Mechanism of aluminum hydroxide layer formation by surface modification of aluminum

In this study, a new, relatively simple and rapid fabrication method for forming an Al(OH)₃ film on Al substrates was demonstrated. This method, i.e., alkali surface modification, is simply comprised of dipping the substrate in a 5 × 10⁻³ M NaOH solution at 80 °C for 1 min and then immersing it in boiling water for 30 min. After alkali surface modification, an Al(OH)₃ film was formed on Al substrate, and its chemical state and crystal structure were confirmed by XPS and TEM. The Al(OH)₃ layer was composed of three regions: an amorphous-rich region, a region of mixed amorphous and crystal domains, and a crystalline-rich region near the Al(OH)₃ layer surface.     

Pyridine-thermal synthesis and high catalytic activity of CeO2/CuO/CNT nanocomposites

Carbon nanotubes (CNTs) were controllably coated with the uninterrupted CuO and CeO₂ composite nanoparticles by a facile pyridine-thermal method and the high catalytic performance for CO oxidation was also found. The obtained nanocomposites were characterized by transmission electron microscopy, scanning electron microscopy, X-ray diffraction as well as X-ray photoelectron spectroscopy. It is found that the CuO/CeO₂ composite nanoparticles are distributed uniformly on the surface of CNTs and the shell of CeO₂/CuO/CNT nanocomposites is made of nanoparticles with a diameter of 30-60 nm. The possible formation mechanism is suggest as follows: the surface of CNTs is modified by the pyridine due to the π-π conjugate role so that the alkaline of pyridine attached on the CNT surface is more enhanced as compared to the one in the bulk solvent, and thus, these pyridines accept the proton from the water molecular preferentially, which result in the formation of the OH⁻ ions around the surface of CNTs. Subsequently, the metal ions such as Ce³⁺ and Cu²⁺ in situ react with the OH⁻ ions and the resultant nanoparticles deposit on the surface of CNTs, and finally the CeO₂/CuO/CNT nanocomposites are obtained. The T₅₀ depicting the catalytic activity for CO oxidation over CeO₂/CuO/CNT nanocomposites can reach ∼113 °C, which is much lower than that of CeO₂/CNT or CuO/CNT nanocomposites or CNTs.     

Native oxidation of ultra high purity Cu bulk and thin films

The effect of microstructure and purity on the native oxidation of Cu was studied by using angle-resolved X-ray photoelectron spectroscopy (AR-XPS) and spectroscopic ellipsometry (SE). A high quality copper film prepared by ion beam deposition under a substrate bias voltage of −50 V (IBD Cu film at V_s = −50 V) showed an oxidation resistance as high as an ultra high purity copper (UHP Cu) bulk, whereas a Cu film deposited without substrate bias voltage (IBD Cu film at V_s = 0 V) showed lower oxidation resistance. The growth of Cu₂O layer on the UHP Cu bulk and both types of the films obeyed in principle a logarithmic rate law. However, the growth of oxide layer on the IBD Cu films at V_s = 0 and −50 V deviated upward from the logarithmic rate law after the exposure time of 320 and 800 h, respectively. The deviation from the logarithmic law is due to the formation of CuO on the Cu₂O layer after a critical time.     

Enhancement of output performance of Cu2ZnSnS4 thin film solar cells—A numerical simulation approach and comparison to experiments

The formation of stable, low resistance and nonrectifying contacts to Cu₂ZnSnS₄ (CZTS) thin film photovoltaic material are the major and critical challenges associated with its effect over the output performance of fabricated solar cells. The solution of continuity equation in one dimension for a soda lime glass substrates (SLG) |Mo | CZTS | CdS | ZnO:Al cell structure is considered in the simulation of its current–voltage characteristics that is governed by the back contact material, acceptor concentration as well as thickness of the CZTS layer. Our primary simulation shows a 6.44% efficiency of the CZTS solar cell which is comparable to reported experimental data if these parameters are not optimized. However, by optimizing them a simulated conversion efficiency as high as 13.41% (V_oc=1.002 V, J_sc=19.31 mA/cm², fill factor (FF)=69.35%) could be achievable. The solar cell with a back contact metal work function of 5.5 eV, an absorber layer's thickness of 2.68 μm and an acceptor concentration of 5×10¹⁶ cm⁻³ were optimum. The presented optimization is ideal and subject to experimental verification with a precise control of the process parameters along with reduced surface as well as bulk recombination, secondary phases and thermalization losses.     

Adsorption and photocatalytic degradation of methylene blue on Zn1−xCuxS nanoparticles prepared by a simple green method

Nanoparticles of Zn_1−xCu_xS with various dopant contents (0 ≤ x ≤ 0.15) were prepared in water by refluxing for 90 min at about 95 °C. Powder X-ray diffraction (XRD) patterns of the nanoparticles demonstrate that loading of Cu²⁺ ions does not change the crystal structure of ZnS. Scanning electron microscopy (SEM) images demonstrate that size of the nanoparticles decreases with increasing Cu²⁺ ions. UV-Vis diffuse reflectance spectra (DRS) of the nanoparticles show significant absorption in visible light region. Adsorption capacity of the nanoparticles for methylene blue (MB) increases with mole fraction of copper ions. Photocatalytic activity of the nanoparticles toward photodegradation of MB was evaluated under visible light irradiation. The results indicate that Zn_0.85Cu_0.15S nanoparticles exhibit highest photocatalytic activity among the prepared samples. Moreover, effects of refluxing time applied for preparation of the nanoparticles and calcination temperature were investigated.     

Investigation of oxygen states and reactivities on a nanostructured cupric oxide surface

Nanostructured copper (II) oxide was formed on clean copper foil at room temperature using activated oxygen produced by RF discharge. CuO particles of approximately 10-20 nm were observed on the surface by Scanning Tunneling Microscopy (STM). The copper states and oxygen species of the model cupric oxide were studied by means of X-ray Photoelectron Spectroscopy (XPS). These oxide particles demonstrated abnormally high reactivity with carbon monoxide (CO) at temperatures below 100 °C. The XPS data showed that the interaction of CO with the nanostructured cupric oxide resulted in reduction of the CuO particles to Cu₂O species. The reactivity of the nanostructured cupric oxide to CO was studied at 80 °C using XPS in step-by-step mode. The initial reactivity was estimated to be 5 × 10⁻⁵ and was steadily reduced down to 5 × 10⁻⁹ as the exposure was increased. O1s spectral analysis allowed us to propose that the high initial reactivity was caused by the presence of non-lattice oxygen states on the surface of the nanostructured CuO. We established that reoxidation of the partially reduced nanostructured cupric oxide by molecular oxygen O₂ restored the highly reactive oxygen form on the surface. These results allowed us to propose that the nanostructured cupric oxide could be used for low temperature catalytic CO oxidation. Some hypotheses concerning the nature of the non-lattice oxygen species with high reactivity are also discussed.     

Studies on chelating adsorption properties of novel composite material polyethyleneimine/silica gel for heavy-metal ions

Firstly, the coordination processes of line-type polyethyleneimine with Cu²⁺, Cd²⁺ and Zn²⁺ were studied by using visible light absorption spectroscopy and chelation conductivity titration method, and the structures of the chelates were determined. Afterwards, polyethyleneimine (PEI) was grafted onto the surface of silica gel particles via the coupling effect of γ-chloropropyl trimethoxysilane (CP), and the novel composite adsorption material PEI/SiO₂ with strong adsorption ability towards heavy-metal ions was prepared. The chelating adsorption properties of PEI/SiO₂ for Cu²⁺, Cd²⁺ and Zn²⁺ were researched by both static (batch) and dynamic (flow) methods. The experiment results show that water-soluble polyamine PEI with line-type structure reacts with Cu²⁺, Cd²⁺ and Zn²⁺ easily and quantitatively, and water-soluble chelates with four ligands are formed. The composite material PEI/SiO₂ possesses very strong chelating adsorption ability for heavy-metal ions, and the saturated adsorption amount can reach 25.94 mg g⁻¹ and 50.01 mg g⁻¹ for Cu²⁺ under static and dynamic conditions, respectively. The isothermal adsorption data fit to Langmuir equation, and the adsorption is typical chemical adsorption with monomolecular layer. The adsorbing ability of PEI/SiO₂ towards the three kinds of the ions follows the order of Cu²⁺ > Cd²⁺ > Zn²⁺. The pH value has great influence on the sorption, and at pH 6-7, the adsorption capacity is the greatest. The fact that adsorption capacity increases with temperature rising indicates the adsorbing process of PEI/SiO₂ for metal ions is endothermic. As diluted hydrochloric acid is used as eluent, the adsorbed heavy-metal ions are eluted easily from PEI/SiO₂, and the regeneration and reuse without decreasing sorption for PEI/SiO₂ are demonstrated.     

Microgravimetric and voltammetric study of Zn underpotential deposition on platinum in alkaline medium

The microgravimetric and voltammetric responses of a polycrystalline Pt electrode in 0.1 mol L⁻¹ NaOH solution in the presence and the absence of 1.6 × 10⁻⁴ Zn²⁺, at 0.1 V s⁻¹ were analyzed. During the positive potential sweep, the water molecules are progressively substituted by OH⁻ ions, prior to PtO formation. The voltammetric charges obtained under the Zn_ads dissolution peaks suggest that 0.7 monolayers are deposited, with each Zn ad-atom occupying one active site and transferring two electrons. The total loss of mass due to the dissolution of the Zn ad-layer was 136.6 ng cm⁻² and the mass increase due to PtO formation was found to be only 12 ng cm⁻² less than the theoretical ones, 157.5 and 37.4 ng cm⁻², respectively, indicating that both processes are overlapped. In this way it is proposed that an adsorbed by-layer of Zn and OH⁻ ions is formed.     

Metal ion release and surface composition of the Cu-18Ni-20Zn nickel-silver during 30 days immersion in artificial sweat

In order to study nickel ion release associated with nickel allergy, Cu-18Ni-20Zn nickel-silver alloy was immersed in artificial sweat and Ringer physiological solution for 30 days. Dissolution of metal ions was measured as a function of time, and the characteristics of the solid surface layer formed after 30 days were studied by SEM/EDS and XPS. The dissolution of nickel prevails over dissolution of copper and zinc. Nickel release in artificial sweat is approximately 10 times higher than in Ringer physiological solution and in both solutions the nickel release exceeds 0.5 μg cm⁻² week⁻¹, the threshold above which the allergy is triggered. Evidence of selective nickel dissolution is reported. The composition of the surface layer formed in artificial sweat and in Ringer physiological solution differs in the content of nickel and chlorine. In artificial sweat, the major constituents of the surface layer are dominantly oxides, Cu₂O and ZnO, with traces of chlorine. In Ringer physiological solution, the composition of the surface layer changes to a mixture of oxides, chlorides and/or oxychlorides. Two components peaks were detected in the Cl 2p_3/2 peak; however, it was not possible to distinguish the exact nature of the chloride compound formed. The mechanism of nickel release is discussed as a function of the composition of the solution.     

Preparation of organic acid anion-modified magnesium hydroxides by coprecipitation: A novel material for the uptake of heavy metal ions from aqueous solutions

New layered magnesium hydroxides whose brucite layers had been bridged with malate²⁻ and tartrate²⁻ were prepared by dropwise addition of Mg(NO₃)₂ to malate and tartrate solutions at a constant pH of 10.5. Malate²⁻ and tartrate²⁻ may have been also absorbed on the surfaces of hydroxides. In the case of using citrate solution, Mg(OH)₂ absorbed with citrate³⁻ was produced. These materials were found to take up Cu²⁺ rapidly from an aqueous solution at pH 5.0. Copper uptake by precipitates is attributed to the formation of chelate complexes of Cu²⁺ with citrate³⁻, malate²⁻, and tartrate²⁻.     

Room temperature ferromagnetism in Fe doped CuO nanorods

One dimensional CuO and Fe doped CuO nanorods have been synthesized by template free solution phase hydrothermal methods. The typical diameter and the length of the Cu_1−xFe_xO nanorods (x=0, 0.02, 0.05, 0.10) are 20-25 and 300-400 nm. Pure CuO nanorods show weak ferromagnetism and the introduction of Fe within CuO lattice improves significantly the ferromagnetic property with the Curie temperature far above room temperature. The shape anisotropy is the key point to understand ferromagnetism in Fe doped CuO nanorods.     

Spectroscopical splitting of Cu ion energy levels in magnesium lead fluoro silicate glasses

Homogeneous 40.0 MgO-(10-x) PbF₂-50.0 SiO₂: x CuO glasses were prepared using melt-quenching technique under controlled conditions. Spectroscopic studies (UV-vis absorption, ESR, FT-IR) are carried out for these glasses. One broad characteristic visible absorption band is observed around 700-850 nm in these glasses, the optical band gap decreases as the content of the CuO increases in the glass network up to 0.7 mol % then reversal trend is observed. ESR spectra of all these glasses show resonance peaks characteristic of Cu²⁺ ions and hyperfine splitting is resolved with increasing the CuO content in the glass network. From the observed ESR spectra, the spin-Hamiltonian parameters have been evaluated and indicate that Cu²⁺ ions have octahedral coordination with a strong tetragonal distortion in these glasses. By correlating ESR and optical absorption data, the molecular orbital coefficients have been evaluated. FT-IR spectra give important information about the nature of bonds in the glass matrix. The density of the glasses is also measured and is found to decrease with the increase CuO contents in the glass matrix. The physical parameters along with spectroscopic parameters are measured.     

Cu-Zn-Al mixed metal oxides derived from hydroxycarbonate precursors for H2S removal at low temperature

One series of Cu-Zn and two series of Cu-Zn-Al hydroxycarbonate precursors with varying metal molar ratios were prepared via co-precipitation or multi-precipitation method, and the mixed metal oxides obtained by calcination of the precursor materials were used as adsorbents for H₂S removal in the range of 25-100 °C. The results of H₂S adsorption tests showed that these mixed oxides, especially two series of Cu-Zn-Al mixed metal oxides exhibited markedly high breakthrough sulfur capacities (ranging from 4.4 to 25.7 g S/100 g-sorbent with increase of Cu/Zn molar ratio) at 40 °C. Incorporation Cu and/or Al decreased the mean crystalline sizes of ZnO and CuO species in the Cu-Zn and Cu-Zn-Al mixed metal oxide adsorbents by decreasing of mean crystalline sizes of hydroxycarbanate phases mainly including hydrozincite, aurichalcite and malachite, segregation of Al phase, etc. Higher breakthrough sulfur capacity of each adsorbent in two ternary series than that of the corresponding adsorbent in binary series should be ascribed to the enhancement of the dispersion of ZnO and/or CuO species with incorporation of aluminum, thereby increasing the overall rate of reaction between the adsorbent and H₂S by reducing the thickness of potential sulfide shell on the outer layer of the oxide crystalline grains and increasing the area of the interface for the exchange of HS⁻/S²⁻ and O²⁻. For each series of adsorbents, the breakthrough sulfur capacity increased with the increase of Cu/Zn molar ratio regardless of changes of the dispersion of CuO and/or ZnO. This phenomenon might be mainly attributed to faster rate of the lattice diffusion of HS⁻, S²⁻ and O²⁻ or exchange of HS⁻/S²⁻ and O²⁻ during the sulfidation of CuO than that during the sulfidation of ZnO due to less rearrangement of the anion lattice.     

CuO-PAA hybrid films: Chemical synthesis and supercapacitor behavior

We report the synthesis of CuO-Poly (acrylic) acid (PAA) hybrid thin films by a cost-effective spin coating technique for supercapacitor application. Coated films were annealed at 300, 400 and 500 °C, to study the annealing effect on the supercapacitor behavior. Further films were characterized by X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform-Raman spectroscopy (FT-Raman) and Fourier transform-Infrared spectroscopy (FT-IR) techniques. Energy dispersive spectroscopy (EDS) shows the formation of amorphous blend of CuO and Cu₂O phases at 300 °C. Further, films annealed at 400 and 500 °C exhibit polycrystalline phase pure CuO with monoclinic structure. The scanning electron microscopy (SEM) micrographs show the transition of island-like structure to CuO crystals surrounded by PAA grafted composite ring with increase in annealing temperature. The possible growth mechanism of PAA and CuO bonding is discussed. Cyclic voltammetry (CV) is employed to calculate the specific capacitance (C_sp) in 1 M H₂SO₄ electrolyte. It is observed that the C_sp increases from 41 to136 F g⁻¹ with increase in annealing temperature.     

Growth and characterization of CuxS (x=1.0, 1.76, and 2.0) thin films grown by solution growth technique (SGT)

Thin films of Cu_xS (x=1.0, 1.76, and 2.0) were grown by solution growth technique (SGT). The deposition parameters such as pH of solution, deposition time, and deposition temperature were optimized. The deposited films were annealed in Ar atmosphere at 250 °C. The changes in structural and optical transport phenomenon of annealed films have been studied. The surface morphology and composition of films were studied by SEM micrographs and EDAX analysis, respectively, and the surface roughness was calculated by atomic force microscopy (AFM). The XRD study showed the polycrystalline nature of annealed film. The lattice parameters of different phases of the material were calculated from the XRD pattern. The absorption coefficient varies in the range of 1×10⁵-6×10⁵ cm⁻¹. The optical bandgaps of CuS, Cu_1.76S, and Cu₂S are 1.72, 2.11, and 2.48 eV, respectively.     

Field emission property of copper nitride thin film deposited by reactive magnetron sputtering

Copper nitride (Cu₃N) thin film was deposited on silicon (Si) substrate by reactive magnetron sputtering method. X-ray diffraction measurement showed that the film was composed of Cu₃N crystallites with anti-ReO₃ structure and exhibited preferential orientation of [1 0 0] direction. The field emission (FE) result showed that Cu₃N film had a turn-on electric field of about 3 V/μm at a current density of 1 μA/cm² and a current density of 700 μA/cm² was obtained at the electric field of 24 V/μm. The emission mechanism inferred by Fowler-Nordheim (FN) plot is shown as following: thermal electron emission at low field region and tunneling electron emission at high field region.     

Structural and magnetic properties of Cu1−xMnxO nanocrystal prepared by combustion synthesis

Nanoscale Cu_1−xMn_xO powder is prepared by using the combustion synthesis technique with two different fuels. The structural properties of the powder are determined using Rietveld refinement of X-ray diffraction data, high-resolution transmission electron microscopy, and Fourier transform infrared spectroscopy, while its magnetic properties are analyzed by means of hysteresis loop and temperature dependence of magnetization. The results show that (1) the Cu_1−xMn_xO nanocrystal is of monoclinic CuO structure, with grain size of 10-30 nm varying with the type of fuel, the nitrate/fuel ratio (N/F), and the Mn concentration, the doping of Mn has a little influence on the lattice parameters; (2) when the Mn concentration is higher than 7%, a small amount of impurity phase of CuMn₂O₄ appears and annihilates the potential cation vacancies; (3) all of the samples with x≥5% exhibit low-temperature ferromagnetism with the Curie temperature of ∼90 K, which increases slightly by raising the Mn concentration; (4) the paramagnetic moment per Mn ion is around 2-4 bohr magneton above the Curie temperature, which decreases with increasing Mn concentration, implying that the nearest Mn ions are antiferromagnetically coupled and the ferromagnetic order could originate from the super-exchange of next nearest Mn ions along the [1 0 1?] direction.     

Variable temperature EPR spectra of Copper (II) ions in kainite crystals

X-band electron paramagnetic resonance (EPR) studies on divalent copper ions embedded in KMgClSO₄·3H₂O single crystals have been performed at low temperature (123 K). The angular variation of the EPR spectra reveals the presence of two Cu²⁺ sites, which have different orientations. The spin-Hamiltonian parameters of this six-coordinated cupric ion have been evaluated from the EPR spectra at 123 K. The forbidden lines due to Δm_I=±1 transitions are observed in between allowed transitions. The temperature variation EPR studies have also been performed both for a single crystal and a polycrystalline sample. The ground state wavefunction of Cu²⁺ ions has been estimated and is found to be an admixture of d_3z²−r² and d_x²−y². The temperature variation of the EPR spectra reveals that Cu²⁺ ions exhibit dynamic Jahn-Teller effect. From the polycrystalline EPR data, the temperature dependent magnetic susceptibilities are evaluated and discussed.     

A density functional theory study on the adsorption and dissociation of N2O on Cu2O(1 1 1) surface

Density functional theory has been employed to investigate the adsorption and the dissociation of an N₂O at different sites on perfect and defective Cu₂O(1 1 1) surfaces. The calculations are performed on periodic systems using slab model. The Lewis acid site, Cu_CUS, and Lewis base site, O_SUF are considered for adsorption. Adsorption energies and the energies of the dissociation reaction N₂O → N₂ + O(s) at different sites are calculated. The calculations show that adsorption of N₂O is more favorable on Cu_CUS adsorption site energetically. Cu_CUS site exhibits a very high activity. The Cu_CUS-N₂O reaction is exothermic with a reaction energy of 77.45 kJ mol⁻¹ and an activation energy of 88.82 kJ mol⁻¹, whereas the O_SUF-N₂O reaction is endothermic with a reaction energy of 205.21 kJ mol⁻¹ and an activation energy of 256.19 kJ mol⁻¹. The calculations for defective surface indicate that O vacancy cannot obviously improve the catalytic activity of Cu₂O.     

Failure behavior of ITO diffusion barrier between electroplating Cu and Si substrate annealed in a low vacuum

A structure of Cu/ITO(10 nm)/Si was first formed and then annealed at various temperatures for 5 min in a rapid thermal annealing furnace under 10⁻² Torr pressure. In Cu/ITO(10 nm)/Si structure, the ITO(10 nm) film was coated on Si substrate by sputtering process and the Cu film was deposited on ITO film by electroplating technique. The various Cu/ITO(10 nm)/Si samples were characterized by a four-point probe, a scanning electron microscope, an X-ray diffractometer, and a transmission electron microscope. The results showed that when the annealing temperature increases near 600 °C the interface between Cu and ITO becomes unstable, and the Cu₃Si particles begin to form; and when the annealing temperature increases to 650 °C, a good many of Cu₃Si particles about 1 μm in size form and the sheet resistance of Cu/ITO(10 nm)/Si structure largely increases.