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S Supporting Information
*
1. INTRODUCTION
Over the past decade, Brnsted acidic materials have attracted
enormous attention for various applications, such as catalysis,
fuel cell electrolytes, and proton exchange membrane.19
Among the many types of Brnsted acidic materials, sulfonicacid-functionalized Brnsted acidic ionic liquids (SFILs) have
been considered one of the most promising species. Cole et al.
designed the rst SFILs, which featured an alkanesulfonic acid
group covalently tethered to the imidazolium or phosphonium
cation, and then, a variety of SFILs including ammonium-based
SFILs, pyridinium-based SFILs,10 benzimidazole-based SFILs,11
and even modied silica-based SFILs12 have been synthesized
in the past decade. These SFILs have been widely used as novel
acid catalyst or dual solventcatalyst for alkylation reaction,
Fischer esterication,10,13,14 polymerization,15,16 biodiesel production,17,18 and hydrolysis of cellulose,12,19 due to their
distinctive properties, such as high catalytic activities, tunable
acidities, superior reactionseparation coupling behavior and
recyclability. In addition, acidic ionic materials bearing an active
proton or an available proton site have recently been the
subject of extensive study for their possible use in constructing
water-free proton transport channels5,6,2025 by suitably
designing their molecular shape and nanostructured aggregation, which can be useful for the development of new
electrolytes for the next generation of fuel cells. The
microenvironment of the proton, i.e., the microstructure and
interaction around the acidic proton, is the key factor for these
Brnsted acidic materials in determining the proton con 2015 American Chemical Society
DOI: 10.1021/acs.jpcc.5b02814
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K r(r r0)2
Bonds
Dihedrals
N
i=1
K ( 0)2
Angles
[1 + cos(n )]
12 6
4ij ij ij + i j
r
rij
rij
j=i+1
ij
(1)
where N is the number of atoms, ij and ij are the LennardJones parameters for atom pair, and qi is the partial charge on
atom i. The Lennard-Jones terms for cross interactions were
derived using LorentzBerthelot combining rules. The forceeld parameters including the atom types, Lennard-Jones
parameters, and molecular terms were mostly taken from the
Generalized Amber force eld (GAFF), which was found to be
capable of simulating imidazolium-based ILs and other
functional ILs with good prediction performance by many
researchers.32,3638,43 The force-eld parameters developed by
Lopes et al.3840 was adopted for several functional groups in
this work.
2.2. Charge Parameterization. For most of the reported
simulations of ILs, the charges of the cation and anion were set
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[PSPy][HSO4]
[PSPy][H2PO4]
[PSPy][Tfo]
simulation
experiment
1.45
1.46
1.42
1.50
1.48
1.44
Figure 2. Sitesite RDFs of [PPy][Tfo] and [PSPy][Tfo] between the oxygen atoms on [Tfo] and the heavy atoms on the cation.
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Figure 3. Colored SDFs for the anions around the cations with the
isovalue 3.5 (a) [PPy][Tfo] (b) [PSPy][Tfo], where subscripts v and
h stand for the vertical and horizontal views on the pyridine ring plane.
(Red isosurfaces represent the anions [Tfo], and small cyan, white,
blue, yellow, and red spheres represent carbon, hydrogen, nitrogen,
sulfur, and oxygen atoms, respectively.)
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Figure 7. Coulombic charge density proles along the z-direction. (a) Entire liquid slab for [PPy][Tfo]. (b) Zoomed-in on the top interface for
[PPy][Tfo]. (c) Entire liquid slab for [PSPy][Tfo]. (d) Zoomed-in on the top interface for [PSPy][Tfo].
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Figure 8. Number density proles of the backbone atoms of [PPy][Tfo], [PSPy][Tfo], and [HSPy][Tfo] at 423 K (dashed lines correspond to the
atoms of anions at the interface).
Figure 9. Number density proles of the backbone atoms of [PSPy][HSO4] and [PSPy][H2PO4] at 423 K (dashed lines correspond to the atoms of
anions at the interface).
NDPs of three ILs ([PPy][Tfo], [PSPy][Tfo] and [HSPy][Tfo]) are presented in Figure 8. As observed in Figure 8a, the
terminal carbon atoms (C9) of the propyl groups of
[PPy][Tfo] seem to locate in the outmost position of the
interfacial region, successively followed by C8 atoms and C7
atoms, which is in good agreement with the simulation and
experimental results in the previous report that the alkyl chain
was inclined to be perpendicular to the surface and pointing
into the vacuum.59,60 As for the distribution of the anion
[Tfo], represented by the C3 and S2 atoms of the anion, tends
to be aligned with the surface normal and the anionic CF3
groups are exposed at the surface. However, as shown in Figure
8b, when adding sulfonic acid groups into the terminal methyl
group of the propyl group, the ordering preference of the alkyl
tails of the [PSPy]+ cation is almost the opposite of that
observed in [PPy]+, with the order of C7atoms, C8 atoms, C9
atoms, and S1 atoms from the vacuum side into the bulk liquid.
Moreover, it can be inferred, from the position of the terminal
carbon atom (C6) of pyridine ring in Figure 8a and 8b, that the
pyridine ring of the [PSPy]+ cation prefers to locate in the
outer region of the surface, whereas the pyridine ring in [PPy]+
tends to stay in the inner part. The sharp contrast in ordering
preference of the alkyl tails and pyridine rings illustrates the
reverse ordering of the cations of these two ILs at the interface,
presumably due to the addition of the sulfonic acid group that
could enhance the polarity of the side chain of cation, indicating
that the tail-tuning strategy has a signicant impact on the
microstructure of the interface. Moreover, the interfacial
structure of [HSPy][Tfo] shown in Figure 8c is analogous to
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Figure 10. Snapshots of the simulation boxes containing 512 ions, using a color code (the anions and pyridinium rings were colored in red and the
side chain in green) to investigate the interfacial structure (a) [PPy][Tfo] and (b) [PSPy][Tfo].
Figure 11. Orientational ordering parameters of ILs (a) [PPy][Tfo], (b) [PSPy][Tfo], and (c) [HSPy][Tfo] along the Z-axis.
anions and pyridinium rings in red and the side chain in green.
The comparison between the bulk phase and the interface
phase in each picture shows that the side chain of [PPy][Tfo]
shown in Figure 10a exhibits a trend pointing toward the
vacuum side, whereas the side chain of [PSPy][Tfo] shown in
Figure 10b was covered by the anions and pyridinium rings.
This observation is consistent with that drawn from analyzing
the number density ordering of the atoms shown in Figure 8a,b.
3.6. Orientational Ordering Parameters. Figure 11 and
12 illustrate the distribution of the orientational ordering of the
Figure 12. Orientational ordering parameters of ILs (a) [PSPy][HSO4], and (b) [PSPy][H2PO4] along the Z-axis.
side chain and pyridine rings, which can be studied using the
following correlation function:
1
P2( ) = < [3cos2( ) 1]>
2
where is the angle between a specic vector in the moleculexed structure and the z-axis parallel to the surface normal. The
z-direction space was divided into 4050 bins, and each vector
event was sorted into the correct bin. The angle between the
vector and z-aixs was calculated for each molecule in the
system, then giving second Legendre polynomial P2() for each
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ASSOCIATED CONTENT
S Supporting Information
*
AUTHOR INFORMATION
Corresponding Author
*E-mail: xinghb@zju.edu.com.
Notes
ACKNOWLEDGMENTS
The research was supported by the National Natural Science
Foundation of China (21222601, 91434115, and 21436010),
the Zhejiang Provincial Natural Science Foundation of China
(LR13B060001), the Fundamental Research Funds for the
Central Universities of China (2014XZZX003-17), and the
Program for New Century Excellent Talents in University of
China (NCET-13-0524).
REFERENCES
4. CONCLUSION
In this work, we have investigated the microscopic structural
features of some representative SFILs by performing MD
simulation using the ion pair charge approach.
When the sulfonic acid group is tethered to the terminal
position of the alkyl chain, a strong interaction between the
sulfonic acid group and the anions was found. The type of
anions plays a critical role in determining the intensity of the
interaction between the sulfonic acid proton and the anions in
the order [PSPy][Tfo] < [PSPy][HSO4] < [PSPy][H2PO4],
which has a pronounced eect on the proton microenvironments of the SFILs. Less basic anions can lead to a much
weaker association of sulfonic acid protons with anions due to
the reduced protonanion interactions. In addition, the
terminal sulfonic acid group (tail functional group) could
lead to a nanostructured aggregation in the bulk phase similar
to the nonfunctionalized alkyl chain does.
The analysis of various density proles reveals that, for
dierent SFILs, the side chains of the cations all tend to locate
in the inner part of the interface, with the pyridinium rings of
the cations exposed in the outer region at the surface, which is
opposite to the case of nonfunctionalized IL. The enhancement
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probability for the anions to locate in the inner part of the
interface. The alkyl chain of the [HSPy]+ cation exhibits a more
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The present results show some structural characteristics of
SFILs in both the bulk liquid and interfacial regions, and the
ndings oer some insight into the proton microenvironments
of SFILs, which is highly instructive for the development of
new SFILs and proton conductive materials.
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