Strahlungschemie der Kohlenwasserstoffe. 4. Mitteilung. Toluol

Hoigné, Jürg; Gaeumann, T.

doi:10.1002/hlca.19610440741

Cited by 12 publications

(3 citation statements)

References 9 publications

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“…Previous work has shown that the major products in radiolysis of toluene are hydrogen and dimeric materials mainly consisting of bibenzyl, bitolyls, and benzyltoluenes. − The rupture of C–H bonds on the methyl group is the dominant process, leading to the formation of bibenzyl . The overall reaction for toluene giving rise to molecular hydrogen and bibenzyl (see Supporting Information for a discussion on the production of major products in radiolysis of toluene and their interaction with Pd 2+ ions) would be …”

Section: Resultsmentioning

confidence: 99%

“…25 Radiolytic synthesis has also been successful in preparing metal-supported clusters for catalytic applications. 26−28 These synthesis routes use the chemical effects of the absorption of high-energy radiation, typically 60 Co γ-rays or 2−20 MeV electrons, 29,30 by precursorcontaining liquids to form nanostructures by reproducing a selective reducing/oxidizing environment. Conditions to generate free radicals of strong reducing potential can be found and exploited for different applications.…”

Section: ■ Introductionmentioning

confidence: 99%

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Gaining Control over Radiolytic Synthesis of Uniform Sub-3-nanometer Palladium Nanoparticles: Use of Aromatic Liquids in the Electron Microscope

Abellán

Parent

Hasan³

et al. 2016

Langmuir

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Synthesizing nanomaterials of uniform shape and size is of critical importance to access and manipulate the novel structure-property relationships arising at the nanoscale, such as catalytic activity. In this work, we synthesize Pd nanoparticles with well-controlled size in the sub-3 nm range using scanning transmission electron microscopy (STEM) in combination with an in situ liquid stage. We use an aromatic hydrocarbon (toluene) as a solvent that is very resistant to high-energy electron irradiation, which creates a net reducing environment without the need for additives to scavenge oxidizing radicals. The primary reducing species is molecular hydrogen, which is a widely used reductant in the synthesis of supported metal catalysts. We propose a mechanism of particle formation based on the effect of tri-n-octylphosphine (TOP) on size stabilization, relatively low production of radicals, and autocatalytic reduction of Pd(II) compounds. We combine in situ STEM results with insights from in situ small-angle X-ray scattering (SAXS) from alcohol-based synthesis, having similar reduction potential, in a customized microfluidic device as well as ex situ bulk experiments. This has allowed us to develop a fundamental growth model for the synthesis of size-stabilized Pd nanoparticles and demonstrate the utility of correlating different in situ and ex situ characterization techniques to understand, and ultimately control, metal nanostructure synthesis.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Gaining Control over Radiolytic Synthesis of Uniform Sub-3-nanometer Palladium Nanoparticles: Use of Aromatic Liquids in the Electron Microscope

Abellán

Parent

Hasan³

et al. 2016

Langmuir

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“…CHa-CeHrCHs* -CH3-C6H4• + CH3• (5) The increase in Grom with temperature, which rises too steeply to give an Arrhenius type plot, may be due to the increased probability of escape of methyl radicals from the solvent cage in which they are formed and to the higher activation energy for abstraction compared with addition reactions of these radicals. Since the yield of CH4 in solid p-xylene is much less than the unscavengeable yield in the liquid phase, the latter, which is independent of temperature, must arise by two or more processes, which may be analogous to those for H2 production.…”

Section: Fig 2•-mentioning

confidence: 99%

The Radiolysis of the Xylene Isomers and Ethylbenzene

Verdin¹

1963

J. Phys. Chem.

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The G-values f o r the formatLon of H2 and CH4 in tne 6 0~o y-radiolysis of the xylene isomers and ethylbenzene have been compared. The presence of iodine does not a f f e c t OH2, but reduces GCH4 t o a limiting value. Por p-xylene %2 and the unscavengeable CH4 yield a r e independent of temperature from 20' t o 1 1 0 ' C, whereas the t o t a l CH4 yield increases s i x f o l d over thds range. The H2 and CH4 yields a r e greatly reduced i n t h e solid s t a t e , and i n the liquid s t a t e benzene shows a protective effect on the wields of both gases. The formation of CH4 and C2 -hydrocarldbns was c o~. with the C6 -and C, -products f o r p-xylene and ethylbenzene, and isom,:isation has been shown t o occur t o a negligible exte:.~. The production of high molecular weight products was measured f o r the xylenes, and i s independent of dose r a t e and temperature f o r liquid p-xylene, but i s decreased i n t h e s o l i d s t a t e . The r e s u l t s are q u a l i t a t i v e l y consistent with the reactions of radicals and exc i t e d molecules. L E G A L N O T I C E

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Pyrolyse von Aromaten. 1. Mitteilung. Biphenyl

Gäumann

Rayroux

1962

Helvetica Chimica Acta

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The products of the pyrolysis of light and heavy biphenyl are molecular hydrogen (or deuterium respectively), benzene, terphenyl and quaterphenyl. Several kinetic ways are discussed to explain the activation energy of 66 ± 8 kcal/mole for the decomposition of biphenyl, its isotope effect and the isomeric distribution of the terphenyls (10%, o, 48% m, 42% p) and quaterphenyls (1%oó, 11% om′, 8% op′, 29% mm′, 39% mp′, 9,12% pp′) produced. There are not enough data to allow a clearcut decision of their way of formation.

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Strahlungschemie der Kohlenwasserstoffe. 4. Mitteilung. Toluol

Abstract: The behaviour of toluene and its mixtures with iodine under the influence of ionising radiation is examined. All the more important dimers are identified and a kinetic way of their formation is proposed in comparison with analogous reactions of thermally produced radicals.

Cited by 12 publications

References 9 publications

Gaining Control over Radiolytic Synthesis of Uniform Sub-3-nanometer Palladium Nanoparticles: Use of Aromatic Liquids in the Electron Microscope

Gaining Control over Radiolytic Synthesis of Uniform Sub-3-nanometer Palladium Nanoparticles: Use of Aromatic Liquids in the Electron Microscope

The Radiolysis of the Xylene Isomers and Ethylbenzene

Pyrolyse von Aromaten. 1. Mitteilung. Biphenyl

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