Highly Mesoporous Metal-Organic Frameworks as Synergistic Multimodal Catalytic Platforms for Divergent Cascade Reactions

Article abstract of DOI:10.1002/anie.201916578

Rational engineering and assimilation of diverse chemo- and biocatalytic functionalities in a single nanostructure is highly desired for efficient multistep chemical reactions but has so far remained elusive. Here, we design and synthesize multimodal catalytic nanoreactors (MCNRs) based on a mesoporous metal-organic framework (MOF). The MCNRs consist of customizable metal nanocrystals and stably anchored enzymes in the mesopores, as well as coordinatively unsaturated cationic metal MOF nodes, all within a single nanoreactor space. The highly intimate and diverse catalytic mesoporous microenvironments and facile accessibility to the active site in the MCNR enables the cooperative and synergistic participation from different chemo- and biocatalytic components. This was shown by one-pot multistep cascade reactions involving a heterogeneous catalytic nitroaldol reaction followed by a [Pd/lipase]-catalyzed chemoenzymatic dynamic kinetic resolution to yield optically pure (>99 % ee) nitroalcohol derivatives in quantitative yields.

Full text of DOI:10.1002/anie.201916578

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Accepted Article
Title: Highly Mesoporous Metal Organic Frameworks as Synergistic
Multimodal Catalytic Platforms for Divergent Cascade Reactions
Authors: Soumen Dutta, Nitee Kumari, Sateesh Dubbu, Sun Woo
Jang, Amit Kumar, Hiroyoshi Ohtsu, Junghoon Kim, Masaki
Kawano, Seung Hwan Cho, and In Su Lee
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201916578
Angew. Chem. 10.1002/ange.201916578
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COMMUNICATION
Highly Mesoporous Metal Organic Frameworks as Synergistic
Multimodal Catalytic Platforms for Divergent Cascade Reactions
[
a,b]
[a,b]
[a,b]
[a,b]
[a,b]
Soumen Dutta, Nitee Kumari, Sateesh Dubbu, Sun Woo Jang, Amit Kumar, Hiroyoshi
[
c]
[b]
[b]
[c]
*[a,b]
Ohtsu, Junghoon Kim, Seung Hwan Cho, Masaki Kawano, and In Su Lee
Abstract: Rational engineering and assimilation of diverse chemo-
and bio-catalytic functionalities in single nanostructure is highly
desired for efficient multi-step chemical reactions but remain an
elusive task in synthetic nanoscience. Here, we design and
synthesize mesoporous metal organic framework (MOF)-based
multimodal catalytic nanoreactors (MCNRs) consisting of
conditions and poor molecular transport still remain as main
hurdles in their usage in divergent cascade reactions.[4]
Hybrid structures having MOFs as crystalline porous well-
enginearable nano-housing composed of designer inorganic
nodes (ions or clusters) and organic ligands, can accommodate
variety of metal nanocrystals (NCs)[5] or biomolecules[6] at the
interior defective sites and have found many applications in
catalysis, biosensing, therapy, molecular delivery and energy-
conversion. The enormous design adaptability of pore geometries
having unique chemical functionality with high pore volume of
MOFs,[ can simultaneously allow judicious allocation of catalytic
metal NCs and also efficiently intake guest enzyme at the desired
MOF-sites, protecting them from deactivation[ concomitantly
generating the catalytic unsaturated inorganic metal sites.[9]
However, size incompatibility of bulky enzymes and NCs with
much smaller gateway pores of MOF-exteriors results in their
restricted diffusion-mediated assembly through conventional pore
entrapment method,[10] therefore, triggering the need of
customizable different metal nanocrystals in
a spatio-selective
manner, stably anchored enzymes in mesopores and coordinatively
unsaturated metal cationic MOF-nodes, all within the single
nanoreactor space. Such highly intimate and diverse catalytic
mesoporous microenvironment and facile active-site accessibility in
MCNR affected one-pot multi-step cascade reactions involving
heterogeneous catalytic nitro-aldol reaction followed by [Pd/lipase]-
catalyzed chemoenzymatic dynamic kinetic resolution yielding
optically pure (ee > 99%) nitroalcohol derivatives in quantitative yields
by the co-operative and synergistic participation from different chemo-
bio-catalytic components.
7]
8]
synthesizing hierarchically meso- and micro-porous MOFs as
host matrix,[11] which may overcome low enzyme loading
efficiency and slow flux rate of reactants, where enzyme ingress
into the large pores easily accessible to the substrates, while its
The high efficiency of biochemical reactions leading to the
synthesis and assembly of biomolecules, is attributed to the
nature’s extensive use of cascade chemistry.[1] In chemical and
pharmaceutical manufacturing, the bio-inspired multi-module
cascade catalysis which combine the reactivity, selectivity and
robustness of natural enzymes together with synthetic catalysts
are highly desired which can circumvent tedious workups, the
intermediate-decomposition and the time and cost; however, the
reaction parameters of different catalysts usually deactivate either
of the catalysts during the cascade process.[ The rational
integration of different catalysis modules into single hybrid
nanoarchitecture without compromising their reactivity and
stability are challenging due to the difference in their structure,
size, composition, surface chemistry, and active-site reactivity. So
far, several strategies have emerged to integrate natural enzymes
with synthetic catalysts using supports such as mesoporous
silica,[ metal-organic frameworks (MOFs),[3b] reduced graphene
small
pores
offer
the
selective
pathway
for
intermediates/reactants/ products. Here, we introduce design
synthesis and application of multimodal catalytic nanoreactors
(MCNRs) for realizing divergent cascade reactions involving
heterogeneous and biocatalytic steps, by ingeniously assimilating
three catalytic counterparts: metal NCs, enzyme-biocatalysts and
intra-MOF coordinatively unsaturated metal cationic nodes as
heterogenized homogeneous catalysts within in situ generated
metal organic-mesopores (Scheme 1). As the key step for the
synthesis of MCNRs, we exploited polyvinylpyrrolidone (PVP), an
amphiphilic non-ionic polymer, for the generation of mesopores
2]
(>20 nm) during the crystallization of cobalt-based zeolitic
imidazolate frameworks (ZIF67) via a transient competitive
coordination chemistry and massive evolution of unsaturated
metal sites.
3a]
[
3c]
[3d]
oxide,
and polymeric matrices,
where the compatibility
between carriers and enzymes, insufficient exposure of active
sites, low reactivity of heterogeneous phase under ambient
In a typical procedure to synthesize defect-rich metal nodes
in porous ZIF67 (DP-ZIF67), PVP was added as metal-
coordinating bulky polymer during the formation of ZIF67-
domains to induce partial disruption of imidazole-Co(II) catenation
process and generate high mesoporosity in the resulting DP-
ZIF67 crystals. The transmission electron microscopy (TEM)
images of DP-ZIF67 showed typical rhombic dodecahedron
morphology similar to pristine ZIF67 with ca. 800 nm size, having
contrast gradient throughout all the crystals, signifying the
presence of large pores (20-40 nm) (Figure 1a, S1a, S4). Further,
the field emission scanning electron microscope (FE-SEM)
images of the DP-ZIF67 revealed the roughened surface of the
crystals and presence of open pores, which was also
authenticated from high-angle annular dark-field scanning TEM
[a]
Dr. S. Dutta, Dr. N. Kumari, Dr. S. Dubbu, S. W. Jang, Dr. A. Kumar,
Prof. I. S. Lee
Center for Nanospace-confined Chemical Reactions (NCCR),
Pohang University of Science and Technology (POSTECH), Pohang
37673, South Korea
E-mail: insulee97@postech.ac.kr (I. S. L.)
[
b]
c]
Dr. S. Dutta, Dr. N. Kumari, Dr. S. Dubbu, S. W. Jang, Dr. A. Kumar,
J. Kim, Prof. S. H. Cho, Prof. I. S Lee
Department of Chemistry, Pohang University of Science and
Technology (POSTECH), Pohang 37673, South Korea
[
Dr. H. Ohtsu, Prof. M. Kawano
Department of Chemistry, School of Science, Tokyo Institute of
Technology, Tokyo 152-8550, Japan
(HAADF-STEM) images (Figure 2b-c, S1b). Additionally, the
Supporting information for this article is given via a link at the end of
the document.
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Scheme 1. Synthetic strategy towards multimodal catalytic nanoreactors (MCNRs) containing coordinately unsaturated Co2+ (violet colored metal sites), Pd NCs
and CalA inside DP-ZIF67.
focused ion beam-slicing followed by TEM (FIB-TEM) revealed
numerous hexagonal nanoplates (~600−800 nm) containing
randomly distributed mesopores (average size = 30±9 nm),
endorsing the consistent mesoporous channels reaching even to
the core-region of the DP-ZIF67 (Figure 1d). In X-ray diffraction
mesoporosity (Figure S5), evidently suggesting possible
coordination modulation of Co(II) sites by bulky sized
metallophillic PVP polymers which is critical for the generation of
large sized mesopores in DP-ZIF67.[
11b]
Notably, for generating
the desired mesoporosity, optimum amount of PVP with respect
to Co(II) was required (350 mg of PVP for 0.5 mmol of Co2+ ions)
as lower amount of PVP could not generate any mesopores and
larger amounts of PVP slowed down the formation of MOF (Figure
S7).
Further, to identify any PVP-induced chemical change in the
coordination environment of metal sites, X-ray photoelectron
spectrum (XPS) for Co 2p and N 1s of ZIF67 and DP-ZIF67 were
analyzed (Figure S8). In comparison to the pristine ZIF67,
significant broadening of XPS peaks for both Co and N was
observed for DP-ZIF67 confirming the changed coordination
behaviors of Co (Figure S8c, d) — the typical peaks at 781.1 and
797.0 eV in the Co 2p spectra are attributed to Co 2p3/2 and Co
2p1/2, respectively, corresponding to the fully tetra-coordinated
(
XRD) analysis the characteristic peaks of DP-ZIF67 confirmed
the original framework structure of ZIF67 having high crystallinity
Inset; Figure 1e). In Brunauer–Emmett–Teller (BET)
measurements, the vertical N -sorption isotherm at relatively low
P/P for DP-ZIF67 and ZIF67 (Figure S3) exhibited the intrinsic
microporous structures for both the materials, however, H
hysteresis loop in P/P = 0.4–0.8 range implied the additional
(
2
0
4
0
presence of mesopores for only DP-ZIF67, also the BET surface
2
area of DP-ZIF67 and ZIF67 were found to be 1654 and 1672 m
-
1
g , respectively; in addition, the Barrett–Joyner–Halenda (BJH)
size distribution plot also verified the presence of mesopores
having diameters centered at 22 and 40 nm (Figure 1e) in DP-
ZIF67. When the synthesis of DP-ZIF67 was attempted without
using any PVP, it could only generate the solid ZIF67 with no
4
Co(II)-N system (Figure 1f); the other pair of peaks at 779.9 and
Figure 1. (a) TEM and (b) FESEM images of DP-ZIF67. Red arrows in panel b indicate the open pore structure in DP-ZIF67. Inset in panel (a) and (b) show low
magnification TEM and FESEM images of DP-ZIF67 (i) and ZIF67 (ii). (c) HAADF-STEM image of DP-ZIF67 (inset: low magnification image), (d) TEM image of DP-
ZIF67 after the treatment of focused ion beam (FIB) to visualize the cross section. Red arrows point out to the pores in dissected DP-ZIF67 (inset: low magnification
FIB-TEM image). (e) Pore size distribution plot and XRD pattern (inset) for ZIF67 and DP-ZIF67. Deconvoluted XPS spectra of ZIF67 and DP-ZIF67 for (f) Co 2p
(
g) N 1s, (h) FTIR spectra for different samples.
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7
N
95.5 eV are attributed to the unsaturated cobalt species in Co–
analyses of the Pd@DP-ZIF67/CalA illustrated the well-
maintained crystalline structure and morphology of the MOF, with
evenly dispersed Pd NCs and enzymes, as also confirmed from
HAADF-STEM and EDS-mapping analysis (Figure 2d, S19).
Notably, the incorporation of Pd NCs into the pores of MOFs
reduces the available pore size of DP-ZIF67 as verified from the
BJH plot of Pd@DP-ZIF67, which has been reflected in lowered
CalA loading capacity compared to DP-ZIF67, but still possesses
large-sized pores (5-17 nm) for high quantity of enzyme
encapsulation (Figure 2e). Furthermore, after enzyme
encapsulation, BJH analysis of Pd@DP-ZIF67/CalA showed
absence of large mesopores, which inferred enzymes, occupied
the mesopores of DP-ZIF67 while retaining unsaturated Co
centers as confirmed from XPS (Figure 3e, S19, S20).
[
12]
x
(x<4) geometry,
and the unsaturated Co sites present in
ZIF67 (7.8%) are significantly increased to 18.3% in case of DP-
ZIF67. Moreover, the variation in deconvoluted N 1s XPS spectra
is prominent for instance, the quantity of N-Co is considerably
decreased from 80% in ZIF67 to 68% in DP-ZIF67 (Figure 1g),
and thus corroborates the existence of large number of ligand-
free unsaturated Co sites in DP-ZIF67. The thermogravimmetric
analyses (TGA) patterns of ZIF67 and DP- ZIF67 were found to
be identical showing ~42 and 40% weight loss, respectively, after
heating at 800°C under N
showed identical Fourier transform infrared (FTIR) spectra
Figure S9), where the characteristic – C=O stretching vibration
2
gas environment; also both materials
(
-
1
corresponding to PVP at1666 cm was absent, however the
presence of peak at 1654 cm (shifted to lower wave number from
1
-
1
-1
666 cm ) in the unwashed-DP-ZIF67 (TEM image, Figure S10),
could be ascribed to the feasible intermediates formation through
coordination of Co(II) ions and carbonyl oxygen of PVP during the
growth of DP-ZIF67 crystal (Figure 1h), thereafter following the
purification step, PVP unbinds and vanishes from the mesopores
(Scheme S1). To demonstrate the generality of our approach,
different type of mesoporous ZIF8 (Zn-imidazole MOF), with
large-sized pores was also synthesized (Figure S12c).
Next, with the intention of integrating catalytic functionality
in the pores of MOFs, the pre-synthesized PVP-capped Pd NCs
(2.6 ± 0.3 nm) were added to the precursor mixture while
crystalizing the MOF, resulting the formation of Pd NCs stably and
homogeneously encapsulated inside mesopores of DP-ZIF67
(Pd@DP-ZIF67) (Figure 2a, S13, S14). The crystal structure of
the hybrid material exhibited identical XRD diffraction patterns as
that of DP-ZIF67, suggesting unaffected structural and
composition of MOF after Pd NCs-functionalization (Figure S15a).
Further, the HAADF-STEM image and EDS-elemental mapping
confirmed the presence of Pd NCs with homogeneous distribution
throughout the DP-ZIF67 (Figure 2b). XPS analyses revealed
high degree of unsaturation in Co sites (Co-N
x
= 17.3%, N-Co =
71%) in Pd@DP-ZIF67 similar to the parent DP-ZIF67 (Figure
S15b, c), with the presence of dominating Pd(0) species. Similarly,
we also synthesized Pt@DP-ZIF67 by introducing PVP capped Pt
NCs (Figure S17); and by sequentially adding different metal NCs,
hierarchically segregated core@shell-type distribution of different
metal NCs was also realized within DP-ZIF67 crystal (namely,
PtCore/PdShell@DP-ZIF67 (Figure 2c). Further, with the intention of
advancing Pd@DP-ZIF67 for targeted chemo-biocatalytic
cascade reactions, additional inclusion of large-sized biocatalysts
was attempted, where the large mesoporous channels (20-40 nm)
with open apertures within MOF-architecture can encapsulate
and stabilize the enzymes and then interconnected MOF-
microchannels can effectively permit the reactant/product
transport. For this, Pd@DP-ZIF67 was incubated with Candida
antractica lipase A (CalA; ca. 6.3 × 5.6 × 4.2 nm in size), where
the amount of final loaded enzyme was 26.5% as measured by
Bradford assay (inset; Figure 2e, S18), and the FTIR spectrum of
Pd@DP-ZIF67/CalA exhibited C=O stretching vibration for
Figure 2. (a) TEM image and HRTEM image (inset), (b) HAADF-STEM and
EDS mapping of Pd (inset) of Pd@DP-ZIF67. HAADF-STEM and EDS mapping
(
inset) of (c) PtCore/PdShell@DP-ZIF67 and (d) Pd@DP-ZIF67/CalA. (e) Pore
size distribution plot of Pd@DP-ZIF67 and Pd@DP-ZIF67/CalA: inset shows
enzyme encapsulation kinetics for various substrates such as Pd@DP-ZIF67 (i),
and DP-ZIF67 (ii). (f) FTIR spectra for Pd@DP-ZIF67 (i), CalA (ii), and Pd@DP-
ZIF67/CalA (iii).
We envisioned Pd@DP-ZIF67/CalA to be multimodal
catalytic platform for carrying out such cascade reactions, where
unsaturated metallic nodes of MOF acting as Lewis acidic
catalytic sites for nitroaldol reaction, Pd-NCs as racemization
catalyst and CalA for enzymetic kinetic resolution coexist within a
-
1
amide-I of the enzyme at 1660 cm , along with other
characteristic peaks for ZIF67 (Figure 2f). The enzyme content in
Pd@DP-ZIF67/CalA was also verified by inductively coupled
plasma optical emission spectrometry (ICP-OES) measurement
of S (cysteine residues in CalA) (Table S1). TEM and XRD
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Figure 3. (a) Schematic illustration of the cascade reaction catalyzed by Pd@DP-ZIF67/CalA, (b) Kinetics of nitrol-aldol reaction catalyzed by DP-ZIF67 and
various control catalysts. (c) The Pd@DP-ZIF67/CalA and various control catalysts catalyzed cascade catalysis to obtain enantiomerically pure β-nitroacetate,
in high yield showing the co-immobilization of the catalysts has immense effect on the product enantiomeric excess (ee) and yield of the product. (d) Reaction
yield, ee values and time of five cycles using Pd@DP-ZIF67/CalA as the catalyst for the conversion of p-anisaldehyde to β-nitroacetate product. (e) Substrate
scopes of cascade nitro aldol followed by dynamic kinetic resolution of various aldehydes.
single nanoreactor space, which can carry out all chemo-
enzymatic steps efficiently and synergistically. To evaluate the
catalytic performance of Pd@DP-ZIF67/CalA, the nitroaldol
reaction (Henry reaction) catalyzed by unsaturated cobalt(II)
sites[13] of ZIF67 followed by the Pd NCs-catalyzed racemization
of resulting secondary nitro alcohol which was coupled with lipase
catalyzed acylation of alcohol in one-pot cascade manner, was
chosen.[14] After optimizing the reaction conditions (Table S2), we
conducted the cascade reaction in THF:toluene (4:1) solvent at r.t.
with p-anisaldehyde and nitromethane using 0.1 mol% N,N-
diisopropylethylamine and vinylacetate as the acyl donor in the
presence of the Pd@DP-ZIF67/CalA (Figure 3), to obtain desired
enantiopure chiral acetylated nitroalcohol, with >97% conversion
yield (Figure S22) and an >99% enantiomeric excess (>99% ee),
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with a substrate concentration of 1 mM (Figure S23). To verify the
high activity of defect rich site of Co(II) in DP-ZIF67 for nitroaldol
(entry 1-4) (Figure S34-39) without showing any significant
electronic effect of substituents; whereas, in the case of
crotonaldehyde, the expected nitroacetate product could not be
isolated, due to the in situ conversion to a different product as
characterized from NMR spectroscopy (entry 5) (Figure S40-41).
In conclusion, we devised a synthetic strategy to construct
ultra-large mesopores (20-40 nm) in MOF-crystals with the aid of
competitive coordination chemistry by metallophilic polymer
(PVP) and ingeniously integrated different catalytic modalities:
coordinatively unsaturated metal cations as Lewis acids-,
heterogeneous metal NCs- and enzyme-based catalysis within a
single mesoporous MOF-nanohousing. Such proximal
engineering of different catalytic functionalities in single MOF-
nanoplatform can synergistically perform multistep divergent
cascade reactions under ambient conditions — nucleophilic
addition, chiral center generation, racemization and kinetic
resolution, affording final product in excellent yields and
enantiomeric excess. Present work would lead to the revenues in
overcoming drawbacks and blurring the divisions and limitations
of conventional homogeneous, heterogeneous and biocatalytic
platforms.
3 2 2
reaction, control experiments, with Co(NO ) ·6H O, mixture of
Co(NO ·6H O and imidazole, and solid ZIF67 displayed very
)
3 2
2
poor catalytic reactivities compared to the DP-ZIF67 (Figure 3b).
Interestingly, DP-ZIF67 pre-treated with excess ligand (2-
methylimidazole, 2-MeIm) afforded poor yield of the nitroaldol
product due to the saturation of catalytic Co(II) sites by 2-MeIm,
suggesting the crucial role of uncoordinated Co(II) sites present
in the mesoporous morphology (Figure 3b, S24). Further to prove
the efficacy of our integrated multimodal catalytic platform, the
physical mixture of DP-ZIF67, PdNCs and CalA afforded only ca.
20% ee; similarly, the physical mixture of Pd@DP-ZIF67 and
CalA@DP-ZIF67 also provided very poor ee (ca. 38%) of the
nitroacetate product. In another control experiment, physical
mixture of Pd@DP-ZIF67 and free CalA for cascade catalysis
resulted only ca. 24% ee of the product, inferring that
immobilization of CalA in MOF mesopores could not only increase
the stability and active sites exposure of enzyme in spite of being
in non-polar organic solvent, but also locally provide enhanced
substrate concentration for kinetic resolution step. In all these
control experiments, the lower yields (35-63%) (Figure S25-26) of
nitroacetates also corroborated the advantage of integrated
design resulting in to the high reactivity of Pd@DP-ZIF67/CalA.
Above control experiments (Figure 3c) where isolating PdNCs or
CalA from MOF and adding them as a physical mixture, afforded
much inferior yields and enantioselectivities due to the possible
side-reactions and deactivation of isolated enzymes and PdNCs.
These observations can rationalize the importance of ingeniously
integrated design of the catalyst where three chemo- & bio-
catalytic modules function in a synergistic fashion much superior
to the isolated catalytic entities added as the physical mixtures:
implementing to a nitroaldol-DKR-esterification cascade reaction,
mesoporous MOF nano-housing having massively uncoordinated
Acknowledgements
This work was supported by the Basic Science Research Program
through the National Research Foundation of Korea (NRF)
funded by the Ministry of Science, ICT & Future Planning (MSIP)
(
Grant NRF-2016R1A3B1907559) (I.S.L.). We would like to thank
Dr. Jin Young Koo and Prof. Hee Cheul Choi for helpful discussion.
Keywords: nanocatalyst • mesoporous MOF • cascade reaction
•
multimodal catalyst • chemo-bio-catalyst
metal
nodes, activates
aldehyde-substrate
generating
[
[
1]
2]
R. Ye, J. Zhao, B. B. Wickemeyer, F. D. Toste, G. A. Somorjai, Nat. Catal.
nitroalcohols concentrated locally within the vicinity of well-
protected PdNCs and enzymes for successive highly efficient
reversible-DKR and esterification reaction due to the confined
nanoscale proximities of the three catalytic entities.[3a,15]
Additionally, the Pd@DP-ZIF67/CalA were easily recovered by
centrifugation after the reaction (Figure 3d) and exhibited
moderately affected (>89%) residual activity, affording 86% yield
and >80% ee of product after five successive recycling-steps.
Although, the reaction time was found to be consistent up to 2nd
cycle, while in the next cycles, slight longer reaction times (3rd
cycle: 24 h, 4th cycle 28 h, 5th cycle: 35 h) were noticed. Further
the TEM, HRTEM, HAADF-STEM, EDS mapping analyses after
each catalytic cycle revealed no significant change in the
morphology of the ZIF67, PdNCs and CalA loading and their
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th
aggregation up to 5 cycle (Figure S27-S31), however ICP
analyses revealed the loss of some Pd and S contents after 4th
and 5th cycles (Figure S32). After 5th catalytic cycle the
reappearance of mesopores in BJH analyses also suggested the
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in Figure S33. Further, the scope of Pd@DP-ZIF67/CalA was
extended to the differently substituted aryl and aliphatic
aldehydes. As shown in Figure 3e, the Pd@DP-ZIF67/CalA
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[6]
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Angewandte Chemie International Edition
10.1002/anie.201916578
COMMUNICATION
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COMMUNICATION
A multimodal catalytic nanoreactor
consisting of metal nanocrystals,
stably anchored enzymes and
coordinatively unsaturated metal
nodes inside the mesopores of metal
organic framework is established to
accomplish one-pot multi-step
cascade reactions.
Soumen Dutta, Nitee Kumari, Sateesh
Dubbu, Sun Woo Jang, Amit Kumar,
Hiroyoshi Ohtsu, Junghoon Kim,
Seung Hwan Cho, Masaki Kawano,
and In Su Lee*
Page No. – Page No.
Highly Mesoporous Metal Organic
Frameworks as Synergistic
Multimodal Catalytic Platforms for
Divergent Cascade Reactions
This article is protected by copyright. All rights reserved.