X-ray absorption investigations of copper resinate blackening in a XV century Italian painting

Investigations of the darkening phenomenon of copper resinate observed in a XV century easel painting were carried out by X-ray absorption spectroscopy (XAS) at the GILDA beamline of the European synchrotron radiation facility (ESRF, Grenoble, France). X-ray absorption near edge structure and extended X-ray absorption fine structure (EXAFS) measurements were collected at the Cu K-edge on an original painting sample, as well as on fresh pigment standards and on painting models. The study was aimed at providing structural information of the oxidation states and the local chemical environment (neighbouring atoms and bond distances) of copper in the unaltered and blackened pigments in order to elucidate the discoloration mechanism. Complementary information on optical and molecular properties of copper resinate were obtained by UV-vis and Fourier transform infrared spectroscopies. EXAFS analysis evidenced that the local chemical environment of Cu in copper resinate can be described using neutral copper acetate as a model. It consists, essentially, of bimetal Cu²⁺ carboxylate complexes with a distorted octahedral coordination. Such a structure is retained in the blackened pigment, although some differences were observed. It has been found that the alteration takes place without change of the valence state of Cu(II) ions, while the formation of the copper oxides CuO and Cu₂O responsible for the embrownment is excluded. On the basis of the XAS results we deduced that discoloration of copper resinate may be related to local modification of the copper coordination structure as evidenced by the observation of an increase of the Cu–Cu and Cu–C distances in the EXAFS spectra. PACS  78.70.Dm; 61.10.Ht     

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.     

Selective CO oxidation in hydrogen-rich gas over CuO/CeO2 catalysts

A series of CuO/CeO₂ catalysts with different Cu-Ce compositions were synthesized by co-precipitation method and characterized by X-ray diffraction, H₂-TPR, CO-TPD, SEM and X-ray photoelectron spectroscopy (XPS) techniques. The effects of Cu-Ce composition and water vapor on the catalytic properties for the selective CO oxidation in the hydrogen-rich gas were investigated. The results indicated that CuO (10%)/CeO₂ catalyst remained the maximum CO conversion and selectivity at 140 and 160 °C, while the performance of CuO/CeO₂ catalysts deteriorated with the CuO molar ratio further increased. The interfacial CuO and CeO₂ interaction and synergistic effect enhanced the redox properties of CuO/CeO₂ catalyst and the highly dispersed copper species were proposed as the active sites for the selective CO oxidation. The blockage of catalytic active sites by absorbed water and the formation of CO-H₂O surface complexes reduced the activity of CuO (10%)/CeO₂ catalyst. The decreasing of surface lattice oxygen and absorbed oxygen species and the agglomeration of copper particles were the plausible interpretations for the deactivation of CuO (10%)/CeO₂ catalyst.     

Characterization of copper-exchanged Na-A,X and Y zeolites with X-ray photoelectron spectroscopy and transmission electron microscopy

Copper-exchanged sodium- A, X and Y zeolites have been characterized with X-ray photoelectron Spectroscopy (XPS), with supporting electron microscopy and X-ray diffraction measurements. Under reducing conditions (CO, H₂, 250–450° C), four distinct chemical states of copper have been identified. These are intrazeolite Cu(II), Cu(I) and 1 nm metal clusters, and externally segregated copper metal crystallites. We report spectroscopic data for both the Cu 2p_{$\text{3}\text{2}$} and Auger L₃M_4,5M_4,5 lines. Whereas Cu(II) and metallic copper crystallites have normal spectroscopic parameters, Cu(I) and 1 nm Cu clusters in the reduced zeolites lie in new areas of the two-dimensional chemical state plot.The reduction sequence of Cu(II), Cu(I), Cu clusters and Cu crystallites is different on the A zeolite compared with X and Y. One nm metal clusters are identified as an intermediate phase on the A with transmission electron microscopy (TEM) and XPS prior to external diffusion and crystallite formation. The ease of formation of the cluster intermediate in the A zeolite may be a consequence of the larger diffusion barrier imposed by the 0.42nm supercage aperture compared with the 0.74nm aperture in the X and Y zeolites.     

The electronic structure of SrTiO3 and some simple related oxides (MgO,Al2O3, SrO,TiO2)

The valence band density of states (VBDOS) of the insulating oxides SrTiO₃, TiO₂, SrO, MgO and Al₂O₃ obtained by X-ray photoelectron spectroscopy (XPS), are reported. Qualitatively, the VBDOS of these oxides are similar to one another. The XPS results are compared with results from soft X-ray emission spectroscopy (XES), ultraviolet photoemission spectroscopy (UPS), and theoretical calculations. There are some differences (in particular for TiO₂) between the XES and XPS results, which are probably due to matrix element effects enhancing different features of the VBDOS in the two techniques. The XPS results definitively establish the position of the O 2s level, which had been erroneously assigned in previous low-energy UPS measurements. Cluster-type calculations are demonstrated to give a reasonable representation of the VBDOS for the oxides.     

Characterization of Cr/SiO2 catalysts and ethylene polymerization by XPS

Cr/SiO₂ catalysts with 1 or 3 wt.% Cr loadings and different chromium precursors were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). A method to determine chromium species in the sample was developed through the decomposition of the Cr 2p XPS spectrum in Cr⁶⁺ and Cr³⁺ standard spectra. The results of the binding energy from the Cr 2p region and of the distribution of chromium species allowed to evaluate the dynamic photo-reduction of the surface chromium species during XPS analysis. Photo-reduction of surface Cr⁶⁺ to Cr³⁺ species was verified for all samples supported in silica, depending on the precursor and chromium content. Bulk CrO₃ and Cr₂O₃ standards did not reveal variation in the binding energy of Cr 2p_3/2, but a physical mixture of CrO₃ with SiO₂ presented photo-reduction. The behavior of this mixture resembled to the catalysts and suggests the participation of the surface hydroxyls of silica in the photo-reduction process. XPS intensity measurements for assessing dispersion of chromium oxide were used to compare the calcined and reduced catalysts to different chromium precursors. Polyethylene chains were detected by in situ XPS, while oligomerization products were not observed.     

Study of the influence of hole concentration on high-Tc superconductivity of cuprates Bi-2212 by X-ray photoelectron spectroscopy

In this paper, we report the observation of X-ray photoelectron spectra (XPS), which were obtained from high-T_c superconducting compounds Bi-2212 with some percentage of 3d elements (Fe, Co, and Ni) substituted for copper. The changes in characteristics of XPS spectra Sr 3d and Cu 2p_3/2 with the doping content were explained in the relation to the hole concentration on CuO₂ planes, which resulted in high-T_c superconductivity.     

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.     

Synthesis and characterization of superhydrophobic functionalized Cu(OH)2 nanotube arrays on copper foil

Superhydrophobic functionalized cupric hydroxide (Cu(OH)₂) nanotube arrays were prepared on copper foils via a facile alkali assistant surface oxidation technique. Thus nanotube arrays of Cu(OH)₂ were directly fabricated on the surface of copper foil by immersing in an aqueous solution of NaOH and (NH₄)₂S₂O₈. The wettability of the surface was changed from surperhydrophilicity to superhydrophobicity by chemical modification with 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FAS). The morphologies, microstructures, crystal structure, chemical compositions and states, and hydrophobicity of the films on the copper foil substrates were analyzed by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and water contact angle measurement. It was found that the rough structure of the surface helped to magnify the wettability. The static contact angle (CA) for water is larger than 160° and the contact angle hysteresis (CAH) is lower than 5° on the modified surface. The high roughness of the nanotube arrays along with the generated C-F chains by chemical modification contributed to the improved superhydrophobicity. The present research is expected to be significant in providing a new strategy for the preparation of novel multifunctional materials with potential industrial applications on copper substrates.     

Corrosion behaviour of AISI 304 stainless steel with Cu coatings in H2SO4

The work addresses the influence of cementation and electrodeposition of copper coatings on the corrosion resistance of AISI 304 stainless steel immersed in 30 wt.% H₂SO₄ at temperatures of 25 and 50 °C. Corrosion process was evaluated by gravimetric tests, DC measurements and electrochemical impedance spectroscopy (EIS). The specimen surfaces were analysed by scanning electron microscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction. The corrosion performance of AISI 304 stainless steel in sulphuric acid solution was greatly improved by copper coatings. The amount of copper deposited by the cementation process was sufficient to protect the stainless steel of corrosion. A greater amount of copper obtained by electrodeposition treatments does not supply further improvement in the corrosion behaviour. The improved corrosion resistance is related to copper dissolution at the initial stages of immersion tests and the presence of Cu²⁺ in the solution, which makes the medium more oxidizing, increasing the stability of the passive layer. In addition, the presence of copper at the surface reduces the overpotential of cathodic reaction, enabling the transition from an active region to the passive one.     

Surface chemistry and catalytic activity of Ni/Al2O3 irradiated with high-energy electron beam

The radiation effects induced effects by electron beam (EB) treatment on the catalytic activity of Ni/γ-Al₂O₃ were studied for the carbon dioxide reforming of methane with different EB energy and absorbed radiation dose. Transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to determine the change in structure and surface states of Ni/γ-Al₂O₃ catalyst before and after the EB treatment. Higher energy EB treatment is useful for increasing the proportion of the active sites (such as Ni⁰ and NiAl₂O₄-phase) on the surface. The increase of Ni/Al-ratio indicates that the Ni dispersion on the surface increased with the EB-treatment, resulting in an increase of the active sites, which leads to improving the catalytic activity. XPS measurement also showed a decrease of the surface carbon with EB dose. The maximum 20% increase in the conversion of CO₂/CH₄-mixture into CO/H₂ gas was observed for the catalyst treated with 2 MeV energy and 600 kGy dose of EB relative to untreated.     

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.     

焙烧温度对Ni/CuO-ZrO2-CeO2-Al2O3催化剂在甲烷自热重整反应中积炭行为的影响

以Na₂CO₃为沉淀剂,在pH=9时,采用并流沉淀法制备了Ni/CuO-ZrO₂-CeO₂-Al₂O₃催化剂,催化剂中活性组分Ni的负载量(质量分数)为10%．采用TPO、SEM和XPS等方法研究了载体焙烧温度对催化剂积炭行为的影响．结果表明,载体焙烧温度为800 oC制备的Ni/CuO-ZrO₂-CeO₂-Al₂O₃催化剂不存在高温烧炭峰,可以避免由于积炭而降低反应的活性．反应40 h后,催化剂表面出现表面碳酸盐和非活性丝状积炭,这些物种可能会导致催化剂活性降低．     

Effect of copper ions implantation on corrosion behavior of zircaloy-4 in 1 M H2SO4

In order to study the effect of copper ion implantation on the aqueous corrosion behavior, samples of zircaloy-4 were implanted with copper ions with fluences ranging from 1 × 10¹⁶ to 1 × 10¹⁷ ions/cm², using a metal vapor vacuum arc source (MEVVA) operated at an extraction voltage of 40 kV. The valence states and depth distributions of elements in the surface layer of the samples were analyzed by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES), respectively. Glancing angle X-ray diffraction (GAXRD) was employed to examine the phase transformation due to the copper ion implantation. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zircaloy-4 in a 1 M H₂SO₄ solution. It was found that a significant improvement was achieved in the aqueous corrosion resistance of zircaloy-4 implanted with copper ions when the fluence is smaller than 5 × 10¹⁶ ions/cm². The corrosion resistance of implanted samples declined with increasing the fluence. Finally, the mechanism of the corrosion behavior of copper-implanted zircaloy-4 was discussed.     

X-Ray photoelectron spectroscopy (XPS) and radiotechnetium labelling of products from the reaction of tetrahydridoborate with transition metal salts

X-ray photoelectron Spectroscopy (XPS) was used to show that a black “boride”product arising from thermolysis of a non-aqueous copper borohydride solution contains boron in a surface-altered state, whereas similar cobalt, nickel and iron products prepared in water contain boron as the corresponding metal boride. A similar product prepared from CuSO₄ and NaBH₄ in water is known to be an effective carrier of radiotechnetium, as is that formed from copper borohydride. It is here shown that the products prepared from iron, cobalt or nickel salts are in fact more efficient radiotechnetium carriers than are the copper products.     

Effect of laser irradiation on the structure and valence states of copper in Cu-phosphate glass by XPS studies

The effect of laser irradiation using three different wavelengths (IR, visible and UV) generated from Nd:YAG laser on the local glass structure as well as on the valence state of the copper ions in copper phosphate glass containing CuO with the nominal composition 0.30(CuO)-(0.70)(P₂O₅), has been investigated by X-ray photoelectron spectroscopy (XPS). The presence of asymmetry and satellite peaks in the Cu 2p spectrum for the unirradiated sample is an indication of the presence of two different valence states, Cu²⁺ and Cu⁺. Hence, the Cu 2p_3/2 spectrum was fitted to two Gaussian-Lorentzian peaks and the corresponding ratio, Cu²⁺/Cu_total, determined from these relative areas clearly shows that copper ions exist predominately (>86%) in the Cu²⁺ state for the unirradiated glass sample under investigation. For the irradiated samples the symmetry and the absence of satellite peaks in the Cu 2p spectra indicate the existence of the copper ions mostly in Cu⁺ state. The O 1s spectra show slight asymmetry for the irradiated as well as unirradiated glass samples which result from two contributions, one from the presence of oxygen atoms in the P-O-P environment (bridging oxygen BO) and the other from oxygen in an P-O-Cu and PO environment (non-bridging oxygen NBO). The ratio of NBO to total oxygen was found to increase with laser power.     

Optimization of cuprous oxide nanocrystals deposition on multiwalled carbon nanotubes

Cu (I) phenyl acetylide was used as a source of copper to achieve a homogeneous distribution of Cu₂O nanocrystals (10–80 nm) decorated on multiwalled carbon nanotubes (MWCNTs) having an average diameter of 10 nm. Pristine MWCNTs were first oxygen-functionalized by treating them with a mixture of concentrated (H₂SO₄/HNO₃ : 3/1) acids and the products were characterized by X-ray powder diffraction, transmission and scanning electron microscopy, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy and thermogravimetric analysis. An easy, efficient and one-step impregnation method was followed to produce copper-containing nanoparticles on the MWCNTs. The copper-treated MWCNTs dried at room temperature were seen to be well decorated by copper-containing nanoparticles on their outer surface. The MWCNTs were then heat-treated at 400 °C in a nitrogen atmosphere to produce a homogeneous distribution of cuprous oxide nanocrystals on their surface. By varying the ratio of copper to oxygen-functionalized MWCNTs, Cu₂O nanocrystals decorated on MWCNTs with different copper content can be obtained.     

Electroless plating of copper on polyimide films modified by surface-initiated atom-transfer radical polymerization of 4-vinylpyridine

Surface modification of polyimide (PI) films were first carried out by chloromethylation under mild conditions, followed by surface-initiated atom-transfer radical polymerization (ATRP) of 4-vinylpyridine (4VP) from the chloromethylated PI surfaces. The composition and topography of the PI surfaces modified by poly(4-vinylpyridine) (P4VP) were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), respectively. The P4VP brushes with well-preserved pyridine groups on the PI surface was used not only as the chemisorption sites for the palladium complexes without prior sensitization by SnCl₂ solution during the electroless plating of copper, but also as an adhesion promotion layer to enhance the adhesion of the electrolessly deposited copper to the PI surfaces. The T-peel adhesion strength of the electrolessly deposited copper on the modified PI surface could reach about 6.6 N/cm. Effects of the polymerization time and the activation time in the PdCl₂ solution on the T-peel adhesion strength of the electrolessly deposited copper in the Sn-free process to the modified PI surface were also studied.     

Facile preparation of superhydrophobic copper surface by HNO3 etching technique with the assistance of CTAB and ultrasonication

Superhydrophobic rough structure was prepared on copper wafer via HNO₃ etching technique with the assistance of Cetyltrimethyl Ammonium Bromide (CTAB) and ultrasonication. After modification of 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FDTES), the copper wafer showed stable superhydrophobicity. The morphologies, chemical compositions and hydrophobicity of the substrates were analyzed by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and water contact angle measurement. Dense and spherical micropits appeared on copper wafer after it was etched by 5 M nitric acid with 1.2 mM CTAB under ultrasonication for 20 min. The SEM results indicated that the joint action of CTAB and ultrasonication caused the formation of dense and spherical micropits.