A new Tb(III)-functionalized layer-like Cd MOF as luminescent probe for high-selectively sensing of Cr3+

Article abstract of DOI:10.1039/c7ce01795b

A new layer-like metal-organic framework {[Cd₄(NDIC)₄·5DMF·H₂O]DMF}_n (NDIC = 5-(5-norbonene-2,3-dicarboximide) isophthalic acid) was synthesized by solvothermal method. It was used as a parent framework to encapsulate Tb³⁺ cations in Cd-MOF. The obtained composite Tb(3+)@Cd-MOF exhibited excellent luminescence and produced a remarkable quenching effect in the luminescence emission of Tb³⁺ upon the introduction of Cr³⁺. Subsequently, Tb(3+)@Cd-MOF was developed as a highly selective and sensitive probe for detection of Cr³⁺. In particular, the luminescence probe of Cr³⁺ had a low detection limit (7.5 × 10^-8 M), a broad linear range (1 × 10^-7-5 × 10^-6 M). A paper strip coated with Tb(3+)@Cd-MOF was also shown to be highly selective to Cr³⁺ under the irradiation of 254 nm UV light of by the naked eyes. This is the first example for detecting metal ions based on a lanthanide functionalized new metal-organic framework (MOF).

Full text of DOI:10.1039/c7ce01795b

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Tb(III)-Functionalized a new layer-like Cd MOF as luminescent probe for highly selectively
Sensing Cr3+
Wang Yi 2a, Yang Huan 1a*, Gang Cheng2 , Yunying Wu1, Shaomin Lin1
Received 00th January 20xx,
Accepted 00th January 20xx
A
new layer-like metal-organic framework {[Cd4(NDIC)4 • 5DMF • H2O]DMF}n (NDIC = 5-(5-Norbonene-2,3-
DOI: 10.1039/x0xx00000x
dicarboximide)Isophthalic acid) has been synthesized with solvothermal method. It was used as a parent framework to
sensitize via encapsulating Tb3+ cations in Cd-MOF. The obtained composite Tb(3+)@Cd-MOF shows excellent
luminescence which performs a remarkable quenching effect in the luminescence emission of Tb3+ upon the introduction
of Cr3+. Subsequently, Tb(3+)@Cd-MOF was developed as a highly selective and sensitive probe for detection of Cr3+. Most
importantly, the luminescence probe of Cr3+ shows a low detection limit (7.5×10-8M), a broad linear range (1×10-7-×5×10-6
M) . A paper strip coated with Tb(3+)@Cd-MOF was also shown to be highly selective for Cr3+ under the irradiation of UV
light of 254 nm by the naked eyes. This is first example for detecting metal ions based on a lanthanide functionalized a
new metal-organic framework (MOF).
www.rsc.org/
Fortunately, the incorporation of lanthanide ions within MOF
Introduction
using postsynthetic modification method should be expected
to perform the similar luminescent sensing function of
lanthanide MOFs.31,32
Metal−organic frameworks (MOFs) have emerged a crystalline
hybrid materials builting from an assembly of metal ions and
organic linkers, have been extensively studied in a variety of
applications in the past few years, such as catalysis.1,2
magnetism,3,4 gas storage and separation,5,6 energy storge.7,8,9
Among the large number of MOFs, LnMOFs have been
receiving increasing attention due to their unique
luminescence properties such as high luminescence quantum
yield, long-lived emission, large Stokes shifts, and sharp line
emissions.10-14 The combination of these intrinsic luminescent
features together with the inherent porosity of MOFs provides
an effective platform for chemical sensing.15,16 In the past
decade, studies on luminescent Ln-MOFs for sensing metal
ions,17,18 anions,19,20 small molecules21-25 and temperature26-28
Cr3+ and Cr3+-containing proteins is identified as an
essential trace element of the human body for maintaining
proper functioning of biological processes. Deficient or
excessive intake may cause the loss of some physiological
functions and diseases including ovulatory infertility.33-36
Recent scientific studies show that low concentrations of Cr3+
could cause alterations in cell signaling, while high
concentrations may lead to genotoxic DNA lesions, sewage
from the industrial waste water forms one of the major
sources of Cr3+. Most chromium reacts with the hides during
the industrial process, while the rest chromium remains in the
solid and waste water, and these are considered to be major
sources of chromium environment pollutant. Therefore, it is
necessary to detect Cr3+ at trace levels. Some detection
methods for chromium ions have been developed for Cr3+,
such as inductively coupled plasma massspectroscopy (ICP-MS),
have been reported. However, it also remains
a great
challenge to design and synthesis of the desired Ln-MOFs
through direct synthesis due to the high coordination number
29,30
and flexible coordination mode of lanthanide ions.
atomic adsorption spectrometry (AFS), and synchrotron
37-39
radiation X-rayspectrometry.
However, disadvantages
such as time-consuming, sophisticated instruments and
complicated preparation process have restricted the
development of the techniques. Therefore, it is necessary to
develop simple, rapid, sensitive and cost-effective approaches
for this purpose. The wide variety of luminescent LnMOFs and
their inherent synthetic versatility seems to make them ideal
for metal ions recognition.
In our context, a new layer like Cd-MOF{[Cd4(NDIC)4•5DMF•
H2O]DMF}n was designed and synthesized based on 5-(5-
Norbonene-2,3-dicarboximide)Isophthalic acid (NDIC) ligand
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through a facile solvothermal approach. Subsequently, novel
luminescence material of lanthanide-doped Cd-MOF was
obtained through encapsulating Tb3+ cations in Cd-MOF. What
is more, Tb(3+)@Cd-MOF was developed as highly selective
and sensitive luminescence probe targeting Cr3+ ions in ethanol
solution. The possible sensing mechanisms toward to Cr3+
were also discussed in detail. As expected, Tb(3+)@Cd-MOF is
suitable for becoming one luminescence probe with high
selectivity and sensitivity.
performed with a Netzsch sta 449f3 at a heating rate of 5
℃
min-1. Luminescence spectra were recorded on Horiba ihr320
fluorescence spectrophotometer at room temperature. The
amounts of metal ions in Tb(3+)@Cd-MOF were measured by
inductively coupled plasma mass spectrometry (ICP-MS, Icap
Qc, Thermofisher, Germany)
Synthesis of 5-(5-Norbonene-2,3-dicarboximide)Isophthalic acid
(NDIC)
0.1 mol (16.4g) Norbonenedianhydrideand and 0.1mol (18.1g)
5-Aminoisophthalic acid were dissolved 200 mL acetic acid and
allowed to react under reflux for 2 h, then slowly cooling to
room temperature, the precipitate was filtered off and washed
with acetic acid and distilled water, the product was dried
under 100℃. The synthesis method is performed in FigS1
Synthesis of {[Cd4(NDIC)4•5DMF•H2O]DMF}n (Cd-MOF)
5-(5-Norbonene-2,3-dicarboximide) Isophthalic acid (NDIC)
0.0165g (0.05mmol) and 100 uL 1mol/L Cd(NO3)2 dissolved in 3
mL DMF. The mixture was sealed in 15 mL Teflon -lined
stainless autoclave. The autoclave was heated at 80
℃for 3
days then slowly cooling to room temperature. The resulting
colorless prism crystal were obtained in 65% yield based on
NDIC .
Preparation of Tb(3+)@Cd-MOF
Cd-MOF (100 mg) is immersed in ethanol solution of
Scheme 1. Selected organic ligands in the selfꢀassembly of CdꢀMOF.
Tb(NO3)3
·6H2O (10 mL, 2 mmol) for 2 days. After separating by
centrifugation and washing with ethanol to remove redundant
Tb3+, the samples was dried at 60
EXPERIMENTAL SECTION
°C for 6 h.
Luminescence Sensing Experiment
Materials
The as-prepared Tb(3+)@Cd-MOF (2 mg) was dispersed into in
3
ethanolic solution of MNO3 (4 mL, 1
×
10− molL-1).(Mn+ =K+,
All the reagents and solvents were purchased from different
companies, and directly used as received without further
purication.
Mg2+, Pb2+, Zn2+, Ag+, Cd2+, Co2+, Cr3+) to form a suspension at
room temperature. The mixtures were used for luminescence
measurements. The luminescence data were collected at the
room temperature.
Single crystal X-ray crystallography
A block-like single crystal of Cd-MOF was sealed in a capillary
tube under an optical microscope with some mother liquor
inside in order to prevent desolvation of the sample. Single
crystal X-ray diffraction data was collected on a Rigaku Oxford
CCD diffractometer at 293 K using graphite monochromated
Mo Ka radiation (λ=0.71073 A). All absorption corrections were
performed by using the multiscan program, The structure
were analyzed by direct methods and refined by full-matrix
least squares on F^2 with the SHELXTL-97 program. Non-
hydrogen atoms were refined with anisotropic displacement
parameters during the final cycles. Crystal data and other
information on the structure determination are performed in
Table S1.
Results and discussion
3.1 Description of crystal structure
Cd-L (1) crystallizes in the chiral space group P21, and the
asymmetric unit consist of three parts, one coordinated
DMF(part 1), four Cd atoms and four ligands constitute part 2
and part 3(Fig.1a). The Cd2+ adopt two similar coordination
modes, the MOF form one enantiomer of a mesomeric chiral
product after symmetric growth (Fig 1d). As shown in Fig 1b, in
part 2, the Cd(1) atom displays a distorted octahedron
geometry,the Cd(1) atom is six-coordinated by two pairs of
chelating carboxylate oxygen atoms from two different L2-
anion [Cd1-O1=2.356(1)Å,Cd1-O2=2.311(5)Å,Cd1-O5=2.433(8)
Å, Cd1-O6=2.335(2)Å] and two carboxylate oxygen atoms
from two ligands[Cd1-O3=2.196(6)Å,Cd1-O7a=2.216(2)Å].
Different from Cd(1), the six-coordinated Cd(2) atom is bound
to O by three carboxylate oxygen atoms from three ligands
IR absorption spectra of the MOF and HL ligand in KBr pellet
were carried out in the range of 400–
4000 cm-1 on a IR
Affinity-1 FT-IR spectrometer. Powder X-ray diffraction (PXRD)
patterns were collected using a Rigaku Miniflex 600 X-ray
diffractometer using Cu Ka radiation (1.5418°A) at room
temperature. Thermogravimetric analysis (TGA) was
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O6=2.324(4)Å, Cd2 O8a=2.246(5)Å],
ARTICLE
is well matched with the simulated PXRD pattern based on
single crystal X-ray diffraction data, which indicates a high
purity of the Cd-MOF(CCDC: 1555655). The PXRD pattern of
the synthesized Tb(3+)@Cd-MOF is in good agreement with
the simulated Cd-MOF. The result shows that the preparation
of the Tb(3+)@Cd-MOF is successful and the Cd-MOF could
retain their crystallinity.
[Cd2
−
O4=2.242(6)Å, Cd2
−
−
two oxygen atoms from two coordinated DMF molecules[Cd2-
O13=2.235(3)Å,Cd2-O14=2.280(5)Å]and one oxygen atom
from one coordinated water molecule[Cd2-O15=2.338(6)Å]. In
part 3, the coordination mode is the same except O15 from
coordinated DMF. As shown in Fig.3c, HL2- ligands adopted
two kinds of coordination modes to connect to Cd2+ ions,
giving a 1D polymeric chain. The linkers also bridge the Cd2+
ions to produce 2D layers (Fig.1d and Fig S2 in supporting
information).The MOF was chosen as host to encapsulate Tb3+
cations by one uncoordinated carbonyl group in its pores.
The thermal stability of Cd-MOF was studied as shown in
Fig. 2(b). The first weight loss below 100°C is ascribed to the
release of the surface water molecules. The second weight loss
between 120 °C and 150 °C corresponds to the loss of
coordinated DMF molecule . The third weight loss from 350 °C
to 400 °C corresponds to the loss of ligand. Afterwards, The
final plateau from 500 °C corresponds to cadmium oxide. The
Tb(3+)@Cd-MOF was also monitored by TG analysis from 0 to
600 °C (Figure 1b). The TGA of Tb(3+)@Cd-MOF exhibits three
events of weight losses and shows good thermal stability
(b)
(a)
similar to Cd-MOF. The first step occurs in the range of 200
−
250 °C, which assigns to the partial decomposition of the
linker. The second weight loss from 350 °C to 400 °C
corresponds to the decomposition of the remaining organic
ligand. The final plateau from 500 °C corresponds to oxide.
As shown in Figure 3,The absorption peak at 1705 cm-1 is
assigned to the υc=o vibrations of free carboxyl grafted on the
(c)
ligand
,
the absorption peak at 1564 cm-1 belongs to
coordinated υc=o in Cd-MOF. Subsequently, Cd-MOF was
immersed in ethanol solution of Tb(NO3)3 for Tb3+-
encapsulation by binding to the uncoordinated-COOH of Cd-
MOF. the absorption band of Cd-MOF show a significant red-
shift (about 13 nm) after connecting to Tb3+ , illustrating the
interactions between the Tb3+ and free-COOH of Cd-MOF.
40After introducing Tb3+ into the Cd-MOF, the compounds not
affect the crystalline integrity, as shown by the PXRD patterns
(Fig. 2a).
(d)
(a)
Figure 1 (a) Asymmetric unit of CdꢀMOF (b) Coordination mode of metal ions
(b)
(c) Two Coordination modes of ligand (d) Twoꢀdimensional structure of Cdꢀ
MOF
3.2 Purity and thermal stability
In order to explore application of Cd-MOF material, the purity
and thermal stability of the material were investigated. Figure
2(a) shows the PXRD patterns of the Cd-MOF and Tb(3+)@Cd-
MOF from 5° to 50°, the PXRD pattern of as prepared Cd-MOF
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M(NO3)x (M = K+, Mg2+, Pb2+, Zn2+, Ag+, Cd2+, Co2+, Cr3+
respectively). The luminescent spectrum were recorded in
Figure 5(a). The results revealed that various metal ions display
markedly different effects on the luminescence of Tb3+ ions.
For example, as shown in Figure 5(b), the luminescence
intensity at 546 nm is decreased when Mg2+, Pb2+, Zn2+, Ag+,
Cd2+, Co2+ are introduced. In the contrast, the luminescence
intensity increased when K+ is introduced . The addition of Cr3+
induced the noticeable quench of luminescence intensity of
Tb3+, which contributes to probe Tb(3+)@Cd-MOF to be useful
for selectively sensing Cr3+.
(a)
Fig. 2 (a) Powder Xꢀray diffraction patterns of Tb(3+)@CdꢀMOF. and single Xꢀ
ray simulated CdꢀMOF. (b) TGA of CdꢀMOF and Tb(3+)@CdꢀMOF.
(b)
Fig. 3 IR spectra of ligand,CdꢀMOF and Tb(3+)@CdꢀMOF.
3.3 Luminescence Properties of Tb(3+)@Cd-MOF
As expected, after postsynthetic functionalization of Tb3+, the
emission spectrum of the product exhibits characteristic
emission of Tb3+. The sharp lines centered at 489, 545, 592 and
612 nm can be ascribed to 5D4
→ −
7FJ (J = 3 6) transitions of Tb3+.
Under UV-light irradiation, Tb(3+)@Cd-MOF shows strong
green luminescence which can be readily observed by naked
eye, indicating the antenna effect occurs.
Fig. 5 (a) Diagrams of the 5D4ꢀ7F5 transition intensities of the Tb(3+)@CdꢀMOF.
at 546 nm in various metal ions .(b) Emission spectra of the Tb(3+)@CdꢀMOF.
after being immersed in metal ions at room temperature (λex= 303 nm).
To further prove that the fluorescence quenching by Cr3+,
concentration-dependent studies in the luminescence
intensities of Tb(3+)@Cd-MOF when Cr3+ ions were carried out.
However, the PL intensity for Cr3+-induced samples are quite
different for the Tb(3+)@Cd-MOF. As shown in Figure 6a, the
luminescence intensity of the Tb(3+)@Cd-MOF decreases with
the increase of Cr3+ concentration from 1×10-7 to 5×10-6 M.
The linear correlation coefficient (R) in the Ksv curse of
Tb(3+)@Cd-MOF with Cr3+ is 0.9939, the relationship between
the luminescence intensity of Tb(3+)@Cd-MOF and the
Fig. 4 The excitation (dashed) and emission (solid) spectra of the Tb(3+)@Cdꢀ
MOF
concentration of Cr3+ is well fitted by the Stern
–Volmer
equation:30
In light of the excellent luminescence of Tb(3+)@Cd-MOF,
we examine the potential application of Tb(3+)@Cd-MOF for
detecting metal ions. The as-prepared powder of Tb(3+)@Cd-
MOF was dispersed in an ethanol solution of 0.001 mol L-1
I0/I = 1 + Ksv[M]
where the values I0 and I are the luminescence intensity of the
Tb(3+)@Cd-MOF before and after addition of Cr3+, respectively,
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[M] is the Cr3+concentration. Ksv is the quenching constant, luminescence is completely quenched, indicating that the
the value is calculated as 1.81
105, which reveals a strong selectivity for Cr3+ is not interfered by the existence of other
quenching effect on the Tb(3+)@Cd-MOF luminescence. The ions.
×
detection limit is about 7.5 ×10-8M
(Δ
S/N=3)41, the result
suggests that Cr3+ also can be detected quantitatively using
Tb(3+)@Cd-MOF.
(a)
Fig.
7
The 5D4ꢀ7F5 transition intensities of the Tb(3+)@CdꢀMOF upon the
addition of different metal ions(1×10ꢀ3 M) (blue) and subsequent addition of
Cr3+(1×10ꢀ3 M) (red) (λex= 303 nm).
To make the detection simple and portable, we fabricated a
luminescence test paper for rapid detection of metal ions.
Hence, the sensing of Cr3+ was carried out. The test paper was
prepared by immersing a filter paper (2. 0
×
1.0 cm2) in the
ethanolic solution of Tb(3+)@Cd-MOF(0.5mg/mL) then drying
it in air for 24h at room temperature. For the detection of Cr3+,
the test paper was immersed in the in ethanolic solution of
metal ions(1×10-3 M, K+, Mg2+, Pb2+, Zn2+, Ag+, Cd2+, Co2+ , Cr3+)
and then dried in the air . In Figure 8, under the irradiation of
UV light of 254 nm, the luminescent colors of the test paper
changed from green to dark green and finally black with the
different metal ions(left to right: K+, Mg2+, Pb2+, Zn2+, Ag+, Cd2+,
Co2+ , Cr3+). Considering the results above, we can distinguish
the colors of different metal ions by our naked eyes.
(b)
Fig. 8 Luminescent response of Tb(3+)@CdꢀMOF coated paper strips to various
metal ions(1×10ꢀ3 M) under UV light (254nm) (left to right: K+, Mg2+, Pb2+, Zn2+
Ag+, Cd2+, Co2+ , Cr3+).
,
3.4 Quenching mechanism
Up to now, the quenching effect on luminescence of MOFs by
metal ions is attributed to three reasons: (1) the interaction
between metal ions and ligands; (2) the collapse of the crystal
structure (3) the ions exchange between central metal ions of
MOFs and the targeted metal ions.41 Herein, the possible
sensing mechanism for the luminescence quenching by the
metal ions has been further studied. The powder XRD was
employed to study on the structural data of the original and
Tb(3+)@Cd-MOF treated with Cr3+. As shown in Figure 9 , the
PXRD of is different from that of Tb(3+)@Cd-MOF, suggesting
that the basic frameworks changed. We speculate that the
remarkable quenching effect of Tb(3+)@Cd-MOF by Cr3+
results from the collapse of the crystal structure.
Fig. 6 (a) Stern–Volmer plots describe the dependency of the luminescent
intensities on the Cr3+ concentration over the range of 5×10ꢀ6ꢀ1×10ꢀ7 M in
ethanol solution. (b) Luminescence emission spectra of Tb(3+)@CdꢀMOF
dispersed in ethanol upon incremental addition of Cr3+ ethanol solution (λex=
303 nm)
The Tb(3+)@Cd-MOF is dispersed in the solution
containing Cr3+ and other metal ions, which include K+, Pb2+,
Zn2+, Ag+, Co2+, respectively. When excited at 303 nm, the
luminescence intensity of the Tb(3+)@Cd-MOF dispersed in
the ethanolic solution of other metal ions (1
×
10-3 M, K+, Pb2+,
Zn2+, Ag+, Co2+, respectively) changes differently compared to
the primitive one, as shown in Figure 7. However, when the
Tb(3+)@Cd-MOF is immersed in the ethanolic solution of
mixed ions (1
measurement of the luminescence intensity shows that the
× ×
10-3 M other metal ions + 1 10-3 M Cr3+), the
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In summary, a new layer like Cd-MOF({[Cd4(NDIC)4 • 5DMF •
H2O]DMF}n based on 5-(5-Norbonene-2,3-
dicarboximide)Isophthalic acid has been prepared which was
used as host to sensitize Tb3+ cations by one uncoordinated
carbonyl group in its pores. The characters of PXRD, TGA and
luminescent measurements demonstrate that this framework
can be explored as potential luminescent material for sensing
of Cr3+. Studying of the luminescence properties reveals that
Tb(3+)@Cd-MOF can develop as
a highly selective and
sensitive probe for detection of Cr3+ (detection limit, 7.5×10-8
M) via luminescence quenching of Tb3+. Under the irradiation
of UV light, the colors of luminescence test paper treated with
different metal ions can be observed changing from green to
dark by naked eyes, respectively. Further study and
speculation of the mechanism illustrate that the collapse of
the crystal structure lead to the quenching effect of
Tb(3+)@Cd-MOF. The present results may provide a facile
route to design luminescence Ln-MOF for sensing and further
studies are currently under way.
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Conflicts of interest
9
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