A general and efficient approach for tuning the crystal morphology of classical MOFs

Article abstract of DOI:10.1039/c7cc07698c

This communication introduces a general approach toward the size/morphology-controlled synthesis of classical MOFs with 2-methylimidazole (2-MI) as a competitive ligand and a base to accelerate the nucleation of crystallization. A higher concentration of 2-MI and a suitable polarity and solubility of the solvent will accelerate the nucleation of the crystal, resulting in nanometer size particles. However, larger crystals can be obtained via the further growth of nanoparticles with prolonging the reaction time. Such a serendipitous discovery may inspire future researchers to design new MOF materials with desired structures.

Full text of DOI:10.1039/c7cc07698c

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc
first methanofullerene derivatives of Sc
3
N@C2n (2n
=
68 and 80). Synthesis of the
3
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A general and efficient approach for tuning crystal morphology of
classical MOFs
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
a, b
a
Changyan Guo , Yonghong Zhang , Yuan Guo , Liugen Zhang , Yi Zhang , Jide Wang *
DOI: 10.1039/x0xx00000x
www.rsc.org/
1
d,2d,8a
This paper introduces
a
general approach toward the gas separation and heterogeneous catalysis.
To synthesize the size/morphology-controlled MOF crystals
usually depends on the precise control over MOF nucleation,
growth and the development of procedures to induce MOF
size/morphology-controlled synthesis of classical MOFs with 2-
methylimidazole (2-MI) as a competitive ligand and base to
accelerated the nucleation of crystallization. The higher
concentration of 2-MI, suitable polarity and solubility of the
solvent will accelerating the nucleation of the crystal, resulting in
nanometer size particles. While, larger crystals can be obtained
via the further growth of nanoparticles with prolonging the
reaction time. Such a serendipitous discovery may inspire future
1
0
formation on specific substrates. To date, several strategies
have been developed for the synthesis of nanosized MOFs in
the presence of additives. These include: (i) initiation solvent:
the solvent-induced precipitation favors fast nucleation and
slows the crystal growth rate, resulting in nanometer size
1
1
particles; (ii) surfactant-assisted synthesis: the surfactant acts
researchers to design new MOFs materials with desired structures. as a capping agent or inhibitor during the synthetic process,
decreases the surface energy and total system energy via
Metal-organic frameworks (MOFs), refer to a class of highly dipole-dipole interactions or van der Waals forces that slow
2
b,8b,12
ordered, promising crystalline porous materials composed of down the crystal growth rate;
(iii) hard templates: hard
inorganic and organic units linked into one-, two-, or three- templates can also be used to tune the MOF particle
1
2a,13
1
dimensional networks. Over the past decade, owing to their
morphology and porosity;
(iv) coordination modulation: in
some cases, the modulator acts indirectly by altering the
acid/base equilibria of either the starting materials or the
intermediate species to promote the formation of
diverse frameworks, extremely large surface areas, tailorable
molecular cavities, feasible post-synthetic modifications, and
2
exceptional thermal and chemical stability, MOFs have been
coordination bonds between the metal ions and organic
Despite a
widely applied, including but not limited in gas separation and
2b,8b,10,14
linkers to fabricate the MOF nanocrystals.
3
storage, heterogeneous catalysis, adsorption of organic
4
growing number of methods for regulating MOFs morphology
and size by involving different reagents and templates, most of
them are only applicable to specific materials. To develop a
general and efficient approach for tuning crystal size and
morphology of different MOFs is still needed, which will
effectively synthesize size/morphology-controlled MOFs with
excellent catalytic or adsorption performances.
5
molecules and drug delivery.
6
The main researches in this field have been focused on the
design, synthesis, characterization, and application of bulk
MOF materials, suggesting that the functionalities and utilities
7
of molecular materials are greatly influenced by their chemical
composition, size and morphology. Recently, nano-sized MOF
8
materials (NMOFs) have been examined for prospective
applications in heterogeneous catalysis, porous membranes,
Herein, we report a general, rapid, straightforward method
to obtain classical MOFs with unusual morphology and size for
the first time using 2-MI as a coordination modulator. The
nano Co-MOF-74 and HKUST-1 can be obtained in 60% and 80%
yields at room temperature for a few minutes, respectively.
Control experiments indicated that the crystal nucleation and
growth were affected via both coordination and deprotonation
equilibria of 2-MI. MOFs with different sizes can be obtained by
adjusting the concentration of 2-MI, polarity and solubility of
the solvent and reaction time.
8
a,8c,9
biomedical imaging and controlled drug release.
Since
NMOFs usually exhibit unique or enhanced properties for
easier transportation of guest molecules, short diffusion
pathways and exposed active sites within the nano-MOF
2
b,2d,8b
crystals.
The synthesis of NMOFs with special
morphology has proven to be an important factor in extending
these materials to more unique, prosperous applications, e.g.,
Our experimental subsequently convinced that 2-MI could also
be used as an effective competition and capping agent to control
the morphology and size of Co-MOF-74, MOF-5, HKUST-1, Ni-MOF-
7
2
4, and H N-Fe-MIL-101 crystals, respectively. Powder X-ray
diffraction (PXRD) of the MOFs obtained using 2-MI showed
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diffraction patterns identical to those of the unregulated samples, was also found in the EtOH and DMF:EtOH:H
2
O (1:1:1 v/v/v) solvent
which indicated that the MOFs structure was not affected by 2-MI systems (Fig. 2), while the crystal growth rate in DMF:EtOH:H
2
O
and pure MOFs was obtained (Fig. 1). The scanning electron (1:1:1 v/v/v) was slower and required incubating or heating. This
microscopy (SEM) (Fig. 1) results showed that 2-MI had a process was monitored using UV-vis spectroscopy. As shown in Fig.
.
2
pronounced effect on the size and morphology of MOFs. In the 2, the absorption peak of the Co(NO
3
)
6H
2
O solution was located at
absence of 2-MI, the Co-MOF-74 crystals had a flower-like 518 nm (Fig. 2a). The characteristic peak bathochromic shifted to
morphology with a diameter of approximately 100 μm (Co-MOF-74- 540 nm after 2-MI was added, and new absorption peaks located at
1
), which was identical to those synthesized using a classical 587 nm and 658 nm were generated by the coordination of 2-MI
1
5
4
solvothermal method. In the presence of 4 mM 2-MI, spherical with Co(II) (Fig. 2b). When slowly adding H dhtp to the mixed
monodispersed microcrystals with an average size of 10 μm were solution, the color of the solution gradually became lighter, and the
formed, and the spherical crystals stacked with many small characteristic peak located at 587 nm formed by the coordination
hexahedral prisms via aggregation of small nuclei or nanoparticles. effects of the 2-MI with Co(II) rapidly decreased in intensity (Fig. 2c).
A spherical Ni-MOF-74 approximately 2 microns in size was At the same time, the absorption peak of Co(II) gradually increased,
obtained by adding 4 mM 2-MI, and its morphology was more which indicated that the coordination between 2-MI and Co(II)
uniform than that of Ni-MOF-74 synthesized without 2-MI. addition was destroyed by adding of H
Furthermore, a flaky, two-dimensional MOF-5; HKUST-1 with a size absorbs peaks of 2-MI with Co(II) completely disappeared after
of 10 nm and H N-Fe-MIL-101 with a uniform morphology were also stirred for 30 min in the presence of 1 mmol H dhtp at room
obtained via the competitive coordination of 2-MI. All above results temperature (Fig. 2d). The crystal formation in the solution involves
4
dhtp. The coordination
2
4
1
7
indicate that 2-MI is suitable for regulating the size and nucleation followed by growth. All above results referred to a
morphology of MOFs with different metals and structures, and it is competitive interaction between H dhtp and 2-MI with cobalt ions
4
18
a general, straightforward method for the synthesis of nano- or during the nucleation and crystal growth processes.
microscale MOFs with excellent performances.
.
Fig. 2 UV-vis absorption spectra of different samples. a: Co(NO
3 2 2
) 6H O; b: 2-
MI was added dropwise to solution a; c: H dhtp was added dropwise into
4
solution b; d: solution c was stirred for 30 min at room temperature.
Fig. 1 SEM and PXRD images of Co-MOF-74, Ni-MOF-74, MOF-5, HKUST-1,
and H N-Fe-MIL-101 without and with regulation by 2-MI.
2
The influence of the reaction conditions on the nucleation and
growth of MOFs were monitored to obtain insights into the
To further understand the relationship between crystal evolution process of Co-MOF-74 morphologies and sizes. The PXRD
nucleation and growth with 2-MI in this approach, Co-MOF-74 was (Fig. S2-5) and TEM (Fig. S6) measurements showed that the
selected as a template to study the mechanism of crystal growth. diffraction patterns obtained with different conditions were
Upon adding 2-MI to a cobalt nitrate solution, the colour of the identical to the simulated pattern, indicating that pure Co-MOF-74
mixture gradually deepened and became purple (Fig. S1). This result was formed. The SEM (Fig. S7-11) results clearly indicated that the
1
6
showed that 2-MI was coordinated with Co(II) in MeOH solution.
However, when 2,5-dihydroxyterephthalic acid (H
dhtp) was added times (Fig. S11) had a deeper influence on the morphology and size
concentration of 2-MI (Fig. S7), solvents (Fig. S10) and reaction
4
to the purple solution, the colour gradually changed until a of Co-MOF-74, and the size-controlled fabrication was illustrated by
yellowish-brown precipitate was produced. The same phenomenon Fig. 3. The formation of carboxylate based MOFs is primarily
2
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dependent upon the degree of deprotonation of carboxylic
TGA experiments were performed on Co-MOF-74 prepared under
2
a
linkers. In the absence of 2-MI, the degree of deprotonation of different conditions. Fig. S12 showed that all four MOFs had similar
dhtp is low, since deprotonation is only depend on the thermal stabilities, and the crystal structure decomposed higher
H
4
decomposition of DMF to formed dimethyl amine as base at high than 400 °C. Notably, the TGA curves of the Co-MOF-74-2, Co-MOF-
temperature. In another case, a relatively slow nucleation process is 74-3 and Co-MOF-74-4 referred to a rapid weight loss before 250 °C,
7
followed by extremely fast particle growth, only bulk Co-MOF-74 in indicating that the solvent molecules in the MOFs obtained via the
size of about 100 μm was formed. While, in the presence of 2-MI, addition of 2-MI are easily removed and that most of the solvent
more deprotonated H dhtp ions were available for coordination molecules were removed before 250 °C. This difference could be
4
with metal ions, resulting in increasingly accelerated nucleation attributed to the atoms situated on the surface of the small nano-
rates and therefore decreasing crystal size to approximately 1 μm particles have fewer neighbors than the internal atoms, which
as the 2-MI concentration increased. The 2-MI not only acts as resulted in a lower binding energy per atom as the particle size
competitive ligands at the metal centers but also serves as the base decreased. Such feature can be used to effectively remove
for the deprotonation of the bridging ligands. Thus, it will affect molecules within the MOF pores, releasing its macropores and
crystal nucleation and growth via both coordination and providing assistance for gas adsorption and catalysis.
8
b
deprotonation equilibria.
The nucleation rate was accelerated by the addition of 2-MI, the Co-MOF-74 were type I according to the IUPAC classification of
2
The N adsorption/desorption isotherms of those four types of
1
8b
subsequent crystal growth may involve the Ostwald ripening at the isotherm shapes (Fig. S13),
expense of metal ions and linkers as well as smaller nanoparticles to with the literature.
yield MOF crystals. The formation of large particles at the cost of specific surface area and pore volume gradually decreased. With
small particles is presumably due to the energy difference between the increase of washing times, specific surface area and pore
and this result is in good agreement
With the decrease of crystal size, both the
1
e, 15
2
b
8
a
large and small nanoparticles. Fig. 3 indicated that the DMF was volume increased. However, the average pore size increased, and it
propitious to the dissolution of H dhtp and small particles, resulting may be caused by the presence of hierarchical pores; another
in the growth of larger particles, and crystals about 10 μm in size reason is because of 2-MI adsorbed in the crystal pores just like the
can be obtained in DMF:H O (1:1 (v/v)) and DMF:MeOH:H O (1:1:1 DMF, and with the departure of guest molecules, resulting in an
v/v/v)). In the MeOH:H O (1:1 (v/v)), spherical nanocrystals with increase in pore size. (Fig. S13a, pore-size distributions calculated
4
2
2
(
2
diameters of 300-500 nm were obtained at room temperature (Co- using DFT and Horvath-Kawazoe (HK) method can be found in Fig.
MOF-74-3). This is because that the increasing of the polarity of S14-18). The larger pore size is favorable for the entry and
solvent facilitates the exchanging between the metal ions and the transmission of macromolecules. In catalytic reactions, substrate
ligand, and therefore accelerating the nucleation of the crystal. And molecules can be easily introduced into the macropores to perform
also, the rapid decrease of supersaturation will reduce the growth reactions, and this will improve the contact rate of the substrate
1
f, 19
of nano nucleus to obtained nanosized crystal.
size decreased to about 20-30 nm at room temperature (Co-MOF- selectivity.
4-4) in MeOH. MeOH is beneficial to accelerate the nucleation of To verify the crystal morphology and size on its application
While, the crystal and the active sites, which will enhance the catalytic rate and
7
crystal, but not conducive to the rapid dissolution and growth of properties, we used the micro- and nanosized crystals prepared by
small nuclei, resulting in smaller crystals. So, the crystals with this method for the catalytic oxidation reaction of 2,3-dihydro-1H-
different sizes can be obtained by adjusting the solvent system. indene. Table 1 showed that the catalytic conversion of Co-MOF-74-
Additionally, when the reaction time was shortened to 10 min, 1 obtained by the literature method was 73%. Surprisingly, the
small uniform of spherical crystals were obtained with an average conversion of 2,3-dihydro-1H-indene to 2,3-dihydro-1H-inden-1-one
size of 800 nm (Co-MOF-74-2). As the time was prolonged to 12 or catalyzed by the catalysts (Co-MOF-74-2, Co-MOF-74-3 and Co-
2
4 h, the increase in particle size could be resulted from further MOF-74-4) with smaller sizes and larger pore diameters increased
growth via aggregation of small nuclei or nanoparticles which to 90%-93%. The size and morphology of a crystal have a profound
7, 19
formed extremely fast in the presence of 2-MI.
Producing impact on its catalytic performance. The large-pore-diameter MOFs
various crystal sizes changed from 800 nm to several micrometers.
exhibit unique or enhanced properties by providing easier
transportation of guest molecules and have short diffusion
pathways and exposed active sites within the MOF crystals. These
Table 1. Comparison of the catalytic performance for the oxidation of 2,3-
a
dihydro-1H-indene.
Co-MOF-74 (5 mg)
TBHP (3 equiv.)
O
OH
2
H O (1 mL)
+
+ Others
6
0 oC, 12 h
A
B
C
D
b
Entry
Catalyst
Conversion
Yield (%)
(
%)
73
90
93
90
B
C
D
3
1
2
3
4
Co-MOF-74-1
Co-MOF-74-2
Co-MOF-74-3
Co-MOF-74-4
58
12
77
83
81
8
6
6
5
4
3
Fig. 3 The evolution process of Co-MOF-74 morphologies and sizes by 2-MI.
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a
Conditions: A (0.2 mmol), catalyst (5 mg), TBHP (0.6 mmol), Solvent (1 mL), 60
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C, 12 h. Conversion and yield were determined by GC.
advantages give the MOFs regulated by 2-MI an excellent catalytic
rate and selectivity.
4
5
In summary, we have developed a general, rational
approach to fabricate size and shape controllable particles
from classical MOFs by using 2-MI as a coordination
modulator. The nucleation rate was accelerated by the
addition of 2-MI via both coordination and deprotonation
equilibria, and the crystal size of Co-MOF-74 decreased with
increasing of the 2-MI concentration. In addition, the crystal
size can be adjusted by controlling the polarity and solubility of
the solvent and the reaction time. The TGA test and N2
adsorption/desorption isotherms results indicated that the Co-
MOF-74 obtained by the addition of 2-MI provided better
catalytic potential due to the solvent molecules within the Co-
MOF-74 pores were easily removed, and their larger pore size,
which is favourable to the entry and transmission of
macromolecules. This conclusion was confirmed by further
catalytic experiments, and the regulated catalysts have better
catalytic performance than that of the crystals synthesized
using the literature method. We believe that this approach will
serve as a useful archetypical template to develop other
carboxylate-based MOF crystals with better performances in
heterogeneous catalysis.
2
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J. An, S. J. Geib and N. L. Rosi, J. Am. Chem. Soc., 2009, 131,
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This work is supported by the National Natural Science
Foundation of China (Grant No. 21162027 and 21261022).
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