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Title: Molecular chemisorption of N2 on IrO2(110)

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.5142210 · OSTI ID:1773788
 [1];  [2]; ORCiD logo [3];  [3];  [3];  [4]; ORCiD logo [2]; ORCiD logo [3]
  1. Univ. of Florida, Gainesville, FL (United States); University of Florida
  2. The Ohio State Univ., Columbus, OH (United States)
  3. Univ. of Florida, Gainesville, FL (United States)
  4. ExxonMobil Research and Engineering, Annandale, NJ (United States)
+ Show Author Affiliations

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.

Research Organization:
Univ. of Florida, Gainesville, FL (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-03ER15478
OSTI ID:
1773788
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 7 Vol. 152; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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