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Title: Molecular chemisorption of N2 on IrO2(110)

Abstract

We investigated the adsorption of N2 on stoichiometric and O-rich IrO2(110) surfaces using temperature programmed desorption (TPD) experiments and density functional theory (DFT) calculations. TPD shows that N2 desorbs predominantly from the stoichiometric-IrO2(110) surface in a well-defined peak at 270 K for N2 coverages below about 0.5 ML, and that a shoulder centered near 235 K develops in the N2 TPD traces as the coverage approaches saturation, indicating that adsorbed N2 molecules become destabilized at high N2 coverage. Experiments of N2 adsorption onto O-rich IrO2(110) surfaces provide evidence that N2 adsorbs exclusively on the coordinatively-unsaturated Ir atoms (Ircus) of the surface, and that pre-adsorbed O-atoms (“on-top” oxygen) stabilize adsorbed N2 molecules, causing the main N2 TPD peak to shift toward higher temperature with increasing oxygen coverage. Consistent with prior results, our DFT calculations predict that an N2 molecule preferentially adsorbs into an upright configuration on an Ircus atom of the IrO2(110) surface and achieves a binding energy of about 100 kJ/mol. The computed binding energy agrees well with our experimental estimate of ~90 kJ/mol for low N2 coverages on stoichiometric IrO2(110). Lastly, the DFT calculations also quantitatively reproduce the observed stabilization of N2 by co-adsorbed on-top O-atoms and predict themore » destabilization of N2 on IrO2(110) as the N2 adlayer becomes crowded at high coverage.« less

Authors:
 [1];  [2]; ORCiD logo [1];  [1];  [1];  [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Florida, Gainesville, FL (United States)
  2. The Ohio State Univ., Columbus, OH (United States)
  3. ExxonMobil Research and Engineering, Annandale, NJ (United States)
Publication Date:
Research Org.:
Univ. of Florida, Gainesville, FL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1773788
Alternate Identifier(s):
OSTI ID: 1600848
Grant/Contract Number:  
FG02-03ER15478
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 152; Journal Issue: 7; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemical bonding; Electron diffraction; Chemisorption; Temperature programmed desorption; Temperature programmed reaction spectroscopy; Density functional theory; Adsorption; Surface and interface chemistry; Crystal lattices; Quadrupole mass spectrometry

Citation Formats

Martin, R., Kim, M., Lee, C. J., Shariff, M. S., Feng, F., Meyer, R. J., Asthagiri, A., and Weaver, J. F. Molecular chemisorption of N2 on IrO2(110). United States: N. p., 2020. Web. https://doi.org/10.1063/1.5142210.
Martin, R., Kim, M., Lee, C. J., Shariff, M. S., Feng, F., Meyer, R. J., Asthagiri, A., & Weaver, J. F. Molecular chemisorption of N2 on IrO2(110). United States. https://doi.org/10.1063/1.5142210
Martin, R., Kim, M., Lee, C. J., Shariff, M. S., Feng, F., Meyer, R. J., Asthagiri, A., and Weaver, J. F. Thu . "Molecular chemisorption of N2 on IrO2(110)". United States. https://doi.org/10.1063/1.5142210. https://www.osti.gov/servlets/purl/1773788.
@article{osti_1773788,
title = {Molecular chemisorption of N2 on IrO2(110)},
author = {Martin, R. and Kim, M. and Lee, C. J. and Shariff, M. S. and Feng, F. and Meyer, R. J. and Asthagiri, A. and Weaver, J. F.},
abstractNote = {We investigated the adsorption of N2 on stoichiometric and O-rich IrO2(110) surfaces using temperature programmed desorption (TPD) experiments and density functional theory (DFT) calculations. TPD shows that N2 desorbs predominantly from the stoichiometric-IrO2(110) surface in a well-defined peak at 270 K for N2 coverages below about 0.5 ML, and that a shoulder centered near 235 K develops in the N2 TPD traces as the coverage approaches saturation, indicating that adsorbed N2 molecules become destabilized at high N2 coverage. Experiments of N2 adsorption onto O-rich IrO2(110) surfaces provide evidence that N2 adsorbs exclusively on the coordinatively-unsaturated Ir atoms (Ircus) of the surface, and that pre-adsorbed O-atoms (“on-top” oxygen) stabilize adsorbed N2 molecules, causing the main N2 TPD peak to shift toward higher temperature with increasing oxygen coverage. Consistent with prior results, our DFT calculations predict that an N2 molecule preferentially adsorbs into an upright configuration on an Ircus atom of the IrO2(110) surface and achieves a binding energy of about 100 kJ/mol. The computed binding energy agrees well with our experimental estimate of ~90 kJ/mol for low N2 coverages on stoichiometric IrO2(110). Lastly, the DFT calculations also quantitatively reproduce the observed stabilization of N2 by co-adsorbed on-top O-atoms and predict the destabilization of N2 on IrO2(110) as the N2 adlayer becomes crowded at high coverage.},
doi = {10.1063/1.5142210},
journal = {Journal of Chemical Physics},
number = 7,
volume = 152,
place = {United States},
year = {2020},
month = {2}
}

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