A TPD‐MS study of the interaction of coumarins and their heterocyclic derivatives with a surface of fumed silica and nanosized oxides CeO2/SiO2, TiO2/SiO2, Al2O3/SiO2

Kulyk, Kostiantyn; Ishchenko, V. B.; Palyanytsya, B.B.; Khylya, Volodymyr; Borysenko, M.V.; Kulyk, T. V.

doi:10.1002/jms.1765

Cited by 25 publications

(27 citation statements)

References 34 publications

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“…Here, we employed a method that uses the linear form of the Arrhenius equation. The procedure used was described in detail earlier . More details can also be found in the Supporting Information.…”

Section: Experimental Methodsmentioning

confidence: 99%

“…Te mperature-programmed desorption experiments were carried out with an electron ionization MKh-7304A monopole mass spectrometer (Sumy,U kraine) that was adapted for TPD measurements. [26,49] About 20 mg of samples were used for each run. Before the TPD measurements, the samples were degassed to ca.…”

Section: Temperature-programmedd Esorption Mass Spectrometry (Tpd Ms)mentioning

confidence: 99%

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Kinetics of Valeric Acid Ketonization and Ketenization in Catalytic Pyrolysis on Nanosized SiO₂, γ‐Al₂O₃, CeO₂/SiO₂, Al₂O₃/SiO₂ and TiO₂/SiO₂

et al. 2017

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Valeric acid is an important renewable platform chemical that can be produced efficiently from lignocellulosic biomass. Upgrading of valeric acid by catalytic pyrolysis has the potential to produce value added biofuels and chemicals on an industrial scale. Understanding the different mechanisms involved in the thermal transformations of valeric acid on the surface of nanometer-sized oxides is important for the development of efficient heterogeneously catalyzed pyrolytic conversion techniques. In this work, the thermal decomposition of valeric acid on the surface of nanoscale SiO , γ-Al O , CeO /SiO , Al O /SiO and TiO /SiO has been investigated by temperature-programmed desorption mass spectrometry (TPD MS). Fourier transform infrared spectroscopy (FTIR) has also been used to investigate the structure of valeric acid complexes on the oxide surfaces. Two main products of pyrolytic conversion were observed to be formed depending on the nano-catalyst used-dibutylketone and propylketene. Mechanisms of ketene and ketone formation from chemisorbed fragments of valeric acid are proposed and the kinetic parameters of the corresponding reactions were calculated. It was found that the activation energy of ketenization decreases in the order SiO >γ-Al O >TiO /SiO >Al O /SiO , and the activation energy of ketonization decreases in the order γ-Al O >CeO /SiO . Nano-oxide CeO /SiO was found to selectively catalyze the ketonization reaction.

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Section: Experimental Methodsmentioning

confidence: 99%

Section: Temperature-programmedd Esorption Mass Spectrometry (Tpd Ms)mentioning

confidence: 99%

Kinetics of Valeric Acid Ketonization and Ketenization in Catalytic Pyrolysis on Nanosized SiO₂, γ‐Al₂O₃, CeO₂/SiO₂, Al₂O₃/SiO₂ and TiO₂/SiO₂

et al. 2017

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“…We should note that deamination at~500°C was observed in our previous work [15] on thermal transformations of a series of primary biogenic amines (histamine, tryptamine, and tyramine) on the silica surface. However, deamination in the case of these biogenic amines proceeds as the result of parallel reactions with bond breakage in the a-and b-postions to the nitrogen atom.…”

Section: Resultsmentioning

confidence: 93%

Kinetics and mechanism of the deamination of primary aliphatic amines on the silica surface

et al. 2011

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Temperature-programmed desorption mass spectrometry was used to study the reaction of a series of primary amines (isobutylamine, isopentylamine, 1-pentylamine, 1-hexylamine, and 1-heptylamine) with a fumed silica surface. A mechanism was proposed and the kinetic parameters of the formation of alkenes from the chemisorbed aliphatic amine fragments on the silica surface were determined. A linear correlation was found between the activation energy and Taft constants for the substituents at the reaction site.Microporous and mesoporous basic catalysts hold great promise for use in fine organic synthesis [1]. Acid catalysts such as zeolites are commonly used in chromatography and catalysis [2]. However, these catalysts have weak basic properties. Thus, a current problem entails enhancing the basicity of these materials by the substitution of the oxygen atoms in the zeolite structure by various aliphatic amines [3][4][5]. The introduction of the amine NH group into the structure of silica catalysts enhances the Lewis basicity, permitting use of these materials in base catalysis, in particular, in oxidation [6] and especially in Knoevenagel reactions [7]. Furthermore, zeolites with basic properties are candidates for the replacement of liquid bases such as piperidine, alkali metal hydroxides, and alkali metal alkoxides in industrial processes [8].Studies have been carried out in the past decade on the properties of these new nitrogen-containing materials. Thus, Corma et al. [9] investigated the mechanisms of nitration by means of quantum-chemical calculations. Various workers have carried out NMR and IR spectral investigations of nitrogen-containing molecular sieves [3,5,10]. The major factors affecting the catalytic properties of nitrogen-containing silicates such as temperature, Si/Al atomic ratio, and nature of the nitrogen-containing modifier have been elucidated [5].However, a number of questions have not been resolved pertaining to the nature of the interaction of the nitrogen-containing compounds with the surface of the silica materials and the mechanism of the thermal transformations of the cross-linked nitrogen-containing groups during the synthesis of basic silica catalysts. 1760040-5760/11/4703-0176

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“…All desorption peaks were recorded. Full details of this TPD MS setup, equipment used, and kinetics determination methods are given elsewhere …”

Section: Methodsmentioning

confidence: 99%

Dimethylsilanone Generation from Pyrolysis of Polysiloxanes Filled with Nanosized Silica and Ceria/Silica

et al. 2016

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Temperature‐programmed desorption mass spectrometry (TPD MS) was used to study the pyrolysis of PDMS and its composites with nanosized silica and ceria/silica. The results suggest that the elusive organosilicon compound, dimethylsilanone, is generated from PDMS over a broad temperature range (in some cases starting at 70 °C). The presence of nano‐oxides catalyzes this process. Ions characteristic of the fragmentation of dimethylsilanone under electron ionization are assigned with the aid of DFT structure calculations. Possible reaction mechanisms for dimethylsilanone generation are discussed in the context of the calculated kinetic parameters. Observed accompanying products of PDMS pyrolysis, such as tetramethylcyclodisiloxane and hexamethylcyclotrisiloxane, indicate that multiple channels are involved in the dimethylsilanone release.

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A TPD‐MS study of the interaction of coumarins and their heterocyclic derivatives with a surface of fumed silica and nanosized oxides CeO₂/SiO₂, TiO₂/SiO₂, Al₂O₃/SiO₂

Cited by 25 publications

References 34 publications

Kinetics of Valeric Acid Ketonization and Ketenization in Catalytic Pyrolysis on Nanosized SiO₂, γ‐Al₂O₃, CeO₂/SiO₂, Al₂O₃/SiO₂ and TiO₂/SiO₂

Kinetics of Valeric Acid Ketonization and Ketenization in Catalytic Pyrolysis on Nanosized SiO₂, γ‐Al₂O₃, CeO₂/SiO₂, Al₂O₃/SiO₂ and TiO₂/SiO₂

Kinetics and mechanism of the deamination of primary aliphatic amines on the silica surface

Dimethylsilanone Generation from Pyrolysis of Polysiloxanes Filled with Nanosized Silica and Ceria/Silica

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A TPD‐MS study of the interaction of coumarins and their heterocyclic derivatives with a surface of fumed silica and nanosized oxides CeO2/SiO2, TiO2/SiO2, Al2O3/SiO2

Cited by 25 publications

References 34 publications

Kinetics of Valeric Acid Ketonization and Ketenization in Catalytic Pyrolysis on Nanosized SiO2, γ‐Al2O3, CeO2/SiO2, Al2O3/SiO2 and TiO2/SiO2

Kinetics of Valeric Acid Ketonization and Ketenization in Catalytic Pyrolysis on Nanosized SiO2, γ‐Al2O3, CeO2/SiO2, Al2O3/SiO2 and TiO2/SiO2

Kinetics and mechanism of the deamination of primary aliphatic amines on the silica surface

Dimethylsilanone Generation from Pyrolysis of Polysiloxanes Filled with Nanosized Silica and Ceria/Silica

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A TPD‐MS study of the interaction of coumarins and their heterocyclic derivatives with a surface of fumed silica and nanosized oxides CeO₂/SiO₂, TiO₂/SiO₂, Al₂O₃/SiO₂

Kinetics of Valeric Acid Ketonization and Ketenization in Catalytic Pyrolysis on Nanosized SiO₂, γ‐Al₂O₃, CeO₂/SiO₂, Al₂O₃/SiO₂ and TiO₂/SiO₂

Kinetics of Valeric Acid Ketonization and Ketenization in Catalytic Pyrolysis on Nanosized SiO₂, γ‐Al₂O₃, CeO₂/SiO₂, Al₂O₃/SiO₂ and TiO₂/SiO₂