A bifunctional metal-organic framework featuring the combination of open metal sites and Lewis basic sites for selective gas adsorption and heterogeneous cascade catalysis

Article abstract of DOI:10.1039/c6ta05098k

A bifunctional MOF (JUC-199) featuring dual functionality, open metal sites (Zn²⁺) and Lewis basic sites (-NH₂), has been successfully synthesized using a custom-designed ligand. JUC-199 demonstrated good selective gas sorption behaviours with IAST selectivity values of 9, 30, 37 and 64 at 298 K and 101 kPa for CO₂/CH₄, CO₂/N₂, C₂H₆/CH₄ and C₂H₄/CH₄ respectively; surpassing those of most MOFs reported thus far. Moreover, JUC-199 can serve as a heterogeneous cascade catalyst to efficiently catalyse the tandem one-pot deacatalization-Knoevenagel condensation reaction.

Full text of DOI:10.1039/c6ta05098k

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Journal of Materials Chemistry A
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ARTICLE TYPE
A bifunctional metal-organic framework featuring the combination of
open metal sites and Lewis basic sites for selective gas adsorption and
heterogeneous cascade catalysis
[a, b]
[a]
[b]
[b]
[b]*
Hongming He,
Zhu[
Fuxing Sun, Briana Aguila, Jason A. Perman, Shengqian Ma and Guangshan
a]*
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
2
+
A bifunctional MOF (JUC-199) featuring dual functionality, open metal sites (Zn ) and Lewis basic sites
-NH ), has been successfully synthesized using a custom-designed ligand. JUC-199 demonstrated good
selective gas sorption behaviours with IAST selectivity values of 9, 30, 37 and 64 at 298 K and 101 kPa for
CO /CH , CO /N , C /CH and C /CH respectively; surpassing those of most MOFs reported thus
(
2
1
0
2
4
2
2
2
H
6
4
2
H
4
4
far. Moreover, JUC-199 can serve as a heterogeneous cascade catalyst to efficiently catalyse the tandem
one-pot deacatalization-Knoevenagel condensation reaction.
[
25-27]
sensing,[28-32] drug delivery,[33-35] and
separation and storage,
optical devices.
[
36-38]
Introduction
Inspired by the investigations on MOFs, their
structures and properties can be designed and tuned through the
judicious combination of organic linkers molecules and metal-
containing secondary building units (SBUs). Hence, we postulate
that if the ligands containing Lewis basic sites (LBSs) and the
SBUs possessing unsaturated open metal sites (OMSs) are utilized,
it is anticipated to afford bifunctional MOFs that are capable of
selectively adsorbing gas molecules and also serving as
heterogeneous catalysts for acid-base one-pot reactions. Recently,
much effort has been devoted to obtaining multifunctional MOFs
1
2
2
3
3
4
4
5
0
5
0
5
0
5
Energy crises and environmental pollution represent some
worldwide issues needing to be addressed with urgency. In
particular, the escalating anthropogenic carbon dioxide (CO )
2
emissions have drawn special attention from chemists and
materials scientists in recent years because it is the primary source
of greenhouse gases causing dire environmental concerns.[1-4]
Among all the separation technologies, adsorption separation is
one of the most promising approaches.[5-8] In addition, methane
5
5
6
6
0
5
0
5
(
CH
considerably cleaner energy source for our daily lives and a useful
feedstock chemical to prepare various chemicals in the
4
), as the main component of natural gas and biogas, is a
[39]
for multi-disciplinary applications. Pal and co-workers reported
[40]
a copper MOF that exhibited gas sorption and catalytic abilities.
C
1
However, the catalytic properties from copper, in the MOF, were
only obtained after modification by transmetalation. Their MOF
showed selective gas adsorptions for CO over N , CH and H . In
2 2 4 2
[
9,
petrochemical industries, such as acetylene and chloromethane.
1
0]
However, a small quantity of hydrocarbon impurities with
methane will hinder its cleaner qualities over other fossil fuels. At
the present, growing interest to develop porous materials that
efficiently capture or separate post-combustion CO
addition, their porous MOF additionally catalysed Knoevenagel
condensation reactions using the basic sites and not the Lewis acid
2
or purify CH
4
[40]
sites. Therefore, multifunctional MOFs, combining acidic and
from natural gas and biogas are desired.
basic sites, should undergo systematic investigations to determine
their built-in properties for gas sorption, separation and catalysis.
Recently, there is an escalating interest in the development of
one-pot, sequential and multi-capable reactions because of their
comparably higher efficiency, less waste, lower cost and fewer
purification steps.[11-13] These multi-step cascading reactions have
spurred great attention in developing and exploration upcoming
materials as catalysts. Nonetheless, it is usually very difficult to
develop a catalyst requiring both acidic and basic components
because these moieties can easily deactivate each other. Therefore,
it remains a challenge to develop site-isolating and multifunctional
heterogeneous catalysts that can promote one-pot sequential
reactions.
Metal-organic frameworks (MOFs),[14-21] are a new class of
porous crystalline materials that have attracted tremendous interest
due to their strong application scope in catalysis,
[
22-24]
gas
8
Scheme 1 The ligand H TBCB.
This journal is © The Royal Society of Chemistry [year]
[journal], [year], [vol], 00–00 | 1

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DOI: 10.1039/C6TA05098K
Journal of Materials Chemistry A
Page 2 of 7
The documented studies with amine-functionalization ligands in 45 (s) (Fig. S1).
[
41-44]
MOFs for introducing LBSs into the framework,
inspired our ligand design of 2,2’,6,6’-Tetrakis[3,5-bis-3,5-
benzenedicarboxylate] benzidine (H TBCB) that features two
amino functional groups (Scheme 1). Self-assembly of TBCB
have
X-ray structure determination and structure refinement
8
The single crystal data of JUC-199 was obtained from a Bruker
SMART APEX II CCD-based diffractometer with graphite
monochromatized Mo-Kα radiation (λ=0.71073 Å) at room
-
8
5
2
+
ligand with Zn ions under solvothermal conditions afforded a
three-dimensional (3D) microporous MOF called JUC-199 having 50 temperature. Corrections for incident and diffracted beam
a chemical formula of [Zn (TBCB)(H O) ]•5DMAc (DMAc =
absorption effects were applied to the date using the SADBAS
4
2
6
[
45]
N,N-Dimethylacetamide). By design, the resultant microporous
MOF features both OMSs and LBSs, which render it with
program.
The crystal structure can be determined by a
1
0
combination of direct methods and refined by the full matrix least-
squares against F values using the SHELXTL program.
2
[46]
interesting performances in selective gas adsorption (CO
2
over
All
CH and N , and CH over C and C
4
2
4
2
H
6
2 4
H
) and allow 55 non-hydrogen atoms were located successfully from Fourier maps
heterogeneous catalysis for the tandem one-pot deacatalization-
Knoevenagel condensation reaction (as shown in Scheme 2).
and refined by anisotropic thermal parameters. Due to some
disordered solvent molecules in JUC-199, their diffraction
contributions were removed by using the PLATON/SQUEEZE.
[
47,
4
8]
The guest molecules can be calculated from the results of TGA
and elemental analyses. Crystal data of JUC-199 is listed in Table
and the selected bond lengths and bond angles are summarized
60
1
in Table S2.
Table 1 Crystal data and structure refinement for JUC-199
Compound
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
α (º)
JUC-199
C H O N Zn
64 77 27 7 4
1635.1
Monoclinic
P2 /c
1
12.4957(10)
15.3163(14)
24.254(2)
90.00
1
5
Scheme 2 Schematic illustration of this bifunctional MOF for selective gas
adsorption and heterogeneous cascade catalysis.
β (º)
γ (º)
V (Å )
Z
ρ calc g cm
μ (mm )
Nref
102.304(2)
90.00
4535.3(7)
4
0.872
1.090
3
Experimental section
-
3
-
1
Materials and methods
11550
2
2
3
3
4
0
5
0
5
0
All the chemical reagents were received from commercial sources
F(000)
R(int)
Goodness-of-fit on F
1188.0
0.0403
0.988
0.0474, 0.1407
0.0671, 0.1489
and used without further purification. HY zeolite (SiO
was purchased from ZEOLYST. H TBCB synthesis details are
found in the supplementary information. Powder X-ray-diffraction
PXRD) patterns were acquired on a Scintag X1 diffractometer
with Cu-Kα (λ = 1.5418 Å) at 50 kV, 40 mA in the range of 4-40°
2θ). Thermogravimetric analyses (TGA) for all measurements
2 2 3
/Al O = 30)
2
8
R
R
1
, wR
, wR
2
[I > 2σ(I)]
(all data)
1
2
(
Results and discussion
(
6
5
Structure
were carried on a Perkin-Elmer TGA thermogravimetric analyser
under air flow at a heating rate of 10 °C/min from 30 to 800 °C.
Elemental analyses on C, H and N were obtained using a Perkin-
Elmer 240 analyzer. Fourier-transform infrared spectra (FT-IR)
were performed on a Nicolet Impact 410 FT-IR spectrometer in the
Single-crystal X-ray diffraction study revealed that JUC-199
crystallized in the monoclinic space group P2 /c. The
asymmetrical unit of the host framework contains two independent
Zn ions, one half of the TBCB ligand, and three terminal water
molecules (Fig. S2). As shown in Fig. 1a, Zn1 is four-coordinated
by four carboxylate oxygen atoms from four different ligands
1
2+
-8
-
1
4
000-400 cm range using KBr pellets. All gas sorption
measurements were acquired on the surface area analyser ASAP
020.
Synthesis of JUC-199
A mixture of Zn(NO
mg, 0.006 mmol), DMAc (3.5 mL), H
aqueous HNO solution (2.0 M) was sealed in a 20 mL capped
7
7
8
0
5
0
2
(
Zn1-O, 1.9059(19)-1.9478(24) Å), while Zn2 is octahedrally
coordinated by three oxygen atoms from three carboxylate oxygen
atoms and three oxygen atoms from three terminal water molecules
(Zn2-O, 2.0436(19)-2.2034(19) Å). Eight carboxylate groups of
each ligand are all connected with [Zn
adopt a chelating mode and the other two take a monodentating
mode. Each [Zn (COO) ] unit is linked with four ligands and each
ligand connects eight [Zn (COO) ] SBUs to form a 3D porous
framework architecture (Fig. 1b). The solvent accessible volume
of JUC-199 is about 64.2% as calculated using PLATON/VOID.
Topologically, the binuclear inorganic cluster and the ligand could
3
)
2
•6H
2
O (15 mg, 0.05 mmol), H
8
TBCB (5
2
O (1 mL) and two drops of
3
2 4
(COO) ] SBUs, six of them
vessel. The as-synthesized brown crystals can be obtained at 85
°C for 3 days in an oven. The yield is about 62 % (based on the
2
4
ligand). Element analysis (%) Calc. for C64
77 27 7 4
H O N Zn : C, 46.97;
2
4
H, 4.71; N, 5.99; Found: C, 46.75; H, 4.79; N, 6.07. Selected FT-
-
1
IR data (KBr pellet, cm ): 2935 (br), 1619 (s), 1412 (s), 1356 (s),
261 (s), 1186 (s), 1020 (s), 783 (s), 717 (s), 660 (s), 592 (s), 463
[47]
1

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DOI: 10.1039/C6TA05098K
Page 3 of 7
Journal of Materials Chemistry A
be simplified as four-connected and eight-connected nodes,
respectively. Thus, the network of JUC-199 can be regarded as a
4,8)-net with the topology alb-4, 8-P2 /c (Fig. 1c) and Schläfli
calculated by TOPOS software.[49-
The thermogravimetric analyses of JUC-199 (Fig. S3) showed
(
1
1
0
14
4
5
symbol is {4 ·6 ·8 }·{4 ·6}
5
2
1]
5
a weight loss of 33.86% before 200 °C, corresponding to the
calculated percentage content of guest and terminal solvent
molecules (calculated 34.21%). Powder X-ray diffraction (PXRD)
patterns of JUC-199 confirmed the phase purity of the bulk
crystalline material (Fig. S4). In addition, JUC-199 exhibited good
stability in air and water vapour, which was confirmed by the
PXRD patterns (Fig. S5).
1
0
Fig. 2 N
2
sorption isotherms of the activated sample at 77 K (solid symbols:
40
adsorption and open symbols: desorption).
We further investigated the sorption behaviours of activated
JUC-199 for some other small gases. The adsorption enthalpy (Qst
was calculated from the adsorption isotherms at 273 and 298 K
using the virial method. The CO adsorption capacity was observed
)
2
3
-1
-1
3
-1
-1
4
5
5
6
6
7
5
0
5
0
5
0
to be 55 cm g (2.46 mmol g ) and 40 cm g (1.78 mmol g ) at
2
Q
73 K and 298 K respectively under 1 atm pressure (Fig. 3a). The
st of CO was 29 kJ mol at zero loading (Fig. 3f and Fig. S8)
2
which was higher than that of most “benchmark MOFs”, such as
-
1
-
1
[53]
-1 [54]
CuBTTri (21 kJ mol ), MOF-5 (17 kJ mol ), UMCM-1 (12
-
1
[55]
-1 [56]
kJ mol ), and NOTT-140 (25 kJ mol ), and is comparable to
-
1 [57]
that of MIL-53(Cr) (32 kJ mol ), HKUST-1 (hydrated) (30 kJ
mol ) and MAF-2 (27 kJ mol-1)[59]. JUC-199 high adsorption
enthalpy is mainly due to the strong interactions of CO with both
exposed Zn sites and amino functional groups. In addition, the
sorption isotherms of N and CH were also measured at 273 K and
98 K under 1 atm pressure (Fig. 3b and 3c). The adsorption
-1 [58]
2
2
4
2
Fig. 1 (a) The ligand and the inorganic cluster in JUC-199; (b) the
spacefill pattern of 3D framework (Zn: green; C: gray; O: red; N:
blue); (c) the simplified topology structure. The hydrogen atoms
are omitted for clarity.
3
-1
-1
3
-1
2
capacities for N are 6.3 cm g (0.28 mmol g ) and 3.5 cm g
(0.16 mmol g ) at 273 K and 298 K respectively; and the values
are 16 cm g (0.72 mmol g ) and 11 cm g (0.51 mmol
g ) at 273 K and 298 K respectively. At zero loading, the Qst of N
4
are 16 and 22 kJ mol , respectively (Fig. 3f, Fig. S9 and
S10). In order to estimate the practical separation ability for CO
2 2 2 4
theoretical gas mixtures of CO /N and CO /CH are evaluated by
the IAST model,
adsorption from experimental single-component isotherms. The
dual-site Langmuir-Frendlich equation was employed to fit the
data (Fig. 4a) with excellent correlation coefficients. The estimated
selectivity data were obtained from a function of pressure at a
general feed composition of landfill gas (50/50, m/m) at 298 K
under 101 kPa (Fig. 4b). At 298 K and 101 kPa, the selectivity
1
5
-
1
3
-1
-1
3
-1
for CH
4
-
1
2
Gas sorption properties
-
1
and CH
To assess the permanent porosity of JUC-199, the freshly prepared
samples were soaked in dry methanol, which was further
2
,
2
2
3
3
0
5
0
5
[
52]
desolvated using a supercritical CO
2
dryer.
The N
2
sorption
[60]
a method used to determine binary mixture
isotherms of the activated sample at 77 K (Fig. 2) revealed a
completely reversible type-I behaviour, a characteristic of
microporous materials. Based on the N
2
adsorption data, the
Brunauer-Emmett-Teller (BET) surface area and Langmuir surface
2
-1
2
-1
area of JUC-199 were calculated to be 821 m g and 953 m g ,
3
-1
respectively with a corresponding pore volume of 0.36 cm g . As
shown in Figure S6, the pore size distribution ranged from 7.79 to
2 4 2 2
values for CO /CH and CO /N are 9 and 30, respectively, which
1
0.29 Å (as determined using the Horvath-Kawazoe method). The
are significantly higher than those of many reported MOFs under
surface area is smaller than the theoretically calculated accessible
[61-63]
the same conditions.
2
-1
surface area of 1171 m g (Fig. S7), which is mainly attributed to
the partial pore blockage or collapse of the host framework during
activation. As shown in Fig. S4, the PXRD pattern of the activated
sample indicated that the main original skeleton was still retained
after activation. However, some extra peaks appeared in the PXRD
patterns because of the partial collapse of the host framework after
guest removal.

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DOI: 10.1039/C6TA05098K
Journal of Materials Chemistry A
Page 4 of 7
30
2 2 4 2 4 2 6
Fig. 4 Gas sorption isotherms of CO , N , CH , C H and C H along with
the dual-site Langmuir-Freundlich (DSLF) fits (a and c); gas mixture
adsorption selectivity are predicted by IAST for JUC-199 at 298 K and 101
kPa (b and d).
35
Catalytic property
Up to now, only a few MOFs have been reported for the acid-base
[68-74]
one-pot reaction with high yields.
Given the existence of both
Fig. 3 Gas sorption isotherms of CO
2
(a), N
2
(b), CH
4
(c), C
2
H
4
(d) and
OMSs and LBSs in the framework, JUC-199 was examined as a
bifunctional acid-base catalyst for one-pot cascade reaction. The
2 6
C H
(e) at 273 K and 298 K; (f) the Qst of these gases for JUC-199.
Additionally, hydrocarbons ethylene and ethane were measured 40 acid-catalyzed acetal hydrolysis and the subsequent base-catalyzed
5
0
5
0
5
at 273 and 298 K under 1 atm pressure (Fig. 3d and 3e). The uptake
Knoevenagel condensation were chosen as the model reaction
(Table 1). In a typical experiment, the catalytic reactions were
carried out in a 20 mL glass reactor vial. A mixture of substrate (1
mmol), malononitrile (1.2 mmol), 1, 4-dioxane (4 mL) with 100
3
-1
-1
3
-1
capacities of C
2
H
4
are 51 cm g (2.26 mmol g ) and 42 cm g
-
1
(
1.87 mmol g ) at 273 and 298 K respectively; and the values for
3
-1
-1
3
-1
-
C
)
2 6
H are 42 cm g (1.90 mmol g ) and 36 cm g (1.62 mmol g
at 273 and 298 K respectively. The Qst values at zero coverage 45 mg of the catalyst was stirred at 363 K for 4 hours. The products
1
-
1
1
1
2
2
are 35 and 32 kJ mol for C
2
H
4
and C
2
H
6
respectively (Fig. 3f, Fig.
were monitored by GC-MS equipped with a DB-5HT column.
JUC-199 effectively catalysed benzaldehyde dimethylacetal (1)
into benzylidenemalononitrile (3) in almost quantitative yield in 4
h (Table 1, entry 1). In contrast, HY zeolite catalysed the first
S11 and S12). The dual-site Langmuir-Frendlich equation was
applied to fit the experimental data (Fig. 4c). As shown in Fig. 4d,
the estimated selectivity data are obtained from a function of
pressure at a general feed composition of landfill gas (50/50, m/m). 50 reaction step from the acidic catalyst (entry 2). MgO, a basic solid
At 298 K and 101 kPa, the C
2
H
6
/CH
4
adsorption selectivity of 37
catalyst, showed little reactivity (entry 3). In addition, when a
mixture of HY zeolite and MgO was employed, the reaction
conversion was lower than that of JUC-199 (entry 4). On the other
hand, the homogeneous catalysts such as HCl and triethylamine
55 (TEA) were applied for the one-pot reaction. The acid catalyst
(HCl) can only efficiently catalyse the quantitative deprotonation
of 1 to 2 (entry 5). On the other hand, TEA as a basic catalyst
support this reactions even after 4 h (entry 6). When the mixture of
HCl (0.05 mmol) and TEA (0.05 mmol) was employed as the
is higher than many reported MOFs, such as Mg-MOF-74 (11.5),
[
64, 65]
NOTT-101 (12) and FIR-7a (14.6).
4 for C /CH
As shown in Fig. 3f, the Qst trends of C
The selectivity value of
6
2
H
4
4
, is also much higher than many reported MOFs.[
66,
6
7]
2
6 2 4 4 2
H , C H , CH , and CO
all steadily decreases with increasing gas adsorption uptake
because the interactions between host and guest molecules reaches
a maximum when all the exposed Zn sites and amino functional
groups become saturated by guest initially and then guest-guest
interactions occur. However, the Qst trend for N differs from the 60 catalyst, the reaction hardly occurred (entry 7). It is well known
2
other gas molecules because there is weak interactions with the
host framework. In addition, these results suggested that JUC-199
could be an efficient microporous material not only for efficiently
that acid and base catalysts can easily neutralise each other in the
homogeneous systems, thus leading to the deactivation of catalysts.
When -Br or -OMe groups were introduced into the phenyl ring,
the corresponding deacetalization-Knoevenagel condensation
65 products were about 94% (entry 8) and 92% (entry 9) under the
same conditions. This phenomenon may be primarily ascribed to
the restricted diffusion of large-sized substitute molecules into the
framework. In addition, it was also observed that the reaction can’t
occur in the absence of a catalyst (entry 10). The results clearly
2 4
capture and separation of CO but also for purification of CH from
natural gas and biogas.
70
demonstrate that JUC-199 can serve as an efficient bifunctional
acid-base catalyst for one-pot deacetalization-Knoevenagel
condensation reaction.

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DOI: 10.1039/C6TA05098K
Page 5 of 7
Journal of Materials Chemistry A
a
b
Table 1. One-pot deacetalization-Knoevenagel condensation reaction.
40 Department of Chemistry, University of South Florida, 4202 East Fowler
Avenue, Tampa, Florida 33620, USA. E-mail: sqma@usf.edu; Fax: +1-
8
13-974-3203; Tel: +1-813-974-5217.
†
Electronic Supplementary Information (ESI) available: PXRD, TGA,
4
5
5
0
FT-IR and so on. CCDC 989570. See DOI:10.1039/b000000x/
1
.
E. D. Bloch, L. J. Murray, W. L. Queen, S. Chavan, S. N. Maximoff,
J. P. Bigi, R. Krishna, V. K. Peterson, F. Grandjean, G. J. Long, B.
Smit, S. Bordiga, C. M. Brown and J. R. Long, J. Am. Chem. Soc.,
2011, 133, 14814.
Entry
R
Catalyst
Conv. 1
Yield 2
[%]
Trace
93
3
Yield 3
[%]
≥99
7
5
35
4
Trace
Trace
94
f
f
f
[
%]
2. Z. Zhang, Z. Z. Yao, S. Xiang and B. Chen, Energy Environ. Sci., 2014,
, 2868.
1
2
3
4
5
6
7
8
9
H
H
H
H
H
H
H
Br
OCH
H
JUC-199
HY zeolite
MgO
≥99
≥99
8
7
3
.
S. Xiang, Y. He, Z. Zhang, H. Wu, W. Zhou, R. Krishna and B. Chen,
b
Nat. Commun., 2012, 3, 954.
HY zeolite+MgO
93
58
96
c
4. J. D. Shakun, P. U. Clark, F. He, S. A. Marcott, A. C. Mix, Z. Y. Liu,
B. Otto-Bliesner, A. Schmittner and E. Bard, Nature, 2012, 484, 49.
5. O. Shekhah, Y. Belmabkhout, K. Adil, P. M. Bhatt, A. J. Cairns and
M. Eddaoudi, Chem. Commun., 2015, 51, 13595.
6. H, He, Y. Song, C. Zhang, F. Sun, R. Yuan, Z. Bian, L. Gao and G.
Zhu, Chem. Commun., 2015, 51, 9463.
HCl
≥99
Trace
Trace
94
92
Trace
≥99
c
55
TEA
Trace
Trace
Trace
Trace
Trace
Trace
d
HCl+TEA
JUC-199
JUC-199
No catalyst
3rd recycle
3
92
Trace
≥99
1
1
0
1
H
60 7. S. D. Burd, S. Ma, J. A. Perman, B. J. Sikora, R. Q. Snurr, P. K.
Thallaapally, J. Tian, L. Wojtas and M. J. Zaworotko, J. Am. Chem.
Soc., 2012, 134, 3663.
a
Reaction conditions: substrate (1 mmol), malononitrile (1.2 mmol), 1, 4-
b
dioxane (4 mL), catalyst (100 mg), 363 K, 4 h. The mixture of HY zeolite
(50 mg) and MgO (50 mg) was employed as the catalyst. 0.1 mmol of
HCl or triethylamine (TEA) was used. The mixture of HCl (0.05 mmol)
and TEA (0.05 mmol) was employed as the catalyst. The yields were
8
9
.
.
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5
d
6
7
7
8
8
9
9
5
0
5
0
5
0
5
1284.
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determined by GC-MS.
5
Furthermore, no detectable leaching of Zn2+ ions were observed
3
1
0
in the reaction solution after removal of JUC-199 as analysed using
inductively coupled plasma (ICP), which confirmed the
heterogeneous nature of the catalyst. It was also easy to separate
and reuse the catalyst after each reaction. In fact, JUC-199 can be
recycled by filtration and washed fresh 1, 4-dioxane to prepare it
for a following reaction. As shown in entry 11, JUC-199 can be
reused for at least three cycles without any loss of activity, and the
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2
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Conclusion
5
2
2
0
In summary, we have successfully designed and synthesized a
microporous MOF with a high density of OMSs and LBSs. It
exhibits high adsorption selectivity for CO
1
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2 4 2
over CH and N , and
CH over C and C . In addition, it can serve as a cooperative
4
2
H
6
2 4
H
2
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catalyst for a one-pot deacetalization-Knoevenagel reaction. We
anticipate that it can offer a common avenue to obtain multi-
functional MOFs. Further work to employ this strategy is ongoing
in our research laboratories.
2
2
5
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Acknowledgment
We are grateful for the financial support of National Basic
Research Program of China (973 Program, grant no.
3
0
2
012CB821700 and 2014CB931804), Major International
1
5, 2033.
(
2
1
Regional) Joint Research project of NSFC (grant no. 100 30. X. Liu, H. Lin, Z. Xiao, W. Fan, A. Huang, R. Wang, L. Zhang and D.
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1120102034), NSFC Project (grant no. 21531003), NSF (DMR-
352065) and USF for financial support of this work.
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Journal of Materials Chemistry A
View Article Online
DOI: 10.1039/C6TA05098K
Entry for the Table of Contents
2
+
A bifunctional MOF featuring the combination of open metal sites (Zn ) and Lewis basic
sites (-NH
catalysis.
2
) has been constructed for selective gas adsorption and heterogeneous cascade