pubs.acs.

org/acscatalysis Letter

Electronic Structure of Atomically Dispersed Supported Iridium

Catalyst Controls Iridium Aggregation
Samira F. Kurtoğlu,∇ Adam S. Hoffman,∇ Deniz Akgül,∇ Melike Babucci, Viktorya Aviyente,
Bruce C. Gates, Simon R. Bare, and Alper Uzun*
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ABSTRACT: Supported iridium complexes, Ir(C2H4)2/support, were characterized by

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X-ray absorption spectroscopy during a temperature ramp to 120 °C in flowing H2.

Iridium in complexes bonded to weak and moderate electron-donor supports, SiO2 and γ-
Al2O3, underwent aggregation, forming nanoparticles and clusters, respectively. When the
support was a strong electron-donor (MgO), iridium remained site-isolated. Density
functional theory calculations confirm the dependence of iridium−support bond strength
on the support’s electron-donor character. Coating the SiO2-supported complexes with 1-
n-ethyl-3-methyl-imidazolium acetate enhanced electron density on the iridium,
hindering its aggregation. These results demonstrate opportunities for stabilizing
atomically dispersed supported noble metals under reducing conditions by choice of
support/ionic liquid sheath combinations.

KEYWORDS: single-site metal, atomically dispersed metal, supported metal, ionic liquid sheath, catalyst stability, metal aggregation,
metal sintering

A tomically dispersed supported metals are drawing wide-

spread attention, because they offer catalytic properties
different from those of conventional supported metals (which
incorporate metal nanoparticles or clusters), and they have the
advantage of maximum utilization of the often-expensive
metals.1−9 The catalytic properties of atomically dispersed
metals are dependent on their ligands, and these include the
supports.10−15
When the metals in these catalysts are noble, they are readily
reduced and sintered, with marked changes in catalytic
properties.7,16−18 One approach to stabilizing the metals
against sintering is to bond them to sites where they are
highly coordinated.3,19,20However, there are tradeoffs: the
greater the number of coordination sites for anchoring the
metal to the support, the smaller the number of sites for
bonding of reactants.21 Alternatively, the support may be
chosen to maximize the strength of the metal−support
bonds22−24 (e.g., by maximizing the electron-donor strength
of the support as a ligand). Because this electron-donor
strength affects the reactivity, one anticipates further tradeoffs
in catalyst design affecting activity, selectivity, and stability.
Another approach to stabilizing supported metals is to
envelope them with ionic liquid (IL) sheaths,11,25−27 and there
are an enormous number of ILs with a wide range of properties
to choose from.28,29 The roles of the supports and IL
sheaths11,25−27 extend to stabilization of atomically dispersed
metals, but investigations of this topic are largely lacking.
Here, we report synergistic ligand effects of supports and ILs
on a supported iridium complex, determining how they
influence the resistance of the iridium to aggregation. The
data show that resistance to sintering in the presence of H2 is
favored by strong electron-donor supports, such as MgO, and
by strong electron-donor IL sheaths, which markedly limit the
metal aggregation, even on the weak electron-donor SiO2
support.
Catalysts incorporating atomically dispersed iridium (1.0
wt % Ir) were synthesized via the reaction of Ir(C2H4)2(acac)
(where acac is acetylacetonato, [CH3COCHCOCH3]−1) or
Ir(CO)2(acac) with each of the high-area supports MgO, γ-
Al2O3, and SiO2, which were dehydroxylated at 700, 500, and
520 °C, respectively.11,30 Characterization by infrared (IR)
spectroscopy demonstrated the dissociation of acac ligands
from the precursors30 upon adsorption and retention of π-
bonded C2H4 (or CO) ligands on the iridium, indicating the
formation of Ir(C2H4)2 (or Ir(CO)2) complexes on the
support (see Figures S1 and S2 in the Supporting Information
(SI)).31,32 Extended X-ray absorption fine structure (EXAFS)
Received: September 7, 2020
Published: October 8, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acscatal.0c03909

12354 ACS Catal. 2020, 10, 12354−12358
ACS Catalysis pubs.acs.org/acscatalysis
data show that the iridium complexes in each sample had
essentially the same local environment (see Figures S3 and S4
in the SI). Modeling of these spectra was consistent with the
lack of any detectable Ir−Ir scattering path, indicating that the
iridium was atomically dispersed on each support (see Table
S1, Figure S5, Table S2, and Figure S6 in the SI). The EXAFS
data further indicate that each Ir atom was surrounded by low-
Z scatterer atoms (characterized by a feature located at ∼1.7 Å
in Fourier-transformed R-space data, where R is the absorber−
scatterer distance). The results are broadly consistent with
those reported.12,30,33 The ν(CO) band positions of Ir(CO)2
complexes on each support provide a measure of electron
densities on Ir sites.11,12 Figure S7 in the SI shows that the
complexes supported on MgO were characterized by a
νsym(CO) of 2068 cm−1 and those on γ-Al2O3 and SiO2 by
νsym(CO) values of 2072 and 2081 cm−1, respectively,
indicating a higher electron density on MgO-supported Ir, as
expected.11,12 When SiO2-supported Ir(CO)2 complexes were
coated with 1-n-ethyl-3-methyl-imidazolium acetate ([EMIM]-
[OAc]), the νsym(CO) band was red-shifted to 2050 cm−1,
confirming the electron-donor character of [EMIM]-
[OAc].11,25−27,34 The electron density on iridium varied with
the support in the following order: SiO2 < γ-Al2O3 < MgO <
SiO2 (when the complex was [EMIM][OAc]-coated), as
expected.11 Density functional theory (DFT) calculations
performed at the level of PBE/6-31G(d,p) confirmed these
results on supported Ir(CO)2 complexes and indicated that
this order is also valid for the supported Ir(C2H4)2 complexes
(Figures S8 and S9, and Tables S3 and S4 in the SI).
Moreover, in the X-ray absorption near edge (XANES) spectra
of the samples incorporating Ir(C2H4)2 complexes, slight shifts
in the energy of the absorption edges were also observed (see
Figure S10 in the SI).
To evaluate the influences of the support and IL coating on
the resistance to aggregation of the iridium, we performed
temperature-programmed reduction (TPR) experiments, rais-
ing the temperature of each sample in flowing pure H2 from
room temperature to 120 °C at a ramp rate of 3 °C/min at
atmospheric pressure as continuous-scan X-ray absorption
spectroscopy (XAS) data were recorded at the Ir LIII-edge at a
time resolution of ∼2.5 min per scan. Initial samples were
those incorporating Ir(C2H4)2 complexes, because these are
more prone to aggregation of the iridium than the Ir(CO)2
complexes, allowing for the investigation of aggregation
behavior at temperatures low enough to ensure that the
structural integrity of the IL sheath is maintained.32
The XANES recorded during TPR include isosbestic points,
demonstrating the transformation of one species to another,
for Ir(C2H4)2 supported on SiO2 and on γ-Al2O3 (see Figures
S11a and S11b in the SI), as had been observed for zeolite Y-
supported Ir(C2H4)2 complexes.35 The TPR-XANES data
show a decrease in white-line intensity for each sample (Figure
1), with those characterizing the MgO-supported complex
indicating only minor changes (Figure S11c in the SI). The
changes were most striking for the SiO2-supported sample, for
which the white-line intensity decreased toward that of metallic
iridium (Figure S11a in the SI). Time-resolved EXAFS results
(Figures 2a−c) provide evidence of the corresponding
structural changes (Figures S12−S15 and Table S5 in the
SI). The intensity of the contribution associated with the low-Z
scatterers (Ir−C and Ir−O, with interatomic distances of ∼1.7
Å) started to decrease at ∼75 °C when the support was SiO2,
accompanied by the appearance of a new feature at ∼2.4 Å,
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Letter
Figure 1. Change in white-line intensity during a temperature ramp
from room temperature to 120 °C in flowing H2 characterizing SiO2-
(red), γ-Al2O3- (blue), and MgO-supported (green) Ir(C2H4)2
complexes and [EMIM][OAc]-coated SiO2-supported (black) Ir-
(C2H4)2 complex. Initial white-line intensities characterizing each
sample were normalized to 1.0 (corresponding XANES spectra of
each sample measured in real time are provided in Figure S11 in the
SI).
which provides evidence of an Ir−Ir scattering path and
demonstrates iridium cluster formation (Figure 2a).35,36 The
intensity of this feature continued to grow as the temperature
increased toward 120 °C, while that characterizing the Ir−low-
Z-scatterer contribution decreased and almost disappeared,
which is consistent with the breaking of iridium−support and/
or iridium−organic ligand bonds (Figure 2a). The pattern was
similar when the support was γ-Al2O3; however, the decrease
in intensity of the feature associated with the coordination of Ir
with low-Z-scatterrers was not strong (Figure 2b). When the
support was MgO, these changes were minimal (Figure 2c).
The EXAFS data characterizing the post-TPR structures
differ significantly from each other (Figures S16−S20 in the
SI). The data show that the final Ir−Ir coordination numbers
in the SiO2- and γ-Al2O3-supported samples were 6.5 ± 0.7 and
3.7 ± 0.4, respectively (see Table S6, and Figures S21 and S22,
in the SI). It was not possible to fit an Ir−Ir scattering path to
the EXAFS data characterizing the MgO-supported sample at
the end of the TPR, indicating the lack of any significant
iridium aggregation on this support (Figure S23 in the SI). The
slight structural changes observed during TPR are likely
associated with the changing ligand environment of the Ir.
These data show that, although the iridium complex supported
on SiO2 was present at a much lower surface density than that
on the other supportsits surface area is higher and the Ir
loading is identicalthe tendency of iridium to aggregate was
much higher on SiO2 (Table S7 in the SI). DFT calculations at
a level of PBE/6-31G(d,p) further support these findings,
indicating that the strength of the metal−support−oxygen
bonds, estimated as the dissociation energy of the complex
from the surface of each support, increase in the order SiO2
(75.6 kcal/mol) < γ-Al2O3 (79.5 kcal/mol) < MgO (98.8 kcal/
mol) (Figure 3, as well as Table S8 and Figure S24 in the SI).
The contrasting degrees of iridium aggregation on the various
supports with different electron-donor character bolster the
inference that increasing electron donation from the support to
https://dx.doi.org/10.1021/acscatal.0c03909
ACS Catal. 2020, 10, 12354−12358
ACS Catalysis pubs.acs.org/acscatalysis
Figure 2. Magnitude of the Fourier-transform of the EXAFS spectra
(data not phase- and amplitude-corrected) measured at the Ir LIII-
edge during a temperature ramp of each sample to 120 °C in flowing
H2. Data obtained on (a) SiO2-supported, (b) γ-Al2O3-supported, (c)
MgO-supported Ir(C2H4)2 complexes, and (d) [EMIM][OAc]-
coated SiO2-supported Ir(C2H4)2 complex (k ranges for each fit
(where k is the wave vector) are stated in Table S5 in the SI).
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Letter
Figure 3. Dependence of degree of iridium aggregation in TPR
(measured by Ir−Ir coordination numbers determined by EXAFS
spectroscopy (red) with an error range of ±10%) characterizing the
post-TPR samples on the strength of Ir−O bonds, indicated by the
average Ir−O bond distances in metal oxide-supported Ir(C2H4)2
complexes calculated by DFT (black) and by DFT-determined
dissociation energies characterizing Ir(C2H4)2 complexes on the
supports. The error bars for Ir−O bond distances were determined on
the basis of the differences between the two separate Ir−O bond
distances associated with the bonding of the iridium to the support.
the iridium species reduces the tendency of the iridium to
undergo reduction, Ir−O bond breaking, and aggregation (see
Figure 3).
To extend the investigation to include the influence of an IL
coating, the sample that was most susceptible to reduction and
aggregation of the iridium, Ir(C2H4)2/SiO2, was coated with an
electron-donating IL, [EMIM][OAc], as observed previ-
ously,11,25,26 and evaluated under identical TPR conditions,
with simultaneous measurement of XAS data.
The EXAFS data characterizing the initial structure are
consistent with the presence of site-isolated iridium complexes,
characterized by the lack of any detectable Ir−Ir contribution
and by the presence of low-Z-scatterer atoms surrounding
iridium (Table S1 in the SI). XANES data recorded during
TPR indicate only minor changes, without evidence that would
justify inferring whether there were isosbestic points (see
Figure 1, as well as Figure S11d in the SI). Consistent with
these results, the EXAFS data gave no evidence of significant
structural changes during the temperature ramp (see Figure 2d,
as well as Figures S12−S15). The spectrum of the sample after
the treatment did not include any evidence of a detectable Ir−
Ir scattering path (see Figures S17, S25, and S26, as well as
Table S9 in the SI). Thus, the IL coating prevented iridium
reduction and aggregation. The stabilization may indicate more
than a ligand effectthe IL sheath may also help to stabilize
the iridium complexes by physically blocking their migration
on the support surface. Nonetheless, as shown else-
where,11,26,27 iridium in these coated samples is accessible to
reactants and catalytically active for 1,3-butadiene hydro-
genation under similar conditions.
In summary, the results demonstrate how to control the
resistance to reduction and aggregation of atomically dispersed
noble metals on supports, presenting opportunities for
controlling stabilities of catalysts in this emerging class. A
limitation in this respect is the thermal stabilities of ILs, which
are influenced significantly by the presence of metal oxide
supports and metal sites.37,38 However, reported results37 show
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ACS Catal. 2020, 10, 12354−12358
ACS Catalysis pubs.acs.org/acscatalysis
that there are many ILs that maintain structural integrity on
various metal oxides at temperatures as high as 350 °C.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acscatal.0c03909.
Synthesis procedure of supported Ir complexes and
[EMIM][OAc]-coated supported Ir complex; details of
IR and XAS measurements and data analysis, computa-
tional methods, additional structural characterization
results of supported Ir complexes and [EMIM][OAc]-
coated supported Ir complex before, during, and after
TPR by combining IR, XANES, EXAFS, and computa-
tional results characterizing charges and bond dissocia-
tion energies (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Alper Uzun − Department of Chemical and Biological
Engineering, Koç University TÜ PRAŞ Energy Center
(KUTEM), and Koç University Surface Science and Technology
Center (KUYTAM), Koç University, 34450 Istanbul, Turkey;
orcid.org/0000-0001-7024-2900; Email: auzun@ku.edu.tr
Authors
Samira F. Kurtoğlu − Department of Chemical and Biological
Engineering and Koç University TÜ PRAŞ Energy Center
(KUTEM), Koç University, 34450 Istanbul, Turkey;
orcid.org/0000-0001-9136-6988
Adam S. Hoffman − SSRL, SLAC National Accelerator
Laboratory, Menlo Park, California 94025, United States
Deniz Akgül − Department of Chemistry, Faculty of Arts and
Sciences, Bogazici University, 34342 Istanbul, Turkey
Melike Babucci − Department of Chemical Engineering,
University of California, Davis, California 95616, United
States; orcid.org/0000-0001-7785-3755
Viktorya Aviyente − Department of Chemistry, Faculty of Arts
and Sciences, Bogazici University, 34342 Istanbul, Turkey;
orcid.org/0000-0001-9430-4096
Bruce C. Gates − Department of Chemical Engineering,
University of California, Davis, California 95616, United
States; orcid.org/0000-0003-0274-4882
Simon R. Bare − SSRL, SLAC National Accelerator Laboratory,
Menlo Park, California 94025, United States
Complete contact information is available at:
https://pubs.acs.org/10.1021/acscatal.0c03909
Author Contributions
∇
These authors contributed equally.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
Work at Koç University was supported by Koç University
TÜ PRAŞ Energy Center (KUTEM). Work at the Stanford
Synchrotron Radiation Lightsource (SSRL) of the SLAC
National Accelerator Laboratory was supported by the U.S.
Department of Energy, Office of Science, Basic Energy
Sciences, under Contract No. DE-AC02-76SF00515 and by
Co-ACCESS, supported by the U.S. Department of Energy,
Office of Science, Basic Energy Sciences, Chemical Sciences,
12357
Letter
Geosciences & Biosciences Division, which also supported the
work at the University of California (Grant No. DE-FG02-
04ER15513). A.U. and S.F.K. thank TARLA for the
collaborative research support. A.U. acknowledges the
METU Prof. Dr. Mustafa N. Parlar Education and Research
Foundation’s 2019 Research Incentive Award.
■
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