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Vanadium oxide deposited on an Rh foil: CO and CO[sub 2] hydrogenation reactivity

Journal Article · · Journal of Catalysis; (United States)
; ;  [1]
  1. Lawrence Berkeley Lab., CA (United States) Univ. of California, Berkeley (United States)

The effects of submonolayer deposits of vanadia on the rates of CO and CO[sub 2] hydrogenation of an Rh foil have been examined. Auger electron spectroscopy (AES), ion scattering spectroscopy (ISS), and temperature-programmed desorption (TPD) have been used to determine the oxide coverage, and X-ray photoelectron spectroscopy (XPS) has been used to determine the oxidation state for VO[sub x] deposits on a rhodium foil. After oxidation (3 [times] 10[sup [minus]6] O[sub 2] at 350[degrees]C), the vanadium valence state is 3+, which corresponds to an oxide stoichiometry of V[sub 2]O[sub 3]. CO chemisorption reduces 34% of the V[sup 3+] to V[sup 2+] at low oxide coverages. The absolute amount of V[sup 2+] in the oxide overlayer after CO titration is found to maximize at a coverage of 0.5 ML. The rates of CO and CO[sub 2] hydrogenation increase upon addition of VO[sub x] to an Rh foil. For CO hydrogenation, the rate maximizes at two times that of the rate on the clean surface at an oxide coverage of 0.4 ML. For CO[sub 2] hydrogenation, the rate maximizes at six times that of the clean surface rate at an oxide coverage of 0.6 ML. The oxide promoter also alters the activation energies, partial pressure dependences, and selectivities for the hydrogenation reactions. A comparison of the kinetic and spectroscopic data reveals a strong correlation between the degree of reducibility of the oxide overlayer and the amount of rate enhancement for CO and CO[sub 2] hydrogenation. 29 refs., 9 figs., 2 tabs.

OSTI ID:
6046061
Journal Information:
Journal of Catalysis; (United States), Journal Name: Journal of Catalysis; (United States) Vol. 139:2; ISSN 0021-9517; ISSN JCTLA5
Country of Publication:
United States
Language:
English