skip to main content

DOE PAGESDOE PAGES

Title: Mononuclear iridium dinitrogen complexes bonded to zeolite HY

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)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Alabama, Tuscaloosa, AL (United States)
  3. Univ. of Alabama, Tuscaloosa, AL (United States)
Publication Date:
OSTI Identifier:
1265415
Grant/Contract Number:
AC05-00OR22725
Type:
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
Research Org:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org:
USDOE
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