Subscriber access provided by UNIV OF NEBRASKA - LINCOLN

Article
Underlying Adsorption Mechanisms of Water in Hydrophobic and
Hydrophilic Zeolite Imidazolate Frameworks: ZIF-71 and ZIF-90
Sofia Calero, and Paula Gómez-Álvarez
J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.5b07360 • Publication Date (Web): 21 Sep 2015
Downloaded from http://pubs.acs.org on September 29, 2015

Just Accepted

“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

The Journal of Physical Chemistry C is published by the American Chemical Society.

1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.
Page 1 of 31 The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32 Molecular understanding of hydration of Zeolitic Imidazolate Frameworks: Adsorption in the gas phase but
33 rapid condensation transition governed by water clustering in ZIF-90, reflecting an amphiphilic character.
34 254x190mm (96 x 96 DPI)
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
 The Journal of Physical Chemistry Page 2 of 31

1
2
3
4
Underlying Adsorption Mechanisms of Water in Hydrophobic and
5
6 Hydrophilic Zeolite Imidazolate Frameworks: ZIF-71 and ZIF-90
7
8
9
10
11 S. Calero and P. Gómez-Álvarez*
12
13
14
15
16 Department of Physical, Chemical and Natural Systems. Universidad Pablo de Olavide.
17
18 ES-41013 Seville, Spain
19
20
21
22
23 *E-mail: [email protected]
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 1
ACS Paragon Plus Environment
Page 3 of 31 The Journal of Physical Chemistry

1
2
3 Abstract
4
5
6 The hydration of porous materials is relevant for separation, transport and catalysis
7
8 purposes, among others. In this respect, Zeolitic Imidazolate Frameworks (ZIFs) have
9
10
received considerable attention since they have shown remarkably resistance to water, as
11
12
13 well as to other organic solvents. Studies on water adsorption in ZIFs are however
14
15 relatively scarce and primarily focused on the effect of the host composition and porosity
16
17
18
on their hydrophobic or hydrophilic nature. In this work, we explore the underlying
19
20 adsorption mechanisms of water in ZIF-71 and ZIF-90, which are experimentally known
21
22 structures. These ZIFs have been reported hydrophobic and hydrophilic, respectively. We
23
24
25 conducted Monte Carlo simulations using previously validated models and force fields to
26
27 compute the adsorption isotherms of water in both ZIFs at room temperature. Although the
28
29 polar functional group in ZIF-90 leads to adsorption in the gas phase, a following rapid
30
31
32 cage filling occurs as in ZIF-71. A consistent description of this phenomenon is provided in
33
34 terms of hydrogen bonding formation between water molecules. In the low coverage-
35
36
regime, the preferential adsorption sites are identified and interactions with water
37
38
39 comprehensively characterized.
40
41
42
43
44
Keywords: cage filling, hydrogen bonds, MOFs, Monte Carlo simulations, adsorption
45
46 energy.
47
48
49
50
51
52
53
54
55
56
57
58
59
60 2
ACS Paragon Plus Environment
 The Journal of Physical Chemistry Page 4 of 31

1
2
3 1. Introduction
4
5
6 In the last decade, there has been an exponential growth of interest in Metal Organic
7
8 Frameworks (MOFs) because of the versatility in tuning their structures and
9
10
functionalities.1 MOFs can be synthesized from various inorganic clusters and organic
11
12
13 linkers, thus possess a wide range of surface area and pore size1 Consequently, MOFs have
14
15 been considered as potential materials for storage, separation, catalysis, and other emerging
16
17
18
applications.2-7 Most experimental and theoretical studies for the uses of MOFs have been
19
20 focused on gas storage and separation,8-11 and only very few studies12-14 were conducted
21
22 using MOFs for adsorption of water despite being of great importance in a variety of
23
24
25 chemical and industrial processes. For applications in aqueous media, chemically stable
26
27 MOFs are desired. However, most common MOFs cannot meet this requirement. Recently,
28
29 the Zeolitic Imidazolate Frameworks (ZIFs) have attracted considerable attention since they
30
31
32 are known to generally exhibit permanent porosity and display a high chemical and also
33
34 thermal stability.15,16 ZIFs are a subset of MOFs with three-dimensional structures
35
36
connected in a tetrahedral arrangement by metal centers, such as Zn or Co, and organic bare
37
38
39 or functionalized imidazolate linkers.17,18 They have topologies resembling inorganic zeo-
40
41 type networks and exhibit similar structural properties. Intriguingly, the substitution of
42
43
44
oxygen atoms in zeolites with tunable organic linkers leads to extra-large cavities. The
45
46 molecular design of ZIFs is currently very active, and exploring their scope for practical
47
48 applications is still in a newborn stage. While much attention has been paid to the
49
50
51 adsorption of small gases and hydrocarbons,17-24 works on water adsorption as well as other
52
53 organic solvents using ZIFs are still very limited. Among the experimental works, Küsgens
54
55 et al.25 reported the water vapor adsorption isotherm at room temperature for ZIF-8
56
57
58 demonstrating the strong hydrophobic character of this material and its remarkable
59
60 3
ACS Paragon Plus Environment
Page 5 of 31 The Journal of Physical Chemistry

1
2
3 hydrothermal stability. Guillaume Ortiz et al.26 investigated the energetic performance of
4
5
6 ZIF-71 in comparison with ZIF-8 in high pressure liquid water intrusion–extrusion
7
8 experiments. Zhang et al.27 studied the impact of ZIF-8 hydrophobicity for the separation of
9
10
ethanol from water, predicting a good adsorption selectivity. Lively et al.28 presented the
11
12
13 isotherm of water adsorption on ZIF-71 and corroborated the hydrophobicity of this
14
15 material, with very low water uptake at pressures below the bulk saturation pressure. On the
16
17
18
theoretical side, with the tremendous growth of computational power, molecular simulation
19
20 has increasingly become a robust tool to assist experiments. Nalaparaju et al.29 conducted a
21
22 computational study of water adsorption in hydrophobic ZIF-71, as well as in hydrophilic
23
24
25 Na-rho-ZMOF (a MOF with anionic framework and Na+ extra-framework cations).
26
27 Amrouche et al.30 studied the low-pressure adsorption of water in a series of ZIFs by using
28
29 the ideal heat of adsorption and Henry constant as descriptors of hydrophobicity or
30
31
32 hydrophilicity. Zhang et al.31 published a study of water and also alcohol adsorption in ZIF-
33
34 8, ZIF-71 and ZIF-90 approached to bio-alcohol recovery. They found the hydrophobic
35
36
ZIF-8 and ZIF-71, especially the latter, more suitable to this end. Ortiz et al.32 demonstrate,
37
38
39 by means of Grand Canonical Monte Carlo simulations on different members of the ZIF
40
41 family, how topology, geometry, and linker functionalization drastically affect the water
42
43
44
adsorption properties of these materials, tweaking the ZIFs from hydrophobic to
45
46 hydrophilic. Zhang et al.33 recently performed a molecular simulation study of separation of
47
48 ethanol from water in ZIF-8,-25, -71, -90, -96 and -97, revealing the importance of the
49
50
51 functional groups for the efficacy of such separation.
52
53 In the previous works, the hydrophobic and hydrophilic nature of a number of ZIF
54
55 materials has been determined, and also rationalized in terms of topology, geometry, and
56
57
58 linker functionalization. A clear fundamental understanding of the microscopic properties
59
60 4
ACS Paragon Plus Environment
 The Journal of Physical Chemistry Page 6 of 31

1
2
3 of water molecules within these porous solids connecting with the observed macroscopic
4
5
6 behavior is likewise indispensable, and comprehensively addressed in this work. We used
7
8 molecular simulation techniques34 to study the adsorption performance, and the underlying
9
10
physics, of water in ZIF-71 and ZIF-90, which are well-known for their hydrophobic and
11
12
13 hydrophilic characters, respectively. The adsorption isotherms of water in both ZIFs were
14
15 computed using Monte Carlo simulations in the Grand Canonical ensemble at room
16
17
18
temperature. Water-water and water-ZIF interactions characterizing the adsorption
19
20 mechanisms were quantitatively evaluated from energetic factors, and structural properties
21
22 such as the Radial Distribution Functions (RDFs) or Hydrogen-Bonded (HB) statistics. The
23
24
25 latter have been calculated in the basis of a specific criterion of hydrogen bonding
26
27 formation applied along the simulation.
28
29
30
31
32 2. Methods
33
34 2.1. Structures
35
36
ZIF-71 [Zn(dcIm)2, where dcIm = 4,5-dichloroimidazolate] possesses a RHO-type topology
37
38
39 consisting on a three-dimensional pore network formed by large α cages of 16.8 Å
40
41 interconnected via small windows of 4.8 Å in a cubic body-centered arrangement.18 The
42
43
44
cell lengths of ZIF-71 are: a = b= c =28.554 Å, and angles α = β = γ = 90º. ZIF-90
45
46 [Zn(icaIm)2, where icaIm = imidazole-2-carboxyaldehyde] belongs to SOD topology with
47
48 an extended 3-D structure with a pore window opening of 3.5 Å and a pore size of 11.2 Å35
49
50
51 The material is made of uniform micropores containing unsaturated –CHO aldehyde
52
53 functional groups. The cell parameters of ZIF-90 are: a = b= c= 17.272 Å, and α = β = γ =
54
55 90º. Figure 1 illustrates the atomic structures of both ZIFs.
56
57
58
59
60 5
ACS Paragon Plus Environment
Page 7 of 31 The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25 Figure 1. Atomic structures of ZIF-71 (left) and ZIF-90 (right). Cl: green, C: grey, H:
26
27
28 white, O: red, N: blue, Zn: cyan. The size is not in the same scale.
29
30
31
32 Table 1 collects a number of structural properties characterizing the pore sizes and
33
34
35 the accessible space (for a probe radius of 1.7 Å) of the targeted ZIFs. Particularly, we
36
37 report the Pore Limiting Diameter (PLD), the Largest Cavity Diameter (LCD), the
38
39
40
Accessible Volume (AV), and the Accessible Surface Area (ASA). They were computed
41
42 using Zeo++,36 a code for a geometric analysis of crystalline porous materials. The PLD
43
44 and LCD agree quite well with the experimental values commented above. The accessible
45
46
47 volume is also consistent with that reported in previous works.33 Note that although the
48
49 LCD of ZIF-71 is larger than this for ZIF-90, the free volume and surface area are lower.
50
51 To give an idea on how the available space distribute within the pores, Figure S1 of the
52
53
54 Electronic Supporting Information (ESI) displays the Pore Size Distributions of both ZIFs.
55
56
57
58
59
60 6
ACS Paragon Plus Environment
 The Journal of Physical Chemistry Page 8 of 31

1
2
3 Table 1. Geometric properties of the studied ZIFs computed using Zeo++ code.36
4
5
6 Accessible Volume and Surface Area are computed for a probe radius of 1.7 Å.
7
8
9 Density / kg·m-3 PLD / Å LCD / Å AV / cm3·g-1 ASA / m2·g-1
10
11
12 ZIF-71 1155 5.4 17.0 0.1725 1120
13
14
15 ZIF-90 988 3.5 11.4 0.1916 1526
16
17
18
19
20
21
22 2.2. Models and force fields
23
24
25 Guest water molecules were described by the rigid, non-polarizable, and five-site
26
27 TIP5P/Ew model.37 The host structures were treated as rigid frameworks since the
28
29 importance of flexibility on adsorption properties has only a marginal effect. ZIF–
30
31
32 water interactions were described by a classical force field including the repulsion-
33
34 dispersion energy, modeled by Lennard-Jones 6-12 potentials, and Coulombic
35
36 interactions, modeled by point charges on the framework atoms of the ZIFs. Both the
37
38
39 Lennard-Jones parameters and the atomic point charges of the ZIFs were taken from
40
41 the earlier work of Zhang et al.,33 who considered the DREIDING force field38 for
42
43
44
the L-J parameters and calculated atomic charges using the Density Functional
45
46 Theory (DFT). Lorentz-Berthelot mixing rules34 were used to obtain the parameters
47
48 characterizing L-J cross interactions.
49
50
51
52
53 2.3. Monte Carlo simulations
54
55 Monte Carlo simulations of water at 298 K were performed using RASPA code39,40 and the
56
57
58 above-described models and force fields. The adsorption of water in the ZIFs was
59
60 7
ACS Paragon Plus Environment
Page 9 of 31 The Journal of Physical Chemistry

1
2
3 computed using the grand canonical ensemble (µVT), in which temperature, volume and
4
5
6 chemical potential are kept fixed. The latter is related to the imposed fugacity, from which
7
8 pressure can be determined using the Peng-Robison equation of state.41 The number of unit
9
10
cells for each structure was chosen in order to get a simulation box larger than twice the
11
12
13 Lennard-Jones cut-off radius, which was set to 12 Å: The simulation box thus contained
14
15 one unit cell of ZIF- 71, and eight unit cells (2×2×2) for ZIF-90. The periodic boundary
16
17
18
conditions34 were exerted in three dimensions, and long-range electrostatic interactions
19
20 were evaluated using the Ewald summation technique.34 Three types of trial moves were
21
22 randomly attempted, namely molecular displacement (25%), rotation (25%), and a swap
23
24
25 between reservoirs (50%) including creation and deletion with equal probability. Each point
26
27 of the isotherms was obtained after equilibration runs of 50 000 cycles followed by
28
29 production runs of 500 000 cycles. Additional simulations in the NVT ensemble were
30
31
32 carried out to obtain results for specific low numbers of molecules.
33
34
35
36 2.4. Criterion of hydrogen-bonding formation
37
38 For an accurate estimation of the HB network of water, we applied a geometric
39
40
41
criterion42 of HB definition over a considerable number of the computed-generated
42
43 configurations along the simulation. According to which, a hydrogen bond between
44
45 two water molecules exists when the
 and
 intermolecular separations are
46
47
48 lower than certain threshold values, which are given by the average distances of the
49
50 first minimum location in the respective  and  functions (3.6 Å and 2.4 Å),43
51
52
and limitation to the angle (30 º) between intermolecular O··· O and covalent O-H
53
54
55 vectors is fulfilled.
56
57
58
59
60 8
ACS Paragon Plus Environment
 The Journal of Physical Chemistry Page 10 of 31

1
2
3 3. Results and discussion
4
5
6 Figure 2 shows the adsorption isotherms of water in ZIF-71 and ZIF-90. The used models
7
8 and force fields allow to reproduce quite accurately the experimental behavior,31 as
9
10
previously shown in Zhang et al.33 On the one hand, the isotherms of water in ZIF-71
11
12
13 belong to S-shaped type V, which signifies the adsorption of the weakly interacting
14
15 adsorbate in a microporous structure. Water has vanishingly small adsorption at low
16
17
18
pressures, and a sharp increase in adsorption approaching saturation rapidly is observed
19
20 above the saturation pressure  (adsorption in the liquid phase). In particular, this
21
22 condensation transition occurs at about 25 kPa (/ ≈ 8). The described behavior is
23
24
25 typical of hydrophobic materials. On the other hand, water uptake is initially negligible in
26
27 ZIF-90 but sharply increases beyond 1 kPa (adsorption in the gas phase), which suggests its
28
29
hydrophilic nature. More specifically, as it is clearly apparent from the inset figure, water
30
31
32 adsorption occurs from / of about 0.4, which is slightly larger than the experimental
33
34 value31 (/ of about 0.3). At relative pressure of 1, the water loading in ZIF-90 is well
35
36
37 coincident with experiments31 (20 mol·kg-1, approximately). At saturation, it notably
38
39 overcomes that in ZIF-71 at saturation. This is likely induced by the larger porosity of ZIF-
40
41 90 (Table 1) as well as to stronger water-ZIF interactions induced by the –CHO groups. On
42
43
44 the basis of the lower onset pressure of water adsorption in ZIF-90 and the larger
45
46 adsorption capacity, we can state that this ZIF represents a better option for applications of
47
48
water adsorption and storage. Although the deviations in ZIF-90 and ZIF-71 are relatively
49
50
51 large, they exhibit a common feature of adsorption: Cage-filling occurs with a sharp
52
53 increase in the uptake. To illustrate this, we plot in Figure 3 the density contours (XY
54
55
56 plane) of water in the simulation box of ZIF-71 (top) and ZIF-90 (bottom) for two low
57
58
59
60 9
ACS Paragon Plus Environment
Page 11 of 31 The Journal of Physical Chemistry

1
2
3 (onset adsorption) close values of fugacity. The rapid uptake mechanism in both ZIFs is
4
5
6 evident from the pictures. In this sense, ZIF-90 shows an amphiphilic character, with some
7
8 parts of its internal surface hydrophilic (adsorption in the gas phase), and some parts
9
10
hydrophobic (abrupt condensation transition).
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40 Figure 2. Adsorption isotherms of water in ZIF-71 (empty squares) and in ZIF-90 (full
41
42
squares). Inset figure shows the vapor adsorption isotherm for ZIF-90 ( = 3.2 kPa).
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 10
ACS Paragon Plus Environment
 The Journal of Physical Chemistry Page 12 of 31

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42 Figure 3. Density contours (XY plane) of water molecules in ZIF-71 (top) at 25 kPa and 30
43
44
kPa, and ZIF-90 (bottom) at 1.5 kPa and 2.0 kPa.
45
46
47
48
49 To deeply elucidate the described water adsorption performance of both ZIFs, we
50
51
52
comprehensively analyzed the systems at the molecular scale in terms of a series of
53
54 energetic and structural properties. In Figures 4 and 5, we quantitatively evaluate the
55
56 energetic factors during the adsorption process. Figure 4 reports the average adsorption
57
58
59
60 11
ACS Paragon Plus Environment
Page 13 of 31 The Journal of Physical Chemistry

1
2
3 energy as a function of the loading. Inset figure shows this magnitude for a low number of
4
5
6 molecules from NVT calculations to examine the very low coverage regime. The values for
7
8 a single water molecule represent the heats of adsorption. The hydrophobic and more
9
10
hydrophilic nature of ZIF-71 and ZIF-90, respectively, is clearly visible from the obtained
11
12
13 values: 16 kJ·mol-1 and 36 kJ·mol-1, approximately. They are much and just slightly lower
14
15 than the heat of vaporization of water, which is 40.9 kJ·mol-1 using the same water model,37
16
17
18
in consistency with the experimental value (about 44 kJ·mol-1 at 25 ºC).44,45 It is thus
19
20 energetically unfavorable for water to break hydrogen bonds in the bulk phase and then be
21
22 adsorbed in ZIF-71, which explains the forced water intrusion by applying pressure. With
23
24
25 increasing loading, the adsorption energy monotonically decreases to about 5 kJ·mol-1 in
26
27 ZIF-71 and to 15 kJ·mol-1 in ZIF-90. Figure 5 collects the guest-guest and host-guest
28
29 contributions to the average intermolecular energy as a function of fugacity. The
30
31
32 information on the latter has been dealt in Figure 4. Water-water potential energy rapidly
33
34 decreases after water intrusion down to value of about -35 kJ·mol-1 in both ZIFs. More
35
36
specifically, the energy is slightly lower in ZIF-71, which is consistent with its hydrophobic
37
38
39 character. The obtained values are somewhat lower (in absolute value) than potential
40
41 energy for the bulk state, reported above, indicating a dense adsorbed phase with weaker
42
43
44
water–water interactions.
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 12
ACS Paragon Plus Environment
 The Journal of Physical Chemistry Page 14 of 31

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33 Figure 4. Average adsorption energy (   − ) as a function of the loading for
34
35
water in ZIF-71 (empty squares) and in ZIF-90 (full squares). Results of the inset figure
36
37
38 were obtained from NVT calculations.
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 13
ACS Paragon Plus Environment
Page 15 of 31 The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29 Figure 5. Guest-guest (black) and host-guest (red) contributions to the intermolecular
30
31 average potential energy in ZIF-71 (empty squares) and ZIF-90 (full squares) as a function
32
33 of fugacity.
34
35
36
37
38 The energetic analysis gives information on the interaction of the adsorbed water
39
40 molecules with the structure and on self-association governing the adsorption mechanisms.
41
42
43 The radial distribution functions g(r) likewise aid to understand the microscopic behavior
44
45 of the water molecules inside the pores by providing information on the average
46
47
48
intermolecular distance and the presence of hydrogen bonds. Figure 6 displays the RDFs in
49
50 both ZIFs for similar water loadings of about 20 mol·kg-1 (after condensation transition).
51
52 Calculations correspond to water oxygen atoms with each other, and with the framework
53
54
55 atoms in order to identify preferential adsorption sites. As reveals the positions of the first
56
57 peaks in Figure 6a, water-water interactions are notably greater than water-host interactions
58
59
60 14
ACS Paragon Plus Environment
 The Journal of Physical Chemistry Page 16 of 31

1
2
3 in ZIF-71, denoting the hydrophobicity of this ZIF. The g(r) of water around Zn framework
4
5
6 atoms of the ZIF reveals negligible interaction. The strongest affinity with water
7
8 corresponds to chlorine atoms of the functional group, with evident first peaks at distances
9
10
below 4 Å. In the second stage, the hydrophilicity of ZIF-90 (Fig. 6b) arises from
11
12
13 interactions of water molecules with the aldehyde oxygen atoms. The strength of this
14
15 interaction is comparable with water-water interactions. Indeed, both first peaks, of
16
17
18  −  and  −  RDFs, are located at almost the same position: 2.75 Å. This
19
20 suggests hydrogen bonding formation between water molecules and ZIF-90. Particularly, as
21
22 apparent from the O-H RDFs depicted in Figure S2 of the ESI, water is the H-bond donor.
23
24
25 Interactions of water molecules with the remaining framework atoms are relatively
26
27 insignificant. As reveals Figure S3 of the ESI, these results characterising interactions of
28
29 water molecules with the surface of ZIF-90 are kept regardless of fugacity, and so of water
30
31
32 loading. Note however that at the highest pressure (Figure S3 d), a clear broadening of the
33
34 peak in  −  RDF is observed, denoting a weakening of this cross hydrogen bonding.
35
36
37
This is likely due to the strong water-water interactions in the highly hydrated structure.
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 15
ACS Paragon Plus Environment
Page 17 of 31 The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52 Figure 6. Radial Distribution Functions of the oxygen atoms of adsorbed water molecules
53
54
55
 between each other and with the framework atoms in ZIF-71 (a) and ZIF-90 (b) for
56
57 similar water loadings of about 20 mol·kg-1 (at 40 kPa and 4 kPa, respectively).
58
59
60 16
ACS Paragon Plus Environment
 The Journal of Physical Chemistry Page 18 of 31

1
2
3 To gain insights into the interactions of water with the structure, we compute the
4
5
6 average minimum distances of water (oxygen atom) to the strongest interacting framework
7
8 sites (chlorine in ZIF-71 and aldehyde oxygen in ZIF-90) in the dilute regime using the
9
10
NVT ensemble. Results are collected in Figure 7. For a single molecule in the system, this
11
12
13 magnitude is 3.7 Å and 3 Å approximately in ZIF-70 and ZIF-90, respectively. These
14
15 average minimum distances decrease with the number of water molecules N until values
16
17
18
slightly above 3 Å for ZIF-71 and 2.5 Å for ZIF-90, supporting the weakly polar and rather
19
20 polar nature of –Cl and –CHO functional groups, respectively. The larger values
21
22 corresponding to the location of the involved first peaks in the above RDFs evidences
23
24
25 weaker interaction of water with the pore surface after condensation in consistency with
26
27 energetic analysis.
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
Figure 7. Average minimum distances from oxygen atom of water  to  in ZIF-71 (a),
48
49
50 and to  in ZIF-90 (b) as a function of the number of adsorbed water molecules N from
51
52 NVT calculations.
53
54
55
56
57
58
59
60 17
ACS Paragon Plus Environment
Page 19 of 31 The Journal of Physical Chemistry

1
2
3 In the following lines, we focused on water-water interactions. The O-O and O-H
4
5
6 RDFs of the adsorbed water in the ZIFs at saturation are given in Figure S4 of the ESI
7
8 together with those for bulk water. We find a strong ordering of water molecules at short
9
10
distance in both materials, with a remarkable O–O first peak at 2.8 Å as for bulk water.
11
12
13 Nevertheless, there is no longer-range order since the second solvation shell characterizing
14
15 bulk water is absent. This is due to excluded volume effects. The O–H RDF for the
16
17
18
adsorbed water in the highly hydrated structures and bulk water is virtually the same: Two
19
20 distinct peaks at 1.9 Å and 3.2 Å characteristic of hydrogen bonding. This correspondence
21
22 between the RDFs lead one to conclude that the structure of water adsorbed in the ZIF
23
24
25 pores at saturation is similar to bulk liquid water.32 This result is reasonable taken the large
26
27 pore sizes of the ZIFs into account. The large available space allows a large number of
28
29 neighboring water molecules promoting hydrogen bonding. However, here we further
30
31
32 investigated the water hydrogen-bonded network through HB statistics, which have been
33
34 evaluated using a geometric criterion of HB definition.42 We found appreciable differences
35
36
of adsorbed water not only with respect to the bulk but also induced by the nature of the
37
38
39 ZIF. Particularly, Table 2 shows the obtained values of the fraction of associated (linked
40
41 through hydrogen bonds) molecules !"" , of the percentage of the latter engaged in i=1-5
42
43
44 hydrogen bonds !# , and of the average number of hydrogen bonds per molecule $%& for
45
46 bulk water43 and adsorbed water at the highest considered pressure. While !"" is virtually
47
48
1 for all the systems, differences in the HB populations are clearly apparent. The tetrahedral
49
50
51 ordering of bulk water is reflected on the high percentages of !' and !( , which are virtually
52
53 the same and about 38 % using the same water model.37 This results in a $%& value of 3.2.
54
55
56 Although adsorbed water retains bulk liquid-like characteristics (!' ∼ 40 %), the
57
58
59
60 18
ACS Paragon Plus Environment
 The Journal of Physical Chemistry Page 20 of 31

1
2
3 percentage of water molecules engaged in 4 hydrogen bonds considerably decreases in
4
5
6 favor to mainly !* . The main difference between water adsorbed in ZIF-71 and ZIF-90 lie
7
8 in this variation: While !* and !( are almost the same and about 25 % in ZIF-71, !*
9
10
11
largely overcomes !( in the case of ZIF-90. These results lead to the respective $%& values
12
13 of 2.9 and 2.7. Thus, despite the larger porosity of ZIF-90, we found a slightly more
14
15 complex water HB network in ZIF-71. This is consistent with guest-guest interactions
16
17
18 reported for both ZIFs in Figure 5. Although framework topology can greatly affect,43 here
19
20 this is likely due to the virtual lack of interactions with the pore surface in ZIF-71.
21
22
23
24
25 Table 2. HB statistics of bulk water and of water adsorbed in ZIF-71 and ZIF-90 at 106 Pa.
26
27 !"" !+ !* !' !( !, $%&
28
29
30 Bulk43 0.99 3.9 17.4 38.3 38.0 2.4 3.2
31
32 ZIF-71 0.97 7.1 23.6 40.9 25.6 2.7 2.9
33
34 ZIF-90 0.98 7.8 30.9 43.6 16.4 1.25 2.7
35
36
37
38
39 Figures 8 and 9 show the results of the previous magnitudes as a function of
40
41
42
fugacity in order to examine H-bonding during the adsorption process. Figure 8a shows a
43
44 steep increase up to roughly 1 of the fraction of associated molecules !"" in both ZIFs at
45
46 about their respective onset pressures of adsorption. As can be seen in Figure 8b, the
47
48
49 behavior of $%& as a function of fugacity is in close relation with the adsorption
50
51 performance in both ZIFs. The hydration mechanism proceeding through water cluster
52
53
formation and growth in hydrophobic materials such as ZIF-71 was expected.43,46 However,
54
55
56 this result reveals that the rapid pore filling is also owing to water clustering even in ZIF-
57
58
59
60 19
ACS Paragon Plus Environment
Page 21 of 31 The Journal of Physical Chemistry

1
2
3 90, rather than to nucleation around the high-energy sites (the aldehyde oxygen framework
4
5
6 atoms). We can thus conclude for the latter that the polar formyl groups in Im linkers shifts
7
8 the onset adsorption pressure to below the bulk saturation pressure, but the mechanisms of
9
10
pore filling keep being governed by molecular association of water. This finding supports
11
12
13 an amphiphilic character for this ZIF. In Figure 9, we plot the HB populations as a function
14
15 of fugacity. Stable values, previously discussed in Table 2, are reached from the lowest
16
17
18
pressures of adsorption, especially in the purely hydrophobic ZIF-71. This corroborates the
19
20 rapid formation of the dense phase by self-association.
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 20
ACS Paragon Plus Environment
 The Journal of Physical Chemistry Page 22 of 31

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52 Figure 8. Fraction of associated water molecules - (a), and average number of hydrogen
53
54
55 bonds per molecule ./ (red) together with the loading (black) (b) as a function of fugacity
56
57 in ZIF-71 (empty squares) and ZIF-90 (full squares).
58
59
60 21
ACS Paragon Plus Environment
Page 23 of 31 The Journal of Physical Chemistry

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53 Figure 9. Percentage of water molecules engaged through 1-5 hydrogen bonds (-0 − -1 ) as
54
55 a function of fugacity in ZIF-71 (a) and ZIF-90 (b).
56
57
58
59
60 22
ACS Paragon Plus Environment
 The Journal of Physical Chemistry Page 24 of 31

1
2
3 4. Conclusions
4
5
6 By using molecular simulation, we characterized the microscopic behavior governing the
7
8 adsorption performance of water in two substantially different ZIFs concerning topology
9
10
and composition, and so nature, namely ZIF-71 and ZIF-90. We computed the adsorption
11
12
13 isotherms of water in both ZIFs at 298 K via Monte Carlo simulations in the grand
14
15 canonical ensemble. Although chlorine functional group of ZIF-71 is weakly polar as
16
17
18
reflects the adsorption in the liquid phase (hydrophobic nature), its interaction with water
19
20 molecules is remarkable in relation to the remaining framework atoms, as reveals the
21
22 Radial Distribution Functions. In ZIF-90, the aldehyde oxygen atom was distinctly found
23
24
25 the strongest interacting site surely involving hydrogen bonds with water molecules, and
26
27 thus responsible of the water intrusion below the bulk saturation pressure (hydrophilic
28
29 nature). The affinity of water to these preferential sites in each ZIF, Cl and Oald, was
30
31
32 quantitatively evaluated in terms of the adsorption energy and the average minimum
33
34 distances in the low-coverage regime from NVT calculations. The distance values for a
35
36
single water molecule in the system were found 3.7 Å in ZIF-71 and 3 Å in ZIF-90, with
37
38
39 respective heats of adsorption of 16 kJ·mol-1 and 36 kJ·mol-1, approximately. The abrupt
40
41 condensation transition observed in the water adsorption isotherms in both ZIFs was
42
43
44
demonstrated, by means of energetic and structural factors, consequence of rapid water
45
46 clustering even in ZIF-90. Instead of nucleation around the Oald high-energy sites, self-
47
48 association of water dominates the adsorption process, as in hydrophobic materials such as
49
50
51 ZIF-71. This suggests an amphiphilic more than hydrophilic character of ZIF-90. Indeed,
52
53 the adsorption energy in dilute regime was found even slightly lower than the heat of
54
55 vaporization of water, and significantly decreases with water uptake. In the highly hydrated
56
57
58 structures, the HB properties of water reveal the absence of the tetrahedral ordering typical
59
60 23
ACS Paragon Plus Environment
Page 25 of 31 The Journal of Physical Chemistry

1
2
3 of the bulk in both ZIFs, and the formation of higher-order water clusters in ZIF-71 despite
4
5
6 its lower accessible space in comparison with ZIF-90. This is ascribed to the weaker
7
8 interactions with the pore surface, which enhances hydrogen bonding formation between
9
10
water molecules.
11
12
13
14
15 Supporting Information: Pore Size Distributions of ZIF-71 and ZIF-90, and
16
17
18
complementary Radial Distribution Functions characterizing the structure of the adsorbed
19
20 water molecules and interactions with the framework atoms. This material is available free
21
22 of charge via the Internet at http:// pubs.acs.org/.
23
24
25
26
27 Acknowledgements
28
29 This work is supported by the European Research Council through an ERC Starting Grant
30
31
32 (ERC2011-StG-279520-RASPA), by the MINECO (CTQ2013-48396-P) and by the
33
34 Andalucía Region (FQM-1851).
35
36
37
38
39 References
40
41 (1) Yaghi, O. M.; O’Keefe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J.
42
43
44
Reticular Synthesis and the Design of New Materials. Nature 2003, 423, 705-714.
45
46 (2) Férey, G. Hybrid Porous Solids: Past, Present, Future. Chem. Soc. Rev. 2008, 37, 191–
47
48 214.
49
50
51 (3) Zhou, H. C.; Long, J. R.; Yaghi, O. M. Introduction to Metal–Organic Frameworks.
52
53 Chem. Rev. 2012, 112, 673–674.
54
55 (4) Metal–Organic Frameworks: Applications from Catalysis to Gas Storage, ed. D.
56
57
58 Farrusseng, Wiley-VCH, Weinheim, 2011.
59
60 24
ACS Paragon Plus Environment
 The Journal of Physical Chemistry Page 26 of 31

1
2
3 (5) Horike, S.; Shimomura, S.; Kitagawa, S. Soft Porous Crystals. Nat. Chem. 2009, 1,
4
5
6 695–704.
7
8 (6) Farha, O. K.; Hupp, J. T. Rational Design, Synthesis, Purification, and Activation of
9
10
Metal-Organic Frameworks Materials. Acc. Chem. Res. 2010, 43, 1166–1175.
11
12
13 (7) Tranchemontagne, D. J.; Mendoza-Cortes, J. L.; O’Keeffe, M.; Yaghi, O. M. Secondary
14
15 Building Units, Nets and Bonding in the Chemistry of Metal-Organic Frameworks.
16
17
18
Chem. Soc. Rev. 2009, 38, 1257–1283.
19
20 (8) Li, J.-R.; Kuppler, R.-J.; Zhou, H.-C. Selective Gas Adsorption and Separation in
21
22 Metal–Organic Frameworks. Chem. Soc. Rev. 2009, 38, 1477-1504.
23
24
25 (9) Ma, S.; Zhou, H. C. Gas Storage in Porous Metal–Organic Frameworks for Clean
26
27 Energy Applications. Chem. Commun. 2010, 46, 44-53.
28
29 (10) Wu, H.; Zhou, W.; Yildirim, T. Methane Sorption in Nanoporous Metal−Organic
30
31
32 Frameworks and First-Order Phase Transition of Confined Methane. J. Phys. Chem. C
33
34 2009, 113, 3029–3035.
35
36
(11) Zhang, Z.; Zhao, Y.; Gong, Q.; Li, Z.; Li, J. MOFs for CO2 Capture and Separation
37
38
39 from Flue Gas Mixtures: The Effect of Multifunctional Sites on their Adsorption
40
41 Capacity and Selectivity. Chem. Commun. 2013, 49, 653-66.
42
43
44
(12) Burtch, N. C.; Jasuja, H.; Walton, K. S. Water Stability and Adsorption in
45
46 Metal−Organic Frameworks, Chem. Rev. 2014, 114, 10575−10612.
47
48 (13) Paranthaman, S.; Coudert, F.-X.; Fuchs, A. H. Water Adsorption in Hydrophobic
49
50
51 MOF Channels, Phys. Chem. Chem. Phys. 2010, 12, 8123–8129.
52
53 (14) Ghosh, P.; Kim, K. C.; Snurr, R. Q. Modeling Water and Ammonia Adsorption in
54
55 Hydrophobic Metal−Organic Frameworks: Single Components and Mixtures J. Phys.
56
57
58 Chem. C 2014, 118, 1102−1110.
59
60 25
ACS Paragon Plus Environment
Page 27 of 31 The Journal of Physical Chemistry

1
2
3 (15) Liu, Y. L.; Kravtsov, V. C.; Larsen, R.; Eddaoudi, M. Molecular Building Blocks
4
5
6 Approach to the Assembly of Zeolite-like Metal-Organic Frameworks with Extra-large
7
8 Cavities. Chem.Commun. 2006, 42, 1488-1490.
9
10
(16) Park, K. S.; Ni, Z.; Cote, A. P.; Choi, J. Y.; Huang, R. D.; Uribe-Romo, F. J.; Chae,
11
12
13 H. K.; O’Keeffe, M.; Yaghi, O. M. Exceptional Chemical and Thermal Stability of
14
15 Zeolitic Imidazolate Frameworks. Proc. Natl. Acad. Sci. U.S.A. 2006, 103, 10186-
16
17
18
10191.
19
20 (17) Phan, A.; Doonan, C. J.; Uribe-Romo, F. J.; Knobler, C. B.; O’Keeffe, M.; Yaghi,
21
22 O. M. Synthesis, Structure, and Carbon Dioxide Capture Properties of Zeolitic
23
24
25 Imidazolate Frameworks. Acc. Chem. Res. 2010, 43, 58-67.
26
27 (18) Banerjee, R.; Phan, A.; Wang, B.; Knobler, C.; Furukawa, H.; O’Keeffe, M.; Yaghi,
28
29 O. M. High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application
30
31
32 to CO2 Capture. Science 2008, 319, 939–943.
33
34 (19) Wang, B.; Cote, A. P.; Furukawa, H.; O’Keeffe, M.; Yaghi, O. M. Colossal Cages
35
36
in Zeolitic Imidazolate Frameworks as Selective Carbon Dioxide Reservoirs. Nature
37
38
39 2008, 453, 207-211.
40
41 (20) Liu, D.-H.; Zheng, C.-C.; Yang, Q.-Y.; Zhong, C.-L. Understanding the Adsorption
42
43
44
and Diffusion of Carbon Dioxide in Zeolitic Imidazolte Frameworks: A Molecular
45
46 Simulation Study. J. Phys. Chem. C 2009, 113, 5004-5009.
47
48 (21) Rankin, R. B.; Lin, J. C.; Kulkarni, A. D.; Johnson, J. K. Adsorption and Diffusion
49
50
51 of Light Gases in ZIF-68 and ZIF-70: A Simulation Study. J. Phys. Chem. C 2009, 113,
52
53 16906-16914.
54
55
56
57
58
59
60 26
ACS Paragon Plus Environment
 The Journal of Physical Chemistry Page 28 of 31

1
2
3 (22) Liu, Y.; Liu, H. L.; Hu, Y.; Jiang, J. W. Development of a Density Functional
4
5
6 Theory in Three-Dimensional Nanoconfined Space: H2 Storage in Metal-Organic
7
8 Frameworks. J. Phys. Chem. B 2009,113, 12326-12331.
9
10
(23) Li, K. H.; Olson, D. H.; Seidel, J.; Emge, T. J.; Gong, H. W.; Zeng, H. P.; Li, J.
11
12
13 Zeolitic Imidazolate Frameworks for Kinetic Separation of Propane and Propene. J. Am.
14
15 Chem. Soc. 2009, 131, 10368-10369.
16
17
18
(24) Perez-Pellitero, J.; Amrouche, H.; Siperstein, F. R.; Pirngruber, G.; Nieto-Draghi,
19
20 C.; Chaplais, G.; Simon-Masseron, A.; Bazer-Bachi, D.; Peralta, D.; Bats, N.
21
22 Adsorption of CO2, CH4, and N2 on Zeolitic Imidazolate Frameworks: Experiments and
23
24
25 Simulations. Chem. – Eur. J., 2010, 16, 1560-1571.
26
27 (25) Küsgens, P.; Rose, M.; Senkovska, I.; Fröde, H.; Henschel, A.; Siegle, S.; Kaskel,
28
29 S. Characterization of Metal-Organic Frameworks by Water Adsorption. Microporous
30
31
32 Mesoporous Mater. 2009, 120, 325–330.
33
34 (26) Ortiz, G.; Nouali, H.; Marichal, C.; Chaplais, G.; Patarin, J. Energetic Performances
35
36
of the Metal-Organic Framework ZIF-8 Obtained Using High Pressure Water Intrusion-
37
38
39 Extrusion Experiments. Phys. Chem. Chem. Phys. 2013, 15, 4888–4891.
40
41 (27) Zhang, K.; Lively, R. P.; Zhang, C.; Koros W. J.; Chance, R. R. Investigating the
42
43
44
Intrinsic Ethanol/Water Separation Capability of ZIF-8: An Adsorption and Diffusion
45
46 Study. J. Phys. Chem. C 2013, 117, 7214–7225.
47
48 (28) Lively, R. P.; Dose, M. E.; Thompson, J. A.; McCool, B. A.; Chance, R. R.; Joros,
49
50
51 W. J. Ethanol and Water Adsorption in Methanol-Derived ZIF-71. Chem. Commun.,
52
53 2011, 47, 8667–8669.
54
55
56
57
58
59
60 27
ACS Paragon Plus Environment
Page 29 of 31 The Journal of Physical Chemistry

1
2
3 (29) Nalaparaju, A.; Zhao, X. S.; Jiang, J. W. Molecular Understanding for the
4
5
6 Adsorption of Water and Alcohols in Hydrophilic and Hydrophobic Zeolitic Metal-
7
8 Organic Frameworks. J. Phys. Chem. C 2010, 114, 11542–11550.
9
10
(30) Amrouche, H.; Creton, B.; Siperstein, F.; Nieto-Draghi, C. Prediction of
11
12
13 Thermodynamic Properties of Adsorbed Gases in Zeolitic Imidazolate Frameworks.
14
15 RSC Adv. 2012, 2, 6028–6035.
16
17
18
(31) Zhang, K.; Lively, R. P.; Dose, M. E.; Brown, A. J.; Zhang, C.; Chung, J.; Nair, S.;
19
20 Koros, W. J.; Chance, R. R. Alcohol and Water Adsorption in Zeolitic Imidazolate
21
22 Frameworks. Chem. Commun. 2013, 49, 3245–3247.
23
24
25 (32) Ortiz, U.; Freitas, A. P.; Boutin, A.; Fuchs, A. H.; Coudert, F-X. What Makes
26
27 Zeolitic Imidazolate Frameworks Hydrophobic or Hydrophilic? The Impact of
28
29 Geometry and Functionalization on Water Adsorption. Phys. Chem. Phys. Chem. 2014,
30
31
32 16, 9940-9949.
33
34 (33) Zhang, K.; Nalaparaju, A.; Chen, Y.; Jiang, J. Biofuel Purification in Zeolitic
35
36
Imidazolate Frameworks: the Significant Role of Functional Groups. Phys. Chem. Phys.
37
38
39 Chem. 2014, 16, 9643-9655.
40
41 (34) Frenkel, D.; Smit, B. Understanding Molecular Simulation; Academic Press: San
42
43
44
Diego, CA, 1996.
45
46 (35) Morris, W.; Doonan, C. J.; Furukawa, H.; Banerjee, R; Yaghi, O. M. Crystals as
47
48 Molecules: Postsynthesis Covalent Functionalization of Zeolitic Imidazolate
49
50
51 Frameworks. J. Am. Chem. Soc. 2008, 130, 12626-12627.
52
53 (36) Willems, T. F.; Rycroft, C. H.; Kazi, M.; Meza, J. C.; Haranczyk, M. Algorithms
54
55 and Tools for High-Throughput Geometry-Based Analysis of Crystalline Porous
56
57
58 Materials. Microporous Mesoporous Mater. 2012, 149, 134-141.
59
60 28
ACS Paragon Plus Environment
 The Journal of Physical Chemistry Page 30 of 31

1
2
3 (37) Rick, S. A Reoptimization of the Five-Site Water Potential (Tip5p) for Use with
4
5
6 Ewald Sums. J. Chem. Phys. 2004, 120, 6085-6093.
7
8 (38) Mayo, S. L.; Olafson, B. D.; Goddard, W. A. DREIDING: a Generic Force Field for
9
10
Molecular Simulations. J. Phys. Chem. 1990, 94, 8897-8909.
11
12
13 (39) Dubbeldam, D.; Torres-Knoop, A.; Walton, K. S. On the Inner Workings of Monte
14
15 Carlo Codes. Mol. Sim. 2013, 39, 1253-1292.
16
17
18
(40) Dubbeldam, D.; Calero, S.; Donald, E.; Snurr, R. RASPA: Molecular Simulation
19
20 Software for Adsorption and Diffusion in Flexible Nanoporous Materials. Mol. Sim.
21
22 2015, DOI 10.1080/08927022.2015.1010082.
23
24
25 (41) Robinson, D. B.; Peng, D. Y.; Chung, S. Y. K. The Development of the Peng-
26
27 Robinson Equation and its Application to Phase-Equilibrium in a System Containing
28
29 Methanol. Fluid Phase Equilib. 1985, 24, 25-41.
30
31
32 (42) Luzar, A.; Chandler, A. Structure and Hydrogen Bond Dynamics of Water-
33
34 Dimethyl Sulfoxide Mixtures by Computer Simulations. J. Chem. Phys. 1993, 98,
35
36
8160–8173.
37
38
39 (43) Calero, S.; Gómez-Álvarez, P. Hydrogen Bonding of Water Confined in Zeolites
40
41 and their Zeolitic Imidazolate Framework counterparts. RSC Adv. 2014, 4, 29571–
42
43
44
29580.
45
46 (44) Lange, N. A. Handbook of Chemistry, McGraw-Hill, New York, 1956.
47
48 (45) Marsh, K. N. Recommended Reference Materials for the Realization of
49
50
51 Physicochemical Properties, Blackwell, Oxford, 1987.
52
53 (46) Desbiens, N.; Demachy, I.; Fuchs, A. H.; Kirsch-Rodeschini, H.; Soulard, M.;
54
55 Patarin, J. Water Condensation in Hydrophobic Nanopores. Angew. Chem., Int. Ed.
56
57
58 2005, 44, 5310−5313.
59
60 29
ACS Paragon Plus Environment
Page 31 of 31 The Journal of Physical Chemistry

1
2
3 Table of Contents Image
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 30
ACS Paragon Plus Environment