Controllable Modular Growth of Hierarchical MOF-on-MOF Architectures

Article abstract of DOI:10.1002/anie.201709738

Fabrication of hybrid MOF-on-MOF heteroarchitectures can create novel and multifunctional platforms to achieve desired properties. However, only MOFs with similar crystallographic parameters can be hybridized by the classical epitaxial growth method (EGM), which largely suppressed its applications. A general strategy, called internal extended growth method (IEGM), is demonstrated for the feasible assembly of MOFs with distinct crystallographic parameters in an MOF matrix. Various MOFs with diverse functions could be introduced in a modular MOF matrix to form 3D core–satellite pluralistic hybrid system. The number of different MOF crystals interspersed could be varied on demand. More importantly, the different MOF crystals distributed in individual domains could be used to further incorporate functional units or enhance target functions.

Full text of DOI:10.1002/anie.201709738

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Accepted Article
Title: Controllable modular growth of hierarchical MOF-on-MOF
architectures
Authors: Yifan Gu, Yi-nan Wu, Liangchun Li, Wei Chen, Fengting Li,
and Susumu Kitagawa
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201709738
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Angewandte Chemie International Edition
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COMMUNICATION
Controllable modular growth of hierarchical MOF-on-MOF
architectures
a, ‡
a, ‡
b
a
a,
c,
Yifan Gu,
Yi-nan Wu,
Liangchun Li, Wei Chen, Fengting Li, * and Susumu Kitagawa *
Abstract: Fabrication of hybrid MOF-on-MOF heteroarchitectures
can create novel and multifunctional platforms to achieve desired
properties. However, only MOFs with similar crystallographic
parameters can be hybridized by the classical epitaxial growth method
(
EGM), which largely suppressed its applications. Herein, we
demonstrated a general strategy called internal extended growth
method (IEGM) for the feasible assembly of MOFs with distinct
crystallographic parameters in an MOF matrix. Various MOFs with
diverse functions could be introduced in a modular MOF matrix to form
3
D core–satellite pluralistic hybrid system. Additionally, the number of
different MOF crystals interspersed could be variable on demand.
More importantly, the different MOF crystals distributed in individual
domains could be used to further incorporate functional units or
enhance target functions.
Scheme 1. Schematic of the formation process of the MOF-on-MOF hybrid
Metal–organic frameworks (MOFs), or porous coordination
polymers (PCPs), are intriguing porous crystalline materials
constructed from inorganic nodes interconnected by organic
structure.
[
1]
spokes.
diversified structure, large surface area, tunable pore size， and
MOFs exhibit distinct features, such as highly
An alternative is to use a previously synthesized MOF and
grow another MOF on the surface of the MOF matrix by lattice
matching for the formation of core–shell MOF-on-MOF hybrids by
[
2]
customizable chemistry. Endowed with such features, great
efforts have been made to functionalize the bulk of the MOF
material by incorporating MOFs with other functional species,
[
7]
the epitaxial growth method (EGM). Based on EGM, the
combination of post-synthetic modification and in situ MOF
surface modification has been proved successful in preparing
several other core–shell, core–shell–shell, and surface-selective
[
3]
[4]
[5]
such as nanoparticles (NPs), biomolecules, nanofibers, and
[
6]
polymers . This integration is an important route for expanding
MOF-based applications as MOF composites often exhibit
enhanced or even unprecedented properties compared with their
[
8]
MOF hybrids. Combining different MOFs into a hybrid material
opens up the possibility of modular devices with multiple
properties, such as united catalysis and purification or enhanced
[
3c]
pristine counterparts. However, the functionalization of MOFs
with other kinds of MOFs remains challenging and relatively
unexplored. Therefore, a promising method is imperative for the
modification of MOFs into MOFs with new functionalities but with
the characteristic features of MOFs.
[
9]
sorption and separation capacity. However, complex designs of
two or more MOFs with similar unit-cell crystallographic
parameters in one particle are only limited to few core–shell MOF
composites prepared by EGM. The application of this synthetic
strategy is limited as most MOFs have distinct unit-cell
parameters. Thus, a new versatile method for the delicate design
and synthesis of composite MOF precursors with novel structures
and tailored compositions is important to expand the applications
[a]
Yifan Gu, Dr. Yi-nan Wu, Dr. Wei Chen, and Prof. Dr. Fengting Li
College of Environmental Science and Engineering, State Key
Laboratory of Pollution Control and Resource Reuse
Tongji University
[10]
of MOF-based materials.
In this work, we first systematically developed a facile
strategy called internal extended growth method (IEGM) to design
and synthesize modular hierarchically structured MOF
composites, overcoming the limitation of lattice matching rule
Siping Rd 1239, 200092 Shanghai, China.
E-mail: fengting@tongji.edu.cn
[
b]
c]
Prof. Dr. Liangchun Li
Shanghai Key Lab of Chemical Assessment and Sustainability,
School of Chemical Science and Engineering
Tongji University
Siping Rd 1239, 200092 Shanghai, China.
Prof. Dr. Susumu Kitagawa
(
Scheme 1). In implementing IEGM, two MOFs with distinct
morphologies and crystal structures (Figure S1), namely, NH
UiO-66(Zr) and NH -MIL-125(Ti) were easily hybridized as MOF-
on-MOF heterostructure through microwave heating in which
NH -UiO-66(Zr) is exposed to NH -MIL-125(Ti) precursors with
2
-
2
[
Institute for Integrated Cell-Material Sciences (WPI-iCeMS)
Kyoto University
2
2
Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
E-mail: kitagawa@iCeMS.kyoto-u.ac.jp
polyvinylpyrrolidone (PVP) as the structure-director agent. The
materials are denoted by MOF-on-MOF(X-Y), where X represents
X mg of NH
dosing quantity (mg). After the simple microwave heating, a
substantial amount of NH -UiO-66(Zr) particles were interspersed
2
-UiO-66(Zr) dosing quantity and Y stands for the PVP
‡
Yifan Gu and Dr. Yi-nan Wu contributed equally to this work
Supporting information for this article is given via a link at the end of
the document.
2
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Angewandte Chemie International Edition
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COMMUNICATION
Figure 2. Ball-and-stick and/or schematic representations of the coordination
phenomenon associated with the systematic growth of the MOF-on-MOF hybrid
structure.
[
11]
PVP in solution is shown in Figure S6.
PVP have a stronger affinity for metallic ions. After 24 h stirring,
the initially monodispersed NH -UiO-66(Zr) NPs (Figure S4a)
The polar groups of
[
12]
2
were coated with layers of PVP (Figure S4b) due to the
electrostatic attraction. When Titanium tetraisopropanolate (TTIP)
4
+
2
was added to the solution, Ti was absorbed onto NH -UiO-
2
Figure 1. (a, b) SEM and (c–e) TEM images of a typical NH -UiO-66(Zr) on
NH
interface of NH
probe used is 16 nm ×16 nm.
2
-MIL-125(Ti) heterostructured hybrid crystal. (f–h) EDS mapping of a typical
66(Zr) probably due to the presence of PVP coated on the metal
cation by coordination. The abundance of Ti atoms in the overlap
junction revealed the existence of Ti atoms in the surface edge of
2
-UiO-66(Zr) and NH -MIL-125(Ti). The resolution of the EDS
2
NH
2
-UiO-66(Zr), as supported by the EDS mapping data (Figure
1
g) and EDX spectrum profile scanning data (Figure S7). This
2
uniformly on a NH -MIL-125(Ti) nanotablet, as confirmed by
layer of Ti atoms was formed due to the coordination
phenomenon caused by PVP (Figure 2). Consequently, the nuclei
scanning and transmission electron microscopy (SEM and TEM).
Figure 1a–d show the images of a typical heterostructured MOF-
on-MOF(80-80) crystal. The contrasting light and shade of the
2 2
of NH -MIL-125(Ti) were aggregated with NH -UiO-66(Zr)
crystals to form micelles (Figure S4c). The new peaks appearing
in the powder XRD (PXRD) analysis (Figure S5) after 30 min
different parts of NH
2
-UiO-66(Zr) visually showed that the NH
2
-
-
UiO-66(Zr) NPs were partly inserted into the surface of the NH
2
2
reaction were assigned to the of NH -MIL-125(Ti) matrices. The
MIL-125(Ti) crystal. The energy-dispersive X-ray spectrometry
EDS) elemental mapping of a selected area of a typical interface
internal extended growth process occurred after the 30 min
reaction. As shown in Figure S4d and e, after nucleation, the self-
(
of these two MOFs shows the distribution of O, Ti, and Zr
elements (Figure 1f–h). The oxygen atoms were evenly
distributed over the entire selected area of the MOF-on-MOF(80-
assembled structure of NH
growth to the desired 3-D nanotablet shape. Typical crystal
structure of NH -MIL-125(Ti) were observed by XRD monitoring
after 1 h reaction (Figure S5). Consequently, a special NH -UiO-
6(Zr) on NH -MIL-125(Ti) hybrid structure was obtained. The
2
-MIL-125(Ti) continued its extended
8
0) particle, as the structures of both NH
MIL-125(Ti) contain oxygen atoms. Zirconium atoms were only
detected in the NH -UiO-66(Zr) part of the particle, whereas
titanium atoms were mainly found in the NH -MIL-125(Ti) part of
the particle. Notably, spots of Ti ions were evenly distributed in
the surface of NH -UiO-66(Zr) part. The crystal structure, porosity,
2 2
-UiO-66(Zr) and NH -
2
2
6
2
2
final products after incubation are shown in Figure S4f. The
junction of the MOF-on-MOF may get through the interaction
2
4
+
4
+
between the pyrrolidone ring of PVP layer and Ti ions leading to
an improved affinity of NH -UiO-66(Zr) to NH -MIL-125(Ti).
Meanwhile, the PVP molecules adsorbed with Ti could be
readily replaced by NH BDC molecules during the ligand
assembly process of NH -MIL-125(Ti), resulting in random MOF-
on MOF morphologies like a Pizza instead of usual core-shell
2
surface fractal property and photoelectron characteristics of the
core–satellite MOF-on-MOF materials were further explored and
shown in supporting information (Figure S2 and S3).
2
2
4
+
2
2
How the two MOFs with distinct morphologies and crystal
structures make heterostructured connection is highly interesting.
High-resolution SEM (Figure S4) and X-ray diffraction (XRD;
Figure S5) were used to elucidate the physical and chemical
changes over time to understand the synthesis mechanism and
the role of PVP in the synthesis process. The formation process
of the core–satellite MOF-on-MOF hybrid structure can be can be
[
12a]
structure.
NH -MIL-125(Ti) were obtained as final products. There were very
few NH -UiO-66 crystals inserted into NH -MIL-125(Ti) crystal
Figure S8). Thus, without PVP, single NH - UiO-66 crystals has
2
Without PVP, physical mixture of NH -UiO-66 and
2
2
2
(
2
almost no impact on in-situ solvothermal crystallization of NH
MIL-125(Ti) nanotablet.
2
-
divided into two stages: aggregated nucleation of NH
2
-MIL-
Manipulating the sizes and morphologies of MOF crystals is
challenging, but it leads to advanced applications given that these
parameters can significantly impact certain properties of bulk
1
25(Ti) and internal extended growth. The aggregated nucleation
occurred within the first 30 min. According to the zeta potential
analysis, PVP showed a negative value of −0.27 mV, whereas
[
13]
NH
2
-UiO-66(Zr) showed a positive value of +1.51 mV when
materials. In this heterostructured system, the number of MOF
crystals interspersed and the size of the MOF matrix can be well
dissolved in the reaction solution. The resonance structure of
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of MOF-76(Tb) and NH
2
-MIL-125(Ti). The fluorescence yield of
MOF-76(Tb) in the mixture might have been quenched by NH
MIL-125(Ti). On the contrary, the fluorescence of separated MOF-
6(Tb) nanorods inserted into the surface of NH -MIL-125(Ti) was
2
-
7
2
well maintained, as it benefited from the unique core–satellite
heteroarchitecture. Ternary MOF-on-MOF system was obtained
successfully by combining NH
2
-UiO-66(Zr) & MOF-76(Tb) and
NH -MIL-125(Ti) (Figure 3e-f and S11e-f). The nitrogen sorption
2
analysis (Figure S14) showed that the ternary hierarchical MOF-
on-MOF obtained kept porous structures of the three bulk MOFs.
The PXRD patterns (Figure 3f) present all characteristic peaks of
the three bulk MOFs, which further suggest the successful
combination of these three MOFs. These special hierarchical
MOF-on-MOF assemblies proved that the IEGM could be
potentially general for the preparation of pluralistic hierarchical
MOFs system, leading to well-defined multicompartment MOFs
systems with great flexibility.
The synergies among different MOFs distributed in individual
domains could be beneficial for enhancing target functions. MOFs
[
15]
are widely used in adsorption and photocatalysis. Adsorption-
photocatalytic Cr(VI) reduction by the micro/mesoporous MOF-
on-MOF system was further investigated (Table S1). As shown in
Figure 4a, relative lower adsorption capacity for Cr(VI) was obtained
on the single NH
presented slightly higher (1.28 mg/g). Interesting, the MIL-
01(Cr)@NH -MIL-125(Ti) materials exhibited enhanced adsorption
2
-MIL-125(Ti) (1.12 mg/g), while MIL-101(Cr)
1
2
capacity on Cr(VI) which could reach up to 3.16 mg/g. The
introduction of MIL-101(Cr) provided extra mesoporous channels
to improve the adsorption of chromium ions in the internal
2
Figure 3. (a) SEM image of the typical MIL-101(Cr) on NH -MIL-125(Ti)
2
microporous NH -MIL-125(Ti), leading to an improved adsorption
heterostructured hybrid crystal. (b) Pore width distribution based on the NLDFT
model of MIL-101, NH -MIL-125, and MIL-101@NH -MIL-125. (c) SEM image
of typical MOF-76(Tb) on NH -MIL-125(Ti) heterostructured hybrid crystal. (d)
Fluorescence emission spectra of MOF-76(Tb), physical mixture of MOF-76(Tb)
with NH -MIL-125(Ti), and MOF76(Tb)@NH -MIL-125. (e) SEM image of the
typical NH -UiO-66(Zr) & MOF-76 on NH -MIL-125(Ti) heterostructured hybrid
crystal. (f) PXRD patterns of NH -UiO-66(Zr)&MOF-76(Tb)@NH -MIL-125(Ti).
capacity. The Cr(VI) could hardly be degraded with single MIL-
101(Cr). After 120 mins of visible light irradiation, 72% of Cr(VI)
2
2
2
was removed from the solution for the MIL-101(Cr)@NH
2
-MIL-
2
2
1
25(Ti), while only 47% of Cr(VI) was removed for single NH -
2
2
2
2
MIL-125(Ti). Considering the fact that the amount of NH -MIL-
2
2
1
25(Ti) in MIL-101(Cr)@NH
2
-MIL-125(Ti) is much smaller than
pure NH
2
-MIL-125(Ti), the heterostructure of MIL-101(Cr)@NH -
2
MIL-125(Ti) is the important influence in the adsorption-
photocatalytic process. Figure S15 exhibits the UV-vis absorption
controlled. As shown in Figure S8, S9 and S10, increasing the
added amounts of PVP and NH -UiO-66(Zr) NPs to the reaction
mixture decelerated the rate of nucleation and consequently
2
spectra and band-gap energy of MIL-101, NH
MIL-101(Cr)@NH -MIL-125(Ti). The introduction of MIL-101(Cr)
crystals without photocatalytic activity did not adversely affect the
photochemical characteristics of the MIL-101(Cr)@NH -MIL-
25(Ti). Meanwhile, the band-gap energy of MIL-101(Cr)@NH
2
-MIL-125(Ti) and
produced larger NH
2
-MIL-125(Ti) crystals and more NH
6(Zr) crystals interspersed. Moreover, not only were NH
6(Zr) on NH
2
-UiO-
-UiO-
2
6
6
2
2
2
-MIL-125(Ti) materials synthesized via the IEGM,
1
2
-
but many other MOF-on-MOF materials were also successfully
fabricated by this method to optimize the design of a novel multi-
2
MIL-125(Ti) was the same as bulk NH -MIL-125(Ti) materials.
This should be attributed to the unique core–satellite
heteroarchitecture, which differs from conventional core-shell
structure where the interior MOFs are mostly sheltered from
external input light. In addition, highly porous MIL-101(Cr) could
act to enrich Cr species and its open mesoporous channels could
not only make the Cr(VI) ions highly accessible to the
compositional
heteroarchitectures were obtained by combining MIL-101(Cr) and
NH -MIL-125(Ti), which was denoted by MIL-101@NH -MIL-125
Figure 3a-b and S11a-b). The prepared MIL-101(Cr)@NH -MIL-
25(Ti) contained the porous frameworks of both MIL-101(Cr) and
-MIL-125(Ti) (Figure S12). Highly porous and fluorescence-
MOFs
system.
Micro/mesoporous
MOF
2
2
(
2
1
NH
2
2
photocatalytic activity sites of NH -MIL-125(Ti), improving the
sensing MOF-on-MOF assemblies were designed by introducing
MOF-76(Tb) into the MOF-on-MOF system (Figure 3c-d and
S11c-d). MOF-76(Tb) is extensively used in fluorescence
detection and sensing because of its outstanding
mass-transfer within the hybrid structure during photocatalytic
process, but also facilitate the release of the photocatalytic
reduction products Cr(III) ions, and finally leading to an enhanced
photocatalytic efficiency (Figure 4b). Therefore, benefiting from
[
14]
photoluminescent performance.
Emmett–Teller Surface Area (SBET) of synthesized MOF-76(Tb)
However, the Brunauer–
the synergies between MIL-101(Cr) and NH
2
-MIL-125(Ti) in this
-MIL-
2
–1
unique core–satellite heteroarchitecture, MIL-101(Cr)@NH
2
was only 59 m g (Figure S13). After combination, the SBET were
2
–1
125(Ti) exhibits high efficiency in the adsorption-photocatalytic
removal of Cr(VI).
7
62 m g , according to the nitrogen sorption isotherm analysis
Figure S13). As shown in Figure 3d, no obvious
photoluminescence signal was detected for the physical mixture
(
In conclusion, a simple and flexible method was developed
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Angewandte Chemie International Edition
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COMMUNICATION
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This work was supported by the Fundamental Research Funds
for the Central Universities, program (2014KJ007) for Young
Excellent Talents in Tongji University, Foundation of State Key
Laboratory of Pollution Control and Resource Reuse (Tongji
University) (PCRRY15007), the National Natural Science
Foundation of China (21501135, 21777119) and Science &
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Technology
Commission
of
Shanghai
Municipality
(
17230711600). This work is also supported by ACCEL project of
JST and JSPS KAKENHI Grant-in-Aid for Specially Promoted
Research (Grant No.25000007). ICeMS is supported by the
World Premier International Research Initiative (WPI) of MEXT.
This work was also supported by Shanghai Tongji Gao Tingyao
[
[
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Environmental
Science
and
Technology
Development
Foundation (STGEF).
Keywords: Metal–organic frameworks • nanostructures •
modular growth • synthesis design• functionalization
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3
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Angewandte Chemie International Edition
10.1002/anie.201709738
COMMUNICATION
COMMUNICATION
‡
‡
A general strategy called internal
extended growth method (IEGM)
was applied to design modular
Yifan Gu, Yi-nan Wu, Liangchun Li,
Wei Chen, Fengting Li* and Susumu
Kitagawa*
hierarchically
composites,
structured
MOF
the
overcoming
limitation of lattice matching. In
addition, the number of MOF crystals
interspersed and the size of the MOF
matrix can be well controlled. IEGM
can optimize the design of novel
multi-compositional MOFs systems
with great flexibility.
Page No. – Page No.
Controllable modular growth of
hierarchical MOF-on-MOF
architectures
This article is protected by copyright. All rights reserved.