The Consequences of Surface Confinement on Free Radical Chemistry

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Mass transport limitations impact the thermochemical processing of fossil and renewable energy resources, which involves the breakdown of cross-linked, macromolecular networks. To Investigate the molecular level details of the consequences of molecular confinement on high temperature (275-500°C) free-radical reaction pathways, we have been examining the pyrolysis of model compounds attached to the surface of non-porous silica nanoparticles through a thermally robust Si-O-C<sub>aryl</sub>, tetha. Pyrolysis of silica-immobilized diphenylalkanes and related ethers have been studied in detail and compared with the corresponding behavior in fluid phases. The diffusional constraints can lead to reduced rates of radical termination on the surface, and enhancement ... continued below

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8 pages

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Birtt, P.F. & Buchanan, A.C., III August 22, 1999.

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Description

Mass transport limitations impact the thermochemical processing of fossil and renewable energy resources, which involves the breakdown of cross-linked, macromolecular networks. To Investigate the molecular level details of the consequences of molecular confinement on high temperature (275-500°C) free-radical reaction pathways, we have been examining the pyrolysis of model compounds attached to the surface of non-porous silica nanoparticles through a thermally robust Si-O-C<sub>aryl</sub>, tetha. Pyrolysis of silica-immobilized diphenylalkanes and related ethers have been studied in detail and compared with the corresponding behavior in fluid phases. The diffusional constraints can lead to reduced rates of radical termination on the surface, and enhancement of neophyl-like rearrangements, cyclization-dehydrogenation pathways, and <i>ipso-</i> aromatic substitutions. Furthermore, studies of two-component surfaces have revealed the importance of a radical relay mechanism involving rapid serial hydrogen transfer steps resulting from the molecular pre-organization on the low fractal dimension silica surface. Key findings are reviewed in this paper, and the implications of these results for fuel processing are described.

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8 pages

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  • American chemical Society National Meeting, New Orleans, LA, August 22-26, 1999

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  • Other: DE00007921
  • Report No.: ORNL/CP-103215
  • Grant Number: AC05-96OR22464
  • Office of Scientific & Technical Information Report Number: 7921
  • Archival Resource Key: ark:/67531/metadc742662

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  • August 22, 1999

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  • Oct. 19, 2015, 7:39 p.m.

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  • Feb. 15, 2016, 12:16 p.m.

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Birtt, P.F. & Buchanan, A.C., III. The Consequences of Surface Confinement on Free Radical Chemistry, article, August 22, 1999; Oak Ridge, Tennessee. (digital.library.unt.edu/ark:/67531/metadc742662/: accessed August 20, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.