pubs.acs.

org/JPCC Article

A Molecular View of the Ionic Liquid Catalyst Interface of SCILLs:

Coverage-Dependent Adsorption Motifs of [C4C1Pyr][NTf2] on Pd
Single Crystals and Nanoparticles
Christian Schuschke, Lukas Fromm, Johannes Träg, Corinna Stumm, Chantal Hohner,
Roman Eschenbacher, Sebastian Grau, Dirk Zahn, Andreas Görling, Tanja Bauer,* and Jörg Libuda
Cite This: J. Phys. Chem. C 2021, 125, 13264−13272 Read Online
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
Downloaded via INDIAN INST OF TECH KHARAGPUR on February 13, 2023 at 08:45:39 (UTC).

ACCESS Metrics & More Article Recommendations *

sı Supporting Information

ABSTRACT: Solid catalysts with ionic liquid layers (SCILLs) are

heterogeneous catalysts coated with a thin layer of an ionic liquid
(IL) to improve their selectivity. In this study, we investigated the
interplay of the room-temperature IL 1-butyl-1-methylpyrrolidinium
bis(trifluoromethylsulfonyl)imide [C4C1Pyr][NTf2] with transition
metal surfaces of both Pd(111) single crystals and Pd nanoparticles
(NPs) supported on highly oriented pyrolytic graphite (HOPG). To
this end, we combine theoretical insights obtained by density
functional theory (DFT) and molecular dynamics (MD) calcu-
lations with experimental data acquired via time-resolved infrared
reflection absorption spectroscopy (TR-IRAS) performed under
ultrahigh vacuum (UHV) conditions. IL monolayer films formed on
Pd(111) and Pd NPs are strongly bound to the surface via the SO2
moiety of the [NTf2]− anion. By combination of IRAS, DFT, and MD, we identify the most common adsorption motifs. Most
importantly, the binding motif of the anion changes as a function of the IL coverage. On supported Pd NPs, additional effects arise
from the particle morphology and from the diffusion of carbon from the support to the Pd NPs. Our results suggest that the effect of
the IL film on the catalytic activity should strongly depend on the local coverage and the morphology of the catalyst NPs.

■ INTRODUCTION
In many processes, catalytic modifiers are used to improve the
selectivity and activity of noble metal based catalysts.1−4 One
particular approach to improve the catalytic performance is the
application of supported ionic liquid (IL) films in the form of a
so-called supported ionic liquid phase (SILP) catalyst or a
solid catalyst with ionic liquid layer (SCILL). In a SILP
catalyst, a molecular catalyst complex is dissolved in an IL film
coating a porous support. 5,6 In a SCILL material, a
conventional supported catalyst is coated with an IL film to
improve the selectivity.7−9 Recently, such SCILL systems have
been developed for the use at industrial scale for selective
hydrogenation reactions.10
Because ILs are highly versatile compounds in terms of their
chemical properties, IL-based catalytic modifiers can be
tailored to suit the specific demand of the process. Typical
ILs combine large organic cations with suitable anions, which
results in a vast number of ionic materials, many of which are
liquid even at room temperature and cover a wide range of
physicochemical properties.11,12 Of special interest for the
catalytic properties is the molecular layer of the IL which is in
direct contact with the active site. The properties of these
adsorbed IL layers may be strikingly different from those of the
bulk IL due to the specific interactions at the interface. To tune
© 2021 The Authors. Published by
American Chemical Society
13264
these interactions, it is possible to select specific ions,13−15
functionalize the ions,15,16 or modify their structure.17 This
allows to tune the interaction strength with the surface, the
interaction with reactants, and also the wetting behavior on the
catalyst.
In spite of the commercial success of the SCILL concept, the
interaction of the IL with the active sites is poorly understood
at the molecular level. Such molecular interactions at the IL/
catalyst interface are addressed best with a surface science
approach.13,18,19 In several studies it has been demonstrated
that it is indeed possible to study the chemical interactions,
orientation, and wetting of ILs on atomically defined
surfaces.20,21 To exploit the full potential of the surface science
approach, such experiments are best performed under ultrahigh
vacuum (UHV) conditions, which is possible because of the
low vapor pressure of many ILs.18,19,22 Furthermore, several
Received: March 9, 2021
Revised: May 31, 2021
Published: June 11, 2021
https://doi.org/10.1021/acs.jpcc.1c02131
J. Phys. Chem. C 2021, 125, 13264−13272
The Journal of Physical Chemistry C
Figure 1. Investigated model systems: (a) molecular structures of the IL anion [NTf2]− and the cation [C4C1Pyr]+; (b) schematic representation of
the in situ IRAS setup to investigate the Pd(111) single crystal and Pd NPs on HOPG.
ILs are sufficiently stable to deposit them by physical vapor
deposition (PVD).23,24 In this way, it is feasible to prepare
ultraclean IL films of well-controlled thickness on atomically
controlled surfaces.25,26 Recently this approach was used to
study growth modes,27−29 the specific interactions of ions with
the surface,13,30 and the effect of preadsorbed reactants.8,31
Previously, a strong focus was on Pd and Pt catalysts, and it
was shown that the site-specific interactions are different on
the two noble metals.17,32 In the present work, we address a
question that has been studied rarely in previous work. We
investigate how the adsorption motifs of the IL change when
we change the IL loading on the catalyst surface. We believe
that these adsorption motifs will be essential for the reactivity
to be explored in future studies. To obtain detailed insights
into the adsorption motifs, we combine infrared reflection
absorption spectroscopy (IRAS) with density functional theory
(DFT) calculations and molecular dynamics (MD) simu-
lations. As a model system we use films of the room-
temperature IL 1-butyl-1-methylpyrrolidinium bis(trifluoro-
methylsulfonyl)imide [C4C1Pyr][NTf2], prepared by PVD on
Pd(111) single crystal surfaces and Pd nanoparticles (NPs)
(see Figure 1a,b). Previously, we performed a similar study on
Pt single crystals and Pt NPs,33 which allows us to compare the
two SCILL systems directly. For all model SCILLs, we observe
strongly adsorbing IL monolayer films covered by a bulklike
phase in which the orientation is successively lost. In spite of
the strong interaction with the metal, the local structure of the
adsorbed IL layer remains flexible. The molecular orientation
and adsorption motifs in these wetting layers change
dynamically as a function of the IL coverage and the surface
morphology.
■
METHODS
Experimental Setup. The IRAS experiments were
performed in an UHV system described in detail in an earlier
publication.34 In brief, the system (base pressure of
1 × 10−10 mbar) features various preparation and character-
13265
pubs.acs.org/JPCC Article
ization tools along with evaporation sources and a remote-
controlled gas dosing system to prepare and investigate films in
situ with a vacuum Fourier-transform infrared (FTIR)
spectrometer (Bruker Vertex 80v).
Preparation of the Pd(111) Single Crystal. The
Pd(111) single crystal (MaTecK) was cleaned by Ar +
sputtering (1 keV, 300 K, 60 min, 8 × 10−5 mbar, Linde,
purity 99.9999%). While in an O2 atmosphere (4 × 10−8 mbar,
Linde, purity 99.999%), the sample was first annealed at 923 K
for 10 min and then cooled below 300 K. Residual oxygen
atoms were removed by a subsequent flash to 923 K in UHV.
The cleanliness of the sample was checked via IRAS,
investigating the stepwise adsorption of CO at 300 K (1 ×
10−6 mbar, Westfalen, 99.97%). The supplied CO was purified
by both a home-built liquid nitrogen cold trap and a
commercial adsorption filter (Pall Gaskleen II) to remove
any traces of carbonyls. After the CO adsorption test, the
surface was briefly heated to 623 K to remove CO.
Preparation of Pd NPs on HOPG. The HOPG crystal
(MikroMasch, ZYA, 0.4° mosaic spread) was cleaned via the
“Scotch tape” method prior to transfer into the UHV chamber.
The sample was annealed at 800 K for 3 min in UHV to
remove residual gases. The HOPG sample was bombarded
with Ar+ (0.5 keV, 300 K, 60 min, 8 × 10−5 mbar) to create the
nucleation sites necessary for the growth of Pd NPs.35,36 Pd
was deposited from a wire (Alfa Aesar, 99.9% metals basis, d =
1 mm) loaded into a commercial electron beam evaporator
(Focus EFM3). The deposition of Pd for 36 min (flux of 3 nA)
at a sample temperature of 300 K led to the formation of a Pd
film with an equivalent thickness of 15 Å, which was calibrated
by a quartz crystal microbalance. The morphology of the Pd
NPs prepared was examined by scanning tunneling microscopy
(STM).
STM Measurements and Characterization of the Pd
NPs. The characterization of the Pd NPs was performed ex situ
after the preparation and IRAS measurements. For this, we
used an AFM/STM system (Keysight Technologies, Series
https://doi.org/10.1021/acs.jpcc.1c02131
J. Phys. Chem. C 2021, 125, 13264−13272
The Journal of Physical Chemistry C pubs.acs.org/JPCC Article

Figure 2. Characterization of the annealing behavior of Pd/HOPG (nominal thickness 15 Å) by ex situ STM images: (a) as prepared (300 K), (b)
after annealing to 500 K, (c) after annealing to 700 K, and by (d) IRAS and CO adsorption at 10−6 mbar CO (300 K, exponentially increasing
doses, ranging from 0.025 to 25.6 langmuirs, and ultimately spectra in a CO atmosphere). Acquisition parameters of the STM images: tunneling
current of 0.1 nA for all images and tunneling bias of 0.3 V for all images, except for the right panel of (a) (0.2 V).

5500 AFM/SPM), which is isolated from vibrations by a
combination of active and passive noise damping. We
conducted the STM measurements using tips that were
manually cut from a PtIr (80:20) wire (MaTecK, 99.99%,
d = 0.25 mm). The STM images were obtained in constant
current mode by using a typical tunneling bias of 0.2−0.3 V
applied to the sample and a tunneling current of 0.1 nA. The
STM images were postprocessed (row-aligning, data-leveling)
by using Gwyddion software (ver. 2.55).37
In Figure 2a−c, selected STM images are shown. They were
recorded ex situ as prepared at 300 K and after annealing to
500 and 700 K. We estimate a particle density of
4.6 × 1012 cm−2 for the Pd NPs on a sample investigated as
prepared (Figure 2a), thus without the annealing step. From
the Pd loading (average thickness of 15 Å, 5.7 × 1015 atoms
cm−2) and the unit cell parameters, we estimate the particles
contain 1300 atoms on average. Assuming a half-spherical
shape, this corresponds to a particle size of 3.8 nm. Annealing
the sample to 500 K leads to a minor growth of the particle size
(Figure 2b). From the particle density (2.3 × 1012 cm−2), we
estimate one particle contains 2500 atoms on average, which
corresponds to a calculated diameter of 4.7 nm. Further
annealing to 700 K induces major particle growth (Figure 2c).
The particles agglomerate to aggregates with an average
diameter of 16 nm. The particle density of these large
aggregates is 1.3 × 1011 cm−2, which corresponds to 45.000
atoms on average.
The CO adsorption and thermal stability of the particles
were investigated by IRAS (Figure 2d). For a full analysis, we
13266
refer to the Supporting Information and Figure S1 therein. In
brief, the CO adsorption on the Pd NPs on HOPG indicates
the presence of mostly (111) facets, with a strong contribution
of defect and edge sites. Particles annealed to 500 K in UHV
show features that indicate the presence of carbon species
originating from the HOPG support. These species occupy
edge sites and strongly increase the signal of on-top CO. Above
700 K, the particles sinter rapidly and the Pd surface decreases.
Deposition of [C4C1Pyr][NTf2]. The IL [C4C1Pyr][NTf2]
(Merck KGA, ≥98%) was evaporated from a glass crucible
placed in a home-built Knudsen cell (see Figure 1a,b) to
prepare the thin films (thickness ∼15 ML). Before the
experiments, the evaporator was separated from the main
chamber by a gate valve, pumped by a separate high-vacuum
line, and moderately baked for 24 h. Before the start of the
deposition, the evaporant was preheated to 400 K while the
sample was protected by a gate valve and a shutter to block the
beam path.
Time-Resolved IRAS Experiments (TR-IRAS). IR spectra
(rate of 1 spectrum/min, spectral resolution of 4 cm−1,
p-polarized light only) were continuously acquired during the
deposition of the IL. For the CO adsorption, spectra were
recorded in UHV after the CO pulse. All data were referenced
to a background spectrum of the clean sample acquired prior
to the experiment.
Density Functional Theory (DFT) Calculations. DFT
calculations of adsorbed IL structures on the Pd(111) surface
were performed with the Vienna Ab initio Simulation Package
(VASP ver. 5.4.1).38−40 The projector-augmented wave
https://doi.org/10.1021/acs.jpcc.1c02131
J. Phys. Chem. C 2021, 125, 13264−13272
The Journal of Physical Chemistry C
method (PAW)41 was used with an energy cutoff of 450 eV
together with the PBE exchange correlation functional.42
Additionally the DFT-D3 correction scheme by Grimme with
the Becke−Johnson damping was employed.43,44 Energies and
geometries were optimized until convergence of 10−7 eV and
forces smaller than 0.05 eV/Å were reached. The system was
modeled by a supercell approach with a six- or four-layered
periodic surface unit cell separated by 20 Å of vacuum. The
bottom half of this metal surface was fixed to bulk geometry,
while the top half was allowed to relax. For the Pd(111)
surface, the experimental lattice constant of 3.890 Å was used.
Three different cells representing different coverages were
calculated. A cell with one isolated IL ion pair in a 6 × 6
orthogonal surface cell (four layers), allowing enough lateral
space to decouple the periodic images, was calculated by using
only the Γ-point. In a 4 × 4 orthogonal unit cell (six layers)
with a 3 × 3 × 1 Monkhorst−Pack k-point sampling45 one ion
pair increasingly interacts with the periodic images, modeling
an ideally “low-density” monolayer. The third cell was chosen
to mimic the monolayer density obtained from the MD
simulations explained subsequently (1.35 ion pairs nm−2).
Therefore, three ion pairs were calculated on a four-layered
8 × 4 orthogonal surface unit cell which was sampled with a
1 × 2 × 1 Monkhorst−Pack k-point mesh. Adsorption energies
(Eads = Emol + Esurf − Esys) were estimated with one IL ion pair
in the gas phase (Emol) as reference. Vibrational spectra were
calculated within the harmonic approximation. The data were
visualized by using the software Avogadro (ver. 1.1.1)46 and
QVibeplot (ver. 1.6.0).47
Molecular Dynamics (MD). Fully atomistic MD simu-
lations were performed with the Large-scale Atomic/Molecular
Massively Parallel Simulator (LAMMPS, code ver. 2017)48 and
the additional GPU package.49−51 The integration time step
was set to 1.0 fs. Electrostatic and van der Waals interactions
were described with the shifted cutoff potentials by using a
distance delimiter of 12.0 Å. To impose constant temperature,
the system was coupled to a Berendsen thermostat with a
relaxation constant of 0.5 ps. For the simulation of bulk IL on
the Pd surface, the simulation cell was coupled to an
anisotropic Berendsen barostat (relaxation only in the
z-direction) with a relaxation constant of 100.0 ps. The
atoms of the Pd slab were kept at fixed positions during the
simulations to avoid the flying-ice-cube effect.52 The force field
parameters for [C4C1Pyr][NTf2] were taken from the GAFF2
(ver. 2.1) parameter set (atom types sy and n2 for sulfur and
nitrogen atoms of NTf2−).53 These parameters reproduce a
reasonably accurate potential energy landscape with respect to
a 2D scan of the dihedral angles C1−S1−N−S2 and S1−N−S2−
C2 (relative to a B3LYP/6-31G* reference), which are critical
for the overall structure of NTf2−. Atomic partial charges were
calculated with the restricted electrostatic potential (RESP)
method54 based on electrostatic potential calculations at the
level of HF/6-31G* with the Gaussian 09 rev. D.01 code.55
The van der Waals parameters for the Pd atoms were adopted
from Heinz et al.56 Local fluctuations of the image charges on
the metal surface induced by the IL are not considered, as
previous studies from our group indicated that the constant
charge approach allows for a reasonable description of
adsorption motifs in terms of structures.57 For an extensive
description of the MD simulation procedure, please refer to the
Supporting Information.
13267
■
pubs.acs.org/JPCC Article
RESULTS AND DISCUSSION
IR Spectrum of [C4C1Pyr][NTf2]. We first consider the IR
spectra of [C4C1Pyr][NTf2] deposited by PVD on Pd(111)
and Pd NPs/HOPG. The IR spectra of multilayer films (∼10
monolayers (ML), while 1 ML is defined as a closed double
layer of chemisorbed species, i.e., ion pairs) are shown in
Figure 3. For both substrates the spectra are nearly identical,
Figure 3. IRAS spectra of the [C4C1Pyr][NTf2] multilayer deposited
via PVD at 300 K, grown on Pd(111) and both pristine and annealed
Pd NPs.
and the bands can be assigned according to previous
studies.29,32,33 In brief, the bands of the anion are found at
1361 cm−1 (ν(SO2)as), 1231 cm−1 (ν(SO2)s + ν(CF3)s), and
1213 cm−1 (ν(NTf2−), comprising ν(SNS)as + ν(CS) +
ν(CF3)s), 1145 cm−1 (ν(SO2)s + ν(CF3)as), and 1065 cm−1
(ν(SNS)as + ν(CF3)s + ν(SO2)s). Because these vibrations
comprise contributions from various stretching modes, we only
list the strongest contribution in the following.
Aliphatic deformations of the cation are visible at 1468 cm−1
(ν(CHx)). However, the cation bands are weak and will not be
analyzed in detail. Comparison of the spectra with DFT and
attenuated total reflection (ATR) data from previous experi-
ments33 proves that the IL is deposited by PVD without
decomposition.
Growth of [C4C1Pyr][NTf2] on Pd(111). To identify
specific adsorption motifs of the first IL layer, we performed
DFT calculations and MD simulations. The [NTf2]− anion can
interact strongly via both SO2 moieties with the surface, which
allows for a variety of binding motifs displayed in Figure 4a.
We denote the motifs with two indices “i−j”, which indicate
the number of oxygen atoms of the respective SO2 moieties i
and j interacting with the surface (for further details on the
analysis, see the Supporting Information). The different
adsorption motifs of the anion were subjected to quantum
chemical calculations to identify their vibrational/IR spectral
signature. The adsorption motifs of the cation are displayed in
Figure 4b.
In Figure 5, we compare (a) spectra simulated by DFT (for
a full set and list of assignment, we refer to the Supporting
Information) with the results of three TR-IRAS experiments
(b−d). Specifically, we consider the deposition of the IL (b)
on Pd(111), (c) on Pd NPs, and (d) on Pd NPs that were
annealed to 500 K prior to deposition of the IL. The DFT
spectra of [NTf2]− (see Figure 5a) depend strongly on the
binding motif and the orientation of the anion (see Figure 4 for
a sketch of the adsorption motifs).
https://doi.org/10.1021/acs.jpcc.1c02131
J. Phys. Chem. C 2021, 125, 13264−13272
The Journal of Physical Chemistry C pubs.acs.org/JPCC Article

Figure 4. Adsorption motifs of the (a) anion [NTf2]− and (b) cation
[C4C1Pyr]+ on Pd(111) as suggested by MD.

Experimentally, we examined the film growth on a clean

Pd(111) surface (see Figure 5b) first. Time-resolved IR spectra
were acquired during the deposition of a multilayer film of the
IL at 300 K (left panel). The peak height was determined to
display the development of selected signals over time (right
panel). At low coverage, we observe two weak bands at 1233
and 1364 cm−1 and one stronger band at 1104 cm−1. With
increasing coverage, the peak at 1233 cm−1 shifts slightly to
lower wavenumbers and grows in intensity. We assign this
signal to contributions of ν(SO2)s. The two signals at 1364 and
1104 cm−1 behave differently. They are visible at low coverage
only, and they are weaker than the signals observed in the full
monolayer (described below). We assign them to the ν(SO2)as
and ν(SO2)s modes of anions specifically adsorbed to the Pd
surface. The experimental data strongly resemble the spectrum
of the “2−2” configuration suggested by DFT calculations for
low IL coverages (see Figure 4 for adsorption motifs). To
understand the spectral appearance, we have to consider the
metal-surface selection rule (MSSR), which only allows for
dynamic dipole moments to be observed with a component
along the surface normal.58 The ν(SO2)as mode is polarized
along the axis spanned by the two oxygen atoms. Therefore,
the SO2 group must be strongly tilted with respect to the
surface to be visible. The ν(SO2)s mode, on the other hand, is
polarized along the axis spanned by the center between the
oxygen atoms and the sulfur atom. Thus, the mode will be
visible if both oxygen atoms interact with the surface
simultaneously. The experimental spectra suggest that both
ν(SNS)as and ν(SO2)as modes are attenuated, and therefore,
they are polarized nearly parallel to the surface. This
observation is in line with the theoretical data which suggest
the adsorption of a majority of species as a cis-isomer via both
SO2 groups in a “2−2” fashion, while the CF3 groups are
directed toward the vacuum. Note that we expect a mixture of
Figure 5. Comparison of [C4C1Pyr][NTf2] film growth on different
prevalent adsorption motifs at this coverage but are only able substrates with theoretical data: (a) DFT calculations of isolated and
to describe to the most abundant species. 1 ML IL on Pd(111), TR-IRAS during the IL deposition via PVD at
In the next step, we investigated the growth of the IL layer 300 K onto (b) Pd(111), (c) pristine Pd NPs, (d) Pd NPs annealed
with MD simulations. We find that the IL molecules (or ion to 500 K. Left column: IRAS spectra; right column: area of all IL
pairs) of a submonolayer (0.5 ML) are not homogeneously bands in the range from range from 950 to 1400 cm−1 (labeled as
distributed over the Pd surface but tend to form IL islands. ν(NTf2−)) of selected IL and CO vibrations.

13268 https://doi.org/10.1021/acs.jpcc.1c02131
J. Phys. Chem. C 2021, 125, 13264−13272
The Journal of Physical Chemistry C
Hence, the system should rather be considered as a Pd surface
that is partially fully covered and partially empty. From a
technical point of view, this affects the MD simulations of
submonolayer systems, as they suffer from an unfavorable
dependence on the simulation box size. With increasing box
size, we do not observe identical structures of homogeneously
distributed IL islands of similar size, but rather structures of
one dominating island and one dominating void. Unfortu-
nately, the computationally accessible box sizes are not big
enough to reach size consistency for such submonolayers.
Accordingly, we cannot describe the most favorable adsorption
motif or the distribution of prevalent motifs.
The tendency to island growth is also indicated by the
estimation of adsorption energy (the list of adsorption energies
is given in Table S5). The adsorption energy is lowest for
isolated species on the surface and increases significantly for
smaller cell sizes. These numbers indicate strong intermo-
lecular interactions leading to the formation of islands instead
of an evenly distributed film, which is in good agreement with
the MD data.
As the coverage increases, the signals of ν(SO2) at
1104 cm−1 disappear. The peak at 1233 cm−1 grows steadily
and shifts to 1212 cm−1, while new signals are observed at
1359, 1139, and 1063 cm−1. As a result, we observe a spectrum
that now rather resembles a combination of the configurations
denoted as “2−1” and “2−0”, as suggested by DFT calculations
for a monolayer coverage of the IL. Furthermore, the observed
spectrum is similar to the spectrum of the multilayer, but
signals differ in shape and intensity. In particular, the signal at
1139 cm−1 is far more intense and the one at 1359 cm−1 is
broader and weaker than in the multilayer. We assign the
signals at 1359, 1212, 1139, and 1063 cm−1 to ν(SO2)as,
ν(NTf2−), ν(SO2)s, and ν(SNS)as, respectively. The strong
symmetric signal of the SO2 group indicates that the oxygen
atoms remain mostly parallel with the surface, with a smaller
contribution of tilted molecules giving rise to the signal of the
ν(SO2)as mode. The appearance of ν(SNS)as indicates that
species with uncoordinated SO2 groups are present. The loss of
species in “2−2” configuration is further supported by the
absence of the characteristic signal of ν(SO2)s at 1104 cm−1.
To some extent the effect may, however, also be enhanced by
intensity transfer.58,59
Again, we rely on DFT spectra to support our assignments.
We suggest the following structures upon comparison of
theoretical and experimental data. Upon saturation of the
monolayer, the molecules remain adsorbed via one SO2 group
(“2−j”), but the other group is either uncoordinated (“2−0”)
or adsorbed to the surface via only one oxygen in a
monodentate fashion (“2−1”). Such species are twisted and
strongly tilted with respect to the surface. To obtain additional
information about the expected abundance of these species, we
performed MD simulations. For the full IL monolayer, our
simulations indicate the presence of around 40% of anions
bound in an upright adsorption motif (“2−0”), in good
agreement with the scenario described above. For a detailed
discussion of the adsorption motifs and their abundance we
refer to the Supporting Information and Figure S7.
The spectral changes around 0.5 ML might be associated
with the growth of IL islands and a corresponding change of
the ratio of anions being located at the edge and in the interior
of IL islands, respectively. We assume that at the low coverage
the IL islands are isolated and comparably small so that most
molecules are located at the edges of these islands. Near
13269
pubs.acs.org/JPCC Article
monolayer coverage, most anions are located in the interior of
the islands. The tendency of the IL islands to contract will
cause individual anions to adopt an upright adsorption motif
(“2−0”), at least if the islands are sufficiently large. This
scenario explains why we start to see the spectral characteristics
of the full monolayer already before full saturation is reached.
In a macroscopic picture, the behavior indicates the formation
of 3D structures, i.e., droplets, and partial dewetting. In
summary, we suggest the formation of a monolayer, which is
less ordered but still affected by the substrate in terms of
orientation and conformation. The monolayer IL structure
comprises several adsorption motifs. Changes of the adsorption
motif are driven by the growth of islands, which, in turn,
changes the prevailing binding mode. In specific, we observe a
transition from species mostly interacting with the surface in a
“2−2” configuration to species which favor an upright
adsorption motif due to increasing intermolecular interactions
(“2−0”, “2−1”).
As the layer thickness increases beyond the monolayer, we
observe a linear increase of all bands, and the spectra more and
more resemble the ATR data published in previous work.33
This indicates the growth of a multilayer in random
orientation. The MD simulations show clearly, however, that
the orientation is not lost for molecules interacting directly
with the Pd surface. In the presence of a liquid IL phase on the
Pd surface, anions at the IL/Pd interface preferably obtain the
“2−2” adsorption motif previously observed for a submono-
layer. In contrast to the monolayer, where we observed around
40% of the anions in an upright adsorption motif (“2−0”), the
interface layer between Pd and the IL liquid bulk phase shows
only around 5% of anions in this configuration (for detailed
information about the distribution of the adsorption motifs, see
the Supporting Information). Instead, the “flat” and spatially
more demanding motifs (“2−2”, “2−1”, “1−1” cis, and “1−1”
trans) are more abundant in the presence of the bulk IL. These
results point to a packing effect: Within the monolayer,
individual anions leave their preferred “2−2” adsorption motif
to allow further ions to adsorb directly on the Pd surface
instead of “floating” individually on the monolayer. The latter
situation would be disfavored in terms of the Coulomb
interactions between ions.
The situation is different if a liquid bulk IL phase is present.
Here, excess ions that detach from the monolayer are stabilized
by the bulk phase. Hence, the transition of the ML to the
interface layer between Pd and the IL bulk phase upon higher
coverage is characterized by a density decrease (from 1.35 to
1.16 anions nm−2). Noteworthy, we found a similar behavior
for the cations, which tend to adsorb preferably in an
orientation that saves space on the surface. The majority of
cations point with their C4 tail away from the surface in the
ML film, while this is not the case in the presence of the bulk
IL phase (see Figure 4 for adsorption motifs).
Lastly, we consider the evidence for the formation of a
closed monolayer on the Pd(111) surface. During the film
growth, we first observe the growth of distinctive spectroscopic
signatures of a chemisorbed species, indicating interactions of
the SO2 groups with the surface. This is followed by a sudden
transition toward the spectroscopic features assigned to the
growth of a randomly oriented multilayer. This transition is
visualized in plots relating peak height to time (Figure 5, right
column).
Related experiments employed the Stark effect60,61 on
adsorbed CO to prove the formation of an intact IL
https://doi.org/10.1021/acs.jpcc.1c02131
J. Phys. Chem. C 2021, 125, 13264−13272
The Journal of Physical Chemistry C
monolayer.31,33 Also, STM and X-ray photoelectron spectros-
copy (XPS) studied showed formation of a chemisorbed
monolayer (wetting layer) on metal surfaces (see ref 62 and
references therein). Only after completion of the monolayer,
either 2D or 3D growth is observed.
Growth of [C4C1Pyr][NTf2] on Pd NPs on HOPG. Next,
we turn to the IL layers on Pd NPs. The Pd NPs feature mostly
(111) facets but are rich in defects as compared to a single
crystal surface. In Figure 5c, we show the IR data recorded
during deposition of the IL on Pd NPs onto HOPG. A
reference experiment, investigating the IL growth on clean
HOPG, can be found in previous work.33 Because the signals
of the multilayer spectrum on Pd NPs were discussed in the
first section, we focus on the monolayer region in the
following.
In the first few spectra, we observe bands at 1220, 1370, and
1116 cm−1 which are similar to those obtained from the
experiment on the Pd(111) surface. The peak at 1220 cm−1
grows linearly and is assigned to coupled vibrations of [NTf2]−.
The latter two are assigned to ν(SO2)as and ν(SO2)s,
respectively. They are visible for a short period only and
disappear at larger coverage. This behavior indicates the
presence of a temporary adsorption structure similar to that in
the submonolayer regime on Pd(111). Nevertheless, the
signals are less well-defined than on Pd(111), which points
to differences in the adsorption geometry. We attribute this
effect to the absence of large (111) facets which prevents the
formation of large IL islands and adsorption in “2−2”
configuration. Note that we also need to consider the MSSR,
which largely holds on HOPG (see ref 63 for details). Species
adsorbed to tilted facets will show bands that were previously
forbidden.
We thus combine the implications of the MSSR with the
coverage-dependent development of selected bands (ν(SO2)as
and ν(SO2)s), which show characteristic differences in the
DFT-derived spectra dependent on the adsorption motif. In
particular, the bands of ν(SO2)as and ν(SO2)s are visible
simultaneously, which points to the presence of different types
of SO2 groups, either in parallel or tilted with respect to the
surface. As a result, we tentatively assign the bands observed at
low coverage to adsorption at defect sites, which leads to
twisted, less space-consuming conformers (mostly “2−1”, less
“2−0”) along with a minor amount of flat-lying “2−2” anions.
In particular, the “2−1” adsorption geometry is favored by
smaller facets and abundant defect sites.
With coverage increasing further, we observe signals of
ν(SO2)as, ν(SO2)s, and ν(SNS)as at 1361, 1141, and
1064 cm−1, respectively. Several of the observed vibrations
are polarized orthogonally in the molecule, which indicates a
loss of orientational order in the layer. For this reason, we
assign the signals to species binding to the surface in a less
defined orientation, involving various motifs associated with
monodentate and bidentate structures (mostly “2−0”, less “2−
1” and “2−2”). While the characteristic growth of islands is not
visible as clearly as on the Pd(111), there still is some
indication for a reorientation of the molecules as a function of
coverage (see the integrated peak area). After completion of
the monolayer, the growth continues with the formation of a
multilayer consisting of molecules with nearly random
orientation.
As a third sample, we investigated HOPG loaded with a
similar amount of Pd (15 Å) and annealed it to 500 K to
induce the migration of carbon into/onto the Pd NPs (Figure
13270
pubs.acs.org/JPCC Article
5d). In the Supporting Information, we qualitatively discuss
the adsorption of carbon species to defects, edges, and (100)
facets. We observe identical signals for both HOPG samples
during the growth of an IL submonolayer and monolayer
(assignment in the previous paragraph). However, the signals
of the submonolayer are visible for a shorter time only, and the
transition to the multilayer growth is less distinct. We attribute
both effects to the defect sites already partly occupied by
carbon, making them less attractive for the IL. While we
cannot describe these effects on an atomic level, we conclude
that the presence of carbon species gives rise to less specific
binding and disorder in the monolayer. As for all other
samples, the multilayer is not affected by the modification of
the substrate and mainly shows molecules of random
orientation.
Concludingly, similar adsorption motifs are observed on all
three surfaces, but the prevailing adsorption motif is dependent
on the IL coverage and morphology of the support. In general,
the presence of smaller facets and of defects leads to greater
disorder of the IL monolayer film.
■ CONCLUSIONS
In conclusion, we investigated the assembly of a Pd-based
model SCILL system. We combined theoretical insights
obtained by DFT and MD calculations with experimental
data acquired via time-resolved IRAS experiments performed
under UHV conditions. To this end, we deposited the room-
temperature IL [C4C1Pyr][NTf2] onto Pd(111) and Pd NPs
supported on HOPG. The main conclusions of the study are
summarized in the following:
(1) Adsorption of isolated IL species: The growth of the IL
film on Pd(111) indicates that there are strong
intermolecular interactions with the IL submonolayer.
The [NTf2]− anion adopts cis configuration and adsorbs
specifically via both SO2 groups (“2−2” adsorption motif
prevalent) to the Pd surface. The IL forms monolayer
islands which rapidly grow with increasing coverage.
(2) Monolayer growth: Near monolayer coverage, the IL
adsorption motif within these islands changes. We
identify mono- and bidentate binding motifs, in which
one SO2 group is lifted or partially lifted from the surface
(“2−0”, “2−1” adsorption motifs prevalent). We
attribute the change in the adsorption motif to the
formation of larger islands in which the IL layer is
compressed. On Pd NPs, the absence of large facets
hinders the formation of well-defined structure. Thus,
the adsorption motifs of the [NTf2]− are less specific
than on Pd(111).
(3) Multilayer growth: Upon transition to the multilayer
film, MD suggests a reorientation of the chemisorbed
species on the Pd surface in the presence of the IL bulk.
We propose that this effect originates from the fact that
ions expelled from the monolayer can be easily
accommodated in the multilayer film. For all substrates,
the preferential molecular orientation is lost for the
physisorbed species on top of the first monolayer.
Our results show that the adsorption motif and orientation
of the IL in the first monolayer depend strongly on the local IL
coverage. Furthermore, the surface morphology also plays an
important role. These findings will be of importance when the
IL film is used as a catalytic modifier. We expect that the effect
https://doi.org/10.1021/acs.jpcc.1c02131
J. Phys. Chem. C 2021, 125, 13264−13272
The Journal of Physical Chemistry C
of the IL on coadsorbed reactants and their reactivity will
critically depend on the local IL coverage.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpcc.1c02131.
Full set of DFT spectra; visualization of the binding
motifs; list of adsorption energies; description of the
MD simulation procedure (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Tanja Bauer − Interface Research and Catalysis, ECRC,
Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058
Erlangen, Germany; orcid.org/0000-0002-6399-2954;
Email: tanja.tb.bauer@fau.de
Authors
Christian Schuschke − Interface Research and Catalysis,
ECRC, Friedrich-Alexander-Universität Erlangen-Nürnberg,
91058 Erlangen, Germany; orcid.org/0000-0002-5635-
1112
Lukas Fromm − Lehrstuhl für Theoretische Chemie, Friedrich-
Alexander-Universität Erlangen-Nürnberg, 91058 Erlangen,
Germany
Johannes Träg − Lehrstuhl für Theoretische Chemie, CCC,
Friedrich-Alexander-Universität Erlangen-Nürnberg, 91052
Erlangen, Germany
Corinna Stumm − Interface Research and Catalysis, ECRC,
Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058
Erlangen, Germany; orcid.org/0000-0003-4646-8234
Chantal Hohner − Interface Research and Catalysis, ECRC,
Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058
Erlangen, Germany; orcid.org/0000-0003-0803-147X
Roman Eschenbacher − Interface Research and Catalysis,
ECRC, Friedrich-Alexander-Universität Erlangen-Nürnberg,
91058 Erlangen, Germany
Sebastian Grau − Interface Research and Catalysis, ECRC,
Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058
Erlangen, Germany
Dirk Zahn − Lehrstuhl für Theoretische Chemie, CCC,
Friedrich-Alexander-Universität Erlangen-Nürnberg, 91052
Erlangen, Germany
Andreas Görling − Lehrstuhl für Theoretische Chemie,
Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058
Erlangen, Germany; orcid.org/0000-0002-1831-3318
Jörg Libuda − Interface Research and Catalysis, ECRC,
Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058
Erlangen, Germany; orcid.org/0000-0003-4713-5941
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcc.1c02131
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was funded by the Deutsche Forschungsgemein-
schaft (DFG, German Research Foundation), Project-ID
431791331, SFB 1452. Furthermore, the authors acknowledge
support by the DFG via the projects 322419553 and
453560721 and additional support by the DFG within the
13271
pubs.acs.org/JPCC Article
SPP 1708 “Material Synthesis near Room Temperature”
(Project-ID 252578361).
■ REFERENCES
(1) Welton, T. Ionic liquids in catalysis. Coord. Chem. Rev. 2004,
248, 2459−2477.
(2) Wasserscheid, P.; Welton, T. Ionic Liquids in Synthesis, 2nd ed.;
Wiley: New York, 2007; Vol. 1.
(3) Steinrück, H.-P.; Wasserscheid, P. Ionic Liquids in Catalysis.
Catal. Lett. 2015, 145, 380−397.
(4) Werner, S.; Haumann, M.; Wasserscheid, P. Ionic Liquids in
Chemical Engineering. Annu. Rev. Chem. Biomol. Eng. 2010, 1, 203−
230.
(5) Riisager, A.; Fehrmann, R.; Haumann, M.; Wasserscheid, P.
Supported Ionic Liquid Phase (SILP) catalysis: An Innovative
Concept for Homogeneous Catalysis in Continuous Fixed-Bed
Reactors. Eur. J. Inorg. Chem. 2006, 2006, 695−706.
(6) Mehnert, C. P. Supported Ionic Liquid Catalysis. Chem. - Eur. J.
2005, 11, 50−56.
(7) Kernchen, U.; Etzold, B. J. M.; Korth, W.; Jess, A. Solid Catalyst
with Ionic Liquid Layer (SCILL) − A New Concept to Improve
Selectivity Illustrated by Hydrogenation of Cyclooctadiene. Chem.
Eng. Technol. 2007, 30, 985−994.
(8) Arras, J.; et al. How a Supported Metal is Influenced by an Ionic
Liquid: In-depth Characterization of SCILL-Type Palladium Catalysts
and Their Hydrogen Adsorption. J. Phys. Chem. C 2010, 114, 10520−
10526.
(9) Barth, T.; Korth, W.; Jess, A. Selectivity-Enhancing Effect of a
SCILL Catalyst in Butadiene Hydrogenation. Chem. Eng. Technol.
2017, 40, 395−404.
(10) Szesni, N.; et al. Catalyst Composition for Selective
Hydrogenation with Improved Characteristics. U.S. Patent
WO2013057244A1, 2013.
(11) Welton, T. Room-Temperature Ionic Liquids. Solvents for
Synthesis and Catalysis. Chem. Rev. 1999, 99, 2071.
(12) Wasserscheid, P.; Keim, W. Ionic LiquidsNew “Solutions”
for Transition Metal Catalysis. Angew. Chem., Int. Ed. 2000, 39, 3772−
3789.
(13) Maier, F.; et al. Insights into the Surface Composition and
Enrichment Effects of Ionic Liquids and Ionic Liquid Mixtures. Phys.
Chem. Chem. Phys. 2010, 12, 1905−1915.
(14) Lovelock, K. R. J.; et al. Influence of Different Anions on the
Surface Composition of Ionic Liquids Studied Using ARXPS. J. Phys.
Chem. B 2009, 113, 2854−2864.
(15) Schernich, S.; et al. Interactions of Imidazolium-Based Ionic
Liquids with Oxide Surfaces Controlled by Alkyl Chain Functional-
ization. ChemPhysChem 2013, 14, 3673−3677.
(16) Xu, T.; et al. Gluing Ionic Liquids to Oxide Surfaces: Chemical
Anchoring of Functionalized Ionic Liquids by Vapor Deposition onto
Cobalt (II) Oxide. Angew. Chem. 2017, 129, 13310.
(17) Bauer, T.; et al. Palladium-Mediated Ethylation of the
Imidazolium Cation Monitored In Operando on a Solid Catalyst
with Ionic Liquid Layer. ChemCatChem 2017, 9, 109−113.
(18) Steinrück, H.-P. Surface Science Goes Liquid ! Surf. Sci. 2010,
604, 481−484.
(19) Steinrück, H.-P.; et al. Surface Science and Model Catalysis
with Ionic Liquid-Modified Materials. Adv. Mater. 2011, 23, 2571−
2587.
(20) Cremer, T.; et al. Physical Vapor Deposition of [EMIM]-
[Tf2N]: A New Approach to the Modification of Surface Properties
with Ultrathin Ionic Liquid Films. ChemPhysChem 2008, 9, 2185−
2190.
(21) Xu, T.; et al. Interaction of Ester-Functionalized Ionic Liquids
with Atomically-Defined Cobalt Oxides Surfaces: Adsorption,
Reaction and Thermal Stability. ChemPhysChem 2017, 18, 3443−
3453.
(22) Wasserscheid, P. Volatile Times for Ionic Liquids. Nature 2006,
439, 797.
https://doi.org/10.1021/acs.jpcc.1c02131
J. Phys. Chem. C 2021, 125, 13264−13272
The Journal of Physical Chemistry C
(23) Leal, J. P.; et al. The Nature of Ionic Liquids in the Gas Phase.
J. Phys. Chem. A 2007, 111, 6176−6182.
(24) Armstrong, J. P.; et al. Vapourisation of Ionic Liquids. Phys.
Chem. Chem. Phys. 2007, 9, 982−990.
(25) Freund, H. J.; et al. Preparation and Characterization of Model
Catalysts: From Ultrahigh Vacuum to in Situ Conditions at the
Atomic Dimension. J. Catal. 2003, 216, 223−235.
(26) Libuda, J. Reaction Kinetics on Model Catalysts: Molecular
Beam Methods and Time-Resolved Vibrational Spectroscopy. Surf.
Sci. 2005, 587, 55−68.
(27) Mehl, S.; et al. Ionic-Liquid-Modified Hybrid Materials
Prepared by Physical Vapor Codeposition: Cobalt and Cobalt
Oxide Nanoparticles in [C1C2Im][OTf] Monitored by in Situ IR
Spectroscopy. Langmuir 2016, 32, 8613−8622.
(28) Cremer, T.; et al. Interfaces of Ionic Liquids and Transition
Metal SurfacesAdsorption, Growth, and Thermal Reactions of
Ultrathin [C1C1Im][Tf2N] Films on Metallic and Oxidised Ni(111)
Surfaces. Phys. Chem. Chem. Phys. 2012, 14, 5153−5163.
(29) Sobota, M.; et al. Toward Ionic-Liquid-Based Model Catalysis:
Growth, Orientation, Conformation, and Interaction Mechanism of
the [Tf2N]− Anion in [BMIM][Tf2N] Thin Films on a Well-Ordered
Alumina Surface. Langmuir 2010, 26, 7199−7207.
(30) Schernich, S.; et al. Interactions Between the Room-
Temperature Ionic Liquid [C2C1Im][OTf] and Pd(111), Well-
Ordered Al2O3, and Supported Pd Model Catalysts from IR
Spectroscopy. J. Phys. Chem. C 2014, 118, 3188−3193.
(31) Bauer, T.; et al. Ligand Effects at Ionic Liquid-Modified
Interfaces: Coadsorption of [C2C1Im][OTf] and CO on Pd(111). J.
Phys. Chem. C 2016, 120, 4453−4465.
(32) Sobota, M.; et al. Ligand Effects in SCILL Model Systems: Site-
Specific Interactions with Pt and Pd Nanoparticles. Adv. Mater. 2011,
23, 2617−2621.
(33) Schuschke, C.; et al. Dynamic CO Adsorption and Desorption
Through the Ionic Liquid Layer of a Pt Model Solid Catalyst with
Ionic Liquid Layers. J. Phys. Chem. C 2019, 123, 31057−31072.
(34) Schuschke, C.; et al. Solar Energy Storage at an Atomically
Defined Organic-Oxide Hybrid Interface. Nat. Commun. 2019, 10,
2384.
(35) Kettner, M.; Stumm, C.; Schwarz, M.; Schuschke, C.; Libuda, J.
Pd Model Catalysts on Clean and Modified HOPG: Growth,
Adsorption Properties, and Stability. Surf. Sci. 2019, 679, 64−73.
(36) Kettner, M.; et al. Pd-Ga model SCALMS: Characterization
and Stability of Pd single Atom Sites. J. Catal. 2019, 369, 33−46.
(37) Nečas, D.; Klapetek, P. Gwyddion: An Open-Source Software
for SPM Data Analysis. Cent. Eur. J. Phys. 2012, 10.
(38) Kresse, G.; Furthmüller, J. Efficiency Of Ab-Initio Total Energy
Calculations For Metals and Semiconductors Using A Plane-Wave
Basis Set. Comput. Mater. Sci. 1996, 6, 15−50.
(39) Kresse, G.; Furthmüller, J. Efficient Iterative Schemes for Ab
Initio Total-Energy Calculations Using a Plane-Wave Basis Set. Phys.
Rev. B: Condens. Matter Mater. Phys. 1996, 54, 11169−11186.
(40) Kresse, G.; Hafner, J. Ab Initio Molecular Dynamics for Liquid
Metals. Phys. Rev. B: Condens. Matter Mater. Phys. 1993, 47, 558−561.
(41) Kresse, G.; Joubert, D. From Ultrasoft Pseudopotentials to the
Projector Augmented-Wave Method. Phys. Rev. B: Condens. Matter
Mater. Phys. 1999, 59, 1758−1775.
(42) Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient
Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 3865−3868.
(43) Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A Consistent and
Accurate Ab Initio Parametrization of Density Functional Dispersion
Correction (DFT-D) for the 94 Elements H-Pu. J. Chem. Phys. 2010,
132, 154104.
(44) Grimme, S.; Ehrlich, S.; Goerigk, L. Effect of the Damping
Function in Dispersion Corrected Density Functional Theory. J.
Comput. Chem. 2011, 32, 1456−1465.
(45) Monkhorst, H. J.; Pack, J. D. Special Points for Brillouin-Zone
Integrations. Phys. Rev. B 1976, 13, 5188−5192.
13272
pubs.acs.org/JPCC Article
(46) Hanwell, M. D.; et al. Avogadro: An Advanced Semantic
Chemical Editor, Visualization, And Analysis Platform. J. Cheminf.
2012, 4, 17.
(47) Laurin, M. QVibeplot: A Program to Visualize Molecular
Vibrations In Two Dimensions. J. Chem. Educ. 2013, 90, 944−946.
(48) Plimpton, S. Fast Parallel Algorithms for Short-Range
Molecular Dynamics. J. Comput. Phys. 1995, 117, 1−19.
(49) Brown, W. M.; Wang, P.; Plimpton, S. J.; Tharrington, A. N.
Implementing Molecular Dynamics on Hybrid High Performance
Computers − Short Range Forces. Comput. Phys. Commun. 2011, 182,
898−911.
(50) Brown, W. M.; Kohlmeyer, A.; Plimpton, S. J.; Tharrington, A.
N. Implementing Molecular Dynamics on Hybrid High Performance
Computers − Particle−Particle Particle-Mesh. Comput. Phys.
Commun. 2012, 183, 449−459.
(51) Brown, W. M.; Yamada, M. Implementing Molecular Dynamics
on Hybrid High Performance ComputersThree-Body Potentials.
Comput. Phys. Commun. 2013, 184, 2785−2793.
(52) Harvey, S. C.; Tan, R. K.-Z.; Cheatham, T. E. The Flying Ice
Cube: Velocity Rescaling in Molecular Dynamics Leads to Violation
of Energy Equipartition. J. Comput. Chem. 1998, 19, 726−740.
(53) Wang, J.; Wolf, R. M.; Caldwell, J. W.; Kollman, P. A.; Case, D.
A. Development and Testing of a General Amber Force Field. J.
Comput. Chem. 2004, 25, 1157−1174.
(54) Bayly, C. I.; Cieplak, P.; Cornell, W.; Kollman, P. A. A Well-
Behaved Electrostatic Potential Based Method Using Charge
Eestraints for Deriving Atomic Charges: The RESP Model. J. Phys.
Chem. 1993, 97, 10269−10280.
(55) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
et al. Gaussian 09, rev. D.01; Gaussian, Inc.: Wallingford, CT, 2013.
(56) Heinz, H.; Vaia, R. A.; Farmer, B. L.; Naik, R. R. Accurate
Simulation of Surfaces and Interfaces of Face-Centered Cubic Metals
Using 12−6 and 9−6 Lennard-Jones Potentials. J. Phys. Chem. C
2008, 112, 17281−17290.
(57) Buraschi, M.; Sansotta, S.; Zahn, D. Polarization Effects in
Dynamic Interfaces of Platinum Electrodes and Ionic Liquid Phases:
A Molecular Dynamics Study. J. Phys. Chem. C 2020, 124, 2002−
2007.
(58) Hoffmann, F. M. Infrared Reflection-Absorption Spectroscopy
of Adsorbed Molecules. Surf. Sci. Rep. 1983, 3, 107.
(59) Hollins, P. The Influence of Surface Defects on the Infrared
Spectra of Adsorbed Species. Surf. Sci. Rep. 1992, 16, 51−94.
(60) Boxer, S. G. Stark Realities. J. Phys. Chem. B 2009, 113, 2972−
2983.
(61) Lambert, D. K. Vibrational Stark Effect of Adsorbates at
Electrochemical Interfaces. Electrochim. Acta 1996, 41, 623−630.
(62) Lexow, M.; Maier, F.; Steinrück, H.-P. Ultrathin Ionic Liquid
Films on Metal Surfaces: Adsorption, Growth, Stability and Exchange
Phenomena. Adv. Phys. X 2020, 5, 1761266.
(63) Heidberg, J.; Warskulat, M.; Folman, M. Fourier-Transform-
Infrared Spectroscopy of Carbon Monoxide Physisorbed on Highly
Oriented Graphite. J. Electron Spectrosc. Relat. Phenom. 1990, 54,
961−970.
https://doi.org/10.1021/acs.jpcc.1c02131
J. Phys. Chem. C 2021, 125, 13264−13272