CN105753891A - Rare earth organic framework material for fluorescence detection of trace water and preparation method of rare earth organic framework material - Google Patents
Rare earth organic framework material for fluorescence detection of trace water and preparation method of rare earth organic framework material Download PDFInfo
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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Abstract
The invention discloses a rare earth organic framework material for fluorescence detection of trace water and a preparation method of the rare earth organic framework material. The rare earth organic framework material is an orderly microporous crystalline material, and the general structural formula of the material is [(CH3)2NH2]2[Ln6(mu3-OH)8(L-NH2)6(H2O)6]*(G)7, wherein Ln in the formula is Eu<3+>, Tb<3+> or Gd<3+>, L-NH2 is a chainlike phthalic acid organic ligand with an amino group function group and G represents a solvent in pores. The rare earth organic framework material is synthesized with a solvothermal method, the synthesis method adopts a simple process, the condition is mild, the yield is higher, and the product stability is good. The rare earth organic framework material has the properties of characteristic emission of rare earth and fluorescence of the ligand, the specific value of two emission peaks and the content of water in the solvent are in a better linear relation, and ratio type detection of trace water can be realized; the light color remarkably changes with the change of the water content, and the material can be used for colorimetric type detection of trace water. The sensitivity of a probe is high, the response speed is high, the detection limit is low, and the material can be recycled and is expected to be used practically in fields of detection and monitoring of trace water.
Description
Technical field
The present invention relates to a kind of rare earth organic framework materials and preparation method thereof, in particular for the rare earth of trace water fluoroscopic examination
Organic framework materials and preparation method thereof.
Background technology
Under normal circumstances, the major impurity during water is organic solvent.Water in Organic Solvents content is the important of organic solvent quality
Index, it directly affects the usefulness of organic solvent, to accurate synthesis with to separate test most important, largely affects
The carrying out of chemical reaction and productivity, even can determine the product types of reaction.Additionally, water content index also pole in petroleum industry
It is important, and the existence of water not only can reduce the performance of electromotor, and emulsifying and noted phase separation phenomena can occur the most when the temperature decreases,
And then blocking fuel channel, bring fatefulue damage to electromotor.Therefore the mensuration of Water in Organic Solvents content is most important
Also it is one of problem analysis of the most often meeting.Measuring the conventional chemical analysis method of Water in Organic Solvents content is classical card
Er Feixiufa, this method in nineteen thirty-five propose, although through significant improvement, but still exist reaction rate slowly, be easily disturbed,
The shortcomings such as precision is poor, toxicity is big.The additive method measuring water content has spectrophotography, gas chromatography, liquid chromatograph
Method and infrared spectrometry etc., but these detection method expensive equipment, process are complicated, it is impossible to realize in situ detection and monitoring in real time.
And fluorescence detection method has, and simple to operate, highly sensitive, fast response time, anti-electromagnetic interference capability be strong, non-cpntact measurement
Etc. advantage, have been subjected to pay close attention to widely and study.Use single glow peak fluorescent dye to Water in Organic Solvents content
Detection studied widely, but this type of probe sensitivity be easily subject to probe core concentration, excitation source stability and
The impact of the factors such as detector stability, uses the fluorescent probe of ratio type can overcome this kind of defect, it is achieved water content accurate
Detection.Additionally, monitoring and the in situ detection in real time of water content can be realized than the fluoroscopic examination of color base, in chemical reaction and industry
Preparation process has fine application prospect.
Summary of the invention
It is an object of the invention to provide a kind of good stability, fast response time, highly sensitive, capacity of resisting disturbance strong, repeats
Property good, and can realize Real-time Water content monitoring the rare earth organic framework materials for trace water fluoroscopic examination and preparation
Method.
For achieving the above object, the present invention is for the rare earth organic framework materials of trace water fluoroscopic examination, for the crystalline substance of orderly micropore
State material, its general structure is [(CH3)2NH2]2[Ln6(μ3-OH)8(L-NH2)6(H2O)6]·(G)7, in formula, Ln is Eu3+、
Tb3+Or Gd3+, L-NH2For the chain dioctyl phthalate organic ligand amino p-phthalic acid with amido functional group, G represents duct
Interior solvent.
Above-mentioned L-NH2Can be 2-amino p-phthalic acid, 2,5-diaminourea p-phthalic acids, 2,3,5,6-tetraminos be to benzene
Dioctyl phthalate, 2-amino-[1,1 '-biphenyl]-4,4 '-dicarboxylic acids or 2 '-amino-[1,1 ': 4 ', 1 "-terphenyl]-4,4 "-dicarboxylic acids.
The preparation method of the rare earth organic framework materials for trace water fluoroscopic examination of the present invention, uses solvent-thermal method,
Specifically comprise the following steps that
Rare-earth salts is dissolved in organic solvent in molar ratio with the organic ligand containing carboxylic acid together with 1:1, is subsequently adding deionization
Water, o-fluorobenzoic acid and nitric acid, wherein o-fluorobenzoic acid is 8:1 with the mol ratio of organic ligand, organic solvent, deionized water
It is 73:6:4 with the volume ratio of nitric acid.Put in airtight reactor after mix homogeneously, react 1-3 days at 100 DEG C～120 DEG C,
Naturally cool to room temperature, centrifugation, clean, obtain the rare earth organic framework materials for trace water fluoroscopic examination.
In the present invention, described rare-earth salts can be europium nitrate, Terbium nitrate (Tb(NO3)3), Gadolinium trinitrate, Europium chloride, terbium chloride, Gadolinium trichloride,
Acetic acid europium, acetic acid terbium or gadolinium.
In the present invention, the organic ligand of described carboxy-containing acid group be structural formula be the 2-amino p-phthalic acid of (a), structure
Formula is the 2 of (b), 5-diaminourea p-phthalic acid, and structural formula is the 2 of (c), 3,5,6-tetramino p-phthalic acids, structural formula
For (d) 2-amino-[1,1 '-biphenyl]-4,4 '-dicarboxylic acids or 2 '-amino that structural formula is (e)-[1,1 ': 4 ', 1 "-terphenyl]-4,4 "-
Dicarboxylic acids
In preparation process of the present invention, organic solvent used can be DMF, N,N-dimethylacetamide,
Any one in N, N-diethyl acetamide, dimethyl sulfoxide, acetonitrile, ethanol, methanol, dioxane and oxolane
Or several mixing by any ratio.
The beneficial effects of the present invention is:
1, the rare earth organic framework materials preparation method of the present invention is simple, and productivity is up to 70%～75%.The rare earth prepared is organic
Frame structure is novel, and for face-centred cubic structure, product crystallization degree is high, good stability, can various organic solvents (N,
Dinethylformamide, N,N-dimethylacetamide, N, N-diethyl acetamide, acetonitrile, ethanol, methanol, dimethyl
Sulfoxide, dioxane and oxolane), boiling water, the condition such as the PBS solution of pH=7.4 and soda acid (pH=1～13)
Lower holding structural integrity.Crystal is water white octahedron, and size is about 0.5mm × 0.5mm × 0.5mm.
2, the rare earth organic framework materials that the present invention prepares has the characteristic emission of rare earth and the fluorescence of part, this material simultaneously
Luminescent properties has the strongest dependence with water content in solvent, can be used for ratio and the colorimetric detection of trace water in organic solvent.Join
Body fluorescence intensity has preferable linear relationship with the ratio of rare earth ion characteristic emission intensity with water content, can realize self calibration
Detection, detection limit low (volume ratio is 0.005%), fast response time, two emission peak intensity rates just can reach in 2 seconds
Balance, capacity of resisting disturbance is strong, and testing result is not affected by the external factor such as concentration and probe concentration and temperature, overcomes employing in the past
When single-shot photopeak fluorescent dye detects, sensitivity is by detection centre concentration, excitation source stability and detector stability shadow
The defect rung.
3, the rare earth organic framework materials that prepared by the present invention can have trace water concentration range (volume ratio is 0.005%-5%)
Obvious fluorescence response, greatly, color change substantially, is used for trace water compared to other reported at present to emission peak Strength Changes
The material of detection has higher sensitivity and lower detection limit.
4, the rare earth organic framework materials luminous efficiency that the present invention prepares is high, and the quantum efficiency in aqueous solution is 12%～25%,
Quantum efficiency in oxolane is 2%～7%, and the quantum efficiency in ethanol is 1.2%～5%, and luminous naked eyes are visible, send out
There is significant change in light color, glow color is tapered to indigo plant along with the increase of water content by redness with the change of water content
Color, it is possible to achieve realtime imaging and in situ detection, is expected to obtain actual application in the detection of trace water and monitoring field.
5, the rare earth organic framework materials that the present invention prepares can be reused, and after testing 6 circulations, structure remains in that completely,
Fluorescent characteristic does not change, good cycle, can greatly reduce cost in actual application.
Accompanying drawing explanation
Fig. 1 is the mono-crystalline structures schematic diagram of rare earth organic framework materials prepared by the present invention: figure a (left figure) is the three-dimensional knot of crystal
Composition, figure b (right figure) is the secondary construction unit of six cores；
Fig. 2 is rare earth organic framework materials EuBDC-NH prepared by the present invention2Two emission peak intensity rate (I430/I614) with
The linear relationship of water content in oxolane (THF)；
Fig. 3 is rare earth organic framework materials EuBDC-NH prepared by the present invention2Luminous face in the oxolane of different water contents
The chromaticity coordinates change of color.
Detailed description of the invention
Example 1:
Utilizing six nitric hydrate europiums and 2-amino p-phthalic acid, by solvent structure, the rare earth of high stability has machine frame
Frame material EuBDC-NH2, its concrete synthetic route is as follows:
By the 2-amino p-phthalic acid of 0.725mmol, the six nitric hydrate europiums of 0.725mmol and the adjacent fluorobenzene of 5.8mmol
Formic acid is dissolved in the DMF of 36.5mL, is subsequently adding the deionized water of 3mL and the nitric acid of 2mL,
Put in the reactor of airtight 100mL after stirring, react 60 hours in 110 DEG C of constant temperature ovens, cold with stove
But arriving room temperature, centrifugation solid-liquid, solid DMF cleans and obtains rare earth organic framework materials three times
Crystal EuBDC-NH2, crystal is water white octahedron, and size is about 0.5mm × 0.5mm × 0.5mm, produces
Rate is 75%.
Determining its structural formula by Oxford Xcalibur Gemini Ultra single crystal diffractometer, test result shows: this material
Structural formula is [(CH3)2NH2]2[Eu6(μ3-OH)8(1,4-BDC-NH2)6(H2O)6] 7DMF, belonging to cubic system, space group is
Fm-3m, cell parameter isα=β=γ=90 °, unit cell volume isZ=4,
Dc=1.418g cm-3.The mono-crystalline structures figure of the rare earth organic framework materials of preparation is as it is shown in figure 1, this material is by six metals
From molecular cluster [Eu6(μ3-OH)8(O2C-)12] and the three-dimensional network knot of organic bridge ligand 2-amino p-phthalic acid formation
Structure, the most each Eu3+Ion and nine oxygen atom ligands, in these nine oxygen atoms, oxygen atom comes from the moisture of coordination
Son, four oxygen atoms come from four μ3-OH bridge joint group and four oxygen atoms come from four independent parts.Close on
Eu3+Ion passes through μ3The hydroxy-acid group of-OH group and deprotonation connects and forms the secondary construction unit of six cores
[Eu6(μ3-OH)8(O2C-)12], secondary construction unit is connected the face-centered cubic forming three-dimensional further by 2-amino p-phthalic acid
Structure.
Obtain rare earth organic framework materials be colourless transparent crystal, be shaped as octahedron, can various organic solvents (N,
Dinethylformamide, N,N-dimethylacetamide, N, N-diethyl acetamide, acetonitrile, ethanol, methanol, dimethyl
Sulfoxide, dioxane and oxolane), boiling water, the condition such as the PBS solution of pH=7.4 and soda acid (pH=1～13)
Lower holding structural integrity.The lowest excited triplet energy level using part is 21053cm-1, part can be good at sensitization Eu3+
Ionoluminescence.Under ultraviolet excitation, this crystal of solid-state launches obvious europium ion characteristic fluorescence, and quantum efficiency is 1.84%.
And the characteristics of luminescence in solvent has the strongest dependence with water content in solvent.EuBDC-NH2It is dispersed in oxolane
In, along with the increase of water content, Eu3+Characteristic emission intensity (at 614nm) be gradually lowered, and the fluorescence (430 of part
At nm) it is gradually increased along with the increase of water content.Under low concentration, the intensity rate of the two glow peak presents with water content
Preferably linear relationship (see Fig. 2), 0%-5% concentration range formula is fitted:
I430/I614=0.39194x+0.01206, the volumn concentration of water, I during wherein x is oxolane430For organic ligand
Fluorescence intensity, I614For Eu3+Characteristic emission intensity.This rare earth organic framework materials is to trace water as seen from Figure 3
Detection has excellent performance, and detection limit is low, and linear relationship is good.And the luminous efficiency of this rare earth organic framework materials is high,
Quantum efficiency in aqueous solution is 12%～25%, its glow color along with water content increase (volume ratio from 0% to 5%) by
Redness tapers to blueness, can realize realtime imaging and the in situ detection of trace water in oxolane.
Example 2:
Utilizing six nitric hydrate europiums and 2-amino p-phthalic acid, by solvent structure, the rare earth of high stability has machine frame
Frame material EuBDC-NH2, its concrete synthetic route is as follows:
By the 2-amino p-phthalic acid of 0.725mmol, the six nitric hydrate europiums of 0.725mmol and the adjacent fluorobenzene of 5.8mmol
Formic acid is dissolved in the DMF of 36.5mL, is subsequently adding the deionized water of 3mL and the nitric acid of 2mL,
Put in the reactor of airtight 100mL after stirring, react 60 hours in 110 DEG C of constant temperature ovens, cold with stove
But arriving room temperature, centrifugation solid-liquid, solid DMF cleans and obtains rare earth organic framework materials three times
EuBDC-NH2, productivity is 75%.
EuBDC-NH2In ethanol, quantum efficiency is 5.3%, along with the increase of water content, Eu in dispersion3+Characteristic emission
Intensity (at 614nm) reduces, and the fluorescence of part (at 430nm) increases along with the increase of water content.Under low concentration,
The intensity rate of the two glow peak and water content present preferable linear relationship, and 0%-5% concentration range formula is fitted:
I430/I614=0.34647x+0.21753, the percentage composition of water, I during wherein x is ethanol430Fluorescence for organic ligand is strong
Degree, I614For Eu3+Characteristic emission intensity.Can be seen that the detection of trace water is had excellent by this rare earth organic framework materials
Performance, detection limit is low, and linear relationship is good.And the luminous efficiency of this rare earth organic framework materials is high, its glow color along with
The increase of water content is tapered to blueness by aubergine, can realize realtime imaging and the in situ detection of trace water in alcohol solvent.
EuBDC-NH2Disperse other organic solvent also has same phenomenon, show that this material may be used for various organic molten
The ratio of trace water and colorimetric detection in agent.
Example 3:
Utilizing six nitric hydrate terbiums and 2-amino p-phthalic acid, by solvent structure, the rare earth of high stability has machine frame
Frame material TbBDC-NH2, its concrete synthetic route is as follows:
By the 2-amino p-phthalic acid of 0.725mmol, the six nitric hydrate terbiums of 0.725mmol and the adjacent fluorobenzene of 5.8mmol
Formic acid is dissolved in the DMF of 36.5mL, is subsequently adding the deionized water of 3mL and the nitric acid of 2mL,
Put in the reactor of airtight 100mL after stirring, react 60 hours in 110 DEG C of constant temperature ovens, cold with stove
But arriving room temperature, centrifugation solid-liquid, solid DMF cleans and obtains rare earth organic framework materials three times
TbBDC-NH2, productivity is 70%.
Powder X-ray diffraction shows, TbBDC-NH2With EuBDC-NH2Isomorphism, is also belonging to the crystalline substance of face-centred cubic structure
Body, outward appearance is octahedra shape, can various organic solvents (DMF, N,N-dimethylacetamide, N,
N-diethyl acetamide, acetonitrile, ethanol, methanol, dimethyl sulfoxide, dioxane and oxolane), boiling water, pH=7.4
PBS solution and soda acid (pH=1～13) etc. under the conditions of keep structural integrity.Under ultraviolet excitation, this crystal of solid-state is sent out
Penetrating obvious terbium ion characteristic fluorescence, quantum efficiency is 1.55%.And the characteristics of luminescence in solvent has very with water content in solvent
Strong dependence.TbBDC-NH2It is dispersed in oxolane, along with the increase of water content, Tb3+Characteristic emission strong
Degree reduces, and the transmitting fluorescence (at 430nm) of part increases along with the increase of water content.Under low concentration, the two is sent out
The intensity rate of photopeak and water content present preferable linear relationship, and 0%-5% concentration range formula is fitted:
I430/I545=0.73602x+3.58996, the percentage composition of water during wherein x is oxolane, I is luminous intensity.Permissible
Finding out that this rare earth organic framework materials has excellent performance to the detection of trace water, detection limit is low, and linear relationship is good.?
TbBDC-NH2Disperseing also to have in other organic solvent same phenomenon, its glow color is along with the increase of water content is by green
Color tapers to blueness and shows that this material may be used for ratio and the colorimetric detection of trace water in various organic solvent.
Above-mentioned detailed description of the invention is used for illustrating the present invention, but the present invention should not be limited to this embodiment and accompanying drawing institute is public
The content opened.So every without departing from the equivalence completed under spirit disclosed by the invention or amendment, both fall within the present invention and protect model
Enclose.
Claims (5)
1. the rare earth organic framework materials for trace water fluoroscopic examination, it is characterised in that this rare earth organic framework materials is
The crystalline material of micropore in order, its general structure is [(CH3)2NH2]2[Ln6(μ3-OH)8(L-NH2)6(H2O)6]·(G)7, in formula
Ln is Eu3+、Tb3+Or Gd3+, L-NH2For the chain dioctyl phthalate organic ligand amino p-phthalic acid with amido functional group,
G represents the solvent in duct.
2. the method for the preparation rare earth organic framework materials for trace water fluoroscopic examination described in claim 1, including following
Step:
Rare-earth salts is dissolved in organic solvent in molar ratio with the organic ligand containing carboxylic acid together with 1:1, is subsequently adding deionization
Water, o-fluorobenzoic acid and nitric acid, wherein o-fluorobenzoic acid is 8:1 with the mol ratio of organic ligand, organic solvent, deionized water
It is 73:6:4 with the volume ratio of nitric acid.Put in airtight reactor after mix homogeneously, react 1-3 days at 100 DEG C～120 DEG C,
Naturally cool to room temperature, centrifugation, clean, obtain the rare earth organic framework materials for trace water fluoroscopic examination.
The preparation method of the rare earth organic framework materials for trace water fluoroscopic examination the most according to claim 2, it is special
Levy and be that rare-earth salts used is europium nitrate, Terbium nitrate (Tb(NO3)3), Gadolinium trinitrate, Europium chloride, terbium chloride, Gadolinium trichloride, acetic acid europium, second
Acid terbium or gadolinium.
The preparation method of the rare earth organic framework materials for trace water fluoroscopic examination the most according to claim 2, it is special
Levy be the organic ligand of carboxy-containing acid group used be structural formula be the 2-amino p-phthalic acid of (a), structural formula is (b)
2,5-diaminourea p-phthalic acid, structural formula is the 2 of (c), 3,5,6-tetramino p-phthalic acids, and structural formula is (d) 2-
Amino-[1,1 '-biphenyl]-4,4 '-dicarboxylic acids or 2 '-amino that structural formula is (e)-[1,1 ': 4 ', 1 "-terphenyl]-4,4 "-dicarboxylic acids.
The preparation method of the rare earth organic framework materials for trace water fluoroscopic examination the most according to claim 2, it is special
Levy and be that organic solvent used is DMF, N,N-dimethylacetamide, N, N-diethyl acetamide,
In dimethyl sulfoxide, acetonitrile, ethanol, methanol, dioxane and oxolane any one or several by any ratio
Mixing.
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