Physical and chemical modification of zinc carboxylate‐containing lubricants by molecular structure changes

Andor, J.A.; Berkesi, Ottó; Dreveni, I.; Varga, Erika

doi:10.1002/ls.3010110202

Cited by 13 publications

(20 citation statements)

References 26 publications

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“…The migrating Sn species during reaction are hypothesized to be volatile tin carboxylates formed via the reaction between SnO x species and heptanoic acid. 35 These tin species may decompose on Pd sites located on and within nearby silica particles or simply be deposited on the silica support. 35 The and Van Krevelen mechanism (Scheme 1D).…”

Section: Activity Of Pdsn Catalystsmentioning

confidence: 99%

“…35 These tin species may decompose on Pd sites located on and within nearby silica particles or simply be deposited on the silica support. 35 The and Van Krevelen mechanism (Scheme 1D). [36][37][38] Addition of a metal capable of hydrogen spillover, such as Pt, facilitates reduction of the metal oxide, thus promoting aldehyde formation.…”

Section: Activity Of Pdsn Catalystsmentioning

confidence: 99%

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Vapor phase deoxygenation of heptanoic acid over silica-supported palladium and palladium-tin catalysts

Kaylor

Xie

Kim

et al. 2016

Journal of Catalysis

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Silica-supported Pd and PdSn catalysts were prepared by ion exchange or incipient wetness impregnation and characterized with H 2 chemisorption, X-ray diffraction, in situ Sn K-edge X-ray absorption near edge structure (XANES), and transmission electron microscopy. The activity of the catalysts was evaluated in the deoxygenation of vapor-phase heptanoic acid at 0.1 MPa and 573 K. A Pd catalyst synthesized via ion exchange formed nanoparticles of 1.1 ± 0.4 nm and was more stable in heptanoic acid conversion compared to a Pd catalyst synthesized via incipient wetness impregnation having nanoparticles of 2.4 ± 0.5 nm. The addition of Sn to a Pd catalyst by either co-impregnation of precursors or physical mixing of supported monometallic catalysts improved the overall catalyst stability. Moreover, Sn addition expanded the reaction network from primarily decarbonylation over Pd to include dehydration and decarboxylative ketonization over PdSn. Electron microscopy confirmed the physical migration of Sn during catalytic reaction. In situ XANES analysis during the deoxygenation of a carboxylic acid suggests that partially reduced SnO x is the active Sn phase associated with Pd nanoparticles under reaction conditions.

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Section: Activity Of Pdsn Catalystsmentioning

confidence: 99%

Section: Activity Of Pdsn Catalystsmentioning

confidence: 99%

Vapor phase deoxygenation of heptanoic acid over silica-supported palladium and palladium-tin catalysts

Kaylor

Xie

Kim

et al. 2016

Journal of Catalysis

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“…However, under water-free conditions, these zinc salts exist in a linear coordination polymer structure (referred to as “chain complex,” shown in Fig. 1F) ( 23 ). We were able to reproduce the spectral features of the chain and oxo complex in liquid zinc palmitate (ZnPa; zinc hexadecanoate).…”

Section: Resultsmentioning

confidence: 99%

2D-IR spectroscopy for oil paint conservation: Elucidating the water-sensitive structure of zinc carboxylate clusters in ionomers

et al. 2019

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The molecular structure around metal ions in polymer materials has puzzled researchers for decades. This question has acquired new relevance with the discovery that aged oil paint binders can adopt an ionomer structure when metal ions leached from pigments bind to carboxylate groups on the polymerized oil network. The characteristics of the metal-polymer structure are expected to have important consequences for the rate of oil paint degradation reactions such as metal soap formation and oil hydrolysis. Here, we use two-dimensional infrared (2D-IR) spectroscopy to demonstrate that zinc carboxylates formed in paint films containing zinc white pigment adopt either a coordination chain– or an oxo-type cluster structure. Moreover, it was found that the presence of water governs the relative concentration of these two types of zinc carboxylate coordination. The results pave the way for a molecular approach to paintings conservation and the application of 2D-IR spectroscopy to the study of polymer structure.

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“…Meanwhile, ν as (COO − ) (1531 cm −1 ) and ν s (COO − ) (1403 cm −1 ) of the syn‐syn bridged carboxylate groups become very weak. Some reports have shown that zinc oxocarboxylates (Zn 4 O(OOCR) 6 , R = alkyl or aryl) can be formed when zinc carboxylates were treated in a hot ketone solution 36, 40. The Zn 4 O(O 2 CR) 6 complex possesses a central O atom, which is surrounded by four Zn atoms in a perfect tetrahedral coordination.…”

Section: Resultsmentioning

confidence: 99%

“…At lower temperatures such as RT, the organozinc compound existed in a form of linear chain polymer as verified by the IR spectra analyzed above. When annealed at a higher temperature (≥120 °C), this kind of linear chain polymer can be converted to zinc oxocarboxylates (Scheme b) 40. Such zinc oxocarboxylates are more feasible to crystallize than the linear polymer of zinc carboxylates.…”

Section: Resultsmentioning

confidence: 99%

Organozinc Compounds as Effective Dielectric Modification Layers for Polymer Field‐Effect Transistors

Liu

Zou

et al. 2012

Adv Funct Materials

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The interface between the organic semiconductor and dielectric plays an important role in determining the device performance of organic field‐effect transistors (OFETs). Although self‐assembled monolayers (SAMs) made from organosilanes have been widely used for dielectric modification to improve the device performance of OFETs, they suffer from incontinuous and lack uniform coverage of the dielectric layer. Here, it is reported that by introduction of a solution‐processed organozinc compound as a dielectric modification layer between the dielectric and the silane SAM, improved surface morphology and reduced surface polarity can be achieved. The organozinc compound originates from the reaction between diethylzinc and the cyclohexanone solvent, which leads to formation of zinc carboxylates. Being annealed at different temperatures, organozinc compound exists in various forms in the solid films. With organozinc modification, p‐type polymer FETs show a high charge carrier mobility that is about two‐fold larger than a control device that does not contain the organozinc compound, both for devices with a positive threshold voltage and for those with a negative one. After organozinc compound modification, the threshold voltage of polymer FETs can either be altered to approach zero or remain unchanged depending on positive or negative threshold voltage they have.

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Physical and chemical modification of zinc carboxylate‐containing lubricants by molecular structure changes

Cited by 13 publications

References 26 publications

Vapor phase deoxygenation of heptanoic acid over silica-supported palladium and palladium-tin catalysts

Vapor phase deoxygenation of heptanoic acid over silica-supported palladium and palladium-tin catalysts

2D-IR spectroscopy for oil paint conservation: Elucidating the water-sensitive structure of zinc carboxylate clusters in ionomers

Organozinc Compounds as Effective Dielectric Modification Layers for Polymer Field‐Effect Transistors

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