A Bifunctional Europium-Organic Framework with Chemical Fixation of CO2 and Luminescent Detection of Al3+

Article abstract of DOI:10.1021/acs.inorgchem.6b01407

A novel three-dimensional lanthanide-organic framework {[Eu(BTB)(phen)]·4.5DMF·2H₂O}_n (1) has been synthesized. Structural characterization suggests that framework 1 possesses one-dimensional channels with potential pore volume, and the large channels in the framework can capture CO₂. Interestingly, investigations on the cycloaddition reaction of CO₂ and epoxides reveal that compound 1 can be considered as an efficient catalyst for CO₂ fixation with epoxides under 1 atm pressure. Importantly, 1 can be reused at least five times without any obvious loss in catalytic activity. Furthermore, the luminescent explorations of 1 reveal that 1 can act as a recyclable sensor of Al³⁺, and the corresponding detection limit can reach 5 × 10^-8 M (1.35 ppb), which is obviously lower than the United States Environmental Protection Agency's recommended level of Al³⁺ in drinking water (200 ppb). These results show that 1 has a level of sensitivity higher than that of other reported MOF-based sensors of Al³⁺.

Full text of DOI:10.1021/acs.inorgchem.6b01407

Article
pubs.acs.org/IC
A Bifunctional Europium−Organic Framework with Chemical
Fixation of CO2 and Luminescent Detection of Al3+
Hang Xu,†,‡ Bin Zhai,§ Chun-Shuai Cao,†,‡ and Bin Zhao*,†,‡
†Department of Chemistry, Nankai University, Tianjin 300071, China
‡Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071, China
§College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000, China
S
* Supporting Information
ABSTRACT: A novel three-dimensional lanthanide−organic
framework {[Eu(BTB)(phen)]·4.5DMF·2H2O}n (1) has been
synthesized. Structural characterization suggests that frame-
work 1 possesses one-dimensional channels with potential
pore volume, and the large channels in the framework can
capture CO2. Interestingly, investigations on the cycloaddition
reaction of CO2 and epoxides reveal that compound 1 can be
considered as an efficient catalyst for CO2 fixation with
epoxides under 1 atm pressure. Importantly, 1 can be reused at
least five times without any obvious loss in catalytic activity.
Furthermore, the luminescent explorations of 1 reveal that 1
can act as a recyclable sensor of Al3+, and the corresponding
detection limit can reach 5 × 10−8 M (1.35 ppb), which is
obviously lower than the United States Environmental Protection Agency’s recommended level of Al3+ in drinking water (200
ppb). These results show that 1 has a level of sensitivity higher than that of other reported MOF-based sensors of Al3+.
neous catalysts, can be reused to reduce the cost. Therefore, it
is necessary to explore Ln-MOF-based catalysts for chemical
fixation of CO2 with epoxides.
INTRODUCTION
■
As an emerging class of porous materials, lanthanide-supported
metal−organic frameworks (Ln-MOFs) are receiving extensive
attention owing to not only their diversified structures and
topologies1 but also their promising applications in gas storage/
separation,2 optical properties,3 magnetism,4 heterogeneous
catalysis,5 chemical sensing,6−8 etc.9 In these types of
applications, the catalytic reaction for CO2 conversion is
gradually becoming a hot issue as the excess emission of CO2
causes a series of environmental problems such as global
warming and ocean acidification.10 Until now, quite a lot of
effort has been focused on converting CO2 into high value
added products,11 and the coupling reaction of CO2 with
epoxides to provide cyclic carbonates is considered as one of
the best strategies for CO2 conversion due to not only its
excellent reactivity and high atom efficiency but also the
significant and extensive applications of cyclic carbonates as
aprotic polar solvents, precursors for affording polycarbonates,
and chemical intermediates in organic synthesis.12 In terms of
cycloaddition reaction with CO2 and epoxides, many catalysts
have been developed and exhibit fine activity, but comparably,
only a few MOF-based catalysts have been reported,12 and
porous Ln-MOFs are considered as ideal candidates for CO2
conversion with epoxides for following reasons: (1) porous Ln-
MOFs can significantly adsorb CO2, (2) large-sized porosity in
Ln-MOFs may enrich epoxides to increase the substrate
concentration, (3) Ln3+ ions act as Lewis acidic sites to enhance
catalytic activities,5e−g and (4) stable Ln-MOFs, as heteroge-
On the other hand, as luminescent materials, many Ln-
MOFs as chemical sensors have been investigated, and those
chemical sensors mainly focused on the detection of Cu2+, Fe3+,
Zn2+, F−, PO43−, explosives, acetone, etc.6−8 However, in these
studies, just three examples are associated with the detection of
Al3+,8 which is the most abundant metallic element in the
earth’s crust and can be accumulated in human body to damage
nervous system, leading to Alzheimer’s disease and Parkinson’s
syndrome, and other issues.8 Nowadays, with the casual
discarding of aluminum products and the erosion of acid rain,
the environment is directly exposed to more and more Al3+,
which poses a serious threat to human health. Therefore,
effective detection of Al3+ is urgent to prevent Al3+ from
harming human health, and it is necessary to develop new Ln-
MOFs as recyclable luminescent sensors to detect Al3+ with
high sensitivity.
In this contribution, a Ln-MOF {[Eu(BTB)(phen)]·
4.5DMF·2H2O}n (1) was obtained based on a high C3
symmetric ligand, 1,3,5-benzenetribenzoate (H3BTB), and
framework 1 exhibits one-dimensional (1D) open channels
with potential pore volume of 56.1% and high thermal stability.
In terms of CO2 conversion, compound 1 can effective catalyze
Received: June 10, 2016
© XXXX American Chemical Society
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the cycloaddition reaction with CO2 and epoxides under 1 atm
pressure of CO2, and investigations of the recycling perform-
ance suggest that 1 as catalyst can be reused at least five times
without any obvious loss in catalytic activity. On the other
hand, luminescent investigations of compound 1 reveal that 1
can act as a recyclable luminescent sensor for detecting Al3+
with 5 × 10−8 M (1.35 ppb), which is far lower than the United
States Environmental Protection Agency’s recommended level
of Al3+ in drinking water (200 ppb) and represents the lowest
detection limit among MOF-based sensors so far.8
volume of 1 is as high as 56.1%, calculated by the PLATON
program. From the topological point of view, each dinuclear
[Eu2] unit is coordinated by six BTB3− anions; thus, the [Eu2]
unit can be considered as a 6-connected node. Each BTB3−
anion is bridging three [Eu2] units; thus, it can be regarded as a
3-connected node. According to this simplification, the
structure of compound 1 can be simplified as a (3,6)-connected
3D framework with topology symbol of flu-3 (Figure 1d).13
Powder X-ray Diffraction Analyses (PXRD) and
Thermogravimetric Analyses (TGA). The powder XRD
diffraction (PXRD) of compound 1 is recorded in Figure S1,
and the synthesized PXRD of 1 is almost identical to the
simulated one, suggesting that the purity of compound 1 is
high.
To study the stability of compound 1, thermogravimetric
analyses (TGA) were measured under N2 atmosphere. As
shown in Figure S2, from room temperature to 165 °C, a
weight loss of 32.12% can be observed, which corresponds to
the loss of H2O and DMF molecules (calcd: 32.21%).
Subsequently, TGA curves show a weight loss of 15.93%
between 265 and 421 °C, corresponding to the loss of
coordinated phen molecules (calcd: 15.91%). Then, compound
1 starts to decompose above 521 °C. The high thermostability
of structures is possibly attributed to the robust BTB ligands.
Catalytic Properties. In our initial investigations on the
reaction of CO2 with epoxides, styrene oxide (1a) was selected
as a model substrate to explore the optimized reaction
conditions, and the corresponding results are recorded in
Table 1. First, the reaction was conducted using 3.5 mol %
EXPERIMENTAL SECTION
■
Preparation of {[Eu(BTB)(phen)]·4.5DMF·2H2O}n (1). A mixture
of Eu(NO3)3·6H2O (0.1 mmol, 44.6 mg), H3BTB (0.1 mmol, 43.8
mg), and 1,10-phen (0.2 mmol, 36.0 mg) in DMF (4 mL) and H2O (2
mL) was sealed in a 15 mL Teflon-lined stainless steel autoclave. The
autoclave was heated at 100 °C for 3 days under autogenous pressure
and then cooled to room temperature at a rate of 2 °C/h under
ambient conditions. The crystals were obtained and washed with
DMF. Yield: 85%, based on Eu(NO3)3·6H2O. Elemental analysis (%)
Calcd for compound 1: C 55.68, H 5.17, N 8.04. Found: C 55.53, H
5.20, N 7.99.
RESULTS AND DISCUSSION
■
Structure. Single crystal X-ray diffraction analysis revealed
that compound 1 crystallizes in the monoclinic system with
space group C2/c, and the asymmetric unit contains an eight
coordinated Eu3+ ion into square antiprism geometry (Figure
1b), which is achieved by six carboxylic oxygen atoms and two
nitrogen atoms from 1,10-phenanthroline. Two crystallo-
graphically equivalent Eu3+ ions are bridged by four carboxyl
groups into a binuclear unit as secondary unit buildings
(SUBs), which are further linked by BTB3− into a three-
dimensional (3D) framework exhibiting atypical 1D open
channels (Figure 1c). Additionally, the total potential pore
Table 1. Cycloaddition Reaction of CO2 with Styrene Oxide
a
under Various Conditions
b
entry
catalyst 1 (mol %)
TBAB (mol %)
T (°C)
yield (%)
1
2
3
4
5
6
7
3.5
3.5
3.5
3.5
3.5
0
2.5
2.5
2.5
5
60
70
80
60
70
70
70
36.38
57.13
68.25
70.75
>99
5
5
38.61
<1
3.5
0
a
Reaction conditions: styrene oxide (1a, 240.3 mg, 2.0 mmol),
solvent-free, catalyst 1, CO2 (0.1 MPa), 12 h, 40 mg catalyst 1 loading
b
(based on metal center, about 3.5 mol %). Total yield of 1b
1
determined by H NMR spectroscopy using 1,3,5-trimethoxybenzene
as an internal standard.
compound 1 and 2.5 mol % cocatalyst (tetrabutylammonium
bromide, TBAB) under solvent-free conditions and 0.1 MPa
CO2, and the corresponding cyclic carbonate was obtained in
36.38% yield at 60 °C (entry 1, Table 1). Then, the yield
gradually enhanced as the temperature was increased (entries 2
and 3), but the yield was still no more than 70% until 80 °C.
Therefore, to avoid higher temperatures consuming too much
energy, cocatalyst TBAB was added to 5 mol % in this reaction.
As shown in entries 4 and 5, the yield can reach 70.75% at 60
°C, and over 99% yield can be obtained at 70 °C. Comparably,
Figure 1. (a) Coordinated environments of BTB3−. (b) Coordinated
environments of Eu3+. (c) 3D framework of 1 along the c direction.
(d) Simplified flu-3 topology network of 1.
B
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only 38.61% yield was obtained under 5% TBAB without
compound 1, suggesting that 1 plays an important role in this
reaction. Therefore, the optimized reaction conditions should
be loaded 3.5 mol % catalyst 1 and 5 mol % TBAB at 70 °C.
Importantly, cycloaddition reactions under atmospheric
pressure of CO2 to afford cyclic carbonates is still rarely
reported.12a
To further explore the catalytic generality of compound 1,
several typical epoxides substrates were examined for this
cycloaddition reaction. Under the optimized conditions, all of
the corresponding cyclic carbonates were obtained in excellent
yields (68.66−99%, Table 2). The results clearly show that
compound 1 possesses the capacity of catalyzing a cyclo-
addition reaction with extensive epoxides.
Table 2. Synthesis of Various Cyclic Carbonates from CO2
a
and Epoxides with Catalyst 1
Figure 2. Recycle tests with 1 for the cycloaddition reaction of CO2
with styrene oxide.
leakage from the robust framework occurred, resulting in high
recoverable performance.
According to reported work,12a a possible mechanism for the
cycloaddition reaction with CO2 and epoxides was proposed.
First, framework 1 with 1D channels can enrich CO2 and the
substrate. Second, as shown in Figure S5, the coupling reaction
starts to bind with the Lewis acidic Eu3+ site through the
oxygen atom of epoxide, which activates an epoxy ring. Finally,
the nucleophilic Br− attacks the less-hindered carbon atom to
open the epoxy ring. In the next step, the interaction between
CO2 and the oxygen anion of the opened epoxy ring occurs to
form an alkylcarbonate salt, and the corresponding cyclic
carbonate is obtained through intramolecular ring closure.
Thus, the corresponding cyclic carbonate is successfully
obtained in a high yield.
Luminescent Behaviors and Sensing Properties.
Under excitation at 300 nm, five characteristic emission peaks
of compound 1 appear at 535, 591, 614, 655, and 697 nm
(Figure S6),7c,8c which are attributed to D1 → 7F1 and 5D0 →
5
7FJ (J = 1, 2, 3, or 4) transitions of Eu3+ ions, respectively. On
the basis of the transition rules of Eu3+ ions, when Eu3+ ions
locate at an inversion center, the magnetic dipole transitions
(5D0 → 7F1) are regnant, emitting orange light; when Eu3+ ions
locate at a noninversion center, the electric dipole transitions
(5D0 →7F2) are dominant, emitting red light. As shown in
Figure S6, the emission intensities at 591 nm are weaker than
those at D0 → F2 transitions (614 nm), which is indicative
that Eu3+ ions locate at noninversion center sites, agreeing with
the structural analyses.7c,8c
a
Reaction conditions: epoxides (2.0 mmol), solvent-free, 40 mg
5
7
catalyst 1 loading (based on metal center, about 3.5 mol %), TBAB
(32.4 mg, 0.1 mmol, 5 mol %), CO2 (0.1 MPa), 70 °C, 12 h.
b
1
Determined by H NMR spectroscopy using 1,3,5-trimethoxyben-
zene as an internal standard.
Generally, luminescent MOF-supported materials may be
sensitive to some guest cations. Hence, the luminescent
investigations of 1 were further carried out as follows: 4 mg
samples of 1 were dispersed in 3.8 mL of ethanol solution into
suspension by the ultrasound method for 40 min, and then 0.2
mL of an M(NO3)x ethanol solution (1 × 10−2 M) (M = Al3+,
Li+, Na+, K+, Cs+, Mg2+, Ca2+, Sr2+, Ba2+, Ag+, Mn2+, Cr3+, Fe2+,
Co2+, Ni2+, Zn2+, Cu2+, or Fe3+, respectively) were slowly added
into the above solutions into 1-M suspensions (5 × 10−4 M).
Under the perturbation of the above cations, the luminescence
intensities of resultant suspensions were recorded by a
fluorescence spectrophotometer, and only regnant emission
transitions (614 nm) were shown in Figure 3. Obviously, Al3+
exhibits the most significant quenching effect on the emission
As a stable heterogeneous catalyst, compound 1 can be
simply separated from the reaction mixture through centrifu-
gation and filtration. Hence, the recycle performance of 1 as a
catalyst was explored, and the corresponding results are
recorded in Figure 2. To our excitement, excellent catalytic
activity of 1 still could be observed after being employed five
times, indicative that 1 can be reused at least five times. Then,
the PXRD patterns and inductively coupled plasma (ICP)
results were further obtained (Figure S4 and Table S2), and the
results remain consistent with the simulated results of 1,
revealing that used 1 is still stable and only trace amounts of
C
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5
7
Figure 3. Luminescence intensity of the D0 → F2 transitions (614 nm) of 1-M in 5 × 10−4 M different cations.
of 1, while other cations have a negligible effect on the emission
or decrease the luminescent intensity. However, the lumines-
cent change between Al3+ and other quenchable cations can be
clearly observed as the much stronger quenching effect of Al3+
on the emission. Furthermore, mixed cations were also tested
for luminescence (Figure S7), and the emission was still
quenched after mixed cations were added, indicating that the
quenching effect of Al3+ on the emission is not significantly
influenced by other introduced cations. The different behavior
between Al3+ and other cations on the emission are clearly
observed, revealing that 1 is a promising luminescent sensor of
Al3+.
reported MOF-based sensors of Al3+ (Table S3). To further
explore the quenching effect of Al3+ on the emission, a
luminescence intensity vs Al3+ concentration chart was made
(Figure 4), which can be linearly fitted by the equation I0/I =
1.04 + Ksv[Al3+] (I0 and I represent the luminescent intensity of
1 before and after dropping Al3+, respectively; [Al3+] represents
the concentration of Al3+, and Ksv represents quenching rate
constant), which is close to the Stern−Volmer equation I0/I =
1 + Ksv[Al3+]. The Ksv value was calculated to be 1.59 × 104 L/
mol, revealing that Al3+ displays a high quenching efficiency on
the emission of compound 1.
Most luminescent sensors are not widely used in practical
applications because they are costly and can be difficult to
recycle. Hence, fast and simple recycling methods are important
research topics for luminescent probes. In view of recyclable
performance, we washed the used 1 with ethanol several times,
and recycled samples were tested using luminescence and
PXRD. As shown in Figures 5 and S4, the resultant
luminescence and PXRD results are still in accord with the
original results after being recycled five times, which is
indicative that compound 1 as an Al3+ sensor can be reused
at least five times without an obvious loss in luminescence
response. Additionally, the corresponding ICP reveals that
recycled samples do not contain Al3+ (Table S2), indicating that
recovered luminescence is attributed to removal of Al3+ on the
surface.
In addition, to study the detection limit of the Al3+ sensor, we
prepared a series of ethanol suspensions of 1-Al3+. As shown in
Figure 4, the luminescence intensity of 1 gradually decreases as
Next, the possible mechanism is discussed. Generally, there
are the following reasons to quench the emission: first, collapse
of the framework is a common way to quench the
luminescence. For compound 1, the well-matched PXRD
results (Figure S8) reveal that the framework is still intact after
the introduction of Al3+, suggesting that luminescence
quenching is not caused by collapse of the framework. Second,
the BTB3− ligand in compound 1 can efficiently absorb energy
from the UV spectrum and transfer energy to Eu3+, resulting in
the characteristic luminescence spectrum of compound 1.
Comparably, Al3+ shows negligible photon-absorption at 300
nm (excitation wavelength), suggesting that the introduction of
Al3+ ions have no obvious effect on the energy absorption of the
ligand to further influence the emission. Third, the collision
interaction between structure 1 and free Al3+ ions may consume
the energy and reduce the luminescent intensity.14 In addition,
the concentration of Al3+ and the luminescent intensity can be
Figure 4. Emission spectra of 1 with different concentrations of Al3+
ions and the luminescence intensity vs the Al3+ concentration plot.
Al3+ increases, and the decreased luminescence still can be
clearly observed under the concentration of Al3+ at about 5 ×
10−8 M, which is indicative that the detection limit of this Al3+
sensor can reach 5 × 10−8 M (1.35 ppb), which is lower than
the United States Environmental Protection Agency’s recom-
mended level of Al3+ in drinking water (200 ppb). Therefore, 1
displays the lowest detection limit compared to those of the
D
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Figure 5. Emission intensity of 1 after being recycled five times (dominant emission under the excitation wavelength of 300 nm).
fitted well into the Stern−Volmer equation, indicating that the
quenching process can be attributed to the dynamic process
mechanism (namely, the collision interaction). Thus, a possible
quenching mechanism is proposed as follows: the introduction
of Al3+ may consume the energy through the collision
interaction and further decrease the energy transfer from
BTB to Eu3+ centers, resulting in the luminescence quenching
of compound 1.
ACKNOWLEDGMENTS
■
This work was supported by the 973 Program (Grant
2012CB821702), NSFC (Grants 21571107 and 21421001),
SFC of Tianjin (Grant 15JCZDJC37700), the 111 Project
(Grant B12015) and the MOE Innovation Team (Grants
IRT13022 and IRT-13R30) of China.
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■
In summary, a novel 3D lanthanide−organic framework
{[Eu(BTB)(phen)]·4.5DMF·2H2O}n was obtained based on
a carboxylate ligand (H3BTB) with C3 symmetry. The
characterization of structures showed that compound 1 has
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ASSOCIATED CONTENT
■
S
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.6b01407.
PXRD, TGA, ICP, and luminescent spectra (PDF)
Crystallographic information for 1 (CIF)
Additional crystallographic information for 1, CCDC:
1414991 (PDF)
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: zhaobin@nankai.edu.cn; Fax: (+86)-22-23502458.
Notes
The authors declare no competing financial interest.
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DOI: 10.1021/acs.inorgchem.6b01407
Inorg. Chem. XXXX, XXX, XXX−XXX