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Interfaces: Adsorption, Reactions, Films, Forces, Measurement Techniques, Charge

Transfer, Electrochemistry, Electrocatalysis, Energy Production and Storage
Investigation of the Water Adsorption Properties and
Structural Stability of MIL-100(Fe) with Different Anions
Yen-Ru Chen, Kai-Hsin Liou, Dun-Yen Kang, Jiun-Jen Chen, and Li-Chiang Lin
Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.7b04399 • Publication Date (Web): 13 Mar 2018
Downloaded from http://pubs.acs.org on March 15, 2018

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Page 1 of 32 Langmuir

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3 Investigation of the Water Adsorption Properties and
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6 Structural Stability of MIL-100(Fe) with Different Anions
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8 Yen-Ru Chen,1 Kai-Hsin Liou,1 Dun-Yen Kang,1 Jiun-Jen Chen,2,* and Li-Chiang Lin3,*
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11 Department of Chemical Engineering, National Taiwan University
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13 No. 1, Sec. 4, Roosevelt Rd., Taipei 10617, Taiwan
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17 Green Energy and Environment Research Laboratories, Industrial Technology Research
18 Institute
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20 No. 195, Sec. 4, Chung Hsing Rd., Chutung, Hsinchu 31040, Taiwan
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25 William G. Lowrie Department of Chemical and Biomolecular Engineering, The Ohio State
26 University
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28 151 W. Woodruff Avenue, Columbus, OH 43210, United States
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31 * Corresponding authors: J.-J. Chen (JiunJenChen@itri.org.tw); L.-C. Lin
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33 (lin.2645@osu.edu)
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3 Abstract
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6 Investigating metal-organic frameworks (MOFs) as water adsorbents has drawn increasing
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attention for their potential in energy-related applications such as water production and heat
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11 transformation. A specific MOF, MIL-100(Fe), is of particular interest for its large adsorption
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13 capacity with the occurrence of water condensation at a relatively low partial pressure. In the
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15 synthesis of MIL-100(Fe), depending on the reactants, structures with varying anion
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17 terminals (e.g., F-, Cl-, or OH-) on the metal trimer have been reported. In this study, we
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19 employed molecular simulations and density functional theory calculations for investigating
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the water adsorption behaviors and the relative structural stability of MIL-100(Fe) with
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24 different anions. We also proposed a possible defective structure and explored its water
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26 adsorption properties. The results of this study are in good agreement with the experimental
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28 measurements and are in support of the observations reported in the literature.
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30 Understandings toward the spatial configurations and energetics of water molecules in these
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32 materials have also shed light on their adsorption mechanism at the atomic level.
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39 Keywords: Water vapor adsorption, Metal-organic frameworks, Structural stability, Monte
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41 Carlo simulations, Density functional theory calculations
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3 Introduction
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6 Metal-organic frameworks (MOFs) are an emerging class of crystalline
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microporous/mesoporous materials, composed of metal clusters and organic ligands. MOFs
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11 possess a variety of properties such as high porosity, large surface area, and diverse
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13 functionality, thus providing opportunities in fields including, but not limited to, gas
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15 separations,1-5 catalysis,6-9 drug delivery,10-14 gas storage,15-16 and adsorption refrigeration.17-
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In recent years, using MOFs as water adsorbents has drawn increasing attention. MOFs
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19 have been demonstrated for their promise in dehumidification22 and fresh water production.23
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As examples, Seo et al. showed that, in terms of adsorption capacity and kinetics, MIL-
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24 100(Fe) and MIL-101(Cr) can outperform conventional water sorbents such as SAPO-34,
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26 NaX, and silica gel.22 Furukawa et al. demonstrated that MOF-801 possesses a high water
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28 uptake at a low humidity of P/P0=0.1 and can be regenerated under mild conditions.24 Such
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30 properties make MOF-801 a promising material for the production of fresh water from
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32 ambient air. The large adsorption capacity at a low relative pressure of MOFs also makes
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them potential adsorbents in heat pumps for more efficient heat transformation.20-21
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39 Among MOFs reported to date as water adsorbents, MIL-100(Fe) is of particular interest.17,25-
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41 The water adsorption capacity of as-synthesized MIL-100(Fe) can reach as much as 0.75 g-
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43 water/g-MOF at 298 K,17 which transcends many other existing MOF materials (e.g., ZIF-8
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45 of 0.01 g/g at 308 K and HKUST-1 of 0.60 g/g at 298 K).27 MIL-100(Fe) consists of iron(III)
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and 1,3,5-bezenetricarboxylic (1,3,5-BTC). Its atomic structure can be seen in Figure 1,
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50 which has two distinct types of cages with diameters of 2.5 nm and 2.9 nm.28-29 It has a
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52 structure formula of FeIII3O(H2O)2X(C6H3(CO2)3)2•nH2O, where X can be F-, or OH-,30
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54 depending on the synthesis conditions. The high water adsorption capacity of MIL-100(Fe)
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56 may be attributed to its large surface area (BET surface area is as high as 2300 m2 g-1)31 and
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3 open-metal sites that strongly coordinate with water molecules.31 In addition to the large
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5 capacity, the capillary condensation of water in the framework (i.e., a sharp increase in the
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7 adsorption isotherm due to the clustering of water molecules) occurs at a low relative
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9 pressure P/P0 of 0.25-0.4, a range suitable for heat transformation applications.17,20
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14 The first experimental synthesis of MIL-100(Fe) reported in the literature involves the use of
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16 hydrofluoric acid (HF),29 a highly toxic chemical.30 Several modified synthesis approaches
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18 have been therefore developed to avoid using hydrofluoric acid.9,30,32-34 Using the so-called
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20 HF-free syntheses, no evident change in the structure of MIL-100(Fe) was found, except that
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22 fluorine at the terminal position of the metal cluster (or so-called metal trimer) is replaced by
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another anion.30 As noted above, hydroxide may replace the terminal fluoride in MIL-100(Fe)
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27 obtained from an HF-free synthesis.35 Although MIL-100(Fe) structures with hydroxide have
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29 been observed using HF-free conditions, we expect that MIL-100(Fe) with Cl- might be
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31 possibly obtained as chloride ions are also commonly available in HF-free syntheses.
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33 Accordingly, in this study, we considered MIL-100(Fe) structures with three different anions
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35 (F-, Cl-, and OH-). For convenience, these structures were denoted hereafter as MIL-
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100(Fe)_F, MIL-100(Fe)_Cl, and MIL-100(Fe)_OH, respectively.
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42 Although no apparent structural change has been identified, the anions in MIL-100(Fe) play
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44 an important role in its stability and crystallinity. The fluoride-functionalized terminal
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46 appears to help stabilize the formation of trimeric inorganic building units in MIL-100(Fe),
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48 which leads to more effective crystallization compared to other anions.25 The better
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crystallinity of MIL-100(Fe)_F also results in a high cyclic stability for water adsorption.17,36
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53 Compared to MIL-100(Fe)_F, MIL-100(Fe)_OH has been found to possess a smaller particle
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3 size and relatively poorly-defined crystal morphology.30 It has also been reported that this
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5 structure suffers from a low structural stability in aqueous phase.37
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9 Although MIL-100(Fe)_F has been widely explored both experimentally and computationally
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for its potential as water adsorbents,17,38 the atomic-level understandings toward the influence
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14 of alternative anions in MIL-100(Fe) on their water adsorption properties and structural
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16 stability have yet been achieved. In this work, molecular simulations and density functional
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18 theory (DFT) calculations were employed to systematically investigate MIL-100(Fe)_F,
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20 MIL-100(Fe)_Cl, and MIL-100(Fe)_OH. Monte Carlo simulations in a grand canonical
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22 ensemble (GCMC) or canonical ensemble (NVT) were carried out to simulate their water
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adsorption isotherms as well as to understand the spatial distribution and energetics of water
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27 molecules adsorbed in the frameworks. The ground state energy of each structure was also
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29 computed using DFT to reveal the relative structural stability. Furthermore, we investigated
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31 the water adsorption properties of a possible MIL-100(Fe) with defects.
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3 Computational Details
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6 Structures. The structures used in this work (see Figure 1) were adopted from the Cambridge
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Crystallographic Data Centre (CCDC: 640536)29 with some modifications. First, we removed
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11 residual water molecules inside the pores. Next, the unit cell was converted into a primitive
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13 cell in order to reduce the computational cost. We then attached F-, Cl-, or OH- ions onto the
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15 metal trimer, leading to the so-called MIL-100(Fe)_F, MIL-100(Fe)_Cl, or MIL-100(Fe)_OH
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17 structures, respectively. Note that each trimer only has one anion for the overall charge
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19 neutrality of the structures. These three structures (containing approximately 2800 atoms per
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primitive unit cell) were subsequently relaxed by a cascade of the steepest descent, adjusted
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24 basis set Newton-Raphson, and quasi-Newton methods. The structural relaxation was
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26 performed using the Forcite module in the commercial Materials Studio® with the
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28 DREIDING39 force field. The convergence criteria for energy, force, and displacement were
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30 set to 2×10-5 kcal mol-1, 0.001 kcal mol-1 Å-1, and 0.001 Å, respectively. The atomic
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32 coordinates of these three structures can be found in the Supporting Information.
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37 Adsorption Isotherms. Monte Carlo simulations in a grand canonical ensemble (GCMC),
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39 implemented in an open-source package RASPA 2.0,40 were carried out to compute the
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41 adsorption isotherms of water in these three MIL-100(Fe) structures. The temperature of
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43 adsorption was set to 300 K. Intermolecular potentials were described using both van der
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45 Waals interactions (6-12 Lennard-Jones potential) and long-range Coulombic interactions.
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The Lennard-Jones parameters of the framework atoms were adopted from the DREIDING39
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50 force field, while their partial charges were assigned by the extended charge equilibrium
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52 method (EQeq).41 Water molecules were modeled using the widely used 4-site TIP4P-Ew42
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54 model. The Lorenz-Berthelot mixing rule was applied to determine the Lennard-Jones
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56 parameters between two dissimilar atoms. The pair-wise Lennard-Jones potential was shifted
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3 and truncated at a cut-off radius of 12 Å without tail corrections, while the long-range
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5 electrostatic interactions were calculated by the Ewald summation technique with a precision
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7 of 1×10-6. A total of approximately 110 million Monte Carlo attempts including random
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9 insertion, deletion, reinsertion, rotation, and translation of water molecules were carried out
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in each of these calculations. The relative ratio of these moves was set respectively to 4: 4: 4:
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14 1: 1. 100 million moves were conducted firstly to ensure that equilibrium had been achieved,
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16 and the loading reached approximately a constant after a certain number of Monte Carlo
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18 attempts during the system initialization. Subsequently, additional 10 million Monte Carlo
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20 steps were conducted in each calculation to calculate the average loading.
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Adsorption Distribution and Energetics. To investigate the spatial distribution of adsorbed
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27 water molecules within the framework as well as the corresponding adsorption energetics at a
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29 specific loading, Monte Carlo simulations in a canonical ensemble (NVT) at 300 K were
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31 conducted. The detailed settings of the NVT simulations were similar to that of GCMC
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33 calculations but in the absence of random insertion and deletion moves. NVT simulations
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35 were also used to compute the binding geometry of a single water molecule in MIL-100(Fe).
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In these calculations, we performed simulations at a low temperature of 5 K, ensuring the
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40 adsorbed phase closes to the lowest energy state. Five replicas of the NVT calculations for
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42 each structure were carried out with different initial configurations, and tens of millions
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44 Monte Carlo moves were opted in each of the replica. The configuration with the lowest
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46 energy was identified as the binding geometry.
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Structural Stability. We used the ground state energies of MIL-100(Fe) structures with
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53 varying anions to probe their relative structural stability. Considering the size of MIL-
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55 100(Fe) structures (i.e., ~2800 atoms in the primitive unit cell), it is computationally
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3 prohibited to compute the ground state energy of these structures using DFT. We therefore
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5 constructed small clusters, comprising of one metal trimer and six ligands, as shown in Figure
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7 2 to represent the corresponding full periodic structures. To maintain the neutrality of the
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9 cluster and to reduce computational costs, two carboxyl groups in the 1,3,5-BTC linker were
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replaced by hydrogen atoms. The ground state energy of these clusters was calculated using
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14 DFT implemented in the CASTEP43 module of Materials Studio®. Plane-wave periodic DFT
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16 that involves few convergence parameters (e.g., cutoff energy and number of k-points) was
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18 adopted, and many pioneering efforts have been made for the program optimization.44-45 With
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20 a reasonable vacuum space, periodic DFT could be an effective way to study non-periodic
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22 cluster systems.46 In these calculations, the generalized gradient approximation (GGA) in the
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scheme of Perdew–Burke–Ernzerhof (PBE)47 was opted as the exchange-correlation
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27 functional without applying additional dispersion corrections. A plane wave energy cutoff of
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29 340.0 eV and the Monkhorst–Pack k-point 1×1×1 mesh48 were used. At least 7 Å of vacuum
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31 space was included to minimize the interaction between periodic images. The convergence
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33 criteria for energy, force, and displacement were 1×10-5 eV/atom, 0.03 eV Å-1, and 0.001 Å,
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35 respectively. In this study, in order to make a meaningful comparison of the computed ground
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state energies of these clusters that possess different chemical compositions, we further
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40 assumed the following two reactions:
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44 MIL-100(Fe)_F + HCl ⇌ MIL-100(Fe)_Cl + HF Eq. (1)
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MIL-100(Fe)_F + H2O ⇌ MIL-100(Fe)_OH + HF Eq. (2)
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51 From Eq. (1), we defined the relative energy difference between MIL-100(Fe)_F and MIL-
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53 100(Fe)_Cl to be represented by the difference between E(MIL-100(Fe)_F) – E(HF) and
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55 E(MIL-100(Fe)_Cl) – E(HCl). Similarly, from Eq. (2), the energy difference between MIL-
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3 100(Fe)_F and MIL-100(Fe)_OH can be quantified by the difference between E(MIL-
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5 100(Fe)_F) – E(HF) and E(MIL-100(Fe)_OH) – E(H2O). E(HF), E(HCl), and E(H2O) are
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7 respectively the ground state energies of gas phase HF, HCl, and H2O molecules. These
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9 energies were computed using exactly the same level of theory and the same simulation
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dimension as that adopted in the cluster calculations. All of the above calculations were
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14 carried out in the gas phase instead of in a solvent-mediated environment such as under the
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16 synthesis condition and/or the condition when the material is filled (or partially filled) with
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18 water molecules. Nonetheless, given all of the studied structures are very similar, the gas
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20 phase assumption should serve as a decent first-order approximation. Further, as discussed
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22 below, our calculation results are in good agreement with those reported experimentally.
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3 Results and Discussion
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6 Water Adsorption. Water adsorption isotherms in MIL-100(Fe)_F, MIL-100(Fe)_Cl, and
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MIL-100(Fe)_OH at 300 K computed by GCMC simulations are summarized in Figure 3.
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11 Isotherms are presented as a function of the relative pressure (P/P0) with P0 to be 3750 Pa at a
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13 room temperature according to TIP4P-Ew water model.49 The calculated water isotherm of
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15 MIL-100(Fe)_F is in agreement with the experimental ones.17,25 Compared to a previous
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17 computational study,38 our isotherm resembles the experimental data more accurately, which
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19 may be attributed to the adopted water models. In this work, the 4-site TIP4P-Ew model was
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adopted, whereas the 3-site SPC/E water model was opted in the previous work. It has been
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24 shown in our previous study that the TIP4P-Ew model may better describe water adsorption
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26 properties,50 and it has also been widely adopted in the calculations of adsorption in
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28 nanoporous materials.51-53 Additionally, Figure 3 shows that the isotherm of MIL-100(Fe)_F
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30 possesses a plateau at an uptake of approximately 0.4 g-water/g-MOF (i.e., corresponding to
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32 P/P0 of 0.40-0.53 in the simulated isotherm), and this interesting phenomenon can be found
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in both experimental and simulation isotherms. It has been hypothesized that this may be
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37 caused by the difference in water adsorption characteristics between two distinct cages of
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39 MIL-100(Fe).17,25 As illustrated in Figure 1, two sizes of cages (2.5 and 2.9 nm) are present in
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41 MIL-100(Fe). At a low pressure, water molecules may preferentially adsorb in the small
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43 cages (2.5 nm) due to the more favorable interactions between water and the framework until
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45 saturation. Thereafter the adsorption in the large cages (2.9 nm) occurs, thus leading to the
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observed plateau. To validate this hypothesis, snapshots of the water configurations adsorbed
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50 in MIL-100(Fe)_F at various pressures are taken from our simulations and shown in Figure 4.
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52 For a clear presentation, the MIL-100(Fe) framework is shown as sticks with green and
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54 orange colors (represent small and large cage structures, respectively), while the space-filling
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56 style was used for water molecules. These atomistic configurations clearly indicate that at a
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3 low pressure (P/P0 < 0.27), water molecules indeed first occupied the small cages. The
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5 condensation of water in the small cages occurred at a P/P0 between 0.27 and 0.40. At a P/P0
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7 of 0.40, Figure 4 shows that the small cages became completely filled with a density of water
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9 determined to be around 0.9 g/cm3, whereas nearly no water molecule was adsorbed in the
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large cages. This preferential adsorption in different types of cages observed in our
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14 simulations also agrees with previous findings in related structures.23,25-26,54
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18 The water adsorption capability in MIL-100(Fe) with different anions (Figure 3)
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20 demonstrates that the water uptake in both MIL-100(Fe)_Cl and MIL-100(Fe)_OH at 300 K
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22 is substantially lower than that of MIL-100(Fe)_F although these three structures possess a
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nearly identical saturation uptake due to their similar pore structures. Specifically, the sharp
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27 increase in the adsorption isotherm of both MIL-100(Fe)_Cl and MIL-100(Fe)_OH occurs at
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29 a notably higher pressure, thus suggesting a weaker water-framework interaction was
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31 involved in these two structures. As a consequence, different from MIL-100(Fe)_F, the
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33 adsorption isotherms of both MIL-100(Fe)_Cl and MIL-100(Fe)_OH do not possess a plateau.
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35 Because of their relatively weaker water-framework interactions, the difference in the
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adsorption characteristics between two types of cages becomes marginal. Additionally, this
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40 also indicates that both MIL-100(Fe)_Cl and MIL-100(Fe)_OH may be relatively less
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42 promising adsorbent candidates for applications such as water harvesting and heat
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44 transformation.
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48 Adsorption Energetics and Binding Geometries. To gain insights into the adsorption
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energetics of water in MIL-100(Fe) with different terminal anions, the guest-host and guest-
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53 guest (i.e., guest: water molecules; host: the framework) interaction energies were calculated
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55 using NVT simulations (see Figure 5). As discussed above, MIL-100(Fe)_F was indeed
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3 identified to possess the strongest host-guest interaction among the three MOF structures
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5 (Figure 5a) in the low-loading region (below 0.04 g-water/g-MOF). Compared to MIL-
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7 100(Fe)_Cl and MIL-100(Fe)_OH, the host-guest interaction energy for MIL-100(Fe)_F is
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9 lower by as much as 10 kJ/mol. The strong host-guest interaction in MIL-100(Fe)_F explains
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its significantly higher water uptake in the low-pressure region. This is also reflected on the
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14 absence of the sharp uptake increase in both MIL-100(Fe)_Cl and MIL-100(Fe)_OH at a low
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16 relative pressure, as the guest-host interaction has been known to facilitate the occurrence of
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18 water condensation in confined environments. At a higher loading (> 0.2 g-water/g-MOF),
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20 the guest-host interaction energies among the three MOF structures become comparable.
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22 Under this condition, most water molecules are anticipated to be at a distance from the
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framework surface, thus making the overall difference in host-guest interaction become
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27 relatively insignificant. For this, we have computed the accumulative number of water
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29 adsorbed in the two distinct cage types of the MIL-100(Fe)_F structure as a function of the
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31 distance from the center of the cages (see the Supporting Information Figures S1 and S2 for
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33 the adsorption in the large and small cages, respectively). For water adsorption in the small
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35 cages as an example, at a low loading (0.043 g/g) water molecules are preferentially adsorbed
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38 at a distance of 14-17 Å away from the center of the cages (i.e., near the cage surface), as
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40 suggested in Figure S1. As noted above, this confirms that the host-guest interaction should
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42 play a critical role in adsorptive behaviors in this low-pressure region. By contrast, at a high
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44 loading (0.945 g/g), our results show that most of the water are located near the center (within
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14 Å of the center of the cage). Specifically, approximately 80% of the total water molecules
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49 are adsorbed away from the cage surface and therefore, guest-guest interactions should
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51 dominate the total energies. Interestingly, our analysis shown in Figures S1 and S2 also
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53 indicates that the density of adsorbed water in both cages can be notably different. It was
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55 found that the adsorbed amount of water molecules in the small cages is greater than that in
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3 the large cages, leading to a denser adsorbed phase in the small cages. In agreement with a
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5 recent study by Choi et al., the density of adsorbed phase may differ drastically, which
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7 depends on the pore structure and surface chemistry.55 Furthermore, for the guest-guest
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9 interactions shown in Figure 5b, it was found that water molecules in MIL-100(Fe)_F have
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the least favorable interactions (i.e., highest energy values). This may be attributed to the
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14 weaker guest-host interaction found in MIL-100(Fe)_Cl and MIL-100(Fe)_OH, thus allowing
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16 the agglomeration of water molecules with a more favorable configuration. In other words,
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18 the less constrain imposed by the host-guest interactions may lead to more favorable guest-
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20 guest contributions.
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Figure 5a shows that there is an interesting local maximum energy in the guest-host
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27 interaction at the loading of approximately 0.1 g-water/g-MOF for all of the three structures,
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29 and a corresponding local minimum can be seen in the guest-guest interaction (Figure 5b).
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31 This behavior indicates a possible configuration change for water molecules adsorbed in the
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33 framework. At a low loading condition (less than 0.05 g/g, water molecules are dispersedly
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35 adsorbed in the framework), these water molecules are located in a way to maximize its
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interaction with the framework. When the concentration of adsorbed water increases, a
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40 change in the configuration for those initially adsorbed water molecules may be needed in
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42 order to gain strong water-water interactions and subsequently lower the overall energy,
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46 The binding geometry and distance of water in MIL-100(Fe)_F, MIL-100(Fe)_Cl, and MIL-
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48 100(Fe)_OH determined by NVT calculations at a low temperature are summarized in Figure
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6. In all of the three MIL-100(Fe) structures, the water binding configuration was found to be
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5 field point of view, the negatively charged anion can help stabilize the positively charged
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7 hydrogen atoms of water. Similarly, the same effect exists between the negatively charged
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9 oxygen atom of water and the positively charged open-metal site. The hydrogen (H2O)-anion
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12 distance is shorter in MIL-100(Fe)_F (1.87 Å) relative to that in MIL-100(Fe)_OH (2.19 Å)
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14 and MIL-100(Fe)_Cl (2.28 Å), demonstrating that F- possesses the strongest interaction with
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16 water. The oxygen (H2O)-metal site distance was found to be correspondingly larger in MIL-
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18 100(Fe)_F (3.49 Å) relative to that in MIL-100(Fe)_OH (3.22 Å) and MIL-100(Fe)_Cl (3.17
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21 Å).
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26 Structural Stability and Defective MIL-100(Fe). To understand the structural stability of
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28 MIL-100(Fe)_F, MIL-100(Fe)_Cl, and MIL-100(Fe)_OH, the ground state energy of their
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30 representative clusters as introduced previously were calculated and compared. The relative
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32 energy can serve as a proxy to indicate the stability of the basic building unit in MIL-100(Fe).
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34 As shown in Figure 7, MIL-100(Fe)_F was found to be more stable than MIL-100(Fe)_OH
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by approximately 0.8 eV. This value is deemed as significant, which is far beyond the
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39 thermal energy of 0.025 eV at the room temperature. This finding supports the observation
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41 reported in the literature that MIL-100(Fe) synthesized in the absence of HF (i.e., structures
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43 with hydroxide) tends to be notably less stable.30,37 Interestingly, MIL-100(Fe)_Cl was
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45 identified to be potentially more stable than MIL-100(Fe)_F. However, we should note that
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47 our energy calculations do not consider the presence of adsorbed molecules. For instance,
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upon water vapor adsorption, the stronger interactions between H2O and metal trimers with F-
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52 relative to that between H2O and trimers with other anions may also influence the structural
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54 stability. Additionally, although MIL-100(Fe)_Cl is predicted to be more thermodynamically
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56 stable than MIL-100(Fe)_OH, the fact that MIL-100(Fe)_Cl structures were not observed
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3 experimentally in HF-free conditions suggests that solvent molecules involved in the
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5 synthesis may also play a role. Nonetheless, our calculations have, for the first time, shed
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7 light on the relative structural stability of MIL-100(Fe) with varying anions.
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11 As noted above, based on our DFT calculations, the metal trimer cluster of MIL-100(Fe)_OH
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13 was identified to be notably less stable compared to that of MIL-100(Fe)_F and MIL-
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15 100(Fe)_Cl. It is therefore expected that MIL-100(Fe)_OH may be potentially more prone to
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structural defects. In this study, considering its relatively unstable trimer clusters, we
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20 proposed a defective MIL-100(Fe)_OH structure that has metal-node missing defects (see
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22 Figure 8 for illustration) with a density of one missing metal node out of 68 nodes in the
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24 primitive cell of MOF-100(Fe). The atomic coordinates of the defect structure can be found
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26 in the Supporting Information. Similar types of defects have been also studied in another
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28 well-studied MOF, UiO66.56-58 Same as the analysis carried out for defect-free frameworks,
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we have also computed the adsorption isotherms using GCMC simulations in this metal-node
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33 missing structure. Figure 9 shows that the uptake in the defective MIL-100(Fe)_OH structure
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35 was predicted to be lower than that of the corresponding defect-free one. Specifically, the
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37 uptake of water in the defective MIL-100(Fe)_OH structure is nearly zero even at a relative
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39 pressure of approximately 1.0. In the absence of the metal nodes, the interactions between
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41 adsorbed water molecules and the framework are anticipated to become overall weaker. As
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shown in Supporting Information Figure S3, the host-guest interaction is weaker in the MIL-
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46 100(Fe)_OH structure with metal-node missing defects, in particular in the low-pressure
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48 region. Given the host-guest interactions at a low loading can facilitate the condensation of
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50 water adsorbed in the framework, such defective structure accordingly shows a lower
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52 adsorption ability. Our calculations also infer that MIL-100(Fe)_OH may have a relatively
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54 poor cyclic stability with a reduction in adsorption ability, which is in good agreement with
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previously reported experimental results that MIL-100(Fe) synthesized in absence of HF
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5 We should note that it remains unknown whether the proposed defective structure is stable in
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7 the presence of water. The defective structure is possibly an intermediate structure before the
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9 complete degradation of the materials. A detailed investigation of the structural degradation
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can be an important subject of future studies.
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6 We employed Monte Carlo techniques (GCMC and NVT simulations) and density functional
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theory (DFT) calculations to investigate the water adsorption behaviors and relative structural
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11 stability of MIL-100(Fe) with different terminal anions (F-, Cl-, or OH-). Our calculated
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13 adsorption isotherm in MIL-100(Fe)_F is in agreement with that measured experimentally,
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15 and both simulation and experiment isotherms show an obvious plateau. By visualizing the
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17 atomic-level adsorption configurations at varying pressures, it was found that the plateau can
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19 be attributed to the difference in adsorption characteristics of two distinct types of cages in
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MIL-100(Fe). Small cages, which provide a stronger interaction to water molecules
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24 compared to large cages, were found to be completely filled with water at a notably lower
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26 pressure. Amongst these three structures, due to the strongest interaction between the
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28 terminal F- anion and water molecules, the adsorption isotherm in MIL-100(Fe)_F has the
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30 largest adsorption capability with the occurrence of water condensation at a much smaller
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32 relative pressure. From the ground state energy calculations by DFT, MIL-100(Fe)_F was
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identified to be significantly more stable than MIL-100(Fe)_OH. This result agrees with the
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37 experimental observations where MIL-100(Fe)_F was demonstrated to have higher
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39 crystallinity with better defined morphology. Considering the relatively poor stability of
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41 MIL-100(Fe)_OH, a possible defective MIL-100(Fe)_OH structure (i.e., metal-node missing
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43 defects) was proposed and studied. This proposed defective structure appears to have a lower
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45 water uptake compared to the defect-free one, inferring that these less stable materials are
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prone to a poor cyclic stability in adsorption. Overall, the outcomes of this study are in
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50 support of the experimental findings reported in the literature, while the atomistic
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52 understandings achieved have shed light on the water adsorption mechanism in MIL-100(Fe)
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54 with different anions.
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21 Figure 1. Illustration of the cage structure (left) and the building unit (right) of MIL-100(Fe).
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24 Figure 2. Illustration of the cluster model used for the ground state energy calculations.
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Figure 3. GCMC-calculated and experiment-measured17,25 water adsorption isotherms at 300
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49 Figure 4. (a) Illustration of two distinct types of cages in MIL-100(Fe). (b) Snapshots of
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Host-Guest Energy
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(kJ/mol)
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18 0.0 0.2 0.4 0.6 0.8 1.0
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Guest-Guest Energy

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(kJ/mol)

Original_OH
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35 Loading (g/g)
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Total Energy (kJ/mol)

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50 Loading (g/g)
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53 Figure 5. (a) Host(framework)-guest(water), (b) guest-guest, and (c) total interaction
54 energies as a function of the water uptake in MIL-100(Fe)_F, MIL-100(Fe)_Cl, and MIL-
55 100(Fe)_OH.
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Figure 6. The binding configurations of water molecules and the corresponding distances of
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21 Figure 7. The relative energies of MIL-100(Fe) clusters with different terminal anions (i.e.,
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26 Figure 8. Illustration of (a) defect-free MIL-100(Fe) and (b) metal-node missing MIL-100(Fe)
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29 Figure 9. The GCMC-calculated water adsorption isotherm of the metal-node missing MIL-
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3 Associated Content
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5 Supporting Information Available. The supporting information includes additional figures
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7 referred in the main article (i.e., accumulative number of water adsorbed in MIL-100(Fe)_F
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9 and the host-guest interaction energy of water in the defective MIL-100(Fe)_OH structure) as
10
11 well as the structural information of all structures studied in this work. This material is
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available free of charge via the Internet at http://pubs.acs.org.
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17
AUTHOR INFORMATION
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19 Author Contributions
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22 This study was developed and completed through contributions by all authors.
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28 Acknowledgement
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31 This work was supported by the Bureau of Energy of the Ministry of Economic Affairs,
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33 Taiwan. The authors also gratefully thank Ohio Supercomputer Center (OSC) for
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35 computational resources.59
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