CN110330664A - A kind of Eu/Tb-BHM-COOH complex and its preparation method and application - Google Patents
A kind of Eu/Tb-BHM-COOH complex and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of Eu/Tb-BHM-COOH complexs and its preparation method and application, belong to rare earth luminescent material field.The Eu/Tb-BHM-COOH complex is mainly by EuCl3·6H2O、TbCl3·6H2O and BHM-COOH are prepared.Energy can be effectively transferred to terbium ion or europium ion by metal-organic framework material Eu/Tb-BHM-COOH complex provided by the invention, so that the metal-organic framework material has high excellent luminescent properties.Due to Fe3+Competitive absorb between Eu/Tb-BHM-COOH complex will lead to Fe3+Fluorescence intensity quenching so that Eu/Tb-BHM-COOH complex is to Fe3+It, can be to Fe with selectivity3+It is identified and is detected.
Description
Technical field
The present invention relates to rare earth luminescent material fields, and in particular to a kind of Eu/Tb-BHM-COOH complex and its preparation side
Method and application.
Background technique
Rare earth element is to be located at III B race element in the periodic table of elements, contains 17 kinds of elements, the unique 4f electricity of rare earth element
Sublayer structure determines that optical property, the characteristics of luminescence of rare earth ion depend primarily on the property of rare earth ion 4f shell electron.
With the variation of 4f shell electron number, rare earth ion shows different electron transition form and energy level transition extremely abundant.
Therefore, rare earth ion, which can be absorbed or emit, forms diversified luminous material from ultraviolet to the light of the various wavelength of infrared region
Material.The excellent luminance characteristic of rare earth ion is to make high efficient luminous material using it to lay a good foundation.
Metal organic framework (MOFs) is the main multiple tooth organic ligand of nitrogen oxygen by aromatic acid or alkali, passes through coordinate bond and nothing
The network structure crystal that machine center hydridization is formed, therefore the Porous coordination polymer that is otherwise known as.Due to its structure (cluster chemistry
Progress) and function adjustability (maturation of relevant organic synthesis is modified after preparing and synthesize to ligand), the synthesis tuning of MOFs
Property makes it be different from traditional porous inorganic material, and allows reasonably to design many interesting properties, as stability,
Porosity, chemical functionality and chirality.
Currently, luminous metal-organic framework materials have been obtained and widely apply: such as synthesis fluorescent optical sensor, being made
It is linear to shine with nonlinear optical element, as catalysis material etc..Wherein the application of most practicability is in environmental area
And biological field.Take into account the luminescent metal organic framework material of aperture structure and light-emitting function at present oneself become very potential
Sensing material.By the development of recent decades, many luminous metal-organic framework materials, oneself be widely used in anion,
In cation, small molecule, steam and other sensing process.Some couples of Cu have been prepared at present2+、Zn2+、Mg2+、Fe3+Equal gold
Belonging to ion and small organic molecule has the metal-organic framework material of fluorescence identifying ability.
Fe3+It is widely present in nature and human body, to playing an important role in environment and the ecosystem and human body institute
One of required microelement.Due to Fe3+Be prevalent in cell metabolism, electronics transfer enzymatic, oxygen transport and DNA and
In the biochemical processes such as RNA synthesis, iron ion is excessive or shortage can lead to anaemia, mental deterioration, arthritis, diabetes, cancer etc.
Body illness.Therefore, to Fe3+It detects particularly important.Currently, to Fe3+Detection be mainly the following detection method: light splitting
Photometry, chromatography, electrochemical process.These methods are in detection Fe3+When the used time it is longer, and need equipment it is huge and expensive, and
And detection accuracy is low, it is insensitive.Therefore, it is impossible to meet to Fe3+Real-time, quick detection, and be not able to satisfy in Fe3+Concentration compared with
Detection when low, detection efficiency is low and sensitivity is low.
Therefore, Fe can be identified by how designing one kind3+Metal-organic framework material, and by the metal-organic framework material
For detecting the Fe in aqueous solution3+Ion is still a challenge.
Summary of the invention
In view of the above shortcomings of the prior art, the purpose of the present invention is to provide a kind of Eu/Tb-BHM-COOH cooperations
Object can not identify Fe to solve metal-organic framework material in the prior art3+The problem of.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that it is such:
A kind of Eu/Tb-BHM-COOH complex, has the following structure general formula:
Wherein, Ln is Eu and Tb.
The present invention also provides a kind of preparation methods of Eu/Tb-BHM-COOH complex, include the following steps:
(1) 1:(6~10 in molar ratio): 1 takes hexabromo methylbenzene, 5- Hydroxy M Phthalic Acid dimethyl ester, sodium hydroxide to set
It mixes in a round bottom flask, good solvent is added, stirring dissolves solid, and reactant is warming up to 60~160 DEG C, is condensed back
React 8~20h；Excessive ice cold water is added after fully reacting into solution, rotate and filters out to obtain white precipitate, it will be white
It is deposited in vacuum drying oven dry 6h, obtains gray solid；Gray solid is added in methanol solution, it is molten to add NaOH
Liquid is acidified to acidity with dilute hydrochloric acid, is precipitated after reacting 8h, is repeatedly washed and dry with deionized water, obtains BHM-
COOH；The general structure of the BHM-COOH are as follows:
The reaction equation of step (1) is as follows:
(2) in molar ratio (1~12): (1~12): 1 takes EuCl3·6H2O、TbCl3·6H2O, BHM-COOH is placed in
In 20mL reaction kettle, deionized water and NaOH solution is added, and 10~20min is stirred at room temperature in mixture, hexamethylene is added
Alcohol simultaneously stirs the mixture for 10~30min；Reaction kettle containing the mixture is heated to 80~120 DEG C, isothermal reaction 3~
6 days, obtain Eu/Tb-BHM-COOH complex crude product.The reaction equation of step (2) is as follows:
(3) Eu/Tb-BHM-COOH complex crude product is filtered out into oily impurity while hot, for several times with ethanol washing, then at
50~70 DEG C of 5~7h of vacuum drying are to get the Eu/Tb-BHM-COOH complex arrived after purification.
Good solvent in the step (1) is chloroform, n,N-Dimethylformamide, a kind of or more in tetrahydrofuran
Kind.Cyclohexanol in the step (2) is the cyclohexanol for being put into 55 DEG C of baking oven inside holding 0.5h and being warmed.
The present invention also provides a kind of preparation method of fluorescent optical sensor, using the Eu/Tb-BHM-COOH complex,
Specifically comprise the following steps:
A, by after Eu/Tb-BHM-COOH complex and PLA (polylactic acid) solution physical blending, ultrasonic 30min；
B, using the tape casting drop film, Eu/Tb-BHM-COOH-PLA fluorescence membrane, the as described fluorescent optical sensor is made.
Wherein, in the step a, the solid-to-liquid ratio of the Eu/Tb-BHM-COOH complex and PLA solution be 1~5:1~
10.The concentration of the PLA aqueous solution is 5~20g/L.
Invention additionally discloses a kind of by fluorescent optical sensor Fe for identification3+Application, the fluorescent optical sensor is by described
The preparation method of fluorescent optical sensor is made.
Compared with prior art, the present invention has the advantage that
1, it since BHM-COOH ligand provided by the invention has 12 coordination sites, is grafted on 12 coordination sites
There are europium ion or terbium ion, the ability of the coordination of europium ion or terbium ion and BHM-COOH ligand is enhanced, to have in metal
In machine frame frame material Eu/Tb-BHM-COOH complex, energy can be effectively transferred to terbium ion or europium ion, so that institute
Complex is stated with excellent luminescent properties.Due to Fe3+Competitive absorb between Eu/Tb-BHM-COOH complex can lead
Cause Fe3+Fluorescence intensity quenching, therefore the Eu/Tb-BHM-COOH complex can be realized to Fe3+Selective recognition and
Detection.
2, the preparation method of the Eu/Tb-BHM-COOH complex in the present invention is simple, relative inexpensiveness, is suitable for industry
It produces and uses.
3, the present invention by after Eu/Tb-BHM-COOH complex and PLA solution physical blending, then using the tape casting by dripping
Film preparation has the film of Eu/Tb-BHM-COOH complex, which is fluorescent optical sensor, and the preparation method is easy to operate,
Reaction time is short, and relative inexpensiveness, can be used for industrial production use.
4, the fluorescent optical sensor that the present invention is prepared is able to achieve to Fe3+Accurate identification.Either deposited in single ionic
In the case where still different kinds of ions is mixed, can realize to Fe3+Accurately identify, and do not influenced by anion.
By the Fe for fluorescent optical sensor being added dropwise various concentration3+, it is found that fluorescence lifetime does not change, eliminate dynamic quenching,
Therefore, fluorescent optical sensor prepared by the present invention is to Fe3+Detection belong to static quenching.Quenching is the reason is that analyte (Fe3+) with match
Competitive absorb closed between object leads to Fe3+Fluorescence intensity quenching.
The fluorescent optical sensor that the present invention is prepared can be in Fe3+Concentration is 3.38 × 10-4M quenching 80% or so, have compared with
High detection sensitivity.Also, the fluorescent optical sensor is in detection Fe3+It can be reused with deionized water flushing afterwards, repeat to drip
Determine and clean 10 times, remains to accurately identify Fe3+, there is good repeatable energy.Therefore, fluorescent optical sensor prepared by the present invention
There can be extensive prospect in pollutant monitoring and field of biomedicine.
Detailed description of the invention
Fig. 1 is the infrared spectrum analysis figure of ligand BHM-COOH prepared by the present invention and complex Eu/Tb-BHM-COOH
(pressing potassium bromide troche).
Fig. 2 is fluorescence titration spectrogram of the fluorescent optical sensor prepared by the present invention to 14 metal ion species.
Fig. 3 is that various concentration FeCl is added dropwise3The fluorescence titration spectrogram of solution.
Fig. 4 is the partial enlarged view of Fig. 3, and wavelength is 500~580nm.
Fig. 5 is that various concentration Fe (NO is added dropwise3)3The fluorescence titration spectrogram of solution.
Fig. 6 is in FeCl3Stern-Volmer curve in solution.
Fig. 7 is in Fe (NO3)3Stern-Volmer curve in solution.
Fig. 8 is single ionic to Fe3+Interference experiment fluorescence titration spectrogram, wherein ordinate value be at 547nm
Luminous intensity.
Fig. 9 is that different kinds of ions is mixed to Fe3+Interference experiment fluorescence titration spectrogram, wherein ordinate value be
Luminous intensity at 547nm.
Figure 10 is that titration Fe is recycled to fluorescent optical sensor3+Circulation experiment fluorescence titration spectrogram, wherein ordinate value is
The luminous intensity at 547nm.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples.
One, the preparation of Eu/Tb-BHM-COOH complex
(1) hexabromo methylbenzene 2.54g (4mmol), 5- Hydroxy M Phthalic Acid dimethyl ester 5.04g (24mmol) is taken to be added
In 250mL round-bottomed flask, DMF (50mL) then is added, mixture solution is heated to 150 DEG C, and sodium hydroxide 0.96g is added
(4mmol) is condensed back 10h.
It is changed to distilling apparatus after fully reacting, solvent is distilled off, then heats to obtain by vacuum drying oven at 60 DEG C
Gray solid.Gray solid is added in the methanol solution of 120ml, 1.8g NaOH configuration is added in the distilled water of 30ml
It is added drop-wise in methanol solution at NaOH solution, and by NaOH solution, after reacting 8h, removes methanol with rotary evaporator, will remain
Solution pour into deionized water (300mL), being acidified to pH with dilute hydrochloric acid is about 3.Precipitated product is obtained after stirring.Pass through filtering
Sediment is collected, is washed with deionized 3 times, and be dried overnight at 60 DEG C by vacuum drying oven.Obtain ligand BHM-COOH.
(2) BHM-COOH 0.3g (0.24mmol), EuCl are weighed3·6H2O 0.3225g (0.72mmol), TbCl3·
6H2O 1.1g (2.1mmol), is placed in 50mL reaction kettle, and 6mL deionized water and 0.5mL, the 2mol/L that concentration is are removed in addition
NaOH solution, and mixture is stirred at room temperature.After 10min, 7mL, 55 DEG C of cyclohexanol warmed are added and stir mixture
Mix 15min.Reaction kettle is placed on baking oven to keep reacting 5 days at 100 DEG C, obtains Eu/Tb-BHM-COOH complex crude product.
(3) Eu/Tb-BHM-COOH complex crude product is filtered out into oily impurity while hot, with the ethanol washing 3 of 500ml
It is secondary, 6h is dried in vacuo then at 50~70 DEG C to get the Eu/Tb-BHM-COOH complex arrived after purification.
The ligand BHM-COOH being prepared and complex Eu/Tb-BHM-COOH is subjected to infrared spectrum analysis, analysis knot
Fruit is as described in 1.As can be known from Fig. 1, the infrared spectrum curve of ligand BHM-COOH and complex Eu/Tb-BHM-COOH are much like,
In 3460cm-1Corresponding-OH characteristic absorption peak at left and right, ligand is in 1730cm-1There is a characteristic absorption peak at place, is C=O
Stretching vibration, and the characteristic absorption peak of complex is in 1623cm-1Place is the stretching vibration of C=O.Therefore, the stretching vibration of C=O
It is mobile towards lower wave number, this is because C=O and Eu3+/Tb3+Coordination lead to its weakened.Thus illustrate complex
Preparation be successful.
Two, the preparation of fluorescent optical sensor
A, the PLA of 1g is taken, single-necked flask is packed into, the chloroform of 100ml is added, 2h is stirred at room temperature, obtains 10g/L
PLA solution.After the PLA solution physical blending that the Eu/Tb-BHM-COOH complex and 5mL concentration for taking 5mg to prepare are 10g/L,
Ultrasonic 30min.
B, Eu/Tb-BHM-COOH-PLA fluorescence membrane is made by the tape casting drop film at room temperature, the as described fluorescence passes
Sensor.
Three, the application of fluorescent optical sensor
Embodiment 1
It is filled respectively with centrifuge tube and takes prepared M (Cl)xSolution, the M (Cl)xThe concentration of solution is 1 × 10-2Mol/L,
Wherein, M Fe3+、Al3+、Ba2+、Ca2+、Co2+、Cr3+、Cu2+、Fe2+、K+、Mg2+、Na+、Li+、Pb2+And Zn2+.All fluorescence
Titration experiments all carry out under the conditions of 25 ± 0.5 DEG C, and Eu/Tb-BHM-COOH-PLA film is respectively placed in cuvette, is added 3
~5ml deionized water, then titrates.The 120 above-mentioned solution of μ L are separately added into each cuvette with pipettor, in excitation wavelength
The variation of record observation fluorescence intensity in the case where 314nm.
For fluorescence titration spectrogram as shown in Fig. 2, abscissa is above-mentioned 14 metal ion species, ordinate is relative intensity I/
I0.It takes and M (Cl) is not addedxThe fluorescent optical sensor of solution is initial before titrating in the emissive porwer of 547nm as a control group
Fluorescent emission intensity is denoted as I0.It is added M (Cl)xFluorescent optical sensor after solution is glimmering after the emissive porwer of 547nm is titration
Light emitting intensity, is denoted as I.
As can be seen from Figure 2, Fe is only added dropwise in 14 kinds of ions3+Change obvious, addition Fe3+Afterwards, what is obtained is relatively strong
Degree about 0.2, fluorescence is quenched.And after other 13 intermediate ions are added, relative intensity is between 0.8~1.2, and variation is not
Obviously.Therefore, Eu/Tb-BHM-COOH fluorescent optical sensor prepared by the present invention can be realized to Fe3+Accurately identify.
Embodiment 2
Take 1 × 10-2The FeCl of mol/L3Solution, gradually be added dropwise (5 μ L, 10 μ L, 15 μ L, 20 μ L, 25 μ L, 30 μ L, 45 μ L,
55 μ L, 65 μ L, 90 μ L, 120 μ L) into the cuvette for being placed with fluorescent optical sensor, fluorescent optical sensor is detected to Fe3+The spirit of identification
Sensitivity.It is same that 1 × 10- is added2mol/L Fe(NO3)3Solution (5 μ L, 10 μ L, 15 μ L, 20 μ L, 25 μ L, 30 μ L, 35 μ L, 40 μ
L, 50 μ L, 80 μ L, 110 μ L, 140 μ L) into the cuvette for being placed with fluorescent optical sensor, and anion is excluded to there is fluorescence biography
The influence of sensor.Various concentration FeCl is added dropwise3The fluorescence titration spectrogram of solution is as shown in figure 3, wavelength putting in 500~580nm
Big figure is as shown in Figure 4.Various concentration Fe (NO is added dropwise3)3The fluorescence titration spectrogram of solution is as shown in Figure 5.
It is found that Fe is added from Fig. 3~53+Afterwards, FeCl is either added3Or Fe (NO3)3, the quenching of fluorescence intensity
Value reach 80% or so (fluorescence intensity after quenching value=(fluorescence intensity after fluorescence intensity-quenching before quenching)/quenching,
Fluorescence intensity level is taken from 547nm), there is good recognition effect.In order to study in aqueous solution to Fe3+The quenching of ion
Ability, we calculate quenching constant (K using Stern-Volmer (SV) equation (formula 1)SV)。
I0/ I=1+KSV[C] (1)
Wherein I0For Fe is not added3+When ion, fluorescence intensity at 547nm, I is that Fe is added3+After ion at 547nm
Luminous intensity, [C] is Fe3+The concentration of ion.
Referring to Fig. 6 and Fig. 7, quenches curve and show good linear dependence.FeCl3In Ksv value be 1.45 × 10-4, Fe (NO3)3In Ksv value be 1.27 × 10-4.It follows that anion detects Fe to fluorescent optical sensor3+It does not interfere with.And
And Eu/Tb-BHM-COOH fluorescent optical sensor prepared by the present invention is to Fe3+Detectable concentration reach 3.38 × 10-4M compares it
His sensor detectable concentration, Eu/Tb-BHM-COOH fluorescent optical sensor is to Fe3+Detection have good selectivity.
Embodiment 3
It is filled respectively with centrifuge tube and takes prepared M (Cl)xSolution, the M (Cl)xThe concentration of solution is 1 × 10-2Mol/L,
Wherein, M Fe3+、Al3+、Ba2+、Ca2+、Co2+、Cr3+、Cu2+、Fe2+、K+、Mg2+、Na+、Li+、Pb2+And Zn2+.Take 13 it is glimmering
Optical sensor is respectively placed in cuvette, and 3~5ml deionized water is added, will remove Fe3+Other 13 solution outside solution is respectively with shifting
Liquid device takes 120 μ L to be added drop-wise in each cuvette, then 120 μ L Fe are added dropwise into each cuvette with pipettor3+Solution is swashing
The variation of observation fluorescence intensity is recorded in the case where sending out wavelength 314nm, as a result as shown in Figure 8.As it can be observed in the picture that being first separately added into
One of 13 kinds of ions ion, then adds Fe3+, fluorescent optical sensor is had no effect on to Fe3+Identification.
Embodiment 4
Prepare mixed ion solutions, wherein the concentration of the ion in mixed ion solutions is 1 × 10-2mol/L.No. 1 molten
Liquid is Cr3+、Al3+、Ca2+、Ba2+And Co2+Mixed solution, No. 2 solution are Li+、k+、Na+、Pb2+、Mg2+Mixed solution, No. 3
Solution is Zn2+、Pb2+、Cr3+、Fe2+、Cu2+Mixed solution, No. 4 be Li+、k+、Pb2+、Zn2+、Cr3+、Al3+、Ba2+、Mg2It is mixed
Solution is closed, No. 5 are to include except Fe3+The mixed solution of 13 kinds of outer ions.It is reconfigured 1 × 10- of concentration2The Fe of mol/L3+It is molten
Liquid.It takes five fluorescent optical sensors to be respectively placed in cuvette, 3~5ml deionized water is added, by 1~No. 5 mixed solution respectively with shifting
Liquid device takes 120 μ L to be added drop-wise in each cuvette, then 120 μ L Fe are added dropwise into each cuvette with pipettor3+Solution is swashing
The variation of observation fluorescence intensity is recorded in the case where sending out wavelength 314nm, as a result as shown in Figure 9.As can be known from Fig. 9, different kinds of ions
Mixing do not influence fluorescent optical sensor identification Fe3+Identification.
Embodiment 5
Configure Fe3+Concentration is 1 × 10-2The solution of mol/L takes a fluorescent optical sensor to be placed in cuvette, and addition 3~
5ml deionized water takes 120 μ L Fe with pipettor3+Solution is added drop-wise in cuvette, is recorded in the case where excitation wavelength 314nm
Observe fluorescence intensity.Then the deionized water of the fluorescent optical sensor after using is rinsed 3 times, then Fe is added dropwise3+Solution.It is repeated 10 times
Fe is added dropwise3+Solution and 3 steps are rinsed with deionized water, examines the service life of fluorescent optical sensor.Testing result such as Figure 10
It is shown.
It can be seen from fig. 10 that although Eu/Tb-BHM-COOH fluorescent optical sensor is to Fe3+Quenching effect clearly,
Intensity, but after deionized water is repeatedly rinsed, fluorescence intensity still can be restored to very high level.It is glimmering to illustrate prepared by the present invention
Repeatability is good for optical sensor, can be used multiple times, and still maintains to Fe3+Accurately identify.
The fluorescent optical sensor that the present invention is prepared is able to achieve to Fe3+Accurate identification.Either exist in single ionic
Or it in the case that different kinds of ions is mixed, can realize to Fe3+Accurately identify, and do not influenced by anion.This
Inventing the fluorescent optical sensor being prepared can be in Fe3+Concentration is 3.38 × 10-4M quenching 80% or so, detection spirit with higher
Sensitivity.Also, the fluorescent optical sensor is in detection Fe3+It can be reused with deionized water flushing afterwards, repeat to titrate and clean 10
It is secondary, it remains to accurately identify Fe3+, there is good repeatable energy.Therefore, fluorescent optical sensor prepared by the present invention can pollute
Analyte detection and field of biomedicine have extensive prospect.
Finally, it should be noted that technical side the above examples are only used to illustrate the technical scheme of the present invention and are not limiting
Case, those skilled in the art should understand that, modification or equivalent replacement of the technical solution of the present invention are made for those, and
The objective and range for not departing from the technical program, are intended to be within the scope of the claims of the invention.
Claims (9)
1. a kind of Eu/Tb-BHM-COOH complex, which is characterized in that have the following structure general formula:
Wherein, Ln is Eu and Tb.
2. a kind of preparation method of Eu/Tb-BHM-COOH complex, which comprises the steps of:
(1) 1:(6~10 in molar ratio): 1 takes hexabromo methylbenzene, 5- Hydroxy M Phthalic Acid dimethyl ester, sodium hydroxide to be placed in circle
It is mixed in the flask of bottom, good solvent is added, stirring dissolves solid, and reactant is warming up to 60~160 DEG C, is condensed back reaction 8
~20h；Excessive ice cold water is added after fully reacting into solution, rotate and filters out to obtain white precipitate, by white precipitate
Dry 6h, obtains gray solid in vacuum drying oven；Gray solid is added in methanol solution, adds NaOH solution, instead
After answering 8h, it is acidified to acidity with dilute hydrochloric acid, is precipitated, repeatedly washed with deionized water and dry, obtain BHM-COOH；
(2) in molar ratio (1~12): (1~12): 1 takes EuCl3·6H2O、TbCl3·6H2O, BHM-COOH is placed in 20mL reaction
In kettle, deionized water and NaOH solution is added, and 10~20min is stirred at room temperature in mixture, cyclohexanol is added and will be mixed
It closes object and stirs 10~30min；Reaction kettle containing the mixture is heated to 80~120 DEG C, isothermal reaction 3~6 days, is obtained
Eu/Tb-BHM-COOH complex crude product；
(3) Eu/Tb-BHM-COOH complex crude product is filtered out into oily impurity while hot, for several times with ethanol washing, then at 50~
70 DEG C of 5~7h of vacuum drying are to get to Eu/Tb-BHM-COOH complex after purification, and structural formula is as shown in claim 1.
3. the preparation method of Eu/Tb-BHM-COOH complex according to claim 2, which is characterized in that the BHM-
The general structure of COOH are as follows:
4. the preparation method of Eu/Tb-BHM-COOH complex according to claim 2, which is characterized in that the step
(1) good solvent in is chloroform, n,N-Dimethylformamide, one or more in tetrahydrofuran.
5. the preparation method of Eu/Tb-BHM-COOH complex according to claim 2, which is characterized in that the step
(2) cyclohexanol in is the cyclohexanol for being put into 55 DEG C of baking oven inside holding 0.5h and being warmed.
6. a kind of preparation method of fluorescent optical sensor uses the Eu/Tb-BHM-COOH complex, which is characterized in that specific
Include the following steps:
A, by after Eu/Tb-BHM-COOH complex and PLA solution physical blending, ultrasonic 30min；
B, using the tape casting drop film, Eu/Tb-BHM-COOH-PLA fluorescence membrane, the as described fluorescent optical sensor is made.
7. the preparation method of fluorescent optical sensor according to claim 6, which is characterized in that in the step a, the Eu/
The solid-to-liquid ratio of Tb-BHM-COOH complex and PLA solution is (1~5): (1~10).
8. the preparation method of fluorescent optical sensor according to claim 6, which is characterized in that the concentration of the PLA aqueous solution
For 5~20g/L.
9. a kind of by fluorescent optical sensor Fe for identification3+Application, which is characterized in that the fluorescent optical sensor is by claim 6-
The preparation method of 8 described in any item fluorescent optical sensors is made.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909029A (en) * | 2020-08-24 | 2020-11-10 | 北京石油化工学院 | Preparation method of Eu/Tb (OH) (BDC) for detecting creatinine |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584873A (en) * | 2012-02-15 | 2012-07-18 | 浙江大学 | Double rare earth metal-organic framework material for temperature detection and synthesis method thereof |
| CN104193770A (en) * | 2014-08-01 | 2014-12-10 | 浙江大学 | Dual-rear-earth organic framework material for physiological temperature detection and preparation method of dual-rear-earth organic framework material |
| CN105086996A (en) * | 2015-08-26 | 2015-11-25 | 重庆理工大学 | Luminescent material with cyclotriphosphazene cross-linked rare-earth complexes and method for preparing luminescent material |
| CN106432341A (en) * | 2016-09-12 | 2017-02-22 | 重庆理工大学 | Hyperbranched CTP-TPY (Cyclotriphosphazene Terpyridyl), preparation method and recognition method of metal ions |
| CN106497549A (en) * | 2016-10-21 | 2017-03-15 | 中国科学院长春光学精密机械与物理研究所 | A kind of europium terbium is co-doped with luminescent material and preparation method thereof, application |
| CN106832311A (en) * | 2016-11-28 | 2017-06-13 | 南京工业大学 | The multicolor luminous crystalline materials of Eu MOF and Tb MOF green light crystal materials and preparation method thereof |
| US20180195990A1 (en) * | 2017-01-09 | 2018-07-12 | King Abdullah University Of Science And Technology | Gas sensors and methods of detecting gas |
| CN109232654A (en) * | 2018-11-08 | 2019-01-18 | 重庆理工大学 | A kind of Eu/Tb-TCP-COOH complex luminescent material and its preparation method and application |
| CN110003278A (en) * | 2019-04-23 | 2019-07-12 | 重庆理工大学 | A kind of six core tripolyphosphazene europium complex luminescent materials of excited by visible light and its preparation method and application |
-
2019
- 2019-07-18 CN CN201910651074.4A patent/CN110330664B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584873A (en) * | 2012-02-15 | 2012-07-18 | 浙江大学 | Double rare earth metal-organic framework material for temperature detection and synthesis method thereof |
| CN104193770A (en) * | 2014-08-01 | 2014-12-10 | 浙江大学 | Dual-rear-earth organic framework material for physiological temperature detection and preparation method of dual-rear-earth organic framework material |
| CN105086996A (en) * | 2015-08-26 | 2015-11-25 | 重庆理工大学 | Luminescent material with cyclotriphosphazene cross-linked rare-earth complexes and method for preparing luminescent material |
| CN106432341A (en) * | 2016-09-12 | 2017-02-22 | 重庆理工大学 | Hyperbranched CTP-TPY (Cyclotriphosphazene Terpyridyl), preparation method and recognition method of metal ions |
| CN106497549A (en) * | 2016-10-21 | 2017-03-15 | 中国科学院长春光学精密机械与物理研究所 | A kind of europium terbium is co-doped with luminescent material and preparation method thereof, application |
| CN106832311A (en) * | 2016-11-28 | 2017-06-13 | 南京工业大学 | The multicolor luminous crystalline materials of Eu MOF and Tb MOF green light crystal materials and preparation method thereof |
| US20180195990A1 (en) * | 2017-01-09 | 2018-07-12 | King Abdullah University Of Science And Technology | Gas sensors and methods of detecting gas |
| CN109232654A (en) * | 2018-11-08 | 2019-01-18 | 重庆理工大学 | A kind of Eu/Tb-TCP-COOH complex luminescent material and its preparation method and application |
| CN110003278A (en) * | 2019-04-23 | 2019-07-12 | 重庆理工大学 | A kind of six core tripolyphosphazene europium complex luminescent materials of excited by visible light and its preparation method and application |
Non-Patent Citations (5)
| Title |
|---|
| CHEN, ZHIJIE等: "Enriching the Reticular Chemistry Repertoire with Minimal Edge-Transitive Related Nets: Access to Highly Coordinated Metal-Organic Frameworks Based on Double Six-Membered Rings as Net-Coded Building Units", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| EUBANK, JARROD F.等: "The Quest for Modular Nanocages: tbo-MOF as an Archetype for Mutual Substitution, Functionalization, and Expansion of Quadrangular Pillar Building Blocks", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| HE, YUAN-CHUN等: "Luminescent Anionic Metal–Organic Framework with Potential Nitrobenzene Sensing", 《CRYSTAL GROWTH & DESIGN》 * |
| JIA, PENG等: "Selective sensing of Fe3+ ions in aqueous solution by a biodegradable platform based lanthanide metal organic framework", 《SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY》 * |
| 贾鹏: "基于稀土配合物荧光平台的构建及传感性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909029A (en) * | 2020-08-24 | 2020-11-10 | 北京石油化工学院 | Preparation method of Eu/Tb (OH) (BDC) for detecting creatinine |
| CN111909029B (en) * | 2020-08-24 | 2022-09-06 | 北京石油化工学院 | Preparation method of Eu/Tb (OH) (BDC) for detecting creatinine |
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