Solid-state thermal conversion of a nanoporous metal-organic framework to a nonporous coordination polymer

Article abstract of DOI:10.1039/c5ra08350h

A nanoporous metal-organic framework of Zn(BDC)(4,4′-Bipy)_0.5·(DMF)(H₂O)_0.5 (1·DMF·H₂O; H₂BDC = 1,4-benzenedicarboxylic acid, 4,4′-Bipy = 4,4′-bipyridine, DMF = N,N-dimethylformamide) which was also recognized as MOF-508 and has a pillared 2D square-grid net, was synthesized under reflux conditions. By thermal treatment of 1·DMF·H₂O at 350 °C, it converts to a nonporous three-dimensional coordination polymer of Zn(BDC)(4,4′-Bipy) (2). During the solid-state structural transformation of 1·DMF·H₂O to 2, a Zn(BDC) (3) unit was removed. Thus we have a mixture of compounds 2 and 3 at 350 °C. In addition, 1·DMF·H₂O and a mixture of 2 and 3 powders with microrod morphologies, were used for the preparation of ZnO nanomaterials. With calcination of the host framework of 1·DMF·H₂O, ZnO nanoprticles can be fabricated. The same process with a mixture of 2 and 3 results in the formation of agglomerated ZnO nanoparticles with similar morphology to the initial precursor.

Full text of DOI:10.1039/c5ra08350h

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Solid-state thermal conversion of a nanoporous
metal–organic framework to a nonporous
coordination polymer†
Cite this: RSC Adv., 2015, 5, 50778
*
Fatemeh Shahangi Shirazi and Kamran Akhbari
A nanoporous metal–organic framework of Zn(BDC)(4,40-Bipy)0.5$(DMF)(H2O)0.5 (1$DMF$H2O; H2BDC ¼
1,4-benzenedicarboxylic acid, 4,40-Bipy ¼ 4,40-bipyridine, DMF ¼ N,N-dimethylformamide) which was
also recognized as MOF-508 and has a pillared 2D square-grid net, was synthesized under reflux
conditions. By thermal treatment of 1$DMF$H2O at 350 ꢀC, it converts to a nonporous three-dimensional
coordination polymer of Zn(BDC)(4,40-Bipy) (2). During the solid-state structural transformation of
1$DMF$H2O to 2, a Zn(BDC) (3) unit was removed. Thus we have a mixture of compounds 2 and 3 at 350
ꢀC. In addition, 1$DMF$H2O and a mixture of 2 and 3 powders with microrod morphologies, were used
for the preparation of ZnO nanomaterials. With calcination of the host framework of 1$DMF$H2O, ZnO
nanoprticles can be fabricated. The same process with a mixture of 2 and 3 results in the formation of
agglomerated ZnO nanoparticles with similar morphology to the initial precursor.
Received 6th May 2015
Accepted 2nd June 2015
DOI: 10.1039/c5ra08350h
www.rsc.org/advances
bipyridine) for the rst time was recognized by J. T. Hupp at
2005.16 This nanoporous MOF was also reported by K. Kim at this
year.17 This MOF has primitive cubic framework which composed
of paddle-wheel {Zn2(COO)4} units, which are bridged by the
BDC2ꢁ ligands to form a distorted 2D square grid. The 2D square
grids are pillared by 4,40-Bipy molecules, to form a 3D framework.
Two of the 3D frameworks interpenetrate in MOF-508a
(1$DMF$H2O), reducing the pore size. Thus, a dense doubly
interpenetrating 3D framework is formed with pores that can be
tuned by double interpenetration to have 1D channels of
Introduction
Metal–organic frameworks (MOFs) provide a unique opportunity
for developing advanced functional materials.1 In particular,
nanoporous metal–organic frameworks have received extensive
attention because of their potential applications such as in gas
storage,2 separation processes,3 drug delivery,4 sensor tech-
nology,5 heterogeneous catalysis,6 hosts for metal colloids or
nanoparticles,7 luminescence,8 non-linear optics (NLO),9
magnetism,10 and recently, useful heat transformation including
cooling applications11 through reversible water de- and adsorp-
tion. On the other hand, the solid-state structural transformation
is one of the interesting topics in the crystal engineering eld of
metal–organic frameworks (MOFs) and coordination polymers
(CPs).12 Solid-state transformation of MOFs is typically associated
with the loss, addition, substitution, and/or modication of
building components of them. This process including the
expansions of the metal coordination numbers, thermal
dissociation/association, condensation, rearrangement of bonds
or the removal or exchange of solvents.13 J-P. Zhang, et al. were
reported temperature- or guest-induced structural trans-
formations of a nanoporous MOF,14 however, reports on struc-
tural transformation of porous MOFs to nonporous coordination
polymers are very sparse.15 Zn(BDC)(4,40-Bipy)0.5 (MOF-508;
˚
approximately 4.0 ꢂ 4.0 A in cross section. They found that the
guest-free phase MOF-508b (1) reveals that the framework retains
the overall connectivity, but the {Zn2(COO)4} paddle-wheel clus-
ters are signicantly distorted, and the 4,40-Bipy linkers are
bent.18 B. Chen et al. used this microporous MOF for highly
selective GC separation of alkanes.18 M. Kondo et al. presented a
method to selectively synthesize crystal polymorphs of
Zn(BDC)(4,40-Bipy)0.5, as a pillared 2D Kagome nets by simply
´
changing the crystallization temperature. The framework of this
´
polymorph with 2D Kagome nets has a larger pore window (7.7 ꢂ
19
˚
˚
4.9 A along the a axis and 5.2 ꢂ 14 A along the c axis). In this
work we wish to report solid-state structural transformation of a
nanoporous MOF of Zn(BDC)(4,40-Bipy)0.5$(DMF)(H2O)0.5
(1$DMF$H2O) with the pillared 2D square-grid net to a nonpo-
rous coordination polymer of Zn(BDC)(4,40-Bipy) (2) upon
thermal treatment at 350 ꢀC.
H2BDC
¼
1,4-benzenedicarboxylic acid, 4,40-Bipy
¼
4,40-
School of Chemistry, College of Science, University of Tehran, P.O. Box 14155-6455,
Tehran, Islamic Republic of Iran. E-mail: akhbari.k@khayam.ut.ac.ir; Fax: +98 21
66495291; Tel: +98 21 61113734
Results and discussion
The reaction between benzene-1,4-dicarboxylic acid (H2BDC)
† Electronic supplementary information (ESI) available: Other synthetic
procedures, gures and XRD patterns are available. See DOI: 10.1039/c5ra08350h 4,40-bipyridine (4,40-Bipy) and Zn(NO3)2$6H2O in DMF under
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reux condition at 150 ꢀC results in formation of white powder
which was dried at room temperature (Scheme 1). As was
mentioned earlier, two polymorphs were recognized for
Zn(BDC)(4,40-Bipy)0.5. Under reux condition, we may obtain
´
pillared 2D square-grid net or pillared 2D Kagome net
Zn(BDC)(4,40-Bipy)0.5 (Fig. S1a in the ESI†). A comparison
between the XRD patterns simulated from single crystal X-ray
data of these two polymorphs (Fig. S2a and b in the ESI†) and
that of the prepared powder (Fig. S2c in the ESI†), approved the
formation of Zn(BDC)(4,40-Bipy)0.5$(DMF)(H2O)0.5 (1$DMF$H2O)
with pillared 2D square-grid network (Fig. 1a). It composed of
paddle-wheel {Zn2(COO)4} unit, which are pillared by 4,40-Bipy
molecules (Fig. S1c in the ESI†).
TGA data indicated that 1$DMF$H2O releases its guest
molecules over the temperature range 25–145 ꢀC to form the
guest-free phase Zn(BDC)(4,40-Bipy)0.5 (1), which is thermally
stable to 360 ꢀC.18 B. Chen et al. preparedꢀsingle crystals of 1 by
heating a sample of 1$DMF$H2O at 120 C under vacuum for
24 h.18 By single-crystal X-ray crystallography, they showed that
the guest-free phase (1) is signicantly different from that of the
as synthesized 1$DMF$H2O (Fig. S1c and d in the ESI†).18
In order to nd out, what happens by thermal treatment of
1$DMFꢀ$H2O at higher temperatures, a sample of it was heated
at 350 C in a furnace and static atmosphere of air. The XRD
pattern of the resulting powder (Fig. S2g in the ESI†) is
completely different with the simulated XRD pattern from
single crystal X-ray data of 1 (Fig. S2d and S3 in the ESI†). A
broad search was done in literature about Zn(II) compounds
with the same BDC2ꢁ and 4,40-Bipy ligands. We found out that
the XRD pattern of the sample which was heated at 350 ꢀC
(Fig. S2g in the ESI†) approximately matches with the simulated
XRD pattern from single crystal X-ray data of Zn(BDC)(4,40-Bipy)
(2) (Fig. S2f in the ESI†). Zn(BDC)(4,40-Bipy) (2) is a nonporous
Fig.
1
A
fragment of (a) Zn(BDC)(4,40-Bipy)0.5$(DMF)(H2O)0.5
(1$DMF$H2O) MOF with pillared 2D square-grid network and (b)
nonporous three-dimensional coordination polymer of Zn(BDC)(4,40-
Bipy) (2).
In order to conde this happening, we synthesized [Zn2(-
three-dimensional coordination polymer which for the rst BDC)2(H2O)2$(DMF)2]n (3$2H2O$2DMF) MOF and prepared the
time was reported by J. Tao et al.20 In 2, Zn metal ion is bridged activated sample of Zn(BDC) (3) (see ESI†). The extra peak at 2q
by BDC2ꢁ ligands to form a linear or zigzag coordination chain ¼ 15ꢀ (Fig. S2g in the ESI†) which does not observed in simu-
(Fig. S2e in the ESI†), and adjacent chains are further linked by lated pattern of 2, completely matches with that exists in
BDC2ꢁ ligands to form two-dimensional rectangular [Zn(BDC)] Fig. S2e,† approved that conversion of Zn(BDC)(4,40-Bipy)0.5
-
sheet. Adjacent sheets are pillared by 4,40-Bipy spacers into a $(DMF)(H2O)0.5 (1$DMF$H2O) to Zn(BDC)(4,40-Bipy) (2) is
three-dimensional coordination network through the covalently accompanied with removal of Zn(BDC) (3). In TGA analysis
linking mode of .4,40-Bipy–MII–4,40-Bipy–MII., which feature (Fig. S4 in the ESI†), mass loss calculations of compounds 2 and
cuboidal [Zn16(BDC)8(4,40-Bipy)8] structural units.20 Two fold 3 mixture showed that in the rst stage between 290–410 ꢀC,
interpenetration of the above three-dimensional coordination removal of BDC2ꢁ from compound Zn(BDC) (3) occurred with
networks results in stable crystal structure of it (Fig. 1b).20 mass loss of 27.5% (calcd 26.67%). The second stage which
According to the following equation, during the conversion of begin at 410 ꢀC up to 525 ꢀC, attributed to decomposition
1$DMF$H2O to 2, a Zn(BDC) unit with a paddle-wheel structure process of compound 2 and formation of ZnO. It should be
should be removed (Scheme 1).
mentioned that these results also approved the J. Tao et al.
results on no chemical decomposition observed for complex 2
up to 403 ꢀC.20 Thus this conversion is one of the rare instance
solid-state structural conversion of porous MOF to nanoporous
coordination polymer which also indicated that activation
process of MOFs and preparation guest free samples of them
should be carried out carefully.
The “before and aer” structures provide insight into the
mechanism and the driving force for these solid-state framework
rearrangements. Fig. 2 shows the changes in Zn(II) coordination
sphere during this solid-state structural transformation. In
Scheme 1 The produced material from the reaction of H2BDC, 4,40-
Bipy and Zn(NO3)2$6H2O in DMF under reflux condition and conver-
sion of it to nonporous coordination polymer of 2.
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addition to removal of one Zn(BDC) (3) unit (with paddle-wheel metal oxides, ZnO is probably the most widely used inorganic
structure), during this transformation one Zn–O coordination oxide in advanced materials and industrial chemicals such as
bond of two bidentate bridging carboxylate groups are breaking electronic materials, sunscreen cosmetics, pigments and food
and two new Zn–N coordination bonds from 4,40-Bipy ligand are additives.30 Thus in order to preparation of zinc oxide nano-
forming (Fig. 2). Thus the Zn(II) ions in 1 and 2 have coordina- structures and consideration the role of the guest free solvent
tion number of ve with ZnO4N and ZnO3N2 coordination molecules and porosity on formation of different morphologies
spheres, respectively.
of zinc oxide nanostructures, calcination of 1$DMF$H2O and
TGA data showed that there was no chemical decomposition mixture of 2 and 3 powders with microrod morphologies
ꢀ
up to 403 ꢀC for complex 2. Two fold interpenetration of the (Fig. 3a and b respectively) were done at 550 C in static atmo-
three-dimensional coordination networks in 2 and its non- sphere of air. The XRD patterns of residues obtained from
porosity result in highly stable crystal structure.20 Thus the pore calcination process (Fig. S5 in the ESI†) are in agreement with
destruction in 1$DMF$H2O during the solid-state structural the typical wurtzite structure of ZnO (hexagonal phase, space
˚
conversion of nanoporous framework to nonporous coordina- group P63mc, with lattice constants a ¼ 3.24982(9) A, c ¼
˚
tion polymer and formation of 2 with higher thermal stability 5.20661 A, Z ¼ 2, JCPDS no. 36-1451).
than 1 are two driving force during this conversion.
Fig. 3c shows the SEM images of ZnO nanoparticles obtained
The conversion of the MOF into metal oxide nanoparticles from calcination of the 1$DMF$H2O host framework. The cor-
has been used as a new strategy for preparing nanoscale func- responding particle size distribution histogram (Fig. S6a in the
tional entities.21 In this method, the secondary building units of ESI†) showed that these nanoparticles have diameters between
MOF that are mostly composed of metal oxide clusters in 50–100 nm, but the frequency (number of nanoparticles in each
angstrom scale were transformed into metal oxide nano- size distribution) of nanoparticles with 80–90 nm diameter are
materials by thermal treatments. Search in the case of fabrica- higher than others. If we consider the SEM images of ZnO
tion nanomaterials from metal–organic frameworks, as new nanostructures, which obtained from calcination mixture of 2
precursors, indicates that nanomaterials such as ZnO nano- and 3 powders (Fig. 3d), it is obvious that, very different
particles from [Zn2(btec)(DMF)2]n, (btec ¼ 1,2,4,5-benzenete- morphologies compared with that obtained from calcination of
tracarboxylate, DMF ¼ N,N-dimethylformamide),22 Zn2(1,4- 1$DMF$H2O is fabricated. In fact, calcination mixture of 2 and 3
bdc)2(dabco), (1,4-bdc ¼ 1,4-benzenedicarboxylate, dabco ¼ 1,4- microrods with interpenetrated nonporous network (in 2) and
diazabicyclo[2.2.2]octane),23 TiO2 nanoparticles from MIL-125 no guest solvent molecules (in 3 MOF channels) results in
and MIL-125-NH2,24 CuO nanostructures from {[Cu2(BDC- removal of the organic parts of 2, 3 and formation of agglom-
NH2)2(dabco)]DMF$3H2O,25 and Co3O4 nanoparticles from erated ZnO nanoparticles with similar morphology to initial
Co3(NDC)3(DMF)4, (NDC
¼
2,6-naphthalene-dicarboxylate; precursor (Fig. 3b) and with particle size distribution of 40–
DMF ¼ N,N0-dimethyl formamide)26 were prepared. In addi- 100 nm (Fig. 5b in the ESI†), which is smaller than that observed
tion to metal oxide nanomaterials, metal–organic frameworks from 1$DMF$H2O (Fig. 5a in the ESI†), but the tendency of the
also can be used for preparation of porous carbons. For ZnO nanoparticles to aggregate is increased. In addition, the
example, L. Zhang, et al. were reported the thermal decompo- frequencies of nanoparticles with size distribution of 70–80 nm
sition of MOF-5 to ZnO which was covered by amorphous are higher than others (Fig. S6b in the ESI†). Results of our work
carbon, resulting in the C/ZnO nanoparticles. The removal of indicate that probably fully solvated MOFs such as 1$DMF$H2O
ZnO could generate the mesoporous amorphous carbon with a
large surface area of 1844 m2 gꢁ1
.
In another work, nano-
27
porous carbon particles with different particle sizes are
synthesized by simple carbonization of monodispersed zeolitic
imidazolate framework-8 (ZIF-8) crystals.28 Nanoporous carbon
is prepared by direct carbonization of Al-based porous coordi-
nation polymers (Al-PCP), too.29 Metal oxides are used in several
applications such as microelectronic circuits, sensors, fuel cells,
anticorrosion coatings and catalysts. Among the large family of
Fig. 3 SEM images of (a) compound 1$DMF$H2O microrods, (b)
mixture of compounds 2 and 3 microrods after thermal treatment of
1$DMF$H2O at 350 ꢀC, (c) ZnO nanoparticles, fabricated from calci-
Fig. 2 Schematic representation of changes in Zn(II) coordination nation process of 1$DMF$H2O microrods and (d) agglomerated
sphere during the solid-state structural transformation of 1$DMF$H2O nanoparticles of ZnO fabricated from calcination process of
(left) to 2 (right) upon thermal treatment at 350 ꢀC.
compounds 2 and 3 microrods at 550 ꢀC.
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can be used for preparation ZnO nanoparticles. In fact the role XRD powder pattern based on single crystal data were prepared
of organic ligands and free guest solvent molecules in using TOPOS and Mercury soware. X-ray powder diffraction
1$DMF$H2O MOF is similar to the role of polymeric stabilizers (XRD) measurements were performed using a Philips X'pert
in formation nanoparticles. With removal of the guest solvent diffractometer with mono chromatized Cu-Ka radiation. The
molecules from the channels of the host framework and samples were characterized with a scanning electron micro-
conversion of the porous MOF to nonporous coordination scope (Philips XL 30) with gold coating.
polymer, the tendency of nanoparticles to agglomerate, due to
Synthesis of Zn(BDC)(4,40-Bipy)0.5$(DMF)(H2O)0.5 (1)
large specic surface area as well as high surface energy, was
increased. Finally with regard to various applications of ZnO
nanomaterials such as light-emitting diodes,31 photodetec-
tors,32 photodiodes,33 gas sensors,34 and dye-sensitized solar
cells (DSSCs),35 it seems that preparation of ZnO nanomaterials
from their MOFs is one of the simple and effective methods
which may be applied for preparation of them.
White powder of Zn(BDC)(4,40-Bipy)0.5$(DMF)(H2O)0.5 (1) was
synthesized by dissolving 5 mmol (0.831 g) benzene-1,4-
dicarboxylic acid (H2BDC), 5 mmol (1.485 g) Zn(NO3)2$6H2O
and 2.5 mmol (0.390 g) 4,40-Bipy in 50 mL DMF. The resulting
mixture was reuxing at 150 ꢀC for 12 hours. 5 hours aer
beginning of the reux reaction, white precipitate was formed.
Aer ltering, the white precipitate was washed with DMF, and
dried at room temperature for 2 days. d.p. ¼ above 300 ꢀC, yield:
1.354 g, 69.5% based on nal product, IR (selected bands; in
cmꢁ1): 531 w, 631 m, 747 s, 826 s, 1018 w, 1065 w, 1094 w, 1216
w, 1389 vs., 1503 s, 1601 vs., 1676 vs. and 2600–3600 br. Anal.
calc. for C16H16N2O5.5Zn: C, 49.31; H, 4.14; N, 7.19 found; C,
49.40; H, 4.10; N, 7.25%.
Conclusion
In summary, white powder of Zn(BDC)(4,40-Bipy)0.5$(DMF)(H2O)0.5
(1$DMF$H2O) with pillared 2D square-grid net was prepared
under reux condition at 150 ꢀC. It composed of paddle-wheel
{Zn2(COO)4} unit, which are pillared by 4,40-Bipy molecules. TGA
data indicated that the guest-free phase Zn(BDC)(4,40-Bipy)0.5 (1) is
thermally stable to 360 ꢀC. By thermal treatment of 1$DMF$H2O at
350 ꢀC, it converts to Zn(BDC)(4,40-Bipy) (2) which is a nonporous
three-dimensional coordination polymer. During the solid-state
structural transformation of 1$DMF$H2O to 2, a Zn(BDC) unit
(3) with paddle-wheel structure was removed. Finally we have
mixture of compounds 2 and 3 at 350 ꢀC. This conversion is one of
the rare instance solid-state structural conversion of porous MOF
to nanoporous coordination polymer which also indicated that
activation of MOFs and preparation guest free samples of them
should be carried out carefully. Compound 2 which is a nonpo-
rous coordination polymer and has a two fold interpenetration of
the three-dimensional coordination networks is stable up to 403
ꢀC. Thus the pore destruction in 1$DMF$H2O during the solid-
state structural conversion of nanoporous framework to nonpo-
rous coordination polymer and formation of 2 with higher
thermal stability than 1 are two driving force during this conver-
sion. In addition, 1$DMF$H2O and mixture of 2 and 3 powders
with microrod morphologies, were used for preparation of ZnO
nanomaterials. With calcination the host framework of
1$DMF$H2O, ZnO nanoprticles can be fabricated. The same
process on mixture of 2 and 3 results in formation of agglomer-
ated ZnO nanoparticles with similar morphology to initial
precursor. The role of organic ligands and free guest solvent
molecules in 1$DMF$H2O MOF is similar to the role of polymeric
stabilizers in formation nanoparticles.
Conversion of 1 to mixture of Zn(BDC)(4,40-Bipy) (2) and
Zn(BDC) (3) upon thermal treatment
White powder of Zn(BDC)(4,40-Bipy)0.5$(DMF)(H2O)0.5 (1) were
heated at 350 ꢀC in a furnace and static atmosphere of air for 5
hours. d.p. ¼ above 300 ꢀC, IR (selected bands; in cmꢁ1): 517 m,
631 m, 749 s, 826 m, 1014 w, 1045 w, 1072 w, 1105 w, 1154 w,
1221 m, 1396 vs., 1504 s and 1607 vs. Anal. calc. for
C
13H8NO4Zn: C, 50.76; H, 2.62; N, 4.55 found; C, 50.88; H, 2.55;
N, 4.48%.
Preparation ZnO nanostructures from compounds 1–3
In order to preparation of zinc oxide nanostructures, aer well
grinding of 1 and mixture of 2 and 3 for 15 minutes, calcination
of well scattered powder of them as a very thin lm were done at
ꢀ
550 C in a furnace and static atmosphere of air for 3 hours.
Acknowledgements
The authors would like to acknowledge the nancial support of
University of Tehran for this research under grant number 01/1/
389845.
Notes and references
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50782 | RSC Adv., 2015, 5, 50778–50782
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