Surface reactions of ethanol over UO2(100) thin film

Mudiyanselage, K.; Burrell, A. K.; Sadowski, J. T.; Idriss, H.

doi:10.1021/acs.jpcc.5b08577

Title: Surface reactions of ethanol over UO₂(100) thin film

Full Record
Other Related Research

Abstract

The study of the reactions of oxygenates on well-defined oxide surfaces is important for the fundamental understanding of heterogeneous chemical pathways that are influenced by atomic geometry, electronic structure, and chemical composition. In this work, an ordered uranium oxide thin film surface terminated in the (100) orientation is prepared on a LaAlO₃ substrate and studied for its reactivity with a C-2 oxygenate, ethanol (CH₃CH₂OH). With the use of synchrotron X-ray photoelectron spectroscopy (XPS), we have probed the adsorption and desorption processes observed in the valence band, C 1s, O 1s, and U 4f to investigate the bonding mode, surface composition, electronic structure, and probable chemical changes to the stoichiometric-UO₂(100) [smooth-UO₂(100)] and Ar⁺-sputtered UO₂(100) [rough-UO₂(100)] surfaces. Unlike UO₂(111) single crystal and UO₂ thin film, Ar-ion-sputtering of this UO₂(100) did not result in noticeable reduction of U cations. Upon ethanol adsorption (saturation occurred at 0.5 ML), only the ethoxy (CH₃CH₂O^–) species is formed on smooth-UO₂(100) whereas initially formed ethoxy species are partially oxidized to surface acetate (CH3COO–) on the Ar⁺-sputtered UO₂(100) surface. Furthermore, all ethoxy and acetate species are removed from the surface between 600 and 700 K.

Authors:

S. D. Senanayake; Mudiyanselage, K. ^[1]; Burrell, A. K. ^[2]; Sadowski, J. T. ^[1]; Idriss, H. ^[3]

Brookhaven National Lab. (BNL), Upton, NY (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Centre for Research and Innovation (CRI) (Saudi Arabia)

Publication Date:: Thu Oct 08 00:00:00 EDT 2015

Research Org.:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1235892

Report Number(s):: BNL-111755-2016-JA
Journal ID: ISSN 1932-7447; R&D Project: CO009; KC0302010

Grant/Contract Number:: SC00112704

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 119; Journal Issue: 44; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    S. D. Senanayake, Mudiyanselage, K., Burrell, A. K., Sadowski, J. T., and Idriss, H. Surface reactions of ethanol over UO2(100) thin film.  United States: N. p., 2015. 
Web.  doi:10.1021/acs.jpcc.5b08577.

Copy to clipboard


                    S. D. Senanayake, Mudiyanselage, K., Burrell, A. K., Sadowski, J. T., & Idriss, H. Surface reactions of ethanol over UO2(100) thin film.  United States.  https://doi.org/10.1021/acs.jpcc.5b08577

Copy to clipboard


                    S. D. Senanayake, Mudiyanselage, K., Burrell, A. K., Sadowski, J. T., and Idriss, H. Thu .  
"Surface reactions of ethanol over UO2(100) thin film".  United States.  https://doi.org/10.1021/acs.jpcc.5b08577.  https://www.osti.gov/servlets/purl/1235892.

Copy to clipboard


                    
@article{osti_1235892,

  title        = {Surface reactions of ethanol over UO2(100) thin film},

  author       = {S. D. Senanayake and Mudiyanselage, K. and Burrell, A. K. and Sadowski, J. T. and Idriss, H.},

  abstractNote = {The study of the reactions of oxygenates on well-defined oxide surfaces is important for the fundamental understanding of heterogeneous chemical pathways that are influenced by atomic geometry, electronic structure, and chemical composition. In this work, an ordered uranium oxide thin film surface terminated in the (100) orientation is prepared on a LaAlO3 substrate and studied for its reactivity with a C-2 oxygenate, ethanol (CH3CH2OH). With the use of synchrotron X-ray photoelectron spectroscopy (XPS), we have probed the adsorption and desorption processes observed in the valence band, C 1s, O 1s, and U 4f to investigate the bonding mode, surface composition, electronic structure, and probable chemical changes to the stoichiometric-UO2(100) [smooth-UO2(100)] and Ar+-sputtered UO2(100) [rough-UO2(100)] surfaces. Unlike UO2(111) single crystal and UO2 thin film, Ar-ion-sputtering of this UO2(100) did not result in noticeable reduction of U cations. Upon ethanol adsorption (saturation occurred at 0.5 ML), only the ethoxy (CH3CH2O–) species is formed on smooth-UO2(100) whereas initially formed ethoxy species are partially oxidized to surface acetate (CH3COO–) on the Ar+-sputtered UO2(100) surface. Furthermore, all ethoxy and acetate species are removed from the surface between 600 and 700 K.},

  doi          = {10.1021/acs.jpcc.5b08577},

  journal      = {Journal of Physical Chemistry. C},

  number       = 44,

  volume       = 119,

  place        = {United States},

  year         = {Thu Oct 08 00:00:00 EDT 2015},

  month        = {Thu Oct 08 00:00:00 EDT 2015}

}

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.5b08577

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 3 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:

XPS and NEXAFS study of the reactions of acetic acid and acetaldehyde over UO₂(100) thin film

Journal Article Mudiyanselage, K. ; Burrell, A. K. ; Senanayake, S. D. ; ... - Surface Science

The reactions of two C2 oxygenates, acetaldehyde (CH₃CHO) and acetic acid (CH₃COOH), over the (100) terminated surface of UO₂ thin film are investigated. The UO₂ film (ca. 100 nm thick) was prepared on a LaAlO₃ (100) substrate and its reactions were studied by high-resolution synchrotron X-ray photoelectron spectroscopy (XPS – C 1 s, O 1 s, and U 4f) and Near-Edge X-ray Absorption Fine Structure (NEXAFS – C K-edge). Results show a strong interaction of both molecules with the (100) surface at 300 K. Adsorption of acetic acid at 280 K produces acetates. Upon heating their population steadily decreased (XPSmore »« less
Cited by 6
https://doi.org/10.1016/j.susc.2018.10.017

Full Text Available
Ethanol Conversion over La_0.7Sr_0.3MnO_3–x(100): Autocatalysis, Adjacent O-Vacancies, Disproportionation, and Dehydrogenation

Journal Article Chen, Bo ; Xiong, Chuanye ; Jiang, De-en ; ... - ACS Catalysis

The mechanism for catalytic conversion of ethanol over La_0.7Sr_0.3MnO_3–x(100) surface to acetaldehyde and ethene was investigated. Pre-exposure temperature-programmed reaction (PE-TPR) experiments were performed in which ethanol was introduced to oxidized or reduced surfaces followed by heating. In particular, sequential PE-TPR experiments were conducted to incrementally and gradually reduce the surface. The products and their ratios were investigated as a function of surface reduction. The data show that acetaldehyde and ethene production is catalyzed with hydrogen abstraction and oxygen abstraction reactions occurring by intermediates in vacancies at various temperatures >400 K. Adsorption of acetaldehyde followed by a temperature-programmed reaction does notmore »« less
https://doi.org/10.1021/acscatal.0c03241

Full Text Available
NUCLEAR ENGINEERING DEPARTMENT, PROGRESS REPORT, SEPTEMBER 1-DECEMBER 31, 1960

Technical Report

BS>H 7 : Progress is reported for various projects in reactor theory and physics. Data are given for the total neutron and activation cross sections of Dy/sup 164/ as a function of neutron energy. Chemistry and Chemical Engineering. Some radiation research projects are reported. The yields of gas and polymer from radiolysis of C/sub 6/F/sub 16/ and C/sub 8/F/sub 16/ were determined. High-temperature galvanic cells were used at 700 to 950 deg C to measure the thermodynamic properties of ThC/sub 2/. No evidence of complex formation was found in the u-v spectra of KCl-PbCl/sub 2/ mixtures. The effect of Na/supmore »« less
Coupling of Carbon Monoxide Molecules over Oxygen Defected UO2 (111) Single Crystal and Thin Film Surfaces

Journal Article Senanayake, S ; Waterhouse, G ; Idriss, H ; ... - Langmuir

While coupling reactions of carbon-containing compounds are numerous in organometallic chemistry, they are very rare on well-defined solid surfaces. In this work we show that the reductive coupling of two molecules of carbon monoxide to C{sub 2} compounds (acetylene and ethylene) could be achieved on oxygen-defected UO{sub 2}(111) single crystal and thin film surfaces. This result allows in situ electron spectroscopic investigation of a typical organometallic reaction such as carbon coupling and extends it to heterogeneous catalysis and solids. By using high-resolution photoelectron spectroscopy (HRXPS) it was possible to track the changes in surface states of the U and Omore »« less
https://doi.org/10.1021/la0519103
The Reactions of Water Vapour on the Surfaces of Stoichiometric and Reduced Uranium Dioxide: A High Resolution XPS Study

Journal Article Senanayake, S ; Waterhouse, G ; Chan, A ; ... - Catalysis Today

The reaction of water with stoichiometric and O-defective UO{sub 2} thin film surfaces is studied by high-resolution photoelectron spectroscopy using synchrotron X-rays radiation. The decomposition of D{sub 2}O molecules and the oxidative healing of defects on the reduced surfaces was observed and quantified. D{sub 2}O adsorption on the stoichiometric UO{sub 2} surface at 300 K showed small amounts of OD species (ca. 532 eV) probably formed on trace amounts of surface defects, while at 95 K D2O ice (533.5 eV) was the main surface species. On the contrary, a large signal of OD species was seen on the 300 K-Ar{supmore »« less
https://doi.org/10.1016/j.cattod.2006.07.040

Similar Records

Title: Surface reactions of ethanol over UO2(100) thin film

Abstract

Citation Formats

Title: Surface reactions of ethanol over UO₂(100) thin film