The local structure of SO2 and SO3 on Ni(1 1 1): A scanned-energy mode photoelectron diffraction study

O 1s and S 2p scanned-energy mode photoelectron diffraction (PhD) data, combined with multiple-scattering simulations, have been used to determine the local adsorption geometry of the SO₂ and SO₃ species on a Ni(1 1 1) surface. For SO₂, the application of reasonable constraints on the molecular conformation used in the simulations leads to the conclusion that the molecule is centred over hollow sites on the surface, with the molecular plane essentially parallel to the surface, and with both S and O atoms offset from atop sites by almost the same distance of 0.65 Å. For SO₃, the results are consistent with earlier work which concluded that surface bonding is through the O atoms, with the S atom higher above the surface and the molecular symmetry axis almost perpendicular to the surface. Based on the O 1s PhD data alone, three local adsorption geometries are comparably acceptable, but only one of these is consistent with the results of an earlier normal-incidence X-ray standing wave (NIXSW) study. This optimised structural model differs somewhat from that originally proposed in the NIXSW investigation.     

Adsorption structure of glycine on TiO2(1 1 0): A photoelectron diffraction determination

High-resolution core-level photoemission and scanned-energy mode photoelectron diffraction (PhD) of the O 1s and N 1s states have been used to investigate the interaction of glycine with the rutile TiO₂(1 1 0) surface. Whilst there is clear evidence for the presence of the zwitterion CH₂COO⁻ with multilayer deposition, at low coverage only the deprotonated glycinate species, NH₂CH₂COO is present. Multiple-scattering simulations of the O 1s PhD data show the glycinate is bonded to the surface through the two carboxylate O atoms which occupy near-atop sites above the five-fold-coordinated surface Ti atoms, with a Ti-O bondlength of 2.12 ± 0.06 Å. Atomic hydrogen arising from the deprotonation is coadsorbed to form hydroxyl species at the bridging oxygen sites with an associated Ti-O bondlength of 2.01 ± 0.03 Å. Absence of any significant PhD modulations of the N 1s emission is consistent with the amino N atom not being involved in the surface bonding, unlike the case of glycinate on Cu(1 1 0) and Cu(1 0 0).     

Formation of copper islands on a native SiO2 surface at elevated temperatures

A combination of in situ X-ray photoelectron spectroscopy analysis and ex situ scanning electron- and atomic force microscopy has been used to study the formation of copper islands upon Cu deposition at elevated temperatures as a basis for the guided growth of copper islands. Two different temperature regions have been found: (I) up to 250 °C only close packed islands are formed due to low diffusion length of copper atoms on the surface. The SiO₂ film acts as a barrier protecting the silicon substrate from diffusion of Cu atoms from oxide surface. (II) The deposition at temperatures above 300 °C leads to the formation of separate islands which are (primarily at higher temperatures) crystalline. At these temperatures, copper atoms diffuse through the SiO₂ layer. However, they are not entirely dissolved in the bulk but a fraction of them forms a Cu rich layer in the vicinity of SiO₂/Si interface. The high copper concentration in this layer lowers the concentration gradient between the surface and the substrate and, consequently, inhibits the diffusion of Cu atoms into the substrate. Hence, the Cu islands remain on the surface even at temperatures as high as 450 °C.     

The interactions of thiophene with polycrystalline UO2

We have studied the adsorption and desorption of thiophene on polycrystalline UO₂ as function of coverage, over the temperature range 100-640 K, using X-ray photoelectron spectroscopy (XPS), temperature programmed desorption (TPD) and electron stimulated desorption (ESD). Thiophene is found to adsorb molecularly on stoichiometric UO₂. C 1s and S 2p XPS spectra are measured at different thiophene exposures and at different temperatures; they show no evidence for the presence of dissociation fragments, confirming that thiophene adsorbs and desorbs molecularly on a polycrystalline stoichiometric UO₂ surface. The variation of the S 2p and C 1s intensity as function of exposure, together with ESD measurements of O⁺ as function of exposure, can be connected to the growth mode of a thiophene film on UO₂; the thiophene film converts from a flat-lying configuration to an inclined structure as coverage increases. The effects of X-rays, UV, and electron irradiation on thiophene films have been studied in two different coverage regimes, monolayer and multilayer. Irradiation leads to a modification of thiophene films, and appreciable concentrations of species stable to 640 K are present on the surface for both regimes. The XPS results suggest that irradiation induces polymerization and oligomerization, as well as formation of thiolates and dissociation fragments of thiophene. The adsorption and reactivity of thiophene on defective UO₂ surfaces have also been studied. The O vacancies and defects in the oxide surface cause cleavage of C-H and C-S bonds leading to the dissociation of thiophene at temperatures as low as 100 K. These results illustrate the important role played by O vacancies in the chemistry of thiophene over an oxide surface.     

Polysulfobetaine films prepared by electrografting technique for reduction of biofouling on electroconductive surfaces

The sulfobetaine films were prepared on stainless steel and golden surfaces. In the first step, the poly(2-(dimethylamino)ethyl methacrylate) film was created by employing the electrografting polymerization technique. In the second step, this film was modified to polysulfobetaine, i.e. the polymer film bearing the zwitterionic groups. The presence of the electrografted film and its modification were determined by contact angle measurements, infrared spectroscopy in reflectance mode and X-ray photoelectron spectroscopy. The prepared films were homogeneous with the thickness from about 5 to 26 nm as determined by X-ray photoelectron spectroscopy. The atomic force microscopy measurements showed the increase of surface roughness upon the surface coating. In vitro tests using adherent RAT-2 fibroblast cells and fluorescently labelled bovine serum albumin proteins showed that prepared polysulfobetaine films can be used in applications requiring the resistance against cell attachment and biofouling.     

Chemisorption and reactivity of furan on Pd{111}

XPS, HREELS, ARUPS and Δø data show that furan chemisorbs non-dissociatively on Pd{111} at 175 K, the molecular plane being significantly tilted with respect to the surface normal. Bonding involves both the oxygen lone pair and significant π interaction with the substrate. The degree of decomposition that accompanies molecular desorption is a strong function of coverage: 40% of the adsorbate desorbs molecularly from the saturated monolayer. Decomposition occurs via decarbonylation to yield CO_a and H_a followed by desorption rate limited loss of H₂ and CO. It seems probable that an adsorbed C₃H₃ species formed during this process undergoes subsequent stepwise dehydrogenation ultimately yielding H₂ and C_a.     

Structure analysis of W(0 0 1)2 × 1-O surface at room and liquid nitrogen temperatures

Surface structure of O-adsorbed W(0 0 1) surface after annealing to 1200 K has been analyzed by low energy electron diffraction at 77 K as well as at room temperature. The optimum structure has tungsten missing rows and oxygen double rows. Furthermore, the R-factor is minimized at the structure that O atoms are adsorbed on one of the two different threefold hollow sites of the (1 1 0) facet appearing on the W(0 0 1)2 × 1 with missing row. However, the results suggest that two domains of O atoms adsorbed on both the two different threefold hollow sites coexist. Then, I-V curves have been analyzed as a function of the mixing ratio of the two domains having different O adsorption sites at room and low temperatures. The energy difference between these two sites has been estimated to be 6.5 meV from the temperature dependence of the mixing ratio.     

Hydrogen adsorption on Gd(0001)

The electronic structure of hydrogen adsorbate-induced states on Gd(0001) was investigated by means of photoelectron spectroscopy with linearly polarized radiation. The E vector of the incoming photon beam is rotatable. Clean and well-ordered rare-earth (0001) surfaces exhibit a highly localized surface state near the Fermi edge. After the adsorption of hydrogen, the surface state disappears and an additional sharp feature at about 4 eV binding energy is observed. For this latter state, the ratio of the radial matrix elements as well as the relative phase shifts were determined to be R=R_p/R_f=2.4±0.3 and δ_f−δ_p=310±10°, respectively. The removal of the Gd surface state by hydrogen adsorption was investigated by means of scanning tunneling microscopy (STM) and spectroscopy (STS). The removal of the surface state exhibits domain-like behavior, with surface steps acting as domain boundaries. The tunneling spectra reveal that hydrogen adsorption causes a dramatic reduction in the differential conductivity near the Fermi level.     

Electronic structure investigation of the Ag(1 1 0)(n×1)O surfaces––new photoemission results for an old problem

We have used angle-resolved photoelectron spectroscopy to investigate the occupied antibonding electron states of the Ag(1 1 0)(n×1)O surface along different directions in the surface Brillouin zone. We present experimental evidence that several earlier results obtained along (along the Ag–O chains) contain admixtures from contamination, most probably from carbonate-like contributions. New results are obtained along and (perpendicular to the chains). These data indicate that the n=2 structure is stabilized by repulsive electronic interaction between neighbouring chains, which diminishes drastically for n=3 and disappears almost completely at n4. This observation points to a strain field within the substrate which stabilizes the geometry between n=3 (interchain distance 8.7 Å) and n=8 (23.1 Å). Its existence is indirectly seen in the n-dependence of the surface phonon energies at , which can be explained quantitatively by umklapp-processes induced by the lateral periodicity of the strain field. We compare our photoemission results for (2 × 1)O with available surface band structure calculations.     

Initial growth of platinum on oxygen-covered Ni(1 1 0) surfaces

The initial growth of Pt on the Ni(1 1 0)-(3 × 1)-O and NiO(1 1 0) surfaces has been studied by coaxial impact collision ion scattering spectroscopy (CAICISS), low energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS). Prior to Pt deposition, the atomic structure of the near-surface regions of the Ni(1 1 0)-(3 × 1)-O and NiO(1 1 0) structures were studied using CAICISS, finding changes to the interlayer spacings due to the adsorption of oxygen. Deposition of Pt on the Ni(1 1 0)-(3 × 1)-O surface led to a random substitutional alloy in the near-surface region at Pt coverages both below and in excess of 1 ML. In contrast, when the surface was treated with 1800 L of atomic oxygen in order to form a NiO(1 1 0) surface, a thin Pt layer was formed upon room temperature Pt deposition. XPS and LEED data are presented throughout to support the CAICISS observations.     

Density functional theory calculation of 2p core-electron binding energies of Si,P, S,Cl, and Ar in gas-phase molecules

Density functional theory (DFT) calculations have been performed on the gas-phase 2p core-electron binding energies (CEBEs) of Si, P, S, Cl, and Ar in 145 cases using the following procedure: ΔE_KS (scalar-ZORA + E_xc)/TZP//HF/6-31G(d). ΔE_KS is the difference in the total Kohn–Sham energies of the 2p-ionized cation and the neutral parent molecule calculated by DFT using different exchange-correlation functionals E_xc with triple-zeta polarized basis set, at molecular geometry optimized by HF/6-31G(d), and relativistic effects have been estimated by scalar zeroth-order regular approximation. Among the 26 functionals tested, the form of E_xc giving the best overall performance was found to be the combination of OPTX exchange and LYP correlation functionals. For that functional, the average absolute deviation (AAD) of the 145 calculated CEBEs from experiment is 0.26 eV. There are seven other exchange-correlation functionals that led to AADs of less than 0.30 eV. Some functionals give lower AADs than E_xc = OPTX-LYP for some individual elements. In the case of Si, for example, the combination of either mPW91-PBE or Becke88-Perdew86 led to an AAD of only 0.10 eV for 56 silicon-containing molecules. Another example is the case of the argon atom, for which the choice of E_xc = OPTX-Perdew86 yields a value for CEBE equal to the experimental value.     

Isothermal reduction kinetics of nickel oxide using hydrogen: Conventional and Weibull kinetic analysis

The powder sample of nickel oxide was synthesized by sol-gel procedure. The isothermal reduction of nickel oxide using hydrogen was investigated by thermogravimetric analysis at five operating temperatures: 245, 255, 265, 275 and 300 °C. The kinetic triplet (E_a, A and f(α)) was determined using conventional and Weibull kinetic analysis. Both the kinetically procedures show that the reduction process considered can be explained with a two-step kinetic model. It is established that at lower temperatures (245 °C?T?255 °C), the reduction process considered is governed by two-parameter Šesták-Berggren autocatalytic model (first step) and at higher temperatures (T?265 °C), the reduction process is governed by Fn reaction model with different values of parameter n (second step). In this paper, the complex manner of dependence of the Weibull shape parameter (β) on temperature is established. With alterations of Weibull shape parameter from lower temperatures (β>1) to higher temperatures (β<1), it was concluded that isothermal reduction process of NiO using hydrogen can be described by a multistep reaction mechanism. These results are confirmed by the evaluated density distribution functions (ddf) of apparent activation energies (E_a), which show variations in basic characteristics at lower and higher operating temperature regions. Also, in this paper, it was shown that the shape parameter (β) of Weibull distribution function can represent the behaviour index, which indicates the kinetic pattern of the mechanism controlling the process studied.     

Non-contact atomic force microscopy imaging of TiO2(100) surfaces

Atomically resolved non-contact fm mode atomic force microscopy images have been obtained from TiO₂(100) surfaces. The 1×1 surface is observed, as well as the 1×3 phase previously imaged with STM. The morphology of the latter reconstruction consists of (110) microfacets. An additional reconstruction with 1×3 symmetry is observed, which is assigned to a phase intermediate between the 1×1 and 1×3-microfacet terminations.     

Ultra-thin Si overlayers on the TiO2 (1 1 0)-(1 × 2) surface: Growth mode and electronic properties

The growth of thin subnanometric silicon films on TiO₂ (1 1 0)-(1 × 2) reconstructed surfaces at room temperature (RT) has been studied in situ by X-ray and ultra-violet photoelectron spectroscopies (XPS and UPS), Auger electron and electron-energy-loss spectroscopies (AES and ELS), quantitative low energy electron diffraction (LEED-IV), and scanning tunneling microscopy (STM). For Si coverage up to one monolayer, a heterogeneous layer is formed. Its composition consists of a mixture of different suboxides SiO_x (1 < x ? 2) on top of a further reduced TiO₂ surface. Upon Si coverage, the characteristic (1 × 2) LEED pattern from the substrate is completely attenuated, indicating absence of long-range order. Annealing the SiO_x overlayer results in the formation of suboxides with different stoichiometry. The LEED pattern recovers the characteristic TiO₂ (1 1 0)-(1 × 2) diagram. LEED I-V curves from both, substrate and overlayer, indicate the formation of nanometric sized SiO_x clusters.     

A New Spectrophotometric Method with Di-2-Pyridyl Ketone Benzoylhydrazone for Determination of Nickel(II)

Abstract

Nitrogen-containing heterocyclic hydrazones have been used as analytical reagents, mainly to metallic ion spectrophotometric determinations in natural water samples. Using the reagent di-2-pyridil ketone benzoilhydrazone (DPKBH) we have developed a spectrophotometric method for the determination of Ni(II) in samples of several sources. DPKBH was used in excess in order to coordinate Ni(II) and the highest sensitivity was obtained in 50% v/v ethanol solutions when ammonium acetate buffer was added to maintain pH?6.

Analysis for Ni(II) in natural water is frequently performed by EAAS following preconcentration involving solvent extraction. While these methods are sensitive, they also require relatively expensive instrumentation and are generally time-consuming. In contrast, the advantages of the proposed method are the use of simple instrumentation and the possibility of its application in the field. The method is fast, shows high sensitivity, good precision and several samples can be prepared and measured until 10 hours later .

The best order for the addition of reagents, stability of the complex, effect of the reagents excess and foreign ions besides composition of the complex are here reported. A linear behavior was observed between absorbance and nickel concentration. The favorable range is 8.50×10^?7 to 1.72×10^?5 mol.L^?1. The correlation coefficient is 0.997. The intercept of the linear curve is 3.55×10^?3 and the slope is 4.00×10⁴cm^?1.moI^?1.L. The standard error of the intercept and slope is 3.73×10^?3 and 4.48×10^?4, respectively.     

An ordered surface ternary alloy of a c(6 × 4) structure formed on Cu(0 0 1) by substitutional coadsorption of Mg and Bi

A c(6 × 4) structure formed on Cu(0 0 1) by the coadsorption of Mg and Bi atoms at room temperature has been determined by a tensor low energy electron diffraction analysis. It is an ordered surface ternary alloy with a thickness of single layer, in which Mg, Bi and Cu atoms are mixed in the top layer. In the primitive unit cell, there are one Mg, four Bi, six Cu atoms and one vacancy in the top layer, and substituted Mg and Bi atoms form MgBi₄ plane clusters being arranged in the c(6 × 4) order. Structural parameters show that Mg-Bi bond distances in the MgBi₄ cluster are 3.01 and 3.07 Å, which are shorter than the summation of metallic radii of Mg and Bi. It is concluded that a direct, attractive interaction between Mg and Bi atoms plays critical role in the formation of the c(6 × 4) structure.     

Spatially resolved dynamics of the TiO2(1 1 0) surface reconstruction

We use low-energy electron microscopy to image the reversible transformation of the TiO₂(1 1 0) surface between a high-temperature 1 × 1 structure and a low-temperature 1 × 2 structure. The reconstruction dynamics are novel: 1 × 2 bands nucleated during cooling at the steps of the starting 1 × 1 surface and then grew laterally from the steps. The transformation kinetics are dominated by mass flow from the surface to the bulk, a process that facilitates converting the high-density 1 × 1 phase to the lower-density 1 × 2 phase. We have also imaged how the 1 × 1 surface reconstructs to 1 × 2 phase after sufficient oxygen is removed from the crystal’s bulk during vacuum annealing. 1 × 2 bands also nucleated and grew laterally from the initial 1 × 1-surface’s steps. However, because this isothermal 1 × 1-to-1 × 2 transition occurs largely by mass redistribution on the surface, the steps of the initial 1 × 1 surface and final 1 × 2 surface are offset. We propose models of mass redistribution during the 1 × 1/1 × 2 phase transition to explain this effect. We conclude that the phase transition is first-order because it always occurred by the nucleation and growth of discrete phases. Finally, we show that quenching can roughen TiO₂’s surface by forming pits and that changing temperature causes step motion on 1 × 2 surfaces.     

Electrochemical formation of porous superlattices on n-type (1 0 0) InP

The present work deals with the electrochemical formation of superlattice structures on n-type (1 0 0) InP in HCl solutions. The superlattices consist of a stack of two layers with alternating high and low porosity on n-type material obtained by changing the anodizing current or the potential periodically in HCl solutions. The superlattice structures were characterized by scanning electron microscopy. The pore morphology and structure depend strongly on the electrochemical conditions. For anodization with low currents (e.g., 1 or 10 mA) or at low potentials (e.g., 1.5 V_Ag/AgCl), a porous layer with a facet-like structure was formed. For higher currents or potentials, such as 50 or 100 mA or 3 V_Ag/AgCl, respectively, a tree-like structure with random and/or tangled branches was observed. Finally, samples anodized at 5 V_Ag/AgCl, show a porous layer with a regular array of straight pores. The morphology and structure of the stacks of the porous layers can be controlled in the nanometer range, depending on the electrochemical conditions.