org/Langmuir
2010 American Chemical Society
MIL-101 is a chromium terephthalate-based mesoscopic metal-organic framework and one of the most porous
materials reported to date. In this study, we investigate the adsorption of CO2 and CH4 in dehydrated and hydrated
MIL-101 and the effect of terminal water molecules on adsorption. The atomistic structures of MIL-101 are constructed
from experimental crystallographic data, energy minimization, and quantum mechanical optimization. The adsorption
isotherm of CO2 predicted from molecular simulation agrees well with experiment and is relatively insensitive to the
method (Merz-Kollman or Mulliken) used to estimate the framework charges. Both the united-atom and five-site
models of CH4 predict the isotherm fairly well, though the former overestimates and the latter underestimates.
Adsorption first occurs in the microporous supertetrahedra at low pressures and then in the mesoscopic cages with
increasing pressure. In the dehydrated MIL-101, more adsorbate molecules are located near the exposed Cr2 sites than
the fluorine saturated Cr1 sites. The terminal water molecules in the hydrated MIL-101 act as additional interaction sites
and enhance adsorption at low pressures. This enhancement is more pronounced for CO2 than for CH4, because CO2 is
quadrapolar and interacts more strongly with the terminal water molecules. At high pressures, however, the reverse is
observed, as the presence of terminal water molecules reduces free volume and adsorption. For the adsorption of CO2/
CH4 mixture, a higher selectivity is found in the hydrated MIL-101.
Langmuir 2010, 26(11), 87438750 Published on Web 01/27/2010 DOI: 10.1021/la904502h 8743
Article Chen et al.
Figure 1. Unit cell of dehydrated MIL-101 constructed from experimental crystallographic data, energy minimization, and density
functional theory calculation (see the text for details). The pentagonal and hexagonal windows are enlarged for clarity. Color code: Cr,
orange polyhedra; F, cyan; C, blue; O, red; H, white.
with adsorbates.14 Further, gas cluster formation for adsorption In this study, we investigate the adsorption of CO2 and CH4 in
in MOFs was observed at subcritical temperatures.15 Several MIL-101 at 303 K combining quantum mechanics and molecular
recent reviews have highlighted the central importance of mole- simulation. To examine the role of terminal water molecules
cular simulations in characterizing MOFs for adsorption coordinated to metal sites, the adsorption is examined in both
applications.16-18 dehydrated and hydrated structures. We first introduce the
There has been considerable interest in gas adsorption in the molecular models in section 2, and in section 3, the simulation
MIL (Material Institute Lavoisier) series of MOFs. Upon CO2 methods are briefly described. In section 4, the adsorption
adsorption in MIL-53, a structural transformation was observed isotherms, simulation snapshots, and radial distribution functions
between the large- and narrow-pore forms.19 The favorable sites in are presented and discussed. The adsorption of the CO2/CH4
MIL-53 (Al, Cr) and MIL-47 (V) were identified for CO2 adsorp- mixture is also examined. The concluding remarks are summar-
tion to elucidate the adsorption mechanism and breathing effect.20 ized in section 5.
A record high uptake of 40 mmol/g at 303 K and 50 bar was found
for CO2 in MIL-101.21 A related study reported the adsorp- 2. Models
tion properties of CO2 and CH4 along with C3H8, SF6, and Ar MIL-101 is assembled by corner-sharing supertetrahedra,
in MIL-101 using a standard gravimetric method.22 MIL-101 is a which consist of Cr3O trimers and 1,4-benzenedicarboxylic
chromium terephthalate-based mesoscopic MOF and one of acids.23 The supertetrahedra are microporous with an 8.6 A free
the most porous materials reported to date. It is stable in air or aperture. The 4 vertices and 6 edges of the supertetrahedra are
boiling water, and its structure is not altered in organic solvents occupied by the trimers and organic linkers, respectively. MIL-101
or solvothermal conditions. These remarkable properties and the
has an augmented three-dimensional MTN zeotype structure
highly porous structure have resulted in great interest in MIL-101
with a very large cell volume (702 000 A3). Two types of
for gas storage, catalysis, drug delivery, and other versatile applica-
mesoporous quasi-spherical cages exist in MIL-101: a small cage
tions.23 Despite a number of experimental studies in this unique
of 20 supertetrahedra and a free diameter of 29 A accessible
MOF,24 we are not aware of any molecular simulation study
through a pentagonal window with a 12 A aperture, and a large
reported for gas adsorption in MIL-101. However, such molecular
cage of 28 supertetrahedra and a free diameter of 34 A accessible
information is important to understand the microscopic adsorp-
through both hexagonal and pentagonal windows with a 14.7
tion behavior and facilitate the development of new superadsor-
16 A2 aperture. MIL-101 is highly porous with BET and Lang-
bents.
muir surface areas of about 4100 ( 200 and 5900 ( 300 m2/g,
respectively. Each octahedral Cr is bonded to 4 oxygen atoms
(14) Dubbeldam, D.; Krishna, R.; Snurr, R. Q. J. Phys. Chem. C 2009, 113, 19317. from carboxylates, 1 3O oxygen atom, and 1 terminal site. The
(15) Krishna, R.; van Baten, J. M. Langmuir 2009, in press.
(16) Duren, T.; Bae, S. Y.; Snurr, R. Q. Chem. Soc. Rev. 2009, 38, 1237. terminal site could be occupied by a fluorine atom or a terminal
(17) Keskin, S.; Liu, J.; Rankin, R. B.; Johnson, J. K.; Sholl, D. S. Ind. Eng. water molecule. As a consequence, there are 3 terminal sites in
Chem. Res. 2009, 48, 2355.
(18) Krishna, R. J. Phys. Chem. C 2009, 113, 19756. each Cr3O trimer and the ratio of fluorine to water is 1:2. The
(19) Ramsahye, N. A.; Maurin, G.; Bourrelly, S.; Llewellyn, P. L.; Devic, T.; terminal water molecules can be removed after dehydration, thus
Serre, C.; Loiseau, T.; Ferey, G. Adsorption 2007, 13, 461. providing exposed metallic Lewis acid sites in MIL-101.23
(20) Ramsahye, N. A.; Maurin, G.; Bourrelly, S.; Llewellyn, P. L.; Serre, C.;
Loiseau, T.; Devic, T.; Ferey, G. J. Phys. Chem. C 2008, 112, 514. Figure 1 shows a unit cell of dehydrated MIL-101, in which the
(21) Llewellyn, P. L.; Bourrelly, S.; Serre, C.; Vimont, A.; Daturi, M.; Hamon, pentagonal and hexagonal windows are enlarged for clarity. We
L.; De Weireld, G.; Chang, J. S.; Hong, D. Y.; Hwang, Y. K.; Jhung, S. H.; Ferey,
G. Langmuir 2008, 24, 7245.
constructed the unit cell in a three-step process based on experi-
(22) Chowdhury, P.; Bikkina, C.; Gumma, S. J. Phys. Chem. C 2009, 113, 6616. mental crystallographic data and computational methods. Each
(23) Ferey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F.; Dutour, J.; Surble, Cr3O trimer in the crystallographic data was coordinated with
S.; Margiolaki, I. Science 2005, 309, 2040.
(24) Hong, D. Y.; Hwang, Y. K.; Serre, C.; Ferey, G.; Chang, J. S. Adv. Funct. three terminal water molecules. In the first step, all disordered and
Mater. 2009, 19, 1. terminal water molecules in the crystallographic data were
Figure 2. Optimized geometry and Merz-Kollman (MK) charges of the Cr3O trimer with terminal fluorine and water molecules in (a)
dehydrated and (b) hydrated MIL-101. The cleaved bonds of Cr3O (indicated by the circles) were saturated by methyl group. Color code: Cr,
orange; F, cyan; C, blue; O, red; H, white.
Figure 3. Electrostatic potential maps around the Cr3O trimer in (a) dehydrated and (b) hydrated MIL-101.
removed (actually only the oxygen atoms of water molecules were into heavier atoms and p-type polarization into hydrogen atoms.
removed as the hydrogen atoms were not in the data). To In both dehydrated and hydrated MIL-101, the optimized dis-
construct hydrated MIL-101, one terminal water molecule in tance from F to Cr1 was found to be approximately 1.86 A. In the
each Cr3O trimer was removed. In the second step, hydrogen and hydrated MIL-101, the oxygen atom (OW) of terminal water to
fluorine atoms were added to phenyl rings and exposed Cr sites Cr2 is about 2.26 A.
(one in each Cr3O trimer). For hydrated MIL-101, hydrogen The DFT calculations also gave electrostatic potential maps
atoms were also added to the oxygen atoms of terminal water around the trimer. Figure 3 illustrates that the fluorine atom
molecules. The unit cell was then energetically minimized using possesses large electronegativity in both dehydrated and hydrated
Materials Studio,25 in which the framework atoms were repre- MIL-101. The significant difference is the electric fields generated
sented by the universal force field (UFF).26 The phenyl rings in by the terminal H2O molecules in the hydrated MIL-101. As we
experimental crystallographic data were slightly nonplanar and shall see, this has an intriguing effect on adsorption. The atomic
transformed to planar after energy minimization. In the third charges of MIL-101 framework atoms were fitted to the electro-
step, geometry optimization was conducted by density-functional static potentials using the Merz-Kollman (MK) scheme.27,28 It is
theory (DFT) in DMol326 to precisely determine the positions of worthwhile to note that the concept of atomic charges is solely an
the added hydrogen and fluorine atoms. Because of the very large approximation, and no unique straightforward method is cur-
number of atoms in a unit cell, the DFT optimization was rently available to determine them on a rigorous level. To evaluate
performed on a Cr3O trimer as shown in Figure 2. To maintain the sensitivity of framework charges, the Mulliken population
the original hybridization, the cleaved bonds of the trimer were analysis29 was also used to estimate the charges.29 The MK and
saturated by methyl groups. The Becke exchange plus Lee- Mulliken charges are listed in Figure 2 and Supporting Informa-
Yang-Parr correlation functional and all-electron core potentials tion Figure S1, respectively.
were used. The double- numerical polarization (DNP) basis set The free volumes of the dehydrated and hydrated MIL-101
was adopted, which is comparable to the 6-31G(d,p) Gaussian- structures were estimated by Monte Carlo method.30 A single
type basis set. The DNP basis set incorporates d-type polarization
(27) Singh, U. C.; Kollman, P. A. J. Comput. Chem. 1984, 5, 129.
(28) Besler, B. H.; Merz, K. M., Jr.; Kollman, P. A. J. Comput. Chem. 1990, 11,
(25) Materials Studio, 4.3 ed.; Accelrys, San Diego, 2008. 431.
(26) Rappe, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard, W. A.; Skiff, W. M. (29) Mulliken, R. S. J. Chem. Phys. 1955, 23, 1833.
J. Am. Chem. Soc. 1992, 114, 10024. (30) Myers, A. L.; Monson, P. A. Langmuir 2002, 18, 10261.
Figure 5. Adsorption isotherms of CO2 and CH4 based on the number of adsorbed molecules per unit cell.
experimental data are included from the study by Llewellyn et al.21 of CH4 in both dehydrated and hydrated MIL-101 are in good
They measured the adsorption of CO2 and CH4 in three MIL-101 agreement with the experimental data. The dehydrated MIL-101
samples, namely, MIL-101a as-synthesized, MIL-101b activated exhibits greater adsorption than its hydrated counterpart at high
by ethanol, and MIL-101c activated by ethanol and KF.21 These pressures. As will be seen, however, the opposite is observed at
samples differ primarily in the amount of residual terephthalic low pressures due to the presence of terminal water molecules.
acid and in the density of Lewis acid Cr sites (500, 700, and CO2 adsorption is apparently greater than CH4 because CO2
1000 mol/g, respectively). CH4 adsorption was found to be has a quadrupole moment and thus interacts more strongly with
essentially the same in all three samples. However, CO2 adsor- the adsorbent. The simulated isotherms of CO2 in dehydrated and
ption was affected by the activation method, and the extent of hydrated MIL-101 compare fairly well with the experimental data
adsorption increased in the order of MIL-101a < MIL-101b < in MIL-101b and MIL-101c samples. The deviations can be
MIL-101c.21 Among the three samples, MIL-101b and MIL-101c attributed primarily to the difference between theoretical model
were activated more thoroughly and contained less residual and real sample. In our study, the model does not contain any
terephthalic acid and more open Cr sites; consequently, they residual terephthalic acid, though some probably remained in the
had stronger interactions with CO2 and larger free volume than sample. CO2 uptake in MIL-101 at 50 bar ranges from 30 to 40
MIL-101a. The dehydrated MIL-101 model in our study is similar mmol/g depending on the activation method, which is higher than
to experimental MIL-101b and MIL-101c rather than MIL-101a. that in IRMOF-1 (22 mmol/g)3 and Cu-BTC (11 mmol/g),3 and
As seen in Supporting Information Figure S4, the predicted CO2 comparable to that in MOF-177 (33.5 mmol/g at 42 bar)3 and
adsorption from the MK and Mulliken charges match well with UMCM-1, IRMOF-10, and IRMOF-14 (40-45 mmol/g).10
the experimental data of MIL-101b and MIL-101c. This validates Similar to that observed in CH4 adsorption, the dehydrated
the models and force fields used in our study and suggests that MIL-101 exhibits greater adsorption for CO2 at high pressures,
CO2 adsorption is relatively insensitive to the method, either MK but the reverse is true at low pressures, which will be further
or Mulliken, for the framework charges. Unless otherwise stated, discussed below.
the results for CO4 presented below are based on the MK charges. Figure 5 shows the adsorption isotherms of CO2 and CH4 on
4.2. United-Atom and Five-Site Models of CH4. To the basis of the number of adsorbed molecules per unit cell. At low
examine the performance of the united-atom and five-site models pressures, the adsorption particularly of CO2 in the hydrated
of CH4, Supporting Information Figure S3 shows the adsorption MIL-101 is greater than in the dehydrated framework. Interest-
isotherms of CH4 in the dehydrated MIL-101 predicted from both ingly, the opposite is observed at high pressures. Such a phenom-
models. Because CH4 adsorption was found experimentally to be enon was recently also found for the adsorption of CO2 and CH4
insensitive to the activation method, only the experimental data in in microporous Cu-BTC40 and of CO2/H2 mixture in charged soc-
MIL-101c are included in Supporting Information Figure S3. The MOF.41 At low pressures, the enhanced adsorption in the
predictions of both united-atom and five-site models are in fairly hydrated MIL-101 is attributed to the terminal water molecules
good agreement with the experimental data, especially at low that act as additional adsorption sites; thus, adsorbates experience
pressures. Nevertheless, the united-atom model overestimates, stronger interactions. As seen in Figure 5a, the enhancement is
whereas the five-site model underestimates the extent of adsorp- more pronounced for CO2 than CH4. This is because CO2 is a
tion. Such a trend was also observed in CH4 adsorption on graphite quadrapolar molecule and interacts strongly with the charged
and in graphitic slit pores and attributed to the better packing of hydrogen and oxygen atoms of the terminal water molecules.
the united-atom model in confined space.39 Unless otherwise However, the united-atom model of CH4 can only interact with
stated, the results for CH4 are based on the united-atom model. water molecules through a weak dispersion potential. It can be
4.3. Adsorption of Pure CO2 and CH4. Figure 4 shows the expected that the enhancement would be larger if using the five-
adsorption isotherms of CO2 and CH4 in both dehydrated and site model of CH4. At high pressures, the pores in MIL-101 are
hydrated MIL-101 on a gravimetric basis. CH4 uptake increases largely filled by adsorbate, and the free volume is a dominant
almost linearly with increasing pressure and is still not saturated factor in determining adsorption capacity. Apparently, the term-
at 50 bar because of the very porous structure of MIL-101. This inal water molecules occupy part of the volume and prevent the
implies that the interaction between CH4 and the MIL-101 is
framework from accommodating more adsorbate molecules.
weak and a higher pressure is needed to attain saturation. Despite
a slight overestimation at high pressures, the simulated isotherms
(40) Yazaydin, A. O.; Benin, A. I.; Faheem, S. A.; Jakubczak, P.; Low, J. J.;
Willis, R. R.; Snurr, R. Q. Chem. Mater. 2009, 21, 1425.
(39) Do, D. D.; Do, H. D. J. Phys. Chem. B 2005, 109, 19288. (41) Jiang, J. W. AIChE J. 2009, 55, 2422.
Figure 6. Snapshots of CO2 and CH4 in a pentagonal window in the dehydrated MIL-101 at 10, 100, and 1000 kPa. Color code: Cr, orange; F,
cyan; C, blue; O, red; H, white; CO2, green; CH4, pink.
Figure 10. Adsorption of equimolar CO2/CH4 mixture: (a) isotherm and (b) selectivity.
within a shell from r to r r, V is the system volume, and Ni and distribution functions discussed here provide useful insights into
Nj are the numbers of the i and j species. Figure 7 shows the g(r) of the favorable interaction sites in the dehydrated MIL-101.
CO2 and CH4 around the Cr1 and Cr2 atoms in the dehydrated We next consider the hydrated MIL-101, in which both Cr1 and
MIL-101 at various pressures, respectively. For all four cases Cr2 sites are coordinated and thus exhibit similar g(r). As shown in
shown, pronounced peaks are observed at r = 5-9 A, revealing Supporting Information Figure S5, the g(r) are almost the same for
that the supertetrahedra are preferential adsorption sites. CO2-Cr1 and CO2-Cr2, and also for CH4-Cr1 and CH4-Cr2.
Furthermore, two additional peaks are observed in the g(r) of While there are peaks at 5-9 A, no peaks or shoulders are observed
CO2-Cr1. This is attributed to the attractions between fluorine at 3.5 A, which are significantly different from Figure 7. The
atoms (bonded to Cr1 sites) and CO2 molecules in two neighbor- pressure dependence of the g(r) is similar to that in the hydrated
ing supertetrahedra. As illustrated by the electrostatic potential framework, that is, the peak decreases with rising pressure.
maps in Figure 3, fluorine atoms possess large electronegativity Figure 9 shows the radial distribution functions of CO2 and
and, therefore, interact strongly with CO2 molecules. CH4 around the oxygen atoms (OW) of the terminal water
There is a distinct difference in the short region of g(r) around molecules in the hydrated MIL-101 at 10, 100, 1000, and 5000
Cr1 and Cr2. In the dehydrated MIL-101, the Cr1 sites are bonded kPa, respectively. Similar to the g(r) of CO2-Cr2 and CH4-Cr2 in
with fluorine atoms, whereas the Cr2 sites are exposed. Small Figure 7, peaks and shoulders are observed in the g(r) of
peaks are observed in the g(r) of CO2-Cr2 at r = 3.5 A; though CO2-OW and CH4-OW at r = 3.8 A. The reason is that the
there are no peaks in the g(r) of CH4-Cr2, shoulders exist in the terminal water molecules act as additional adsorption sites,
region r = 3-4 A. In marked contrast, such peaks and shoulders especially for CO2. Comparing Figures 7 and 9, we find that the
are not seen around the Cr1 sites. That is, the adsorbate molecules peaks and shoulders are broader in the latter, suggesting that the
are closer to the Cr2 rather than the Cr1 sites. Because of the terminal water molecules result in stronger interactions with
quadrapole moment, CO2 interacts more strongly with the Cr2 adsorbates than do the exposed Cr2 sites. As a consequence,
sites than CH4, leading to the peaks in g(r) of CO2-Cr2. Figure 8 adsorption at low pressures is greater for both CO2 and CH4 in the
schematically demonstrates the locations of CO2 and CH4 mole- hydrated MIL-101.
cules around the Cr2 sites. We should note that the region near the 4.4. Adsorption of CO2/CH4 Mixture. Adsorption of an
Cr2 sites is substantially smaller than the size of supertetrahedra; equimolar mixture of CO2 and CH4 was also simulated in the
therefore, the peaks in g(r) at 3.5 A are much lower and narrower dehydrated and hydrated MIL-101. The isotherm in Figure 10a
than those at 5-9 A. shows that the extent of adsorption of each component is not
With increasing pressure, the number of adsorbed molecules substantially affected by hydration. With a closer look, however,
increases. As defined by eq 1, g(r) is the local density relative to the we see that CO2 adsorption at low pressures is marginally higher in
overall density. The peaks in g(r) at 5-9 A decrease as pressure the hydrated MIL-101 than in the dehydrated counterpart. At high
increases, since the local density increases less rapidly than the pressures, there is no discernible difference in adsorption between
overall density. Similar behavior was also observed in our recent the two structures. In contrast, CH4 adsorption in dehydrated
studies for the adsorption of gas and water in charged rho zeolite- MIL-101 is slightly higher at moderate and high pressures. The
like MOF.42,43 Interestingly, different behavior is found for the separation factor of the mixture is quantified by selectivity Si/j =
peaks at 3.5 A close to the exposed Cr2 sites. Specifically, the peak (xi/xj)(yj/yi), where xi and yi are the mole fractions of component i
of CO2-Cr2 increases with increasing pressure from 10 to 100 and in adsorbed and bulk phases, respectively. As shown in Figure 10b,
then to 1000 kPa, but decreases from 1000 to 5000 kPa. This with increasing pressure the selectivity of CO2/CH4 first increases,
implies that the number of CO2 molecules near the exposed Cr2 then drops rapidly, and finally increases slightly over the pressure
sites increases up to 1000 kPa; however, these regions are small range under study. The initial increase is due to the preferential
and get saturated beyond 1000 kPa. Unlike CO2-Cr2, the adsorption of CO2 in the multiple supertetrahedra. Upon adsorp-
shoulder of CH4-Cr2 still increases marginally when pressure tion occurring in the less attractive windows and mesoporous cage,
rises from 1000 to 5000 kPa. This is because the interaction of the selectivity drops. At high pressures, the selectivity increases
CH4-Cr2 is weaker than that of CO2-Cr2; thus, the CH4 because of the cooperative attractions between the dominantly
saturation on the Cr2 sites occurs at higher pressure. The radial adsorbed CO2 molecules. Interestingly, the selectivity of CO2/CH4
is higher in the hydrated MIL-101, implying that the separation
efficacy could be enhanced by introducing terminal H2O mole-
(42) Babarao, R.; Jiang, J. W. J. Am. Chem. Soc. 2009, 131, 11417.
(43) Nalaparaju, A.; Babarao, R.; Zhao, X. S.; Jiang, J. W. ACS Nano 2009, cules. This was also observed in the adsorption of CO2/CH4 in
2563. Cu-BTC40 and of CO2/H2 in charged soc-MOF.41