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CdSe nanowires (CdSe-NWs) at large scale were obtained through a simple and clean method. The reaction was carried out without complexing agents which often facilitate the preferential nanostructure growth. In this work, CdSe-NWs with lineal and zigzag shape around 40 and 130 nm in diameter with a wurtzite-type structure were synthesized. Quantitative EDX analysis indicated the stoichiometric formation of CdSe, while both HRTEM and HAADF-STEM analysis ruled out the presence of other phases such as CdO or nanotubes formation, respectively. Diameter and length of the nanowires varied with the reaction time and temperature. This synthesis method makes the nanostructures purification process easier and also is non-toxic and its high conversion make it an efficient method for obtaining CdSe-NWs.

Behavior of matter at the nanoscale differs fromthat of the bulk due to confinement and surface effects. Here, we report a direct observation of liquid-like behavior of a single grain boundary formed by cold-welding Au nanoparticles, 40 nm in size, by mechanical manipulation in situ TEM. The grain boundary rotates almost freely due to the free surfaces and can rotate about 90 degrees. The grain boundary sustains more stress than the bulk, confirming a strong bonding between the nanoparticles.Moreover, this technique allows the measurement of the surface diffusion coefficient from experimental observations, which we compute for the Au nanoparticles. This methodology can be used for any metal, oxide, semiconductor or combination of them.

CdSe nanowires (CdSe-NWs) at large scale were obtained through a simple and clean method. The reaction was carried out without complexing agents which often facilitate the preferential nanostructure growth. In this work, CdSe-NWs with lineal and zigzag shape around 40 and 130 nm in diameter with a wurtzite-type structure were synthesized. Quantitative EDX analysis indicated the stoichiometric formation of CdSe, while both HRTEM and HAADF-STEM analysis ruled out the presence of other phases such as CdO or nanotubes formation, respectively. Diameter and length of the nanowires varied with the reaction time and temperature. This synthesis method makes the nanostructures purification process easier and also is non-toxic and its high conversion make it an efficient method for obtaining CdSe-NWs.

Behavior of matter at the nanoscale differs fromthat of the bulk due to confinement and surface effects. Here, we report a direct observation of liquid-like behavior of a single grain boundary formed by cold-welding Au nanoparticles, 40 nm in size, by mechanical manipulation in situ TEM. The grain boundary rotates almost freely due to the free surfaces and can rotate about 90 degrees. The grain boundary sustains more stress than the bulk, confirming a strong bonding between the nanoparticles.Moreover, this technique allows the measurement of the surface diffusion coefficient from experimental observations, which we compute for the Au nanoparticles. This methodology can be used for any metal, oxide, semiconductor or combination of them.

There is strong interest in studying changes in mechanical properties with reducing grain size. The rational is that consequent dislocation glide cannot be sustained, resulting in an increase in material strength. However, this comes with the cost of a reduction in ductility. It has been shown that coherent twin boundaries in nanostructured Cu improve the ductility to 14% [Lu et al., Science 324 (2009) p. 349]. In this paper, we report for the first time the compression of individual nanoparticles using an in situ force probing holder in the transmission electron microscope. Four types of nanoparticles were tested, three with twin boundaries (decahedra, icosahedra and a single twin) and one free of defects (octahedral). Our results indicate the yield strength of the twinned nanoparticles is between 0.5 and 2.0 GPa. The total malleability for the twinned particles range from 80 to 100%. In addition, experimental results were reproduced by MD simulations of the compression phenomena and suggest that the outstanding mechanical properties are related with partial dislocation multiplication at twin boundaries.

There is strong interest in studying changes in mechanical properties with reducing grain size. The rational is that consequent dislocation glide cannot be sustained, resulting in an increase in material strength. However, this comes with the cost of a reduction in ductility. It has been shown that coherent twin boundaries in nanostructured Cu improve the ductility to 14% [Lu et al., Science 324 (2009) p. 349]. In this paper, we report for the first time the compression of individual nanoparticles using an in situ force probing holder in the transmission electron microscope. Four types of nanoparticles were tested, three with twin boundaries (decahedra, icosahedra and a single twin) and one free of defects (octahedral). Our results indicate the yield strength of the twinned nanoparticles is between 0.5 and 2.0 GPa. The total malleability for the twinned particles range from 80 to 100%. In addition, experimental results were reproduced by MD simulations of the compression phenomena and suggest that the outstanding mechanical properties are related with partial dislocation multiplication at twin boundaries.

An effort to develop smaller, well-dispersed catalytic materials electrochemically on high-surface-area carbon supports is required for improved fuel cell performance. A high-surface-area carbon material of interest is carbon nano-onions (CNOs), also known as multilayer fullerenes. The most convenient synthesis method for CNOs is annealing nanodiamond particles, thus retaining the size of the precursors and providing the possibility to prepare very small nanocatalysts using electrochemical techniques. In terms of pure metal catalysts, platinum is the most common catalyst used in fuel cells. The combination of Pt nanoparticles with CNOs could lead to new catalytic nanomaterials. In this work, this was accomplished by using a rotating disk− slurry electrode (RoDSE) technique. The Pt/CNO catalysts were prepared from slurries that contained functionalized CNOs and K2PtCl6 as the platinum precursor in aqueous 0.1 M H2SO4 solution. X-ray photoelectron spectroscopy results showed that 37% of the Pt on the CNOs is metallic Pt whereas 63% had higher binding energies, which is evidence of higher oxidation states or the presence of Pt atoms and clusters on CNOs. However, aberration-corrected scanning transmission electron microscopy of the Pt/CNOs confirmed the presence of Pt atoms and clusters on CNOs. Thermal gravimetric analysis showed the excellent thermal stability of the Pt/CNOs and a lower onset potential for the electrochemical oxidation of methanol compared to that of commercial Pt/Vulcan catalyst material. The computational method confirmed the Pt atoms' location at CNOs surface sites. Geometric parameters for distances between Pt atoms in the 3Pt/CNOs molecular system from our theoretical calculations are in agreement with the respective parameters obtained experimentally. The combination of CNO with RoDSE presents a new highly dispersed catalyst nanomaterial.

The morphology of crystalline precipitates in a solidstate matrix is governed by complex but tractable energetic considerations driven largely by volume strain energy minimization and anisotropy of interfacial energies. Spherical precipitate morphologies are favored by isotropic systems, while anisotropic interfacial energies give energetic preference to certain crystallographically oriented interfaces, resulting in a faceted precipitate morphology. In conventional solid−solution precipitation, a precipitate’s morphological evolution is mediated by surface anchoring of capping molecules, which dramatically alter the surface energy in an anisotropic manner, thereby providing exquisite morphology control during crystal growth. Herein, we present experimental evidence and theoretical validation for the role of a ternary element (Na) in controlling the morphology of nanoscale PbS crystals nucleating in a PbTe matrix, an important bulk thermoelectric system. The PbS nanostructures formed by phase separation from a PbI2-doped or undoped PbTe matrix have irregular morphologies. However, replacing the iodine dopant with Na (1−2 mol %) alters dramatically the morphology of the PbS precipitates. Segregation of Na at PbTe/PbS interfaces result in cuboidal and truncated cuboidal morphologies for PbS. Using analytical scanning/transmission electron microscopy and atom-probe tomography, we demonstrate unambiguously that Na partitions to the precipitates and segregates at the matrix/ precipitate interfaces, inducing morphological anisotropy of PbS precipitates. First-principles and semiclassical calculations reveal that Na as a solute in PbTe has a higher energy than in PbS and that Na segregation at a (100) PbTe/PbS interface decreases the total energy of matrix/precipitate system, resulting in faceting of PbS precipitates. These results provide an impetus for a new strategy for controlling morphological evolution in matrix/precipitate systems, mediated by solute partitioning of

There is strong interest in studying changes in mechanical properties with reducing grain size. The rational is that consequent dislocation glide cannot be sustained, resulting in an increase in material strength. However, this comes with the cost of a reduction in ductility. It has been shown that coherent twin boundaries in nanostructured Cu improve the ductility to 14% [Lu et al., Science 324 (2009) p. 349]. In this paper, we report for the first time the compression of individual nanoparticles using an in situ force probing holder in the transmission electron microscope. Four types of nanoparticles were tested, three with twin boundaries (decahedra, icosahedra and a single twin) and one free of defects (octahedral). Our results indicate the yield strength of the twinned nanoparticles is between 0.5 and 2.0 GPa. The total malleability for the twinned particles range from 80 to 100%. In addition, experimental results were reproduced by MD simulations of the compression phenomena and suggest that the outstanding mechanical properties are related with partial dislocation multiplication at twin boundaries.

An effort to develop smaller, well-dispersed catalytic materials electrochemically on high-surface-area carbon supports is required for improved fuel cell performance. A high-surface-area carbon material of interest is carbon nano-onions (CNOs), also known as multilayer fullerenes. The most convenient synthesis method for CNOs is annealing nanodiamond particles, thus retaining the size of the precursors and providing the possibility to prepare very small nanocatalysts using electrochemical techniques. In terms of pure metal catalysts, platinum is the most common catalyst used in fuel cells. The combination of Pt nanoparticles with CNOs could lead to new catalytic nanomaterials. In this work, this was accomplished by using a rotating disk− slurry electrode (RoDSE) technique. The Pt/CNO catalysts were prepared from slurries that contained functionalized CNOs and K2PtCl6 as the platinum precursor in aqueous 0.1 M H2SO4 solution. X-ray photoelectron spectroscopy results showed that 37% of the Pt on the CNOs is metallic Pt whereas 63% had higher binding energies, which is evidence of higher oxidation states or the presence of Pt atoms and clusters on CNOs. However, aberration-corrected scanning transmission electron microscopy of the Pt/CNOs confirmed the presence of Pt atoms and clusters on CNOs. Thermal gravimetric analysis showed the excellent thermal stability of the Pt/CNOs and a lower onset potential for the electrochemical oxidation of methanol compared to that of commercial Pt/Vulcan catalyst material. The computational method confirmed the Pt atoms' location at CNOs surface sites. Geometric parameters for distances between Pt atoms in the 3Pt/CNOs molecular system from our theoretical calculations are in agreement with the respective parameters obtained experimentally. The combination of CNO with RoDSE presents a new highly dispersed catalyst nanomaterial.

The morphology of crystalline precipitates in a solidstate matrix is governed by complex but tractable energetic considerations driven largely by volume strain energy minimization and anisotropy of interfacial energies. Spherical precipitate morphologies are favored by isotropic systems, while anisotropic interfacial energies give energetic preference to certain crystallographically oriented interfaces, resulting in a faceted precipitate morphology. In conventional solid−solution precipitation, a precipitate’s morphological evolution is mediated by surface anchoring of capping molecules, which dramatically alter the surface energy in an anisotropic manner, thereby providing exquisite morphology control during crystal growth. Herein, we present experimental evidence and theoretical validation for the role of a ternary element (Na) in controlling the morphology of nanoscale PbS crystals nucleating in a PbTe matrix, an important bulk thermoelectric system. The PbS nanostructures formed by phase separation from a PbI2-doped or undoped PbTe matrix have irregular morphologies. However, replacing the iodine dopant with Na (1−2 mol %) alters dramatically the morphology of the PbS precipitates. Segregation of Na at PbTe/PbS interfaces result in cuboidal and truncated cuboidal morphologies for PbS. Using analytical scanning/transmission electron microscopy and atom-probe tomography, we demonstrate unambiguously that Na partitions to the precipitates and segregates at the matrix/ precipitate interfaces, inducing morphological anisotropy of PbS precipitates. First-principles and semiclassical calculations reveal that Na as a solute in PbTe has a higher energy than in PbS and that Na segregation at a (100) PbTe/PbS interface decreases the total energy of matrix/precipitate system, resulting in faceting of PbS precipitates. These results provide an impetus for a new strategy for controlling morphological evolution in matrix/precipitate systems, mediated by solute partitioning of

There is strong interest in studying changes in mechanical properties with reducing grain size. The rational is that consequent dislocation glide cannot be sustained, resulting in an increase in material strength. However, this comes with the cost of a reduction in ductility. It has been shown that coherent twin boundaries in nanostructured Cu improve the ductility to 14% [Lu et al., Science 324 (2009) p. 349]. In this paper, we report for the first time the compression of individual nanoparticles using an in situ force probing holder in the transmission electron microscope. Four types of nanoparticles were tested, three with twin boundaries (decahedra, icosahedra and a single twin) and one free of defects (octahedral). Our results indicate the yield strength of the twinned nanoparticles is between 0.5 and 2.0 GPa. The total malleability for the twinned particles range from 80 to 100%. In addition, experimental results were reproduced by MD simulations of the compression phenomena and suggest that the outstanding mechanical properties are related with partial dislocation multiplication at twin boundaries.

The loss-loss region of the electron energy loss spectrum (EELS) is dominated by the zero loss peak (ZLP) and peak intensities due to plasmon excitations. The width of the zero loss peak represents the energy spread of the system and its intensity is governed by the degree to which electrons were not inelastically scattered and were collected by the spectrometer (Ie less counts means more inelastic scattering, more counts mean less inelastic scattering). The plasmon peaks are generally due to excitations of collective oscillations in the valence electrons of the sample. In semiconducting materials, the valence electrons are highly localised and different phases can be readily mapped according to differences in plasmon energy, Ep. In metallic systems the valence electrons are not as localised and the 'electron gas' will be strongly influenced by the presence of nearby phases so as to equilibrate Fermi levels, making differences in plasmon energies subtle near interfaces.

The loss-loss region of the electron energy loss spectrum (EELS) is dominated by the zero loss peak (ZLP) and peak intensities due to plasmon excitations. The width of the zero loss peak represents the energy spread of the system and its intensity is governed by the degree to which electrons were not inelastically scattered and were collected by the spectrometer (Ie less counts means more inelastic scattering, more counts mean less inelastic scattering). The plasmon peaks are generally due to excitations of collective oscillations in the valence electrons of the sample. In semiconducting materials, the valence electrons are highly localised and different phases can be readily mapped according to differences in plasmon energy, Ep. In metallic systems the valence electrons are not as localised and the 'electron gas' will be strongly influenced by the presence of nearby phases so as to equilibrate Fermi levels, making differences in plasmon energies subtle near interfaces.

The loss-loss region of the electron energy loss spectrum (EELS) is dominated by the zero loss peak (ZLP) and peak intensities due to plasmon excitations. The width of the zero loss peak represents the energy spread of the system and its intensity is governed by the degree to which electrons were not inelastically scattered and were collected by the spectrometer (Ie less counts means more inelastic scattering, more counts mean less inelastic scattering). The plasmon peaks are generally due to excitations of collective oscillations in the valence electrons of the sample. In semiconducting materials, the valence electrons are highly localised and different phases can be readily mapped according to differences in plasmon energy, Ep. In metallic systems the valence electrons are not as localised and the 'electron gas' will be strongly influenced by the presence of nearby phases so as to equilibrate Fermi levels, making differences in plasmon energies subtle near interfaces.

The loss-loss region of the electron energy loss spectrum (EELS) is dominated by the zero loss peak (ZLP) and peak intensities due to plasmon excitations. The width of the zero loss peak represents the energy spread of the system and its intensity is governed by the degree to which electrons were not inelastically scattered and were collected by the spectrometer (Ie less counts means more inelastic scattering, more counts mean less inelastic scattering). The plasmon peaks are generally due to excitations of collective oscillations in the valence electrons of the sample. In semiconducting materials, the valence electrons are highly localised and different phases can be readily mapped according to differences in plasmon energy, Ep. In metallic systems the valence electrons are not as localised and the 'electron gas' will be strongly influenced by the presence of nearby phases so as to equilibrate Fermi levels, making differences in plasmon energies subtle near interfaces.