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

Babucci, Melike; Hoffman, Adam S.; Debefve, Louise M.; Kurtoglu, Samira F.; Bare, Simon R.; Gates, Bruce C.; Uzun, Alper

doi:10.1016/j.jcat.2020.04.022

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

Journal Article · Wed Jul 01 00:00:00 EDT 2020 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2020.04.022· OSTI ID:1647022

Babucci, Melike ^[1];

^[2]; Debefve, Louise M. ^[3]; Kurtoglu, Samira F. ^[4]; Bare, Simon R. ^[2]; Gates, Bruce C. ^[3]; Uzun, Alper ^[4]

Koç Univ., Istanbul (Turkey); Koç Univ. ÜPRASß Energy Center (KUTEM), Instanbul (Turkey); Univ. of California, Davis, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Univ. of California, Davis, CA (United States)
Koç Univ., Istanbul (Turkey); Koç Univ. ÜPRASß Energy Center (KUTEM), Instanbul (Turkey)

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.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515; FG02-04ER1551

OSTI ID:: 1647022

Alternate ID(s):: OSTI ID: 1775864

Journal Information:: Journal of Catalysis, Vol. 387; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 12 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
supported metal complexes
ionic liquid
ligand effect
partial hydrogenation
1
3-Butadiene hydrogenation

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

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