, where a local minimum is observed at 700 °C ranged in 3.75 ≤ Eg ≤ 2.42 eV, caused by the anatase → rutile crystalline phase transformation. The photoluminescence shows that radiative bands show a gradual red-shift as the temperature increases due to the continuous change of Eg.

Pressure-induced phase transition and fracture in α-MoO3 nanoribbons

MoO3 nanoribbons were studied under different pressure conditions ranging from 0 to 21GPa at room temperature. The effect of the applied pressure on the spectroscopic and morphologic properties of the MoO3 nanoribbons was investigated by means of Raman spectroscopy and scanning electron microscopy techniques. The pressure dependent Raman spectra of the MoO3 nanoribbons indicate that a structural phase transition occurs at 5GPa from the orthorhombic α-MoO3 phase (Pbnm) to the monoclinic MoO3-II phase (P21/m), which remains stable up to 21GPa. Such phase transformation occurs at considerably lower pressure than the critical pressure for α-MoO3 microcrystals (12GPa). We suggested that the applanate morphology combined with the presence of crystalline defects in the sample play an important role in the phase transition of the MoO3 nanoribbons. Frequencies and linewidths of the Raman bands as a function of pressure also suggest a pressure-induced morphological change and the decreasing of the nanocrystal size. The observed spectroscopic changes are supported by electron microscopy images, which clearly show a pressure-induced morphologic change in MoO3 nanoribbons.

Fabrication of nanocrystalline alloys Cu–Cr–Mo super satured solid solution by mechanical alloying

This work discusses the extension of solid solubility of Cr and Mo in Cu processed by mechanical alloying. Three alloys processed, Cu–5Cr–5Mo, Cu–10Cr–10Mo and Cu–15Cr–15Mo (weight%) using a SPEX mill. Gibbs free energy of mixing values 10, 15 and 20 kJ mol−1 were calculated for these three alloys respectively by using the Miedema's model. The crystallite size decreases and dislocation density increases when the milling time increases, so Gibbs free energy storage in powders increases by the presence of crystalline defects. The energy produced by crystallite boundaries and strain dislocations were estimated and compared with Gibbs free energy of mixing values. The energy storage values by the presence of crystalline defects were higher than Gibbs free energy of mixing at 120 h for Cu–5Cr–5Mo, 130 h for Cu–10Cr–10Mo and 150 h for Cu–15Cr–15Mo. During milling, crystalline defects are produced that increases the Gibbs free energy storage and thus the Gibbs free energy curves are moved upwards and hence the solubility limit changes. Therefore, the three alloys form solid solutions after these milling time, which are supported with the XRD results.

Interaction of water molecules with the electric field of an ionic-crystal surface

A theoretical investigation of the coulombic interaction of water molecules with an ideal surface of an ionic crystal is conducted. The calculation is based on the Fourier transform of the long-range part of an coulombic potential with subsequent summation of its Fourier images and tabulation of the results. The method is numerically tested when solving the problem concerning the interaction with the surface of a silver iodide crystal. A comparison of the electric field near an ideal crystalline surface and its finite fragment is performed. The data obtained point to a strong dependence of electrochemical properties of the surface on the presence of crystalline defects on it.

Controlled Rate Thermal Analysis of kaolinite dehydroxylation: effect of water vapour pressure on the mechanism

The present kinetic study is focused on one aspect of kaolinite dehydroxylation, namely the influence of water vapour pressure in the 10 −3 to 5 hPa range and in the presence of crystalline defects. The experimental problem of keeping, throughout the dehydroxylation, the pressure gradients negligible around and within the sample is solved by means of Controlled Rate Evolved Gas Detection (CR-EGD). The dehydroxylation rate selected is as low as 0.014 h −1 (which corresponds to a duration of 70 h for the whole experiment). Moreover, more than 20 independent measurements of the apparent Arrhenius energy of activation are carried out all along the dehydroxylation, with help of the rate–jump method, and therefore, without any assumption about the rate law of the determining step. In these conditions, the apparent Arrhenius energy of activation measured during the dehydroxylation of a poorly crystallised kaolinite is shown to be constant in the range 0.02< α<0.84 (under 10 −3 hPa) and in the range 0.18< α<0.80 (under 5 hPa), indicating that the rate law obeys the Arrhenius law in this range of extent of reaction. The corresponding activation energies obtained are (233±15) kJ/mol under 10 −3 hPa and only (188±10) kJ/mol under 5 hPa. Although this decrease is in contradiction with previously published results, it can be interpreted by considering that, under 10 −3 hPa, diffusion is the limiting step whereas, under 5 hPa, the part of water desorption probably becomes predominant.

Laser-stimulated mass transfer in metals

Mass transfer in iron and nickel stimulated by pulsed laser radiation is studied by the radioactive isotope method. New experimental results are obtained and an analysis in terms of kinetic equations is given. It is shown: (a) exposure of the metal surface to high intensity pulsed laser radiation leads to an accelerated atomic migration into the sample; (b) an effective retardation, the value of which depends upon the presence of crystalline defects in metals has an essential influence on the atomic migration rate stimulated by the laser; (c) multiple laser loading results in a concentration maximum formed inside the sample, the depth displacement of which depends upon the energy of light flux and the number of pulsed loadings. [Russian Text Ignored]