Two chelating-amino-functionalized lanthanide metal-organic frameworks for adsorption and catalysis

Article abstract of DOI:10.1039/c4dt02048k

Two chelating-amino-functionalized lanthanide metal-organic frameworks, Er-DADQ and Eu-DADQ, were synthesized with a flexible dicarboxylate ligand based on quinoxaline (H₂DADQ = N,N′-dibenzoic acid-2,3-diaminoquinoxaline). N₂ adsorpt

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ARTICLE
Two ChelatingꢀAminoꢀFunctionalized Lanthanide Metalꢀ
Organic Frameworks for Adsorption and Catalysis
Cite this: DOI: 10.1039/x0xx00000x
Yu Zhu, Yanmei Wang, Pan Liu, Changkun Xia, Yunlong Wu, Xiaoqing Lu and Jimin
Xie*
Received 00th January 2012,
Accepted 00th January 2012
Two chelatingꢀaminoꢀfunctionalized lanthanide metalꢀorganic frameworks, ErꢀDADQ and Euꢀ
DADQ, were synthesized with a flexible dicarboxylate ligand based on quinoxaline (H DADQ
2
DOI: 10.1039/x0xx00000x
=
N, N’ꢀdibenzoic acidꢀ2, 3ꢀdiaminoquinoxaline). N adsorption indicates they exhibits stable
2
2
ꢀ1
www.rsc.org/
microporous framework with BET surface area of 136.78 m g . CO adsorptions have also
2
been studied at different temperatures. The amino groups in the MOFs enhanced the uptakes of
RhB with COOH groups. RhBꢀMO and RhBꢀCV separations can also been successfully
conducted. The MOFs act as efficient Lewis acid catalyst for the cyanosilylation of aldehydes
and ketones in high yields in short reaction time due to the higher Lewis acidity and the open
sites of the metal ions after activation.
of the materials due to the results in infinite rodꢀshaped or discrete
Introduction
[
8]
lanthanide cluster secondary building units (SBUs)
.
Multiple carboxylate ligands have been widely used as bridging
ligands to build MOFs. Elongated dicarboxylate ligands have been
widely used to construct porous MOFs because of their versatile
coordination modes as well as their ability to act as Hꢀbond
acceptors and donors to assemble supramolecular structures .
A dicarboxylic acid ligand based on quinoxaline with functional
amino sites has been designed yet for MOFs with multi applications
Recently, the design and construction of porous metal organic
frameworks (MOFs) bridged by organic ligands with carboxyl
groups have been attracted a great deal of interest in material
chemistry, owing to their extraordinary molecular topologies and
[
9]
[1]
fascinating chemical and physical properties such as gas storage
,
[
2]
[3]
heterogeneous catalysis , photoluminescent
and magnetism
[
4]
behaviours . Though some series of complexes constructed on
carboxylate ligands with distinctive architectures and diversity of
functions have been explored, the design of MOFs with excellent
properties that combine high porosity with multiꢀproperties still
poses one of the major challenges in the pursuit of multifunctional
(
H DADQ= N, N’ꢀdibenzoic acidꢀ2, 3ꢀdiaminoꢀquinoxaline). The
2
size between the terminals carboxyl is about 15 Å and it provides the
possibility of large pores even metalꢀorganic nanotubes (MONTs)
[
10]
.
Moreover, grafting amino groups into the channels of porous
[
5]
materials is another strategy that has been applied for enhancing
materials . One challenge is to control the target structures due to
the coordination geometry of the central metal ions and connective
features of the organic ligands, which have big influences on the
resulted structures and functionalities of the porous materials.
[
11]
adsorption of the acidic CO molecule . The alkaline group in the
2
ligands will impact on the MOFs’ ability of CO absorptions.
2
Herein we report crystal structures of two 3D porous carboxylic
LnMOFs based on H DADQ as linkers and trivalent lanthanide (III)
2
Among these MOFs, MOFs with lanthanide ions (LnMOFs), have
been much less explored than their transition metal MOFs and
attracted increasing attention because of their versatile structures and
interesting properties combining light emission, magnetism,
catalysis and molecular separation properties arising from 4f
ions (Er and Eu) as connectors. The functionalized channels show
good separations of RhBꢀMO and RhBꢀCV mixtures, as well as CO2
absorption. The metal ions act as strong Lewis acid sites for
catalyzing the cyanosilylation of aldehydes and ketones in very short
reaction time with noꢀsolvent reactions.
[
6]
electrons . LnMOFs with flexible coordination motifs can create
coordinative unsaturated metal centers, which have great potential to
Experimental
[
7]
be excellent heterogeneous catalysts . The guest solvents in the
holes can be removed after activation to form permanent pores. The
water molecules coordinated to the metal centers can also been taken
off to give unsaturated metal centers which is essential for the
Materials and Physical Measurements
All of the starting materials employed were purchased from
catalytic property. Meanwhile, the flexibility of the coordination commercial sources and used as received without further purification.
geometry of lanthanides is a positive factor for high thermal stability Elemental analyses for C, H and N were determined with a Perkinꢀ
Elmer 240. Fourier transform infrared (FTꢀIR) spectra were
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Jou4Drnal Name
measured as KBr pellets on a Nicolet FTꢀ170SX spectrometer in the structures were then refined again by using the data generated.
ꢀ
1
ꢀ1
range of 400 cm ꢀ4000 cm . Thermogravimetric analysis (TGA) Crystal data and details of the structure determination for the three
experiments were carried out on an integrated thermal STA 449C compounds are listed in Table S1.
analyzer heated from room temperature to 800 °C under N2 Gas Adsorption Experiments
atmosphere. Powder Xꢀray diffraction (PXRD) patterns were
Prior to gas adsorption experiments, the samples were soaked in
collected on a Rigaku D/max2500VB3+/PC diffractometer equipped methanol to exchange solvents, which was then followed by
with CuꢀKα radiation (λ = 1.5406 Å). The UVꢀVis spectra were evacuation under a dynamic vacuum at 120 °C for the 8 hours. All
measured on UVꢀ2450 spectrophotometer
the gas adsorption isotherms were measured using a Micromeritics
ASAP 3Flex analyzer employing a standard volumetric technique up
Synthesis of H DADQ
2
Dichloroquinoxaline (3 mmol, 0.600 g) and 4ꢀaminobenzoic acid to saturated pressure. The N adsorption isotherms were monitored
2
(
12 mmol, 1.60 g) were added to a flask with 100 mL ethanol. The at 77 K. while CO adsorption isotherms were obtained at 273 K and
2
clear mixture was refluxed for 24h and a yellow solid was 293 K.
precipitated, filtered and washed with cold ethanol, finally dried in Dye Adsorption and Desorption Experiments
vacuum. Yield: 0.95g (80%). Anal. Calcd. For C H N O : C,
Compound (10mg) was added into a 5 mL of 50 mg/L dyeꢀ
2
2
16
4
4
6
6.00, H, 4.02, N, 13.99%. Found: C, 65.74, H, 4.21, N, 13.89 %. IR containing water solution under stirring at room temperature. The
−1
(cm ): 3314(w), 3146(w), 2839(m),1672(s), 1634(s), 1609(m), solution was centrifuged, and the clear liquid was analyzed by UVꢀ
1
1
556(s), 1515(s), 1475(m), 773(m), 1407(m), 1296(m), 1240(m), vis absorption spectroscopy. For desorption experiments, the dyes
186(m), 1108(w), 858(w), 761(w), 680(w), 600(w). The product loaded powders were placed in 5 mL fresh water in a glass bottle and
was dissolved in DMF/H O (1:1) solution and yellow prism crystals the dyes releases were also measured by UVꢀvis absorption
2
were formed after two weeks.
Synthesis of {[Er(H0.5DADQ) (H O) ]·5H O} (ErꢀDADQ)
spectroscopy. Separation experiments were carried out by adding
5mg compound to 10 mL RhBꢀMO or RhBꢀCV mixtures.
2
2
2
2
n
A mixture containing H DADQ (0.0300 g, 0.075 mmol) and Catalytic Test for Aldehyde and Ketone Cyanosylation Reaction
2
Er(NO ) ·6H O (0.0700 g, 0.15 mmol) in 3 mL of DMF/H O (1:1)
Into a 10 mL screwꢀcap vial was successively placed
3
3
2
2
and 0.6 mL of 6 M HCl solution was sealed in a Teflonꢀlined aldehyde (1.0 mmol) in trimethylsilyl cyanide (TMSCN, 2
autoclave and heated at 120 °C under autogenous pressure for two mmol) and desolvated compound (2.5 mol%) was then added to
days and then allowed to cool to room temperature. The yellow initiate the reaction with ultrasound for an hour in the sealed
crystals were washed with DMF, water and airꢀdried. Yield: 54% vial. To less reactive the ketones cyanosylation reaction, the
(
based on H DADQ). Anal. Calcd for C H ErN O (Mr: 1091.12): reaction time extended to three hours with the same ratio of the
2 44 43 8 15
C, 48.43; H, 3.97; N, 10.27%. Found: C, 51.18; H, 3.92; N, 11.46%. reactants. After the reaction completed, the catalyst was
ꢀ
1
IR (cm ): 3403(w), 3314(w), 3043(w),1655(s), 1596(s), 1531(w), removed by centrifugation and then filtered with THF quickly.
1
6
396(s), 1304(w), 1240(m), 1180(m), 867(w), 786(w), 750(m), The conversion of aldehydes and ketones were determined by
83(w), 597(w), 570(w).
gas chromatography (GC, Agilent 7890A) analysis and GCꢀMS
(HP 6890) spectra with those of authentic samples.
Synthesis of {[Eu(H0.5DADQ) (H O) ]·5H O} (EuꢀDADQ)
2
2
2
2
n
The preparation of EuꢀDADQ was similar to that of ErꢀDADQ
except that Eu(NO ) ·6H O (0.0670 g, 0.15 mmol) was used instead
Results and discussion
3
3
2
of Er(NO ) ·6H O (0.0732 g, 0.15 mmol). The yellow crystals were
3
3
2
ErꢀDADQ and EuꢀDADQ were characterized by PXRD, TGA
analysis, and FTꢀIR spectroscopy. The experimental PXRD patterns
for ErꢀDADQ and EuꢀDADQ were measured at room temperature as
shown in Fig S1. The peak positions of the simulated and
experimental PXRD patterns are in agreement with each other,
suggesting their good phase purity. The PXRD pattern of activated
ErꢀDADQ indicates that the framework is stable after removing the
solvent in the channels (Fig S2). The chemical stability of ErꢀDADQ
was also examined by suspending samples in methanol, alcohol,
acetone and dichloromethane for one week. The PXRD patterns
collected for each samples confirmed that ErꢀDADQ retaining their
crystalline after immersing in different solvents (Fig S3). TGA
analysis of ErꢀDADQ and EuꢀDADQ revealed that all the MOF
materials have good thermal stabilities, since they start to decompose
beyond 300 °C (Fig S4).
washed with DMF, H O and airꢀdried. Yield: 34% (based on
2
H DADQ). Anal. Calcd for C H EuN O (Mr: 1075.82): C, 49.12;
2
44 43
8
15
ꢀ
1
H, 4.03; N, 10.42%. Found: C, 52.11; H, 3.88; N, 11.43%. IR (cm ):
3
1
5
406(w), 3312(w), 3048(w),1651(m), 1599(s), 1570(m), 1396(s),
306(w), 1306(m), 1182(m), 861(w), 786(s), 751(w), 683(m),
96(w), 571(w).
XꢀRay crystallographic structure determinations
The Xꢀray intensity data for the three compounds were collected
on a Rigaku Saturn 724+ CCD diffractometer with graphite
monochromatized Mo Kα radiation (λ = 0.71073 Å). The crystal
structures were solved by direct methods using difference Fourier
[
12]
synthesis with SHELXTS
, and refined by fullꢀmatrix leastꢀ
[
13]
squares method using the SHELXLꢀ97 program
. The nonꢀ
hydrogen atoms were refined with anisotropic displacement
parameters. Hydrogen atoms except for those of guest molecules
were added according to theoretical models. The solvent molecules
in ErꢀDDAQ and EuꢀDDAQ were highly disordered and were
impossible to been found in the Fourier maps and fixed in the ideal
position. To resolve this issue, the contribution of solvent electron
The characteristic absorption peaks of the main functional groups
in FTꢀIR spectra for all the compounds are listed in Fig S5. The
−
asymmetric stretching vibrations υ (COO ) were observed in about
as
−1
−
1
596 cm and symmetric stretching vibrations υ (COO ) in 1396
s
cm . The above stretching vibrations shifted to lower values by 20
−1
[
14]
density was removed by SQUEEZE routine in PLATON . The
2
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ꢀ
1
3
cm , compared to the carbonyl frequencies of free H DADQ ligand. accessible volume of 833.9 Å (approximately 18.7% of unit cell) by
2
−
−
−1
The difference ꢁ(υ (COO )−υ (COO )) was around 198 cm , excluding the guest water molecules. For a better insight into the
characteristic for coordinated carboxylate groups
Structure of H DADQ
as
s
[
16]
.
nature of this complicated 3D framework, network topological
approach has been regarded as essential tool for the design and
2
[
17]
The chemical structure of H DADQ is illustrated in Fig 1. From analysis of MOFs . The ErꢀOꢀC rods which can be simplified as a
2
the crystal structure, two flexible CꢀNꢀC angles are 127.70 and [ErC O ] SBU (Fig 4b) in this structure are constructed from 8ꢀ
4
2
1
29.83°, which can be slightly adjusted when constructing the MOFs coordinated Er (III) centers, where each is bonded to carboxyl
with metal ions (Fig S6). The two carboxyl points can catch the groups of six DADQ linkers (Fig 4c), resulting in parallel packing of
[
18]
metal ions and form the MOFs with 1D, 2D and 3D frameworks. sra type
The lengths of the arms are about 7.44 Å and 7.53 Å separately, and
the distance between the two carboxyl groups is about 15 Å. All
these provide the possibility of constructing the complexes with
large porosities. There are strong πꢀπ interactions between Cg (C16ꢀ
C21) and quinoxaline rings with the centroid to centriod distance of
.
3
.5784 Å.
Fig 1. Chemical structure of H DADQ
2
Because of the isostructural ErꢀDADQ and EuꢀDADQ, the
Fig 2. (a) View of the asymmetric unit of ErꢀDADQ; (b) View of the
local coordination environment of Er(III) atom; (c) Polyhedron of
coordination center.
structure and properties of ErꢀDADQ are described in detail here as
a representative example. ErꢀDADQ crystallizes in the orthorhombic
space group Pccn. The ORTEP view of ErꢀDADQ is shown in Fig
2
a. The symmetric unit contains half crystallographically
1
.5ꢀ
independent Er(III) ion, one H0.5DADQ
ligand and one
coordinated water molecule. As shown in Fig 2b, each Er ion is
eightꢀcoordinated by oxygen atoms from six ligands and two water
molecules to finish a distorted square antiprism coordination
geometry. The ErꢀO (carboxylate) bond distances vary from 2.253(4)
to 2.447(4) Å, and the ErꢀO (water) bond distance is 2.403(4) Å
(
Table S2). The OꢀErꢀO bond angles vary from 69.48(14)° to
48.33(14)°. Obviously, the polyhedron of the Er(III) coordination
sphere for ErꢀDADQ is best described as a distorted dodecahedron
Fig 2c). The two carboxylates of the ligand exhibit two different
1
(
1
1
coordination modes: µ ꢀ η : η mode chelating one Er atom as well as
the ƞ mode. The chelating carboxylate groups which connect two Er
2
1
ions to bridge a centroꢀsymmetric one dimensional metal chains with
a Er···Er distance of 5.006 (1) Å, which do not indicate any
significant direct interactions between the metal atoms but is
constrained by the bridging geometry (Fig 4a). The one dimensional
metal chains are linked via the bridging ligands to form the infinite Fig 3. Packing diagram of ErꢀDADQ, showing the 1D channels
three dimensional frameworks with 8.47 Å × 8.47 Å dimensions along c axis.
(atomꢀtoꢀatom distances) along the c axis, as shown in Fig 3. It is
worthy note that there are strong πꢀπ interactions between the
adjacent quinoxaline planes of ligands with the centroidꢀcentroid
distance of 3.6726 Å. PLATON calculated suggested a solventꢀ
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4Drn
starts to take up CO2 from the lowꢀpressure region, and the
ꢀ
3
ꢀ1
adsorption amount gradually increases to ca. 26 cm g (4.9 wt%) at
73 K. Taking the 18.7% void volume into consideration, the
2
amount of CO adsorption at low pressure is good enough compared
2
to some MOFs reported such as Zn (BPNDC) (bpy) (52.6 % void
2
2
[
20]
volume, 4.7 wt% )
and Zn(DHBP)(DMF) (39.0 % void volume,
2
[
21]
0
.56 wt% )
.
Fig 4. (a) View of the 1D metal chain; (b) The inorganic polyhedral
SBU. (c) View of crystalline framework with inorganic SBUs with a
sra net.
Fig 7. UVꢀvis absorption spectra of desorption of RhB, MO and CV
absorbed ErꢀDADQ in water solutions.
Fig 5. N adsorption isotherm of ErꢀDADQ at 77 K.
2
Fig 8. UVꢀvis absorption spectra of separation of RhBꢀMO and
RhBꢀCV mixtures with ErꢀDADQ.
We also employed the dye adsorption/desorption experiments
with different harmful dyes suspended in water solution. We screen
ErꢀDADQ for its ability to take up rhodamine B (RhB), methyl
orange (MO) and crystal violet (CV) at room temperature in water
solution. The adsorption abilities were measured by UVꢀvis
absorption spectroscope. As shown in Fig S9, RhB was well
absorbed; however, MO and CV were slightly absorbed. The length
Fig 6. CO adsorptions of ErꢀDADQ at 273 K and 293 K.
2
[22]
of RhB molecule is ca. 17 Å, and the width is ca. 6 Å . The width
of MO is ca. 2.5 Å which indicates good passing ability from the
channels. The carboxylic groups of RhB can be fixed in the channels
with the association with the chelating NꢀH groups, while MO which
has no acid groups is not the favour guest. Contrasting the infrared
spectra between ErꢀDADQ and RhB absorbed ErꢀDADQ, a new
To investigate the permanent porosity of desolvated ErꢀDADQ,
the adsorption isotherm of N as a probe gas molecule was measured
2
at 77 K. The uptake of N increases when pressurized and reach to
2
ꢀ
3
ꢀ1
about 94.58 cm g (STP) indicating a BET surface area of 136.78
2
ꢀ1
m g . The pore size of ErꢀDDAQ is about 4.68 Å using Horvathꢀ
Kawazoe (HK) method (Fig S7). The adsorption experiments of CO2
were also measured at 273 K and 293 K (Fig. 6). The PXRD pattern
of ErꢀDDAQ shows that there is no apparent change after the N2
ꢀ
1
strong and wide peak was found at 3405 cm , which is the result of
the association between COOH of RhB and amine groups (Fig S10).
As a result, the hostꢀguest interaction will be the essential point for
the dye uptakes between RhB and MO. The PXRD pattern of RhB
absorbed ErꢀDADQ is shown in (Fig S12). The length and width of
adsorption (Fig S8). Adsorption measurements of CO were carried
2
out up to about 800 torr. CO with higher polarizability can well
2
[23]
CV are ca.13 and 8.5 Å, respectively . The adsorbent can uptake
interact with desolvated ErꢀDADQ which is mainly due to the
chelatingꢀamino groups which can have strong interactions with the
CV slightly though the channels are a little small than the width of
CV. We attributed it to the breathing transitions after activate of sra
CO molecules as well as the open metal sites in the framework. It
2
4
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[
24]
topologies
. To verify the interaction between the hostꢀguest
molecular which enhanced the adsorptions, we participate in the
desorption experiment. MO and CV adsorbed ErꢀDADQ release
about 40% and 11% after stirring for 6h. The difference is mainly
due to the sizes of the dyes. The CV molecules are too big to escape
most from the channels, while the smaller MO molecules can pass
though the channel more easily. In addition, the adsorbents with
RhB hardly release the RhB, which confirmed our hypothesis of
hostꢀguest interactions (Fig 7).
In light of the remarkable difference between these three dyes in
the adsorption behaviour, it can be forecast that the ErꢀDADQ may
has the ability to separate the dye mixtures with RhB/MO or
RhB/CV. ErꢀDADQ were used to separate dye mixtures with equal
amounts of RhB/MO or RhB/CV. After stirring for 6h, we can see
the colour changes in the adsorption process as illustrated in Fig
S11. The UVꢀVis spectra of the mixtures before and after adsorption
have been measured (Fig 8). The results indicate clearly that Erꢀ
DADQ is a good material for the separation of the RhB/MO and
RhB/CV mixtures.
Fig 9. The conversions of cyanosilylation of benzaldehyde in
different solvents catalyzed by desolvated ErꢀDADQ.
Scheme 1 The cyanosilylation reaction in the presence of ErꢀDADQ.
Scheme 2 The possible catalytic mechanism for cyanosilylation
reaction with ErꢀDADQ after activation
Table 1. Comparison of the catalytic activity for ErꢀDADQ:
aldehydes or ketones cyanosilylation reaction performed with
different substrates.
a
ꢀ1
b
The reaction using ErꢀDADQ as a Lewis acid catalyst was
conducted in our work. As we know, cyanosilylation reaction is
Entry
Substrate
Yield (%)
TOF (h )
[
25]
1
98(0.5)
39.2
>39.6
8.1
widely used to test the Lewis acid catalysis of MOFs . Carbonyl
compounds can be catalyzed by the Lewis acid with cyanide to gain
the useful cyanohydrin trimethylsilyl ethers (Scheme 1). First, the
materials were tested with benzaldehyde as the standard molecule
and varying the different solvents (Fig. 9). The results are
summarized in Table 1. Comparatively, we found that the sample
without solvent presents the highest catalytic activity with a TOF
2
3
4
>99
61(1.2)
>99
ꢀ
1
value of 39.2 h . Indeed, TMSCN acted both as reagent and solvent
here. ErꢀDADQ showed more than 99% conversions in the
cyanosilylation of benzaldehyde and 4ꢀchlorobenzalꢀdehyde in only
one hour. Meanwhile, 4ꢀchloroacetophenone and 2ꢀchloroacetoꢀ
phenone could be completely conversed when extending reaction
times to three hours, while acetophenone and 4ꢀbromoacetophenone
afforded lower yields (61(1.2)% and 81(0.6)%). The electronꢀ
withdrawing groups which are advantageous to the nucleophilic
reactions make the difference indeed. We attribute the high
conversions to high Lewis acid and the open metal sites after
>39.6
5
6
>99
>39.6
10.8
81(0.6)
a
Yield determined by GCꢀMS, an average value of three runs (the value in the
removing the coordinated H O and solvents. The possible catalytic
b
2
parentheses is standard deviation TOF = (yield) / ((mol% cat.) t).
mechanism for cyanosilylation reaction in the case of ErꢀDADQ has
been reasonably predicted in Scheme 2. The observed catalytic
activities are already ahead of most of the cyanosilylation reactions
[
25]
with different MOFs reported under noꢀsolvent condition
. The
heterogeneity of the reaction was confirmed by the filtration test
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DOI: 10.1039/C T02048K
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(Table S4). To demonstrate their recyclability, successive reactions
W. Liao, G. M. Sun, X. Z. Tian, Y. Zhu, Z. J. Yuan, S. J. Liu, W. Y.
were carried out for cyanosilylation of benzaldehyde for the same
Xua, and X. F. Feng, Chem. Commun., 2012, 48, 1006ꢀ1008.
reaction time, showing that the recovered catalyst can be reused (5) (a) X. Feng, J. G. Wang, B. Liu, L. Y. Wang, J. S. Zhao and S. Ng, Cryst.
without an appreciable loss after five cycles at least (Table S3). The
PXRD pattern of the retrieved catalyst was identical with that of the
fresh catalyst (Fig S13).
Growth Des., 2012, 12, 927ꢀ938. (b) Y. Yang, L. Ge, V. Rudolph, Z. H.
Zhu, Dalton Trans., 2014, 43, 7028ꢀ7036.
(6) L. F. Wang, L. C. Kang, W. W. Zhang, F. M. Wang, X. M. Ren and Q. J.
Meng, Dalton Trans., 2011, 40, 9490ꢀ9497.
(
7) (a) M. Gustafsson, A. Bartoszewicz, B. MartinꢀMatute, J. L. Sun, J.
Grins, T. Zhao, Z. Y. Li, G. S. Zhu and X. D. Zou, Chem. Mater. 2010,
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Conclusions
In summary, for the purpose of porous materials for multi
applications, we have synthesized
a new chelatingꢀaminoꢀ
functionalized ligand and constructed two microporous LnMOFs (8) (a) Z. J. Lin, R. Q. Zou, W. Xia, L. J. Chen, X. D. Wang, F. H. Liao, Y.
with sra net successfully using solvothermal reactions. The
X. Wang, J. H. Lin and A. K. Burrell, J. Mater. Chem., 2012, 22, 21076ꢀ
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chelatingꢀamino groups lie in channels enhancing the CO and RhB
2
adsorptions. RhBꢀMO and RhBꢀCV separations can be successfully
conducted and the results demonstrate well enough. In comparison (9) (a) H. X. Deng, S. Grunder, K. E. Cordova, C. Valente, H. Furukawa, M.
with other crystalline porous MOFs, our LnMOFs catalyze the
aldehydes and ketones with higher yields and TOFs, which are
responsible for the strong Lewis acid of Ln(III) ions after activation.
Hmadeh, F. Gándara, A. C. Whalley, Z. Liu, S. Asahina, H. Kazumori,
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Acknowledgements
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This work was partly supported by National Natural Science
Foundation of China (21171075/B010303, 21103073/B030201),
innovation project for graduate student research of Jiangsu Province
Huang, T. W. Tseng, Y. S. Wen, G. H. Lee, S. M. Peng, and Lu, K. L.
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Graphical Abstract
The chelating-amine groups lie in channels enhance CO
LnMOFs also show good catalytic activities.
2
and dyes adsorptions. The

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