ARTICLE

pubs.acs.org/JPCC

Molecular Insight into the Adsorption and Diffusion of Water in

the Versatile Hydrophilic/Hydrophobic Flexible MIL-53(Cr) MOF
Fabrice Salles,† Sandrine Bourrelly,‡ Herv
e Jobic,§ Thomas Devic,|| Vincent Guillerm,||
Philip Llewellyn,‡ Christian Serre,|| G
erard Ferey,|| and Guillaume Maurin*,†
†
Institut Charles Gerhardt Montpellier
UMR CNRS 5253, UM2, ENSCM-Universit
e Montpellier 2, Place E. Bataillon,
34095 Montpellier Cedex 05, France
‡
Laboratoire Chimie Provence, Universit
es d’Aix-Marseille I, II et III - CNRS, UMR 6264, Centre de Saint J
er^ome,
13397 Marseille, France
§
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Institut de Recherches sur la Catalyse et l’Environnement de Lyon, CNRS- Universit
e Lyon 1, UMR 5256,
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2 Avenue Albert Einstein, 69626 Villeurbanne Cedex, France

)

Institut Lavoisier, UMR CNRS 8180, Universit
e de Versailles Saint-Quentin-en-Yvelines, 45 Avenue des Etats-Unis,
78035 Versailles Cedex, France

bS Supporting Information
ABSTRACT: Prior to envisage any implication of metal

organic framework (MOF) materials in industrial applications
such as gas storage/separation, it is of primary importance to
examine beyond their stability under humidity, the interactions
between water and MOF surfaces. Regarding the MOF type
MIL-53(Cr), the situation becomes more complex due to the
breathing of its structure upon water adsorption that induces a
structural transition between a narrow pore (NP) and a large
pore (LP) forms. The resulting shrinkage/reopening of the
framework leads to crucial modifications of the hydrophobicity/hydrophilicity character of the material. A combination of molecular
simulations (Grand Canonical Monte Carlo and molecular dynamics) and experimental techniques (quasi-elastic neutron scattering
and gravimetry/volumetry) allows a complete elucidation of the adsorption and diffusion mechanisms in play in this structure. It also
provides a microscopic explanation of the hydrophilic and mildly hydrophobic behaviors of the NP and LP forms respectively. The
arrangements of water within the two porosities are then discussed and compared to those usually observed for the liquid state.
Furthermore, the self-diffusivity for water in these two structural forms significantly differs both in magnitude and mechanism with a
normal and single file one-dimensional diffusion mechanisms in the LP and NP forms, respectively. Indeed, this anomalous behavior
of the MIL-53(Cr) upon water adsorption implies a strong modification of its hydrophilic/hydrophobic character. This unusual
behavior opens a promising direction to improve the selectivity of MOFs in industrial applications such as purification of alcohols
without the need for functionalization procedures.

’ INTRODUCTION any implication of these solids in industrial applications regarding

Metal
organic frameworks (MOFs) or porous coordination gas adsorption/separation, it is of primary importance to both
polymers first appeared at the end of the 1990s.1,2 They are a examine their stability under humidity and to understand the
class of hybrid organic
inorganic materials, which are built up interactions between water and the MOF surface which are
from inorganic subunits (transition metals, main group elements, known to significantly either alter or improve their adsorption/
lanthanides, and so forth) and organic moieties (polyphos- separation performances with respect to different gases.29
33 In
phonates, polycarboxylates, imidazolates, and so forth). The that way, the stability of a wide range of MOFs under water
emergence of novel MOF structures has been almost exponential atmosphere has already been evaluated.18,34 For instance,
since the first reporting of MOF-5 by Yaghi et al.1,3 Their direct4
6 the Material of the Institut Lavoisier (MIL) series do not show
and postsynthetic functionalizations3,7
9 have further allowed any significant alteration of their porosity upon water adsorp-
the preparation of a wide range of hybrid materials, offering a way tion,32,33,35 and especially the flexible MIL-53 solid, while some
to both modulate their interactions with different types of guest other MOFs including MOF-177, MOF-5, and HKUST-1 are
molecules10
15 and to enhance their thermal stability in air2,16,17
or water.18 All these features make them very promising candi- Received: March 7, 2011
dates in different areas including gas capture/separation, catalysis Revised: April 19, 2011
and drug encapsulation.2,10,11,19
28 However, prior to envisage Published: May 06, 2011

r 2011 American Chemical Society 10764 dx.doi.org/10.1021/jp202147m | J. Phys. Chem. C 2011, 115, 10764–10776
The Journal of Physical Chemistry C ARTICLE

unstable.36
40 In contrast, only a few experimental adsorption

isotherms are available in the literature for such materials32,41
44
and the exploration of the interactions between polar molecules,
that is, water and alcohols, and the MOF surfaces is scarcely
investigated so far.31,32,43
45 It has been thus experimentally
evidenced that, while most of the investigated MOFs are hydro-
philic giving rise to interactions via hydrogen bonds between
their pore walls and the polar molecules,32
45 some others show
a V-type isotherm characteristic of the hydrophobic nature of their
surfaces.41 From a modeling standpoint, most of the studies were Figure 1. Evolution of the structure of MIL-53(Cr) upon adsorption of
concentrated on determining the location of the polar molecules water. LP = large pore form, NP = narrow pore form.
within the porosity of some MOFs using either energy mini-
mization techniques based on classical force fields or quantum effect on the arrangement of the water molecules within the
calculations.32,39,45
47 Exploring the behavior of water confined porosity of both MILs is then pointed out by a direct comparison
in nanoporous materials is also of fundamental interest as atte- with the microscopic behavior of the same molecule in the liquid
sted by the large number of studies devoted to this topic since the state. Finally, molecular dynamics is coupled with quasi-elastic
past few years on different solids including zeolites, mesoporous neutron scattering experiments in order to shed some light into
silicas, activated carbons and more recently on MOFs.48
57 In the dynamics of water in these hybrid materials, which has not
this latter case, Paranthaman et al.58 have employed Grand been addressed so far in any MOF type solids.
Canonical Monte Carlo simulations to characterize the hydro-
phobic behavior of the Al(OH)(1,4-naphthalenedicarboxylate)
which is a one-dimensional (1D) MOF type material. ’ MATERIALS AND METHODS
Here, one aims at providing molecular insight into the adsorp-
tion and diffusion processes of water occurring in the MIL- Sample Preparation. MIL-53(Cr) and MIL-47(V) were
53(Cr) solid.59 This chromium terephthalate (L) formulated synthesized and activated according to the published proce-
Cr(OH)(L) presents a 1D pore system associated with a high dures.59,63,66 Hydrogenated samples were used for the isotherm
structural flexibility either with temperature or pressure60
62 or in measurements, whereas deuterated MIL-53(Cr) was selected for
presence of various guest molecules. This behavior was attributed the neutrons scattering experiments. This latter was prepared
to a reversible structural switching between a narrow (NP) and a from d4-terephthalic acid (Euristotop, France) and hydroge-
large pore (LP) form, implying variations in cell volume up to nated solvent as already reported.67
30% in presence of CO2.63
65 This investigation follows a recent Adsorption Measurements. The adsorption isotherms were
study reported by some of us which revealed an anomalous water obtained by gravimetry measurements. The laboratory-made
adsorption behavior of this solid at low pressure that was not fully adsorption apparatus includes a symmetrical balance and allows
explained at the microscopic scale.32 A preliminary step consisted a continuous introduction of vapor to the sample in a slow
of conducting molecular dynamics in the NσT ensemble to enough manner to ensure quasi-equilibrium between the vapor
validate the force field65 selected for representing the MIL- and the solid and a high-resolution isotherm plot.32 For each
53(Cr)/H2O interactions, by successfully capturing the two series of experiments, this quasi-equilibrium condition is verified
consecutive structural switching upon water adsorption from by stopping the vapor introduction and ensuring that no change
the LP to the NP forms followed by a reopening of the structure in pressure or mass is observed. A typical adsorption
desorption
at higher pressure as shown by ex-situ X-ray diffraction isotherm takes around 10 days. To carefully measure the deso-
(see Figure 1). Grand Canonical Monte Carlo simulations based rption of the water vapor from the fully hydrated MIL-47(V), a
on this force field were then employed to predict both the new experimental procedure was used32 in which the porous
absolute adsorption isotherm and enthalpy, which are further solid is initially immersed in an excess of liquid and then slowly
compared to gravimetry/microcalorimetry data. The complex evacuated under controlled vacuum conditions, usually through a
shape of the adsorption isotherm at low pressure is then capillary toward vacuum.
interpreted in light of the structural transitions in play. The Quasi-Elastic Neutron Scattering. The quasi-elastic neutron
resulting modification of the water affinity of the MIL-53(Cr) scattering (QENS) measurements were performed on the time-
when one switches from the LP to the NP forms is further of-flight spectrometer IN6, at the Institut Laue-Langevin, in
discussed by a careful inspection of the microscopic adsorption Grenoble, France. The incident neutron energy was taken as
mechanism for water in the two structures. As far as we know, it is 3.12 meV, corresponding to a wavelength of 5.1 Å. Once scat-
the first time that the hydrophobic/hydrophilic character of a tered by the sample, the neutrons are analyzed as a function of
solid can be tuned by a structural transition that leads to the flight time and angle. Groupings of spectra were made outside
observation of a V-type shape isotherm at low pressure. The so- the Bragg peaks of MIL-53(Cr), the average wavevector transfer,
observed “hydrophobic” character of the LP form is further Q, ranging from 0.27 to 1.6 Å
1. The line shape of the elastic
compared to the water adsorption behavior of its isostructural energy resolution could be fitted by a Gaussian function, whose
rigid V(O)(L) or MIL-47(V) counterpart.66 In this latter ma- half-width at half-maximum (HWHM) varied from 40 μeV at
terial, the substitution of the μ2-OH vertices by the μ2-O groups small Q to 50 μeV at large Q. After measuring the scattering of the
at the MOF surface is expected to enhance its hydrophobicity. At empty MIL, different water concentrations were adsorbed in situ
this point, one emphasizes how the adjustment of the partial at 300 K, starting from the LP form. After the second loading, the
charges carried out by the atoms of the hydrophobic MIL-47 transition to the NP form was observed. The water concentra-
framework is a critical step to get a better agreement between tions were determined from a comparison of the equilibrium
experimental and simulated adsorption isotherms. The confinement pressures with an adsorption isotherm. The largest loading
10765 dx.doi.org/10.1021/jp202147m |J. Phys. Chem. C 2011, 115, 10764–10776
The Journal of Physical Chemistry C ARTICLE

corresponded to 6 H2O/uc (unit cell), so that the reopening of

the structure was not observed.

’ COMPUTATIONAL METHODS
Microscopic Models and Force Fields. The periodic models
of the MIL-47(V) and the large pore (LP) form of MIL-53(Cr)
were built using the atomic coordinates available in the
literature59,66 while the partial charges of both MILs were taken
from our preliminary density functional theory (DFT) calcula-
tions.67 The 12-6 Lennard-Jones (LJ) interatomic potential
parameters and the intramolecular terms for describing the Figure 2. Evolution of the unit cell volume of the MIL-53(Cr) structure
flexible MIL-53(Cr) come from our previous study which has as a function of the number of adsorbed water molecules per unit cell,
successfully captured the breathing of this solid in presence of obtained by molecular dynamics simulations (empty squares) at 300 K.
CO2.65 The 12-6 LJ parameters for the MIL-47(V) were also For comparison, the experimental values are reported when available
taken from our recent investigation.67 (full triangles). The distinction between the LP and NP forms is
The water molecule was treated by the TIP4P-2005 model provided.
developed by Abascal and Vega.68 Such a four-site model has
been successfully used to reproduce the experimental vapor
then run for 10 ns (i.e., 10  106 steps with a time step of 1 fs)
liquid phase equilibrium data. The corresponding partial charges after 1 ns of equilibration. The configurations were further stored
expressed in electron units are 0.5564, 0, and 1.1128 for the H, O, every 3000 timesteps. The self-diffusivities DS were then deter-
and M ((placed on the bisector of the HOH angle at 0.1546 Å mined for each investigated H2O concentration (c) using Einstein
from the oxygen) sites, respectively. The LJ term is centered only relations72 as reported in eq 1
on the oxygen nucleus. * +
1 1 N
The adsorbate/adsorbent LJ interatomic potential parameters
were then calculated using Lorentz
Berthelot mixing rules.
DS ðcÞ ¼ lim
t f ¥ 6t N
j¼1
∑
jj rj ðtÞ
rj ðoÞjj 2 ð1Þ
Molecular Dynamics. Molecular dynamics (MD) simulations
were performed using the DL_POLY_2.19 program69 in the In this equation, Æ...æ denotes an ensemble average, r(t) are the
NσT ensemble, which was able to simulate both the size and positions of the tagged guest molecule while N corresponds to the
shape changes. The Berendsen and Nos
e-Hoover thermostats number of H2O molecules in the simulation volume. Further, in
and barostats were considered for the calculations with the same order to improve the statistics of the calculation, multiple time
relaxation times as used in our previous simulations.65 MD origins, as described elsewhere,72 were used while the DS values
simulations were first conducted at 300 K starting with the were averaged over 5 independent trajectories. Complementary
empty LP structure of the MIL-53(Cr) loaded by a number of MD simulations were performed at different temperatures in the
water molecules ranging from 0.5 to 8 per unit cell, in order to range [300
500 K] for a loading of 2 H2O/uc in order to extract
follow the evolution of the structural features of this material as a the activation energies from the linear least-squares fit to the
function of the water content. Each MD was run for 2 ns with a Arrhenius plots of ln(DS) = f(1000/T).
time step of 1 fs, using 32 unit cells to get good statistics and the The rotational dynamics for water molecules in the MIL-
critical size in order to maintain a consistent cutoff distance of 12 53(Cr) was further determined from these MD runs by calculat-
Å (rc < L/2, L = the smallest length of box) during the whole MD ing the orientational autocorrelation function A(t) defined by
simulations. The electrostatic interactions were calculated using eq 2
the Ewald summation.70 The SHAKE-RATTLE and the usual 5
Velocity Verlet algorithms were used to constrain rigid bonds ÆAð0ÞAðtÞæ ¼ Æð3 cos2 θð0Þ
1Þð3 cos2 θðtÞ
1Þæ ð2Þ
and to integrate the equations of motion. The water molecule 8
was maintained as rigid and the QUATERNION algorithm was where θ is the angle between the molecular end-to-end vector
used to treat the motion of the adsorbate while the framework and the MOF coordinate system. Instead of using a fit of the
was considered as flexible, consistent with our previous study.65 autocorrelation function with three exponential components as
The diffusion process of water was further explored by means proposed by Saengsawang et al.,73 we considered here the time at
of MD simulations run in the NVT ensemble using the Nos
e- which the autocorrelation function drops down to 1/e as the
Hoover thermostat at 300 K for both rigid LP and NP forms. characteristic average time for the rotational reorientation of the
Different water contents ranging between 0.5 to 4 and 0.5 to 8 molecule, following the same approach reported by Wehring
H2O molecules per unit cell in the NP and LP forms respectively et al..74
are investigated. The structure generated by the MD calculations Grand Canonical Monte Carlo Simulations. Grand Canonical
in the NσT ensemble for 5 H2O/uc, was considered as an Monte Carlo (GCMC) simulations were performed by means of the
“average” one that can fairly represent the NP form in the whole Complex Adsorption and Diffusion Simulation Suite (CADSS)
range of pressure explored for this structure. The framework code75 with typically 2.0  108 Monte Carlo steps following 1.5 
atoms of both NP and LP structures were then maintained fixed 107 steps for equilibration. The Ewald summation was also used for
during the MD simulations. We have previously pointed out that calculating the electrostatic interactions while the short-range con-
this assumption does not affect the diffusivity of other adsorbate tributions were computed with a cutoff distance of 12 Å to be
species within the porosity of this structure.67,71 For each loading, consistent with MD calculations. The simulations were conducted at
the initial configurations were generated by preliminary Monte 300 K using both the NP and LP structures as rigid, considering
Carlo simulations in the NVT ensemble. MD simulations were simulation boxes as 32 unit cells that allowed us to evaluate the
10766 dx.doi.org/10.1021/jp202147m |J. Phys. Chem. C 2011, 115, 10764–10776
The Journal of Physical Chemistry C ARTICLE

one (1486 Å
3). A drop in the unit cell volume occurs for 1.5
H2O/uc attaining a value of 950 Å
3, consistent with a NP form.59
For 5 H2O/uc corresponding to the adsorbed amount on the first
plateau of the experimental adsorption isotherm (Figure 3a),
the structure is still in its NP version with a unit cell volume of
1012 Å
3, which is in very good agreement with the one previously
determined by ex-situ X-ray diffraction for similar loading
(1020 Å
3). Further, above 5 H2O/uc, an expansion of the unit
cell volume occurs, suggesting a progressive swelling of this form,
as emphasized for other guest molecules.63,65 This is not
experimentally confirmed in this case since the ex-situ X-ray
diffraction measurements were not performed continuously in
the whole range of pressures investigated by the simulations. The
structure then returns to the LP form for 8 H2O/uc with a
simulated volume of 1475 Å
3 very close to the initial empty form.
Indeed, our simulations predict the predominance of the LP form
at very low loading and above 5 H2O/uc, while the NP version is
present in the intermediate range of loading. In addition to the
agreement between the simulated unit cell volume and the
experimental one available for two loadings, these conclusions
are also consistent with the presence of substeps in the isotherms
around 1 and 6 H2O/uc assigned to the two consecutive
structural switchings from LP to NP and from NP to LP
(see Figure 3a). At higher loadings, the unit cell volumes slightly
increase. This result is also consistent with the recent findings
reported by Guillou et al.76 that determined a unit cell volume of
1550 Å
3 for the superhydrated LP structure. This whole set of
data allowed us to validate the force field used here to describe
the intermolecular water/water and water/MIL framework inter-
actions in complement to the intramolecular interactions within
the MIL-53(Cr) framework.
A further step consisted of simulating the adsorption iso-
Figure 3. (a) Simulated H2O absolute adsorption isotherms at 300 K therms and enthalpies for the rigid NP and LP forms at 300 K
for the LP (open squares) and NP (open circles) compared to the (see Figures 3) using the so-validated force field. Figure 3a
gravimetry data (triangles). (b) Calculated and experimental H2O
adsorption enthalpy following the same labels than in (a). (c) Compar-
reports the two simulated isotherms for pressures varying from 0
ison between the composite adsorption isotherm (open circles), to 50 mbar, close to the saturation pressure at 300 K (∼37 mbar).
built from the simulated isotherms obtained individually for the LP One can observe the following two distinct behaviors: while the
and NP forms and the (LP, NP) fractions estimated from infrared adsorption isotherm calculated for the NP form presents a rapid
spectroscopy32 and the experimental gravimetry adsorption isotherm increase of the adsorbed amount up to a saturation of 5 H2O
(solid lines). molecules/uc, the adsorption in the LP form starts with a very
small uptake at low pressure (5 mbar) leading to the presence of a
absolute adsorption isotherms and the adsorption enthalpies. A plateau, followed by a sudden increase up to reach 21 H2O/uc at
composite approach that we already successfully employed for other 40 mbar. In this latter case, one obtains a type-V isotherm usually
gases12,64,71 in this material, was further considered to describe a observed for systems where the adsorbate/adsorbent interaction
simulated adsorption isotherm in the whole range of pressure by is rather weak. Indeed, the interaction between the water
considering the isotherms calculated in both rigid LP and NP forms molecules and the MIL-53(Cr) framework at low pressure
and the fractions of the two forms present along the pressure range strongly differs in both forms. This different behavior is also con-
that were taken from previously reported infrared measure- firmed from an energetic point of view. As observed in Figure 3b,
ments.32,64,65 the adsorption enthalpies calculated at low coverage significantly
deviate with values centered around
50 and
39 kJ 3 mol
1 for
the NP and the LP forms, respectively, that need to be compared
’ RESULTS AND DISCUSSION to the vaporisation enthalpy for water (∼
44 kJ 3 mol
1)77 at
The structural evolution of the MIL-53(Cr) solid (see Figure 1) room temperature. Both isotherm and enthalpy profiles simu-
upon water adsorption was first investigated using NσT MD lated for the LP form in the low domain of pressure thus suggest a
simulations based on the force field described above. Figure 2 soft hydrophobic-like behavior of this structure while the water
summarizes the simulated unit cell volumes for MIL-53(Cr) as a adsorption is favored in the NP version. It results that such a
function of the water loading which varies from 0.5 to 8 H2O water-assisted structural transition drastically modifies the hy-
molecules/uc in order to span the whole pressure range of the drophobic/hydrophilic character of the MIL-53(Cr) material.
adsorption isotherm (Figure 3a). For 0.5 and 1 H2O/uc, the The comparison of these simulated data with both experimental
structure remains in its initial LP form with a unit cell volume at adsorption isotherm and enthalpy (Figure 3a,b), recently re-
1510 Å
3 very close to the one simulated in absence of water ported by some of us,32 is then employed to validate such
(1490 Å
3) that further compares very well with the experimental findings. One first observes that the experimental adsorption
10767 dx.doi.org/10.1021/jp202147m |J. Phys. Chem. C 2011, 115, 10764–10776
The Journal of Physical Chemistry C ARTICLE

In order to quantitatively analyze the experimental adsorption

isotherm and more particularly in the two transition regions
where both LP and NP forms can coexist, a “composite”
approach is required. It is based on the determination of a global
adsorption isotherm from those calculated individually in both
rigid NP and LP forms using eq 3

N sim ðpÞ ¼ XLP

sim
ðpÞNLP
sim
ðpÞ þ XNP
sim
ðpÞNNP
sim
ðpÞ ð3Þ

where XLP(p) and XNP(p) are the fractions of the LP and NP

forms respectively for a given pressure p, that have been
previously extracted from infrared measurements,32 NNP(p)
and NLP(p) are the adsorbed amounts of H2O simulated in the
NP and LP rigid forms respectively and N(p) the total uptake for
a given pressure p. The resulting simulated “composite” adsorp-
tion isotherm is in good agreement with the experimental one
obtained by gravimetry (note that, for the high pressure range,
the comparison is made with the experimental desorption branch
as seen in Figure 3c). Our simulations predict a pressure for the
first structural LP to NP transition slightly shifted compared to
the experimental one. This deviation can be explained by the fact
that our calculations are based on the NP/LP fractions estimated
by infrared spectroscopy whose equilibrium conditions can
slightly differ from those considered during the gravimetry
measurements.32
Such behaviors could be rationalized by simply looking at the
exposure of the hydrophilic (inorganic part) and hydrophobic
(aromatic ring) parts of the framework (see Figure 1). Whereas
both parts are accessible toward guests in the LP form, the NP
form presents rather segregated hydrophobic and hydrophilic
Figure 4. The 2D density plots for water in the NP form of MIL-53(Cr) portions, associated with an almost close packing of the phenyl
at 300 K obtained from GCMC simulations through the xy plane for rings which becomes less accessible toward guests. To get some
1 H2O/uc. Red regions correspond to the higher probability of contain- insights into the microscopic adsorption mechanism, the prob-
ing H2O molecules (a). Typical arrangements of the water molecules in ability density of water in the pore of the NP form was calculated
the NP form obtained at low (1 mbar) (b) and high loadings (10 mbar)
(c). The distances (in Å) reported in green and blue correspond to the
from the analysis of the configurations stored during the GCMC
interactions between the water molecules and the MOF framework simulations. At low loading, the water molecules are homoge-
while those in white are between water molecules. neously distributed within all the pores of the MIL-53(Cr) as
shown in Figure 4a. Further, in addition to the hydrogen bonds
they establish between each other, the water molecules interact
isotherm shows two steps, confirming small uptake at very strongly with the two opposite pore walls of the material via
low pressure with the presence of a plateau that corresponds hydrogen bonds between (i) their oxygen atoms Ow and the
to the adsorption occurring initially in the LP form. Such protons of the μ2-OH groups and (ii) their protons Hw and the
“hydrophobic” character of the MIL-53(LP) form is also oxygen atoms of the carboxylate groups as illustrated in Figure 4,
confirmed by the very low experimental adsorption enthalpy c. It is clearly stated from the radial distribution functions calcu-
measured at the initial stage of adsorption (
35 kJ 3 mol
1)32 lated at low loading for the Ow
Ow pair (Figure 5a) that the
(Figure 3b) in agreement with the simulated value (
39 kJ 3 hydrogen bonds are slightly stronger than in the bulk state with
mol
1), which both remain significantly below the vaporisa- characteristic mean Ow
Ow distances of 2.6 and 2.8 Å
,68
tion enthalpy. For the pressure range comprised between 7 respectively. One can further notice from Figure 5b that the
and 30 mbar, the experimental isotherm is well described by average Ow
H(μ2-OH) distances (1.6 Å
) are shorter than the
the simulated one for the NP structure (Figure 3a), which ones between the water molecules (Ow
Hw of 1.9 Å
). This
supports that this form is predominantly present in this range means that the interactions between the water molecules and the
of pressure as claimed above. One notices that the adsorbed MIL-53(Cr) surface are stronger than those in play between the
amount does not reach a plateau but rather continuously water molecules themselves, which is in agreement with a higher
increases, consistent with the predicted progressive swelling acidity of the μ2-OH group. Moreover, the water molecules are
of the NP form as reported by Figure 2. Further, the experi- highly orientated along the direction of the tunnel whatever the
mental adsorption enthalpy reaches in this range of pressures loading, as illustrated in Figure 4b,c for different loadings. These
a plateau around
58 kJ 3 mol
1 which is in agreement with resulting geometries are consistent with those previously re-
the value calculated for the water adsorption in the NP form ported by DFT calculations and ex-situ X-ray diffraction.32
(
55 kJ 3 mol
1) (Figure 3b). Above 30 mbar, the isotherm The situation drastically differs in the case of the LP form of
shows a sudden uptake which corresponds to the second the MIL-53(Cr). One first observes that the water molecules are
structural switching (from the NP to the LP form) as not homogeneously distributed within all the pores of the
discussed above. material at the low pressure. As a typical illustration, Figure 6a
10768 dx.doi.org/10.1021/jp202147m |J. Phys. Chem. C 2011, 115, 10764–10776
The Journal of Physical Chemistry C ARTICLE

Figure 5. Radial distribution functions for Ow
Ow interactions (Ow for oxygen water) in MIL-53(Cr)-LP and -NP, MIL-47(V) and bulk water (a),
Ow
H(μ2-OH) (dash lines) and Ow
Hw (straight lines) in MIL-53(Cr) LP and NP (b), and Ow
O(μ2-OH or -O) in MIL53(Cr)-LP and NP and in
MIL-47(V) (c) at low loading. The blue, red, and green lines correspond respectively to the MIL-53(Cr)-LP, -NP and MIL-47(V). The bulk water is
represented by black lines.

clearly shows that only one pore is partially filled while the others change of the affinity of this zeolite from an hydrophobic to a
are almost empty that is consistent with a soft hydrophobic hydrophilic character.78 One can thus suspect that the presence
character of this structure as mentioned above. When the of the μ2-OH group plays a similar role allowing the water
pressure increases, the filling of the pores occurs in such a way molecules to initiate the formation of clusters and condensate.
that the water molecules form small clusters instead of interacting Such statement would result on a fully hydrophobic character of
each with the pore wall (Figure 6b,c). This is mainly due to the MIL-47(V) structure that is confirmed by our simulations
stronger water/water interactions compared to the H2O/MIL (Figure 7). Indeed, the distribution of water molecules is strongly
surface (see RDFs in Figure 5), as already observed in the case of heterogeneous, as shown in Figure 7a, with either completely
the adsorption of water and alcohol in silicalite78 and in ZIF,44 empty or filled pores, consistent with the behavior previously
respectively. Indeed, there is only limited intermediate filling pointed out in several zeolites including silicalite-1 and DAY
state of the channel although one observes some transitional qualified as hydrophobic solids.87 This trend remains true up to
intervals when the pore gets filled (Figure 6a). Such a behavior high pressures. As confirmed by the RDF plots in Figure 5c, the
has already been reported for water in several zeolites55,75 and interactions between the H2O molecules and the pore wall of
more recently in the MOFs.58,79
81 At higher pressure, the MIL-47(V) is comparable to those observed for the MIL-53-
hydration mechanism imposes a water cluster-growth adsorption (Cr)-LP. The water molecules are then arranged in a such a way
process similarly to the case of silicalite or NaA55,82,83 and to form clusters within the center of the porosity. They are
typically accepted as the water adsorption mechanism in most constituted by up to 12 H2O at high loading as illustrated in
porous solids.84 Typical configurations are provided in Figure 6c Figure 7c. This situation becomes more similar to the number of
at high loadings with the formation of a cluster constituted by 10 water molecules implicated in the clusters (14 for tetrahedral
H2O molecules with a cylindrical/spherical shape in a similar way clusters) for the bulk water, while the number of hydrogen bonds
than in the liquid phase where up to 14 water molecules are between water molecules at saturation (2.9) remains lower than
implicated in the formation of the tetrahedral clusters.85 Such an in the bulk phase.
arrangement is in good agreement with those recently elucidated The simulation of the adsorption isotherms in the case of MIL-
in this material by ex-situ X-ray diffraction experiments.76 At the 47(V) imposes to rescale the partial charges. Indeed, as seen in
saturation, up to 2.5 hydrogen bonds per water molecules can be Figure 8a, the comparison between experimental data and
formed in this LP form. Although this number is larger than those simulated results shows a large discrepancy if we consider the
calculated at the saturation in the NP form (1.8), it remains lower previous partial charges validated for CH4 and CO2 adsorption
than in the bulk water (3.6 hydrogen bonds).86 and diffusion.64,65,67 As suggested previously by other authors,57,58,88,89
If one compares now this behavior with those observed in the one way to take into account that the water adsorbed in porous
isostructural MIL-47(V) where the μ2-OH sites of the LP form solids is in a less polarizing media than in bulk water consists of
are substituted by the μ2-O group with a lower affinity for water, adjusting the partial charges of the atoms of the pore wall, which
one would expect a more pronounced hydrophobic character of allows one to simulate correctly the condensation of water in
the MIL surface. This behavior is consistent with previous studies hydrophobic solids before the saturation pressure. Here, four
in silicalite where the presence of chemical defaults leads to the different charges distributions were tested: 100 (if we consider
10769 dx.doi.org/10.1021/jp202147m |J. Phys. Chem. C 2011, 115, 10764–10776
The Journal of Physical Chemistry C ARTICLE

Figure 6. The 2D density plots for water in the LP form of MIL-53(Cr)

at 300 K obtained from GCMC simulations through the yz plane for
1 H2O/uc. Red regions correspond to the higher probability of contain- Figure 7. The 2D density plots for water in the MIL-47(V) (a) at 300 K
ing H2O molecules (a). Typical arrangements of the water molecules in obtained from GCMC simulations through the xy plane obtained for
the LP form obtained at low (2 mbar) (b) and high loadings (15 mbar) 1H2O/uc. Red regions correspond to the higher probability of contain-
(c). The distances (in Å) reported in green and white correspond to ing H2O molecules. Typical arrangements of the water molecules in the
those separating the water molecules and the framework and between MIL-47(V) at low loading (10 mbar) (b) and high loading (40 mbar)
water molecules themselves, respectively. In blue, additional information (c). The distances (in Å) reported in green and white correspond to
is reported for distance between the water molecules and the oxygen of distances between water molecules
framework and between water
the carboxylate groups. molecules
water molecules, respectively. In blue, additional informa-
tion is reported for distance between water molecules and carboxylate
the partial charges calculated by Rosenbach et al.67), 70 (if we oxygen.
consider only 70% of all the partial charges from Rosenbach
et al.67), 50, and 30%. It comes that the calculations performed 30 mbar in MIL-47(V) (vs 15 mbar in the LP structure), that
with 30% of the initial charges reproduce better the experimental is, closer to the saturation pressure of water.
condensation zone (15
33 mbar vs ∼30 mbar) (Figure 8a). An Molecular dynamics simulations were further employed at
additional charge distribution, already proposed to simulate the 300 K to explore the concentration dependence of the self-
adsorption of alkanes in MIL-47(V),90 has also been tested but it diffusivity (DS) for water in the two MIL-53(Cr) forms. The
does not improve the description of the experimental data (see corresponding evolutions of DS as a function of the loading are
Supporting Information Figure S1), predicting a condensation at provided in Figure 9. Note that the reported DS correspond to
higher pressure. orientationnally averaged values, while the MSD plots show that
We should note that in the case of the hydrophilic NP form of the displacements mainly occur along the direction of the tunnel.
MIL-53(Cr) material, there is no need to rescale the charges to One observes that DS decreases gradually when the loading
modulate the water
pore wall interaction as attested by the very increases for both forms. Such decreasing DS profiles are
good agreement between experimental and simulated low cover- explained by the decrease of the free space available for the
age enthalpies. For consistency, the LP form is also simulated diffusion combined to an increase of the water/water interactions
using the same partial charges. The comparison of the when the adsorbate concentration increases. Further, the diffu-
isotherm obtained for MIL-47(V) and the MIL-53(Cr)-LP is sivity remains faster in the LP form within the whole range of
given in the Figure 8b. One clearly shows that the hydrophobic water loading with DS values ranging from 8  10
10 to 1.5 
character is less marked in the MIL-53(Cr)-LP form than 10
11 m2 3 s
1 and from 10
9 to 2.5  10
11 m2 3 s
1 in the NP
in MIL-47(V), where the hydration process starts only at and LP versions, respectively. This result is not surprising as the
10770 dx.doi.org/10.1021/jp202147m |J. Phys. Chem. C 2011, 115, 10764–10776
The Journal of Physical Chemistry C ARTICLE

Figure 11. Arrhenius plots for extracting the activation energy for
2 H2O/uc at 300 K in both LP (solid circles) and LP forms (open
squares) of MIL-53(Cr).

clays (1.4  10
10 m2 3 s
1)91,92 and zeolites NaY (5.0 

10
10 m2 3 s
1 at 400 K).93
A further step consisted of comparing these simulated data
with those obtained by QENS measurements. The QENS
spectra (Figure 10) can be analyzed only in terms of hydrogen
motions, because of the large incoherent cross-section of this
Figure 8. (a) Influence of the partial charges distribution (100% black; atom. In principle, such spectra contain information on both
70% red; 50% green; 30% blue) on the adsorption isotherm of MIL- rotational and translational motions of water. However, by fitting
47(V) at 300 K and comparison with the experimental data (cyan curve).
(b) Comparison between the simulated adsorption isotherms for MIL-
the measured intensities by scattering functions corresponding to
47(V) (stars) and for the LP form of MIL-53(Cr) (squares). these two motions, it becomes clear that the translation was too
slow to produce any quasi-elastic broadening. This implies
that the self-diffusion coefficient of water is lower than 5 
10
10 m2 3 s
1, whatever the loading that is consistent with the
range of values predicted by our simulations. Experiments with a
higher energy resolution, such as those proposed by Paoli et al.,94
would be necessary to characterize the translational diffusion of
water in MIL-53(Cr). However, it was possible to derive a
rotational diffusion coefficient, DR, by fitting simultaneously all
spectra. The so-obtained values range between 4 and 6 
1010 s
1, DR being larger at smaller concentration. From
simulations, the averaged correlation time for water molecules
in the LP form is about 50 ps at low loading (1H2O/uc) while it
reaches 2 ns at high loading (7H2O/uc) (Supporting Informa-
Figure 9. Self-diffusion coefficients for water calculated at 300 K in both tion Figures S2 and S3), which is within the same order of magni-
the NP (empty squares) and the LP (solid circles) forms of MIL-53(Cr). tude than those determined by PFG NMR in the case of alkanes
The mean error bar for the simulated DS is estimated to be 10%. in Cu-BTC.74 Further, the DR value calculated for 1 H2O/uc in
the LP form is 1.4  1010 s
1 within the same range of magnitude
than those obtained by QENS but much lower than in the bulk
water (1.5 ps and 60  1010 s
1).92 In the case of the NP form, it
is rather difficult to estimate such time as the high confinement
strongly limits the degree of freedom of the water molecules.
The activation energies for the diffusion in both MIL-53(Cr)
structures have been calculated for a loading of 2 H2O/uc by
determining the diffusion coefficients at three temperatures (300,
400, and 500 K) (Figure 11). As already emphasized for other
gases in this solid,67,71,95
97 the diffusion process is a temperature
activated process and follows an Arrhenius law. Figure 11 reports
Figure 10. Comparison between experimental and fitted QENS spectra activation energies of 39.5 and 29.8 kJ 3 mol
1 for the NP and LP
obtained at 300 K for H2O in MIL-53(Cr). The solid line results from forms, respectively, that are within the same range of values than
the convolution of a rotational diffusion model with the instrumental those previously observed in zeolites such as NaX (48 kJ 3 mol
1)
resolution (6 H2O/uc, Q = 1.35 Å
1). and NaY (35 kJ 3 mol
1).93 This trend is consistent with a faster
diffusivity simulated in the LP form.
confinement degree is much higher in the NP structure. A further step consisted of analyzing the MD trajectories in
Further, these ranges of DS values are lower than those order to provide a full picture of the diffusion mechanism in this
obtained in the liquid state at 300 K, that is, 2.3  10
9 material. Regarding the LP form, the diffusion process is found to
m2 3 s
1, while in the LP form, they are slightly higher compared be of 1D type as previously observed for other gases67,71,95
97 in the
to the situation in other confined nanoporous solids including same form of this solid. An illustration is provided in Figure 12a
10771 dx.doi.org/10.1021/jp202147m |J. Phys. Chem. C 2011, 115, 10764–10776
The Journal of Physical Chemistry C ARTICLE

Figure 12. Typical illustration of the 1D microscopic diffusion mechan-

ism of H2O in the LP form of MIL-53(Cr) through the xz plane at (a)
low loading (2 H2O/uc) deduced from the 2D probability density plots
extracted from the MD runs. Panel b illustrates the 1D type diffusion
mechanism at high loadings through the xy plane, confirming the jump
sequence between the μ2-OH groups at low loadings through the xy
plane, between the white dash lines.

Figure 14. Illustration of the single-file diffusion mechanism in the NP

form of MIL-53(Cr) through the xz plane (corresponding to the pore
section); the sequence of the blue, yellow, and green water molecules is
not modified as illustrated in the three snapshots extracted from the MD
trajectory at different times corresponding to 0.5, 1, and 2 ns.

motions of the water are predominantly orientated along the

direction of the tunnel, this behavior remaining true whatever the
H2O loading. Further, one can imagine (Figure 12a,b) a jump
sequence between two consecutive μ2-OH groups that act as
steric barriers, the displacements along the two other axes being
negligible with the absence of any density probability.
In contrast, the diffusion mechanism for water in the NP form
is strongly confined in the middle of the pores; the displacements
of the water molecules occur through a more restricted diffusion
corridor involving simultaneous interactions with the two oppos-
ing sides of the same pore. This behavior is illustrated from the
Figure 13. Typical illustration of the microscopic diffusion mechanism 2D density plots calculated in the NP form at low loading
of H2O in the NP form of MIL-53(Cr) through the xy plane at (a) low (1H2O/uc) (see Figure 13a); the same situation is also observed
loading (2 H2O/uc) and (b) through the xz plane at high loading at intermediate and higher loadings. Further, the 2D density plots
(4 H2O/uc) from the 2D probability density plots calculated by MD represented through the xz plane (Figure 13b) suggests that the
simulations. diffusion is more continuous along the direction of the tunnel
rather than a jump sequence observed in the LP form. One can
where the trajectory of H2O at low concentration in this LP form determine a diffusion corridor section of 5 Å
, that is very similar
can be roughly drawn by following the higher density region to the ones we previously reported for other adsorbates mol-
provided by the 2D density plots. It is clearly observed that the ecules in such a material.98 Because of the high confinement in
10772 dx.doi.org/10.1021/jp202147m |J. Phys. Chem. C 2011, 115, 10764–10776
The Journal of Physical Chemistry C ARTICLE

this NP structure, the water molecules tend to move via a ’ ASSOCIATED CONTENT
single-file diffusion process, that is, the water molecules are not
able to cross each other along the direction of the tunnel. This bS Supporting Information. Additional simulated data in-
peculiar dynamical behavior is illustrated by three snapshots cluding Figures S1, S2, and S3. This material is available free of
extracted from the MD trajectory for 2 H2O/uc at different charge via the Internet at http://pubs.acs.org.
time intervals (Figures 14) which clearly show that the
sequence of the water molecules along the tunnel remains ’ AUTHOR INFORMATION
the same along the simulation. Such an unusual diffusion type
Corresponding Author
is consistent with what has already been evidenced in the case *E-mail: guillaume.maurin@univ-montp2.fr.
of CO2 in the same NP form.71 Further analysis allowed us to
estimate a mean residence time of the H2O molecules around
the μ2-OH groups for a loading of 2 H2O/uc to be 50 ps in this ’ ACKNOWLEDGMENT
NP form. As a comparison, this value is significantly higher
This work was supported by French programs ANR CO2
than the one we previously determined for H2 in the LP form
NoMAC (ANR-06-CO2-008). We thank the Institut Laue-
(5 ps).95
Langevin, Grenoble, France, for the provision of neutron beam
One should notice that the self-diffusivity for water is almost
time and Dr. M. M. Koza for his help during the measurements
similar in both forms at very low loading (0.5 H2O/uc). Such a
on the IN6 spectrometer. We are very grateful to Dr. Qingyuan
behavior can be explained by the fact that the global diffusion
Yang from Beijing University of Chemical Technology for
mechanism of the water molecules is governed by two factors:
providing us the CADSS GCMC code.
the residence time spent by the water molecules close to the μ2-
OH groups and the jump time required to pass from one μ2-OH
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