Selective oxidation of methanol and ethanol on supported ruthenium oxide clusters at low temperatures Metadata

Metadata describes a digital item, providing (if known) such information as creator, publisher, contents, size, relationship to other resources, and more. Metadata may also contain "preservation" components that help us to maintain the integrity of digital files over time.

Available Formats

Dublin Core: XML Dublin Core: JSON Dublin Core: Text Dublin Core: RDF/XML UNTL: XML Access METS: XML

Title

  • Main Title Selective oxidation of methanol and ethanol on supported ruthenium oxide clusters at low temperatures

Creator

  • Author: Liu, Haichao
    Creator Type: Personal
  • Author: Iglesia, Enrique
    Creator Type: Personal

Contributor

  • Sponsor: United States. Department of Energy. Division of Chemical Sciences.
    Contributor Type: Organization
    Contributor Info: USDOE Director. Office of Science. Office of Basic Energy Sciences. Chemical Sciences Division
  • Sponsor: British Petroleum. Methane Conversion Cooperative Research Program. University of California at Berkeley (United States)
    Contributor Type: Organization

Publisher

  • Name: Lawrence Berkeley National Laboratory
    Place of Publication: Berkeley, California
    Additional Info: Ernest Orlando Lawrence Berkeley National Laboratory, Berkeley, CA (United States)

Date

  • Creation: 2004-03-04

Language

  • English

Description

  • Content Description: RuO2 domains supported on SnO2, ZrO2, TiO2, Al2O3, and SiO2 catalyze the oxidative conversion of methanol to formaldehyde, methylformate, and dimethoxymethane with unprecedented rates and high combined selectivity (>99 percent) and yield at low temperatures (300-400 K). Supports influence turnover rates and the ability of RuO2 domains to undergo redox cycles required for oxidation turnovers. Oxidative dehydrogenation turnover rates and rates of stoichiometric reduction of RuO2 in H2 increased in parallel when RuO2 domains were dispersed on more reducible supports. These support effects, the kinetic effects of CH3OH and O2 on reaction rates, and the observed kinetic isotope effects with CH3OD and CD3OD reactants are consistent with a sequence of elementary steps involving kinetically relevant H-abstraction from adsorbed methoxide species using lattice oxygen atoms and with methoxide formation in quasi-equilibrated CH3OH dissociation on nearly stoichiometric RuO2 surfaces. Anaerobic transient experiments confirmed that CH3OH oxidation to HCHO requires lattice oxygen atoms and that selectivities are not influenced by the presence of O2. Residence time effects on selectivity indicate that secondary HCHO-CH3OH acetalization reactions lead to hemiacetal or methoxymethanol intermediates that convert to dimethoxymethane in reactions with CH3OH on support acid sites or dehydrogenate to form methylformate on RuO2 and support redox sites. These conclusions are consistent with the tendency of Al2O3 and SiO2 supports to favor dimethoxymethane formation, while SnO2, ZrO2, and TiO2 preferentially form methylformate. These support effects on secondary reactions were confirmed by measured CH3OH oxidation rates and selectivities on physical mixtures of supported RuO2 catalysts and pure supports. Ethanol also reacts on supported RuO2 domains to form predominately acetaldehyde and diethoxyethane at 300-400 K. The bifunctional nature of these reaction pathways and the remarkable ability of RuO2-based catalysts to oxidize CH3OH to HCHO at unprecedented low temperatures introduce significant opportunities for new routes to complex oxygenates, including some containing C-C bonds, using methanol or ethanol as intermediates derived from natural gas or biomass.
  • Physical Description: vp.

Subject

  • Keyword: Natural Gas
  • Keyword: Ruthenium Oxides
  • STI Subject Categories: 10 Synthetic Fuels
  • Keyword: Methylal
  • Keyword: Secondary Reactions
  • STI Subject Categories: 37 Inorganic, Organic, Physical And Analytical Chemistry
  • Keyword: Oxidation
  • Keyword: Biomass
  • Keyword: Catalysts
  • Keyword: Kinetics
  • Keyword: Dehydrogenation
  • Keyword: Reaction Kinetics
  • Keyword: Methanol
  • Keyword: Formaldehyde
  • Keyword: Transients Ruthenium Oxide Oxidation Of Methanol And Ethanol
  • Keyword: Ethanol
  • Keyword: Acetaldehyde
  • STI Subject Categories: 03 Natural Gas
  • Keyword: Isotope Effects
  • STI Subject Categories: 09 Biomass Fuels
  • Keyword: Ruthenium Oxide Oxidation Of Methanol And Ethanol

Source

  • Journal Name: Journal of Physical Chemistry B; Journal Volume: 109; Journal Issue: 6; Other Information: Submitted to Journal of Physical Chemistry B: Volume 109, No.6; Journal Publication Date: 2005

Collection

  • Name: Office of Scientific & Technical Information Technical Reports
    Code: OSTI

Institution

  • Name: UNT Libraries Government Documents Department
    Code: UNTGD

Resource Type

  • Article

Format

  • Text

Identifier

  • Report No.: LBNL--54295
  • Grant Number: AC03-76SF00098
  • Office of Scientific & Technical Information Report Number: 837401
  • Archival Resource Key: ark:/67531/metadc785326

Note

  • Display Note: OSTI as DE00837401
Back to Top of Screen