The Interaction of Carbon Monoxide with Rhodium on Potassium-Modified CeO2(111)

Mullins, David R.

doi:10.1016/j.susc.2016.01.024

The Interaction of Carbon Monoxide with Rhodium on Potassium-Modified CeO₂(111)

Journal Article · Wed Feb 03 00:00:00 EST 2016 · Surface Science

DOI:https://doi.org/10.1016/j.susc.2016.01.024· OSTI ID:1324072

Mullins, David R. ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

The adsorption and reactions of CO adsorbed on Rh particles deposited on K-covered CeO₂(111) were studied by temperature programmed desorption and photoelectron spectroscopy. K deposited on CeO₂(111) forms a KO_X over-layer by extracting O from the ceria and partially reducing some of the Ce⁴⁺ to Ce³⁺. CO does not adsorb on the KO_X / CeO_2-X(111) surface in the absence of Rh particles. CO adsorbed on Rh / K / CeO₂(111) adsorbs molecularly on the Rh at 200 K. As the surface is heated the CO spills-over and reacts with the KOX to form carbonate. The carbonate decomposes at elevated temperature to produce CO and CO₂. The carbonate stabilizes the KO_X so that K desorbs at a higher temperature than it would in the absence of CO. When the Rh and K deposition are reversed so that K is deposited on both the Rh and the CeO²(111), CO adsorbs as CO^2- at 200 K. The CO^2- decomposes below 350 K to produce gas phase CO and adsorbed CO3^2- and CO. The CO is stabilized by the K on the Rh and desorbs above 540 K. The carbonate decomposes into gas phase CO and CO₂.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-98CH10886; AC05-00OR22725

OSTI ID:: 1324072

Alternate ID(s):: OSTI ID: 1354588
OSTI ID: 1359908

Journal Information:: Surface Science, Journal Name: Surface Science Vol. 652; ISSN 0039-6028

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

Quantitative electron spectroscopy of surfaces: A standard data base for electron inelastic mean free paths in solids Seah, M. P.; Dench, W. A. Surface and Interface Analysis, Vol. 1, Issue 1 https://doi.org/10.1002/sia.740010103	journal	February 1979
Interaction of CO with Rh Supported on Stoichiometric and Reduced CeO2(111) andCeO2(100) Surfaces Stubenrauch, J.; Vohs, J. M. Journal of Catalysis, Vol. 159, Issue 1 https://doi.org/10.1006/jcat.1996.0063	journal	March 1996
Co Dissociation on rh Deposited on Reduced Cerium Oxide thin Films Mullins, D. R.; Overbury, S. H. Journal of Catalysis, Vol. 188, Issue 2 https://doi.org/10.1006/jcat.1999.2679	journal	December 1999
CO adsorption on alkali-metal covered Ni(100) Kiskinova, M. P. Surface Science, Vol. 111, Issue 3 https://doi.org/10.1016/0039-6028(81)90410-6	journal	November 1981
The properties of K and coadsorbed CO + K on Ru (001) Weimer, J. J.; Umbach, E.; Menzel, D. Surface Science, Vol. 159, Issue 1 https://doi.org/10.1016/0039-6028(85)90106-2	journal	August 1985
The properties of K and coadsorbed CO + K on Ru(001) Weimer, J. J.; Umbach, E.; Menzel, D. Surface Science, Vol. 155, Issue 1 https://doi.org/10.1016/0039-6028(85)90409-1	journal	June 1985
Multilayer growth of potassium on a Pt(111) surface Pirug, G.; Winkler, A.; Bonzel, H. P. Surface Science, Vol. 163, Issue 1 https://doi.org/10.1016/0039-6028(85)90855-6	journal	November 1985
Photoelectron spectroscop1c studies of the adsorption of CO2 on potassium-promoted Rh(111) surface Kiss, János; Révész, Károly; Solymosi, Frigyes Surface Science, Vol. 207, Issue 1 https://doi.org/10.1016/0039-6028(88)90245-2	journal	December 1988
Photoelectron spectroscopic studies on the dissociation of CO on potassium-dosed Rh(111) surface Kiss, János; Klivényi, Gábor; Révész, Károly Surface Science, Vol. 223, Issue 3 https://doi.org/10.1016/0039-6028(89)90680-8	journal	December 1989
Spectroscopic study of K-induced activation of CO2 on Pt(111) Liu, Z. M.; Zhou, Y.; Solymosi, F. Surface Science, Vol. 245, Issue 3 https://doi.org/10.1016/0039-6028(91)90031-M	journal	April 1991
The interaction of oxygen and potassium on the Ru(001) surface Rocker, Gerd H.; Huang, Chen; Cobb, Cathy L. Surface Science, Vol. 250, Issue 1-3 https://doi.org/10.1016/0039-6028(91)90707-Y	journal	July 1991
An ellipsometric study of potassium adsorption on TiO2(110) Hayden, B. E.; Nicholson, G. P. Surface Science, Vol. 274, Issue 2 https://doi.org/10.1016/0039-6028(92)90532-B	journal	August 1992
K overlayer oxidation studied by XPS: the effects of the adsorption and oxidation conditions Lamontagne, B.; Semond, F.; Roy, D. Surface Science, Vol. 327, Issue 3 https://doi.org/10.1016/0039-6028(94)00845-0	journal	April 1995
Adsorption and reactivity of CO2 on the K/Cu(110) interface and the effect of photon irradiation Thomsen, E. V.; Jørgensen, B.; Onsgaard, J. Surface Science, Vol. 304, Issue 1-2 https://doi.org/10.1016/0039-6028(94)90755-2	journal	March 1994
A photoemission investigation of the adsorption of potassium on perfect and defective TiO2(110) surfaces Heise, Rainer; Courths, Ralf Surface Science, Vol. 331-333 https://doi.org/10.1016/0039-6028(95)00247-2	journal	July 1995
Alkali-metal-affected adsorption of molecules on metal surfaces Bonzel, H. P. Surface Science Reports, Vol. 8, Issue 2 https://doi.org/10.1016/0167-5729(88)90007-6	journal	January 1988
The effect of potassium on the chemisorption of carbon monoxide on the Rh(111) crystal face Crowell, J. E.; Somorjai, G. A. Applications of Surface Science, Vol. 19, Issue 1-4 https://doi.org/10.1016/0378-5963(84)90054-0	journal	November 1984
Adsorption and reaction of H2O and CO on oxidized and reduced Rh/CeOx(111) surfaces Kundakovic, Lj.; Mullins, D. R.; Overbury, S. H. Surface Science, Vol. 457, Issue 1-2 https://doi.org/10.1016/S0039-6028(00)00332-0	journal	June 2000
Reaction of potassium with thin epitaxial NiO() films Schulze, M.; Reissner, R. Surface Science, Vol. 507-510 https://doi.org/10.1016/S0039-6028(02)01362-6	journal	June 2002
Metal–support interactions between Pt and thin film cerium oxide Mullins, D. R.; Zhang, K. Z. Surface Science, Vol. 513, Issue 1 https://doi.org/10.1016/S0039-6028(02)01704-1	journal	July 2002
Photoelectron spectroscopy study of K adsorption on ZnO(100) Ozawa, K.; Edamoto, K. Surface Science, Vol. 524, Issue 1-3 https://doi.org/10.1016/S0039-6028(02)02480-9	journal	February 2003
Coverage dependent promoter action: K coadsorption and reactions with CO and CO2 on Pd{110} Pratt, Stephanie J.; King, David A. Surface Science, Vol. 540, Issue 2-3 https://doi.org/10.1016/S0039-6028(03)00735-0	journal	August 2003
Interaction of atomic hydrogen with potassium on MgO(100) Huang, H. H.; Jiang, X.; Zou, Z. Surface Science, Vol. 376, Issue 1-3 https://doi.org/10.1016/S0039-6028(96)01407-0	journal	April 1997
Electron spectroscopy of single crystal and polycrystalline cerium oxide surfaces Mullins, D. R.; Overbury, S. H.; Huntley, D. R. Surface Science, Vol. 409, Issue 2 https://doi.org/10.1016/S0039-6028(98)00257-X	journal	July 1998
Adsorption sites in coadsorption systems determined by photoemission spectroscopy: K and CO coadsorbed on Rh(111) Strisland, F.; Beutler, A.; Jaworowski, A. J. Surface Science, Vol. 410, Issue 2-3 https://doi.org/10.1016/S0039-6028(98)00361-6	journal	August 1998
Potassium adsorption and reaction with water on MgO(100) Huang, H. H.; Jiang, X.; Zou, Z. Surface Science, Vol. 412-413 https://doi.org/10.1016/S0039-6028(98)00488-9	journal	September 1998
Ordered cerium oxide thin films grown on Ru(0001) and Ni(111) Mullins, D.R.; Radulovic, P.V.; Overbury, S.H. Surface Science, Vol. 429, Issue 1-3, p. 186-198 https://doi.org/10.1016/S0039-6028(99)00369-6	journal	June 1999
Surface sensitivity of Auger-electron spectroscopy and X-ray photoelectron spectroscopy Powell, C. J.; Jablonski, A.; Tilinin, I. S. Journal of Electron Spectroscopy and Related Phenomena, Vol. 98-99 https://doi.org/10.1016/S0368-2048(98)00271-0	journal	January 1999
Surface to bulk charge transfer at an alkali metal/metal oxide interface Lindsay, R.; Michelangeli, E.; Daniels, B. G. Surface Science, Vol. 547, Issue 1-2 https://doi.org/10.1016/j.susc.2003.10.014	journal	December 2003
Photoelectron spectroscopy study of the K-covered ZnO(101̄0) surface; annealing-induced changes in the electronic structure and the chemical composition Ozawa, K.; Edamoto, K. Surface Science, Vol. 547, Issue 3 https://doi.org/10.1016/j.susc.2003.10.038	journal	December 2003
Adsorption and reaction of methanol on thin-film cerium oxide Mullins, D. R.; Robbins, M. D.; Zhou, J. Surface Science, Vol. 600, Issue 7 https://doi.org/10.1016/j.susc.2006.02.011	journal	April 2006
Organic Reactions at Well-Defined Oxide Surfaces Barteau, Mark A. Chemical Reviews, Vol. 96, Issue 4 https://doi.org/10.1021/cr950222t	journal	January 1996
Potassium coadsorption induced dissociation of carbon monoxide on the rhodium(111) crystal surface: an isotope mixing study Crowell, J. E.; Tysoe, W. T.; Somorjai, G. A. The Journal of Physical Chemistry, Vol. 89, Issue 9 https://doi.org/10.1021/j100255a011	journal	April 1985
CO ₂ Adsorption As a Flat-Lying, Tridentate Carbonate on CeO ₂ (100) Albrecht, Peter M.; Jiang, De-en; Mullins, David R. The Journal of Physical Chemistry C, Vol. 118, Issue 17 https://doi.org/10.1021/jp501201b	journal	April 2014
Support effects in the dissociation of CO on Rh/CeO₂(111) Stubenrauch, J.; Vohs, J. M. Catalysis Letters, Vol. 47, Issue 1, p. 21-25 https://doi.org/10.1023/A:1019007710818	journal	January 1997
The effects of surface geometry and island formation on alkali‐promoted surfaces: The coadsorption of CO and K on Ni(110) Whitman, Lloyd J.; Ho, W. The Journal of Chemical Physics, Vol. 83, Issue 9 https://doi.org/10.1063/1.449007	journal	November 1985
Layer resolved spectroscopy of potassium adsorbed on a Ru(001) surface: Photoemission and thermal desorption study Hrbek, J.; Shek, M. ‐L.; Sham, T. K. The Journal of Chemical Physics, Vol. 91, Issue 9 https://doi.org/10.1063/1.457531	journal	November 1989
Alkali Doping in Heterogeneous Catalysis Mross, W. D. Catalysis Reviews, Vol. 25, Issue 4 https://doi.org/10.1080/01614948308078057	journal	December 1983
Catalytic Synthesis of Hydrocarbons over Group VIII Metals. A Discussion of the Reaction Mechanism Bell, Alexis T. Catalysis Reviews, Vol. 23, Issue 1-2 https://doi.org/10.1080/03602458108068076	journal	January 1981
High-Resolution X-Ray Photoemission Spectrum of the Valence Bands of Gold Shirley, D. A. Physical Review B, Vol. 5, Issue 12 https://doi.org/10.1103/PhysRevB.5.4709	journal	June 1972
Adsorption of potassium on Cr 2 O 3 ( 0001 ) at ionic and metallic coverages and uv-laser-induced desorption Wilde, M.; Beauport, I.; Stuhl, F. Physical Review B, Vol. 59, Issue 20 https://doi.org/10.1103/PhysRevB.59.13401	journal	May 1999
Interaction and diffusion of potassium on Cr 2 O 3 ( 0001 ) / C r ( 110 ) Zhao, W.; Kerner, G.; Asscher, M. Physical Review B, Vol. 62, Issue 11 https://doi.org/10.1103/PhysRevB.62.7527	journal	September 2000
A laser drilled aperture for use in an ultrahigh vacuum gas doser Hagans, Patrick L.; DeKoven, Benjamin M.; Womack, Joseph L. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 7, Issue 6 https://doi.org/10.1116/1.576346	journal	November 1989

Cited By (1)

Atomic structures and local electronic properties of K- and Rh-modified ceria/Pt(111) inverse model catalysts Chen, Haoran; Rong, Wenhui; Huang, Zhichao The Journal of Chemical Physics, Vol. 151, Issue 18 https://doi.org/10.1063/1.5128960	journal	November 2019

Similar Records

Studies of the coadsorption of deuterium and carbon monoxide with silver on rhodium and the adsorption of 2,4,6-trinitrotoluene on clean and carbon covered platinum

Thesis/Dissertation · Fri Dec 31 23:00:00 EST 1982 · OSTI ID:5676710

Water Dissociation on CeO2(100) and CeO2(111) Thin Films

Journal Article · Sat Dec 31 23:00:00 EST 2011 · Journal of Physical Chemistry C · OSTI ID:1050914

Rh-Promoted Methanol Decomposition on Cerium Oxide Thin Films

Journal Article · Sat Dec 31 23:00:00 EST 2005 · J. Phys. Chem. B · OSTI ID:913980

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY