Electrochemically induced reversible solid state transformations: electrosynthesis of Ag2Cu2O4 by room temperature oxidation of Ag2Cu2O3

Electrochemical oxidation at room temperature of a slurry of Ag₂Cu₂O₃ yields a new silver copper oxide, formulated as Ag₂Cu₂O₄, with one more atom of oxygen per unit formula, that can in turn revert to the original precursor. The resulting oxide presents a different electronic and crystal structure from its precursor, as shown by XPS, X-ray and electron diffraction. This phase transformation involves a radical structural change from a 3D to a 2D network, as well as electronic changes involving silver and oxygen. The potential of electrochemical techniques to induce crystal-chemical solid state transformations is analyzed.     

Surface chemical analysis of copper powder used in additive manufacturing

Additive manufacturing (AM) has during years gained significant interest owing to its endless component design possibilities. One of the most popular AM techniques is laser powder bed fusion (LPBF), which selectively melts metal powder layer-by-layer in a chamber with protective argon atmosphere. This technique is attractive for realizing Cu-based products in which the high electrical conductivity of Cu is combined with component design possibilities. The successful use of Cu powder not only poses challenges owing to the high reflectivity and thermal conductivity of Cu but also involves the important concern of controlling the powder surface chemistry since the powder surface constitutes the main source of oxygen. It is of crucial importance to control the oxygen level in order to maintain good electrical conductivity and brazing ability of the AM-fabricated Cu-part. In LPBF, fine spherical powder with size of 10–60 μm is used, providing significant specific surface area, and this powder is also usually recycled several times, and hence, the role of powder surface chemistry is evident. Two kinds of copper powder with purities 99.70 and 99.95 wt% were analysed in both virgin and in used conditions after numerous printing cycles using LPBF. The powder was analysed by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). A clear difference between the two powder grades in terms of surface chemistry was observed. The oxide thickness and bulk oxygen content increased for both powder grades after recycling. The surface oxides under different conditions are identified and the effect of powder purity on the oxide formed is discussed.     

Cu_xCo_(1-x)/Al_2O_3/FeCrAl整体式催化剂上甲苯催化燃烧(英文)

以FeCrAl合金薄片为基底,Al2O3浆料为过渡胶体,不同摩尔比的Cu、Co为催化活性组分,制备了一系列CuxCo1-x/Al2O3/FeCrAl(x=0-1)新型整体式催化剂.采用X射线粉末衍射(XRD),扫描电子显微镜(SEM),X光电子能谱(XPS)和程序升温还原(TPR)等手段对催化剂的结构进行了表征.在微型固定床反应器上评价了催化剂的催化甲苯燃烧性能.研究结果表明:在所制备的整体式催化剂上,当Cu含量比较低时,形成了Cu-Co-O固溶体;当Cu含量比较高时,可以测得CuO的衍射峰.催化剂表面颗粒大小和形貌与Cu、Co摩尔比密切相关.在催化剂表面,Co以Co2+和Co3+价态存在,而Cu主要以Cu2+价态存在.催化剂中的Cu可以改善Co的氧化还原性,从而有利于催化剂活性的提高.在所制备的催化剂中,Cu0.5Co0.5/Al2O3/FeCrAl催化剂具有最好的活性,甲苯在374oC可以完全催化燃烧消除.     

Effect of atomization on surface oxide composition in 316L stainless steel powders for additive manufacturing

The initial oxide state of powder is essential to the robust additive manufacturing of metal components using powder bed fusion processes. However, the variation of the powder surface oxide composition as a function of the atomizing medium is not clear. This work summarizes a detailed surface characterization of three 316L powders, produced using water atomization (WA), vacuum melting inert gas atomization (VIGA), and nitrogen atomization (GA). X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy analyses were combined to characterize the surface state of the powders. The results showed that the surface oxides consisted of a thin (~4 nm) iron oxide (Fe₂O₃) layer with particulate oxide phases rich in Cr, Mn, and Si, with a varying composition. XPS analysis combined with depth-profiling showed that the VIGA powder had the lowest surface coverage of particulate compounds, followed by the GA powder, whereas the WA powder had the largest fraction of particulate surface oxides. The composition of the oxides was evaluated based on the XPS analysis of the oxide standards. Effects of Ar sputtering on the peak positions of the oxide standards were evaluated with the aim of providing an accurate analysis of the oxide characteristics at different etch depths.     

Plasma-assisted oxidation of Cu(100) and Cu(111)

Oxidized copper surfaces have attracted significant attention in recent years due to their unique catalytic properties, including their enhanced hydrocarbon selectivity during the electrochemical reduction of CO₂. Although oxygen plasma has been used to create highly active copper oxide electrodes for CO₂RR, how such treatment alters the copper surface is still poorly understood. Here, we study the oxidation of Cu(100) and Cu(111) surfaces by sequential exposure to a low-pressure oxygen plasma at room temperature. We used scanning tunnelling microscopy (STM), low energy electron microscopy (LEEM), X-ray photoelectron spectroscopy (XPS), near edge X-ray absorption fine structure spectroscopy (NEXAFS) and low energy electron diffraction (LEED) for the comprehensive characterization of the resulting oxide films. O₂-plasma exposure initially induces the growth of 3-dimensional oxide islands surrounded by an O-covered Cu surface. With ongoing plasma exposure, the islands coalesce and form a closed oxide film. Utilizing spectroscopy, we traced the evolution of metallic Cu, Cu₂O and CuO species upon oxygen plasma exposure and found a dependence of the surface structure and chemical state on the substrate''s orientation. On Cu(100) the oxide islands grow with a lower rate than on the (111) surface. Furthermore, while on Cu(100) only Cu₂O is formed during the initial growth phase, both Cu₂O and CuO species are simultaneously generated on Cu(111). Finally, prolonged oxygen plasma exposure results in a sandwiched film structure with CuO at the surface and Cu₂O at the interface to the metallic support. A stable CuO(111) surface orientation is identified in both cases, aligned to the Cu(111) support, but with two coexisting rotational domains on Cu(100). These findings illustrate the possibility of tailoring the oxidation state, structure and morphology of metallic surfaces for a wide range of applications through oxygen plasma treatments.

A low-pressure oxygen plasma oxidized Cu(100) and Cu(111) surfaces at room temperature. The time-dependent evolution of surface structure and chemical composition is reported in detail for a range of exposure times up to 30 min.     

Copper oxides: kinetics of formation and semiconducting properties. Part I. Polycrystalline copper and copper-gold alloys

The anodic formation of Cu(I) and Cu(II) oxides on polycrystalline copper and copper-gold alloys (4 and 15 at% Au) in deoxygenated 0.1 M KOH was examined by voltammetry, chronoamperometry, and chronopotentiometry with a synchronous registration of photocurrent and photopotential, in situ spectroscopy of photocurrent as well as XPS and SEM measurements. The band gap of p-Cu₂O is 2.2 eV for indirect optical transitions independent of the concentration of gold in Cu-Au alloy. It grows on CuOH or n-Cu₂O underlayer. The increase of anodic potential results in a thickening of oxide film which is a mixture of Cu(I) and Cu(II) oxides. The latter is a p-type semiconductor with a low photosensitivity. The rate of oxide formation on the alloys is lower than on copper. The structure-dependent properties of the oxide phase on the alloys and copper are different. Copper is prone to corrosive oxidation even in deoxygenated alkaline solution by the traces of molecular oxygen. The corrosive growth of Cu(I) oxide film occurs according to the parabolic law. After the cathodic polarization, the surface of copper remains free of corrosive oxide no longer than 15–20 min. The preliminary anodic formation even of a thin Cu₂O film as well as the alloying of copper with gold suppresses the corrosive oxidation of copper.     

Copper-cerium oxide catalysts for the selective oxidation of carbon monoxide in hydrogen-containing mixtures: II. Physicochemical characterization of the catalysts

The copper-cerium oxide catalysts were characterized using a set of physicochemical techniques including in situ FTIR spectroscopy, XPS, and XRD. It was found that copper segregated on the surface of cerium oxide and its states were labile and dependent on catalyst pretreatment conditions. Copper in a dispersed state was responsible for the reaction of CO oxidation in the presence of H₂ on the copper-cerium oxide catalysts. It is likely that this state of copper was composed of two-dimensional or three-dimensional surface clusters containing Cu⁺ ions.     

Iron(III) Oxide Graphite Composite Electrodes: Application to the Electroanalytical Detection of Hydrazine and Hydrogen Peroxide

Composite electrodes based on iron(III) oxide, Fe₂O₃, carbon powder and epoxy resin have been prepared and characterized using electrochemical methods and X‐ray photoelectron spectroscopy (XPS). Initially composite electrodes were made by mixing micron sized carbon powder surface with iron(III) oxide. However, the voltammetric responses were unsatisfactory. Therefore, a new type of composite electrodes was made using carbon powder modified with iron(III) oxide via a wet impregnation procedure. This technique involves saturation of the carbon powder with iron(III) nitrate followed by thermal treatment at ca. 623 K forming iron(III) oxide on the surface of the carbon powder.     

State of the Cu electrode surface studied by X-ray photoelectron and Auger spectroscopies

Annealing of the copper plate in flame was found (by XPS and X-ray Auger spectroscopy) to enrich the surface copper layers in oxygen in the forms of Cu₂O and adsorbed oxygen. The changes in the surface layers of the copper cathode due to annealing can be the origin of the earlier found enhancement of its activity in the electrocatalytic hydrogenation of citral and trans-2-allyl-6-R-1,2,3,6-tetrahydropyridines (R = Me, All, Ph). This method of the copper electrode pre-treatment provides its long durability, an insignificant decrease in the electrocatalytic activity in time, and the reproducibility of the electrocatalytic hydrogenation of unsaturated organic compounds.     

Comparative investigation on copper oxides by depth profiling using XPS, RBS and GDOES

Depth profiling has been performed by using X-ray photoelectron spectrometry (XPS) in combination with Ar-ion sputtering, Rutherford backscattering spectrometry (RBS) and glow discharge optical emission spectrometry (GDOES). The data obtained by XPS have been subjected to factor analysis in order to determine the compositional layering of the copper oxides. This leads to two or three relevant components within the oxide layers consisting of Cu₂O or CuO dependent on the sample preparation. GDOES measurements show sputtering profiles which are seriously influenced by a varying sputter rate. To ensure the results obtained so far, RBS measurements of the oxide layers have been carried out in order to discover artefacts of the other methods used and to demonstrate the excellent suitability of RBS for quantitative analysis of these layers. Chemical analysis consisting of (1) carrier-gas fusion analysis (CGFA) and (2) selective dissolution of Cu₂O/CuO allows the determination of the total amount of oxygen and copper, respectively, and can serve as a cornerstone of quantitative analysis.     

XPS,UPS, and STM studies of nanostructured CuO films

A Cu₁O_1.7 oxide film containing a large amout of superstoichiometric oxygen was obtained by low-temperature oxidation of metallic copper in the oxygen plasma. An STM study of the film structure showed that ～10 nm planar copper oxide nanocrystallites with particles packed parallel to the starting metal surface. In an XPS study, the spectral characteristics of the Cu2p and O1s lines indicated that particles with a CuO lattice formed (E _bnd(Cu2p _3/2) = 933.3 eV and a shake-up satellite, E _bnd(O1s) = 529.3 eV). The additional superstoichiometric oxygen is localized at the sites of contact of nanoparticles in the interunit space and is characterized by a state with the binding energy E _bnd(O1s) = 531.2 eV. Due to the formation of a nanostructure in the films during low-temperature plasma oxidation, the resulting copper oxide has a much lower thermal stability than crystalline oxide CuO.     

Thermal transformations in nanosized copper layers

The thermal treatment of copper films 3–168 nm thick over the temperature range 373–600 K for 1–120 min was shown to result in the formation of copper(I) oxide. Depending on the initial film thickness and temperature, the kinetic curves of the degree of transformation were satisfactorily described by a linear, inverse logarithmic, parabolic, or logarithmic law. Contact potential difference and photo-electromotive force measurements were used to suggest a model including the stages of oxygen adsorption, charge carrier redistribution in the Cu₂O-Cu contact field (negative on the side of Cu₂O), and copper(I) oxide formation.     

Surface Characterisation of Water-Atomised Al–Zn–Mg–Cu Alloy Powders by SIMS and AES

 The present paper focuses on the characterisation of surface composition and alloying element in-depth distribution of water-atomised Al–Zn–Mg–Cu alloy powders by secondary ion mass-spectrometry and Auger electron spectroscopy. A pronounced segregation of Mg and some impurities (Fe, Ca, S) concurrently with some Zn depletion are observed on the powder surface. The oxide film formed on the powder surface mainly consists of Al and Mg oxides. The film is non-uniform in thickness: rather coarse surface oxide islands coexist with surface areas covered by a thin (<1.8 nm) oxide layer. The extent of surface oxidation is strongly affected by solidification conditions: The average thickness of the surface oxides increases with increasing particle size or with decreasing cooling rate. All alloying elements are homogeneously distributed in the bulk of individual particles. No significant differences in chemical composition between different particles of a given powder are observed. Received November 26, 1999. Revision September 25, 2001.     

Surface composition of PdCuAu ternary alloys: a combined LEIS and XPS study

PdCuAu ternary alloy samples with different composition were synthesized on top of ZrO₂‐modified porous stainless steel disks by the sequential electroless deposition technique. The structure, morphology and bulk composition of the samples were characterized by X‐ray diffraction (XRD), scanning electron microscopy and energy dispersive X‐ray spectroscopy (EDX). Complete alloy formation with a pure fcc phase for the Pd₇₁Cu₂₆Au₃, Pd₇₀Cu₂₅Au₅ and Pd₆₇Cu₂₄Au₉ samples and a bcc structure for the Pd₆₂Cu₃₆Au₂ and Pd₆₀Cu₃₇Au₃ samples were obtained upon annealing at 500 °C for 120 h as revealed by XRD. A combination of low‐energy ion scattering (LEIS) and X‐ray photoelectron spectroscopy (XPS) was used to investigate the surface properties of the PdCuAu alloys. XPS results confirmed alloy formation under the annealing conditions. XPS analysis also revealed that the near‐surface regions of the alloys became enriched in Pd with respect to the bulk composition determined by EDX. In contrast, LEIS and angle‐resolved XPS analyses showed that the top‐most surface layers in all samples were copper‐rich compared with the bulk composition. This high Cu surface concentration could impart resistance to bulk sulfide formation to the PdCuAu alloy membranes. Copyright © 2015 John Wiley & Sons, Ltd.     

Characterization and Activity of Cu‐MnOx/γ‐Al2O3 Catalyst for Hydrogenation of Carbon Dioxide

The effect of manganese on the dispersion, reduction behavior and active states of surface of supported copper oxide catalysts have been investigated by XRD, temperature‐programmed reduction and XPS. The activity of methanol synthesis from CO₂/H₂ was also investigated. The catalytic activity over CuO‐MnO_x/γ‐Al₂O₃ catalyst for CO₂ hydrogenation is higher than that of CuO/γ‐Al₂O₃. The adding of manganese is beneficial in enhancing the dispersion of the supported copper oxide and make the TPR peak of the CuO‐MnK_x/γ‐Al₂O₃ catalyst different from the individual supported copper and manganese oxide catalysts, which indicates that there exists strong interaction between the copper and manganese oxide. For the CuO/γ‐Al₂O₃ catalyst there are two reducible copper oxide species; α and β peaks are attributed to the reduction of highly dispersed copper oxide species and bulk CuO species, respectively. For the CuO‐MnO_x/γ‐Al₂O₃ catalyst, four reduction peaks are observed, α peak is attributed to the dispersed copper oxide species; β peak is ascribed to the bulk CuO; γ peak is attributed to the reduction of high dispersed CuO interacting with manganese; δ peak may be the reduction of the manganese oxide interacting with copper oxide. XPS results show that Cu⁺ mostly existed on the working surface of the Cu‐Mn/γ‐Al₂O₃ catalysts. The activity was promoted by Cu with positive charge which was formed by means of long path exchange function between Cu? O? Mn. These results indicate that there is synergistic interaction between the copper and manganese oxide, which is responsible for the high activity of CO₂ hydrogenation.     

Structure and growth of oxides on polycrystalline nickel surfaces

The oxidation of polycrystalline nickel (Ni) metal surfaces after exposure to oxygen gas (O₂) at 25 and 300 °C and pressures near 130 Pa, was studied using X‐ray photoelectron spectroscopy (XPS). Oxide structures involving both divalent (Ni²⁺) and trivalent (Ni³⁺) species could be distinguished using Ni 2p spectra, while surface adsorbed O₂ and atomic oxygen (O) species could be differentiated from bulk oxide (O^2?) using O 1s spectra. Oxide thicknesses and distributions were determined using QUASES^?, and the average oxide thickness was verified using the Strohmeier formula. The reaction kinetics for oxide films grown at 300 °C followed a parabolic mechanism, with an oxide thickness of greater than 4 nm having formed after 60 min. Exposure at 25 °C followed a direct logarithmic mechanism with an oxide growth rate about four to five times slower than at 300 °C. Reaction of a Ni (100) single crystal under comparable conditions showed much slower reaction rates compared to polycrystalline specimens. The higher reaction rate of the polycrystalline materials is attributed to grain boundary transport of Ni cations. Oxide thickness was measured on a microscopic scale for polycrystalline Ni exposed to large doses of O₂ at 25 and 300 °C. The thickness of oxide was not strongly localized on this scale. However, the QUASES^? analysis suggests that there is localized growth on a nanometric scale—the result of island formation. Copyright © 2007 John Wiley & Sons, Ltd.     

Mechanochemical Activation of Cu–CeO<Subscript>2</Subscript> Mixture as a Promising Technique for the Solid-State Synthesis of Catalysts for the Selective Oxidation of CO in the Presence of H<Subscript>2</Subscript>

A new ecologically clean method for the solid-phase synthesis of oxide copper–ceria catalysts with the use of the mechanochemical activation of a mixture of Cu powder (8 wt %) with CeO₂ was developed. It was established that metallic copper was oxidized by oxygen from CeO₂ in the course of mechanochemical activation. The intensity of a signal due to metallic Cu in the X-ray diffraction analysis spectra decreased with the duration of mechanochemical activation. The Cu¹⁺, Cu²⁺, and Ce³⁺ ions were detected on the sample surface by X-ray photoelectron spectroscopy. The application of temperature-programmed reduction (TPR) made it possible to detect two active oxygen species in the reaction of CO oxidation in the regions of 190 and 210–220°C by a TPR-H₂ method and in the regions of 150 and 180–190°C by a TPR-CO method. It is likely that the former species occurred in the catalytically active nanocomposite surface structures containing Cu–O–Ce bonds, whereas the latter occurred in the finely dispersed particles of CuO on the surface of CeO₂. The maximum conversion of CO (98%, 165°C) reached by the mechanochemical activation of the sample for 60 min was almost the same as conversion on a supported CuO/CeO₂ catalyst.     

Nickel- and copper-containing oxide films on titanium

We have studied the composition and structure of films 20–30 μm thick prepared by plasmaassisted electrochemical oxidation (PEO) and additionally modified by impregnation in aqueous solutions of nickel and copper nitrates and then annealed. The investigative tools used were powder X-ray diffraction, electron probe microanalysis (EPMA), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy. Unmodified film/titanium composites have a certain catalytic activity in CO oxidation to CO₂ at temperatures above 300°C; for modified layers, these temperatures are noticeably higher. Modification influences the surface structure, relief, and elemental composition. Relations between the composition and catalytic properties of the oxide layers are discussed.     

Solid state studies on cobalt and copper tungstates nano materials

The cobalt and copper tungstates of the composition Co_1?xCu_xWO₄ (where x = 0.0, 0.3, 0.5, 0.7 and 1.0) were synthesized by co-precipitation method. The compounds were characterized by Thermogravimetric Differential Scanning Calorimeter, X-ray powder diffraction, Infrared spectroscopy, Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) techniques. The Rietveld refinements of X-ray powder diffraction data for the composition Cu_0.5Co_0.5WO₄ reveal the triclinic structure with Pī symmetry. The SEM and TEM studies of the compounds show average particle size in the range of 30–50 nm. The XPS studies confirmed the 2+ oxidation state of the Co and Cu, whereas W exists in 6+ state. The Diffuse reflectance Ultraviolet–visible spectroscopy illustrates band gaps of the compounds ranging from 2.95 to 2.79 eV. The CoWO₄ shows promising photoluminescence result exhibiting strong emission intensity at 468 nm.     

Effect of copper source on the structure–activity of CuAl2O4 spinel catalysts for CO hydrogenation

Due to the complexity of the structure–activity relationship of the CuAl₂O₄ spinel catalyst, optimization of the catalyst structure is a great challenge. In this paper, three different CuAl₂O₄ spinel catalysts were prepared by the solid-phase method using copper hydroxide, copper nitrate, and copper oxide as the copper source, respectively, to study the difference in the structure of CuAl₂O₄ spinel catalysts induced by the raw materials and the catalytic behavior for CO hydrogenation. The structure of CuAl₂O₄ spinel catalyst was characterized by XRD, BET, SEM, TEM, H₂-TPR and XPS. The activity of CO hydrogenation over the CuAl₂O₄ spinel catalyst without pre-reduction was evaluated in the slurry reactor. The results demonstrated that different copper sources had obvious influence on the CuAl₂O₄ spinel texture properties, surface enrichment degree, as well as decomposition and reduction ability, which further regulated the ratio of Cu⁺/Cu⁰ and thus affected the catalytic performance, especially the alcohol distribution. The CuAl₂O₄ spinel, employing copper hydroxide as the copper source, showed better selectivity of C₂₊OH, which was assigned to a higher ratio of Cu⁺/Cu⁰, along with larger pore size and pore volume. Moreover, the synergistic effect between Cu⁰ and γ-Al₂O₃ improved the selectivity of dimethyl ether.