Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

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 [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)
+ 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 Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-03ER15478
OSTI ID:
1773788
Alternate ID(s):
OSTI ID: 1600848
Journal Information:
Journal of Chemical Physics, Vol. 152, Issue 7; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 15 works
Citation information provided by
Web of Science

References (38)

Pathways for C–H bond cleavage of propane σ-complexes on PdO(101) journal January 2012
Dissociative Chemisorption and Oxidation of H2 on the Stoichiometric IrO2(110) Surface journal December 2017
The X-ray photoelectron spectra of Ir, IrO 2 and IrCl 3 revisited: The X-ray photoelectron spectra of Ir, IrO 2 and IrCl 3 revisited journal March 2017
Structure and reactivity of iridium oxide layers grown on Ir(1 0 0) by oxidation at sub-ambient O 2 pressures journal August 2019
Pathways and kinetics of methane and ethane C–H bond cleavage on PdO(101) journal September 2013
n-alkanes on Pt(111) and on C(0001)∕Pt(111): Chain length dependence of kinetic desorption parameters journal December 2006
LOBSTER: A tool to extract chemical bonding from plane-wave based DFT: Tool to Extract Chemical Bonding journal February 2016
Ab initio Hellmann-Feynman molecular dynamics for liquid metals journal May 1993
n-alkanes on MgO(100). II. Chain length dependence of kinetic desorption parameters for small n-alkanes journal April 2005
Understanding the Intrinsic Surface Reactivity of Single-Layer and Multilayer PdO(101) on Pd(100) journal August 2018
Growth and termination of a rutile IrO2(100) layer on Ir(111) journal October 2016
Facile Dehydrogenation of Ethane on the IrO 2 (110) Surface journal February 2018
The structure-sensitive adsorption of N2 on the (1 × 1) and (5 × 1) surfaces of Ir{100} journal May 1993
A Comparison of N 2 and CO Adsorption on Ru(001) journal January 1997
Adsorption and Oxidation of CH 4 on Oxygen-Rich IrO 2 (110) journal October 2019
Adsorption of small hydrocarbons on rutile TiO2(110) journal August 2016
Surface Chemistry of Late Transition Metal Oxides journal December 2012
Adsorption and abstraction of oxygen atoms on Pd(111): Characterization of the precursor to PdO formation journal April 2008
Nitrogen Adsorption and Dissociation on Fe(111) journal March 1999
A DFT study of ethane activation on IrO 2 (110) surface by precursor-mediated mechanism journal July 2017
Characterization of Various Oxygen Species on an Oxide Surface:  RuO 2 (110) † journal May 2001
Density Functional Theory Study of NH x ( x = 0−3) and N 2 Adsorption on IrO 2 (110) Surfaces journal October 2010
n-alkanes on MgO(100). I. Coverage-dependent desorption kinetics of n-butane journal April 2005
Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations journal August 1993
Analytic projection from plane-wave and PAW wavefunctions and application to chemical-bonding analysis in solids journal September 2013
Density Functional Theory Study of the Oxidation of Ammonia on the IrO 2 (110) Surface journal December 2011
Methanol oxidation on stoichiometric and oxygen-rich RuO 2 (110) journal January 2017
Crystal Orbital Hamilton Population (COHP) Analysis As Projected from Plane-Wave Basis Sets journal June 2011
C–H Bond Activation of Methane via σ–d Interaction on the IrO 2 (110) Surface: Density Functional Theory Study journal March 2012
Adsorption and Oxidation of n -Butane on the Stoichiometric RuO 2 (110) Surface journal April 2016
Low-temperature activation of methane on the IrO 2 (110) surface journal April 2017
Surface Chemistry of Ruthenium Dioxide in Heterogeneous Catalysis and Electrocatalysis: From Fundamental to Applied Research journal March 2012
Oxidation of Nitrided Si(100) by Gaseous Atomic and Molecular Oxygen journal April 2005
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
Adsorption and Activation of Methane on the (110) Surface of Rutile-type Metal Dioxides journal June 2018
Oxidation of a Tb 2 O 3 (111) Thin Film on Pt(111) by Gas-Phase Oxygen Atoms journal August 2014
Adsorption and Oxidation of Ethylene on the Stoichiometric and O-Rich RuO 2 (110) Surfaces journal September 2017
Template-Assisted Growth of Ultrathin Single-Crystalline IrO 2 (110) Films on RuO 2 (110)/Ru(0001) and Its Thermal Stability journal May 2018

Similar Records

Related Subjects

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