Chemical Engineering Journal 166 (2011) 1152–1157

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Facile synthesis of nano-sized metal-organic frameworks,

chromium-benzenedicarboxylate, MIL-101
Nazmul Abedin Khan 1 , In Joong Kang 1 , Hwi Young Seok, Sung Hwa Jhung ∗
Department of Chemistry, Kyungpook National University, SanKyuck-Dong, Buk-Ku, Daegu 702-701, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: A chromium-benzenedicarboxylate (Cr-BDC) named MIL-101 with huge porosity, one of the most widely
Received 30 July 2010 studied metal-organic framework (MOF) materials, has been synthesized in wide range of reaction con-
Received in revised form ditions like various water concentrations, pHs and synthesis methods (electric heating and microwave
13 November 2010
irradiation) to get nano-sized crystals. The crystal size decreases with increasing water concentration and
Accepted 25 November 2010
pH. The decrease of size in diluted reactants may be explained with a smaller rate of crystal growth than
nucleation rate. The decreased size of MIL-101 in diluted condition is different to the synthesis of zeolites,
Keywords:
probably because MOFs are obtained by a simple process of complexation. Moreover, high pH may be
Crystal size
MOFs
beneficial to produce not only benzenedicarboxylate but also chromium trimers, which are needed for
MIL-101 the nucleation of MIL-101 structure. In a selected condition, the MIL-101 having the size of about 50 nm
Acidity can be obtained facilely and reproducibly with relatively high yield, which may lead to enlarging the
Water concentration applications of the valuable MOF material.
Microwave © 2010 Elsevier B.V. All rights reserved.

1. Introduction The shape and size of MOFs have been controlled, especially for
nano-sized MOFs, by a few methods. For example, Qui et al. uti-
Recently remarkable progresses on porous materials have been lized US technique for the synthesis of nanocrystalline MOFs [20].
achieved because of the developments of metal-organic framework Ahn et al. also synthesized MOF-5 and MOF-177 with US at rela-
(MOF) materials, crystalline inorganic–organic porous materials tively high temperature; however, they got quite big crystals even
[1]. The importance of MOF-type materials is due to the huge though the size was smaller than that produced in conventional
porosity and easy tunability of their pore size and shape from synthesis [21]. A family of MOF called zeolitic imidazolate frame-
microporous to mesoporous scale by changing the connectivity works (ZIF) such as ZIF-7 [22]) and ZIF-8 [23] have been synthesized
of the inorganic moiety and the nature of organic linkers [1]. in a reaction condition having excess linkers (imidazoles) concen-
Moreover, MOFs have lots of potential applications including gas trations to form ZIFs with size less than 50 nm. Reaction conditions
adsorption/storage [2], separation [3], catalysis [4], adsorption of also have been changed or optimized to synthesize MOFs with
organic molecules [5], drug delivery [6], luminescence [7], elec- various morphologies. MOF-177 crystals were prepared in vari-
trode materials [8], carriers for nanomaterials [9], magnetism [10], ous morphologies by changing the reaction conditions; however,
polymerization [11] and imaging [12]. micrometer-sized crystals were usually obtained [24].
So far, the syntheses of MOF-type materials have been studied MW irradiation has also been used, and the size obtained is
widely not only for finding new structures but also for searching usually small compared with a material synthesized with a conven-
facile methods such as microwave (MW) [13] and ultrasound (US) tional electrical (CE) heating [25]. We have also shown that the size
synthesis [14]. However, the morphology control of MOFs, espe- of an iron-benzenedicarboxylate (Fe-BDC) can be decreased with
cially to get nano-sized MOFs, has not been investigated in detail US or MW synthesis and the size is in the order of CE > MW > US
even though it is very important because the nanoscale MOFs have synthesis from the very same reaction compositions at the same
potential applications like drug delivery [15,16] and imaging [17]. reaction temperature [26]; however, the crystals are quite big
Moreover, the shape and size of a porous material are very impor- (>0.5 ␮m even with US synthesis). A reverse microemulsion-based
tant for applications such as membrane, catalysis and separation technique and a capping agent were used to get nanoscale MOFs
[18,19]. [17] and size-selected MOF-5 [27], respectively. However, the syn-
thesis procedures are a bit complex and there is a possibility for
auxiliary chemicals to remain in the synthesized MOFs.
∗ Corresponding author. Fax: +82 53 950 6330.
Among the numerous MOFs reported so far, one of the most
E-mail address: sung@knu.ac.kr (S.H. Jhung).
topical solids is the porous chromium-benzenedicarboxylate (Cr-
1
Equally contributed to this work. BDC) called MIL-101 [28,29] (MIL stands for Material of Institut

1385-8947/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2010.11.098
 N.A. Khan et al. / Chemical Engineering Journal 166 (2011) 1152–1157 1153

Table 1
Reaction conditions and results for the synthesis of MIL-101s.a

Sample no. Reaction conditiona Reaction result

b
Molar composition pHinitial Heating method Heating time Particle size (nm)c Yield (%) SBET d PV␮ e

A CrCl3 ·6H2 O:TPA:250 H2 O 2.7 CE 6h 800 32 2735 1.43

B CrCl3 ·6H2 O:TPA:400 H2 O 3.1 CE 24 h 400 42 3160 1.54
C CrCl3 ·6H2 O:TPA:550 H2 O 3.3 CE 24 h 200 40 NDf ND
D CrCl3 ·6H2 O:TPA:250 H2 O 2.7 MW 15 min 200 36 3071 1.51
E CrCl3 ·6H2 O:TPA:400 H2 O 3.1 MW 1h 200 38 3196 1.55
F CrCl3 ·6H2 O:TPA:550 H2 O 3.3 MW 1h 100 35 ND ND
Gg CrCl3 ·6H2 O:TPA:400 H2 O 3.1 CE 24 h 400 42 3160 1.54
H CrCl3 ·6H2 O:TPA:400 H2 O (NaOHh ) 4.0 CE 24 h 100 39 ND ND
Ig CrCl3 ·6H2 O:TPA:250 H2 O 2.7 MW 15 min 200 36 3071 1.51
J CrCl3 ·6H2 O:TPA:250 H2 O (NaOHh ) 4.2 MW 15 min 50 37 3223 1.57
a
Reaction temperature: 210 ◦ C.
b
MW: microwave heating; CE: conventional electric heating.
c
Particle size: average particle size observed by SEM (error: ∼50%).
d
BET surface area (m2 /g).
e
Micropore volume (cm3 /g).
f
ND: not determined.
g
Samples G and I are the same as samples B and D, respectively.
h
NaOH (10 N) solution was added to obtain the pHinitial .

Lavoisier). MIL-101, Cr3 O(F/OH)(H2 O)2 [C6 H4 (CO2 )2 ], has a cubic Reagent & Chemicals) were added to control the pH. Syntheses were
structure and huge pore volume of 1.9 cm3 /g [28,29]. The pore sizes conducted at 210 ◦ C under autogeneous pressure unless otherwise
of MIL-101 are around 2.9–3.4 nm [28,29]. MIL-101 is a very impor- specified. The reaction conditions are summarized in Table 1. The
tant material due to its mesoporous structure and huge porosity, gel of about 20 g was loaded in a 100 ml Teflon autoclave, which
and is widely studied for adsorption [30], catalysis [31] and drug was sealed and placed in a microwave oven (Mars-5, CEM, max-
delivery [32,33]. imum power of 1200 W). The autoclave in the microwave oven
The morphology control of MIL-101 has also been reported by us was heated in about 2 min to the reaction temperature of 210 ◦ C
with MW technique [34]. However, nano-sized MIL-101 (<100 nm) and kept for a predetermined time (MW: 10 or 60 min; CE: 6 or
can be obtained at the very beginning of a reaction, and, therefore 24 h). The microwave power was 400 W throughout the whole
the yield was poor and the reproducibility was not good [34]. MIL- synthesis steps including the heating-up stage. The detailed oper-
101-NH2 (MOF with the MIL-101 structure, made from amino-TPA) ation procedure of the microwave oven is described elsewhere
having the size of 120 nm has been used for drug delivery and imag- [38]. For conventional electric crystallization, the gel of about
ing; however, no detailed synthesis method has been revealed [15]. 20 g was loaded in a Teflon lined autoclave and put in a pre-
It has also been reported that diluted reaction mixtures are bene- heated electric oven for a fixed time. During the microwave and
ficial to produce small-sized MOFs like MIL-101 [35] and Cu-BTC conventional reactions, the reactant mixtures were kept without
[36]. However, the size of MIL-101 is around 150 nm and Cu-BTC is agitation.
quite big to be far from nano-crystals. The synthesis of MIL-101 After the reaction, the autoclave was cooled to room tempera-
in high pH (6.0–6.5) is also reported [37]. However, the size is ture and solid products were recovered by centrifugation, washing
around 200–300 nm. Therefore, it is very attractive to find a facile with water and drying. For the purification, the as-synthesized MOF
synthesis method of a nanocrystalline MOFs, especially the valu- samples were treated for 1 h at 70 ◦ C with N,N-dimethylformide
able MIL-101, by simple changing the reaction conditions. Finally a under ultrasound to follow the purification method [39].
method to produce nano-sized MIL-101 in high yield, without using
a surfactant, capping agent or harmful crystal growth inhibitor, is 2.2. Characterization
a highly desirable for various applications including drug delivery
and imaging. The crystal phase of the samples was verified using an X-ray
In this work, we have suggested a facile method to synthesize diffractometer (MO3X-HF, Model No. 1031, CuK␣ radiation). The
nano-sized MIL-101 by optimizing the reaction conditions like pH yield of the solid product was calculated by comparing the amount
and water concentration and by utilizing the MW irradiation tech- of recovered solid with the expected weight based on chromium.
nique. The nano-sized MIL-101 with size of around 50 nm can be The morphology was examined using a field emission scanning
produced in fairly good yield (37%) by MW irradiation in 15 min electron microscope (Hitachi, S-4300 or S-4800) and a transmission
from diluted reagent mixtures containing a base. To the best of our electron microscope (Philips CM-30 BT). The nitrogen adsorption
knowledge, this is the smallest MOFs that are obtained in fair yield isotherms of purified samples were obtained at −196 ◦ C with a sur-
in solid phase. face area and porosity analyzer (Micromeritics, Tristar II 3020) after
evacuation at 150 ◦ C for 12 h. The surface area and micropore vol-
ume were obtained using the BET equation and t-plot, respectively.
2. Material and methods

2.1. Materials and synthesis method 3. Results and discussion

MIL-101s were synthesized from chromium chloride hexahy- 3.1. Effect of water concentration and MW irradiation on the
drate (CrCl3 ·6H2 O, Aldrich), terephthalic acid (99%, Junsei) and particle size of MIL-101
deionized water similar to the methods [28,29,34] reported ear-
lier. However, the synthesis was carried out without HF with the Fig. 1 shows the SEM images of the MIL-101s synthesized with
reactant molar composition of CrCl3 ·6H2 O:TPA:(250–550)H2 O. To CE and MW techniques from reactant mixtures having different
study the effect of acidity, aqueous solutions of NaOH (10 N, Duksan water concentrations. It is noteworthy that the size decreases with
1154 N.A. Khan et al. / Chemical Engineering Journal 166 (2011) 1152–1157

Fig. 1. FE-SEM images of typical MIL-101s to show the effect of water concentration and microwave irradiation: (a) sample A; (b) sample B; (c) sample C; (d) sample D; (e)
sample E and (f) sample F.

dilution of reaction mixtures with water (compare Fig. 1a, b and tent probably leads to a great reduction of the crystal growth rates
c; compare Fig. 1d, e and f; and see Table 1). The size decreases (compared with the small reduction of nucleation rate). Recently,
further with the application of the MW technique (from compar- it has been reported that diluted reactants are beneficial to reduce
ison between Fig. 1a and d; Fig. 1b and e; Fig. 1c and e, and see the size of MOFs like Cu-BTC [36] and MIL-101 [35]. In the syn-
Table 1), similar to the previous results [25,34]. The size of a mate- thesis of zeolites, it has been reported that the size increases with
rial can generally be adjusted by controlling the nucleation and increasing water concentration [41], probably due to low nucle-
crystal growth rates [18,19]. Namely, smaller crystals are obtained ation rates (compared with crystal growth) in zeolites synthesis
when the nucleation rate is relatively larger than crystal growth under highly diluted conditions. This difference between a zeolite
rate [18,19,40]. Therefore, it can be understood that high water con- and a MOF may be explained with the fact that the nucleation of

Fig. 2. FE-SEM images of typical MIL-101s to show the effect of increased pH and microwave irradiation: (a) sample G; (b) sample H; (c) sample I and (d) sample J.
 N.A. Khan et al. / Chemical Engineering Journal 166 (2011) 1152–1157 1155

(e)
Intensity (a.u)

(d)
(c)

(b)

(a)
6 8 10 12 14 16
o
2 theta ( )
Fig. 3. XRD patterns of typical MIL-101s: (a) calculated MIL-101; (b) sample G; (c)
sample H; (d) sample I and (e) sample J.

MOFs is a quite easy process via simple complexation or ligand

exchange [42]. Formation of small particles under MW heating has
been known [34,43] because of the accelerated formation of nuclei
and homogeneous heating under MW irradiation.

3.2. Effect of acidity on the particle size of MIL-101

As illustrated in Fig. 2 (compare Fig. 2a and b; Fig. 2c and d) and

Table 1, high pH is helpful to further decrease the size of MIL-101.
The beneficial effect of MW irradiation in decreasing the particle
size is confirmed once again in these conditions (compare Fig. 2a
and c; Fig. 2b and d, and see Table 1). Chromium trimers are needed
for the synthesis of MIL-101 structure [28]; therefore, conditions
that are helpful to produce chromium trimers will be beneficial to Fig. 5. SEM (upper) and TEM (lower) images of the smallest MIL-101 synthesized
decrease the size because of increasing nuclei concentration. Actu- in this study (sample J).
ally, it has been known that the concentration of chromium trimers
increases (with decreasing monomer) upon increasing the pH from been reported that relatively high pH (6.0–6.5) played an impor-
2 or 4 depending on the concentration of the Cr(III) concentration tant role in the synthesis of MIL-101 as it promoted the dissolution
[44,45]. Moreover, the deprotonation of TPA into benzenedicar- of the organic acid in water and a pure product was obtained eas-
boxylate will be accelerated with increasing the pH. It has also ily [37]. Therefore, it can be assumed that the nucleation rate may
be accelerated at high pH even though the deprotonation rate is
quite fast compared with the complexation to form MOFs [46]. As
1200 observed, increased concentrations of both chromium trimers and
benzenedicarboxylate will lead to the decrease of size because of
high nuclei concentration. The decrease of a size with increasing pH
Amount adsorbed (cm g )

1000
3 -1

(b) had also been observed in the synthesis of an aluminophosphate

molecular sieve [47].
800
(a)
3.3. Surface area, porosity, yield and images of the smallest
MIL-101
600
All of the synthesized MOFs in this study have the MIL-101 struc-
400 ture and are highly porous. The crystal structure and porosity of a
few MIL-101s are confirmed by Figs. 3 and 4 (and Table 1), respec-
tively. Fig. 5 shows the SEM and TEM images of the smallest MIL-101
200
obtained in this study. The particles which are synthesized in rela-
tively high pH 4.2 (Sample J) show the size of around 50 nm and are
0.0 0.2 0.4 0.6 0.8 1.0 relatively homogeneous as observed by both SEM and TEM. Impor-
Relative pressure (PPo )
-1 tantly, the yield is quite high (37% based on Cr) compared with the
low yield in the synthesis of a small-sized MIL-101 in a different
Fig. 4. Nitrogen adsorption isotherms of typical MIL-101s: (a) sample I and (b) condition (in the presence of HF but without adding a base), which
sample J. is obtained in a few minutes [34]. Moreover, the synthesis in this
1156 N.A. Khan et al. / Chemical Engineering Journal 166 (2011) 1152–1157

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