Heterogeneous photochemical activation of methane on a rhodium catalyst. Formation of an acetyl moiety on the surface

Journal Article · Thu Aug 17 04:00:00 EDT 1995 · Journal of Physical Chemistry

DOI:https://doi.org/10.1021/j100033a042· OSTI ID:102877

Wong, J C.S.; Yates, Jr, J T ^[1]

---

1. Univ. of Pittsburgh, PA (United States)

The photochemical activation of methane over a substrate containing Rh{sup I}(CO){sub 2} species has been studied using transmission infrared spectroscopy. At 233 K, methane activation is achieved by the oxidative addition of the C-H bond to a postulated 16-electron surface species, Rh{sup I}(CO), which is produced by UV (325 nm) photodecomposition of the Rh{sup I}(CO){sub 2} on the surface. The oxidative addition product, Rh(CO)(H)(CH{sub 3}), further undergoes a migratory-insertion reaction in the presence of CO to form a proposed Rh(CO)(H)(COCH{sub 3}) surface species. Isotopic experiments using C{sup 18}O have been performed to confirm the product assignment. An IR spectroscopic study of acetaldehyde and acetone adsorption following the photoreaction suggests that other CH{sub 3}CO-containing species may also be formed on the surface as a result of C-H bond activation followed by CH{sub 3} insertion into the Rh-CO bond region. 74 refs., 6 figs., 2 tabs.

• Sponsoring Organization: USDOE
• OSTI ID: 102877
• Journal Information: Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 33 Vol. 99; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
ACETALDEHYDE
ACETONE
CARBON
CATALYSTS
CHEMICAL ACTIVATION
CHEMICAL BONDS
DECOMPOSITION
HYDROGEN
INFRARED SPECTRA
METHANE
NUMERICAL DATA
OXIDATION
PHOTOCHEMICAL REACTIONS
RHODIUM COMPOUNDS
SURFACES