Density Functional Theory Analysis of the Reaction Pathway for Methane Oxidation to Acetic Acid Catalyzed by Pd in Sulfuric Acid.
Density functional theory has been used to investigate the thermodynamics and activation barriers associated with the direct oxidation of methane to acetic acid catalyzed by Pd cation in concentrated sulfuric acid. Pd cations in such solutions are ligated by two bisulfate anions and by one or two mo...
| Publicado en: | Journal of the American Chemical Society Vol. 128; no. 14; pp. 4650 - 4658 |
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| Autores principales: | , |
| Formato: | Artículo |
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American Chemical Society
4/12/2006
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=20780179&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 20780179 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 4/12/2006 vid: 128 iid: 14 pid: 997 pub: American Chemical Society artinfo: ui: 20780179 10.1021/ja055756i ppf: 4650 ppct: 8 formats: tig: atl: Density Functional Theory Analysis of the Reaction Pathway for Methane Oxidation to Acetic Acid Catalyzed by Pd in Sulfuric Acid. aug: au: Chempath, Shaji Bell, Alexis T. affil: Department of Chemical Engineering, University of California, Berkeley, California 94 720-1462 su: Density functionals Thermodynamics Oxidation Methane Acetic acid Sulfuric acid Palladium sug: subj: Density functionals Thermodynamics Oxidation Methane Acetic acid Sulfuric acid Palladium ab: Density functional theory has been used to investigate the thermodynamics and activation barriers associated with the direct oxidation of methane to acetic acid catalyzed by Pd cation in concentrated sulfuric acid. Pd cations in such solutions are ligated by two bisulfate anions and by one or two molecules of sulfuric acid. Methane oxidation is initiated by the addition of CH across one of the PdO bonds of a bisulfate ligand to form Pd(HSO)(CH)(HSO). The latter species will react with CO to produce Pd(HSO)(CHCO)(HSO). The most likely path to the final products is found to be via oxidation of Pd(HSO)(CH)(HSO) and Pd(HSO)(CHCO)(HSO) to form Pd(η²-HSO)(HSO)(CH)(HSO) and Pd(η²-HSO)(HSO)(CHCO)(HSO), respectively. CHHSO or CHCOHSO is then produced by reductive elimination from the latter two species, and CHCOOH is then formed by hydrolysis of CHCOHSO. The loss of Pd from solution to form Pd(0) or Pd-black is predicted to occur via reduction with CO. This process is offset, though, by reoxidation of palladium by either HSO or O. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2006 holdings: @attributes: islocal: N |
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