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org/JPCB Article

How Do Deep Eutectic Solvents Form Porous Liquids? The Example

of Methyltriphenylphosphonium Bromide: Glycerol and ZIF‑8
Published as part of The Journal of Physical Chemistry B virtual special issue “COIL-9: 9th Congress on Ionic
Liquids”.
Chiara Corsini, Cintia M. Correa, Nicolas Scaglione, Margarida Costa Gomes,* and Agilio Padua*
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sı Supporting Information

ABSTRACT: Porous liquids are new materials that provide

permanent porosity in the liquid phase through the dispersion of
nanoporous solid particles in a bulky solvent. Herein, we aim at
understanding how new sustainable solvents such as deep eutectic
solvent (DES) can be used to form porous stable suspensions for
the capture of gases of interest for sustainable chemistry. The
properties of an ionic DES, methyltriphenylphosphonium bro-
mide/glycerol in a 1:3 molar composition, and its behavior at the
interface with a metal−organic framework (MOF), ZIF-8, are here
investigated by polarizable molecular dynamics simulations. The
structural and dynamic properties of the DES are analyzed in the
bulk liquid and in the interfacial regions with the MOF, namely, in
the accessible cavities exposed at the surface. The porosity of the
suspension is maintained, and it is caused not only by the Coulomb cohesive energy between cations and anions, which prevents the
small anions from entering the pores, but also by the glycerol molecules not penetrating the small aperture of the ZIF-8 structure.
This was further verified by simulating a system composed of glycerol and ZIF-8. Simulations with CO2 show its partition between
the DES and the MOF, with higher concentrations registered in the MOF cavities.

■ INTRODUCTION
Porous liquids are fluid systems with permanent, well-defined
structure of the salt and the molecular compound and by the
composition of the mixture. The similarity in the physical and
cavities that are able to store small molecules. The cavities can chemical properties of DESs prepared from salts and ILs holds
exist in cage molecules or, as in this work, in dispersions of great potential for preparing stable porous ionic suspensions
particles of nanoporous materials in a bulky solvent.1 The use based on DESs.
of ionic solvents allows the formation of stable porous The porous materials used are mostly metal−organic
suspensions that preserve the interesting properties of the frameworks (MOFs), a class of porous materials composed
ionic liquid (IL), such as low vapor pressure, tunable solubility, of metal ions or clusters that act as building units combined
chemical and thermal stability, and wide electrochemical with organic linkers. Because of their distinctive modular
window.2,3 Recently, deep eutectic solvents (DESs) were structure, their physical and chemical properties can be easily
presented as alternatives to ILs to form porous liquids with tailored, making these complexes perfect candidates for a
improved sustainability, biocompatibility, and safety. number of applications in separations, catalysis, and
A DES is formed when two or more compounds are mixed
adsorption. Many MOFs have already been used to prepare
leading to a liquid phase at temperatures significantly lower
porous liquid suspensions,7,8 since they can be chosen to
than those expected for an ideal mixture.4 Deviations from
ideality in mixtures forming DES can originate from specific possess small pore apertures and wide pore cavities, thus
interactions between the components of the mixture, such as
hydrogen bonding, or from an increased variety of Received: December 30, 2023
intermolecular interactions.5,6 A large number of DESs are Revised: February 13, 2024
formed by mixing salts with high melting points, which can act Accepted: February 16, 2024
as hydrogen bond acceptors, and a number of molecular Published: March 4, 2024
compounds act as hydrogen bond donors. The resulting liquid
mixture is mostly an ionic solvent with properties tuned by the

© 2024 American Chemical Society https://doi.org/10.1021/acs.jpcb.3c08490

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The Journal of Physical Chemistry B pubs.acs.org/JPCB Article

preventing the intrusion of a solvent while maximizing gas CO2, using a Drude-induced dipole model. The MOF is
adsorption. represented by a flexible force field in order to provide a more
We recently demonstrated that porous DESs can be faithful description of how molecules permeate its structure.
obtained by dispersing 200 nm particles of a MOF, ZIF-8, in The solvation environments in the DES and their properties at
a DES composed of a voluminous phosphonium salt, the interface with the porous solid are studied using the same
methyltriphenylphosphonium bromide, and glycerol in a polarizable force fields, including CO2 molecules.
molar ratio of 1:3 (Figure 1). The suspensions were reported Simulations are supplemented by gas solubility measure-
ments of CO2 in glycerol and in suspensions of ZIF-8 in
glycerol in order to investigate the existence of permanent free
volume. These data complete previous experimental results
reported on the suspensions of ZIF-8 in the DES composed of
phosphonium bromide and glycerol discussed above.3

■ MATERIALS AND METHODS

Chemicals. Glycerol was supplied by Alfa Aesar with a
purity of 99.5%. ZIF-8, a 2-methylimidazole zinc MOF with a
Figure 1. Chemical structures of the components of the porous DES. pore aperture of 3.4 Šand a pore inner diameter of 11.6 �
Methyltriphenylphosphonium bromide with glycerol in a molar ratio Basolite Z1200 (BASF product 691348)�, was obtained from
of 1:3 ([MePh3P][Br]/Gly) and ZIF-8. Sigma-Aldrich, batch STBG590 V. The solid particles were
sieved through a 11 μm pore-size Nylon Nitex mesh to narrow
the particle size distribution. Carbon dioxide, CO2 4.5 purity
to be stable for over 5 months, and X-ray scattering showed (99.995% purity in moles), was purchased from Air Liquide
that it maintains the microscopic structure of both the solid and used as received. Suspensions of ZIF-8 in glycerol were
particles and the liquid, as previously observed in porous ILs. prepared at room temperature following the procedure
Porosity was confirmed experimentally by a significant increase reported previously3 by weighing the components using a
in gas absorption in the porous suspension, when compared Mettler Toledo New Classic MS balance with an accuracy of
with the DES.3 ±0.01 mg and by stirring the mixture at 430−540 rpm for 5
A more detailed analysis of the solid−liquid interface is min. The compositions of the two samples studied are
needed to elucidate the role played by the salt and the reported in Table S4 in the Supporting Information. Both
molecular compound in the DES in keeping the porosity the pure liquid glycerol and the two suspensions were degassed
available. With ILs, porosity is ensured even in the presence of under primary vacuum for up to 72 h before use.
small anions, owing to the strong Coulomb cation−anion Gas Absorption. The absorption of CO2 in glycerol and in
interactions, leading to cohesive energy that prevents the the ZIF-8 suspensions was measured experimentally at 303 K
separation of cations and anions. It suffices that the ion pair is using the volumetric isochoric saturation method described
voluminous enough to prevent the IL from entering the pores. previously17 at gas pressures up to 1 bar. The amount of gas
In the DES, the organic compound might be small enough to absorbed is calculated from the difference between the two
access the pores and, therefore, limit the porosity of the pressure−volume−temperature measurements. The first meas-
suspensions. Although DESs maintain high cohesive energy urement serves to quantify the initial amount of gas. The
due to hydrogen bonding, it is not clear if this is enough to second, performed when thermodynamic equilibrium is
keep the molecular compound outside the pores or in what attained between the gas and a precise amount of degassed
cases this happens. liquid, allows the calculation of the amount of nondissolved gas
In our previously reported porous DES,3 the size of glycerol remaining in the cell’s headspace and, by difference, of the
(3.6 Å in its smallest dimension) is comparable to the 3.4 Å amount of gas absorbed in the liquid.
apertures in ZIF-8. We formulate the hypothesis, on the basis Molecular Force Field. The DES studied here, methyl-
of a number of literature studies, that either the flexibility of triphenylphosphonium bromide with glycerol in a molar ratio
the ZIF-8 structure9−11 or arguments of molecular affinity of 1:3 ([MePh3P][Br]/Gly) is described by the CL&Pol
(namely, hydrophobicity)12 might determine if porosity is polarizable force field.18 Initial parameters were taken from the
maintained in a DES. CL&P19 and OPLS-AA fixed-charge force fields for the salt and
In this context, molecular dynamics (MD) simulations can glycerol, respectively, as explained in the Supporting
provide a better understanding of the interactions at play Information. Polarizability was added via Drude-induced
between the solid and liquid and of the microscopic structure, dipoles20 following the CL&Pol procedure18 to adapt the
which will lead to an improvement in the design and will help nonpolarizable model. ZIF-8 was described as a fully flexible
unveil the absorption capabilities of these new materials. structure, starting with the AMBER force field model of Zheng
Furthermore, the solvation properties of such systems can also et al.21 Also, for the MOF, polarizability was included using
be tested by including gas molecules in the simulations. Drude dipoles, following the CL&Pol procedure.18,22 For CO2,
Notably, many computational techniques are employed to an already polarizable force field based on Drude dipoles was
study gases in porous materials such as MOF, namely, used,23 which is compatible with the CL&Pol model. With
DFT,13,14 GCMC,14,15 GEMC-MD,15 and MD.16 With flexible these force field choices, we attained uniform and compatible
MOFs such as ZIF-8, a flexible force-field is required to descriptions of the solid, the liquid, and the gas.
truthfully describe its interactions with liquid media and the In the CL&Pol force field,18 a Drude particle of 0.4 Da is
access of molecules or ions to its cavities. attached to each polarizable atom (a Drude core) through a
Herein, we opted to consider polarizability explicit in the harmonic spring with force constant kD = 4184 kJ mol−1. The
entire system, namely, composed of DES, slabs of MOF, and value of the opposite charges on the particles forming the
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Drude dipole is derived from the polarizability of the atom in The equilibrium structural and dynamical properties were
question through the formula α = qD2/kD. Hydrogen atoms studied by performing multiple analyses on the MD trajectories
are treated as nonpolarizable because of their small mass and through self-made scripts and the TRAVIS analyzer.33
small electron density. Their polarizability is taken into
account by adding the corresponding value to the heavy
atoms to which they are bound. The mass and charge of Drude
■ RESULTS AND DISCUSSION
The density of the DES at 353 K obtained from simulation
cores are adjusted to account for the Drude particle. Short- (1.236 ± 0.003) g cm−3 is approximately 2% lower than the
range interactions between Drude particles are damped via experimental value,3 which is a typical level of accuracy for the
Thole functions24,25 with a universal parameter a = 2.6. Tang− CL&Pol force field.18
Toennies damping functions26,27 were applied to smear Liquid-state structural features of DES were investigated by
electrostatic interactions between the hydroxyl hydrogen plotting site−site radial distribution functions (RDFs) between
atoms of the glycerol and Drude dipoles at short-range. The atoms of interest (Figure 2). The two maxima in the P−Br
role of these damping functions is to avoid instabilities in the
trajectories of the Drude dipoles (“polarization catastrophe”)
when the point-charge approximation becomes unsuitable at
short-range. Damping of electrostatic interactions of the Zn
atoms of ZIF-8 with the oxygen atoms of glycerol and all
Drude particles was also applied.
Molecular Dynamics Simulations. Systems consisting of
DES, ZIF-8, and CO2 were studied using MD with the
LAMMPS28 code. Five different systems were considered: the
bulk DES; the DES with dissolved CO2; a slab geometry with
ZIF-8 and DES (and their interface); the slab geometry with
dissolved CO2; and the slab geometry with glycerol and the
MOF. Initial configurations were generated using fftool29 and
Packmol.30 A cutoff of 12 Å was considered for nonbonded Figure 2. Site−site RDFs in the [MePh3P][Br]/Gly DES. Blue: RDF
interactions and tail corrections were applied. The particle− of Br− anions and P atoms of the cation; orange: RDFs of Br− and all
particle particle-mesh method was used to evaluate electro- the hydroxyl H atoms of glycerol. The orange dashed and dotted lines
correspond to the RDFs of Br− with the terminal hydroxyl H and the
static energies with an accuracy of 1 × 10−5. The lengths of
central hydroxyl H of glycerol, respectively.
bonds terminating in hydrogen atoms were constrained using
the SHAKE algorithm. The time step was of fs.
To simulate the pure DES, a cubic box of 120 Å edge was RDF correspond to two ionic solvation shells at the distances
filled with 400 ion pairs and 1200 glycerol molecules for a total expected,34 given the steric hindrance of the methyl and phenyl
of 48,000 atoms with the polarizable force field. An amount of groups around the P atom of the cation.
117 CO2 molecules were introduced in this system, The intense peak at 2.18 Å in the RDF between the bromide
corresponding to 2% of the mass of DES. anion and the hydroxyl H atoms of glycerol (Figure 2) suggests
A slab of MOF made from 3 × 3 × 3 unit cells of ZIF-8 was strong hydrogen bonds. The correlation appears as strong for
built, periodic in the x and y directions, and with the surface the terminal hydroxyl groups as for the central one. These
exposed to the z direction reconstructed by adding hydrogen bonds were confirmed by plotting the angular
methylimidazole groups to the unsaturated Zn atoms. The distribution of the O−H···Br angle as a function of the H···Br
terminal methylimidazole groups were saturated with hydrogen distance (Figure S2). The intense signal near 2 Å at an angle of
atoms on the N, with the charges of the H adjusted to maintain 180° is the clear fingerprint of a hydrogen bond.
the slab neutral.22,31 This resulted in a total of 13,644 atoms Inter- and intramolecular glycerol−glycerol hydrogen bonds
representing the MOF with the polarizable model. To simulate were also studied, as shown in Figure S3. Intermolecular
the composite system, the 3 × 3 × 3 unit cell slab of MOF was glycerol−glycerol H-bonding is barely present in the DES, and
positioned in a periodic, rectangular 52 × 52 × 144 Å box and it is significantly weakened when compared with pure glycerol
due to the presence of the bromide anion, a strong H-bond
put in contact with a section of DES composed of 163 ion pairs
acceptor (Figure S4). A secondary intramolecular H-bond is
and 489 glycerol molecules (or with a section of 943 glycerol
also shown in the combined angle-distance distribution
molecules). The boxes, containing approximately 33,500 functions (CDFs) of Figure S3, with a strong signal at 2 Å
particles in all, were equilibrated in the NPT ensemble by and at an angle between 100 and 125° in the CDF.
coupling the x and y coordinates. A number of 48 molecules of The static structure factor of the DES obtained from
CO2 were added to the previously described configuration, simulation (Figure 3) can be compared with the experimental
forming a new system that was equilibrated following the same wide-angle X-ray scattering (WAXS) data previously pub-
procedure. lished.3 While the calculated peak at q = 1.5 Å−1 appears in
The simulations were carried out at 353 K and 1 bar using a both the simulated and experimental structure factors, a
Nosé−Hoover thermostat and barostat. The Drude degrees of smaller peak at q = 2.5 Å−1 is not seen in the experimental
freedom were thermostated at 1 K, following the established WAXS data.
procedure of cold Drude dipoles, which is an efficient scheme The spatial heterogeneity of the DES at nanometer scale can
to generate a trajectory close to that of relaxed Drude degrees be evaluated by partitioning the total structure factor in partial
of freedom.32 Equilibration runs of 3 ns were followed by contributions.35 We chose a cationic, anionic, and glycerol
production trajectories of 20 ns. partition scheme given by S(q) = Scat−cat(q) + San−an(q) +
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of glycerol and bromide (Figure S5) and show that OH−Br

cross correlations are responsible for the small peak at q = 2.5
Å−1. The OH−OH correlation does not contribute signifi-
cantly to the total structure factor, as was also hinted from the
low peaks in the RDFs of Figure S3. Overall, the analysis of the
structure factors indicates stronger correlations between anions
and glycerol molecules caused by hydrogen bonding compared
to cation−anion correlations, which may be weakened by the
bulky phenyl groups of the cations.
The self-diffusion coefficients, D, of the different compo-
nents of the liquid were computed from mean square
displacements (MSDs). As shown in Table 1, the phospho-
nium cation diffuses almost two times slower than the bromide
anion or glycerol, which is logic given its larger size. If
compared to the self-diffusion coefficients reported from MD
simulations,34 the overall trend is maintained, however, the
self-diffusion coefficients calculated herein are lower (the
literature study made use of the AMBER nonpolarizable force
field).
The solvation shell of CO2 in the DES was analyzed by
simulating a system containing 117 molecules of CO2. Radial
and spatial distribution functions (SDFs) are shown in Figure
4. The peaks in the RDFs between the centers of mass of CO2

Figure 3. Simulated X-ray static structure factors of the DES. Total

S(q) (black) and partial Sα−β(q) (colored). (Top) Partial structure
factors of like−like correlations, cation−cation (blue), anion−anion
(orange), and glycerol−glycerol (green). (Bottom) Partial structure
factors of unlike correlations between cation−anion (blue), cation-
glycerol (orange), and anion-glycerol (green).

9Sgly−gly(q) + 2Scat−an(q) + 6Scat−gly(q) + 6San−gly(q), which are

the partial structure factors shown in Figure 3. Intense peaks
and antipeaks in the small-q region, around 0.5 Å−1, indicate
strong ordering at the nanoscale with lengths around 1.2 nm.
Strong self-correlations appear for cations and glycerol
molecules but not for anions, whose contribution stays within
moderate amplitudes over the q range displayed. This,
combined with high self-diffusivity of the anion (see below),
indicates that the anion is rather evenly distributed throughout
the system, while cations and glycerol molecules form
structured domains.
The absence of a prepeak in the total S(q) near 0.5 Å−1 is
mainly due to the strong cation-glycerol anticorrelation peaks Figure 4. (Top) Center-of-mass RDFs of CO2 with the cation (blue),
anion (orange), and glycerol (green). (Bottom) SDF of the cation
and secondarily to cation−anion anticorrelation (inverted (blue), anion (orange), and glycerol (green). The surfaces displayed
peaks in the partial structure factors). The main total S(q) peak correspond to the iso-density values of 2.0 nm−3, 2.9 nm−3, and 9.2
at 1.5 Å−1 is attributed to adjacency correlations between nm−3 for cation, anion, and glycerol, respectively.
fragments, as seen in the cross partial structure factors.
To attribute the smaller peak at q = 2.5 Å−1, another
partitioning scheme that probes the hydrogen bonded and each component of the DES are moderate, which
fragments was used. The fragments chosen are the OH groups corresponds to a weak spatial correlation. The SDFs show

Table 1. Self-Diffusion Coefficients of the Components of the DES and CO2 in the Systems Tested, Expressed in 10−10 m2 s−1
D/10−10 m2 s−1 DES DES + CO2 MOF + DES MOF + DES + CO2
MePh3P+ 0.65 0.70 0.67a 0.73a
Br− 1.22 1.23 1.43a 1.56a
Gly 1.30 1.30 1.42a 1.42a
CO2 5.97 10.9b

a
In the internal region of the liquid slab. bIn the porous solid region.

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the quadrupolar character of CO2, with cations located near and of the solid are characterized by the distance and height of
the negatively charged oxygen atoms and anions positioned the first maximum of interatomic RDFs (Figure S8). Phenyl
around the positively charged carbon atom. The close groups of the cations and glycerol molecules are most likely to
association between CO2 and the anions is typical of the be found closer to the surface of ZIF-8.
solvation of this molecule in ionic media. We see no evidence of π−π stacking of phenyl groups of the
As shown in Table 1, the self-diffusion coefficient of CO2 is cation and imidazole groups of ZIF-8. The CDFs in Figure S9
6 × 10−10 m2 s−1, compatible with experimental values show that the phenyl groups of the cation are mostly found at
obtained in other hydrophilic DESs of similar viscosity.3,36 an angular range between 50 and 125° with respect to the
Solid−Liquid Interface. By simulating a slab geometry imidazole rings, with a stronger signal at around 90°. The
(Figure 5), we analyzed the solid−liquid interface between the formation of a hydrogen bond between glycerol and the solid
surface is not clearly detected by the CDF in Figure S10. In the
region of the accessible cavities (Figure S11), intramolecular
H-bonding in glycerol is preserved, while intermolecular H-
bonding is lost due to confinement. H-bonding between
glycerol and bromide remains present, even in the confined
region.
The interfacial layer of the liquid in contact with the solid
surface is characterized by an even distribution of positive and
neutral domains, intercalated by small negative domains, as
shown in Figure 6. Furthermore, no particular affinity for the

Figure 5. Screenshot of the DES-ZIF-8 simulation box with slab

geometry at the end of a 20 ns trajectory. The cations, anions, and
glycerol molecules of the DES are represented in blue, orange, and
green, respectively. The dashed red lines mark the limit between the
internal and the exposed half-cavities, accessible to the liquid.

DES and ZIF-8, which is key to understanding the interactions

at play and the organization of the interfacial layers. The
porosity of the system is usually determined by the dimensions
of the molecules in the fluid and by the aperture size of the
MOF. However, in this complex system, many factors, such as Figure 6. Screenshot of the xy plane of DES−ZIF-8 interface, seen
the ionic nature of the solvent, the hydrophobicity of the solid, from the MOF, after a 20 ns trajectory. The cations (blue), anions
and its structural flexibility, play an important role in (orange), and glycerol molecules (green) in the accessible half-cavities
controlling whether the porosity stays available. Therefore, are shown in a van der Waals representation. The components of the
the description of ZIF-8 through a polarizable and flexible DES in the first layer outside the exposed cavities are shown using a
force field is essential. As confirmed in a previous study, the surface representation. (Left) The first layer of Zn (gray) atoms and
the corresponding methyl imidazolate linkers (sticks) are shown.
flexibility of ZIF-8, observed in simulations by the “breathing” (Right) Only the first layer of metal atoms (gray) is represented.
motion of the structure, may allow the intrusion of molecules
of size comparable to the apertures.22
The persistence of porosity was verified by plotting density metal center is noticed when observing the liquid interface
profiles as a function of the z coordinate for the components of over the xy plane since the Zn atoms of ZIF-8 are fully
the system, shown in Figure S7. The components of DES only coordinated by the imidazolate linkers.
occupy the open cavity hemispheres of the surface layer of The mobility of the DES components in the slab geometry
ZIF-8. No molecules or ions pass through the exposed part of was assessed through MSDs. The MSDs of molecules that
the apertures into the intact cavities of the MOF structure. Due were inside the hemispherical cavities at the beginning of
to the confinement provided by the accessible open cavities, a sampling are compared with those of the molecules that started
strong alternation of positive and negative charge centers, in the liquid slab region. Overall (Figure S12), the MSDs of
namely, phosphorus and bromide, can be seen around the first species in the accessible cavities are 1 order of magnitude
two zinc layers, as shown in Figure S7. smaller than those of molecules from the liquid slab. This is an
The density of the DES in the liquid slab (outside of the expected confinement effect in the slit-pore geometry. The
accessible cavities of ZIF-8) is 1.3% lower than the one MSDs in the plane parallel to the surface (xy directions),
calculated in the bulk (values in Table S3). The self-diffusion Figure 7top, show that cation and anion are equally
coefficients of the DES components in liquid slab are collected constrained in the half-cavities, while glycerol is more mobile.
in Table 1, where it is seen that the phosphonium cation The DES components are also partially confined in the
maintains the same diffusivity as in the bulk liquid, while the accessible cavities in the direction perpendicular to the surface,
bromide anion and glycerol diffuse slightly faster. While as shown by the MSD along the z direction in Figure 7bottom.
counterintuitive, faster diffusion in confined liquids has been After almost 1 ns, the glycerol molecule and anions that were
reported experimentally.37 confined in the cavities start to diffuse faster compared to the
A connection-matrix analysis was done between the cation, due to their smaller sizes. The large phosphonium
components of the DES and the accessible portion of the cations are more likely to get immobilized in the hemispherical
MOF. Short-range correlations between atoms of the liquid accessible half-cavities, while the smaller dimensions of the
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average amount of CO2 molecules residing inside the MOF is

41 ± 1 molecules, corresponding to an average loading of 1.50
± 0.04 molecules per ZIF-8 unit cell.
Several computational studies of the adsorption and
diffusion of CO2 in ZIF-8 employ different techniques with
different levels of accuracy leading to somewhat contrasting
results.13−16,21,38 Overall, the flexibility of the MOF plays an
important role in the diffusion,15 while polarizability may affect
the adsorption properties.39 ZIF-8 is characterized by sodalite
topology, where pores of 11.6 Å diameter are connected by
four-membered ring gates along the 100 direction and by
larger six-membered ring gates along the 111 direction. The
larger gates have a diameter of 3.4 Å and are usually
responsible for intercage jumping of molecular hosts.
Favorable adsorption sites can be found by calculating the
SDFs of the C and O atoms of CO2 in the unit cells of ZIF-8.
As shown in Figure 9, the oxygen atoms occupy the sites in

Figure 7. (Top) MSD along the xy plane for molecules initially in the
accessible cavity regions of cation (blue), anion (orange), and glycerol
molecules (green). (Bottom) MSD along z of molecules initially in
the accessible cavity regions (same color code).

bromide anions and glycerol allow them to enter and exit the
open cavities with more ease.
Simulations with Dissolved CO2. To test the actual
availability of the pores in the suspension, a simulation box in
slab geometry with 48 CO2 molecules, initially placed in the
DES region, was equilibrated. After a 20 ns trajectory, the
density profile of CO2 is peaked in the MOF region, while it is
shallow in the central region occupied by the DES, as shown in
Figure 8. A high affinity between CO2 for the ZIF-8 cavities is
shown as the gas molecules move from the liquid region into
the free volume in the pores.
Throughout the simulation, CO2 molecules diffuse in and
out of the MOF, with only 9 out of the 48 molecules never
leaving the interior of the ZIF-8 slab during a 6 ns run. The

Figure 9. Spatial distribution of CO2 in a unit cell of ZIF-8, O atoms

(red surface), and C atoms (white surface). (Top) Facing the four-
membered ring gate. (Bottom) Facing the six-membered ring gate.

proximity of the C4−C5 bond of the imidazole rings, whereas

the C atom is more present toward the center of the
methylimidazole group. This agrees with the GEMC-MD
simulations performed by Zhang et al.15 In the four-membered
gate, we find a decrease in CO2 density in the direction
perpendicular to the methyl groups of the organic linker, with a
distribution of O atoms around 45°, which is in agreement
with the DFT calculations of Fischer and Bell13 In the 6-MR, a
Figure 8. Density profiles as a function of the z coordinate of the peak in the density shows that the gate region is mostly
simulation box. Number densities of the Zn atoms of the MOF occupied by oxygen atoms. In general, it is shown that CO2, as
(gray), all atoms of cations (blue), anions (orange), and all atoms of many other gases, preferentially adsorbs on the organic
glycerol molecules (green) and of CO2 (red). moieties rather than on the metal centers.15,40
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The diffusion of CO2 in the ZIF-8 slab was calculated and open cavities. As shown in Figure S14, the O−H···O hydrogen
reported in Table 1. When compared with the experimental bond shows a wide angular distribution between 25 and 150°,
self-diffusion41 of (1.4 ± 0.1)10−10 m2 s−1 at the same indicating an absence of intermolecular hydrogen bonding.
molecular loading but at lower temperature (298 K), our The self-diffusion coefficient of glycerol in the liquid region
calculated diffusion is greater but in the same order of of the slab is 1.40 × 10−10 m2 s−1, which is larger than the value
magnitude. Without experimental studies of self-diffusion of calculated in bulk glycerol (0.29 × 10−10 m2 s−1). This result is,
CO2 in a wider temperature range, we can only suppose that again, counterintuitive. However, it is coherent with the
this discrepancy is caused by the higher temperature at which experimental results37 that show an increase in the diffusion
the simulation was performed. coefficient of glycerol when confined in nanometer-sized pores.
Glycerol−ZIF-8 Interface. A system in slab geometry with As was observed in the DES, the MSD of glycerol molecules
ZIF-8 and pure glycerol as the liquid was simulated to obtain initially in the accessible cavity region is 1 order of magnitude
further information about whether permanent porosity can be lower than that of the molecules initially in the liquid slab, both
maintained with a molecular compound of moderate size in the perpendicular and in the parallel plane to the surface (Figure
absence of the salt and the corresponding high cohesive S15). The confinement of glycerol in the accessible cavities
energy. Structural features were assessed by plotting density does not change significantly in the presence or absence of the
profiles, shown in Figure 10. Glycerol molecules do not salt.
The simulations presented here predict that porous
suspensions can be formed by ZIF-8 in glycerol. However,
this is not enough to prove that glycerol does not enter the
pores of ZIF-8 at a longer time scale. On this note, intrusion
experiments42 show that glycerol−water mixtures, up to 50%
in glycerol, penetrate the ZIF-8 pores upon gate-opening,
triggered by the application of pressures of several tens of MPa
over several cycles. No other evidence of liquid-phase glycerol
intrusion was found in the literature, except for the work of
Khan et al.43 on glycerol adsorption in ZIF-8 measured via
solid-state NMR. A study of gas-phase adsorption of glycerol
using broadband dielectric spectroscopy was also reported.44
However, in neither of these studies, gas adsorption measure-
ments were performed after saturation with glycerol to confirm
if porosity remained. Therefore, it cannot be excluded that
glycerol was simply adsorbed on the surface of ZIF-8, in the
accessible cavities, and not in the bulk of the MOF structure.
The present gas adsorption measurements (Table S5) confirm
the availability of the pores, resulting in an increase in CO2
adsorption of more than 100% at room temperature (Table
S4) with only 5% w/w of MOF dispersed in glycerol.

Figure 10. (Top) Screenshot of the glycerol−ZIF-8 box after a 20 ns

■ CONCLUSIONS
Polarizable MD simulations focusing on the solid−liquid
trajectory. (Bottom) Density profiles of glycerol atoms (green) and
interface between the [MePh3P][Br]/Gly DES and ZIF-8 were
Zn atoms (gray) as a function of the z coordinate of the simulation
box. carried out to obtain insights into the origin of the porosity of
this stable suspension of a porous solid in a DES. A periodic
slab geometry was used, containing 3 × 3 × 3 unit cells of the
penetrate the bulk region of ZIF-8, and the signal in the MOF (terminated by methylimidazole ligands on the exposed
density profile dampens after the second layer of Zn atoms, surfaces) and ca. 5 nm of liquid region, with all components
corresponding to the end of the accessible cavities. Even in the modeled using a polarizable all-atom force field.
absence of the salt, porosity is therefore retained, so we find The structural study of the DES revealed the formation of
that the origin of porosity is not exclusively linked to Coulomb strong hydrogen bonds between the hydroxyl groups of
interactions between the cation and anion, as in porous ILs. glycerol and bromide, which were also detected by partial
A connection matrix (Figure S13) shows a higher correlation structure factors. Intermolecular glycerol−glycerol hydrogen
between the C atoms of glycerol and the surface imidazole bonds in the DES were compared with the same bonds in pure
rings when compared to the result with the DES (connection glycerol, showing a decrease in the strength of this type of H-
matrix in Figure S8), but this may be explained simply by the bond due to the competition of bromide in the DES.
higher concentration of glycerol. No close contact is found Nanostructuring was identified by partitioning the calculated
between the O atoms of the glycerol and the imidazole groups, total structure factor into partial contributions, which showed
while these were seen at the interface with the DES (Figure that the absence of a visible prepeak in the total structure
S8). The low affinity between ZIF-8 and glycerol is also caused factor is mostly due to cation-glycerol anticorrelations. The
by the strong hydrophobicity of the MOF, which leads to the self-diffusion coefficient of the phosphonium cation was found
formation of a porous system. to be smaller than those of the bromide anion and glycerol,
In the presence of salt, glycerol molecules mostly form which is logical given its larger size. The introduction of CO2
intramolecular hydrogen bonding in the confined region of the in the pure DES showed the typical characteristics of the
2487 https://doi.org/10.1021/acs.jpcb.3c08490
J. Phys. Chem. B 2024, 128, 2481−2489
The Journal of Physical Chemistry B pubs.acs.org/JPCB Article

solvation of this gas in ionic media, namely, a strong affinity for Authors
the anion. Chiara Corsini − Laboratoire de Chimie de l’ENS Lyon,
Analysis of the interface in the composite simulation box CNRS and Université de Lyon, 69364 Lyon, France
showed that neither the ions nor the molecular compound of Cintia M. Correa − Laboratoire de Chimie de l’ENS Lyon,
the DES penetrated into the bulk of the MOF structure, CNRS and Université de Lyon, 69364 Lyon, France
confirming the persistence of porosity. The DES located in the Nicolas Scaglione − Laboratoire de Chimie de l’ENS Lyon,
surface accessible cavities of ZIF-8 still contains glycerol- CNRS and Université de Lyon, 69364 Lyon, France
bromide H-bonds, while intermolecular glycerol−glycerol H- Complete contact information is available at:
bonding is lost. No particular spatial affinity is found between https://pubs.acs.org/10.1021/acs.jpcb.3c08490
the metal centers of ZIF-8 and the components of the liquid.
The mobility of ions and molecules in the accessible half- Notes
cavities at the MOF surface is 1 order of magnitude lower
The authors declare no competing financial interest.
compared to the middle of the liquid slab. The phosphonium
cations, due to their larger size, are more likely to be
immobilized. Introduction of CO2 showed the preference of
the gas to adsorb in the cavities of the solid, thanks to the
■ ACKNOWLEDGMENTS
This work was partially funded by the GREENH3 project
available free volume. The most favorable adsorption sites for (ANR-22-PEHY-0015) of the PEPR-H2, France 2030
CO2 are in the proximity of the C4−C5 bond of the imidazole program.
rings and the center of the methylimidazole group, confirming
that, as in other gases, CO2 preferentially adsorbs on the
organic moieties of ZIF-8.
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