Nature of the Oxygen Species at Ni(110) and Ni(100) Surfaces Revealed by Exposure to Oxygen and Oxygen-Ammonia Mixtures: Evidence for the Surface Reactivity of O- Type Species

Adsorption of dioxygen at clean Ni(110) and Ni(100) surfaces gives rise to two prominent features in the O(1s) spectra at 530 and 531 eV due to O2- and O- type species, respectively. Interaction of ammonia with a Ni(100)-O surface where theta(oxygen) < 0.1 ML favors the dissociation of NH3 giving NHn, (n = 1, 2) and N(a) species. This is accompanied by a decrease in the intensity of the 531 eV feature. On the other hand. a Ni(100)-O surface where the oxygen species are mainly of the O2- type is unreactive, Coadsorption studies of NH3-O-2 mixtures show that at Ni(110) surfaces the uptake of both oxygen and ammonia increase with the proportion of oxygen in the NH3-O-2 mixture. The surface concentrations of the O- species and the NHn species also increase with the increase in the O-2/NH3 ratio while the slope of the plot of sigma(N) versus sigma(O-) is around unity. The results demonstrate the high surface reactivity of the O- species and its role in the dissociation of ammonia. Based on these observations, the possibility of the formation of a surface complex between ammonia and oxygen (specifically O-) is suggested. Results from vibrational spectroscopic studies of the coadsorption of NH3-O-2 mixtures are consistent with those from core-level spectroscopic studies.

Hydroxylation of oxygen-covered Cu(110) and Zn(0001) surfaces by interaction with CH3OH, (CH3)2NH, H2S, HCl and other proton donor molecules

EELS studies provide definitive evidence for the hydroxylation of oxygen-covered Cu(110) and Zn(0001) surfaces on interaction with proton donor molecules such as H2O, CH3OH, HCOOH, NH3 and (CH3)2NH. The occurrence of surface hydroxylation is unambigouusly shown by a study of the interaction of H2S and HCl with an oxygen covered Cu(110) surface.

Temperature-pressure-induced solid-solid < 100 > to < 110 > reorientation in FCC metallic nanowire: a molecular dynamic study

Atomistic simulation of initial < 100 > oriented FCC Cu nanowires shows a novel coupled temperature-pressure dependent reorientation from < 100 > to < 110 > phase. A temperature-pressure-induced solid-solid < 100 > to < 110 > reorientation diagram is generated for Cu nanowire with varying cross-sectional sizes. A critical pressure is reported for Cu nanowires with varying cross-sectional sizes, above which an initial < 100 > oriented nanowire shows temperature independent reorientation into the < 110 > phase. The effect of surface stresses on the < 100 > to < 110 > reorientation is also studied. The results indicate that above a critical cross-sectional size for a given temperature-pressure, < 100 > to < 110 > reorientation is not possible. It is also reported here that for a given applied pressure, an increase in temperature is required for the < 100 > to < 110 > reorientation with increasing cross-sectional size of the nanowire. The temperature-pressure-induced solid-solid < 100 > to < 110 > reorientation diagram reported in the present paper could further be used as guidelines for controlling the reorientations/shape memory in nano-scale applications of FCC metallic nanowires.

An eels study of water, methanol, formaldehyde and formic acid adsorbed on clean and oxygen-covered zinc(0001) surfaces

Water adsorbs molecularly on a clean Zn(0001) surface; on a surface covered with atomic oxygen, however, hydroxyl species is produced due to proton abstraction by the surface oxygen atoms. Methanol, molecularly adsorbed on a clean surface at 80 K, transforms to methoxy species above 110 K. On an atomic oxygen-covered surface, adsorbed methanol gives rise to methoxy species and water, the latter arising from proton abstraction. HCHO adsorbs molecularly at 80 K on both clean as well as oxygen-covered surfaces and polymerizes at higher temperatures. Formic acid does not adsorb on a clean Zn surface, but on an oxygen-covered surface gives rise to formate and hydroxyl species.

A combined XPS-UPS-EELS study of nitrogen adsorbed on clean and barium-promoted iron surfaces: The nature of the precursor to dissociation

For N2 on a clean Fe surface, the adsorbed precursor in a parallel orientation becomes predominant around 110 K, while at lower temperatures it coexists with a weakly adsorbed species. On a Ba-promoted Fe surface, however, N2 is present exclusively in the precursor state in the temperature range 80–150 K following moderate exposure. Besides exhibiting a low N-N stretching frequency of 1530 cm−1, the precursor shows a clear separation between the 5σ and 1π levels in the UPS; the precursor dissociates to give a nitridic species around 160 K.

Universal Stability and Temperature Dependent Phase Transformation in Group VIIIB-IB Transition Metal FCC Nanowires

Atomistic simulation of Ag, Al, Au, Cu, Ni, Pd, and Pt FCC metallic nanowires show a universal FCC -> HCP phase transformation below a critical cross-sectional size, which is reported for the first time in this paper. The newly observed HCP structure is also confirmed from previous experimental results. Above the critical cross-sectional size, initial < 100 >/{100} FCC metallic nanowires are found to be metastable. External thermal heating shows the transformation of metastable < 100 >/{100} FCC nanowires into < 110 >/{111} stable configuration. Size dependent metastability/instability is also correlated with initial residual stresses of the nanowire by use of molecular static simulation using the conjugant gradient method at a temperature of 0 K. It is found that a smaller cross-sectional dimension of an initial FCC nanowire shows instability due to higher initial residual stresses, and the nanowire is transformed into the novel HCP structure. The initial residual stress shows reduction with an increase in the cross-sectional size of the nanowires. A size dependent critical temperature is also reported for metastable FCC nanowires using molecular dynamic, to capture the < 110 >/{111} to < 100 >/{100} shape memory and pseudoelasticity.

Some remarks on the symplectic pairing on the moduli space of representations of the fundamental group of surfaces

This work grew out of an attempt to understand a conjectural remark made by Professor Kyoji Saito to the author about a possible link between the Fox-calculus description of the symplectic structure on the moduli space of representations of the fundamental group of surfaces into a Lie group and pairs of mutually dual sets of generators of the fundamental group. In fact in his paper [3] , Prof. Kyoji Saito gives an explicit description of the system of dual generators of the fundamental group.

Facile C-O bond scission in alcohols on Zn surfaces

Interaction of methanol, ethanol, and 2-propanol with polycrystalline as well as (0001) surfaces of Zn has been investigated by photoelectron spectroscopy and vibrational energy loss spectroscopy. All the alcohols show evidence for the condensed species along with the chemisorbed species at 80 K. With increase in temperature to similar to 120 K, the condensed species desorbs, leaving the chemisorbed species which decomposes to give the alkoxy species. The alkoxy species is produced increasingly at lower temperatures as we go from methanol to 2-propanol, the 2-propoxy species occurring even at 80 K. The alkoxy species undergo C-O bond scission giving rise to a hydrocarbon species and oxygen. The C-O bond cleavage occurs at a relatively low temperature of similar to 150 K. The effect of preadsorbed oxygen is to stabilize the methoxy species and prevent C-O bond scission. On the other hand, coadsorption of oxygen with methanol favors the formation of the methoxy species and gives rise to hydrocarbon species arising from the C-O bond scission even at 80 K.

Effect of chlorine on the adsorption of oxygen on Cu and Ag surfaces

Based on XPS and UVPS studies, it is shown that oxygen is preferentially adsorbed molecularly in the singlet state on Cu and Ag surfaces containing presorbed chlorine. Adsorption of chlorine on Cu and Ag surfaces containing presorbed atomic oxygen causes a disappearance of the oxygen. Extended Hückel calculations predict the observed behaviour.

Nanopatterning by solid-state dewetting on reconstructed ceramic surfaces

We demonstrate ordered array formation of Au nanoparticles by controlled solid-state dewetting of a metal film on stepped alumina substrates. In situ transmission electron microscopy studies reveal that the dewetting process starts with nucleation of ordered dry regions on the substrate. The chemical potential difference between concave and convex surface regions induces anisotropic metal diffusion leading to the formation of nanowires in the valleys. The nanowires fragment due to Rayleigh instability forming arrays of metal nanoparticles on the substrate. The length scale of reconstruction relative to the starting film thickness is an important parameter in controlling the spatial order of the nanoparticles.

Scanning electron microscopy study of worn Al-Si alloy surfaces

A pin-on-disc machine was used to wear Al-Si alloy pins under dry conditions. Unmodified and modified binary alloys and commercial multi-component alloys were tested. The surfaces of the worn alloys were examined by scanning electron microscopy to identify distinct topographical features to aid elucidation of the mechanisms of wear.

Interaction of carbon monoxide with transition metal surfaces

XPS studies of the interaction of carbon monoxide with surfaces of Fe, Co and Ni indicate that at 300 K, the disproportionation reaction is prominent up to exposures of 103 L giving rise to high surface concentrations of carbon. At higher exposures and higher temperatures, dissociation of carbon monoxide accompanied by the formation of surface oxide layers becomes more prominent. In the case of copper, disproportionation is prominent up to 104 L even at 500 K followed by dissociation at higher exposures. These results are also supported by Auger spectroscopic studies.

O2- and O1- types of oxygen species on Ni and barium-dosed Ni and Cu surfaces

He II UPS and XPS study of oxygen adsorption on Ni and barium-dosed Ni and Cu surfaces at 300 K show two types of oxygen species which are assigned to O2- and O1- (ad).

Time dependence of effective slip on textured hydrophobic surfaces

In this paper, we present results on water flow past randomly textured hydrophobic surfaces with relatively large surface features of the order of 50 µm. Direct shear stress measurements are made on these surfaces in a channel configuration. The measurements indicate that the flow rates required to maintain a shear stress value vary substantially with water immersion time. At small times after filling the channel with water, the flow rates are up to 30% higher compared with the reference hydrophilic surface. With time, the flow rate gradually decreases and in a few hours reaches a value that is nearly the same as the hydrophilic case. Calculations of the effective slip lengths indicate that it varies from about 50 µm at small times to nearly zero or “no slip” after a few hours. Large effective slip lengths on such hydrophobic surfaces are known to be caused by trapped air pockets in the crevices of the surface. In order to understand the time dependent effective slip length, direct visualization of trapped air pockets is made in stationary water using the principle of total internal reflection of light at the water-air interface of the air pockets. These visualizations indicate that the number of bright spots corresponding to the air pockets decreases with time. This type of gradual disappearance of the trapped air pockets is possibly the reason for the decrease in effective slip length with time in the flow experiments. From the practical point of usage of such surfaces to reduce pressure drop, say, in microchannels, this time scale of the order of 1 h for the reduction in slip length would be very crucial. It would ultimately decide the time over which the surface can usefully provide pressure drop reductions. ©2009 American Institute of Physics

Microemulsion-mediated synthesis of cobalt (pure fcc and hexagonal phases) and cobalt-nickel alloy nanoparticles

By choosing appropriate microemulsion systems, hexagonal cobalt (Co) and cobalt-nickel (1:1) alloy nanoparticles have been obtained with cetyltrimethylammonium bromide as a cationic surfactant at 500 degrees C. This method thus stabilizes the hcp cobalt even at sizes (<10 nm) at which normally fcc cobalt is predicted to be stable. On annealing the hcp cobalt nanoparticles in H-2 at 700 degrees C we could transform them to fcc cobalt nanoparticles. Microscopy studies show the formation of spherical nanoparticles of hexagonal and cubic forms of cobalt and Co-Ni (1:1) alloy nanoparticles with the average size of 4, 8 and 20 nm, respectively. Electrochemical studies show that the catalytic property towards oxygen evolution is dependent on the applied voltage. At low voltage (less than 0.65 V) the Co (hexagonal) nanoparticles are superior to the alloy (Co-Ni) nanoparticles while above this voltage the alloy nanoparticles are more efficient catalysts. The nanoparticles of cobalt (hcp and fcc) and alloy (Co-Ni) nanoparticles show ferromagnetism. The saturation magnetization of Co-Ni nanoparticles is reduced compared to the bulk possibly due to surface oxidation.