Experimental Study of CO2 CH4 Adsorption On A Dimethyl Functionalized UiO 66 Framework

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Article
Experimental Study of CO, CH, and Water Vapor Adsorption
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on a Dimethyl-Functionalized UiO-66 Framework

Himanshu Jasuja, and Krista S. Walton
J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/jp311857e • Publication Date (Web): 07 Mar 2013
Downloaded from http://pubs.acs.org on March 16, 2013
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Page 1 of 22 The Journal of Physical Chemistry
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Experimental Study of CO2, CH4, and Water Vapor
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12 Adsorption on a Dimethyl-Functionalized UiO-66
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16 Framework
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21 Himanshu Jasuja and Krista S. Walton*
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School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst
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27 Drive NW, Atlanta, Georgia 30332
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30 KEYWORDS: UiO-66; water stability; hydrophobicity; CO2 capture; selectivity
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ABSTRACT: A water resistant, highly robust dimethyl-functionalized UiO-66 analogue (UiO-
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36 66-DM) has been synthesized and characterized using N2 adsorption, powder X-ray diffraction,
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H nuclear magnetic resonance, Fourier transform infrared spectroscopy, and thermo-gravimetric
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analysis followed by mass spectroscopy. High-pressure (up to 20 bar) single-component
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43 adsorption isotherm measurements of CO2 and CH4 have been performed on UiO-66-DM at
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45 different temperatures (293-308 K). Adsorption isotherm data were modeled using the Toth
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48 equation, and isosteric heats of adsorption were calculated using the Clausius-Clapeyron
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50 equation. The Ideal Adsorbed Solution Theory (IAST) was used to calculate mixture
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52 selectivities. Water adsorption experiments show that water adsorption loadings in UiO-66-DM
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55 are reduced by almost 50% compared to the parent material. In the low pressure region,
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57 functionalization of the benzenedicarboxylic ligand by 2,5-dimethyl leads to higher interactions
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with both CO2 and CH4 compared to the parent UiO-66. CO2/ CH4 selectivity calculated from
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6 IAST is higher for UiO-66 in the low pressure region (<5 bar) but for pressures > 5 bar, UiO-66-
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8 DM is more CO2 selective than UiO-66.
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14 1. INTRODUCTION
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17 The synthesis and characterization of porous materials for use as adsorbents and catalysts have
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20 been an active area of research for decades due to numerous uses in applications ranging from
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22 petrochemicals and catalysis to adsorption-based selective separations.1 Traditional porous
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materials such as zeolites and similar oxide-based materials have been a focal point since 1960.2
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27 However, new developments in synthetic zeolites have been limited due to the relatively small
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29 size of the pores, difficulty in the tuning of these pores, and difficulty in chemical modification
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of the surface. Metal-organic frameworks (MOFs), which are made up of metal clusters linked to
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34 each other by organic ligands,3 have provided a significant breakthrough in this regard.4 These
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36 hybrid materials have extremely high surface areas and pore volumes, uniform pore sizes, and
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39 chemical functionalities.5 Moreover, their pore sizes and chemical functionalities can be tuned by
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41 modifying the metal group or organic linker.6,7 Hence, MOFs have attracted considerable interest
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43 for their possible use in a variety of applications.8-10
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47 The practical use of MOFs in many industrial applications such as natural gas sweetening
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49 hinges on the framework stability under harsh conditions such as high pressures up to 60 bar11
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and stability upon exposure to water vapor and acid gases.12 Novel MOFs are appearing at a very
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54 rapid pace,9 and a few water stable examples have emerged recently. Cavka et al. was first to
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56 synthesize a zirconium (IV)-based MOF (UiO-66) with exceptional stability.13 This stability has
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been attributed to the highly oxophilic nature of zirconium (IV), leading to the formation of a
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6 very stable inorganic brick [Zr6O4(OH)4]. These Zr6-octahedra are bound to twelve 1,4-
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8 benzenedicarboxylic acid (BDC) ligands (each Zr atom is 8-coordinated) leading to a 3D
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arrangement of micro pores (6 Å). In 2010, Cohen et al.3 first reported the synthesis of amino-,
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13 bromo-, nitro-, and naphthalene-functionalized UiO-66 MOFs. Later in the same year, Kandiah
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15 et al.14 reported that amino-, bromo-, and nitro-functionalized UiO-66 MOFs also retain high
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18 thermal and chemical stabilities similar to the parent material. Cmarik et al.15 observed high
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20 stability in other UiO-66 variants including methoxy and naphthyl functional groups. Hence, the
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22 UiO-66 framework is quite robust and is exceedingly open to isoreticular functionalization
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25 without losing its high hydrothermal and chemical stabilities.
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28 Schoenecker et al. showed that UiO-66 is quite hydrophilic, i.e., it adsorbs a large amount of
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water vapor at 90% RH (22.42 mmol/g), which is higher than the water adsorption capacities of
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33 traditional adsorbents such as zeolites 5A and 13X and BPL carbon.16 Hence, the UiO-66
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35 framework will be most effective for use in separations under humid conditions only when its
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38 affinity for water is reduced; otherwise, the pores will fill with water vapor, thus reducing the
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40 adsorption capacity of the target gases, e.g., CO2 capture from flue gas/ natural gas streams. The
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42 pore properties and host-guest interactions (hydrophilicity in case of water) can be systematically
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45 tuned in MOFs through pre-synthesis ligand functionalization or post-synthetic modification
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47 (PSM). Thus, their adsorption capacity and selectivity toward a targeted gas can be enhanced.
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The idea of incorporating hydrophobic functional groups into a MOF structure to reduce water
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53 adsorption has been suggested in many literature reports.15, 17-22 However, only a few of these
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55 reports have examined CO2 and CH4 adsorption as well. Ideally, functionalized MOFs should
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enhance the adsorption of the target gas without also enhancing the adsorption of water vapor
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and other mixture components. Cmarik et al.15 evaluated CO2, CH4, N2, and water vapor
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6 adsorption in several variants of UiO-66. The nonpolar naphthyl-functionalized material was
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8 found to suppress water adsorption compared to the parent MOF, but the CO2 loadings were also
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lowered. Cai et al.22 studied the adsorption capacity of CO2 and CH4 on the alkyl-functionalized
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13 MOFs CuMBTC and CuEBTC, with respect to CuBTC or HKUST-1, and found that while water
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15 adsorption is significantly lower, the CO2 loadings at low pressure were unaffected.
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19 Here we report a detailed experimental study of CO2, CH4, and water vapor adsorption on a
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21 new dimethyl-functionalized version of UiO-66 (UiO-66-DM, Fig. 1). This MOF was
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23 developed simultaneously by Huang et al.,23 and our procedure is distinct from their report. In
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26 their work, the water effect on the structure was only qualitatively examined, and no CH4
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28 adsorption data were reported. For comparison with UiO-66-DM, we have also reproduced
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adsorption isotherms for UiO-66 (Figs. 3, 5). Water vapor adsorption isotherms (Fig. 3) at 298 K
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33 were measured up to 90 % RH, and the gas adsorption isotherms at different temperatures (293-
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35 308 K, Figs. 5, S14-16) were measured up to 20 bar. The results show that upon
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38 functionalization with hydrophobic dimethyl moieties, water vapor adsorption has been reduced
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40 by almost 50% compared to the parent material. In fact, the water adsorption loading is now
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42 even less than the water vapor loadings for commercial adsorbents such as zeolites 5A and
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45 13X.16 Moreover, as expected, this functionalization do not render any adverse effect on the high
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47 hydrothermal, chemical, and mechanical stability of UiO-66 framework (Figs. S7-S11). At high
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pressures (> 5 bar) UiO-66-DM has better CO2/CH4 selectivity compared to UiO-66, which is
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52 promising for natural gas sweetening processes where operating pressures can reach up to 60 bar.
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7 DMBDC
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12 (DMBDC)
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18 Figure 1. Synthesis of dimethyl-functionalized UiO-66 (UiO-66-DM).
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Intensity (counts)
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29 1600
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32 400
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35 0
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2Theta (°)
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39 Figure 2. Comparison between PXRD patterns of as-synthesized UiO-66-DM, UiO-66, and the
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41 theoretical pattern of UiO-66 simulated from single crystal data.
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44 2. EXPERIMENTAL SECTION
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48 2.1 MOF Synthesis. All of the employed chemicals were commercially available and used as
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50 received without further purification from the following sources: Sigma-Aldrich, N,N′-
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dimethylformamide (DMF); TCI America, 2,5-dimethyl 1,4-benzene-dicarboxylic acid
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55 (DMBDC); Acros, zirconium (IV) chloride (ZrCl4), 1,4-benzene-dicarboxylic acid (BDC).
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UiO-66. UiO-66 was synthesized and activated as reported by Schoenecker et al.16
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7 UiO-66-DM. Synthesis of UiO-66-DM was performed using a slightly modified procedure of
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9 Lillerud et al.13 reported for the parent UiO-66 MOF. UiO-66-DM was synthesized by
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11 dissolving 0.681 mmol of zirconium (IV) chloride (ZrCl4) and 0.681 mmol of 2,5-dimethyl-1,4-
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14 benzenedicarboxylic acid (DMBDC) in 26.5 mL of DMF at room temperature. The resulting
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16 mixture was divided equally into two 20 mL scintillation vials. These vials were kept in a sand
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bath inside an oven at 393 K for 24 h. The final product was cooled to room temperature and
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21 then washed with DMF three times to remove the unreacted reactants before activation at 473 K.
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23 Similar to the parent material, UiO-66-DM crystallizes as intergrown crystals that are too small
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26 for structure determination by single crystal diffraction.
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29 2.2 Characterization. Successful synthesis of UiO-66-DM was confirmed using 1H nuclear
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31 magnetic resonance (NMR), Fourier transform infrared (FT-IR) spectroscopy, thermo-
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34 gravimetric analysis (TGA) followed by mass spectroscopy (MS), powder X-ray diffraction
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36 (PXRD), and N2 adsorption. Refer to the supporting information (SI) for more details.
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2.3 Water Vapor Adsorption Isotherm Measurements. An Intelligent Gravimetric
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42 Analyzer (IGA-3 series, Hiden Analytical Ltd.) was used to obtain water vapor adsorption
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44 isotherms. A sample size of approximately 45 mg was used for collecting the water vapor
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47 adsorption isotherm. Dry air was used as the carrier gas, with a percentage of it being bubbled
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49 through a vessel filled with deionized water. Two mass flow controllers were used to vary the
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51 ratio of saturated air and dry air so that the relative humidity (RH) could be controlled. Due to
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54 water condensation in the equipment at higher humidities, experiments were conducted up to
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56 90% RH. The total gas flow rate was set at 200 cc/min, and each adsorption/desorption step was
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allowed enough time (maximum time of 24 h) to approach equilibrium. UiO-66-DM was
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6 activated in situ under vacuum at 473 K for 12 h to remove residual solvent molecules before
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8 starting the adsorption measurements. UiO-66-DM was regenerated by heating at 473 K under
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vacuum for 12 h after the water adsorption isotherm measurement and prior to PXRD and BET
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13 analysis.
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16 2.4 High Pressure Gas Adsorption Isotherm Measurements. An Intelligent Gravimetric
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19 Analyzer (IGA-1 series, Hiden Analytical Ltd.) was used to collect pure gas (CO2 and CH4)
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21 adsorption isotherms at various temperatures (293-308 K, Figs. S14-16) and pressures up to 20
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23 bar. UiO-66-DM was activated in situ at 473 K under vacuum until no further weight loss was
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26 observed. After activation, the system was maintained under vacuum, and the temperature was
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28 adjusted to the desired value. A sample size of approximately 30 mg was used for the
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measurements, and a maximum equilibration time of 30 minutes was used for each point in the
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36 3. RESULTS AND DISCUSSION
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40 3.1 Structure Characterization and Physical Properties. The PXRD pattern obtained for
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42 the as-synthesized UiO-66-DM is compared with the pattern simulated from the single-crystal
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44 structure of UiO-66 in Fig. 2. These patterns are consistent with each other, confirming that UiO-
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47 66-DM has the same topology as the parent UiO-66. Evidence of the presence of the dimethyl
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49 moieties on the BDC linker was obtained by characterizing the UiO-66-DM with 1H NMR and
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FTIR spectroscopy. 1H NMR spectrum of activated (under vacuum at 473 K, 12 h) UiO-66-DM
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54 displayed resonances associated with the DMBDC ligand (Fig. S1). The peak at 1650 cm-1 in the
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56 FTIR pattern corresponds to C=O in DMF/DEF.24 Figure S2 shows peaks at 1660 cm-1 and 3430
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cm-1 in the FTIR spectrum of as-synthesized UiO-66-DM which corresponds to C=O in DMF
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6 and O-H in both the inorganic brick [Zr6O4(OH)4] and physisorbed water, respectively. Hence,
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8 an absence of the peak at 1650 cm-1 in the FTIR spectrum of activated UiO-66-DM (Fig. S3)
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confirms the removal of DMF molecules after activation. Moreover, the peak at 3430 cm-1 has
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13 also disappeared for activated UiO-66-DM (Fig. S3), which confirms the removal of physisorbed
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15 water and dehydroxylation of the Zr6O4(OH)4 cornerstone (each Zr atom is 8-coordinated) into
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18 Zr6O6 (each Zr atom is 7-coordinated) during activation. However, Figure S3 is now showing a
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20 peak at ~3680 cm-1 which also represents OH-groups on the Zr6O4(OH)4 corner stone. However,
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22 intensity of this peak is small. This is consistent with the observation made by Valenzano et al.
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25 for the parent UiO-66.25 Thus, heating the as-synthesized UiO-66-DM at 473 K under vacuum is
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27 appropriate for activation. Furthermore, a peak is observed at 2930 cm-1 that corresponds to the
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stretching frequency of the C-H bond in the dimethyl moieties attached to the benzene ring.
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32 Hence, FTIR also confirms the presence of DMBDC ligand in this MOF.
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35 The thermal stability of UiO-66-DM was examined using TGA. The decomposition during the
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38 TGA experiment was followed by mass spectrometry (MS). Figure S4 shows that UiO-66-DM
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40 decomposes at approximately 723 K, which is less than the reported decomposition temperature
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42 of UiO-66 (813 K)13 but still higher than the typical value of 623 K observed for many other
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45 MOFs.13 Dingemans et al.18 synthesized methyl functionalized MOF-5, and also observed a
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47 similar decrease in the thermal stability. UiO-66-NH2 and UiO-66-NO2 have also been shown to
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decompose at a lower temperature compared to UiO-66.14 However, the origin of the differences
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52 in these thermal stabilities is still unclear. Similar to UiO-66,25 the TGA curve for as-synthesized
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54 UiO-66-DM in Fig. S4 shows three weight loss regions before framework decomposition that
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corresponds to dehydration (physisorbed water, T < 373 K), solvent removal (DMF, 373 K < T <
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6 453 K), and dehydroxylation of the Zr6O4(OH)4 cornerstone into Zr6O6 (453 K < T < 553 K).
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9 In Fig. S5, around the decomposition temperature of UiO-66-DM, we see MS signals mainly
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11 due to CO2 (at m/z value of 12, 28, 44), and p-xylene (at m/z value of 91, 106). This suggests
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14 bond cleavage between the linker and the inorganic brick as well as cleavage of the bond
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16 between p-xylene ring and the terminal carboxyl groups. The absence of an MS signal for DMF
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(at m/z value of 38, 42, 73) confirms that heating the as-synthesized UiO-66-DM at 473 K under
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21 vacuum is appropriate for activation. We also observe a weight loss in the temperature range of
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23 473-573 K at m/z value of 18 due to release of water for the activated sample. This shows that
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26 the activated material rehydroxylates or physisorbs water upon exposure to moisture present in
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28 the air during the transfer of the sample to the TGA system. Wiersum et al.26 also showed that
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30 activated/dehyroxylated UiO-66 rehydroxylates upon exposure to water vapor.
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Table 1. Adsorption Loadings at 90% Relative Humidity and BET Surface Areas Before and
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36 After Water Exposure.
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39 Pore Pore Loading,
40 Material Volume† Diameter 90% RH Surface Area* (m2/g)
41 (cm3/g) (Å) (cm3 H2O/g) Before After % loss
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UiO-66 0.52 ~6 0.43 1160 1136 2
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44 UiO-66-DM 0.40 <6 0.24 811 797 2
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46 *BET Analysis
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Obtained from the Dubinin-Astakov model of N2 adsorption at 77K
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Reported from literature16
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52 As expected, N2 adsorption (Fig. S12) at 77 K on the activated UiO-66-DM sample shows that
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54 functionalization by the dimethyl moieties leads to reduced porosity (Table 1) compared to the
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56 parent MOF. The BET surface area of UiO-66-DM is calculated to be 811 m2/g, with a DA pore
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volume of 0.40 cm3/g. Entry to the internal pores of the parent UiO-66 MOF is limited by
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6 triangular windows of 6 Å.13 However, in UiO-66-DM, functionalization by the dimethyl
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8 moieties should further reduce the window opening.
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11 3.2 High Structural Stability. The sensitivity of MOFs under humid conditions is well
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14 known, but water adsorption studies on MOFs are still lacking compared to other adsorbates.21,27-
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Recently, we measured the water vapor adsorption isotherms of several well-known MOFs
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including UiO-66 and it’s several variants and found that this family of MOFs is uniformly
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21 stable in the presence of water.15,16 In the current study, water vapor adsorption measurements
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23 for UiO-66-DM and subsequent stability tests were performed to compare with UiO-66.
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27 In Fig. 3, UiO-66-DM shows significantly lower water adsorption loadings compared to UiO-
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29 66 and, is also even lower than the water vapor loadings for traditional porous materials such as
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31 zeolites 5A and 13X and BPL carbon.16 Among the UiO-66 variants studied by Cmarik et al.,15
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34 the naphthyl functionalized MOF displayed the lowest water adsorption loadings but still
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36 adsorbed approximately 13 mmol/g at 40% RH compared to only 6 mmol/g adsorbed in UiO-66-
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DM under the same conditions. The desorption isotherms of these Zr-MOFs exhibit hysteresis
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41 with a portion of the water being retained. At 0% RH, UiO-66 and UiO-66-DM retain 2.42
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43 mmol/g, and 1.75 mmol/g, respectively. For comparison, UiO-66-NO2 was shown to retain
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almost 6 mmol/g of water after desorption,15 and UiO-66-NH2 retains approximately 3.3
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48 mmol/g.16 Wiersum et al.26 showed that the amount of water retained by UiO-66 after the first
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50 adsorption cycle corresponds to partial rehydroxylation of the sample, and full rehydroxylation
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53 was possible only after the third cycle. This, the same explanation of partial rehydroxylation can
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55 be extended to the functionalized UiO-66 MOFs as well. However, we do expect a different
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57 extent of rehydroxylation to occur after the first cycle for UiO-66-NO2, −NH2, and −DM
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compared to UiO-66 because the amount retained at 0 % RH appears to be related to the polarity
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6 or hydrophilicity of the functional group. Thus, the amount of water retained in the MOFs at 0%
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8 RH follows the trend UiO-66-NO2 > −NH2 > −DM ~ −Naphthyl ~ parent structure.
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11 25
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Loading (mmol H2O/ g MOF)
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UiO-66-DM
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23 0
0 20 40 60 80 100
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25 Relative Humidity (%)
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28 Figure 3. Comparison of water vapor adsorption isotherms at 298 K for the desolvated
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compounds UiO-66-DM and UiO-66 (closed symbols– adsorption; open symbols– desorption).
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33 *Obtained from our previous work16
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36 PXRD patterns for UiO-66-DM before and after water exposure are shown in Fig. 4. Similar
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39 to the previously studied variants,15,16 UiO-66-DM also does not lose its crystallinity and is quite
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41 robust as there is negligible loss in its BET surface area (shown in Table 1) even after exposure
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43 to high levels of humidity. Moreover, functionalization with dimethyl moieties does not render
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46 any adverse effect on the high chemical and mechanical stability of the framework (Figs. S8-
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48 S11), in spite of the slightly lower thermal stability. The volumetric water loadings (cm3/g) at
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50 90% RH are shown in Table 1. It is expected that water should completely fill the pores at
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53 saturation, but for UiO-66, the water volume is slightly lower than the pore volume obtained
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55 from nitrogen adsorption. This may be due to fact that only during water adsorption does the Zr
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inorganic unit undergo rehydroxylation from [Zr6O6] to [Zr6O4(OH)4]. Thus, it is difficult to
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directly compare pore volumes obtained from water adsorption with those obtained by N2
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6 adsorption. The water volume obtained for UiO-66-DM is 40% lower than the pore volume
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8 obtained by N2 adsorption. Similar to UiO-66, this decrease in volume relative to the N2 pore
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volume will have contributions from the rehydroxylation process. However, adsorption
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13 saturation has not been reached at 90% RH, so water does not fully fill the pores of UiO-66-DM.
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15 Thus, the volume should be much lower than the N2 volume.
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41 Figure 4. PXRD patterns for as-synthesized (middle), water vapor-exposed (top), and
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44 regenerated (bottom) UiO-66-DM
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47 Zeolite 13X has often been employed commercially for CO2 separation from gas streams due
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to its high CO2 adsorption capacity under dry conditions, but also must be regenerated at high
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52 temperature (623 K) to retain this capacity and has a high affinity for moisture.32,33 Counter to
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54 this, UiO-66-DM can be regenerated at relatively lower temperatures (473 K). Moreover, at 28
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57 % RH zeolite 13X32 adsorbs 15.11 mmol H2O/g which is ~ 3.5 times more than the water
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adsorption in UiO-66-DM at 30 % RH. Since the pore volume and surface area of zeolite 13X
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6 (0.25 cm3/g, 725 m2/g)34,35 are lower than UiO-66-DM (Table 1), we expect UiO-66-DM to have
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8 a higher capacity for gases such as CO2 at higher pressures and outperform zeolite 13X,
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especially under humid environments. Water adsorption studies on other MOFs, e.g. the DMOF
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13 or Zn-BDC-DABCO family,36,37 also show much lower water loadings than zeolite 13X, but
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15 many of these MOFs lose their crystallinity after exposure to humidity, with the exception of the
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18 tetramethyl and anthracene derivatives. In general, the key to developing high performance
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20 adsorbents is finding a balance between adsorption capacity and selectivity for the target; these
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22 two characteristics are often inverse related.
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26 3.3 CO2 and CH4 Adsorption. Inspired by the high stability and significantly low water
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28 loadings of UiO-66-DM, pure-component CO2 and CH4 adsorption isotherms were measured.
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30 The CO2 and CH4 adsorption isotherms for UiO-66 and UiO-66-DM shown in Fig. 5 exhibit type
31
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33 I isotherms with no hysteresis. CO2 is more strongly adsorbed than CH4 because it has a
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35 relatively high quadrupole moment while CH4 is nonpolar. At high pressure (Fig. 5a), the
36
37 adsorption loadings are higher for the parent material since it has a higher pore volume.
38
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40 However, Fig. 5b shows that CO2 and CH4 loadings at low pressures are slightly enhanced in
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42 UiO-66-DM due to the presence of increased van der Waals interactions from the dimethyl
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moieties; the enhancement is relatively greater for CH4 than CO2. This can be more easily seen
46
47 by comparing the values of Henry’s constants (KH) for CH4 and CO2 adsorption on UiO-66-DM
48
49 and UiO-66 in Table 2. The Toth parameters (Eq S1)38 were used to calculate Henry’s constants
50
51
52 (Figs. 6, S14-15). Results show that functionalization with dimethyl moieties leads to an increase
53
54 in the value of KH (Table 2) by a factor of 2 for CO2 and a factor of 3 for CH4 compared to the
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56 parent MOF. This is disadvantageous from CO2/CH4 selectivity point of view in the low-pressure
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region. These results are different than the behavior observed for UiO-66-Naphthyl where the
4
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6 Henry’s constant is essentially unchanged compared to the parent material.15 Steric factors are
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8 clearly at play in these examples since the BDC in UiO-66-DM is functionalized on both sides of
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the benzene ring and on one side for UiO-66-Naphthyl.
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(a)
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32 (b)
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47
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49 Figure 5. Experimental adsorption-desorption isotherms for CO2 and CH4 in UiO-66, and UiO-
50
51
52 66-DM at 303 K (closed symbols-adsorption; open symbols-desorption): (a) 0−20,000 mbar and
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54 (b) 0−2000 mbar. Lines connecting the adsorption points are to faciliate viewing. *Reported
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56
from literature.26
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8 Table 2. Toth Equation Parameters, Henry’s Constants (KH), and Low Coverage CO2/ CH4
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10 Selectivities at 303 K for UiO-66 and UiO-66-DM.
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12
13
14 KHCO2 = Ns*b KHCH4 = Ns*b Ideal
15 MOF CO2 CH4
Ns b t Ns b t (mmol/g*mbar) (mmol/g*mbar) Selectivity
16 KH(CO2)/KH(CH4)
17
18 UiO-66 10.11 2.06E-04 0.76 42.95 2.28E-05 0.35 2.08E-03 9.78E-04 2.12
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20 UiO-66-DM 07.71 4.92E-04 0.61 10.53 2.58E-04 0.36 3.79E-03 2.72E-03 1.39
21
22
23 The ideal adsorbed solution theory (IAST)39 has been applied to calculate CO2/CH4 selectivity
24
25
26
for an equimolar mixture at 303 K in UiO-66 and UiO-66-DM (Fig 6). Up to 5000 mbar, the CO2
27
28 selectivity over CH4 is higher in UiO-66, but above 5000 mbar, UiO-66-DM has the higher
29
30 selectivity. At low pressure, CH4 molecules are adsorbed in the tetrahedral cages of UiO-66-DM
31
32
33 at a larger concentration compared to CO2 due to enhanced van der Waals interactions with the
34
35 dimethyl moieties. However, in UiO-66 under the same conditions, a larger concentration of CO2
36
37 molecules is adsorbed in the tetrahedral cages.40 Now, when pressure increases beyond 5000
38
39
40 mbar, the CO2/CH4 selectivity is higher for UiO-66-DM because of the competitive adsorption
41
42 behavior in which adsorbed CO2 molecules push CH4 molecules to the octahedral cages. Good
43
44
CO2/ CH4 selectivity at high pressure is advantageous for processes such as natural gas
45
46
47 sweetening where the operating pressure can range up to 60 bar.11 Cu-BTC has been shown to
48
49 have a higher CO2/CH4 selectivity (5-9 for 50:50 CO2/ CH4 mixture)41 compared to UiO-66-DM,
50
51
52
but water adsorbs strongly in Cu-BTC, and it is eventually unstable under humid conditions.
53
54 CO2/CH4 selectivity of UiO-66-DM at high pressures is comparable to other well-known MOFs
55
56 such as MIL-53 (Al, Cr).42,43
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25 Figure 6. CO2/CH4 selectivity for equimolar CO2/CH4 gas mixture in UiO-66, and UiO-66-DM
26
27 at 303 K, calculated using IAST. Lines connecting the points are to faciliate viewing. *Pure
28
29
component excess loading data for CO2 and CH4 adsorption in UiO-66 is taken from literature.26
30
31
32
33
34 The isosteric heat of adsorption was calculated by applying the Clausius-Clapeyron equation
35
36
37 (Eq S2)38 to adsorption isotherms measured at three temperatures (Figs. S14,15). The isosteric
38
39 heats of adsorption (Fig. 7) calculated for CH4 and CO2 on UiO-66-DM at a loading of 0.05
40
41 mmol/g are 30.9 kJ/mol, and 46.8 kJ/mol, respectively. These values are quite high compared to
42
43
44 UiO-66 and its other functionalized versions.15,40,44 The high stability of UiO-66-DM, low
45
46 interaction with water, and good CO2/CH4 selectivity at high pressures compared to UiO-66
47
48 make it a promising adsorbent for adsorption separations at these conditions.
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Figure 7. Isosteric heat of adsorption for CO2 and CH4 in UiO-66-DM as a function of adsorbate
21
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23 loading. Qst is calculated using the Clausius-Clapeyron equation.
24
25
26 4. CONCLUSION
27
28
29
30 In summary, the synthesis and characterization of a new water resistant, highly robust dimethyl-
31
32 functionalized UiO-66 analogue (UiO-66-DM) has been carried out. Our study shows that
33
34 functionalization by dimethyl moieties significantly reduces the water loading by almost a factor
35
36
37 of 2 compared to UiO-66 without altering the high stability of the framework. Moreover, the
38
39 water adsorption loadings and regeneration temperature of UiO-66-DM are significantly lower
40
41 than the benchmark material zeolite 13X. UiO-66-DM also performs better than the parent MOF
42
43
44 for CO2/ CH4 separation at high pressures. While amine groups have been a topic of intense
45
46 focus for CO2 separations, this work shows that nonpolar functional groups may also play an
47
48
49
important role in enhancing CO2 adsorption while lowering interactions with water. UiO-66-DM
50
51 has low affinity for water, is highly robust, and has a good CO2/CH4 selectivity at high pressures.
52
53 In general, understanding the trade-offs between water adsorption behavior and high selectivity
54
55
56 and high capacity for the target will be key to developing new adsorbents for CO2 capture.
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ASSOCIATED CONTENT
4
5
6 Supporting Information.
7
8 1
H NMR spectrum, FT-IR spectra, TG-MS curves, PXRD patterns, and N2 adsorption data. This
9
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11
material is available free of charge via the Internet at http://pubs.acs.org.
12
13
14
15 AUTHOR INFORMATION
16
17 Corresponding Author
18
19
20 *E-mail: krista.walton@chbe.gatech.edu. Fax: +1-404-894-2866. Tel: +1-404-894-5254.
21
22
23 Notes
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25
The authors declare no competing financial interest.
26
27
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29
30
31 ACKNOWLEDGMENT
32
33 This material is based upon work supported by Army Research Office PECASE Award
34
35
36 W911NF-10-1-0079 and Contract W911NF-10-1-0076.
37
38
39
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Experimental Study of CO2 CH4 Adsorption On A Dimethyl Functionalized UiO 66 Framework

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on a Dimethyl-Functionalized UiO-66 Framework

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