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The nature of stable char radicals: An ESR and DFT study of structural and hydrogen bonding requirements

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dc.contributor.author Trubetskaya, Anna
dc.contributor.author Larsen Andersen, Morgens
dc.contributor.author Talbro Barsberg, Søren
dc.date.accessioned 2018-08-03T10:34:36Z
dc.date.issued 2018
dc.identifier.uri http://hdl.handle.net/10344/7024
dc.description peer-reviewed en_US
dc.description.abstract Pyrolysis is a promising way to convert biomass into fuels and chemicals. This reaction is complex and inevitably involves a cascade of radical reactions that lead to char formation, in which some radicals become trapped and stabilized. Their nature is difficult to characterize, and in this respect computational chemistry can be a strong supplementary tool to electron spin resonance spectroscopy and other experimental methods. Here biomass char radicals and oxidation reactivity are studied experimentally, and density functional theory is used to predict the thermodynamic stability and g‐values of carbon‐ and oxygen‐centered radicals of polyaromatic char models including defect structures. Hydroxylated and especially certain dihydroxylated structures provide exceptional stabilization of oxygen‐centered radicals. Hydrogen bonding plays a crucial role, and it is proposed that hydrogen atom transfer couples radical localizations. This is a new proposal on the structural requirements for stabilization of char radicals, which impacts our understanding of pyrolysis mechanisms and char reactivity. en_US
dc.language.iso eng en_US
dc.publisher Wiley and Sons Ltd en_US
dc.relation.ispartofseries ChemPlusChem;83 (8), pp. 780-786
dc.relation.uri https://doi.org/10.1002/cplu.201800284
dc.rights This is the peer reviewed version of the following article: The Nature of Stable Char Radicals: An ESR and DFT Study of Structural and Hydrogen Bonding Requirements Anna Trubetskaya, Mogens Larsen Andersen, and Søren Talbro Barsberg ChemPlusChem 2018, 83 (8), pp. 780-786 which has been published in final form at http://dx.doi.org/10.1002/cplu.201800284 This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. http://olabout.wiley.com/WileyCDA/Section/id-828039.html#terms
dc.subject biomass en_US
dc.subject density functional theory calculations en_US
dc.subject free radicals en_US
dc.subject g-value en_US
dc.subject pyrolysis en_US
dc.title The nature of stable char radicals: An ESR and DFT study of structural and hydrogen bonding requirements en_US
dc.type info:eu-repo/semantics/article en_US
dc.type.supercollection all_ul_research en_US
dc.type.supercollection ul_published_reviewed en_US
dc.identifier.doi 10.1002/cplu.201800284
dc.contributor.sponsor Kempe Foundation en_US
dc.date.embargoEndDate 2019
dc.embargo.terms 2019_06_28 en_US
dc.rights.accessrights info:eu-repo/semantics/embargoedAccess en_US


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