CN108559097A - 3,3 ', 5,5 '-azoxy benzene tetracarboxylic acid europiums（III）Metal coordinating polymer and its synthetic method and application - Google Patents
3,3 ', 5,5 '-azoxy benzene tetracarboxylic acid europiums（III）Metal coordinating polymer and its synthetic method and application Download PDFInfo
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Abstract
The present invention relates to 3,3', 5,5' azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymers and its synthetic method and applications, belong to fluoroscopic examination field of material technology.The metal coordinating polymer of the present invention is using europium as metal center, with H4ABTC is ligand, and the chemical formula of the coordination polymer is：{[Eu2(HABTC)2(H2O)4]·3H2O}n, molecular formula C32H28N4O25Eu2, the metal coordinating polymer belongs to anorthic system, 1 space groups of P.The metal coordinating polymer of the present invention can be used for fluorescent sensor material, can fast selective 2,4,6 trinitrophenols of identification and heavy metal ion Cr6+, high sensitivity, detection limit is low, and repeatable utilization, to 2,4,6 trinitrophenols and heavy metal ion Cr toxic in water body6+Detection have higher reference value, have a good application prospect.
Description
Technical field
The invention belongs to fluoroscopic examination field of material technology, it is more particularly related to 3,3', 5,5'- oxidations are even
Pyridine tetracarboxylic acid europium (III) metal coordinating polymer and its synthetic method and application.
Background technology
Metal organic coordination polymer, also referred to as metal-organic framework (Metal-Organic Frameworks, referred to as
MOFs) material, it be it is a kind of by metal ion and organoligand coordination formed have periodic arrangement, can be in three-dimensional
Spatially extended new material, and a kind of new function crystalline material for receiving significant attention in recent years.It is organic in MOFs
The arrangement of ligand and metal ion or cluster has apparent directionality, can form different frame pore structures, because of its tool
Have the advantages that structure designability, function particularity, this kind of new material be widely used in catalysis, hydrogen storage, absorption and
The fields such as biological medicine.Especially using the material as the application in terms of fluorescent optical sensor, it is particularly subject to pay close attention to.Compared to tradition
Detecting instrument, fluorescent optical sensor made of metal organic coordination polymer is easy to operate, it is cheap, do not depend on electric appliance and set
It sets, may be implemented real-time online detection, and high sensitivity, fast response time is, it can be achieved that fast selective to guest molecule
Identification and detection.
2,4,6- trinitrophenols are one kind of explosive, and abbreviation TNP, pure substance is at room temperature the crystallization of yellowish, one
Denier contacts human body, can cause contact dermatitis, conjunctivitis and bronchitis, can seriously cause slow poisoning and liver, renal damage.
The heavy metal chromium ion of sexavalence is one of pollution sources common in generally acknowledged water body, generally with CrO4 2-And Cr2O7 2-Form deposit
Toxic heavy metal chromium ion not only results in serious environmental pollution, in addition, toxic heavy metal chromium ion accumulates in vivo
It is tired, serious shadow can be will produce to the health of people by food chain transport into the human body, to cause slow poisoning
It rings, therefore how effectively to detect the heavy metal ion in water body is also that people pay close attention to always and the problem of urgent need to resolve.
Current detection TNP and CrO4 2-The state-of-the-art method of ion has：High performance liquid chromatography, electrochemical methods, atom
Absorption spectrometry etc..But detecting instrument and detection method generally existing are of high cost used in above-mentioned detection method, detection
Process is complicated, the cumbersome drawbacks such as low with detection sensitivity of preparation.Therefore, research and develop it is a kind of it is at low cost, easy to operate,
And it efficiently can quickly detect TNP and CrO4 2-The new method of ion is particularly important.
In conclusion existing carry out Selective recognition and detection using the fluorescent optical sensor based on MOFs to guest molecule
Method most has since the advantages that its is of low cost, easy to carry, easy to operate, selectivity is good, high sensitivity is considered as one kind
The detection method of potentiality.But how to pass through the low gold of simple synthetic method acquisition high selectivity, high sensitivity, detection limit
Belong to the TNP and/or CrO of organic coordination polymer base4 2-The fluorescent optical sensor of ion need further to research and develop.
Invention content
In view of the problems of the existing technology, the purpose of the present invention is to provide 3,3', 5,5'- azoxy benzene tetracarboxylic acids
Europium (III) metal coordinating polymer and its synthetic method and the application in terms of fluorescent optical sensor.
In order to realize first above-mentioned purpose of the present invention, the present invention provides 3,3', 5,5'- azoxy benzene tetracarboxylic acids
Europium (III) metal coordinating polymer, the metal coordinating polymer are using europium as metal center, with 3,3', 5,5'- azoxies
Benzene tetracarboxylic acid H4ABTC is ligand, and the chemical formula of the coordination polymer is：{[Eu2(HABTC)2(H2O)4]·3H2O}n, molecule
Formula is C32H28N4O25Eu2, the metal coordinating polymer belongs to anorthic system, P-1 space groups, and cell parameter is：A=6.8148
(6), (8) b=10.0806, c=13.9136 (10)；α=76.301 (7), β=77.426 (7), γ=84.369 (7) are described
The concrete structure formula of metal coordinating polymer is as shown in formula one：
Further, the ligand H described in above-mentioned technical proposal4The chemical structural formula of ABTC is as shown in formula two：
Further, 3,3' described in above-mentioned technical proposal, 5,5'- azoxy benzene tetracarboxylic acid europium (III) metals are matched
Position polymer is lurid tufted crystal.
Another object of the present invention is to provide 3,3' described above, 5,5'- azoxy benzene tetracarboxylic acid europiums (III) gold
Belong to the synthetic method of coordination polymer, described method includes following steps：
(1) at ambient temperature, by six water europium nitrate (Eu (NO3)3·6H2O) aqueous solution is added to ligand H4The second of ABTC
In nitrile solution, after stirring evenly, then dilute nitric acid solution is added dropwise, mixed solution is made；
(2) by gained mixed solution continue stir 20min after, be transferred in ptfe autoclave and seal, with 1 DEG C/
The rate program of min heats up rises to 130 DEG C, and isothermal reaction 72h under the conditions of 130 DEG C by the reaction temperature of reaction kettle, then with 3
DEG C/rate program of min is cooled to 25 DEG C, the target product of the present invention, i.e., 3,3', 5,5'- oxidation of the present invention is made
Azo benzene tetracarboxylic acid europium (III) metal coordinating polymer.
Further, six water europium nitrates described in above-mentioned technical proposal and ligand H4The molar ratio of ABTC is preferably 1：1.
Further, the deionized water described in above-mentioned technical proposal and the volume ratio of acetonitrile are preferably 2：3.
Further, the concentration of six water europium nitrate aqueous solutions described in above-mentioned technical proposal is preferably 0.01mmol/mL,
The concentration of the salpeter solution is preferably 1molL-1。
Further, the molar ratio of the six water europium nitrates and nitric acid described in above-mentioned technical proposal is preferably 0.02：0.5.
A further purpose of the present invention is to provide 3,3' described above, 5,5'- azoxy benzene tetracarboxylic acid europiums (III) gold
Belong to the application of coordination polymer.
Fluorescent sensor material of the one kind for detecting 2,4,6- trinitrophenols, including described above 3,3', 5,5'-
Azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer.
One kind is for detecting heavy metal ion Cr6+Fluorescent sensor material, including described above 3,3', 5,5'- oxygen
Change azo benzene tetracarboxylic acid europium (III) metal coordinating polymer.
Compared with prior art, the present invention has the advantages that：
(1) 3,3' of the invention, the preparation method letter of 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymers
It is single, easy to implement, yield is high, up to 58.6% (with ligand H4On the basis of ABTC)；
(2) 3,3' produced by the present invention, 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer can be used for
Fluorescent sensor material, can Selective recognition 2 in a relatively short period of time, 4,6- trinitrophenols and heavy metal ion Cr6+, sensitive
Degree is high, and does not need expensive instrument and equipment；
(3) using the 3,3' of the present invention, made of 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer
Fluorescent optical sensor, to 2,4,6- trinitrophenols and heavy metal ion Cr6+High selectivity, high sensitivity, detection limit it is low, and can
Recycling, to 2,4,6- trinitrophenols and heavy metal ion Cr toxic in water body6+Detection have higher reference price
Value, has a good application prospect.
Description of the drawings
Fig. 1 is 3,3' made from the embodiment of the present invention 1,5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordination polymerization
The structure chart of object, wherein：(a) be polymer asymmetric cell and with the relevant symmetry atomic diagram of Eu (III) ion；
(b) (i) in, (ii) are polymer respectively along the 2D double-layer structure figures in b axis, a axis directions；(c) { the 4 of 4,8- connections20·
68}{46}2Topology diagram；(d) passing through π ..., pi accumulation acts on the supramolecular structured compositions of the 3D to be formed；
Fig. 2 (a), (b) are respectively the H that embodiment 1 uses4ABTC ligand stocks and product 3,3', 5,5'- azoxybenzene
The infrared spectrogram of tetracarboxylic acid europium (III) metal coordinating polymer；
Fig. 3 is 3,3' made from the embodiment of the present invention 1,5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordination polymerization
The thermogravimetric collection of illustrative plates of object；
Fig. 4 is that for different types of NACs to 3,3', 5,5'- azoxy benzene tetracarboxylic acid europiums (III) are golden in Application Example 1
Belonging to the fluorescence intensity of coordination polymer influences comparison diagram；
Fig. 5 is that for different types of NACs to 3,3', 5,5'- azoxy benzene tetracarboxylic acid europiums (III) are golden in Application Example 1
Belong to the fluorescent quenching efficiency comparative figure of coordination polymer；
Fig. 6 is for TNP in Application Example 2 to 3,3', 5,5'- azoxy benzene tetracarboxylic acids under other NACs disturbed conditions
The fluorescent quenching effect contrast figure of europium (III) metal coordinating polymer；
Fig. 7 is TNP in Application Example 3 to 3,3', 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordination polymerization
The fluorescence quenching titration figure of object；
Fig. 8 is different types of anion in Application Example 5 to 3,3', 5,5'- azoxy benzene tetracarboxylic acid europiums (III)
The fluorescence intensity of metal coordinating polymer influences comparison diagram；
Fig. 9 is CrO in Application Example 64 2-To 3,3', 5,5'- azoxybenzenes four under other anion disturbed conditions
The fluorescent quenching effect contrast figure of formic acid europium (III) metal coordinating polymer；
Figure 10 is CrO in Application Example 74 2-To 3,3', 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal polycomplexation
Close the fluorescence quenching titration figure of object；
Figure 11 is that three kinds of TNP solution of drinking water/tap water/river water in Application Example 9 are added separately to 3,3', 5,
Fluorescence intensity comparison diagram in 5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer when 4 μ l and 8 μ l；
Figure 12 is three kinds of CrO of drinking water/tap water/river water in Application Example 104 2-Solution is added separately to 3,3',
Fluorescence intensity comparison diagram in 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer when 4 μ l and 8 μ l.
Specific implementation mode
It elaborates below to the case study on implementation of the present invention.The implementation case under the premise of technical solution of the present invention into
Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities
Apply case.
The information for including according to the application, to those skilled in the art can be easily to the essence of the present invention
Really description carries out various changes, without departing from spirit and scope of the appended claims.It should be understood that the scope of the present invention is not
Process, property or component defined by being confined to, because these embodiments and other descriptions are just for the sake of schematic
Illustrate certain aspects of the present disclosure.In fact, this field or those skilled in the relevant art obviously can be to embodiment party of the present invention
The various changes that formula is made all cover within the scope of the appended claims.
For a better understanding of the present invention rather than limit the scope of the invention, expression dosage used in this application,
All numbers of percentage and other numerical value, are understood to " about " be modified with word in all cases.Therefore,
Unless stated otherwise, otherwise digital parameters listed in specification and appended book are all approximations, may
It can be changed according to the difference for the desirable properties for attempting to obtain.Each digital parameters at least should be considered as according to being reported
Effective digital and by it is conventional round up method by obtain.
Embodiment 1
The 3,3' of the present embodiment, 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymers, the metal are matched
Position polymer is using europium as metal center, with 3,3', 5,5'- azoxy benzene tetracarboxylic acid H4ABTC is ligand, the polycomplexation
Close object chemical formula be：{[Eu2(HABTC)2(H2O)4]·3H2O}n, molecular formula C32H28N4O25Eu2, the metal polycomplexation
It closes object and belongs to anorthic system, P-1 space groups, cell parameter is：A=6.8148 (6), b=10.0806 (8), c=13.9136
(10)；α=76.301 (7), β=77.426 (7), γ=84.369 (7).The concrete structure formula of the metal coordinating polymer is such as
Shown in formula one in invention content；Wherein：The ligand H4The chemical structural formula of ABTC is as shown in the formula two in content；This implementation
Example product 3,3' obtained above, 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer are lurid tufted
Crystal.
3,3' described above, 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer is with the following method
It is prepared, described method includes following steps：
(1) at ambient temperature, by (0.02mmol, 0.0089g) six water europium nitrate (Eu (NO3)3·6H2O) it is dissolved in 2mL
In deionized water, the europium nitrate aqueous solution of a concentration of 0.01mmol/mL is made；By the H of (0.02mmol, 0.0072g)4ABTC adds
Enter into 3mL acetonitrile solutions and H is made after mixing4The acetonitrile solution of ABTC；By above-mentioned europium nitrate (Eu (NO3)3·6H2O) water
Solution is added to ligand H4In the acetonitrile solution of ABTC, after stirring evenly, then a concentration of 1molL of 0.5mL are added dropwise-1It is dilute
Mixed solution is made in salpeter solution；
(2) mixed solution obtained by step (1) is continued after stirring 20min, is transferred in ptfe autoclave and seals,
The reaction temperature of reaction kettle is risen into 130 DEG C, and isothermal reaction under the conditions of 130 DEG C with the rate program heating of 1 DEG C/min
72h, then 25 DEG C are cooled to the rate program of 3 DEG C/min, the target product of the obtained present invention, i.e., of the present invention 3,3',
5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer.
Take appropriate 3,3' obtained above, the monocrystalline of 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer
Sample carries out X-ray diffraction analysis using X-ray single crystal diffractometer to above-mentioned single crystal samples, the results showed that, the present embodiment
Obtained 3,3', 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymers belong to anorthic system, P-1 space groups.
Contain crystallography independent Eu (III) ion in polymer asymmetric cell it can be seen from Fig. 1 (a), one
HABTC3-Ligand, two water of coordination molecule and one and half lattice hydrone.Wherein, each Eu (III) ion shows distortion
Rectangular anti-prism geometries, they have been separately connected six carboxylate oxygen atoms from five different ligands by eight-coordinate
(O1,O2i,O4ii,O5iii,O7iv,O8iv,symmetry codes:(i)1-x,-y,1-z；(ii)1-x,1-y,1-z；(iii)
x,-1+y,1+z；(iv)+x ,+y, 1+z) and two oxygen atoms (O1W, O2W) from two different water of coordination molecule.Polymer
In, the bonding distance of Eu and O between 2.285 (4) andBetween, bonding angle is between 70.96 (12) ° and 149.99
(14) ° suitable with the bond distance of Eu (III) Carboxylates of report and bond angle range between.
From HABTC it can be seen from Fig. 1 (b)3-The carboxyl of the angle analysis of ligand, 3-, 5-, 3'- and 5'-COO- are distinguished
Using μ2-η1:η1,μ1-η0:η1,μ1-η1:η1andμ1-η1:η0Pattern connects five adjacent Eu (III) ions.Wherein, a pair of
Eu1 and Eu1iAtom is by from two difference HABTC3-The dual connection of carboxylic group of two 3-COO- of ligand forms [Eu2
(COO)2] dimerization volume primitive.In the unit, the shortest distance of Eu ... Eu isEvery four adjacent dimer lists
Member [Eu2(COO)2] by two almost parallel ligand be connected with each other, generate a 2D double-layer network in bc planes.2D is double-deck
Structure has the size to be about along b axisOne-dimensional channels, lattice hydrone is contained in duct.
The integral frame of polymer in order to better understand will simplify the structure for the angle of topology.Wherein,
HABTC3-Ligand is considered as the node of 4- connections, dimerization body unit [Eu2(COO)2] it is considered as the node of 8- connections, each other
It is interconnected to form { the 4 of 4,8- connections20·68}{46}2Novel topological structure (shown in such as Fig. 1 (c)).In addition, difference 2D is double-deck
HABTC3-Phenyl in ligand is mutually parallel and with being significantly overlapped, the spacing in face and face center is each otherShow that there is the effects of very strong π ... pi accumulations between 2D bilayers.Therefore, these π ... pi accumulations interaction handle
The double-deck further connections of 2D form 3D supramolecular structures (shown in such as Fig. 1 (d)), wherein being found that size is about along a axis directionsOne-dimensional open channel, these one-dimensional channels are occupied by dissociating water molecule.
Appropriate H is taken respectively4ABTC ligands and 3,3' obtained above, 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal
Coordination polymer measures the infrared spectrum of ligand and polymer using Fourier Transform Infrared Spectrometer, such as Fig. 2 institutes
Show.As seen from Figure 2, in 1760 and 1660cm-1Neighbouring absorption carries absorption peak, the carbonyl (C=being attributable in carboxylic acid
O) the stretching vibration peak of group.In 1630 and 1575cm-1Neighbouring absorption shows N=N double bonds with the indefinite absorption peak of intensity
Presence.In 1600 and 1500cm-1Strong sharp absorption peak in carrying nearby is absorbed, shows the presence of phenyl ring in structure.From this
Figure can also be seen that the infared spectrum of polymer and ligand is had any different, and peak present on ligand, also have presentation in polymer,
Tentatively polymer is shown to be successfully synthesized.
Using thermogravimetric analyzer, obtained above 3,3', 5,5'- azoxy benzene tetracarboxylic acid europium (III) metals are coordinated
Polymer, within the temperature range of 35-800 DEG C, O2With 10 DEG C of min under atmosphere-1The rate of heat addition carry out thermogravimetry
(TGA), the thermogravimetric collection of illustrative plates of polymer is as shown in Figure 3.Fig. 3 curves show that polymer can attribution in 120-170 DEG C of weight loss
(Obsd.9.84%, Calcd.10.92%) is lost in object and water of coordination molecule, and polymer is in 386-640 DEG C of temperature model
Weight loss in enclosing is attributed to the decomposition of the entire skeleton of polymer, final residue Eu2O3。
Application Example 1
By 3,3' made from embodiment 1,5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer is applied to
2,4,6- trinitrophenols (TNP) in water body are detected, test analysis is carried out by fluorescence spectrum instrument, is as follows：
In a series of polymer-H2(5mM, 50 μ L) 2,4,6- trinitrobenzens are separately added into O suspensions (1mg, 2mL)
Phenol (TNP), 2- nitrophenols (2-NP), 4- nitrophenols (4-NP), para-nitrotoluene (p-NT), meta-nitrotoluene (m-NT),
2,4- dinitrotoluene (DNT)s (2,4-DNT), m-dinitrobenzene (m-DNB), ortho-methylnitrobenzene (n-NT) and nitrobenzene (NB), make
9 kinds of different types of nitryl aromatic class compound (hereinafter referred to as NACs)-polymer-H2O suspensions, in addition, will be not added with any
Polymer-the H of NACs2O suspensions collect corresponding fluorescence data, as shown in Figure 4 respectively as blank control.It can by Fig. 4
Know, is added in the suspension of TNP, the quenching of the fluorescence almost all of polymer, and remaining eight kinds of NACs (2-NP, 4-NP, p-NT,
M-NT, 2,4-DNT, m-DNB, o-NT and NB) influence to the fluorescence of polymer is smaller.It can more intuitively be found out by Fig. 5, contained
Polymer-the H of TNP2O suspensions quenching efficiency is up to 95.66%, almost close to 100%, considerably beyond other eight kinds of NACs.
Application Example 2
In order to explore 3,3' made from embodiment 1,5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer
For detecting the highly selective of TNP, competitive assay has been carried out under the same conditions in above application embodiment 1, TNP has been distinguished
(5mM, 50 μ L) are added in the mixing suspension of polymer and other NACs (5mM, 50 μ L) in addition to TNP, and to be not added with
The polymer of any NACs is as blank control, as long as finding to add TNP, the fluorescence of polymer quenches immediately, such as Fig. 6 institutes
Show, Fig. 6 shows the presence of other NACs to TNP quenching effects almost without interference, it was demonstrated that polymer has a detection of TNP
Have highly selective.
Application Example 3
In order to further explore 3,3' made from embodiment 1, the coordination of 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal
Sensitivity of the polymer in TNP detections, polymer-H is added gradually to by TNP (5mM)2Fluorescence drop is carried out in the suspension of O
Determine quenching experiments.As shown in fig. 7, with the increase of TNP concentration, the fluorescence intensity of polymer continuously decreases.As polymer-H2O
Suspension in when the 5mM TNP solution of 50 μ L is added, the fluorescence intensity almost all quenching of polymer.
Application Example 4
In order to explore 3,3' made from embodiment 1,5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer
Reusability, we by above application embodiment 1 TNP detect after polymer H2Centrifugation is dry afterwards several times for O washings
Dry recycling, and collect fluorescence experiments data.Test result shows that after reusing 5 times, the fluorescence intensity of polymer does not almost have
Become.Meanwhile PXRD test results also show polymer frame structure reused at 5 times after still stablize.
Application Example 5
In order to explore 3,3' made from embodiment 1,5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer
The ability for detecting anion, in a series of polymer-H2It is separately added into Cl in O suspensions (1mg, 2mL)-,Br-,I-,N3 -,
NO2 -,NO3 -,CO3 2-,SO3 2-,SCN-,AcO-And CrO4 2-Solution (25mM, 50 μ L), in addition, to be not added with the polymerization of any anion
Object-H2O suspensions collect corresponding fluorescence data, the results are shown in Figure 8 as blank control.The test result of Fig. 8 shows
Most of anion to the fluorescence intensity of polymer without or only very little interference, and CrO4 2-To the fluorescence intensity of polymer
There is significant quenching effect.
Application Example 6
In order to study 3,3' made from embodiment 1,5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer
For detecting CrO4 2-It is highly selective, carried out competitive assay under the same conditions in above application embodiment 5.By CrO4 2-
(25mM, 50 μ L) are added to polymer and in addition to CrO4 2-In the mixing suspension of other anion (25mM, 50 μ L) in addition,
As long as it was found that adding CrO4 2-, polymer fluorescent quenches immediately, as shown in figure 9, the test result of Fig. 9 show it is other it is cloudy from
The presence of son is to CrO4 2-Quenching effect also demonstrates polymer to CrO almost without interference4 2-Detection have it is highly selective.
Application Example 7
In order to study 3,3' made from embodiment 1,5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer
For detecting CrO4 2-Sensitivity, by CrO4 2-(25mM) is added gradually to polymer-H2Fluorescence titration is carried out in the suspension of O
Quenching experiments.As shown in Figure 10, with CrO4 2-The fluorescence intensity of the increase of concentration, polymer continuously decreases.As polymer-H2O
Suspension in the 25mM CrO of 50 μ L are added4 2-When solution, the quenching of fluorescence intensity almost all.
Application Example 8
In order to study 3,3' made from embodiment 1,5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer
Reusability, we will detect CrO4 2-Polymer H afterwards2Centrifugal drying recycling after O washings several times, and collect glimmering
Light experimental data.Test result shows that after reusing 5 times, the fluorescence intensity of polymer does not almost become.Meanwhile PXRD
Test result also show polymer frame reused at 5 times after still stablize.
Application Example 9
In order to study 3,3' made from embodiment 1,5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer
The ability for detecting TNP in practical applications selects three kinds of water samples (tap water, drinking water and river water sample) to be filtered to remove insoluble
Then TNP is dissolved in the solution that a concentration of 5mM is made into three kinds of water samples by impurity respectively.With three kinds of TNP solution respectively low dense
Two points (4 μ L, 8 μ L) are taken under degree, collect the fluorescence data of the two points, as shown in figure 11.Utilize S-V equations (I0/ I=Ksv
[Q]+1) actual concentrations that experiment with computing obtains, it is compared with theoretical concentration, and calculate its recovery of standard addition.Result of calculation table
Bright, in practical applications, polymer has good recovery of standard addition for detecting TNP.
Application Example 10
In order to study 3,3' made from embodiment 1,5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer
CrO is detected in practical applications4 2-Ability, select three kinds of water samples (tap water, drinking water and river water sample) be filtered to remove it is insoluble
Property impurity, then by CrO4 2-It is dissolved in the solution that a concentration of 25mM is made into three kinds of water samples respectively.With three kinds of CrO4 2-Solution point
It does not take two points (4 μ L, 8 μ L) at low concentrations, collects the fluorescence data of the two points, as shown in figure 12.Utilize S-V equations
(I0/ I=Ksv[Q]+1) actual concentrations that experiment with computing obtains, it is compared with theoretical concentration, and calculate its recovery of standard addition.
Result of calculation shows that in practical applications polymer is for detecting CrO4 2-With good recovery of standard addition.
It is above-mentioned all the experimental results showed that, polymer of the invention can be used as a kind of promising highly selective and sensitive
Property bi-functional fluorescent optical sensor, in water phase TNP and CrO4 2-Long-term, live and reliable detection.
Claims (10)
1.3,3', 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymers, it is characterised in that：The metal coordination
Polymer is using europium as metal center, with 3,3', 5,5'- azoxy benzene tetracarboxylic acid H4ABTC is ligand, the coordination polymerization
The chemical formula of object is：{[Eu2(HABTC)2(H2O)4]·3H2O}n, molecular formula C32H28N4O25Eu2, the metal coordination polymerization
Object belongs to anorthic system, P-1 space groups, and cell parameter is：A=6.8148 (6), b=10.0806 (8), c=13.9136
(10)；α=76.301 (7), β=77.426 (7), γ=84.369 (7), the concrete structure formula of the metal coordinating polymer is such as
Shown in formula one：
2. according to claim 13,3', 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymers, special
Sign is：The ligand H4The chemical structural formula of ABTC is as shown in formula two：
3. according to claim 1 or 23,3', 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymers,
It is characterized in that：The 3,3', 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer is lurid cluster
Shape crystal.
4. a kind of 3,3' according to claim 1 or 2,5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordination polymerization
The preparation method of object, it is characterised in that：Described method includes following steps：
(1) at ambient temperature, by six water europium nitrate (Eu (NO3)3·6H2O) aqueous solution is added to ligand H4The acetonitrile of ABTC is molten
In liquid, after stirring evenly, then dilute nitric acid solution is added dropwise, mixed solution is made；
(2) gained mixed solution is continued after stirring 20min, is transferred in ptfe autoclave and seals, with 1 DEG C/min's
The reaction temperature of reaction kettle is risen to 130 DEG C, and isothermal reaction 72h under the conditions of 130 DEG C by rate program heating, then with 3 DEG C/
The rate program of min is cooled to 25 DEG C, and the target product of the present invention, i.e., 3,3', 5,5'- azoxy of the present invention is made
Benzene tetracarboxylic acid europium (III) metal coordinating polymer.
The system of 3,3' according to claim 4,5,5'- 5. azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer
Preparation Method, it is characterised in that：The six water europium nitrates and ligand H4The molar ratio of ABTC is 1：1.
The system of 3,3' according to claim 4,5,5'- 6. azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer
Preparation Method, it is characterised in that：The volume ratio of the deionized water and acetonitrile is 2：3.
The system of 3,3' according to claim 4,5,5'- 7. azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer
Preparation Method, it is characterised in that：A concentration of 0.01mmol/mL of the six water europium nitrate aqueous solutions, the salpeter solution it is dense
Degree is 1molL-1。
The system of 3,3' according to claim 4,5,5'- 8. azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer
Preparation Method, it is characterised in that：The molar ratio of the six water europium nitrates and nitric acid is 0.02：0.5.
9. fluorescent sensor material of the one kind for detecting 2,4,6- trinitrophenols, it is characterised in that：Including claim 1 or
3,3' described in 2,5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer.
10. one kind is for detecting heavy metal ion Cr6+Fluorescent sensor material, it is characterised in that：Including claims 1 or 2
The 3,3', 5,5'- azoxy benzene tetracarboxylic acid europium (III) metal coordinating polymer.
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