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Title: Unraveling the individual influences of supports and ionic liquid coatings on the catalytic properties of supported iridium complexes and iridium clusters

Abstract

In this work, supported iridium complexes were synthesized by the reaction of Ir(CO)2(acac) (acac = acetylacetonato) with SiO2, γ-Al2O3, and MgO. Extended X-ray absorption fine structure (EXAFS) and infrared (IR) spectra demonstrate that the iridium was present as atomically dispersed species anchored to each support. The samples were treated in flowing H2 at 673 K to form supported iridium clusters. EXAFS spectra and high-angle annular dark-field scanning transmission electron microscopy images demonstrate that the average diameter of the iridium clusters on each support was approximately 1.2 nm. Furthermore, the catalysts before and after cluster formation were coated with each of a family of 1,3-dialkylimidazolium ionic liquids (ILs) having varying electron-donor tendencies probed by their υ(C2H) frequencies determined by IR spectroscopy. The coated and uncoated samples were tested as catalysts for partial hydrogenation of 1,3-butadiene in a flow reactor at 333 K, with turnover frequencies determined from differential conversions. The individual influences of the IL coatings and supports on the catalyst performance were found to depend strongly on whether the iridium was site-isolated complexes or present in clusters. The IL coatings as ligands exerted dominant effects on the clusters as catalysts, whereas the supports exerted dominant effects on the isolated iridiummore » atoms. The results indicate how to tune the effects of metal nuclearity, IL coatings, and supports on the electronic environments and catalytic properties of the metals.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [4];  [2];  [3];  [4]
+ Show Author Affiliations
  1. Koç Univ., Istanbul (Turkey); Koç Univ. ÜPRASß Energy Center (KUTEM), Instanbul (Turkey); Univ. of California, Davis, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  3. Univ. of California, Davis, CA (United States)
  4. Koç Univ., Istanbul (Turkey); Koç Univ. ÜPRASß Energy Center (KUTEM), Instanbul (Turkey)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1647022
Alternate Identifier(s):
OSTI ID: 1775864
Grant/Contract Number:  
AC02-76SF00515; FG02-04ER1551
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 387; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; supported metal complexes; ionic liquid; ligand effect; partial hydrogenation; 1,3-Butadiene hydrogenation

Citation Formats

Babucci, Melike, Hoffman, Adam S., Debefve, Louise M., Kurtoglu, Samira F., Bare, Simon R., Gates, Bruce C., and Uzun, Alper. Unraveling the individual influences of supports and ionic liquid coatings on the catalytic properties of supported iridium complexes and iridium clusters. United States: N. p., 2020. Web. doi:10.1016/j.jcat.2020.04.022.
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Babucci, Melike, Hoffman, Adam S., Debefve, Louise M., Kurtoglu, Samira F., Bare, Simon R., Gates, Bruce C., & Uzun, Alper. Unraveling the individual influences of supports and ionic liquid coatings on the catalytic properties of supported iridium complexes and iridium clusters. United States. https://doi.org/10.1016/j.jcat.2020.04.022
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Babucci, Melike, Hoffman, Adam S., Debefve, Louise M., Kurtoglu, Samira F., Bare, Simon R., Gates, Bruce C., and Uzun, Alper. Wed . "Unraveling the individual influences of supports and ionic liquid coatings on the catalytic properties of supported iridium complexes and iridium clusters". United States. https://doi.org/10.1016/j.jcat.2020.04.022. https://www.osti.gov/servlets/purl/1647022.
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@article{osti_1647022,
title = {Unraveling the individual influences of supports and ionic liquid coatings on the catalytic properties of supported iridium complexes and iridium clusters},
author = {Babucci, Melike and Hoffman, Adam S. and Debefve, Louise M. and Kurtoglu, Samira F. and Bare, Simon R. and Gates, Bruce C. and Uzun, Alper},
abstractNote = {In this work, supported iridium complexes were synthesized by the reaction of Ir(CO)2(acac) (acac = acetylacetonato) with SiO2, γ-Al2O3, and MgO. Extended X-ray absorption fine structure (EXAFS) and infrared (IR) spectra demonstrate that the iridium was present as atomically dispersed species anchored to each support. The samples were treated in flowing H2 at 673 K to form supported iridium clusters. EXAFS spectra and high-angle annular dark-field scanning transmission electron microscopy images demonstrate that the average diameter of the iridium clusters on each support was approximately 1.2 nm. Furthermore, the catalysts before and after cluster formation were coated with each of a family of 1,3-dialkylimidazolium ionic liquids (ILs) having varying electron-donor tendencies probed by their υ(C2H) frequencies determined by IR spectroscopy. The coated and uncoated samples were tested as catalysts for partial hydrogenation of 1,3-butadiene in a flow reactor at 333 K, with turnover frequencies determined from differential conversions. The individual influences of the IL coatings and supports on the catalyst performance were found to depend strongly on whether the iridium was site-isolated complexes or present in clusters. The IL coatings as ligands exerted dominant effects on the clusters as catalysts, whereas the supports exerted dominant effects on the isolated iridium atoms. The results indicate how to tune the effects of metal nuclearity, IL coatings, and supports on the electronic environments and catalytic properties of the metals.},
doi = {10.1016/j.jcat.2020.04.022},
journal = {Journal of Catalysis},
number = ,
volume = 387,
place = {United States},
year = {Wed Jul 01 00:00:00 EDT 2020},
month = {Wed Jul 01 00:00:00 EDT 2020}
}
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