X-Ray Photoelectron Spectroscopy Study on the Chemical Composition of Copper Tarnish Products Formed at Low Humidities

Cano, E.; Lopez, Marco; Simancas, J.; Bastidas, J. M.

doi:10.1149/1.1344547

Cited by 57 publications

(46 citation statements)

References 19 publications

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“…These results indicated that exposure of the copper sulfide films to the ambient atmosphere for 48 hours caused their surfaces to oxidize and form the divalent state of copper [Cu(II)]. The surfaces of the mixed metallic Cu-chalcocite film obtained after 10 min sulfurization and the pure chalcocite film obtained after 20 min sulfurization were covered with a cupric oxide and/or copper hydroxide species overlayer, where the observed binding energies of the additional component peak in the Cu 2 p 3/2 spectra agreed well with the binding energies reported for the divalent state of copper [Cu(II)] in cupric oxide and copper hydroxide [27,31,32]. Note that while the S 2p spectra (figure 2) for the samples sulfurized for 10 and 20 min did not show any evidence of sulfate species (SO 2− 4 ) on the film surfaces, the spectra for the samples sulfurized for 25 and 35 min clearly indicated its existence.…”

Section: Film Composition and Chemical Environment: Xps Analysissupporting

confidence: 77%

“…However, figure 3 shows that as much as 52.3 and 57.3% of the Cu 2 p 3/2 total peak area corresponded to the divalent state of the copper [Cu(II)] overlayer after 25 and 35 min, respectively. This indicated that the surfaces of the roxbyite film obtained after 25 min and the covellite film obtained after 35 min were covered with an overlayer that was not a pure copper sulfate species but consisted of a mixture of copper sulfate, cupric oxide, and copper hydroxide species, where the observed binding energies of the additional component peak in the Cu 2 p 3/2 spectra (figure 3) coincided with the binding energies reported for the divalent state of copper [Cu(II)] in copper sulfate [19,21,22,27] as well as cupric oxide and copper hydroxide [27,31,32]. However, it was difficult to perform a detailed quantitative analysis of the amount of copper sulfate, cupric oxide, and copper hydroxide species present in the overlayers due to the similar and overlapping binding energies of the divalent state of copper [Cu(II)] in the Cu 2 p 3/2 spectra for these species.…”

Section: Film Composition and Chemical Environment: Xps Analysissupporting

confidence: 52%

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Structural studies of copper sulfide films: effect of ambient atmosphere

Kundu

Hasegawa

Terabe

et al. 2008

Science and Technology of Advanced Materials

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We examined the structural properties of copper sulfide films as a function of the sulfurization time of 70-nm-thick Cu films. Copper sulfide films with various phases such as mixed metallic Cu-chalcocite, chalcocite, roxbyite, and covellite phases were formed with increasing sulfurization time. To evaluate the structural stability of various films, all the films were exposed to the ambient atmosphere for the same amount of time. Although the phase structure and stoichiometry of the films were maintained at a greater depth, the near-surface region of the films was oxidized and covered with overlayers of oxide, hydroxide, and/or sulfate species due to the exposure and reaction with the ambient atmosphere. The oxygen uptake and its reactivity with the copper sulfide film surfaces were enhanced with increasing sulfur content of the films. In addition, the type of divalent state of copper formed on the film surfaces depended on the phase structure, composition, and stoichiometry of the films.

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Section: Film Composition and Chemical Environment: Xps Analysissupporting

confidence: 77%

Section: Film Composition and Chemical Environment: Xps Analysissupporting

confidence: 52%

Structural studies of copper sulfide films: effect of ambient atmosphere

Kundu

Hasegawa

Terabe

et al. 2008

Science and Technology of Advanced Materials

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“…7 The relative humidity condition near 100% was obtained placing a recipient with 500 mL of propionic acid solution at the bottom of the desiccator. In these experiments the propionic acid vapor was produced, following the procedure described in previous works [2][3][4][5][6][7][8][9] and in any case, solutions were renewed weekly to prevent degradation of the organic compound.…”

Section: Exposures In Closed Chambermentioning

confidence: 99%

“…[2][3][4][5][6][7][8][9] (2) Where: the term is the vapor partial pressure of pure propionic acid (mm Hg), pH (Pro) is the partial pressure of the propionic acid in the desiccator atmosphere, T is the temperature in K, G is the mass of the propionic acid in grams in a 1000 mL solution, M H 2 O and M H (Pro) are the molecular weights of water and propionic acid and P T is the total pressure under the laboratory conditions (640 mm Hg).…”

Section: Exposures In Closed Chambermentioning

confidence: 99%

“…1 Copper is corroded in presence of these compounds such as formic, acetic and butyric. [2][3][4][5][6][7][8][9] Several studies has been performed to follow copper corrosion in presence of organic acids, and it has been found that the corrosivity of the organic acids vapors in ppmv (parts per million in volume) on copper is given by the following order (from the highest to the lowest level of aggressiveness) acetic > formic > butyric. 6,8,9 At the same time, the mechanism of degradation of copper in these acids includes the formation of a basic copper acetate and an hydrate copper acetate, copper formate and copper butyrate.…”

Section: Introductionmentioning

confidence: 99%

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Study of the copper corrosion mechanism in the presence of propionic acid vapors

Echavarrı́a¹,

Echeverría²,

Arroyave³

et al. 2009

J. Braz. Chem. Soc.

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O mecanismo da interação entre o cobre e os vapores do ácido propiônico é apresentado. As exposições foram realizadas em diferentes tempos e concentração de poluentes. Varredura Catódica, XRD e SEM foram usados para quantificar o grau de deterioração. Os resultados obtidos foram explicados pelo seguinte mecanismo: Uma camada do cuprita (Cu 2 O) é formada imediatamente. Este composto, na presença da água adsorvida é oxidado a tenorita (CuO) com aumento do pH. A hidratação da camada de tenorita beneficia a formação de um hidróxido CuO•xH 2 O. Enquanto o nível do poluente é aumentado, o propionato básico insolúvel é formado (Cu(OH) x (Pro) 2-x ). Concentrações mais elevadas de ácido propiônico acidificam as mono camadas e um composto novo Cu (Pro) 2 •H 2 O começa a se precipitar em pH baixo. Este é o constituinte principal da pátina verdeoliva formada nessas condições. Este mecanismo concorda, em termos gerais, com os propostos em trabalhos precedentes visando estudar a interação entre o cobre e os ácidos acético e fórmico.The interaction mechanism between copper and propionic acid vapors is shown. Exposures were carried out to various pollutant concentrations and times. Cathodic scan, x-ray diffraction (XRD) and scanning electrode microscope (SEM) were used to quantify the degree of deterioration. The results obtained were explained by the following mechanism: A cuprite (Cu 2 O) layer covers the copper surface immediately; this compound in presence of adsorbed water is oxidized to tenorite (CuO). The hydration of the tenorite layer benefits the formation of a hydroxide compound such as CuO•xH 2 O. As the pollutant level is increased, insoluble basic propionate is formed (Cu(OH) x (CH 3 CH 2 COO) 2-x ). Higher concentrations of propionic acid acidify the monolayers and a new compound Cu(CH 3 CH 2 COO) 2 •H 2 O begins to precipitate at low pH, this is the main constituent of the green olive patina formed under these conditions. This mechanism agrees, in general terms, with those proposed in previous works to study the interaction between copper and the acetic and formic acids.

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Copper Single Atoms Chelated on Ligand‐Modified Carbon for Ullmann‐type C−O Coupling

Ruta,

Di Liberto,

Moriggi

et al. 2024

ChemSusChem

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Cross‐coupling reactions are of great importance in chemistry due to their ability to facilitate the construction of complex organic molecules. Among these reactions, the Ullmann‐type C‐O coupling between phenols and aryl halides is particularly noteworthy and useful for preparing diarylethers. However, this reaction typically relies on homogeneous catalysts that rapidly deactivate under harsh reaction conditions. In this study, we introduce a novel heterogeneous catalyst for the Ullmann‐type C‐O coupling reaction, comprised of isolated Cu atoms chelated to a tetraethylenepentamine‐pyrrole ligand that is immobilized on graphite nanoplatelets. The catalytic study reveals the recyclability of the material, and demonstrates the crucial role of the pyrrole linker in stabilizing the Cu sites. The work expands the potential of single‐atom catalyst nanoarchitectures and underscores the significance of ligands in stabilizing metals in cationic forms, providing a novel, tailored catalyst for cross‐coupling chemistries.

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X-Ray Photoelectron Spectroscopy Study on the Chemical Composition of Copper Tarnish Products Formed at Low Humidities

Cited by 57 publications

References 19 publications

Structural studies of copper sulfide films: effect of ambient atmosphere

Structural studies of copper sulfide films: effect of ambient atmosphere

Study of the copper corrosion mechanism in the presence of propionic acid vapors

Copper Single Atoms Chelated on Ligand‐Modified Carbon for Ullmann‐type C−O Coupling

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