Amino-Induced 2D Cu-Based Metal–Organic Framework as an Efficient Heterogeneous Catalyst for Aerobic Oxidation of Olefins

Article abstract of DOI:10.1002/chem.201905249

With the assistance of hydrogen bonds of the o-amino group, we have successfully tuned a coordination structure from a metal–organic polyhedron (MOP) to a two-dimensional (2D) metal–organic framework (MOF). The amino group forms hydrogen bonds with the two vicinal carboxylic groups, and induces the ligand to coordinate with copper ions to form the 2D structure. The obtained 2D Cu-based MOF (Cu-AIA) has been applied as an efficient heterogeneous catalyst in the aerobic epoxidation of olefins by using air as oxygen source. Without the aggregation problem of active sites in MOPs, Cu-AIA possesses much higher reactivity than MOP-1. Furthermore, the amino group of the framework has been used as a modifiable site through post-synthetic metalation (PSMet) to prepare a 2D MOF-supported Pd single-site heterogeneous catalyst, which shows excellent catalytic performance for the Suzuki reaction. It indicates that Cu-AIA can also work as a good 2D MOF carrier for the derivation of other heterogeneous catalysts.

Full text of DOI:10.1002/chem.201905249

A Journal of
Accepted Article
Title: Amino-Induced 2D Cu-Based Metal–Organic Framework as an
Efficient Heterogeneous Catalyst for Aerobic Oxidation of Olefins
Authors: Jia Tang, Mengke Cai, Guanqun Xie, Shixiong Bao, Shujiang
Ding, Xiaoxia Wang, Jinzhang Tao, and Guangqin Li
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To be cited as: Chem. Eur. J. 10.1002/chem.201905249
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10.1002/chem.201905249
Chemistry - A European Journal
RESEARCH ARTICLE
Amino-Induced 2D Cu-Based Metal–Organic Framework as an
Efficient Heterogeneous Catalyst for Aerobic Oxidation of Olefins
Jia Tang,[abc] Mengke Cai,[c] Guanqun Xie,[a] Shixiong Bao,[c] Shujiang Ding,[b] Xiaoxia Wang,*[a]
Jinzhang Tao,[d] and Guangqin Li*[a]
Dedication
Abstract: With the assistance of hydrogen bonds of the o-amino
group, we have successfully tuned the coordination structure from
metal–organic polyhedron (MOP) to two-dimensional (2D) metal–
organic framework (MOF). The amino group forms hydrogen bonds
with the two vicinal carboxylic groups, and induces the ligand to
coordinate with copper ion to form 2D structure. The obtained 2D
Cu-based MOF (Cu-AIA) has been applied as an efficient
heterogeneous catalyst in the aerobic epoxidation of olefins using air
as the oxygen source. Without the aggregation problem of active
sites in MOPs, Cu-AIA possesses much higher reactivity than MOP-
1. Furthermore, the amino group of the framwork has been used as
a modifiable site via post-synthetic metallation (PSMet) to prepare
2D MOF supported Pd single-site heterogeneous catalyst, which
shows excellent catalytic performance for Suzuki reaction. It
indicates that Cu-AIA can also work as a good 2D MOF carrier for
the derivation of other heterogeneous catalysts.
molecules and the inaccessibility of active sites.[15] So far a few
strategies have been applied to solve the above problem.[16-20]
One strategy is to introduce MOPs into nanoporous silica and
confine MOPs in its channels or cavities,[21,22] and the other is to
use MOPs as porous monomers to further convert into
metal−organic
framewoks
(MOFs)
or
supramolecular
polymers.[23-26] Although significant progresses that have been
made, the exploration of new strategies is still a hot research
topic. Recently, two-dimensional (2D) MOFs have attracted
much attention.[27-29] Compared with three-dimensional (3D)
MOFs, active sites that exposed on the surfaces of 2D MOFs
are much easier to approach, which favors the interaction
between substrate molecules and active sites, and facilitates the
mass-transfer of solvent, substrates and products.[30,31] Due to
the interconnected channels and cavities of MOFs,[32-35] active
sites can be accessible after activation, thus it may be a good
strategy to achieve 2D MOF instead of MOP structure by
regulating the inherent binding of ligands with metal ions via the
introduction of specific functional groups. As far as we know,
such a strategy has not yet been reported.
Introduction
The epoxidation of olefins is one of the most important
oxidative reactions due to the wide range of applications of the
resulting epoxides both in industry and academia.[36,37] So far, a
variety of new catalysts have been developed in the past
decades to achieve the efficient transformation from alkenes into
expoxides including both homogeneous catalysts (Ruthenium
porphyrin,[38,39] Manganese complexes,[40,41] Iron complexes,[42-44]
etc[45-48]) and heterogeneous catalysts (silica-supported titanium
catalysts,[49] Mn(III)-polymer catalyst,[50] MOFs,[51-53] etc[54-57]). A
number of oxidants such as alkyl hydroperoxides, H2O2, O2 and
air have been utilized for the epoxidation. With respect to the
environmental and economic consideration, the inexpensive and
eco-friendly O2 and air as the oxidants are no doubt the most
attractive.[58,59] Despite the progress that have been achieved,
development of novel green and efficient catalytic systems for
air-mediated epoxidation is still desirable.
Metal−organic polyhedra (MOPs) as crystalline coordination
materials are constituted by metal ions and organic ligands.[1-3]
Owing to their unique features such as permanent porosity and
unsaturated metal centers, MOPs have showed great potential
for applications in drug delivery,[4] gas adsorption and storage,[5]
chemical sensors[6] and catalysis.[7-10] As a common ligand
isophthalic acid and its corresponding derivatized ligands have
been widely used to prepare MOP materials.[11-13] For example,
Zhou et al prepared the stimuli-responsive MOP via the
coordination
of
the
ligand
5-((2,4-
dimethylphenyl)diazenyl)isophthalic acid with copper ion, and
used in the capture and release of guest molecules.[14] However,
the disadvantages of poor stability and easy aggregation limit
the application of MOPs, especially the removal of the guest
molecules would inevitably result in the aggregation of MOP
In this paper, by inserting an amino group at both of the ortho
position of the two carboxylic groups of isophthalic acid, we have
successfully regulated the coordination of the ligand with copper
ion and constructed a 2D MOF structure rather than MOP
structure under the same synthetic condition. The amino group
forms hydrogen bonds with the two vicinal carboxylic groups,
which induces the ligand to coordinate with copper ion to form
2D structure (Figure 1a). The obtained new Cu-based 2D MOF
(Cu-AIA) as an efficient heterogeneous catalyst has been
applied in catalyzing the aerobic epoxidation of olefins using air
as the oxygen source. Moreover, by the post-synthetic
metallation method (PSMet) Cu-AIA can also be used as a
carrier to support metal active site using the amino group as a
modifiable site. The good catalytic activity of the obtained Cu-
AIA-PC-Pd catalyst for Suzuki–Miyaura coupling confirms the
[a]
Dr. J. Tang, Dr. G. Xie, Prof. X. Wang
School of Environment and Civil Engineering, Dongguan University
of Technology, Dongguan 523808, P. R. China
E-mail: wangxx@dgut.edu.cn
Dr. J. Tang, Prof. S. Ding
Department of Applied Chemistry, School of Science, Xi’an Jiaotong
University, Xi’an 710049, P. R. China
Dr. J. Tang, M. Cai, Dr. S. Bao, Prof. G. Li
MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn
Institute of Functional Materials, School of Chemistry, Sun Yat-Sen
University, Guangzhou 510275, P. R. China
E-mail: liguangqin@mail.sysu.edu.cn
[b]
[c]
[d]
Dr. J. Tao
Guangdong Research Institute of Rare Metals, Guangzhou 510651,
P. R. China
Supporting information for this article is given via a link at the end of
the document.
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10.1002/chem.201905249
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RESEARCH ARTICLE
feasibility of Cu-AIA as a good 2D MOF carrier for supported
heterogeneous catalysts.
Results and Discussion
Structure characterization.
Figure 1. (a) Schematic illustration for the preparation of MOP-1 and Cu-AIA. (b) The photograph of the Cu-AIA crystal sample. (c) X-Ray crystal structure of Cu-
AIA (view down from a-axis). (d) Side view of the 2D sheets. (e) The simulated and measured XRPD patterns of Cu-AIA.
Cu-AIA was prepared by the solvothermal reaction of the AIA
ligand and Cu(NO3)2∙3H2O. The reaction was run in a mixed
solvent of DMF and ethanol at 80 oC for 24 h to give deep green
rectangular block-shaped crystals (Figure 1b). Single crystal X-
ray diffraction shows that Cu-AIA is formulated as
Cu2(AIA)2·2(H2O), and it crystallizes in the orthorhombic space
group Pnma (Figure 1c, d) (see CIF, CCDC 1874182). The
carboxylates of the AIA ligand bridge two copper (II) ions
forming a paddle-wheel type dinuclear secondary building unit
(SBU) Cu2(CO2)4 (Figure 1c). The amino group in the ortho
position forms hydrogen bonds with the carboxylic groups
(Figure 1a), which interestingly induces the ligand and copper
ion to coordinate into a 2D MOF rather than MOP-1 structure
(Figure S1, S2). Each copper (II) ion also coordinates with one
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H2O molecule in the first coordination sphere. The two-
dimensional (2D) layers that bridged SBU through the AIA ligand
are extended by hydrogen bonds to build a 3D supramolecular
architecture due to the coordinated H2O molecule. The Cu⋯Cu
distance is 2.6101(1) Å in Cu2 dinuclear units, and the Cu⋯O
distances are 1.9708(1) and 2.1255(1) Å in the SBU, where the
oxygen atoms are derived from the organic ligand and H2O
molecules, respectively. The MOF is stable in air and insoluble
in common solvents. The experimental and simulated XRD
patterns show the bulk crystals have the same structure as the
individual single crystal (Figure 1e). After being dried, the bulk
crystal sample displays different XRD results from the original
Cu-AIA sample, which indicates the change of the crystalline
form and could be caused by the removal of the solvent (TGA
anaylsis shows the removal of the solvents at 50~200 oC (Figure
and 3350 cm-1 are related to the N–H absorption (the
asymmetric and symmetric), the peaks at 1631 and 1391 cm-1
are ascribed to the anti-symmetric and symmetric vibrations of
the carboxyl groups (C–O), and the C–N vibration appears
around 1258 cm-1.
PSMet as one of the most important strategies among the
post synthetic modifications (PSM) has been well developed to
enhance the application of MOFs in wider fields, including gas
storage, sensing and catalysis.[60,61] Especially PSMet provides
an expansive scope for heterogeneous catalysis.[62] So far, the
PSMet strategy mainly focuses on the performance regulation of
3D MOFs.[63] The PSMet of 2D MOFs has only been reported in
rare cases since the organic frameworks of the reported 2D
MOFs usually have no extra functional groups that can be
modified,[64,65] thus making it less feasible to anchor metal
catalyst by PSMet. Here, we report the preparation of 2D MOF
supported Pd single-site heterogeneous catalyst (Cu-AIA-PC-Pd)
by employing Cu-AIA as a 2D MOF support.
o
o
S3)). However, the peaks of the dried sample at 9.2 , 13 and
18.2 o retain, which indicates the 2D structure of Cu-AIA remains
intact. In FT-IR spectra (Figure S4), two sharp bands at 3450
Figure 2. (a) Schematic illustration for the preparation of Cu-AIA-PC-Pd catalyst. (b) SEM images of Cu-AIA-PC nanosheets (inset: (right) photograph of the
Tyndall effect of Cu-AIA-PC nanosheets suspension in acetone and (left) AFM image of Cu-AIA-PC nanosheets). (c) Out-of-plane and (d) in-plane XRD patterns
of Cu-AIA-PC nanosheets.
The 2D Cu-AIA crystals prepared as above is reacted with 2-
pyridinecarboxaldehyde to form the desired framework (Cu-AIA-
PC) (Figure 2a) via the condensation between the amino group
in the former and the carbonyl group in the latter. Scanning
electron microscopy (SEM) images show the synthesized Cu-
AIA-PC takes on the sheet-like structure with a size of a few
micrometers (Figure 2b). Cu-AIA-PC nanosheets display a
thickness of about 76 nm as determined by atomic force
microscopy (AFM) (inset in Figure 2b). The suspension of Cu-
AIA-PC nanosheets in acetone possesses the Tyndall effect
when a red laser passes it through (inset in Figure 2b). In order
to further examine the crystalline structure of Cu-AIA-PC
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nanosheets, out-of-plane and in-plane X-ray diffractions were
carried out (Figure 2c, d). As shown in Figure 2c, only (001)
diffraction signal is observed for the out-of-plane direction,
suggesting the (001) face of Cu-AIA-PC is parallel to the
substrate. Furthermore, the (010) diffraction signal collected
from the in-plane direction suggests an obvious angular
dependence (Figure 2d). Therefore, the structural information
indicates the (001) orientation of Cu-AIA-PC nanosheets.
Figure 3. (a-f) XPS patterns of Cu-AIA-PC-Pd. (g) XRPD patterns of Cu-AIA, Cu-AIA-PC and Cu-AIA-PC-Pd. (h-l) EDS mapping of Cu-AIA-PC-Pd.
With the pyridyl-containing chelating group, the Cu-AIA-PC is
coordinated with Pd(II) to afford Cu-AIA-PC-Pd via PSMet
method (Figure 2a). XPS was performed to investigate the
chemical state of each element in Cu-AIA-PC-Pd and the
obtained results were shown in Figure 3. The XPS spectrum
shows the presence of C, O, N, Cu and Pd in the sample (Figure
3a). The C 1s spectrogram suggests the presence of C–C (285
eV) and C–O (288 eV) (Figure 3b). The two peaks at 533 and
531 eV in the O 1s spectrogram are assigned to C–O–Cu and
C=O, respectively (Figure 3c), and the two peaks at 400 and 395
eV in the deconvolution of the N 1s spectrum can be ascribed to
the C–NH2 and C=N, respectively (Figure 3d).[66] The Cu 2p
binding energy at 935 eV is corresponding to Cu2+ 2p1/2 and the
broad peaks are the satellites (Figure 3e). The Pd 3d binding
energies at 343 and 338 eV are attributed to Pd2+ 3d3/2 and Pd2+
3d5/2, respectively (Figure 3f). The powder XRD patterns of Cu-
AIA-PC and Cu-AIA-PC-Pd show the same reflection as that of
Cu-AIA, indicating the modification of pyridine-2-aldehyde and
the Pd(II) loading on 2D MOF do not change the 2D MOF crystal
structure (Figure 3g). The EDX mapping images of Cu-AIA-PC-
Pd show the elements of C, O, Cu and Pd are homogeneously
dispersed throughout the MOF nanosheets (Figure 3h-l). The
quantitative measurement with ICP-MS shows that Cu-AIA-PC-
Pd contains 8.3 wt% Pd, which is very close to the EDX result
(8.8 wt%) (Figure S5, Table S1 and S2).
Catalytic performance and reaction mechanism analysis
2D Cu-AIA is directly applied in the epoxidation of olefins using
air as the oxygen source. Firstly, the conditions for the catalytic
epoxidation were optimized using cyclooctene as a model
substrate. As shown in Figure S6, various solvents are screened
to obtain the most suitable solvent for the epoxidation. When
DMF, toluene, ethanol and CH2Cl2 are examined respectively as
the solvent, almost no epoxidation could be observed. In
contrast, 1,4-dioxane and ethyl acetate could afford the epoxide
1 in 25% and 17% yield, respectively. For the solvents of CH3CN,
dioxane, ethyl acetate, CH2Cl2 and toluene, it seems the greater
the polarity, the better the catalytic efficiency. For DMF and
ethanol, they are inclined to coordinate with copper ions, the
active sites for the epoxidation, and reduced the catalytic
efficiency. Acetonitrile is the most appropriate solvent, giving 1 in
32% yield. Control experiment shows that aldehyde as an
essential additive has a significant impact on reaction efficiency,
and no reaction occurs without its presence (Figure S7),
consisting with the report that aldehyde as a sacrificial co-
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reductant plays an important role in the epoxidation reaction.[67]
Aromatic aldehydes both with electron-withdrawing groups (–
NO2, –Br) and with electron-donating groups (–H and –CH3)
show a low epoxidation reactivity. Aliphatic aldehydes and cyclic
aldehydes (cyclo-hexanecarboxaldehyde) could significantly
accelerate the reaction, which suggests the structures of
aldehydes are critical to the catalytic efficiency, and the use of
isobutyraldehyde gives the best yield.
significantly improved by increasing the temperature (Figure S8).
High yield of the epoxidation product can be obtained when the
reaction is conducted in acetonitrile at 80 oC for 24 h in the
presence of Cu-AIA catalyst.
Figure 5. (a) Reusability of Cu-AIA catalyst for the aerobic epoxidation of
cyclooctene (bar: conversion, ball: selectivity) Reaction conditions: 1 mmol of
cyclooctene, 3 mmol of isobutyraldehyde and 5 mL of CH3CN were mixed with
10 mol% catalyst in a 25 mL three-necked round-bottomed flask along with a
condensation tube, and the mixture was stirred with air bubbling from the
bottom of the flask at 80 oC for 24 h. After each reaction, Cu-AIA catalyst was
isolated from the solution, and recovered by washing with CH3CN (3  10 mL)
for another run in which the conversion and selectivity would be detected by
GC-MS. (b) Proposed mechanism for the aerobic epoxidation of cyclooctene
in the presence of Cu-AIA using isobutyraldehyde as a sacrificial co-reductant.
Figure 4. Substrate scope for the aerobic epoxidation of olefins using the Cu-
AIA as a catalyst (bar: conversion, ball: selectivity). Reaction conditions: 1
mmol of olefin, 3 mmol of isobutyraldehyde and 5 mL of CH3CN were mixed
with 10 mol% catalyst in a 25 mL three-necked round-bottomed flask along
with a condensation tube. The mixture was stirred with air bubbling at 80 oC for
24 h.
The effect of the amount of catalyst on the substrate
conversion has also been studied. The conversion of
cyclooctene is only 2% when the reaction is carried out without
Cu-AIA catalyst (Table S3, entry 1), and the conversion
increased steadily from 32% to 91% as the amount of catalyst
increased from 2 mol% to 10 mol% (Table S3, entries 2-4). For
comparison, MOP-1 is also used to catalyze the epoxidation of
cyclooctene, and only 15% conversion is obtained (Table S3,
entry 5), which are remarkably lower than that of Cu-AIA under
the same condition. Thus, it is proposed Cu active sites exposed
on surfaces of the 2D MOF are easier to approach for the
reactants. For the influence of temperature on the epoxidation of
cyclooctene, it is found the conversion of cyclooctene is
Under the optimized conditions, the scope of Cu-AIA was
explored (Figure 4). Cyclic olefins such as cyclooctene and
norbornene show high conversion with excellent selectivity
(>99%) for their corresponding epoxides. Cyclohexene is
converted to cyclohexene oxide smoothly in 62% yield, and the
byproduct 2-cyclohexen-1-one with 34% selectivity is produced.
Substituted styrenes with either electron-withdrawing group (–
NO2) or electron-donating group (–CH3) are oxidized to the
corresponding aldehydes. Styrene is transformed into 1,2-
epoxyethylbenzene contaminated with benzaldehyde (36%
selectivity) as the main by-product. Trans-stilbene is oxidized to
the corresponding epoxide in 75% selectivity with the 24%
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selectivity for benzaldehyde. Linear terminal alkene such as 1-
octene gives the corresponding epoxide cleanly. Sterically
hindered 9-vinylanthracene only affords the corresponding
aldehyde.
To evaluate the stability of Cu-AIA catalyst for the epoxidation
reaction, a leaching test was conducted. The Cu-AIA catalyst is
removed via centrifugation after 2 h of reaction and the
remaining supernatant is allowed to react for another 8 h (Figure
S9). The results show that the conversion of cyclooctene
increases slightly from 35% to 48% without Cu-AIA catalyst,
which should result from the slow oxidation. In addition, no
obvious presence of Cu could be observed in the solution as
analyzed by ICP-MS. Thanks to its good stability, the Cu-AIA
catalyst can catalyze the epoxidation of cyclooctene over six
successive cycles with the same selectivity of >99% for 1,2-
epoxycyclooctane (Figure 5a). The powder XRD results also
indicate that the overall structure of the Cu-AIA catalyst remains
intact after 2 and 4 cycles (Figure S10). The Cu-AIA catalyzed
aerobic epoxidation of cyclooctene is rationalized in Figure 5b.
The isobutyraldehyde I coordinates with the Cu2+ sites of Cu-AIA
II to form the complex III. By losing a hydrogen, an acyl radical
IV was produced. Inermediate IV would then combine with
dioxygen to form an acylperoxy radical V, which is reported to be
the predominant oxidizing species for the expoxidation of olefin
IX into epoxide 2.[68] However, V can also transform into a
copper-acylperoxy VI, another efficient epoxidation species.[69] In
fact, the formation of Cu(IV) species VII may also work in the
expoxidation process.[70] Although the exact epoxidation species
remains to be clarified, the high selectivity of the Cu-AIA catalyst
for the epoxidation reaction is impressive.
Figure 6. Suzuki–Miyaura coupling of 4-iodobenzaldehyde and phenylboronic
acid catalyzed by Cu-AIA-PC-Pd. Reaction conditions:
1 mmol of 4-
iodobenzaldehyde, 1.5 mmol of phenylboronic acid, 1.5 mmol of K2CO3 and
catalyst (1 mol%) were added into 5 mL of ethanol. The mixture was stirred at
room temperature for 6 h.
coupling product in lower yield (Table S4, entry 2). The reactions
of substituted aryl bromides with phenylboronic acid also afford
the corresponding products in good yields (Table S4, entries 7, 9
and 11) except the aryl bromides with 4-CH3 and 4-CH2OH
groups
(Table
S4,
entries
8,
10).
However,
4-
chlorobenzaldehyde and 4-fluorobenzaldehyde show much
lower activities (Table S4, entries 12, 13). The leaching test
shows the heterogeneous catalysis feature of the catalytic
system (Figure S21). After six successive cycles, the Cu-AIA-
PC-Pd catalyst remains substantially active and no significant
decreases in catalytic efficiency (Figure S22). Compared with
the catalysts reported in literatures (Table S5), [73-83] the obtained
Cu-AIA-PC-Pd also exhibits excellent catalytic activity. The
results confirm that Cu-AIA as a 2D carrier to support metal
catalysts is feasible.
In order to expand its application range, Cu-AIA has been
used as a carrier to support Pd catalyst via PSMet method using
the amino group as modifiable sites, and the catalytic activity of
the obtained Cu-AIA-PC-Pd catalyst is firstly evaluated by
Suzuki–Miyaura coupling reaction with 4-iodobenzaldehyde and
phenylboronic acid as model substrates (Figure S16-S19).[71,72]
As shown in Figure 6, no target product can be found without the
catalyst, nor does the reaction proceed in the presence of Cu-
AIA. An excellent conversion of 4-iodobenzaldehyde is obtained
Conclusion
with
1 mol% Pd in Cu-AIA-PC-Pd in 0.5 h, and 4-
iodobenzaldehyde is converted almost completely to the
corresponding product [1,1'-biphenyl]-4-carbaldehyde in 1 h. The
reaction mechanism for the Suzuki–Miyaura reaction has been
proposed in Figure S20. Furthermore, other aryl halides also
have been explored in the reaction (Table S4). The employed
aryl iodides containing electron-withdrawing groups such as 4-
CHO, 4-CN, 4-NO2, 4-CH2-OH proceed satisfactorily, and good
isolated yields (>90%) are obtained (Table S4, entries 1, 3–5). 9-
Iodophenanthrene as a typical macromolecule substrate affords
the corresponding product 9-phenylphenanthrene in an excellent
yield (92.1%). But the reaction of the aryl iodide containing
electron-donating groups (4-CH3) with phenylboronic acid gives
In this paper, the transformation of coordination structure from
MOP to 2D MOF has been achieved using 2-aminoisophthalic
acid instead of isophthalic acid. The amino group in the ortho
position supplies hydrogen bonds to the carboxylic groups and
induces the ligand to coordinate with copper ion to form 2D
structure. In the 2D MOF structure, Cu active sites are better
exposed on surfaces, much easier to approach and avoid the
aggregation problem, which makes the Cu-based 2D MOF (Cu-
AIA) behave as an efficient heterogeneous catalyst for the
aerobic epoxidation of olefins in an air atmosphere. Furthermore,
Cu-AIA has also been used as a carrier to support metal active
sites using the amino group as a modifiable site to PSMet. SEM
images, AFM images and out-of-plane and in-plane XRD
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Acknowledgements
This work was financially supported by the Science Foundation
for Distinguished Scholars of Dongguan University of
Technology (No. 196100041051), the National Natural Science
Foundation of China (No. 51773165 and 51973171), the Young
Talent Support Plan of Xi’an Jiaotong University, the Program
for Guangdong Introducing Innovative and Enterpreneurial
Teams (No. 2017ZT07C069) and Zhongshan Science and
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Keywords: 2D MOF • Aerobic oxidation of olefins • metal-
organic polyhedra • Heterogeneous catalysis • Suzuki–Miyaura
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10.1002/chem.201905249
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RESEARCH ARTICLE
Entry for the Table of Contents
RESEARCH ARTICLE
With the assistance of the
hydrogen bond of o-amino group,
we have tuned the coordination
structure from MOP to 2D MOF.
The amino group forms hydrogen
bonds with the two vicinal
carboxylic groups and induces
the ligand to coordinate with
copper ion to form 2D structure.
The obtained 2D MOF (Cu-AIA)
shows high catalytic activity for
the aerobic oxidation of olefins
under air atmosphere.
Jia Tang, Mengke Cai, Guanqun
Xie, Shixiong Bao, Shujiang Ding,
Xiaoxia Wang*, Jinzhang Tao, and
Guangqin Li*
Page No. – Page No.
Amino-Induced 2D Cu-Based
Metal–Organic Framework as an
Efficient Heterogeneous Catalyst
for Aerobic Oxidation of Olefins
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