CN110408384A - A kind of preparation and application of rare earth metal organic framework materials - Google Patents
A kind of preparation and application of rare earth metal organic framework materials Download PDFInfo
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- CN110408384A CN110408384A CN201910834594.9A CN201910834594A CN110408384A CN 110408384 A CN110408384 A CN 110408384A CN 201910834594 A CN201910834594 A CN 201910834594A CN 110408384 A CN110408384 A CN 110408384A
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The present invention provides a kind of preparation methods of rare earth metal organic framework materials, first with Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics and strontium nitrate are raw material, using second alcohol and water as solvent, Sr-MOF is made by solvent-thermal method, then using Sr-MOF as parent frame, by rear synthetic modification by Eu3+It is encapsulated into the hole of Sr-MOF, obtains rare earth metal organic framework materials Eu3+@Sr‑MOF。Eu3+@Sr-MOF aqueous solution takes on a red color fluorescence in the UV lamp.In Eu3+K is separately added into@Sr-MOF aqueous solution+、Na+、Hg2+、Mg2+、Pd2+、Ag+、Zn2+、Ca2+、Cu2+、Cd2+、Co2+、Ni2+、Fe2+、Cr3+Solution, only Cr3+It is added for Eu3+There is@Sr-MOF solution good Fluorescence quenching effect therefore can be used for fluorescence detection Cr3+。
Description
Technical field
The present invention relates to a kind of preparations of rare earth metal organic framework materials, more particularly to one kind to pass through rear synthetic modification system
The method of standby rare earth metal organic framework materials；Present invention simultaneously relates to the rare earth metal organic framework materials in fluorescence detection
Cr3+Application, belong to organometallic polymer synthesis field and metal ion detection field.
Background technique
Metal-organic framework materials (MOFs) are to be assembled by metal ion (cluster) with organic ligand, are that one kind has very much
The porous hybrid material of future, since this material has the porosity of superelevation, big surface area, metal center and functional group are more
Sample, it is structurally ordered, be concerned the advantages that structure and adjustable aperture, be widely used in catalysis, photoelectricity, gas storage and point
From, absorption, chemical sensitisation, fluorescence detection, medicament storage and release, separate analysis etc..Fluorescence metal organic frame due to
Its organic and inorganic part all can serve as luminescence unit, is sensitized between them by antenna or electronics transfer can generate collaboration
It shines.Rare earth organic framework materials (Ln-MOFs) are excellent because the 4f electrical arrangement of its lanthanide series has as the branch of MOFs
Optical property and receive more and more attention.However, since lanthanide series has the group of the lanthanides of high ligancy and opening
Element site (being formed in situ during activation/desolvation) is tended in conjunction with oxygen/nitrogen donor from organic linker
Fused structure is formed, therefore rationally designing and prepare required Ln-MOF is still a huge challenge.
Chromium is widely used in industry and chemical process, but a large amount of abuses of these ions are brought to air, soil and water
Serious pollution.Chromium tool is there are two types of common oxidation state, that is, Cr(III) and Cr(VI), the toxicity of different valent state Cr is extremely not yet
Together.Cr(III) ion is essential biologic trace element in human nutrition, but they can non-specifically with DNA
It may cause mutation or malignant cell in conjunction with excessive Cr(III) ion.Therefore development has highly sensitive and highly selective
Cr(III) detection method is of great significance to environmental and human health impacts.
Summary of the invention
The object of the present invention is to provide a kind of methods for constructing rare earth metal organic framework materials by rear synthetic modification；
It is a further object of the present invention to provide the rare earth metal organic framework materials of above method preparation in fluorescence detection Cr3+In
Concrete application.
One, the preparation of rare earth metal organic framework materials
By Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics and strontium nitrate are dissolved in ethanol-water mixed solvent, after ultrasonic disperse is uniform, 125 ~
130 DEG C are reacted 70 ~ 72 hours；It filters, is washed with dehydrated alcohol after reaction, air drying obtains Sr-MOF；Again by Sr-
MOF is dispersed in Eu (NO3)3·6H2In O aqueous solution, 45 ~ 48h, filtering are reacted at room temperature, obtained solid product is washed completely with distilled water
It washs to remove remaining Eu3+Ion；Then it is dried in vacuo 20 ~ 24 hours at 70 ~ 80 DEG C, obtains Eu3+@Sr-MOF。
The molar ratio of 1,4,5,8 naphthalenetetracarboxylic acid and strontium nitrate is 1:0.8 ~ 1:1.2.
In ethanol-water mixed solvent, the volume ratio of ethyl alcohol and aqueous solution is 1:1 ~ 1:1.5.
Eu(NO3)3·6H2The concentration of O aqueous solution is 0.5 ~ 1.5mmol/L.
Two, Eu3+The characterization of@Sr-MOF
1, PXRD is analyzed
Fig. 1 is Eu prepared by the present invention3+The powder diffraction (PXRD) of@Sr-MOF, original frame Sr-MOF material and simulation
Figure.As shown in Figure 1, the original frame Sr-MOF and Eu of synthesis3+The PXRD map of@Sr-MOF and the PXRD map of simulation are consistent,
It illustrates that Sr-MOF is successfully synthesized, also indicates that addition Eu3+The precursor skeleton structure of Sr-MOF does not change afterwards, therefore Eu3+Position
In the channel of Sr-MOF rather than on its skeleton.
2, FT-IR is analyzed
Fig. 2 is Eu prepared by the present invention3+The FT-IR of@Sr-MOF and original frame Sr-MOF material schemes.In FT-IR spectrum,
3345cm-1The broad peak at place is the O-H stretching vibration absworption peak in compound containing water, 3578cm-1Locate the spike occurred, by not
The free O-H of coordination causes；In 1594cm-1、1396cm-1And 1346cm-1The symmetrical stretching vibration peak of carboxyl is observed respectively in place
νsCOO-With antisymmetric stretching vibration peak νasCOO-, it means that carboxyl and Sr2+Coordination.Eu is added3+Before, 1768 ~
1700cm-1C=O stretching vibration in range still has, show carboxyl only with part Sr2+Coordination, but Eu is added3+Later C=
O disappears, this illustrates Eu3+@Sr-MOF is successfully synthesized.
3, scanning electron microscope (SEM) photograph
Fig. 3 is Sr-MOF prepared by the present invention and Eu3+The scanning electron microscope (SEM) photograph of@Sr-MOF material.Wherein figure a is Sr-MOF at 2 μm
Scanning electron microscope (SEM) photograph under size, it can be seen that it is that rectangular-shaped crystal is presented, and figure b is Sr-MOF sweeping under 200 μ m in size
Retouch electron microscope, it can be seen that rectangular section is loose porous, this is further Eu3+It is encapsulated into the hole of Sr-MOF and provides possibility
Property.Figure c is Eu3+Scanning electron microscope (SEM) photograph of the@Sr-MOF under 200 μm, after encapsulation, particle becomes clearly, and shape is inhomogenous, but
It is structure there is no variation, only pattern changes.Sr-MOF have big conjugated system, permanent porous structure and
Containing not being coordinated carboxyl, therefore this parent frame is for being sensitized and accommodating Eu3+Effective frame.After encapsulating successfully, Sr-
In MOF organic ligand can by effectively absorb energy and by intermolecular energy transmission in a manner of transfer energy to Eu3+It is real afterwards
Existing fluorescent emission.
4, thermogravimetric analysis
Fig. 4 is Sr-MOF prepared by the present invention and Eu3+The thermogravimetric analysis figure of@Sr-MOF material.Compare Sr-MOF and Eu3+@Sr-
The weightless trend curve figure of MOF, it can be found that working as Eu3+Successful encapsulation is into after Sr-MOF, due to the difference of contained humidity amount, room temperature
Curvilinear trend is slightly different before to 300 DEG C, but their trend is essentially identical after 300 DEG C, is all at 468 DEG C or so
Skeleton starts to collapse.Therefore Eu prepared by the present invention is shown by thermogram3+@Sr-MOF material still keeps higher heat
Stability.
Three, Eu3+@Sr-MOF fluorescence detection Cr3+
1, the detection of metal ion
Take a certain amount of Eu3+@Sr-MOF material, is configured to the aqueous solution that concentration is 4mg/mL, which takes on a red color in the UV lamp
Fluorescence.Eu is pipetted respectively3+@Sr-MOF aqueous solution is separately added into K in 15 colorimetric cylinders+、Na+、Hg2+、Mg2+、Pd2+、Ag+、
Zn2+、Ca2+、Cu2+、Cd2+、Co2+、Ni2+、Fe2+、Cr3+Solion observes the fluorescent effect of each solution.
Fig. 5 is Eu3+Fluorescent effect histogram of the@Sr-MOF material for metal ion.From figure 5 it can be seen that only
Cr3+The addition of ion is for Eu3+@Sr-MOF solution has good Fluorescence quenching effect, although the addition of other metal ions
Eu is reduced to a certain extent3+The fluorescence intensity of@Sr-MOF solution, but cannot all make Eu3+Fluorescence occurs for@Sr-MOF solution
Quenching effect.Therefore, Eu3+The@Sr-MOF property of can choose fluorescence identifying Cr3+。
Fluorescence titration experiment shows Eu3+@Sr-MOF detects Cr3+Minimum detection limit are as follows: 0.15 μm of ol.
2, anti-interference detection
Fig. 6 is Eu3+@Sr-MOF material is used for the fluorescence intensity comparison diagram of anti-interference detection.This means that Cr3+To in aqueous medium
Eu3+The quenching effect of@Sr-MOF is not influenced by coexisting ion, further demonstrates that Eu3+@Sr-MOF can with single selective
Cr in fluorescence detection aqueous solution3+。
In conclusion the present invention is with Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics and strontium nitrate are that raw material passes through using second alcohol and water as solvent
Solvent-thermal method prepares crystal Sr-MOF first, then using Sr-MOF as parent frame, by rear synthetic modification by Eu3+Ion encapsulation
Into the hole of Sr-MOF, Eu is obtained3+@Sr-MOF.The material can emit rare earth Eu3+The characteristic peak of ion, is used for fluorescence
Metal ion is detected, it can be to Cr3+Ion carries out specific detection.
Detailed description of the invention
Fig. 1 is Sr-MOF prepared by the present invention and Eu3+The powder diffractogram of@Sr-MOF.
Fig. 2 is Sr-MOF prepared by the present invention and Eu3+The infrared spectrogram of@Sr-MOF.
Fig. 3 is Sr-MOF prepared by the present invention and Eu3+The scanning electron microscope (SEM) photograph of@Sr-MOF.
Fig. 4 is Sr-MOF prepared by the present invention and Eu3+The thermogravimetric analysis figure of@Sr-MOF.
Fig. 5 is Eu prepared by the present invention3+The detection figure of@Sr-MOF material metal ion.
Fig. 6 is Eu prepared by the present invention3+The anti-interference detection of@Sr-MOF material metal ion.
Specific embodiment
Construct the side of rare earth metal organic framework materials by rear synthetic modification to the present invention below by specific embodiment
Method is described further.
By Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics (0.1 mmol, 30.4 mg) and strontium nitrate (0.1 mmol, 21.2 mg) are dissolved in
In ethyl alcohol (3mL) and water (4mL) solution, it is ultrasonically treated 10min；Mixed solution is transferred in stainless steel autoclave, is protected
It holds 125 ~ 130 DEG C to react 70 ~ 72 hours, after filtering is washed three times with dehydrated alcohol, dries in air, obtain square Sr-MOF；
Take Sr-MOF(100mg) it is dispersed in 10 milliliters of Eu (NO3)3·6H2It is impregnated two days in O aqueous solution (1mmol/L), filtering, institute
Solid is obtained to be washed completely with a large amount of distilled water to remove remaining Eu3+Ion, then vacuum drying 20 ~ 24 is small at 70 ~ 80 DEG C
When, obtain Eu3+@Sr-MOF。
Take a certain amount of Eu3+@Sr-MOF material, is scattered in the solution that concentration 4mg/mL is configured in distilled water；In 365nm
Under ultraviolet lamp, which has macroscopic red fluorescence to export.
Take a certain amount of Eu3+@Sr-MOF material, is scattered in the solution that concentration 4mg/mL is configured in distilled water；Exist respectively
Eu3+K is added in@Sr-MOF solution+、Na+、Hg2+、Mg2+、Pd2+、Ag+、Zn2+、Ca2+、Cu2+、Cd2+、Co2+、Ni2+、Fe2+、Cr3+
Nitrate aqueous solution (10-2M), if the red fluorescence of solution quenches completely under ultraviolet lamp, that illustrate to be added is Cr3+Solution.
Claims (7)
1. a kind of preparation method of rare earth metal organic framework materials is by Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics and strontium nitrate are dissolved in second
In alcohol-water mixed solvent, after ultrasonic disperse is uniform, reacted 70 ~ 72 hours at 125 ~ 130 DEG C；It filters after reaction, use is anhydrous
Ethanol washing, air drying obtain parent frame Sr-MOF；Sr-MOF is dispersed in Eu (NO again3)3·6H2In O aqueous solution, room
Temperature 45 ~ 48h of reaction, filtering, obtained solid product distilled water are washed completely to remove remaining Eu3+Ion；Then 70 ~ 80
It is dried in vacuo 20 ~ 24 hours at DEG C, obtains Eu3+@Sr-MOF。
2. a kind of preparation method of rare earth metal organic framework materials as described in claim 1, it is characterised in that: Isosorbide-5-Nitrae, 5,8- naphthalenes
The molar ratio of tetracarboxylic acid and strontium nitrate is 1:0.8 ~ 1:1.2.
3. a kind of preparation method of rare earth metal organic framework materials as described in claim 1, it is characterised in that: alcohol-water is mixed
In bonding solvent, the volume ratio of ethyl alcohol and aqueous solution is 1:1 ~ 1:1.5.
4. a kind of preparation method of rare earth metal organic framework materials as described in claim 1, it is characterised in that: Eu (NO3)3·
6H2The concentration of O aqueous solution is 0.5 ~ 1.5mmol/L.
5. a kind of preparation method of rare earth metal organic framework materials as described in claim 1, it is characterised in that: final product
Drying is dried in vacuo 20 ~ 24 hours at 70 ~ 80 DEG C.
6. the rare earth metal organic framework materials of method preparation as described in claim 1 are used for fluorescence detection Cr3+。
7. rare earth metal organic framework materials as claimed in claim 6 are used for fluorescence detection Cr3+, it is characterised in that: in Eu3+@Sr-
In the aqueous solution of MOF material, it is separately added into K+、Na+、Hg2+、Mg2+、Pd2+、Ag+、Zn2+、Ca2+、Cu2+、Cd2+、Co2+、Ni2+、
Fe2+、Cr3+Solion, only Cr3+Addition can make Eu3+The red fluorescence of@Sr-MOF solution quenches.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110938215A (en) * | 2019-12-26 | 2020-03-31 | 烟台大学 | Eu3+-MOF material preparation method and application thereof |
| CN112094416A (en) * | 2020-09-23 | 2020-12-18 | 中国药科大学 | Lanthanide coordination polymer fluorescent probe for fluorescence detection of sialic acid in blood plasma, preparation method and detection method |
| CN114682304A (en) * | 2022-04-13 | 2022-07-01 | 江苏理工学院 | CuCd-MOF/GO-x composite material with visible light catalytic degradation performance and preparation and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110938215A (en) * | 2019-12-26 | 2020-03-31 | 烟台大学 | Eu3+-MOF material preparation method and application thereof |
| CN112094416A (en) * | 2020-09-23 | 2020-12-18 | 中国药科大学 | Lanthanide coordination polymer fluorescent probe for fluorescence detection of sialic acid in blood plasma, preparation method and detection method |
| CN112094416B (en) * | 2020-09-23 | 2022-04-26 | 中国药科大学 | Lanthanide coordination polymer fluorescent probe for fluorescence detection of sialic acid in blood plasma, preparation method and detection method |
| CN114682304A (en) * | 2022-04-13 | 2022-07-01 | 江苏理工学院 | CuCd-MOF/GO-x composite material with visible light catalytic degradation performance and preparation and application thereof |
| CN114682304B (en) * | 2022-04-13 | 2023-05-12 | 江苏理工学院 | CuCd-MOF/GO-x composite material with visible light catalytic degradation performance and preparation and application thereof |
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