Hydrolytic Transformation of Microporous Metal-Organic Frameworks to Hierarchical Micro- and Mesoporous MOFs

Article abstract of DOI:10.1002/anie.201506391

A new approach to the synthesis of hierarchical micro- and mesoporous MOFs from microporous MOFs involves a simple hydrolytic post-synthetic procedure. As a proof of concept, a new microporous MOF, POST-66(Y), was synthesized and its transformation into a

Full text of DOI:10.1002/anie.201506391

Angewandte
Chemie
International Edition: DOI: 10.1002/anie.201506391
German Edition: DOI: 10.1002/ange.201506391
Hierarchical Porous Materials Hot Paper
Hydrolytic Transformation of Microporous Metal–Organic
Frameworks to Hierarchical Micro- and Mesoporous MOFs
Yonghwi Kim, Tao Yang, Gyeongwon Yun, Mohammad Bagher Ghasemian, Jaehyoung Koo,
Eunsung Lee, Sung June Cho, and Kimoon Kim*
Dedicated to Professor James A. Ibers on the occasion of his 85th birthday
[
7]
Abstract: A new approach to the synthesis of hierarchical
micro- and mesoporous MOFs from microporous MOFs
involves a simple hydrolytic post-synthetic procedure. As
a proof of concept, a new microporous MOF, POST-66(Y),
was synthesized and its transformation into a hierarchical
micro- and mesoporous MOF by water treatment was studied.
This method produced mesopores in the range of 3 to 20 nm in
the MOF while maintaining the original microporous struc-
ture, at least in part. The degree of micro- and mesoporosity
can be controlled by adjusting the time and temperature of
hydrolysis. The resulting hierarchical porous MOF, POST-
have been reported. Furthermore, most mesoporous MOFs
prepared by conventional solvothermal synthesis have pore
sizes smaller than 5 nm. Recently, considerable efforts have
been devoted to the creation of mesopores of more than 5 nm
[8]
in MOFs. So far, such mesoporous MOFs are produced by
direct synthetic methods, including ligand extension, tem-
plate-assisted synthesis, and imperfect crystallization (defect
[
9–12]
formation).
Since these methods require rather elabo-
rated synthetic procedures, it is highly desirable to develop
a simple and reliable method to produce mesoporous MOFs.
Furthermore, porous materials having both micro- and
mesopores are expected to be useful for many practical
applications, but the synthesis of MOFs with such hierarchical
pore structures in a controlled manner is still challenging.
Recently, we and others investigated the post-synthetic
6
6(Y)-wt, can be utilized to encapsulate nanometer-sized
guests such as proteins, and the enhanced stability and
recyclability of an encapsulated enzyme is demonstrated.
[13]
M
etal–organic frameworks (MOFs) constructed from
modification of MOFs, especially post-synthetic substitu-
tion of metal ions or ligands in MOFs.
[14]
metal ions (or clusters) and organic ligands by self-assembly
are an important class of synthetic porous materials. Thanks
to their well-defined pore structures with high surface areas,
MOFs have been extensively studied for various applications,
such as gas sorption, separation, catalysis, and drug deliv-
Based on these
studies, we envisioned that partial removal of metal ions and/
or ligands of microporous MOFs may generate larger pores
while maintaining the original microporosity, at least in part
(Scheme 1), to produce hierarchical MOFs with micro- and
mesoporosity. Although partial desilication or dealumination
[
1–5]
ery.
As the properties and functions of MOFs are often
[15]
dictated by the size and shape of pores in MOFs, tremendous
has been used to produce hierarchical structures in zeolites,
little attention has been paid to the generation of mesopores
[6]
efforts have been made to control the size of pores in MOFs.
[
16]
However, the pores of most MOFs belong to the micropore
regime (less than 2 nm) and only a few mesoporous MOFs
by partial dissolution of microporous MOFs. Herein, we
report a new approach to the synthesis of hierarchical micro-
and mesoporous MOFs from microporous MOFs by a simple
hydrolytic post-synthetic procedure. As a proof of concept,
we synthesized a new microporous MOF, POST-66(Y), and
studied its transformation into a hierarchical micro- and
mesoporous MOF by simple water treatment. Encapsulation
of an enzyme in the resulting hierarchical MOF with
enhanced enzyme stability and recyclability is also demon-
strated.
[
*] Dr. Y. Kim, Dr. T. Yang, Dr. G. Yun, M. B. Ghasemian, J. Koo,
Prof. Dr. E. Lee, Prof. Dr. K. Kim
Center for Self-assembly and Complexity (CSC)
Institute for Basic Science (IBS)
Pohang, 790-784 (Republic of Korea)
E-mail: kkim@postech.ac.kr
Homepage: http://csc.ibs.re.kr/
J. Koo, Prof. Dr. E. Lee, Prof. Dr. K. Kim
Department of Chemistry
Pohang University of Science and Technology
Pohang, 790-784 (Republic of Korea)
Prof. Dr. K. Kim
Division of Advanced Materials Science
Pohang University of Science and Technology
Pohang, 790-784 (Republic of Korea)
Prof. Dr. S. J. Cho
Department of Chemical Engineering, Chonnam National University
Gwangju, 500-757 (Republic of Korea)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201506391.
Scheme 1. View of hydrolytic post-synthetic transformation in a MOF,
resulting in larger pores by partial removal of constituents.
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Colorless truncated octahedron-shaped crystals of the
new MOF POST-66(Y) were synthesized by a solvothermal
reaction of Y(NO ) ·5H O with H hmtt (methyl substituted
vertices with others to generate an infinite network structure
with additional cuboctahedral cages (Figure 1e). The positive
charge (+ 12 per formula unit) of the framework is balanced
by hydroxide and nitrate ions, suggested by elemental analysis
(EA). POST-66(Y) possesses considerable void space (71%
3
3
2
3
truxene tricarboxylic acid; Figure 1a) in a mixture of DMF,
[14b]
methanol, and water.
The chemical formula of POST-
À3
6
6(Y), [{Y (H O)} (hmtt) ](OH) (NO ) ·70DMF·67H O, was
of the unit cell volume) as well as low density of 0.58 gcm
4
2
3
8
6
3
6
2
[18]
determined by X-ray crystallography, elemental analysis
EA), thermogravimetric analysis (TGA), and NMR spec-
owing to the large octahedral and cuboctahedral cages. The
interconnected cuboctahedral cages form three-dimensional
open channels with an aperture of 1.3 nm diameter (Support-
ing Information, Figure S3).
(
troscopy (Supporting Information, Figures S1,S2). Single-
crystal X-ray diffraction analysis revealed that POST-66(Y)
¯
crystallizes in the space group Fm3c and consists of {Y -
POST-66(Y) showed high thermal stability (> 3508C;
Supporting Information, Figure S4) and permanent porosity
4
1
2+
3À
(
H O)} as secondary building units (SBUs) and hmtt as
2
+
a linker. The Y ions of H O-centered square-planar {Y -
H O)} units are connected through the carboxylates from
eight surrounding hmtt ligands (Figure 1b). In turn, each
3
after evacuation of solvent molecules. N sorption data of
2
4
2
1
2+
(
POST-66(Y) at 77 K showed a type I isotherm with a secon-
2
3À
dary uptake before P/P = 0.1 suggesting the presence of two
0
3À
12+
[19]
triangular hmtt ligand is connected to three {Y (H O)}
kinds of micropores (Figure 2a).
No hysteresis was
4
2
squares to generate an uninodal 8-connected reo net (Fig-
[
17]
ure 1c).
A basic building unit for the structure is an
12+
octahedral cage consisting of six {Y (H O)}
eight hmtt ligands (Figure 1d). Each octahedral cage shares
squares and
4
2
3
À
Figure 2. a) N sorption isotherms of as prepared POST-66(Y) and
2
POST-66(Y)-wt-24h, b) Photographs of POST-66(Y) crystal after soak-
ing in water.
observed during the desorption. The sorption isotherm was
fitted to a BET equation, which gave a surface area of
2
À1
3
À1
2
400 m g and a total specific pore volume of 0.89 cm g .
Many MOFs are known to be unstable in water, as water
molecules can easily bind to metal ions and induce destruc-
tion of MOFs by removal of the metal ions through
[20]
substitution or hydrolysis. We therefore decided to explore
water as a dissolution agent to create additional mesopores in
microporous MOF (Scheme 1). To induce mesopores in the
framework, crystals of POST-66(Y) were immersed in water
at room temperature for 24 h. Although the water-treated
crystals (POST-66(Y)-wt-24h) maintained the original size,
shape and appearance (Figure 2b), its N sorption isotherm
2
after immersing in water exhibited a dramatic change from
a type I to type IV isotherm, which is typical for a mesoporous
[19]
material (Figure 2a).
The pore-size distribution profile,
calculated from the desorption isotherm by the Barrett–
Joyner–Halenda (BJH) method, showed two distinct meso-
pores with a diameter of 3.8 and 13.9 nm (Supporting
Figure 1. a) Structure of hmtt, b) SBU of POST-66, c) crystal structure
of POST-66, d) octahedral cage, and e) cuboctahedral cage.
1
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Information, Figure S6). Also, this sorption isotherm showed
an H1 type hysteresis loop, which is characteristic of well-
[19]
defined cylindrical pore channels. Furthermore, the total
3
À1
specific pore volume increased (from 0.89 cm g
to
3
À1
0
(
.94 cm g ), while the surface area decreased significantly
2
À1
2
À1
from 2400 m g to 620 m g ) owing to the loss of micro-
porosity and emergence of mesoporosity.
The generation of mesopores in POST-66(Y)-wt-24h was
confirmed by various electron microscopic studies. Scanning
electron microscopy (SEM) images (Supporting Information,
Figure S7) exhibited a dramatic morphology change at the
surface of POST-66(Y) after the transformation; the surface
was covered with many grooves and voids of nanometer size,
whereas a very smooth surface was observed before the
transformation. Transmission electron microscopy (TEM)
and scanning transmission electron microscopy (STEM)
images (Figure 3; Supporting Information, Figure S8) illus-
Figure 3. Electron microscopy images of POST-66(Y) after soaking in
water a) TEM, b) STEM images of POST-66(Y)-wt-24h.
trated the development of mesopores with a size mostly
within 10 to 20 nm, consistent with the pore size distribution
obtained by N sorption analysis. The mesopores are also
2
randomly distributed and interconnected with each other to
form three-dimensional mesoporous channels. Despite the
generation of mesopores, POST-66(Y)-wt-24h retained the
original microporous structure, at least partially, as suggested
by both single-crystal and powder X-ray diffraction studies
Figure 4. a) N sorption isotherms, b) pore distribution profiles, and c)
PXRD patterns of POST-66(Y) after soaking in water at room temper-
ature for different periods of time.
2
(
Supporting Information, Figure S10). Although the intensity
was significantly reduced, the remaining diffraction peaks at
the low q region matched well the original unit cell of POST-
6
6(Y). Moreover, the Lewis acidic sites of POST-66(Y) were
in microporosity was observed afterwards (see the first slope
at low P/P0 in Figure 4a; Supporting Information, Fig-
ure S12); 2) mesopores of 3–4 nm in size are generated
rapidly during the first 5–10 min; and 3) after that, a slow
evolution of the mesopores occurs until 24 h: 3–4 nm
mesopores decrease while over 10 nm mesopores increase
(Figure 4b; Supporting Information, Figure S13). A series of
PXRD profiles taken during the hydrolytic transformation
(Figure 4c) confirmed the maintenance of the original micro-
porous structure, at least in part, during the mesopore
generation.
During the hydrolytic transformation of POST-66(Y),
both metal ion and ligand constituting the framework were
expected to be leached out from the MOF. The leaching of
metal ions and ligand was monitored by ICP-AES and UV/
Vis spectroscopy, respectively. As shown in the Supporting
partially preserved in POST-66(Y)-wt-24h as confirmed by
in situ IR spectroscopy using acetonitrile as a probe molecule
[21]
(
Supporting Information, Figure S11).
For a better understanding of the water-induced structural
transformation, the process was monitored at a regular
interval for 24 h. A series of N adsorption and desorption
2
isotherms for the water treated sample (POST-66(Y)-wt)
revealed interesting changes in porosity. First, as time goes by,
a gradual loss of micropores and concomitant emergence of
mesopores were observed (Figure 4; Supporting Information,
Figure S12,S13). As a result, the micropore volume decreased
while the mesopore volume increased (Supporting Informa-
tion, Table S1 and Figure S14). Further careful inspection of
the pore size distribution profiles revealed that: 1) the loss of
micropores occurred mostly within an hour and little change
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[a]
Information, Figure S15, leaching of yttrium ions occurred
rapidly upon water treatment; approximately 19% of yttrium
ions of POST-66(Y) were leached out within 1 h and much
slower leaching was observed afterwards. Surprisingly, how-
ever, almost no hmtt ligand was leached out (< 0.1%) during
the water treatment. It is also interesting to note that the
kinetic profile of the metal leaching is in parallel with that of
Table 1: Inclusion of guest molecules in POST-66(Y)-wt-24h.
Guest
Size
Solution
Loading
À1
[nm)]
[mmolg ]
VB12
Cytc
myoglobin
HRP
1.0”1.6”1.7
2.6”3.2”3.3
2.1”3.5”4.4
4.0”4.4”6.8
MeOH
16.1
11.8
9.4
[b]
[b]
HEPES buffer
HEPES buffer
HEPES buffer
[b]
0.42
the reduction of micropore volumes observed by N sorption
experiments (Supporting Information, Figure S16).
2
[
a] VB12 =Vitamin B , Cyt c=cytochrome c, HRP=horseradish perox-
12
idase. [b] 10 mm, pH 7.4.
Taken together, these results suggest that the microporous
to mesoporous transformation of POST-66(Y) proceeds in
two stages (Supporting Information, Figure S17). The first
stage involves the dissolution of yttrium ions from the MOF,
which results in the formation of mesopores with a size of 3–
in POST-66(Y)-wt-24h (HRP@POST-66(Y)-wt-24h) on co-
oxidation of 4-aminoantiprine (4-AAP) and phenol to N-
antipyryl-p-benzoquinoeimine (APBQ) (Figure 5). The reac-
tion was monitored by following the product formation by
UV/Vis spectroscopy. HRP@POST-66(Y)-wt-24h catalyzed
4
nm at the loss of micropores. In the second stage, the
reorganization of yttrium ions and hmtt ligands at the surface
of the newly formed mesopores leads to the further growth
into a size over 10 nm; at the same time, the formation of
a new amorphous phase occurs at the mesopore surface,
which prevents further leaching of yttrium ions, as indicated
by little loss of yttrium after 1 h (Supporting Information,
Figure S15). The structure of the new amorphous phase at the
molecular level is not clear yet, and needs further investiga-
tions.
À5
À1
the reaction with a reaction rate of 6.94 ” 10 mmolLs ,
while no activity was observed for POST-66(Y)-wt-24h
(Figure 5b; Supporting Information, Table S2). When
HRP@POST-66(Y)-wt-24h was removed by filtration after
5 and 15 min, respectively, there was no further progress in
the reaction, indicating little leaching of the enzyme
from HRP@POST-66(Y)-wt-24h. HRP@POST-66(Y)-wt-
24h could be recycled in several times, with a gradual decrease
À5
À1
When the temperature for the water treatment increased
to 808C, the microporous-to-mesoporous transformation
proceeded more rapidly (Supporting Information, Fig-
ure S18a). For example, a 10 min water treatment at 808C
generated mesopores of 12 nm, which is even larger than
those formed by 12 h treatment at room temperature. Further
treatment with water for 12 h at 808C produced even larger
mesopores in the range of 16 Æ 5 nm (Supporting Informa-
tion, Figure S18b). Similar transformations were also
observed in isostructural MOFs with lanthanide metal ions
such as POST-66(Dy/Tb) (Supporting Information, Fig-
of the reaction rate to 5.1 ” 10 mmolLs after 5 runs
(Supporting Information, Figure S31). Furthermore, when the
reaction was performed in the presence of organic solvents
such as DMSO, HRP@POST-66(Y)-wt-24h showed a better
stability than the free HRP (Supporting Information, Fig-
ure S33). These results suggest that POST-66(Y)-wt can be
utilized as a solid support for immobilization of enzymes to
achieve the better stability and recyclability.
In summary, we presented a new approach to the
construction of hierarchical micro- and mesoporous MOFs
from microporous MOFs by a hydrolytic process. The size of
pores can be controlled by modulating the hydrolysis time and
temperature. The dimension of the mesopores generated by
this method can be as large as 20 nm, which is rather difficult
[7b]
ure S20). The meso-MOF(Tb)
also underwent a similar
transformation to produce much larger mesopores, in the
range of 24 to 38 nm (Supporting Information, Figure S21).
Preliminary results suggest that the hydrolytic transformation
is applicable to other well-known MOFs including MOF-177,
UiO-67, and MIL-100 (Supporting Information, Figures S22,
S24, and S25, respectively) if we carefully control the
hydrolysis conditions such as pH, temperature, time, and
water content of mixed solvents. Further work is in progress
to expand the scope of this approach.
The mesoporosity of POST-66(Y)-wt can be utilized to
immobilize large guest molecules such as proteins and
enzymes, which are too large to be immobilized in conven-
tional microporous MOFs. Encapsulation of several guest
molecules, including vitaminB , cytochrome c, myoglobin,
12
and horseradish peroxidase in POST-66(Y)-wt-24h was
studied by UV/Vis spectroscopy (Table 1; Supporting Infor-
mation, Figure S27). After encapsulation, the colorless POST-
6
6(Y)-wt-24h turned to red or orange color, confirming
successful encapsulation of the guests, while POST-66(Y)
showed no color change even after soaking in vitamin B12
solution (Supporting Information, Figures S28,S29).
After the successful encapsulation, we investigated the
catalytic activity of horseradish peroxidase (HRP) embedded
Figure 5. a) Co-oxidation of 4-AAP and phenol to APBQ, b) Kinetic
traces of the reaction carried out with POST-66(Y)-wt-24h (d) and
HRP@POST-66(Y)-wt-24h (c, g, a); the latter two lines
represent the situation where the catalyst was removed after 5 (g)
and 15 min (a) of the reaction.
1
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to obtain by conventional MOF syntheses. Moreover, this
method does not require an elaborated synthetic procedure to
produce mesopores unlike other methods. This simple
method is also applicable to other MOFs. Furthermore, the
efficient encapsulation of an enzyme in the resulting hier-
archical micro- and mesoporous MOF with enhanced enzyme
stability and recyclability has also been demonstrated. This
approach may provide an exciting opportunity to synthesize
new hierarchical porous MOFs with interesting properties for
various applications.
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Keywords: hierarchical porosity · mesoporous materials ·
metal–organic frameworks · post-synthetic transformation ·
protein immobilization
[
[
[
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