ARTICLE pubs.acs.org/crystal
Syntheses of MetalOrganic Frameworks and Aluminophosphates under Microwave Heating: Quantitative Analysis of Accelerations Enamul Haque, Nazmul Abedin Khan, Chang Min Kim, and Sung Hwa Jhung* Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University, Daegu 702-701, Korea
bS Supporting Information ABSTRACT: Several porous materials such as metalorganic frameworks (MOFs) and aluminophosphates have been synthesized with microwave and conventional electric heating in various temperatures and times to investigate the quantitative acceleration in the synthesis of porous materials by microwaves. From the analysis of the acceleration under microwave heating with the Eyring equation, it can be understood that, irrespective of the type of porous materials, the acceleration by microwaves is mainly due to decreased activation free energy (ΔGq) even though the activation energy (Ea) and activation enthalpy (ΔHq) are increased. The decreased activation free energy is mainly due to the high activation entropy (ΔSq) of microwave synthesis compared with the entropy of conventional electric synthesis. Accelerated synthesis with microwaves may be explained with changes of relative energies of intermediates for high activation entropy.
’ INTRODUCTION Porous materials such as metalorganic frameworks (MOFs), zeolites, and aluminophosphate (AlPO) molecular sieves have attracted considerable attention because of their various applications and well-defined structures. Especially, MOFs18 are very important due to the possibility of designing a structure with a particular pore size and shape from multifunctional ligands and metal ions. MOFs have been widely studied in the field of gas storage,912 catalysis,1316 separations,1722 magnetism,23,24 carriers for nanomaterials,25,26 and drug delivery.27,28 Inorganic porous materials such as aluminosilicate zeolites and AlPO molecular sieves are widely used in catalysis and separation processes while new applications are also presently being developed.29 Therefore, facile and fast crystallization of pure porous materials is very important from the standpoint of applications and characterization. So far, porous materials have been generally synthesized by using conventional electric (CE) heating. Syntheses of zeolites or AlPOs with new heating sources such as microwaves (MWs) have been tried to increase the efficiency of synthesis. The microwave synthesis of porous materials can be a powerful tool to seek efficient synthesis conditions for porous materials that are normally prepared by hydrothermal or solvothermal methods because it offers the distinct advantage of rapid crystallization even though microwave heating does not always lead to accelerated synthesis or rate enhancement in solid preparations.30,31 Microwave irradiation has been regarded as one of the best choices for its several advantages including rapid synthesis,30,31 phase selectivity,3234 narrow particle size distribution,35,36 and facile morphology control37,38 in the syntheses of inorganic porous materials. The characteristics and advantages of microwave synthesis of inorganic porous materials have been summarized in relevant reviews.30,31 The microwave technique has been also tried in the synthesis of MOFs to decrease the reaction time and/or temperature and r 2011 American Chemical Society
to find an alternative effective way to produce them. For example, MOFs have also been synthesized with microwaves to show fast crystallization,3941 phase-selectivity,42,43 and decreased size,44 etc. Although the fast synthesis of porous materials by microwave heating is relatively well-established,3044 the mechanism and engineering for the rate enhancement of the syntheses are still unknown.31,45 Furthermore, no comprehensive study exists to explain why synthesis time is drastically decreased using microwave irradiation. Instead, several hypotheses31,45 have been proposed to explain the fast synthesis, viz., (a) an increase in the heating rate of the reaction mixture, (b) more uniform heating of the reaction mixture, (c) change in association between species within the mixture, (d) superheating of the mixture, (e) creation of hot spots, and (f) enhancement of the dissolution of the precursor gel. According to Conner et al., rapid heating and creation of hot spots are important factors associated with an increase in synthesis rates.45 So far, only a few results have been reported on the quantitative acceleration in the microwave synthesis of porous materials. Gharibeh et al. have suggested that the acceleration of AlPO11/SAPO-11 by microwave synthesis is mainly due to increased reacting sites and/or increased reaction probability.46 Our work on iron benzenedicarboxylate (Fe-BDC)47 and copper benzenetricarboxylate (Cu-BTC)48 syntheses has also demonstrated that the accelerated synthesis is mainly due to high preexponential factor even though the activation energy is increased with the microwave irradiation. However, to the best of our knowledge, there is no quantitative report to suggest the change of thermodynamic parameters such as activation free energy, activation enthalpy, and activation entropy. Received: May 10, 2011 Revised: August 12, 2011 Published: September 08, 2011 4413
dx.doi.org/10.1021/cg200594e | Cryst. Growth Des. 2011, 11, 4413–4421
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Figure 1. XRD patterns of fully crystallized (A) MIL-53(Al), (B) MIL-53(Cr), (C) MIL-47(V), (D) AlPO-5, and (E) AlPO-11. Plots ac in each case represent the XRD patterns of simulated structure, CE (conventional electric)-synthesized sample, and MW (microwave)-synthesized sample, respectively. For the XRD measurement, the MOFs were hydrated after purification and AlPOs were hydrated after calcinations.
The aim of this work is to understand quantitatively the accelerated synthesis of porous materials. The acceleration of the synthesis of MOFs was compared with that of inorganic porous materials (AlPOs) to understand whether there is any difference in kinetics between the two cases. Additionally the acceleration was analyzed to find whether there is any effect of metal ions of isotypic MOFs on the acceleration with microwaves. The accelerated syntheses using microwaves are compared with the conventional syntheses using not only the Arrhenius but also the Eyring equations. Even though the two equations may not be used to interpret the nonequilibrium kinetics of nucleation and crystal growth precisely, the effect of central metal ions on the synthesis kinetics of isotypic MOFs may be compared with them. Moreover, the difference in kinetics between MOF and AlPO syntheses may be evaluated with the two equations. We have selected isotypic metal-BDC49 (such as MIL-53(Cr), MIL-53(Al), and MIL-47(V)) as typical MOF materials. The framework structure of one of the typical MOFs, MIL-53(Al), is composed of infinite AlO4(OH)2 octahedra connected by 1,4benzenedicarboxylate ligand.50 This MOF is important in the field of gas adsorption51 and separation of organic compounds.52 MIL-53(Cr),53 Cr-BDC, is very similar to the MIL-53(Al) in structure and also has been studied for various applications such
as adsorption51 and drug delivery.27 The MIL-53(Al) and MIL53(Cr) having the chemical formula of M(OH)(O2CC6H4 CO2), where M stands for Al3+ or Cr3+, show the breathing phenomenon54,55 upon adsorption and desorption of an adsorbate. The MIL-47(V) (vanadium benzenedicarboxylate with the chemical formula of VO(O2CC6H4CO2)), composed of VO6 octahedra (V is in V4+) linked by a 1,4-benzenedicarboxylate group,56 is used in the field of selective separation and adsorption.22,23,57 AlPO-5 and AlPO-11 (International Zeolites Association codes AFI 58 and AEL,59 respectively) were chosen as two typical inorganic porous materials for this study. AFI type molecular sieves (AFI)58 such as AlPO-5 and SAPO-5 with onedimensional channels of 0.73 nm have attracted much interest because of catalysis, separation, and possible new applications such as nonlinear optics60 and containers for the smallest single-walled carbon nanotubes.61 The AEL molecular sieve has been widely studied for catalysts or catalyst supports for hydroisomerization,62 isomerization,63 and alkylation reaction,64 etc.
’ EXPERIMENTAL SECTION The isotypic MOFs such as MIL-53(Al), MIL-53(Cr), and MIL47(V) were synthesized hydrothermally under autogenous pressure similar to the reported methods.50,53,56 The detailed synthesis procedures 4414
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Figure 3. Crystallization curves of AlPOs synthesized at various reaction temperatures: (A) AlPO-5 synthesized under conventional electric heating; (B) AlPO-5 synthesized under microwave heating; (C) AlPO11 synthesized under conventional electric heating; (D) AlPO-11 synthesized under microwave heating.
Figure 2. Crystallization curves of MOFs synthesized at various reaction temperatures: (A) MIL-53(Al) synthesized under conventional electric heating; (B) MIL-53(Al) synthesized under microwave heating; (C) MIL-53(Cr) synthesized under conventional electric heating; (D) MIL-53(Cr) synthesized under microwave heating; (E) MIL-47(V) synthesized under conventional electric heating; (F) MIL-47(V) synthesized under microwave heating. including the temperature control/measurement method of microwave reaction using MARS-5 (CEM, Matthews, NC, USA) are described in the Supporting Information. The synthesis procedure with conventional electric heating and microwave heating is also reported elsewhere.6567 To remove TPA from the as-synthesized MOFs, purification was carried out at 70 °C using an ultrasonic generator (VC 750; maximum power, 750 W; Sonics & Materials, Inc.) in the presence of N,Ndimethylformamide (DMF) following the reported purification method.68 Briefly, 0.3 g of a MOF such as MIL-53(Al) was suspended in 20 mL of DMF and sonicated for 1 h at 70 °C. The purified MOFs were collected after filtration and dried at 150 °C for 5 h. After drying, the MOF was kept for 1 day or more over saturated NH4Cl aqueous solution to humidify. The AlPOs were calcined at 550 °C overnight and hydrated similarly for nitrogen adsorption and X-ray diffraction (XRD) patterns. The phases of products were identified with an X-ray diffractometer (Mac Science, Model No. 1031, Cu Kα radiation). The XRD crystallinity of the MOFs was calculated by the relative intensity of the (2 0 0) diffraction peak of as-synthesized MOFs, compared with the fully crystallized samples under a selected condition. Even though the assynthesized MOFs and AlPOs contain organic moieties, the results of relative crystallinity do not change noticeably even after the purification of MOFs and AlPOs (to remove the free or occuluded TPA and templates, respectively). The XRD crystallinity of the AlPOs was calculated by the relative intensity of (1 0 0) and (0 0 2) diffraction peaks for AFI and AEL structures, respectively. More detailed procedure to calculate the relative crystallinity is described in the Supporting Information.
The relative rates of nucleation and crystal growth were estimated by the reciprocal of the induction period and the slope of the crystallization curve (crystallinity between 20 and 80%), respectively, similar to the reported methods.46,69,70 The induction period or nucleation time is the time required to observe any crystallinity (XRD intensity of 05% to the fully crystallized samples). The relative rates have been regarded as relative kinetic constants46,69,70 in the calculation of activation energy (Ea), preexponential factor (A), and thermodynamic parameters of activation by using the Arrhenius and Eyring equations. The Ea and A values for nucleation or crystallization were calculated from the determined rate constants of nucleation and crystal growth at various temperatures. The Arrhenius equation, shown as eq 1, was used to obtain Ea and A. The Ea and A were derived from the slope and intercept, respectively, of the logarithm of the Arrhenius equation (eq 2).46,6971 The activation enthalpy (ΔHq), activation entropy (ΔSq), activation free energy (ΔGq), and Ea were also calculated with the Eyring equation,72 presented as eq 3, for both nucleation and crystal growth. The kinetic constants of nucleation and crystal growth were plotted between 1/T and ln(k/T) to follow eq 5, and ΔHq and ΔSq were obtained from the slope and intercept, respectively. ΔGq and Ea were calculated with equations of ΔGq = ΔHq TΔSq and Ea = ΔHq + RT for solution reactions, respectively.72 Arrhenius equation : k ¼ AeEa =RT
ð1Þ
Ea 1 R T kB T ΔGq =RT Eyring equation : k ¼ e h
ð2Þ
ln k ¼ ln A
kB T ΔSq =R ΔHq =RT e e h ΔH q 1 kB ΔSq þ lnðk=TÞ ¼ þ ln 3 R T h R k¼
ð3Þ ð4Þ ð5Þ
where k = kinetic constant, A = preexponential factor, Ea = activation energy, R = gas constant, T = absolute temperature, kB = Boltzmann constant, h = Planck constant, ΔGq = free energy of activation, ΔHq = enthalpy of activation, and ΔSq = entropy of activation. 4415
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Figure 4. Nitrogen adsorption isotherms of fully crystallized porous materials: (A) MIL-53(Al); (B) MIL-53(Cr); (C) MIL-47(V); (D) AlPO-5; (E) AlPO-11. Plots a and b in each case represent the adsorption isotherms of synthesized samples under conventional electric heating and synthesized samples under microwave heating, respectively. The nitrogen adsorption isotherm was obtained using Micromeritics Tristar II 3020 surface area and porosity analyzer at the temperature of liquid nitrogen (196 °C) after evacuation at 150 °C for 15 h. Surface area and micropore volume were calculated with the BET equation and t-plot, respectively, using the nitrogen adsorption isotherms. The crystal morphology of the synthesized porous materials was examined with a field emission scanning electron microscope (Hitachi, S-4300).
’ RESULTS AND DISCUSSION In this study, various porous materials such as MIL-53(Al or Cr), MIL-47(V), AlPO-5, and AlPO-11 have been synthesized hydrothermally using a wide variety of reaction conditions under conventional electric and microwave heating. As shown in Supporting Information Figures S1 and S2, the XRD intensity of as-synthesized porous materials increases with increasing reaction time and saturates at a certain time in all of the syntheses. There is no noticeable change of XRD patterns with further increasing reaction time. The XRD patterns (shown in Figures S1 and S2) of as-synthesized porous materials correspond well with the reported patterns.50,53,56,58,59 The XRD patterns (Figure 1) of the fully crystallized MOFs (after purification and hydration) are also very similar to the patterns reported earlier. 50,53,56
The XRD patterns of the AlPO-5 and AlPO-11 (after calcination and hydration), shown in Figure 1, also correspond well with the reported ones.58,59 There is little change of XRD patterns of AlPOs with calcination to remove templates. As shown in Figures 2 and 3, the crystallinity of MIL-53(Al or Cr), MIL47(V), AlPO-5 and AlPO-11, determined from Figures S1 and S2, changes with reaction temperature and time. All of the crystallization curves show the typical sigmoid forms. Supporting Information Figures S3 and S4 show the typical scanning electron microscopy (SEM) images of the fully crystallized MIL-53(Al,Cr), MIL-47(V), AlPO-5, and AlPO-11. The morphology of the MOFs and AlPOs is relatively homogeneous and does not change noticeably with synthesis temperature (data not shown). The size of the crystals obtained with microwaves is generally smaller than that of products obtained with conventional electric heating (crystal sizes are presented in the captions of Figures S3 and S4). The small size of porous materials with microwave syntheses, due to rapid nucleation and increased population of nuclei, has been reported earlier.73 Even though some crystals are aggregated and inhomogeneous, the crystal purities did not change with reaction conditions including heating methods as evidenced from XRD and porosity (see below) The nitrogen adsorption isotherms of the fully crystallized samples 4416
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MW
CE
MW
CE
MW
CE
MW
CE
MW
CE
18
12 7
140
150
375 300
140 150
130
465
130
5
150
165
150
7.5
210
140
140
12 285
145 130
12
25
135
130
40
215
145
125
320
135
525
180 45
175 185
125
545
315
185
165
660
175
2520
10
160
165
40 20
240
160
140 150
405
660
nucleation time (min)
150
140
temp. methods (°C)
a
qd
e
4.9
14.5
28.1
148
66.8
2.39 102
1.43 10
63.4
8.53 103 125
1
3.26 104 4.54 104
8.33 10
31.0
4.45 103
264
2
27.6
5.56 102
2.67 10 3.33 103 137
2.10 104 32.7
2.15 103 3
1.75 102
62.1
2.00 10
157
8.33 103
58.6
1
1.33 10 123
5.18 103
2.45 104
1
38.8
1.88 102 1.71 104
8.33 10
241
83.1
3.95 104
35.3
112
2
135
79.7
6.06 103
4.76 103
8.33 10 3.51 103
2
7.90 103
4.00 10
4.65 10 126
3.02 104 4.29 103
61.8
2
187
1.41 104
2.50 102
58.4
208
4.76 104
135
131
3
3.13 103
1.91 103
204
6.28 103 1.88 102
5.56 10 2.22 102
3.18 10 145
2.71 104 1.20 103
174
3
41.7
1.84 103
170 7.89 104
151
3
1.52 103
8.40 105
103
3.97 104
71.4 1.11 102
99.5
2.17 104
1.00 101
4.18 10 130
75.2 1.94 103 5.51 103
162
2.50 102 5.00 102
71.7
1.32 104
crystal growth rate (min1)
4.76 104
140
20.1
ΔG ΔH ΔS Ea relative (kJ/mol) (kJ/mol) (J/(mol 3 K)) (kJ/mol) rate f
qd
3
2.47 103
1.52 103
nucleation rate (min1)
qc
nucleation g
131
142
131
143
129
141
144
155
136
147
115
51.3
82.7
55.9
98.5
81.0
226
183
124
91.8
36.6
220
116
211
75.3
147
182
62.4
29.0
130
119
54.7
86.2
59.3
102
84.4
230
187
127
95.3
31.0
35.9
31.6
20.0
20.2
ΔG ΔHq d ΔSq d Eae relative (kJ/mol) (kJ/mol) (J/(mol 3 K)) (kJ/mol) rate f
crystal growth qc
a CE, conventional electric heating; MW, microwave heating. b Calculated from the value of 1/(nucleation time). c Calculated from ΔGq = ΔHq TΔSq. d Calculated with the Eyring equation. e Calculated from Ea = ΔHq‡ + RT. f Relative rate (rMW/rCE), calculated with the Eyring equation at the medium temperature of the syntheses. g Calculated from the slope of a crystallization curve (between 20 and 80% crystallinity).
AlPO-11
AlPO-5
47(V)
MIL-
53(Cr)
MIL-
53(Al)
MIL-
porous mater
b
Table 1. Nucleation and Crystal Growth Rates of Porous Materials at Various Temperatures and Thermodynamic Parameters Obtained with the Eyring Equation
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Figure 5. Arrhenius plots of the syntheses rates of porous materials: (A) nucleation under conventional electric heating; (B) nucleation under microwave heating; (C) crystal growth under conventional electric heating; (D) crystal growth under microwave heating.
Figure 6. Eyring plots of the syntheses rates of porous materials: (A) nucleation under conventional electric heating; (B) nucleation under microwave heating; (C) crystal growth under conventional electric heating; (D) crystal growth under microwave heating.
shown in Figure 4 are typical type-I, illustrating the microporosity of the MOFs and AlPOs. The surface areas and micropore volumes (Supporting Information Table S1), calculated from
adsorption isotherms, are similar to the reported values,50,53,56,74,75 showing the successful synthesis of the MOFs and AlPOs under wide reaction conditions. 4418
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Crystal Growth & Design Scheme 1. Suggested Relative Activation Free Energy, Enthalpy, and Entropy Changes with Synthesis Methods (CE, Conventional Electric Heating; MW, Microwave Heating)
The rates of nucleation and crystal growth were evaluated with the time of the first appearance of XRD peaks and the slope of crystallization curves (between 20 and 80% of the fully crystallized samples), respectively,46,69,70 which are presented in Figures 2 and 3. The times needed for complete nucleation (or induction period) and the rates for nucleation and crystal growth, depending on the types of materials and metal ions and temperatures, are summarized in Table 1. As shown in Table 1, not only MOFs but also AlPOs are synthesized rapidly using microwave heating. The syntheses are completed in hours with microwave heating compared with the conventional synthesis which needs days for complete crystallization. To compare Ea and A of the Arrhenius equation (eq 1) for the synthesis of the porous materials, the rate constants of both nucleation and crystal growth are plotted as shown in Figure 5. The calculated Ea and A values are displayed also in Supporting Information Table S2. It has been reported that microwave heating accelerates the synthesis of porous materials both in the stage of nucleation and crystal growth.46,73,76 As shown in Table S2, the acceleration degrees (rMW/rCE) of nucleation and crystal growth are 4.932.7 and 20.535.9, respectively. There is little effect of the types of porous materials (MOFs and AlPOs) and types of metal ions (Al3+, Cr3+, and V4+) in isotypic MOFs on the acceleration degrees in the microwave syntheses of porous materials. In accordance with previous results,4648 the accelerated syntheses with microwaves are mainly due to the increase of preexponential factors even with an increased activation energy (Table S2). The increased preexponential factor is explained with increased reacting sites and/or increased reaction probability.46 Microwave exposure is also believed to provide more favorable reaction coordinate (selective heating and changing the reaction profile) in the microwave synthesis.77 The kinetics of nucleation and crystal growth is also analyzed with the Eyring equation (eq 3).72 ΔHq and ΔSq are obtained from the slope and intercept, respectively, of the Eyring plot (ln(k/T) vs 1/T) of eq 5. The plots and calculated ΔGq, ΔHq, ΔSq, and Ea are shown in Figure 6 and Table 1, respectively. Ea is obtained with the equation of Ea = ΔHq + RT for solution
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reactons.72 ΔGq is calculated with the equation of ΔGq = ΔHq TΔSq. As shown in Table 1, accelerated degrees and activation energies calculated with the Eyring equation are very similar to the results obtained with the Arrhenius equation (Table S2). ΔGq of microwave syntheses is lower than that of conventional electric syntheses in every case. However, ΔHq and ΔSq are high when the syntheses are carried out with microwave heating (Table 1). The decreased activation free energy of the microwave syntheses is, therefore, mainly due to increased activation entropy. Similar results of microwave acceleration (decreased ΔGq, increased ΔHq, and ΔSq) are observed in the syntheses of other MOFs such as Fe-BDC as presented in Supporting Information Table S3. The relative thermodynamic parameters of microwave and conventional electric syntheses are summarized in Scheme 1. Even though the detailed reason of the difference in thermodynamic parameters cannot be explained at the moment, the difference of activation entropy and enthalpy (accordingly activation free energy) may be due to changes of relative energies of the intermediates with microwave exposure, as suggested by Conner and Tompsett.77 They have also suggested that microwaves may change the reaction profile and provide a more favorable reaction coordinate.77 Therefore, it may be suggested that microwave irradiation leads to less organized intermediates that have high entropy.
’ CONCLUSIONS Various porous materials have been synthesized with microwave and conventional electric heating to understand the accelerated syntheses with microwave irradiation. The acceleration has been analyzed with the Arrhenius and the Eyring equations. Irrespective of the type of materials (MOFs and AlPOs) and type of metal ions (Al3+, Cr3+, and V4+) in isotypic MOFs, microwaves accelerate the syntheses about 533 times for both nucleation and crystal growth. The accelerated syntheses using microwaves are mainly due to increased preexponential factors and decreased ΔGq of the Arrhenius equation and the Eyring equation, respectively. The decreased ΔGq under microwaves is mainly due to increased ΔSq. The accelerated syntheses with microwave exposure may be explained with a more favorable reaction coordinate or changes of relative energies of intermediates for high activation entropy with increased randomness. ’ ASSOCIATED CONTENT
bS
Supporting Information. Text detailing the synthesis procedure and the calculation procedure for relative crystallinity, tables listing reaction conditions and textural properties and nucleation and crystal growth rates, and figures showing typical XRD patterns and SEM images of porous materials. This material is available free of charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION Corresponding Author
*Fax: (+)82-53-950-6330. E-mail:
[email protected].
’ ACKNOWLEDGMENT This work was supported by Midcareer Researcher Program through NRF grant funded by the MEST (Grants R01-20070055718, 2008-0055718, 2009-0083696, and 2010-0028783). 4419
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’ REFERENCES (1) Yaghi, O. M.; O’Keeffe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J. Nature 2003, 423, 705. (2) Ferey, G; Mellot-Draznieks, C.; Serre, C.; Millange, F. Acc. Chem. Res. 2005, 38, 217. (3) Kitagawa, S.; Kitaura, R.; Noro, S. Angew. Chem., Int. Ed. 2004, 43, 2334. (4) Ferey, G. Chem. Soc. Rev. 2008, 37, 191. (5) Ferey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F.; Dutour, J.; Surble, S.; Mirgiolaki, I. Science 2005, 309, 2040. (6) Ma, S. Pure Appl. Chem. 2009, 81, 2235. (7) Natarajan, S.; Mahata, P. Chem. Soc. Rev. 2009, 38, 2304. (8) Kuppler, R. J.; Timmons, D. J.; Fang, Q.-R.; Li, J.-R.; Makal, T. A.; Young, M. D.; Yuan, D.; Zhao, D.; Zhuang, W.; Zhou, H.-C. Coord. Chem. Rev. 2009, 253, 3042. (9) Zhao, X.; Xiao, B.; Fletcher, A.; Thomas, K. M.; Bradshaw, D.; Rosseinsky, M. J. Science 2004, 306, 1012. (10) Dinca, M.; Long, J. R. J. Am. Chem. Soc. 2005, 127, 9376. (11) Rowsell, J. L.C.; Spencer, E. C.; Eckert, J.; Howard, J. A. K.; Yaghi, O. M. Science 2005, 309, 1350. (12) Murray, L. J.; Dinca, M.; Long, J. R. Chem. Soc. Rev. 2009, 38, 1294. (13) Corma, A.; Garcja, H.; Xamena, F. X. Chem. Rev. 2010, 110, 4606. (14) Farrusseng, D.; Aguado, S.; Pinel, C. Angew. Chem., Int. Ed. 2009, 48, 7502. (15) Ma, L.; Abney, C.; Lin, W. Chem. Soc. Rev. 2009, 38, 1248. (16) Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.; Hupp, J. T. Chem. Soc. Rev. 2009, 38, 1450. (17) Kitaura; Seki, K.; Akiyama, G.; Kitagawa, S. Angew. Chem., Int. Ed. 2003, 42, 428. (18) Ma, S.; Sun, D.; Wang, X.-S.; Zhou, H.-C. Angew. Chem., Int. Ed. 2007, 46, 2458. (19) Li, J.-R.; Kuppler, R. J.; Zhou, H.-C. Chem. Soc. Rev. 2009, 38, 1477. (20) Alaerts, L.; Kirschhock, C. E. A.; Maes, M.; van der Veen, M. A.; Finsy, V.; Depla, A.; Martens, J. A.; Baron, G. V.; Jacobs, P. A.; Denayer, J. F. M.; De Vos, D. E. Angew. Chem., Int. Ed. 2007, 46, 4293. (21) (a) Cychosz, K. A.; Wong-Foy, A. G.; Matzger, A. J. J. Am. Chem. Soc. 2009, 131, 14538. (b) Cychosz, K. A.; Wong-Foy, A. G.; Matzger, A. J. J. Am. Chem. Soc. 2008, 130, 6938. (22) (a) Finsy, V.; Verelst, H.; Alaerts, L.; De Vos, D. E.; Jacobs, P. A.; Baron, G. V.; Denayer, J. F. M. J. Am. Chem. Soc. 2008, 130, 7110. (b) Alaerts, L.; Maes, M.; Giebeler, L.; Jacobs, P. A.; Martens, J. A.; Denayer, J. F. M.; Kirschhock, C. E. A.; De Vos, D. E. J. Am. Chem. Soc. 2008, 130, 14170. (23) Kurmoo, M. Chem. Soc. Rev. 2009, 38, 1353. (24) Humphrey, S. M.; Mole, R. A.; Thompson, R. I.; Wood, P. T. Inorg. Chem. 2010, 49, 3441. (25) (a) Moon, H. R.; Kim, J. H.; Suh, M. P. Angew. Chem., Int. Ed. 2005, 44, 1261. (b) Hermes, S.; Schroder, F.; Chelmowski, R.; Woll, C.; Fischer, R. A. J. Am. Chem. Soc. 2005, 127, 13744. (26) Zlotea, C.; Campesi, R.; Cuevas, F.; Leroy, E.; Dibandjo, P.; Volkringer, C.; Loiseau, T.; Ferey, G.; Latroche, M. J. Am. Chem. Soc. 2010, 132, 2991. (27) (a) Horcajada, P.; Serre, C.; Vallet-Regi, M.; Sebban, M.; Taulelle, F.; Ferey, G. Angew. Chem., Int. Ed. 2006, 45, 5974. (b) Horcajada, P.; Serre, C.; Maurin, G.; Ramsahye, N. A.; Balas, F.; Vallet-Regí, M.; Sebban, M.; Taulelle, F.; Ferey, G. J. Am. Chem. Soc. 2008, 130, 6774. (28) Taylor-Pashow, K. M. L.; Della Rocca, J.; Xie, Z.; Tran, S.; Lin, W. J. Am. Chem. Soc. 2009, 131, 14261. (29) Davis, M. E. Nature 2002, 417, 813. (30) Park, S.-E.; Chang, J.-S.; Hwang, Y. K.; Kim, D. S.; Jhung, S. H.; Hwang, J.-S. Catal. Surv. Asia 2004, 8, 91. (31) Tompsett, G. A.; Conner, W. C.; Yngvesson, K. S. ChemPhysChem 2006, 7, 296.
ARTICLE
(32) Jhung, S. H.; Chang, J.-S.; Hwang, J.-S.; Park, S.-E. Microporous Mesoporous Mater. 2003, 64, 33. (33) Jhung, S. H.; Jin, T.; Hwang, J.-S.; Chang, J.-S. J. Nanosci. Nanotechnol. 2007, 7, 2734. (34) Jhung, S. H.; Jin, T.; Kim, Y. H.; Chang, J.-S. Microporous Mesoporous Mater. 2008, 109, 58. (35) Xu, X.; Yang, W.; Liu, J.; Lin, L. Adv. Mater. 2000, 12, 195. (36) Jhung, S. H.; Lee, J. H.; Chang, J.-S. Microporous Mesoporous Mater. 2008, 112, 178. (37) (a) Hwang, Y. K.; Chang, J.-S.; Park, S.-E.; Kim, D. S.; Kwon, Y.-U.; Jhung, S. H.; Hwang, J.-S.; Park, M.-S. Angew. Chem., Int. Ed. 2005, 44, 557. (b) Jhung, S. H.; Yoon, J. W.; Hwang, Y. K.; Chang, J.-S. Microporous Mesoporous Mater. 2006, 89, 9. (38) Sathyaseelan, B.; Anand, C.; Mano, A.; Zaidi, J. S. M.; Chakravarti, R.; Kenawy, E.-R.; Al-Deyab, S. S.; Jayavel, R.; Sivakumar, K.; Vinu, A. Int. J. Nanotechnol. 2010, 7, 1065. (39) Jhung, S. H.; Lee, J.-H.; Chang, J.-S. Bull. Korean Chem. Soc. 2005, 26, 880. (40) (a) Klinowski, J.; Paz, F. A. A.; Silva, P.; Rocha, J. Dalton. Trans. 2011, 40, 321. (b) Choi, J. Y.; Kim, J.; Jhung, S. H.; Kim, H.-K.; Chang, J.-S.; Chae, H. K. Bull. Korean Chem. Soc. 2006, 27, 1523. (41) Ni, Z.; Masel, R. I. J. Am. Chem. Soc. 2006, 128, 12394. (42) Khan, N.; Jhung, S. H. Crystal Growth Des. 2010, 10, 1860. (43) Jhung, S. H.; Lee, J.-H.; Forster, P. M.; Ferey, G.; Cheetham, A. K.; Chang, J.-S. Chem.—Eur. J. 2006, 12, 7899. (44) Jhung, S. H.; Lee, J.-H.; Yoon, J. W.; Serre, C.; Ferey, G.; Chang, J.-S. Adv. Mater. 2007, 19, 121. (45) Conner, W. C.; Tompsett, G.; Lee, K.-H.; Yngvesson, K. S. J. Phys. Chem. B 2004, 108, 13913. (46) Gharibeh, M.; Tompsett, G. A.; Conner, W. C.; Yngvesson, K. S. ChemPhysChem 2008, 9, 2580. (47) Haque, E.; Khan, N.; Park, J. H.; Jhung, S. H. Chem.—Eur. J. 2010, 16, 1046. (48) Khan, N.; Haque, E.; Jhung, S. H. Phys. Chem. Chem. Phys. 2010, 12, 2625. (49) (a) Bourrelly, S.; Llewellyn, P.; Serre, C.; Millange, F.; Loiseau, T.; Ferey, G. J. Am. Chem. Soc. 2005, 127, 13519. (b) Kang, I. J.; Khan, N. A.; Haque, E.; Jhung, S. H. Chem.—Eur. J. 2011, 17, 6437. (50) Loiseau, T.; Serre, C.; Huguenard, C.; Fink, G.; Taulelle, F.; Henry, M.; Bataille, T.; Ferey, G. Chem.—Eur. J. 2004, 10, 1373. (51) Ferey, G.; Latroche; Serre, C.; Millange, F.; Loiseau, T.; Percheron- Guegan, A. Chem. Commun. (Cambridge, U. K.) 2003, 2976. (52) Alaerts, L.; Maes, M.; Giebeler, L.; Jacobs, P. A.; Martens, J. A.; Denayer, J. F. M.; Kirschhock, C. E. A.; De Vos, D. E. J. Am. Chem. Soc. 2008, 130, 14170. (53) Serre, C.; Millange, F.; Thouvenot, C.; Nogues, M.; Marsolier, G.; Lou€er, D.; Ferey, G. J. Am. Chem. Soc. 2002, 124, 13519. (54) Ferey, G.; Serre, C. Chem. Soc. Rev. 2009, 38, 1380. (55) Serre, C.; Mellot-Draznieks, C.; Surble, S.; Audebrand, N.; Filinchuk, Y.; Ferey, G. Science 2007, 315, 1828. (56) Barthelet, K.; Marrot, J.; Riou, D.; Ferey, G. Angew. Chem., Int. Ed. 2002, 41, 281. (57) (a) Alaerts, L.; Maes, M.; Jacobs, P. A.; Denayer, J. F. M.; De Vos, D. E. Phys. Chem. Chem. Phys. 2008, 10, 2979. (b) Khan, N. A.; Jun, J. W.; Jeong, J. H.; Jhung, S. H. Chem. Commun. (Cambridge, U. K.) 2011, 47, 1306. (58) (a) Baerlocher, Ch.; McCusker, L. B.; Olson, D. H. Atlas of Zeolite Structure Types; Elsevier: Amsterdam, 2007; pp 2728. (b) http://izasc.ethz.ch/fmi/xsl/IZA-SC/ft.xsl. (59) (a) Baerlocher, Ch.; McCusker, L. B.; Olson, D. H. Atlas of Zeolite Structure Types; Elsevier: Amsterdam, 2007; pp 2021. (b) See ref 58b. (60) Caro, J.; Marlow, F.; Hoffmann, K.; Striebel, C.; Kornatowski, J.; Girnus, I.; Noack, M.; Kolsch, P. Stud. Surf. Sci. Catal. 1997, 105, 2171. (61) Wang, D.; Tang, Z. K.; Li, G. D.; Chen, J. S. Nature 2000, 408, 50. (62) H€ochtl, M.; Jentys, A.; Vinek, H. Microporous Mesoporous Mater. 1999, 31, 271. 4420
dx.doi.org/10.1021/cg200594e |Cryst. Growth Des. 2011, 11, 4413–4421
Crystal Growth & Design
ARTICLE
(63) H€ochtl, M.; Jentys, A.; Vinek, H. Appl. Catal., A 2001, 207, 397. (64) Yeom, Y. H.; Shim, S. C. J. Mol. Catal. A 2002, 180, 133. (65) Haque, E.; Jeong, J. H.; Jhung, S. H. CrystEngComm 2010, 12, 2749. (66) Jhung, S. H.; Chang, J.-S.; Hwang, Y. K.; Greneche, J.-M.; Ferey, G.; Cheetham, A. K. J. Phys. Chem. B 2005, 109, 845. (67) Jhung, S. H.; Yoon, J. W.; Hwang, J.-S.; Cheetham, A. K.; Chang, J.-S. Chem. Mater. 2005, 17, 4455. (68) Haque, E.; Khan, N.; Lee, J. E.; Jhung, S. H. Chem.—Eur. J. 2009, 15, 11730. (69) Breck, D. W. Zeolite Molecular Sieves; John Wiley & Sons: New York, 1974; pp 333335. (70) Uzcategui, D.; Gonzalez, G. Catal. Today 2005, 107108, 901. (71) Atkins, P.; De Paula, J. Physical Chemistry, 8th ed.; Oxford: New York, 2006; p 807. (72) (a) Winzor, D. J.; Jackson, C. M. J. Mol. Recog. 2006, 19, 389.(b) Engel, T.; Reid, P. Physical Chemistry, 2nd ed.; Prentice Hall: New York, 2010; p 918. (73) Jhung, S. H.; Jin, T.; Hwang, Y. K.; Chang, J. -S. Chem.—Eur. J. 2007, 13, 4410. (74) Jhung, S. H.; Chang, J.-S.; Hwang, Y. K.; Park, S.-E. J. Mater. Chem. 2004, 14, 280. (75) Jhung, S. H.; Lee, J. H.; Chang, J.-S. Microporous Mesoporous Mater. 2008, 112, 178. (76) Gharibeh, M.; Tompsett, G. A.; Conner, W. C. Top. Catal. 2008, 49, 157. (77) Conner, W. C.; Tompsett, G. A. J. Phys. Chem. B 2008, 112, 2110.
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