skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Mononuclear iridium dinitrogen complexes bonded to zeolite HY

Abstract

In this study, the adsorption of N2 on structurally well-defined dealuminated HY zeolite-supported iridium diethylene complexes was investigated. Iridium dinitrogen complexes formed when the sample was exposed to N2 in H2 at 298 K, as shown by infrared spectra recorded with isotopically labeled N2. Four supported species formed in various flowing gases: Ir(N2), Ir(N2)(N2), Ir(C2H5)(N2), and Ir(H)(N2). Their interconversions are summarized in a reaction network, showing, for example, that, in the presence of N2, Ir(N2) was the predominant dinitrogen species at temperatures of 273-373 K. Ir(CO)(N2) formed transiently in flowing CO, and in the presence of H2, rather stable iridium hydride complexes formed. Here, four structural models of each iridium complex bonded at the acidic sites of the zeolite were employed in a computational investigation, showing that the calculated vibrational frequencies agree well with experiment when full calculations are done at the level of density functional theory, independent of the size of the model of the zeolite.

Authors:
 [1];  [2];  [1];  [3];  [1]
  1. Univ. of California, Davis, CA (United States). Dept. of Chemical Engineering & Materials Science
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). National Center for Computational Sciences; Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemistry
  3. Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org.:
DOE Office of Science (SC); USDOE
OSTI Identifier:
1265415
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 21; Journal Issue: 2; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; density functional calculations; dinitrogen adsorption; iridium; supported complexes; zeolites

Citation Formats

Yang, Dong, Chen, Mingyang, Martinez-Macias, Claudia, Dixon, David A., and Gates, Bruce C. Mononuclear iridium dinitrogen complexes bonded to zeolite HY. United States: N. p., 2014. Web. doi:10.1002/chem.201404794.
Yang, Dong, Chen, Mingyang, Martinez-Macias, Claudia, Dixon, David A., & Gates, Bruce C. Mononuclear iridium dinitrogen complexes bonded to zeolite HY. United States. https://doi.org/10.1002/chem.201404794
Yang, Dong, Chen, Mingyang, Martinez-Macias, Claudia, Dixon, David A., and Gates, Bruce C. 2014. "Mononuclear iridium dinitrogen complexes bonded to zeolite HY". United States. https://doi.org/10.1002/chem.201404794. https://www.osti.gov/servlets/purl/1265415.
@article{osti_1265415,
title = {Mononuclear iridium dinitrogen complexes bonded to zeolite HY},
author = {Yang, Dong and Chen, Mingyang and Martinez-Macias, Claudia and Dixon, David A. and Gates, Bruce C.},
abstractNote = {In this study, the adsorption of N2 on structurally well-defined dealuminated HY zeolite-supported iridium diethylene complexes was investigated. Iridium dinitrogen complexes formed when the sample was exposed to N2 in H2 at 298 K, as shown by infrared spectra recorded with isotopically labeled N2. Four supported species formed in various flowing gases: Ir(N2), Ir(N2)(N2), Ir(C2H5)(N2), and Ir(H)(N2). Their interconversions are summarized in a reaction network, showing, for example, that, in the presence of N2, Ir(N2) was the predominant dinitrogen species at temperatures of 273-373 K. Ir(CO)(N2) formed transiently in flowing CO, and in the presence of H2, rather stable iridium hydride complexes formed. Here, four structural models of each iridium complex bonded at the acidic sites of the zeolite were employed in a computational investigation, showing that the calculated vibrational frequencies agree well with experiment when full calculations are done at the level of density functional theory, independent of the size of the model of the zeolite.},
doi = {10.1002/chem.201404794},
url = {https://www.osti.gov/biblio/1265415}, journal = {Chemistry - A European Journal},
issn = {0947-6539},
number = 2,
volume = 21,
place = {United States},
year = {Fri Nov 07 00:00:00 EST 2014},
month = {Fri Nov 07 00:00:00 EST 2014}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993


A b i n i t i o relativistic effective potentials with spin–orbit operators. IV. Cs through Rn
journal, November 1990


Infra-red spectra of nitrogen adsorbed on silica-supported platinum
journal, January 1974

  • Egerton, Terence A.; Sheppard, Norman
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 70, Issue 0
  • https://doi.org/10.1039/f19747001357

Dinitrogen Coordination Chemistry:  On the Biomimetic Borderlands
journal, February 2004


Reactions at Surfaces: From Atoms to Complexity (Nobel Lecture)
journal, April 2008


Binary Dinitrogen Complexes of Rhodium, Rh(N 2 ) n (where n  = 1–4), in Low Temperature Matrices
journal, October 1973


Real-Time Characterization of Formation and Breakup of Iridium Clusters in Highly Dealuminated Zeolite Y
journal, August 2008


A Site-Isolated Iridium Diethylene Complex Supported on Highly Dealuminated Y Zeolite:  Synthesis and Characterization
journal, September 2007


Energy-consistent pseudopotentials and correlation consistent basis sets for the 5d elements Hf–Pt
journal, April 2009


Nitrogen Chemisorption on the Coordinatively Unsaturated Rh Site on Al 2 O 3
journal, January 1996


Infrared spectroscopy at high pressure. Interaction of nitrogen (N2) with rhodium/aluminum oxide at ambient temperature
journal, April 1991


Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988


Titanium-Promoted Dinitrogen Cleavage, Partial Hydrogenation, and Silylation
journal, September 2009


Dinitrogen Cleavage and Hydrogenation by a Trinuclear Titanium Polyhydride Complex
journal, June 2013


Supported Molecular Iridium Catalysts: Resolving Effects of Metal Nuclearity and Supports as Ligands
journal, October 2011


"Sideways" Bonded Dinitrogen in Matrix Isolated Cobalt Dinitrogen, CoN 2
journal, February 1973


Dinitrogen Cleavage by a Three-Coordinate Molybdenum(III) Complex
journal, May 1995


Hydrogen Activation and Metal Hydride Formation Trigger Cluster Formation from Supported Iridium Complexes
journal, March 2012


Results obtained with the correlation energy density functionals of becke and Lee, Yang and Parr
journal, May 1989


Synthesis and crystal structure of Ir(C2H4)2(C5H7O2)
journal, April 2007


Dinitrogen Cleavage by a Diniobium Tetrahydride Complex: Formation of a Nitride and Its Conversion into Imide Species
journal, November 2007


Dinitrogen Irreversible Adsorption on Overexchanged Cu-ZSM-5
journal, December 2002


A new ONIOM implementation in Gaussian98. Part I. The calculation of energies, gradients, vibrational frequencies and electric field derivatives
journal, April 1999


Efficient Approach for the Computational Study of Alcohol and Nitrile Adsorption in H-ZSM-5
journal, February 2012


Reaktionen an Oberflächen: vom Atomaren zum Komplexen (Nobel-Vortrag)
journal, April 2008


Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992


Binary transition metal dinitrogen complexes. I. Matrix infrared and Raman spectra, structure and bonding of Ni(N2)n and Pd(N2)m(n = 1-4 and m = 1-3)
journal, January 1973


Binary transition metal nitrogen compounds; infrared evidence for Ni(N2) x
journal, January 1971


Strong adsorption of dinitrogen on copper-ion-exchanged mordenite at room temperature
journal, January 1993


Infra-red spectra of nitrogen adsorbed on iridium
journal, January 1968


Ab initio relativistic effective potentials with spin‐orbit operators. I. Li through Ar
journal, March 1985


Chemisorptions of Gases on Iron Synthetic Ammonia Catalysts 1
journal, July 1940


Titanium-Promoted Dinitrogen Cleavage, Partial Hydrogenation, and Silylation
journal, September 2009


Dinitrogen Cleavage by a Diniobium Tetrahydride Complex: Formation of a Nitride and Its Conversion into Imide Species
journal, November 2007


Binary Iron−Dinitrogen Compounds Synthesized by Co-deposition of Mass-Selected Fe, Fe 2 , and Fe 3 with N 2
journal, June 2000


Zeolite-Supported Organorhodium Fragments: Essentially Molecular Surface Chemistry Elucidated with Spectroscopy and Theory
journal, June 2009


Hydrogenation and cleavage of dinitrogen to ammonia with a zirconium complex
journal, February 2004


N2 Reduction and Hydrogenation to Ammonia by a Molecular Iron-Potassium Complex
journal, November 2011


Works referencing / citing this record:

High-Energy-Resolution X-ray Absorption Spectroscopy for Identification of Reactive Surface Species on Supported Single-Site Iridium Catalysts
journal, July 2017


High-Energy-Resolution X-ray Absorption Spectroscopy for Identification of Reactive Surface Species on Supported Single-Site Iridium Catalysts
journal, August 2017