An X-ray photoelectron spectroscopic study of some nickel (II) amine complexes

The X-ray photoelectron (XPS) spectra of several Ni(II) diamine complexes, a Ni(II) triamine complex and several Ni(II) diimine complexes are reported in terms of the Ni 2p, Cl 2p and N 1s core level binding energies. Theoretical models are presented to account for the quadratic relationship observed between XPS Ni 2p_{$\text{3}\text{2}$}binding energy shifts and the N-H infrared rocking frequency as related to these complexes. On the basis of this correlation, it is possible to discriminate between free counter-ions coordinated to the metal or involved in cluster-ion formation. Individual XPS data for these complexes are interpreted in terms of the intrinsic nature of the metal environment and an attempt is made to calculate the metal and donor nitrogen atomic charges for selected complexes.     

An XPS,ISS and ESR Comparative Study of Eight-Coordination of Copper (II) Ions in the CuTho Compounds

In this study, we attempted to clarify the coordination state and the distribution of copper (II) ions in the CuThO compounds prepared by coprecipitation, by using several physico-chemical techniques in particular, X-Ray Photoelectron Spectroscopy (XPS).

For atomic ratios Cu/Th ≤ 0.25, the copper (II) species are mainly located near the thoria surface. The Cu2p_3/2 level shows a chemical shift towards the lower binding energy compared to Cu²⁺ ions in CuO and also a net decrease in the intensity of the satellite peak, characteristic of copper (11). A relation between these observations and the covalent character o f Cuzt- 02- bond i s esta- blished. Eightfold coordination of copper (11) i n the thoria lattice i s evident. These conclusions are in good agreement with Electron Spin Resonance (ESR) results.

For a higher atomic ratio (Cu/Th > 0.25), a formation o f copper oxide crystallites i s observed on the thoria surface.     

Auger and X-ray photoelectron spectroscopic and electrochemical characterization of titanium thin film electrodes

Auger (AES) and X-ray photoelectron spectroscopic (XPS) characterizations of electrochemically oxidized titanium are described. Surface oxides on thin (200–250 Å) vacuum deposited titanium films were formed under conditions of linear potential scan in 1 N KClO₄, 1 N HClO₄ and 1 N H₂SO₄. Current/voltage, capacitance/voltage and surface conductance/voltage relationships confirmed the irreversible formation of the surface oxide at thickness of 20–30 Å/V, for low applied potentials. Post moretem analysis of the thin films by AES and XPS indicated a mixture of metal and metal oxides (TiO₂, Ti₂O₃, TiO) on each surface, with the higher oxide states predominating on the electrochemically oxidized films. Observation of the L_IIIM_2,3M_4,5, N(E) signal shape in the Auger spectra of the potentially oxidized oxidized films showed a suboxide TiO-like surface rather than an TiO₂ surface state. Deconvolution of the $\text{Ti}\text{(2}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext><mtext>,\; </mtext><mtext>3</mtext><mtext>2</mtext>}}\text{)}\text{XPS}$ spectra confirmed the coexistence of multiple oxidation states of Ti during electrochemical or atmospheric oxidation of the films. Ion sputtering of each surface was used to characterize the subsurface metal/metal oxide composition and to correlate the oxygen to metal atomic ratio with electrochemical pretreatment.     

The effect of metal particle size on the accessibility of surface atoms to an impinging gas

As an example of similar calculations for any gas/metal combination, the reduced collision frequency Z_r (per second per surface atom) of CO molecules with Pd crystallites of various regular shapes and varied average diameter d_av, is calculated and normalized with respect to that for the close-packed plane Pd (111). Z_r¹¹¹. The ratio $\text{z =}\text{Z}{}_{\mathrm{r}}\text{Z}{}_{\mathrm{r}}{}^{111}$, which describes the relative accessibility of surface atoms to the impinging gas, is obtained for crystallites up to 5 nm in size. It is found that z increases rapidly above ~ 1 as d_av decreases below ~ 3 nm, in agreement with previously reported experimental data.     

Spectroscopic Study of a Hollow Cathode Discharge Operating at Direct and High Frequency Currents - Temperature Measurements

Spectra excited in a hollow cathode discharge operating at high frequency and direct currents have been studied. Samples (La₂O₃ and Y₂O₃) were placed in the copper hollow cathodes and argon was a carrier gas. The excitation temperatures of Ar I, Ar II, Cu I, Y I, Y II and La II in high frequency and direct current hollow cathode discharges have been determined and compared.     

Electric and magnetic properties of the synthetic metal-copper subrodanide Cu(SCN)13

The temperature dependence of the resistance and magnetic susceptibility of the copper subrodanide Cu(SCN)_{$\text{1}\text{3}$} samples were measured at the magnetic field up to 7.3 kG and the temperature range 4.2–400 K. The resistance of the pressed pellet samples linearly increases with the temperature increasing and at 100–150 K the ?(T) line slope smoothly changes. The magnetic susceptibility at zero field linearly decreases with decreasing of the temperature, showing unusual exponential field dependence, which is rather strong at the room temperature and disappears at T → 0. It was concluded that a copper subrodanide is a synthetic metal.     

Octanethiolated Cu and Cu2O nanoparticles as ink to form metallic copper film

The synthesis and spectroscopic characterizations of size-controlled Cu and Cu₂O nanoparticles forming self-assembled 2D superlattices with hexagonal packing are described. The scanning electron microscopy (SEM), nuclear magnetic resonance (NMR), and X-ray photoelectron spectroscopy (XPS) were used to characterize the octanethiol-protected copper nanoparticles. Analysis of XPS confirms the formation of oxidized copper nanoparticles. Conductivity of copper metal film (0.1 μm) on the Si wafer can be improved simply by thermal annealing of copper monolayer protected clusters (MPCs) film (4.8 ± 0.5 × 10² μΩ cm) under air at 300 °C for 1 h, and then for another 5 h under a protective atmosphere of 90% N₂-10% H₂.     

Vibrational spectroscopic and force field studies of copper(II) chloride and bromide compounds,and crystal structure of KCuBr3

Vibrational spectroscopic and force field studies have been performed of 15 related copper(II) chloride and copper(II) bromide compounds, including hydrated salts crystallizing in ternary aqueous systems with alkali and ammonium halides. For halocuprates with distorted octahedral coordination characteristic stretching Raman wavenumbers, corresponding to symmetric stretching Cu^II X modes in the equatorial plane, were found in the ranges 247–288 cm⁻¹ for X = Cl, and 173–189 cm⁻¹ for X = Br, while the low‐wavenumber stretching modes for the weaker axial Cu X interactions varied considerably. The tetrahedral coordination for Cs₂CuCl₄ and Cs₂CuBr₄ leads to somewhat lower Cu X symmetric stretching wavenumbers, 295 and 173 cm⁻¹, respectively. The assignments of the copper–ligand stretching vibrations were performed with the aid of normal coordinate calculations. Correlations between force constants, averaged Cu X stretching wavenumbers and bond distances have been evaluated considering the following aspects: (1) Jahn–Teller tetragonal distortion (axial elongation) of the octahedral copper(II) coordination environment, (2) differences between terminal and bridging halide ligands (3) effects of coordinated water and the influence of outer‐sphere cations. Force constant ratios for terminal and bridging metal–halide bonds reveal characteristic differences between planar and tetrahedrally coordinated M₂X₆ species. In the hydrated copper(II) halide complexes, the halide ligands are more strongly bound than coordinated water molecules. The crystal structure of KCuBr₃ (K₂Cu₂Br₆), which was determined to provide structural information for the force field analyses, contains stacks of planar dimeric [Cu₂Br₆]²⁻ complexes held together by weak axial Cu Br interactions. Copyright © 2007 John Wiley & Sons, Ltd.     

High oxygen pressures and the stabilization of a new mixed valence Cu(III)/Cu(IV)

Abstract

The Cu(III) oxides were investigated first for the unusual copper oxidation state and then for the high-Tc superconductivity. In the last case this property is observed when a mixed copper valence is stabilized : Cu(I)/Cu(II) or Cu(II)/Cu(III). A new mixed valence Cu(III)/Cu(IV) has been stabilized in the three dimensional lattice of the perovskite-type oxide Lal_-xSr_xCuO₃ (0 ≥ ′ ≥ 0,25). Chemical analysis and XPS study confirm the mixed valence. This compound shows metallic properties with an broadening of the conduction band compared to LaCu0₃. Such a behaviour can be explained either by the increase of the covalence of the average Cu-0 bond or by the decrease of the structural distortion induced by the substitution of Sr(II) for La(III). No superconducting property has been detected down to 4K.     

Diffusion and point defects in Cu2O

The diffusion of⁶⁴Cu in Cu₂O has been measured by a serial-sectioning technique as a function of temperature (700–1153°C) and oxygen partial pressure (10^?6?8 × 10^2&#x0304; atm). The oxygen-partial-pressure and temperature dependencies of D¹_Cu suggest that both neutral and singly charged copper vacancies contribute to cation self-diffusion. A defect model involving both neutral and singly charged copper vacancies, electron holes, and singly charged oxygen-interstitial ions is developed and fit to the tracer-diffusion data, the electrical-conductivity data (Maluenda et al.), and the stoichiometry data (O'Keeffe and Moore). The resulting defect data are quantitatively consistent with the chemical-diffusion data (Maluenda et al.) and with a correlation factor $\text{f}{}_{\mathrm{v}}\text{=}\text{2}\text{3}$. The defect data are also quantitatively consistent with the high-temperature oxidation studies of copper metal (Iguchi et al.) and with the copper vacancy being 10 times more mobile than the oxygen-interstitial ion at 10002C.     

Nanocrystalline zeolite beta and zeolite Y as catalysts in used palm oil cracking for the production of biofuel

Nanocrystalline zeolites with crystal size smaller than 100 nm are potential replacement for conventional zeolite catalysts due to their unique characteristics and advantages. In this study, the synthesis of nanocrystalline zeolite Y (FAU) and nanocrystalline zeolite beta (BEA) under hydrothermal conditions is reported. The effect of crystal size on the physico-chemical characteristics of the zeolite, Y (FAU), and beta (BEA) is reported. The properties of nanocrystalline zeolites Y and Beta with crystal size around 50 nm are compared with the microcrystalline zeolite Y and microcrystalline zeolite beta, respectively. The performance of the nanocrystalline zeolite as a catalyst was investigated in the cracking of used palm oil for the production of biofuel. The nanocrystalline zeolite catalytic activity was compared with the activity of microcrystalline zeolite in order to study the effect of crystal size on the catalytic activity. Both nanocrystalline zeolites gave better performance in terms of conversion of used palm oil as well as selectivity for the formation of gasoline fraction. The increase in surface area and improved accessibility of the reactant in nanocrystalline zeolites enhanced the cracking activity as well as the desired product selectivity.     

Synthesis, characterization and catalytic oxidation properties of multi-wall carbon nanotubes with a covalently attached copper(II) salen complex

Hydroxyl functionalized copper(II) Schiff-base, N,N′-bis(4-hydroxysalicylidene)-ethylene-1,2-diaminecopper(II), [Cu((OH)₂-salen)], has been covalently anchored on modified MWCNTs. The new modified MWCNTs ([Cu((OH)₂-salen)]-MWCNTs) have been characterized by TEM, thermal analysis, XRD, XPS, UV-vis, DRS, FT-IR spectroscopy and elemental analysis. The modified copper(II) MWCNTs solid was used to affect the catalytic oxidation of ethylbenzene with tert-butylhydroperoxide as the oxidant at 333 K. The system is truly heterogeneous (no leaching observed) and reusable (no decrease in activity) in three consecutive runs. Acetophenone was the major product though small amounts of o- and p-hydroxyacetophenones were also formed revealing that C-H bond activation takes place both at benzylic and aromatic ring carbon atoms. Ring hydroxylation was more over the “neat” complexes than over the encapsulated complexes.     

Nucleoside-copper(II) system in water and on 13X-zeolite studied by continuous-wave and pulsed-wave ESR

In order to study the effects of large-surface-area solids on the formation of biomacromolecules, copper(II)-nucleosides complexes were studied in water at high pH and after contact with the cavity walls of 13X-zeolite. The results were mainly collected by electron spin resonance in continuous (cw-ESR) and pulsed (ESE) wave. Particular attention was dedicated to adenosine as a nucleoside model for the formation of compounds which were fully characterized in alkaline water solution and after adsorption on commercial 13X-zeolite. In aqueous solution, adenosine was coordinated to copper(II) through deprotonated hydroxyl groups in the 2′ and 3′ positions of the ribose unit, with the formation of [Cu(adenosine)₂(H₂O)₂]²⁻. When adsorbed on zeolite, both cw-ESR and ESE showed that a fraction of the adsorbed complexes did not change their structure and showed high mobility in the zeolite faujasite cavity. The remaining fraction directly interacted with²⁷Al nuclei of the zeolite framework. Other copper(II)-nucleosides behaved in the same manner. Surprisingly enough, alkaline solutions of nucleosides were able to remove copper (II) from zeolite in the form of [Cu(adenosine)₂(H₂O)₂]²⁻ which freely moved in the supernatant aqueous liquid.     

A novel precursor for synthesis of metallic copper nanocrystals by thermal decomposition approach

[Bis(2-hydroxy-1-naphthaldehydato)copper(II)] complex, as a novel precursor, was employed in thermal decomposition process to synthesize metallic copper nanoparticles using oleylamine (C₁₈H₃₇N) as capping agent. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and ultraviolet-visible (UV-vis) spectroscopy. The synthesized copper nanoparticles have a fcc structure with average size 20-35 nm.     

The effect of the next nearest neighbor ion on the X-ray photoelectron spectra of 2p levels for Co2+, Ni2+ and Cu2+ in MgO

The X-ray photoelectron spectra of Co, Ni and Cu 2p levels for samples of M_xMg_1-xO (M = Co, Ni, Cu), CoO, NiO and CuO were compared. The binding energies of metal 2p_{$\text{3}\text{2}$} levels did not change with their concentration. The shake-up satellite main peak intensity ratios and FWHM of metal 2p levels for Co²⁺ and Cu²⁺ in MgO were smaller than those for CoO and CuO. The Ni 2p_{$\text{3}\text{2}$} spectrum for Ni²⁺ in MgO had no shoulder, unlike NiO. Results indicate that next nearest neighbor ions (metal ions) may influence the final states after photoelectron ejection.     

Quantum chemical study of Li-, Na- and K-faujasites

The physico-chemical properties of Li-, Na- and K-zeolites modelled by T₆O₆(OH)₁₂ clusters were studied by the CNDO/2 method. It was shown that the physical characteristics of the zeolite skeleton (charge density, bond strength, electron structure) are practically independent of the type of cation coordinated in its S_II and S_I' cation positions. The studied zeolites differ in the cation charge, which has values of about 0.0, 0.3 and 0.6 for Li, Na and K, respectively, and in the character of the cation-skeleton bonds in the zeolite, whose ionicity decreases in the order, K>Na>62Li. The calculated characteristics of zeolites are employed in the discussion of their interactions with H₂O.     

Proton spin relaxation in the system NaPtY zeolite/water; the state of platinum

In commercial zeolites the longitudinal proton spin relaxation time T₁ of adsorbed molecules is predominantly caused by paramagnetic impurities (0.07 wt% of iron in the starting NaY zeolite). Only 1 wt% of platinum, introduced as [Pt(NH₃)4]²⁺, enhances T₁ of water up to one order of magnitude, depending on the thermal pretreatment of the exchanged zeolite. In connection with the behaviour of the transverse relaxation time T₂ and with the mass spectrum of the gases escaping during thermal pretreatment, it is concluded from the strong effect on T₁ that the Pt²⁺ ions are reduced by the ammonia to atomic platinum and that the Pt atoms migrate preferentially to Fe³⁺ ions. Thus, Fe³⁺ ions, controlling T₁, are covered and up to 90% of paramagnetic sites for water are occupied by Pt atoms, whereas in the case of a statistical distribution of the Pt atoms, the probability for a paramagnetic site to be occupied by platinum amounts to 0.1% to 1%. Presumably, the iron species covered are Fe³⁺ ions in cationic sites of the zeolite, as in this case besides dispersion energy $\text{(E}{}_{\mathrm{dis}}\text{≈}\text{kcal}\text{mol}\text{)}$ polarization energy of the pair Pt-Fe³⁺ comes into play, surmounting E_dis by two orders of magnitude.     

Rotational and hyperfine structure in the yellow system of CuF

Previous spectroscopic studies of copper monofluoride have suggested that the excited electronic state involved in the yellow system is either ³Σ^? or a (¹Π, ¹Σ) “p-complex”. A Doppler-limited (HWHM ? 0.4 GHz), laser-induced fluorescence study of the (0, 0) band of the ⁶³Cu¹⁹F isotopic species was performed in order to make a more definite assignment of the upper state. As a result of increased resolution, many of the rotational lines appear as partially resolved quartets resulting from the ⁶³Cu ($\text{I =}\text{3}\text{2}$) nuclear hyperfine splitting. It was not possible on the evidence available to decide between the alternative assignments for the upper state. Assuming a ³Σ^? state, 200 features were assigned, measured, and fitted by a least-squares procedure to determine values for the parameters (cm^?1) of CuF in the excited state: T₀ = 17 574.9663(12), λ₀ = ? 27.7149(11), λ_D0 = 0.001161(1), B₀ = 0.375035(2), 10⁶D₀ = 0.510(1), γ₀ = 0.01074(6), $\text{b}{}_{\mathrm{F}}\text{(}{}^{63}\text{Cu}\text{) = 0.032(2)}$, $\text{c(}{}^{63}\text{Cu}\text{) = ?0.039(7)}$. The ⁶³Cu hyperfine parameters are interpreted in terms of possible electronic models of CuF in the A state.     

Paramagnetic silver species in irradiated Ag−NaA zeolites. An EPR and ESEEM study

Several polymeric silver clusters have been observed in Ag_x?NaA zeolite (x=1,6) of varying water content, which was exposed to x-rays at 77 K and annealed at higher temperatures.¹⁰⁹Ag₁?NaA zeolite dehydrated at 130°C yields the dimer¹⁰⁹Ag₂ ⁺ and the trimer¹⁰⁹Ag₃ ²⁺ after irradiation at 77 K and annealing at 240 K. Owing to the use of one Ag isotope the EPR spectra of these species are highly resolved exhibitingg and hyperfine anisotropy. By irradiation of¹⁰⁹Ag_x?NaA zeolite (x=1,6) in hydrated form two new trimeric silver clusters I and II are produced. The ratio between I and II depends on the initial Ag content. ESEEM spectra of these species show interaction with aluminum nuclei of the framework and with distant water molecules. If Ag₆?NaA zeolite dehydrated at 130°C is irradiated the hexameric cluster Ag₆ ⁿ⁺ is formed. The ESEEM spectrum shows interaction only to aluminum nuclei. From ESEEM experiments on Ag₆ ⁿ⁺ with added adsorbates (D₂O, CD₃OD) it could be inferred that Ag₆ ⁿ⁺ is only stable if the neighbouring cages do not contain adsorbate molecules.     

Selective adsorption of He,H2 on copper surfaces

The selective adsorption of helium and molecular hydrogen has been experimentally observed on various copper surfaces characterized by a quasi one-dimensional corrugation: Cu(110), (113), (115), (117). Four bound state energy levels for the He-Cu potential and six for H₂-Cu have been measured. They are independent of the surface crystalline structure. They are well fitted by a 9-3 potential from which the well depth is deduced: D = 6.35 meV for He-Cu and D = 22 meV for H₂Cu. The Van der Waals constant C₃ is also estimated from the data. The ratio is approximately the ratio of the static polarizabilities of He and H₂. The semi-empirical formula of Hoinkes is found to agree with the present data.