Characterization of Oxygenaceous Species Formed by Exposure of Ag(111) to Atomic Oxygen

Turano, Marie E.; Farber, Rachael G.; Oskorep, Eleanor C.  N.; Rosenberg, Richard A.; Killelea, Daniel R.

doi:10.1021/acs.jpcc.9b09131

Title: Characterization of Oxygenaceous Species Formed by Exposure of Ag(111) to Atomic Oxygen

Full Record
Other Related Research

Abstract

The uptake and chemical speciation of oxygen in and on Ag(111) surface is described herein. An Ag(111) surface was exposed to gas-phase oxygen atoms under ultrahigh vacuum compatible conditions at various surface temperatures. The O uptake was quantified using temperature-programmed desorption measurements and showed that oxygen exposures at temperatures above 500 K yielded only surface-adsorbed oxygen in a single surface reconstruction. At temperatures below 500 K, O uptake continued past O surface saturation, and a maximum in the uptake with respect to exposure temperature was observed at 450 K. A model where O atoms must diffuse out of subsurface absorption sites to free room for further O describes this observation. The chemical speciation of the oxygenaceous species formed under these conditions was achieved using X-ray photoelectron spectroscopy. These data show that a single O species initially formed on the surface, but at higher coverages, a new, three-dimensional oxygenaceous phase developed. Because of the importance of silver in heterogeneously catalyzed partial oxidation reactions, these results show that oxygen species embedded below the surface plane must be incorporated into accurate models of Ag-surface catalyzed reactions.

Authors:

Turano, Marie E. ^[1]; Farber, Rachael G. ^[1]; Oskorep, Eleanor C. N. ^[1]; Rosenberg, Richard A. ^[2];

^[1]

Loyola Univ. Chicago, IL (United States)
Loyola Univ. Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Publication Date:: Tue Dec 17 00:00:00 EST 2019

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Org.:: National Science Foundation (NSF); Loyola UniversityjChicago; Donors of the American Chemical Society Petroleum Research Fund; USDOE Office of Science (SC), Basic Energy Sciences (BES); Arthur J. Schmitt Foundation

OSTI Identifier:: 1604983

Grant/Contract Number:: AC02-06CH11357; PRF #54770-DNI5

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 124; Journal Issue: 2; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Surface analysis; Desorption; Diffusion; Oxygen; X-ray photoelectron spectroscopy

Citation Formats


                    Turano, Marie E., Farber, Rachael G., Oskorep, Eleanor C.  N., Rosenberg, Richard A., and Killelea, Daniel R. Characterization of Oxygenaceous Species Formed by Exposure of Ag(111) to Atomic Oxygen.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.jpcc.9b09131.

Copy to clipboard


                    Turano, Marie E., Farber, Rachael G., Oskorep, Eleanor C.  N., Rosenberg, Richard A., & Killelea, Daniel R. Characterization of Oxygenaceous Species Formed by Exposure of Ag(111) to Atomic Oxygen.  United States.  https://doi.org/10.1021/acs.jpcc.9b09131

Copy to clipboard


                    Turano, Marie E., Farber, Rachael G., Oskorep, Eleanor C.  N., Rosenberg, Richard A., and Killelea, Daniel R. Tue .  
"Characterization of Oxygenaceous Species Formed by Exposure of Ag(111) to Atomic Oxygen".  United States.  https://doi.org/10.1021/acs.jpcc.9b09131.  https://www.osti.gov/servlets/purl/1604983.

Copy to clipboard


                    
@article{osti_1604983,

  title        = {Characterization of Oxygenaceous Species Formed by Exposure of Ag(111) to Atomic Oxygen},

  author       = {Turano, Marie E. and Farber, Rachael G. and Oskorep, Eleanor C.  N. and Rosenberg, Richard A. and Killelea, Daniel R.},

  abstractNote = {The uptake and chemical speciation of oxygen in and on Ag(111) surface is described herein. An Ag(111) surface was exposed to gas-phase oxygen atoms under ultrahigh vacuum compatible conditions at various surface temperatures. The O uptake was quantified using temperature-programmed desorption measurements and showed that oxygen exposures at temperatures above 500 K yielded only surface-adsorbed oxygen in a single surface reconstruction. At temperatures below 500 K, O uptake continued past O surface saturation, and a maximum in the uptake with respect to exposure temperature was observed at 450 K. A model where O atoms must diffuse out of subsurface absorption sites to free room for further O describes this observation. The chemical speciation of the oxygenaceous species formed under these conditions was achieved using X-ray photoelectron spectroscopy. These data show that a single O species initially formed on the surface, but at higher coverages, a new, three-dimensional oxygenaceous phase developed. Because of the importance of silver in heterogeneously catalyzed partial oxidation reactions, these results show that oxygen species embedded below the surface plane must be incorporated into accurate models of Ag-surface catalyzed reactions.},

  doi          = {10.1021/acs.jpcc.9b09131},

  journal      = {Journal of Physical Chemistry. C},

  number       = 2,

  volume       = 124,

  place        = {United States},

  year         = {Tue Dec 17 00:00:00 EST 2019},

  month        = {Tue Dec 17 00:00:00 EST 2019}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.jpcc.9b09131

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 9 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Real-time scanning tunneling microscopy observations of the oxidation of a Ti/Pt(111)-(2x2) surface alloy using O{sub 2} and NO{sub 2}

Journal Article Shuchen, Hsieh ; Liu, G F ; Koel, Bruce E ; ... - Journal of Vacuum Science and Technology. A, International Journal Devoted to Vacuum, Surfaces, and Films

The authors have used scanning tunneling microscopy (STM), low energy electron diffraction (LEED), and Auger electron spectroscopy (AES) to study the nascent oxidation of an ordered Ti/Pt(111)-(2x2) surface alloy exposed to oxygen (O{sub 2}) or nitrogen dioxide (NO{sub 2}) under ultrahigh vacuum conditions. The Ti/Pt(111)-(2x2) surface alloy was formed by depositing an ultrathin Ti film on Pt(111) and annealing to 1050 K. This produces an alloy film in which the surface layer is pure Pt and the second layer contains Ti atoms in a (2x2) structure, which causes the pattern observed by STM and LEED. Real-time imaging of the surfacemore »« less
https://doi.org/10.1116/1.2969903
Investigating the Elusive Nature of Atomic O from CO₂ Dissociation on Pd(111): The Role of Surface Hydrogen

Journal Article Simonovis, Juan Pablo ; Zhang, Hong ; Rui, Ning ; ... - Journal of Physical Chemistry. C

CO₂ dissociation is a key step in CO₂ conversion reactions to produce value-added chemicals typically through hydrogenation. In many cases, the atomic O produced from CO₂ dissociation can potentially block adsorption sites or change the oxidation state of the catalyst. Here, we used ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and density functional theory (DFT) calculations to investigate the presence of surface species from the dissociation of CO₂ on Pd(111). AP-XPS results show that CO₂ was dissociated to produce adsorbed CO, but dissociated atomic O was not observed at room temperature. We were only able to observe atomic O when CO₂more »« less
https://doi.org/10.1021/acs.jpcc.2c00976

Full Text Available
Role of coverage in determining adsorbate stability: Phenol reactivity on Rh(111)

Journal Article Xu, Xueping ; Friend, C M - Journal of Physical Chemistry; (USA)

The reaction of phenol on Rb(111) has been studied by use of temperature programmed reaction and X-ray photoelectron spectroscopies under ultrahigh vacuum. Phenol undergoes competing molecular desorption and O-H bond cleavage to form adsorbed phenoxy below 300 K. Phenoxy quantitatively reacts to form carbon monoxide (400-500 K) and stoichiometric amounts of surface carbon and dihydrogen. O-H bond cleavage of phenol occurs at temperature as low as 120 K, but no C-H bond cleavage occurs until above 350 K. The decomposition kinetics of the adsorbed phenoxy are strongly dependent on its coverage. At low coverage phenoxy decomposes below 400 K tomore »« less
https://doi.org/10.1021/j100361a021
Activation of carbon dioxide on potassium-modified Ag(111) single crystals

Journal Article Herrera-Fierro, P ; Chottiner, G S ; Scherson, D A - Journal of Physical Chemistry

The adsorption of carbon dioxide on potassium-dosed Ag(111) has been investigated with temperature-programmed desorption (TPD), work function measurements, and Auger electron (AES), X-ray photoelectron (XPS), and high-resolution electron energy loss (HREELS) spectroscopies. Unlike the behavior observed for other K-modified single-crystal metal surfaces, the TPD spectra of near-saturation coverages of CO{sub 2} on K/Ag(111) for K coverages in the range 0.13 <0{sub K} <0.47, where the close-packed monolayer corresponds to 0{sub K} + 1/3, exhibit a sharply defined m/e = 44 peak at 796 {plus_minus} 6 K with no evidence for the desorption of CO at any temperature. Similar TPD experimentsmore »« less
https://doi.org/10.1021/j100188a041
Elucidating the active phases of CoOx films on Au(111) in the CO oxidation reaction

Journal Article Chen, Hao ; Falling, Lorenz J. ; Kersell, Heath ; ... - Nature Communications

Abstract Noble metals supported on reducible oxides, like CoO _x and TiO _x , exhibit superior activity in many chemical reactions, but the origin of the increased activity is not well understood. To answer this question we studied thin films of CoO _x supported on an Au(111) single crystal surface as a model for the CO oxidation reaction. We show that three reaction regimes exist in response to chemical and topographic restructuring of the CoO _x catalyst as a function of reactant gas phase CO/O ₂ stoichiometry and temperature. Under oxygen-lean conditions and moderate temperatures (≤150 °C), partially oxidized films (CoOmore »« less
https://doi.org/10.1038/s41467-023-42301-7

Similar Records