Synthesis and characterization of porous Al(III) metal-organic framework nanoparticles as a new precursor for preparation of Al2O3 Nanoparticles

Article abstract of DOI:10.1016/j.inoche.2011.01.040

A porous aluminum(III) metal-organic framework, [Al₈(OH) ₁₅(H₂O)₃(btc)₃]_n, MIL-110, has been synthesized by hydrothermal method and characterized by elemental analyses, X-ray powder diffrac

Full text of DOI:10.1016/j.inoche.2011.01.040

Inorganic Chemistry Communications 14 (2011) 645–648
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Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Synthesis and characterization of porous Al(III) metal-organic framework
nanoparticles as a new precursor for preparation of Al2O3 Nanoparticles
⁎
Mohammad Sadegh Yazdan Parast, Ali Morsali
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14155–4838, Tehran, Islamic Republic of Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
A porous aluminum(III) metal-organic framework, [Al8(OH)15(H2O)3(btc)3]n, MIL-110, has been synthesized
by hydrothermal method and characterized by elemental analyses, X-ray powder diffraction (XRD) and IR
spectroscopy. MIL-110 (Al) was calcinated at different temperatures under air atmosphere to prepare Al2O3
and in another process MIL-110 (Al) nanoparticles were prepared by using oleic acid. The product of each step
was characterized by scanning electron microscopy, X-ray powder diffraction (XRD) and energy-dispersive X-
ray analysis (EDAX). This study demonstrates that the metal-organic frameworks may be suitable precursors
for the simple one-pot preparation of nanoscale metal oxide materials with different and interesting
morphologies.
Received 2 January 2011
Accepted 28 January 2011
Available online 2 March 2011
Keywords:
Metal-organic framework
Thermal properties
Nano-materials
© 2011 Elsevier B.V. All rights reserved.
Aluminum(III)
Metal-organic frameworks (MOFs) are a novel class of porous
inorganic coordination polymers (material made from metals and
organic compounds) with numerous potential applications. These
fascinating materials have large internal surface areas, ultra low
densities, and uniformly structured pores and channels and because of
these properties, they have a wide variety of applications, including
gas and chemical storage, chemical separations, sensing, selective
catalysis, ion exchange, and drug delivery [1–18].
Besides, in recent years, synthesis of nano inorganic materials with
different morphologies has been of significant interest in material
science and industry [19,20]. Nanoparticles (NPs) that have a
diameter of less than 100 nm behave significantly different from
their bulk form. Among them, crystalline and amorphous metal
oxides, because of their high surface area, chemical and thermally
stable properties, and mesoporous properties, have been extensively
studied for catalyst application at high and low temperatures [21–23].
Besides, recently, increasing investigations have been focused on the
design and construction of nano-scale MOFs (NMOFs). Now the
research on NMOFs focuses on exploration of their synthesis
conditions and applications such as magnetic resonance imaging,
heterogeneous catalysis, anticancer drug delivery and sensing
molecule application [24–29]. There is some report that metal-
organic framework can be used as a good precursor for preparing
nano-porous carbon and metal oxide nanoparticle [30–32].
In the present work we have used oleic acid as a cationic surfactant
for preparation of nano-sized aluminum(III) metal-organic frame-
work and a simple calcination method to prepare Al2O3 nanostruc-
tures from an aluminum(III) metal-organic framework, wherein
MIL-110 (MIL = Materials of the Institut Lavoisier).
All reagents and solvents for the synthesis and analysis were
commercially available from Merck Company and used as received.
X-ray powder diffraction (XRD) measurements were performed using
an X'pert diffractometer of Philips company with monochromated
Cokα radiation (λ=1.78897 Å). The samples were characterized with
a scanning electron microscope (SEM) (Philips XL 30) with gold
coating. IR spectra were recorded on a SHIMADZU- IR460 spectrom-
eter in a KBr matrix.
MIL-110 was prepared in hydrothermal method in two different
pH. In the first method, MIL-110 (Al) was obtained from the reaction
of Al(NO3)3.9H2O (3.5 mmol, 1.314 g)/0.5 Me3btc (1.75 mmol,
0.440 g)/80 H2O (278 mmol, 5 mL) without any additional acid or
base. The reactants were placed in a 23 mL Teflon-lined Parr
autoclave, heated for 3 days at 195 °C in an oven. The resulting
powder was filtered off, washed with water and dried at ambient
temperature (noted as MIL-110{pH7}). For the second synthesis
method MIL-110 (Al) obtained at controlled pH (initial pH=4) from
reaction of mixture containing Al(NO3)3.9H2O (0.874 mmol, 328 mg)/
Me3btc (0.436 mmol, 110 mg)/H2O (270 mmol,5 mL)/NaOH (2 mmol,
0.5 mL 4 M), but the 23 mL Teflon-lined steel Parr autoclave was
operated at 210 °C for only 3 h (noted as MIL-110{pH4}) [33,34].
For preparation of Al2O3, about 50 mg of MIL-110{pH7} was
heated for 12 h at 500 °C and 750 °C MIL-110{pH4} heated at 500 °C
for 3 h. After cooling the weight precipitate was obtained and washed
with EtOH and dried under nitrogen. IR spectrum shows that
calcination was completed and all of the organic compounds were
⁎
Corresponding author. Fax: +98 2182884416.
E-mail address: morsali_a@modares.ac.ir (A. Morsali).
1387-7003/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2011.01.040

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Fig. 1. The XRD patterns of (a) simulated from single crystal X-ray data of MIL-110; (b) powder XRD of MIL-110; (c) powder XRD of Al2O3 prepared by calcinations of MIL-110.
decomposed. But the powder XRD diffraction analysis shows that
product doesn't have high crystallite (Fig. 1c).
structure is hexagonal channels 1.7 nm wide. Interestingly the
powder of MIL-110 is consisting of hexagonal needle-like single
crystals [33,34].
In the synthesis method with pH=4 the crystal size of product is
smaller than in the uncontrolled pH, so we try to prepare metal-
organic framework in nano scale at this pH.
Fig. 1a shows the simulated XRD pattern from single crystal
synchrotron-radiation microdiffraction data and Fig. 1b shows the
XRD pattern for powder MIL-110 (Al) prepared by the hydrothermal
method. Acceptable match were observed between the simulated and
experimental powder X-ray diffraction pattern. This indicates that the
compound obtained in this work is identical to that reported by Ferey
et al. [33,34].
The structure of MIL-110 (Al) has been reported [33,34] and it
shows that this compound was made from aluminum octameric
clusters, linked through the trimesate (btc) ligand. The inorganic
clusters (Fig. 2) are based exclusively on hexa-coordinated aluminum
cations, with three dimers capped above and below by two single Al
octahedral. The dimers consist of two octahedral aluminum sites
sharing an edge through two bridging μ2-OH groups. In the result, the
The morphology, structure and size of the samples were
investigated by Scanning Electron Microscopy (SEM). Fig. 3a and b
shows the SEM image of the treated MIL-110{pH7} for 12 h at 500 °C
and 750 °C, respectively. As it can be seen, there are two different
shapes, cubic structure and the coral structure which the second is
built from aggregated nanoparticles. The calcination was done at
different temperature but in all two cases mixture of cubic structure
and coral structure was obtained. The Al2O3 nanoparticles were
prepared by calcination of MIL-110{pH4}. Fig. 3c shows the SEM
image of Al2O3 nanoparticles obtained from calcination of MIL-110
{pH4} at 500 °C for 3 h. In another case we used oleic acid as a
surfactant to prepare aluminum(III) oxide nanoparticle. In this case
0.05 g of MIL-110{pH4} was added to 10 mL of oleic acid and heated at
180 °C for 4 h and then 1 mL of toluene and 90 mL of ethanol was
added respectively.
The precipitation was segregated by centrifuge and washed with
ethanol for several times to remove the remaining oleic acid and
dried at 60 °C. The IR spectrum (Fig. 4) shows that the compound
was not calcinated in oleic acid. An additional pick at 2929 cm−1 in
IR spectrum refers to the presence of oleic acid which could be
attracted on the surface or penetrated to the pore of porous
compound. Fig. 3d shows the SEM image of this sample and as it
can be seen this sample is made of nano-scale particles of MIL-110.
However, it is interesting, that the treatment of MIL-110 in oleic acid
at 180 °C does not produce aluminum(III) oxide and that this method
caused to produce MIL-110 nanoparticles. This method is the first
one for preparation of nanosize MOF compounds by the surfactant
method. Fig. 5a and b shows the distribution size of Al2O3 and MIL-
110 nanoparticles.
Different morphologies of an Al(III) metal-organic framework as
precursors for synthesis aluminum oxide nanoparticles through both
simple calcination method and oleic acid as a surfactant was studied.
Al2O3 nanostructure obtained from Al(III) metal organic framework
precursor by simple calcination method and morphology of pre-
cursors could determine the morphology of final products. Consider-
ing the wide application of aluminum(III) oxide as substrate and as
catalyst [35–38], we hope that nano and micro Al2O3 with amorphous
Fig. 2. View of the structure of MIL-110 along c, showing the hexagonal Channels.

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647
Fig. 4. IR spectra MIL-110{pH7}, MIL-110{pH4} and MIL-110{pH4} treated in oleic acid.
The additional peak at 2929.70 cm−1 is due to the oleic acid.
Fig. 3. SEM photograph of (a) Al2O3 micro- and nano- structures prepared by
calcination of MIL-110{pH7} at 500 °C for 12 h, (b) Al2O3 micro- and nano-structures
prepared by calcination of MIL-110{pH7} at 750 °C for 12 h, (c) Al2O3 nanostructures
prepared by calcination of MIL-110{pH4} at 500 °C for 3 h and (d) MIL-110{pH4}
nanoparticles prepared by treatment in oleic acid at 180 °C for 3 h.
Fig. 5. Particle size histogram of (a) Al2O3 nanostructures and (b) MIL-110
nanoparticles.
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