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MOF-5 is an important metal–organic framework and has been intensely studied, especially in its
hydrogen storage properties. In this study, we obtained the interpenetrated MOF-5 materials (MOF-5-
int) using N,N0 -dimethylformamide (DMF) or N,N0 -diethylformamide (DEF) as solvents. The
Langmuir surface area of MOF-5-int determined by N2 adsorption is 950–1100 m2 g1, much lower
than the non-penetrated MOF-5 (3000 m2 g1). However, it can store 1.54–1.82 wt% by volumetric
method hydrogen at 77 K and 1 atm, which is higher than the amount stored by the non-penetrated
MOF-5. The MOF-5-int was also characterized by XRD-powder diffraction, thermogravimetric
analysis (TGA), nitrogen adsorption/desorption analysis, scanning electron microscope (SEM) and
X-ray single-crystal structure diffraction. In addition, we found grinding greatly facilitates the
decomposition of the MOF-5-int material by H2O to a nonporous phase ZnBDC$xH2O (within 2–5
min, BDC ¼ 1,4-benzenedicarboxylate), even under low humidity (30%), which calls for careful
handling of the MOF-5 material. The effects of the water content, reaction time, reaction temperature,
molar ratio of Zn(NO3)2 to H2BDC, addition of H2O2, rapid stirring and dilution on the synthesis of
MOF-5-int were studied and the synthetic conditions were optimized. Moreover, Hafizovic et al. (J.
Am. Chem. Soc., 2007, 129, 3612) found the intensity ratio of the powder XRD peak at 9.7 to that at
6.8 (referred to as the R1 value) of MOF-5 can be used to predict its porosity. The lower the intensity
ratio, the more porous it is. In this study, we showed that MOF-5-int can have a very low R1 value but
also a low porosity. The low specific surface area (SSA) is mainly due to its interpenetrated structure
instead of the entrapped zinc species or the mesopores in the material, as previously proposed in the
literature, and associated with the characteristic, very strong peak at 13.8 in its XRD-powder
diffraction pattern. A high R2 value (the ratio of the intensity of the peak at 13.8 to that at 6.8 )
suggests an interpenetrated structure, especially when the R1 value is low. In addition, we found that
although entrapped ZnO or solvent molecules can increase the R1 value, and a low R1 value implies no
zinc species or solvent molecules entrapped in the MOF-5 framework, a high R1 value does not
necessarily suggest the presence of entrapped molecules.
3758 | J. Mater. Chem., 2010, 20, 3758–3767 This journal is ª The Royal Society of Chemistry 2010
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2. Experimental section
Fig. 1 Powder XRD patterns of simulated (a) MOF-5-int and (c) non-
Synthesis of the interpenetrated MOF-5 interpenetrated MOF-5 based on its crystal structure by Mercury 1.4.2
software, (b) the MOF-5-int A synthesized using DMF, (d) the non-
All chemicals were obtained commercially and used without penetrated MOF-5 synthesized by Panella et al.2d digitalized using
further purification. DMF solvent (Sinopharm Chemical Reagent WinDig 2.5, (e) the MOF-5-int B synthesized using DEF.
Co., Ltd, Analytical reagent) was pre-dried over activated mole-
cular sieves (Sinopharm Chemical Reagent Co., Ltd., 4 A, Na-A)
for 3 d and without further distillation. DEF (99%) was purchased
from Acros, Belgium. Zn(OAc)2$2H2O (Analytical regent) was We attempted to synthesize non-interpenetrated MOF-5
purchased from Guangdong XiLong Chemical Co., Ltd. using DEF according to the literature,8,9 with a slight modi-
In a typical synthesis of the MOF-5-int material with a low R1 fication. CHCl3 was used to exchange the DEF solvent in the
value, 0.4399 g (1.4789 mmol) of Zn(NO3)2$6H2O (Aldrich, pores. Instead, MOF-5-int materials were synthesized. The
reagent grade, dry appearance) in 10.0 mL DMF (pre-dried) was detailed experimental data and powder XRD (PXRD) patterns
mixed with 0.1843 g (1.120 mmol) of H2BDC (Sinopharm in a 2q range of 5–50 are given in the ESI† (Table S1 and
Chemical Reagent Co., Ltd, Analytical reagent) in 10.0 mL of Fig. S1, respectively). One such MOF-5-int (denoted as B)
the same DMF, and small amounts of water (180 mL) were with 71% yield (based on eqn (1)) was synthesized with
introduced. The molar ratio of Zn(NO3)2 : H2BDC :- a molar ratio of Zn(NO3)2$6H2O : H2BDC : DEF of
DMF : H2O ¼ 1.0 : 0.76 : 175 : 12.8.7 The mixture was stirred 1 : 0.40 : 85 at 105 C for 24 h and characterized by PXRD
for 10 min and then transferred to a Teflon-lined autoclave and diffraction, TGA, N2 adsorption/desorption analysis (Lang-
heated for 48 h at 120 C. The autoclave was then cooled to r.t. muir surface area: 1052 m2 g1, BET: 797 m2 g1), elemental
outside the oven. The cubic-like, colorless crystals obtained were analysis (found (calc): C 35.34 (35.42); H, 1.57 (1.49)) and low
washed with the pre-dried DMF three times and dried at 150 C pressure H2 adsorption/desorption analysis (1.79 wt% at 77 K
for 12 h in an oven, resulting in a white solid of 0.2846 g (84.9% and 1 atm).
yield based on Zn(NO3)2 and eqn (1)) which was stored in We also attempted to synthesize MOF-5 with a high surface
a desiccator containing silica gel. For long term storage, it was area in DMF according to the method of Zhao et al.2h DMF
stored in a Schlenck vessel under argon. Unless specified, the solvent was degassed by argon for 3–4 h before use. Zhao
above synthetic conditions were applied.7 The product obtained et al. exchanged the product with chloroform at 70 C for 3 d
has a characteristic PXRD pattern, as shown in Fig. 1b, having and dried it under vacuum at 90 C. We dried the product as
low R1 values and high R2 values, and is denoted as the MOF-5- described for the MOF-5-int A. The product obtained (deno-
int A, which was also characterized by TGA and N2 adsorption/ ted as C, 74% yield based on eqn (1)) has an interpenetrated
desorption analysis (Langmuir surface area: 954 m2 g1, BET: structure (section 3.2 and 3.3). It was characterized by PXRD,
724 m2 g1) and low pressure H2 adsorption analysis (1.54 wt% at TGA, elemental analysis (found (calc): C 37.47 (37.44); H,
77 K and 1 atm). 1.69 (1.57)), N2 adsorption/desorption analysis (Langmuir
surface area: 990 m2 g1, BET: 756 m2 g1) and low pressure
4Zn(NO3)2$6H2O + 3H2BDC / Zn4O(BDC)3 H2 adsorption/desorption analysis (1.82 wt% at 77 K and
+ 23H2O + 8HNO3 (1) 1 atm).
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Characterization
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grinding of the sample during the PXRD experiments (Fig. 12 in and TGA evidence. Since our synthetic method is very similar to
section 3.5). their method (see section 3.6), the product we obtained could also
During our synthesis and characterization of the MOF-5-int contain entrapped Zn(OH)2. Thermogravimetric (TG) analyses
C, we found that a high R1 value does not always suggest of two synthesized MOF-5-int A samples (referred to as A1 and
entrapped ZnO or solvent molecules. In an attempted synthesis A2, obtained under slightly different drying conditions using
of MOF-5 with high surface area according to the method of DMF) were carried out in a flowing O2 atmosphere exactly as
Zhao et al.,2h the MOF-5-int C had a high R1 value (1.2), but Hafizovic et al. did,3 and are shown in Fig. 3 together with their
contained no ZnO or solvent molecules according to its TGA XRD-power diffraction patterns. The PXRD patterns show that
curve (see section 3.2) and elemental analysis. When the intensity the R1 value of sample A1 is higher than that of sample A2.
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of the PXRD peak at 9.7 is high, the intensities of the peaks after Consistently, the TG results indicate that sample A1 contained
13.8 also increase. more solvent than sample A2 did. Only about 5% of DMF
solvent was in sample A2, indicating that simply heating the
3.2 TGA of the MOF-5-int recovered sample at 150 C in the oven had removed most
trapped solvent. In regard to sample A1, the 4% weight loss in the
Hafizovic et al.3 found that the high R1 value is caused by the temperature range 20–90 C is assigned to the H2O desorption,
entrapped solvent and Zn(OH)2 (in its non-interpenetrated another weight loss of 13.0% in the range of 100–300 C was
MOF-5 component) based on X-ray single crystal diffraction assigned to DMF desorption. The rather sharp weight loss of
these two samples took place after 375 C, corresponding to the
structural decomposition to ZnO.
Zn(OH)2, if trapped in the pores, would dehydrate at 125 C.
Thus, before 375 C, it has completely converted to ZnO. The
calculated theoretical weight loss for the desolvated, original
MOF-5 upon decomposition to ZnO is 57.7%, whereas the
observed weight losses for samples A1 and A2 are 56.1% and
58.0%, respectively, indicating that there is no zinc species in
sample A2 and only a small amounts of zinc species in sample A1.
The 56.1% corresponds to a dehydrated formula of Zn4O-
(C8H4O4)3$0.27ZnO. The extra ZnO could exist in the pores of
the non-penetrated MOF-5 component or outside of the frame-
work.
In contrast, the MOF-5 material prepared by Hafizovic et al.3
had a much lower weight loss of 46%, due to the trapped zinc
species, corresponding to a dehydrated formula of Zn4O-
(C8H4O4)3$2ZnO. While they only observed 0.5 Zn(OH)2 (later
Fig. 3 TGA curves of the MOF-5-int A samples (A1 (a) and A2 (b)) became ZnO before 200 C) in each cage, corresponding to
synthesized in DMF in flowing O2 (15 mL min1) with a heating rate of a formula of Zn4O(C8H4O4)3$0.5ZnO and no Zn(OH)2 in the
5 C min1. The inset figure is the corresponding XRD-powder diffrac- interpenetrated MOF-5 crystals, consistent with its much smaller
tion patterns of the two samples. pore sizes (the trapped zinc species found in the non-penetrated
MOF-5 was estimated as 7.5 A). 3 Therefore, the extra ZnO might
Fig. 4 TGA curves of the MOF-5-int B synthesized in DEF in flowing Fig. 5 TGA curves of the MOF-5-int C in flowing O2 (15 mL min1)
O2 (15 mL min1) with a heating rate of 5 C min1. The inset figure is the with a heating rate of 5 C min1. The inset figure is the corresponding
corresponding XRD-powder diffraction pattern. XRD-powder diffraction pattern of the sample.
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exist outside of the MOF-5 structures, and one cannot deduce desolvated MOF-5 upon decomposition to ZnO is 54.6%. The
how much interpenetrated MOF-5 is present in their case. formula deduced based on TGA data is Zn4O(BDC)3$0.54ZnO.
The TGA curve of the MOF-5-int B synthesized in DEF is The calculated C and H percentage based on the formula is
shown in Fig. 4. The sample started to decompose at 264 C, 35.42% and 1.49%, consistent with the elemental analysis result
much lower than the MOF-5-int synthesized in DMF (375 C). (35.34% and 1.57%).
However, it is stable under 250 C for 6 h, as indicated by its In an attempt to synthesise MOF-5 with high surface area in
PXRD pattern obtained after the N2 gas adsorption/desorption DMF according to the method of Zhao et al.,2h we obtained the
experiment (Fig. S3 in the ESI†). The weight loss for the MOF-5-int C with a high R1 value instead (Fig. 5). The weight
loss for the desolvated MOF-5 upon decomposition to ZnO is
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57.5% (Fig. 5), very close to the theoretical value (57.7%), indi-
cating that there is no ZnO trapped in the cages. The calculated C
and H percentage based on the formula is 37.44% and 1.57%,
consistent with the elemental analysis results (37.47% and
1.69%). Thus, although entrapped ZnO or solvent molecules can
increase the R1 value, a high R1 value does not necessarily suggest
the presence of trapped molecules in the pore.
A 954 725 759 0.40 5.7 0.13 1.3 (0–0.27) 1.54% H–K: 4.8–8.0 (4.8, 5.5, 6.9)
652
<8.0 A:
747
<10 A: DFT: 5.1, 6.8, 8.0, 19
753
<20 A:
B 1052 797 951 0.40 5.3 0.14 0.68 0.54 1.79% H–K: 4.7–8.0 (4.7, 5.0, 7.0)
654;
<5.9 A: DFT: 5.6, 7.5, 15, 19
885
<8.0 A:
950
<20 A:
C 990 756 866 0.35 5.3 1.2 1.1 0 1.82% H–K: 4.7–8.0 (4.7, 5.3, 7.0)
364
<3.9 A:
446;
6.4–7.3 A: DFT: 3.9, 7.3
866
<8.0 A:
a
Langmuir surface area. b BET surface area. c Surface area obtained using DFT method together with surface areas contributed by certain size pores.
d
Pore volume obtained by H–K method. e Obtained by H–K method. f Moles of ZnO/mole of Zn4O(BDC)3 obtained based on TGA result (see Section
3.2). g wt% H2/absorbed at 77 K and 1 atm. h Pore sizes deduced based on pore size distribution curves (Fig. 6 and 7).
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Fig. 8 Cumulative surface area of the MOF-5-int A (a), B (b) and C (c)
calculated by DFT methods.
Fig. 7 Pore size distribution of the MOF-5-int materials A (a), B (b) and
C (c) calculated by DFT methods.
account for 86, 93 and 100% (b, c) and C (d, e) at 77 K and low pressure.
method, pores smaller than 8.0 A
surface area in A, B, and C, respectively (Table 1).These pores
also account for the majority of the pore volumes (Fig. S6–8 in reached 1.54–1.82 wt% at 77 K and 100 kPa, which is greater
the ESI†). The above evidence again confirms their inter- than the 1.32 wt%, reported under the same conditions, of the
penetrated structures. non-penetrated MOF-5.1b, 6 Considering its much smaller specific
The N2 adsorption/desorption studies also revealed fine surface area, this is significant, indicating that like the inter-
structures of these materials. The pore distribution curves of A penetrated Cu-MOF PCN-6,13 catenation of the MOF-5 material
and B are similar, but are different to that of C. DFT methods is favorable for hydrogen storage. We found MOF-5-int mate-
reveal that there were pores smaller than 3.9 A in C, which rials with relatively high surface areas have better H2 adsorption
account for 42% surface area, while sample A and B contained
few or no pores smaller than 4.7 A (Fig. 8). These findings
suggest that the intensity of the PXRD peak at 9.7 , if not caused
by trapped species, may have correlations with pore structures of
the material.
Hydrogen adsorption/desorption analyses of MOF-5-int
materials (A, B and C) were carried out at 77 K and 0–100 kPa,
and the isothermal adsorption/desorption curves are given in
Fig. 9. As Rowsell et al. found under the same conditions with
a non-penetrated MOF-5 material, only a small part of the
complete isotherm is measured due to the high condensation
pressure of hydrogen at 77 K, and the absence of plateaus indi- Fig. 10 SEM images of the MOF-5-int crystals (the molar ratio of the
cates that surface saturation is not achieved. The adsorption synthetic mixture: 1.0 Zn(NO3)2 : 0.74 H2BDC : 12.9 H2O : 765 DMF).
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In order to find out whether the high intensity of the PXRD peak
at 13.8 is due to the preferred orientation of the crystals, we
ground the MOF-5-int. To our surprise, we found that the des-
olvated MOF-5-int converted to another phase, the nonporous 2
within 2–5 min, even under low humidity (30%) (Fig. 11). Upon
increasing the grinding time, more unidentified peaks appeared.
In a parallel experiment, the MOF-5-int from the same product
was ground in a dry box for the same period of time, and the
PXRD pattern shows the product is still MOF-5, but with less
crystallinity and different peak intensities (Fig. 12). The relative
intensity of the peak at 13.8 to 6.7 even increased, not
decreased, indicating that the high peak intensity is not due to the
preferred orientation of the crystals. The intensity of the peak at
9.7 also increased, which could be due to the adsorption of
solvent molecules in the dry box, or the structure change due to
the grinding. Thus, we concluded that the conversion in air is due
to the reaction of the MOF-5 with the moisture in the air. The
MOF-5-int converted to 2 in air with a speed much slower than
Fig. 11 PXRD patterns of MOF-5 after grinding for (a) 0 (showing MOF-5),
(b) 1 min, (c) 2 min (showing phase 2), (d) 5 min and (e) 12 min in air. (f) The
phase N reported by Thirumurugan and Rao14 (g) ZnBDC$xH2O (1 < x < 2)
reported by Mertens et al.15 (h) The MOCP-H reported by Huang et al.2a (i)
MOF-5 after being exposed to air for 24 h reported by Long et al.2f (j) Simu-
Fig. 12 The powder XRD patterns of (a) the synthesized inter-
lated PXRD pattern of MOF-69c based on its crystal structure. (f)–(i) Were
penetrating MOF-5 material; (b) after sample (a) was ground for 5 min in
obtained by digitalizing curves published in the literature using WinDig 2.5.
dry box.
3764 | J. Mater. Chem., 2010, 20, 3758–3767 This journal is ª The Royal Society of Chemistry 2010
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under grinding, but similar to that reported for the non-pene- 3.6 Effects of reaction conditions on the synthesis of the MOF-
trated MOF-5.2f The non-penetrated MOF-5, since it has the 5-int A
same framework composition, is very likely to also have the same
When one obtains a MOF-5 material with high R1 value, TGA
property when ground. Phase 2 is also observed by Huang et al.2a
and N2 adsorption experiments must be carried out to determine
They referred it as MOCP-H. Using the same conditions to
whether it has an interpenetrated structure. Thus, we think that
synthesize MOCP-H, MOF-5 was obtained by Panella and
optimizing the synthetic conditions for the MOF-5-int A would
Hirscher1a and us, as indicated by its PXRD pattern (Fig. S9 in
be worthwhile, since A always has a low R1 value, indicating no
the ESI†). So the MOCP-H is actually a MOF-5 material,
zinc species or solvent molecules, and a high peak at 13.8 ,
however, when taking the PXRD spectrum, it was ground in
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low, which indicates no trapped molecules in the pores. The B. Panella, M. Hirscher, H. Putter and U. Muller, Adv. Funct.
Mater., 2006, 16, 520; (e) Z. Ni and R. Masel, J. Am. Chem. Soc.,
MOF-5-int materials stored 1.54–1.82 wt% hydrogen at 77 K
2006, 128, 12394; (f) S. S. Kaye, A. Dailly, O. M. Yaghi and
under 100 kPa, the highest among the published MOF-5 J. R. Long, J. Am. Chem. Soc., 2007, 129, 14176; (g)
materials. We also noticed that grinding the MOF-5-int mate- D. J. Tranchemontagne, J. R. Hunt and O. M. Yaghi, Tetrahedron,
rial could turn it into a nonporous phase in a few minutes. 2008, 64, 8553; (h) Z. Zhao, Z. Li and Y. S. Lin, Ind. Eng. Chem.
Res., 2009, 48, 10015.
Some other MOFs might also have similar properties and calls 3 J. Hafizovic, M. Bjorgen, U. Olsbye, P. D. C. Dietzel, S. Bordiga,
for much more careful handling of them. The effect of water C. Prestipino, C. Lamberti and K. P. Lillerud, J. Am. Chem. Soc.,
content, reaction time, reaction temperature, molar ratio of 2007, 129, 3612.
Zn(NO3)2 to H2BDC, and the addition of H2O2 on the 4 C.-S. Tsao, M.-S. Yu, T.-Y. Chung, H.-C. Wu, C.-Y. Wang,
K.-S. Chang and H.-L. Chen, J. Am. Chem. Soc., 2007, 129, 15997.
synthesis of MOF-5-int was studied. The synthetic conditions 5 G. Calleja, J. A. Botas, M. G. Orcajo and M. Sanchez-Sanchez, J.
for the MOF-5-int A were optimized. Dilution does not lead to Porous Mater., 2010, 17, 91.
a non-penetrated structure. The factor controlling the catena- 6 D. Zhao, D. Yuan and H.-C. Zhou, Energy Environ. Sci., 2008, 1, 222.
7 The interpenetrated MOF-5 with low R1 value can also be made
tion behavior of MOF-5 might be the solvent effect or temp- without drying the DMF solvent beforehand. After mixing 0.5210 g
lating effect. Larger solvent molecules or species, such as DEF (1.751 mmol) of Zn(NO3)2$6H2O (Aldrich, regent grade, dry
or zinc species, might fill the pores of the non-penetrated appearance) and 0.2170 g (1.306 mmol) of H2BDC in 20.0 mL of
structure and prevent the further formation of non-penetrated the newly opened analytical pure DMF (H2O # 0.1%), small
amounts of water (180 mL) were purposely introduced. The molar
species. This was supported by the recent study carried out by ratio of Zn(NO3)2 : H2BDC : DMF : H2O ¼ 1.0 : 0.75 : 148 : 11.7.
Choi et al.18 who used 1-methyl-2-pyrrolidone-synthesized non- The rest of the procedures were the same, resulting in white powder,
penetrated MOF-5 under microwave radiation. In addition, we 0.27 g (80% yield based on Zn(NO3)2).
8 (a) S. Hermes, F. Schroder, S. Amirjalayer, R. Schmid and
found that although entrapped ZnO or solvent molecules can
R. A. Fischer, J. Mater. Chem., 2006, 16, 2464; (b) K. Schrock,
increase the R1 value, and a low R1 value implies no zinc F. Schroder, M. Heyden, R. A. Fischer and M. Havenith, Phys.
species or solvent molecules entrapped in the MOF-5 frame- Chem. Chem. Phys., 2008, 10, 4732.
work, a high R1 value does not necessarily suggest the presence 9 J. Gonzalez, R. N. Devi, D. P. Tunstall, P. A. Cox and P. A. Wright,
Microporous Mesoporous Mater., 2005, 84, 97.
of trapped molecules in the cage. 10 To check the effect of zinc source, we heated up 8.0 g Zn(NO3)2$6H2O
at 150 C for 1 h, obtaining a white, sticky solid; according to the lost
Acknowledgements content of H2O, we referred it as Zn(NO3)2$0.45H2O.
11 Y. Liu, Z. Ng, E. A. khan, H.-K. Jeong, C.-B. Ching and z. Lai,
We thank the National Natural Science Foundation of China Microporous Mesoporous Mater., 2009, 118, 296.
12 D. Saha, Z. Wei and S. Deng, Sep. Purif. Technol., 2009, 64, 280.
(Project 20771060) and the Natural Science Foundation of
13 S. Ma, J. Eckert, P. M. Forster, J. W. Yoon, Y. K. Hwang,
Education Department of Jiangsu Province (No. 06KJB150058) J.-S. Chang, C. D. Collier, J. B. Parise and H.-C. Zhou, J. Am.
for financial support of this research. We thank Dr Xueqin An, Chem. Soc., 2008, 130, 15896.
Dr Yaoming Zhou, Mr. Gang Li and Dr Hongbin Du for their 14 A. Thirumurugan and C. N. R. Rao, J. Mater. Chem., 2005, 15, 3852.
15 S. Hausdorf, J. Wagler, R. Mossig and F. O. R. L. Mertens, J. Phys.
help to this project. Chem. A, 2008, 112, 7567.
16 E. Biemmi, S. Christian, N. Stock and T. Bein, Microporous
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