CN109705839A - A kind of rare-earth europium hybrid mesoporous luminescent material of terpyridyl derivative functionalization and its preparation method and application - Google Patents
A kind of rare-earth europium hybrid mesoporous luminescent material of terpyridyl derivative functionalization and its preparation method and application Download PDFInfo
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Abstract
The present invention provides rare-earth europium hybrid mesoporous luminescent materials of a kind of terpyridyl derivative functionalization and its preparation method and application, belong to rare earth mesoporous optochemical sensor field of material technology.Terpyridyl derivative covalent bond is grafted onto hybrid mesoporous material by the present invention by the method for fabricated in situ, obtains the hybrid mesoporous material of terpyridyl derivative functionalization；Then the rare-earth europium hybrid mesoporous luminescent material of terpyridyl derivative functionalization is obtained by ligand exchange reaction again.Preparation method provided by the invention makes gained luminescent material realize organic grafting between inorganic matrix in the level of molecule, and strong operability, favorable reproducibility, without catalyst etc., it is low in cost, and the mechanical performance and thermal stability of gained luminescent material are good, characteristic emission intensity is big, has sensitive selectivity to copper ion.
Description
Technical field
The present invention relates to rare earth mesoporous optochemical sensor field of material technology, in particular to a kind of terpyridyl derivative function
Rare-earth europium hybrid mesoporous luminescent material of energyization and its preparation method and application.
Background technique
Copper is micronutrient minerals needed by human, in close relations with human health, it is body internal protein and enzyme
Important component, and participate in and activate many important enzymes, for maintaining the normal operation of health and organ to have
There is very important effect.Human body, which lacks copper, can cause anaemia, artery exception, cerebral disorders etc., and copper content is superfluous, and liver can be caused hard
Change, diarrhea, dyskinesia and sensory nerve obstacle etc..Therefore, designing has Selective recognition function to copper ion with synthesis
Material has very important significance.
Due to optochemical sensor material have it is highly sensitive, can identify in real time and superiority, the photochemistry such as convenient and efficient pass
Sense material is rapidly developed in cations recognition.Wherein rare earth compounding especially Rare Earth Europium Complex has rare earth member
The feature that the emission band of element is narrow, excitation purity is high, fluorescence lifetime is long.Therefore, novel rare-earth fluorescent sensor increasingly by
The concern of research worker.There are a large amount of relevant document reports both at home and abroad at present, and partial results have been carried out business
Using.
But current rare-earth fluorescent chemical sensor is mostly simple rare-earth complexes luminous material, there are photo-thermal
The defect that stability is poor, mechanicalness is poor.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of hybrid mesoporous hairs of rare-earth europium of terpyridyl derivative functionalization
Luminescent material and its preparation method and application.The rare-earth europium of terpyridyl derivative functionalization provided by the invention is hybrid mesoporous to shine
Material mechanical is good, and thermostabilization is good, and responds to copper ion very sensitive.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of preparation method of the rare-earth europium hybrid mesoporous luminescent material of terpyridyl derivative functionalization, feature exist
In, comprising the following steps:
(1) under the conditions of nitrogen protection, terpyridyl derivative and thionyl chloride is mixed and carry out substitution reaction, obtains acyl
Chloromethylated intermediate；The terpyridyl derivative is terpyridyl carboxylic acid derivates；
(2) acid chloride intermediate, organic solvent, amine and organo silane coupling agent are mixed and carries out carboxylic conjunction reaction, obtained
Presoma；
(3) isothermal holding and hydro-thermal reaction will be successively carried out after the presoma, silicon source, template, water and mixed in hydrochloric acid,
By the template removal in gained hydro-thermal reaction product, the functional mesoporous hybrid material of terpyridyl derivative is obtained；
(4) the functional mesoporous hybrid material of the terpyridyl derivative and binary europium complex are carried out in alcoholic solvent
Ligand exchange reaction obtains the rare-earth europium hybrid mesoporous luminescent material of terpyridyl derivative functionalization.
Preferably, the terpyridyl derivative in the step (1) includes 4'- to phenoxy acetic acid -2,2':6', 2' tri-
Pyridine, 4'- para Toluic Acid -2,2':6', 2' terpyridyl, 4'- neighbour's phenoxy acetic acid -2,2':6', 2' terpyridyl or 4'- neighbour's benzene
Formic acid -2,2':6', 2' terpyridyl；
The molar ratio of the terpyridyl derivative and thionyl chloride is 1:(100~300).
Preferably, the temperature of substitution reaction is 60~75 DEG C in the step (1), and the time is 5~10h.
Preferably, the organic solvent in the step (2) includes in chloroform, n,N-Dimethylformamide and tetrahydrofuran
It is one or more of；
The organo silane coupling agent includes 3- aminopropyl triethoxysilane or 3- aminopropyl trimethoxysilane；
The amine includes one or more of diethylamine, triethylamine, butanediamine and hexamethylene diamine；
The molar ratio of the acid chloride intermediate, amine and organo silane coupling agent is 1:(1~2): (1~1.5).
Preferably, the silicon source in the step (3) is bis- (triethoxysilicane) ethane of 1,2- or ethyl orthosilicate；
The template is P123；
The molar ratio of the presoma and silicon source is 0.95:0.05~0.98:0.02；
The mass ratio of the template, water and hydrochloric acid is 1:(7~8): (2~2.5)；
The molar ratio of the presoma and template is 1:(0.016~0.018).
Preferably, the temperature of isothermal holding is 35~40 DEG C in the step (3), and the time is 18~30h；
The temperature of hydro-thermal reaction is 90~110 DEG C in the step (3), and the time is 24~50h.
Preferably, binary europium complex includes Eu (NTA) in the step (4)3·2H2O、Eu(TTA)3·2H2O or Eu
(DBM)3·2H2O；
The molar ratio of the functional mesoporous hybrid material of the terpyridyl derivative and binary europium complex be 1:(0.8~
1.5)。
Preferably, the temperature of ligand exchange reaction is 60~75 DEG C in the step (4), and the time is 10~15h.
The rare-earth europium of the terpyridyl derivative functionalization of the preparation of preparation method described in above scheme provided by the invention is situated between
Hole hybrid luminescent materials.
The present invention provides the hybrid mesoporous luminous materials of rare-earth europium of the terpyridyl derivative functionalization described in above scheme
Expect the application in copper ion identification.
The present invention provides a kind of preparation sides of the rare-earth europium hybrid mesoporous luminescent material of terpyridyl derivative functionalization
Terpyridyl derivative covalent bond is grafted onto hybrid mesoporous material by method, the present invention by the method for fabricated in situ, obtains three
The functional mesoporous hybrid material of dipyridyl derivatives；Then terpyridyl derivative functionalization is made to be situated between by ligand exchange reaction again
Hole hybrid material exchanges the water of coordination molecule in europium two-element match, to obtain the rare-earth europium of terpyridyl derivative functionalization
Hybrid mesoporous luminescent material.Preparation method provided by the invention make gained luminescent material realized in the level of molecule it is organic with
Grafting between inorganic matrix, so that the mechanical performance and thermal stability of luminescent material are improved, and strong operability, reproducibility
It is good, it is low in cost without catalyst etc..
The present invention provides rare-earth europium Jie of the terpyridyl derivative functionalization of the preparation of preparation method described in above scheme
Hole hybrid luminescent materials, luminescent material surface provided by the invention is regular, is a kind of orderly mesoporous nano luminescent material of sight that is situated between,
And good luminescence property, characteristic emission intensity is big, and thermal stability is good, overcome pure rare-earth complexes luminous material mechanicalness and
The insufficient weakness of stability, and the luminescent material has excellent copper ion sensing capabilities, has sensitive choosing to copper ion
Selecting property.Embodiment the result shows that, luminescent material provided by the invention is that 0.2 μM of copper ion can generate sensitive sound to concentration
It answers, and is that the fluorescence matched curve obtained within the scope of 0.2 μM~20 μM has good linear relationship in copper ion concentration.
Detailed description of the invention
Fig. 1 is 1 gained 4'- of the embodiment of the present invention to phenoxy acetic acid -2,2':6', the rare-earth europium of 2' terpyridyl functionalization
The transmission electron microscope picture of hybrid mesoporous luminescent material；
Fig. 2 is 1 gained 4'- of the embodiment of the present invention to phenoxy acetic acid -2,2':6', the rare-earth europium of 2' terpyridyl functionalization
The solid fluorescence launching light spectrogram of hybrid mesoporous luminescent material；
Fig. 3 is 1 gained 4'- of the embodiment of the present invention to phenoxy acetic acid -2,2':6', the rare-earth europium of 2' terpyridyl functionalization
The hot weight curve of hybrid mesoporous luminescent material；
Fig. 4 is 1 gained 4'- of the embodiment of the present invention to phenoxy acetic acid -2,2':6', the rare-earth europium of 2' terpyridyl functionalization
Fluorescence titration curve of the hybrid mesoporous luminescent material when copper ion is added；
Fig. 5 is 1 gained 4'- of the embodiment of the present invention to phenoxy acetic acid -2,2':6', the rare-earth europium of 2' terpyridyl functionalization
The matched curve of the fluorescence titration result of hybrid mesoporous luminescent material.
Specific embodiment
The present invention provides a kind of preparation sides of the rare-earth europium hybrid mesoporous luminescent material of terpyridyl derivative functionalization
Method, comprising the following steps:
(1) under the conditions of nitrogen protection, terpyridyl derivative and thionyl chloride is mixed and carry out substitution reaction, obtains acyl
Chloromethylated intermediate；The terpyridyl derivative is terpyridyl carboxylic acid derivates；
(2) acid chloride intermediate, organic solvent, amine and organo silane coupling agent are mixed and carries out carboxylic conjunction reaction, obtained
Presoma；
(3) isothermal holding and hydro-thermal reaction will be successively carried out after the presoma, silicon source, template, water and mixed in hydrochloric acid,
By the template removal in gained hydro-thermal reaction product, the functional mesoporous hybrid material of terpyridyl derivative is obtained；
(4) the functional mesoporous hybrid material of the terpyridyl derivative and binary europium complex are carried out in alcoholic solvent
Ligand exchange reaction obtains the rare-earth europium hybrid mesoporous luminescent material of terpyridyl derivative functionalization.
The present invention mixes terpyridyl derivative and thionyl chloride, and substitution reaction is carried out under the conditions of nitrogen protection, is obtained
To acid chloride intermediate.In the present invention, the terpyridyl derivative is terpyridyl carboxylic acid derivates (L-COOH), is preferably wrapped
4'- is included to phenoxy acetic acid -2,2':6', 2' terpyridyl, 4'- para Toluic Acid -2,2':6', 2' terpyridyl, 4'- neighbour's benzene oxygen second
Acid -2,2':6', 2' terpyridyl or 4'- o- benzoic acid -2,2':6', 2' terpyridyl；The terpyridyl derivative and chlorine
The molar ratio for changing sulfoxide is preferably 1:(100~300), more preferably 1:(150~250).
In the present invention, the temperature of the substitution reaction is preferably 60~75 DEG C, and more preferably 65~75 DEG C, the time is preferred
For 5~10h, more preferably 6~8h.The present invention preferably carries out substitution reaction under nitrogen protection and counterflow condition.
After substitution reaction, the present invention preferably removes the thionyl chloride in gained substitution reaction liquid, obtains in acyl chlorides
Mesosome (L-COCl).The present invention preferably distills 20~30min by Rotary Evaporators after substitution reaction, thus by chlorination
Sulfoxide removal, gained acid chloride intermediate (L-COCl) are thick red material.
After obtaining acid chloride intermediate (L-COCl), the present invention is by the acid chloride intermediate, organic solvent, amine and organosilan
Coupling agent mixing carries out carboxylic and closes reaction, obtains presoma (L-COOH-NH2).Acid chloride intermediate is preferably first dissolved in by the present invention
In organic solvent, then amine and organo silane coupling agent are sequentially added into solution.In the present invention, the organic solvent preferably wraps
Include one or more of chloroform, N,N-dimethylformamide and tetrahydrofuran；The organo silane coupling agent preferably includes 3-
Aminopropyl triethoxysilane or 3- aminopropyl trimethoxysilane；The amine preferably include diethylamine, triethylamine, butanediamine and
One or more of hexamethylene diamine；The molar ratio of the acid chloride intermediate, amine and organo silane coupling agent is preferably 1:(1~2):
(1~1.5), more preferably 1:(1.5): (1.2~1.3)；The present invention does not have particular/special requirement to the dosage of the organic solvent, makes
With consumption of organic solvent well known to those skilled in the art, carboxylic can be made to close reaction and gone on smoothly.
In the present invention, the temperature that the carboxylic closes reaction is preferably room temperature, and the time is preferably 2h.The present invention is preferably stirring
Under the conditions of carry out carboxylic close reaction；The present invention does not have particular/special requirement to the revolving speed of the stirring, and carboxylic can be made to close reaction and gone on smoothly
?.It is closed in reaction process in carboxylic, acyl chlorides and amine occur carboxylic and closes reaction generation amide.
Carboxylic closes after the reaction was completed, and the present invention preferably filters obtained carboxylic conjunction reaction solution, then will by rotary evaporation
Organic solvent in filtrate is evaporated off to arrive presoma (L-COOH-NH2)。
After obtaining presoma, the present invention will successively protect after the presoma, silicon source, template, water and mixed in hydrochloric acid
Temperature processing and hydro-thermal reaction, the template in gained hydro-thermal reaction product is removed, and obtains terpyridyl derivative functionalization Jie
Hole hybrid material (L-COOH-MSNs).In the present invention, the template is preferably P123；The silicon source is preferably 1,2- bis-
(triethoxysilicane) ethane or ethyl orthosilicate；In the present invention, when the template is P123, silicon source 1, bis- (three second of 2-
Oxygroup silicon) ethane when, the functional mesoporous hybrid material of gained terpyridyl derivative be periodic mesoporous hybrid material (L-
COOH-PMO)。
In the present invention, the concentration of the hydrochloric acid is preferably 2mol/L；The hydrochloric acid, which can play, to be adjusted solution ph, promotees
The effect of water inlet solution and self assembly.
In the present invention, the molar ratio of the presoma and silicon source is preferably 0.95:0.05~0.98:0.02；The mould
The mass ratio of plate agent, water and hydrochloric acid is preferably 1:(7~8): (2~2.5), more preferably 1:(7.3~7.5): (2.2~2.3)；
The molar ratio of the presoma and template is preferably 1:(0.016~0.018), more preferably 1:(0.0168~0.0173).
The present invention preferably mixes presoma and silicon source, obtains the first mixed liquor, hydrochloric acid is added after template is dissolved in water,
The second mixed liquor is obtained, then the first mixed liquor is added drop-wise in the second mixed liquor under 35~40 DEG C, stirring condition, is dripped
Mixed liquor is carried out isothermal holding by Bi Hou, the present invention.
In the present invention, the temperature of the isothermal holding is preferably 35~40 DEG C, and more preferably 36~38 DEG C, the time is preferred
For 18~30h, more preferably 20~25h；The present invention preferably carries out isothermal holding under agitation.The present invention passes through at heat preservation
Reason improves the condensation degree of dissolved of the hybrid mesoporous material of gained.
After the completion of isothermal holding, the mixed liquor is carried out hydro-thermal reaction by the present invention.In invention, the hydro-thermal reaction
Temperature is preferably 90~110 DEG C, and more preferably 95~105 DEG C, the time is preferably 24~50h, more preferably 36~48h.This hair
Bright that hydro-thermal reaction is preferably carried out in the stainless steel cauldron of polytetrafluoroethylene bushing, the present invention makes presoma by hydro-thermal reaction
Self assembly occurs with silicon source, obtains hybrid mesoporous material.
After the completion of hydro-thermal reaction, the present invention preferably filters the hydro-thermal reaction liquid, and is washed filter cake using deionized water
It is dried after washing to neutrality, obtains hydro-thermal reaction product.The present invention does not have particular/special requirement to the temperature of the drying, can be by filter cake
It is completely dried.
After obtaining hydro-thermal reaction product, the present invention removes the template in hydro-thermal reaction product.The present invention preferably passes through
Soxhlet extraction removes template agent removing, and the extractant of the Soxhlet extraction is preferably ethyl alcohol, and extraction time is preferably 18~28h, more excellent
It is selected as 20~25h.
After the completion of Soxhlet extraction, the product that the present invention preferably obtains Soxhlet extraction is dry, obtains terpyridyl derivative
Functional mesoporous hybrid material.The present invention does not have particular/special requirement to the temperature and time of the drying, can will be after Soxhlet extraction
Product be completely dried.In the present invention, the functional mesoporous hybrid material of gained terpyridyl derivative is yellow powder
End.
After obtaining the functional mesoporous hybrid material of terpyridyl derivative, the present invention is by the terpyridyl derivative function
Change hybrid mesoporous material and binary europium complex carries out ligand exchange reaction in alcoholic solvent, obtains terpyridyl derivative function
The rare-earth europium hybrid mesoporous luminescent material of change.In the present invention, the binary europium complex preferably includes Eu (NTA)3·2H2O、
Eu(TTA)3·2H2O or Eu (DBM)3·2H2O (wherein, NTA: β-naphthoyltrifluoroacetone, TTA:2- thenoyl trifluoropropyl
Ketone, DBM: dibenzoyl methane)；Mole of terpyridyl the derivative functional mesoporous hybrid material and binary europium complex
Than being preferably 1:(0.8~1.5), more preferably 1:1.
In the present invention, the alcoholic solvent is preferably methanol and/or ethyl alcohol；The present invention is preferably first molten by binary europium complex
Solution is added in lysate in alcoholic solvent, then by the functional mesoporous hybrid material of terpyridyl derivative.
In the present invention, the temperature of the ligand exchange reaction is preferably 60~75 DEG C, and more preferably 65~70 DEG C, the time
Preferably 10~15h, more preferably 12~13h；The present invention is preferably stirring and is carrying out ligand exchange reaction under counterflow condition.?
During ligand exchange reaction, because the coordination ability of terpyridyl carboxylic acid nitrogen-atoms is stronger than the coordination ability of hydrone, binary
Water of coordination molecule in europium complex is replaced by the functional mesoporous hybrid material of terpyridyl derivative, to obtain of the invention
Hybrid mesoporous luminescent material.
After the completion of ligand exchange reaction, the present invention preferably filters ligand exchange reaction liquid, will filter obtained solid product
It is dried in vacuo after washing, obtains the rare-earth europium hybrid mesoporous luminescent material of terpyridyl derivative functionalization.In the present invention
In, the washing is preferably ethyl alcohol with detergent；The vacuum drying temperature is preferably 55~65 DEG C, and more preferably 60 DEG C；
The present invention does not have particular/special requirement to the vacuum drying time, can be completely dried the product after washing.
The present invention provides rare-earth europium Jie of the terpyridyl derivative functionalization of the preparation of preparation method described in above scheme
Hole hybrid luminescent materials.Luminescent material provided by the invention realizes organic transferring between inorganic matrix in the level of molecule
It connects, mechanical performance and thermal stability are high, and have excellent copper ion sensing capabilities, have sensitive selectivity to copper ion.
It is hybrid mesoporous luminous that the present invention also provides the rare-earth europiums of the terpyridyl derivative functionalization described in above scheme
Application of the material in copper ion identification.In the present invention, the rare-earth europium of the terpyridyl derivative functionalization is hybrid mesoporous
Luminescent material has copper ion sensing capabilities, and characteristic emission intensity is big, has good illumination effect, and its fluorescence signal energy
Enough to be quenched by copper ion, copper ion additional amount is bigger, and fluorescence signal is poorer.Embodiment shows that terpyridyl of the invention spreads out
The fluorescence signal and copper ion concentration of the rare-earth europium hybrid mesoporous luminescent material of biological functional are closed with good linear fit
System, luminescent material of the invention have broad application prospects in copper ion identification.
It is hybrid mesoporous to a kind of rare-earth europium of terpyridyl derivative functionalization provided by the invention below with reference to embodiment
Luminescent material and its preparation method and application is described in detail, but they cannot be interpreted as to the scope of the present invention
Restriction.
Embodiment 1
(1) by 1mmol 4'- to phenoxy acetic acid -2,2':6', 2' terpyridyl is dissolved in 15mL thionyl chloride solvent,
It is placed in flask, the reaction temperature for controlling solution in flask is 60 DEG C, entire solution back flow reaction 8 hours in a nitrogen atmosphere.
After reaction, it distills 30 minutes, removes thionyl chloride with Rotary Evaporators to get acid chloride intermediate (thick red material is arrived
Matter L-COCl).
(2) 1mmol L-COCl is dissolved in 20mL chloroform, then adds 2mmol triethylamine, is subsequently added into 1.2mmol
3- aminopropyl triethoxysilane reacts two hours under stirring at normal temperature.It after fully reacting, is filtered, is left with Buchner funnel
Filtrate removes organic solvent with Rotary Evaporators to get presoma L-COOH-NH is arrived2。
(3) the hydrochloric acid 60g that 15g deionized water and 2mol/L is added in 2.0g Pluronic P123 surfactant is weighed,
Heating stirring is allowed to dissolve.Under room temperature, bis- (triethoxysilicane) ethane of 1,2- and presoma L-COOH-NH is slowly added dropwise2
Mixed liquor, the molar ratio of 1,2- bis- (triethoxysilicane) ethane and presoma is 0.94:0.06, total amount 1mol, stirring 24
Hour.It is then placed in the stainless steel cauldron that polytetrafluoroethylene (PTFE) is bushing, the crystallization 48 hours under the conditions of 100 DEG C.
After the completion of hydro-thermal reaction, product is washed with deionized to neutrality.It is dried at 60 DEG C, obtains non-template agent removing
Light yellow powder.Then, buff powder is extracted 24 hours in Soxhlet extractor with dehydrated alcohol, is dried to obtain three pyrroles
The functional mesoporous hybrid material of piperidine derivatives is buff powder.
(4) by 0.8mmol binary europium complex Eu (NTA)3·2H2O is dissolved in ethanol solution, and step (3) then are added
The functional mesoporous hybrid material 0.8mmol of the terpyridyl derivative of preparation, is stirred at reflux 12 hours, most under the conditions of 70 DEG C
The solid powder obtained eventually is collected by filtration, and with ethanol washing, vacuum drying is to get 4'- to phenoxy acetic acid -2,2':6', 2' tri-
The rare-earth europium hybrid mesoporous luminescent material of pyridine functional.
Gained 4'- to phenoxy acetic acid -2,2':6', the rare-earth europium hybrid mesoporous luminescent material of 2' terpyridyl functionalization
Characterization result:
Fig. 1 is gained europium hybrid mesoporous luminescent material transmission electron microscope picture, wherein (a) is the transmission electron microscope picture along [100] axis,
(b) for along the transmission electron microscope picture of [110] axis；According to Fig. 1 as can be seen that luminescent material prepared by the present invention is that surface is regular,
It is situated between and sees orderly mesoporous nano luminescent material.
Fig. 2 is the solid fluorescence launching light spectrogram of gained europium hybrid mesoporous luminescent material, and interior attached drawing is that gained europium is mesoporous miscellaneous
Change the picture that luminescent material is shot under the ultraviolet light irradiation of 365nm；According to fig. 2 it can be seen that europium prepared by the present invention is mesoporous
Hybrid luminescent materials have powerful fluorescent emission intensity, can be seen that the hybrid mesoporous luminous material of europium of the invention according to interior attached drawing
Material issues strong red fluorescence under the ultraviolet light irradiation of 365nm.
Fig. 3 is the thermogravimetric curve analysis chart of gained europium hybrid mesoporous luminescent material；According to Fig. 3 as can be seen that system of the present invention
Standby europium hybrid mesoporous luminescent material has excellent thermal stability.
Gained 4'- to phenoxy acetic acid -2,2':6', the rare-earth europium hybrid mesoporous luminescent material of 2' terpyridyl functionalization
Copper ion sensing capabilities are tested:
The europium hybrid mesoporous luminescent material being prepared is configured to the solution of 1mg/mL, carries out fluorescence titration experiment: to
Cu is added in europium hybrid mesoporous luminescent material solution2+Solution (Cu2+The concentration range of solution is 0~200 μM), using fluorescence light
Spectrometer carries out spectrofluorimetry；
Gained fluorescence titration curve is as shown in figure 4, the hybrid mesoporous luminescent material solution that interior attached drawing is 1mg/mL is added 200
The picture shot under the ultraviolet light irradiation of 365nm before and after μM copper ion.According to Fig. 4 as can be seen that Cu is not added2+When europium be situated between
The fluorescence intensity of hole hybrid luminescent materials solution is very strong, with Cu2+Concentration increases, and fluorescence intensity gradually decreases, Cu2+Concentration reaches
When to 200 μM, fluorescence signal is quenched；It can be seen that according to interior attached drawing before copper ion is added, the hybrid mesoporous hair of europium of the invention
Luminescent material shows strong red fluorescence under the ultraviolet light irradiation of 365nm, and after 200 μM of copper ions are added, fluorescence signal is quenched.
It is fitted according to the result of fluorescence titration curve, gained matched curve is as shown in Figure 5；According to Fig. 5 as can be seen that
It is fluorescence intensity and Cu within the scope of 0.2 μM~20 μM in copper ion concentration2+Concentration has good linear relationship (R=
0.99877), illustrate that hybrid mesoporous luminescent material prepared by the present invention can effectively carry out copper ion identification.
Embodiment 2
(1) by 1mmol 4'- to phenoxy acetic acid -2,2':6', 2' terpyridyl is dissolved in 15mL thionyl chloride solvent,
It is placed in flask, the reaction temperature for controlling solution in flask is 70 DEG C, entire solution back flow reaction 8 hours in a nitrogen atmosphere.
After reaction, it distills 30 minutes, removes thionyl chloride with Rotary Evaporators to get thick red material L-COCl is arrived.
(2) 1mmol L-COCl is dissolved in 20mL chloroform, then adds 2mmol triethylamine, is subsequently added into 1.2mmol
3- aminopropyl triethoxysilane reacts two hours under stirring at normal temperature.It after fully reacting, is filtered, is left with Buchner funnel
Filtrate removes organic solvent with Rotary Evaporators to get presoma L-COOH-NH is arrived2。
(3) the hydrochloric acid 60g that 15g deionized water and 2mol/L is added in 2.0g Pluronic P123 surfactant is weighed,
Heating stirring is allowed to dissolve.Under room temperature, bis- (triethoxysilicane) ethane of 1,2- and presoma L-COOH-NH is slowly added dropwise2
Mixed liquor, molar ratio 0.93:0.07, total amount 1mol, stir 24 hours.Be then placed in polytetrafluoroethylene (PTFE) be bushing not
In rust steel reaction kettle, the crystallization 40 hours under the conditions of 100 DEG C.
After the completion of hydro-thermal reaction, product is washed with deionized to neutrality, is dried at 60 DEG C, obtains non-template agent removing
Light yellow powder.Then, gained buff powder is extracted 24 hours in Soxhlet extractor with dehydrated alcohol, is dried to obtain three
The functional mesoporous hybrid material of dipyridyl derivatives is buff powder.
(4) by 0.8mmol binary europium complex Eu (NTA)3·2H2O is dissolved in ethanol solution, is then added above-mentioned
The buff powder of 0.8mmol is stirred at reflux 12 hours under the conditions of 70 DEG C, and finally obtained solid powder is collected by filtration,
With ethanol washing, to get 4'- to phenoxy acetic acid -2,2':6', the rare-earth europium of 2' terpyridyl functionalization is mesoporous miscellaneous for vacuum drying
Change luminescent material.
Embodiment 3
(1) by 1mmol 4'- to phenoxy acetic acid -2,2':6', 2' terpyridyl is dissolved in 15mL thionyl chloride solvent,
It is placed in flask, the reaction temperature for controlling solution in flask is 60~75 DEG C, and back flow reaction 8 is small in a nitrogen atmosphere for entire solution
When.After reaction, it distills 30 minutes, removes thionyl chloride with Rotary Evaporators to get thick red material L-COCl is arrived.
(2) 1mmol L-COCl is dissolved in 20mL chloroform, then adds 2mmol triethylamine, is subsequently added into 1.2mmol
3- aminopropyl triethoxysilane reacts two hours under stirring at normal temperature.It after fully reacting, is filtered, is left with Buchner funnel
Filtrate removes organic solvent with Rotary Evaporators to get presoma L-COOH-NH is arrived2。
(3) the hydrochloric acid 60g that 15g deionized water and 2mol/L is added in 2.0g Pluronic P123 surfactant is weighed,
Heating stirring is allowed to dissolve.Under room temperature, bis- (triethoxysilicane) ethane of 1,2- and presoma L-COOH-NH is slowly added dropwise2
Mixed liquor, molar ratio 0.94:0.06, total amount 1mol, stir 24 hours.Be then placed in polytetrafluoroethylene (PTFE) be bushing not
In rust steel reaction kettle, the crystallization 48 hours under the conditions of 100 DEG C.
After the completion of hydro-thermal reaction, product is washed with deionized to neutrality, is dried at 60 DEG C, obtains non-template agent removing
Light yellow powder.Then, the light yellow powder of gained is extracted 24 hours in Soxhlet extractor with dehydrated alcohol, is dried to obtain three
The functional mesoporous hybrid material of dipyridyl derivatives is buff powder.
(4) by 0.8mmol binary europium complex Eu (TTA)3·2H2O is dissolved in ethanol solution, and step (3) then are added
The functional mesoporous hybrid material 0.8mmol of the terpyridyl derivative of preparation, is stirred at reflux 12 hours, most under the conditions of 70 DEG C
The solid powder obtained eventually is collected by filtration, and with ethanol washing, vacuum drying is to get 4'- to phenoxy acetic acid -2,2':6', 2' tri-
The rare-earth europium hybrid mesoporous luminescent material of pyridine functional.
Embodiment 4
(1) by 1mmol 4'- to phenoxy acetic acid -2,2':6', 2' terpyridyl is dissolved in 15mL thionyl chloride solvent,
It is placed in flask, the reaction temperature for controlling solution in flask is 60~75 DEG C, and back flow reaction 8 is small in a nitrogen atmosphere for entire solution
When.After reaction, it distills 30 minutes, removes thionyl chloride with Rotary Evaporators to get thick red material L-COCl is arrived.
(2) 1mmol L-COCl is dissolved in 20mL chloroform, then adds 2mmol triethylamine, is subsequently added into 1.2mmol
3- aminopropyl triethoxysilane reacts two hours under stirring at normal temperature.It after fully reacting, is filtered, is left with Buchner funnel
Filtrate removes organic solvent with Rotary Evaporators to get presoma L-COOH-NH is arrived2。
(3) the hydrochloric acid 60g that 15g deionized water and 2mol/L is added in 2.0g Pluronic P123 surfactant is weighed,
Heating stirring is allowed to dissolve.Under room temperature, bis- (triethoxysilicane) ethane of 1,2- and presoma L-COOH-NH is slowly added dropwise2
Mixed liquor, molar ratio 0.94:0.06, total amount 1mol, stir 24 hours.Be then placed in polytetrafluoroethylene (PTFE) be bushing not
In rust steel reaction kettle, the crystallization 48 hours under the conditions of 100 DEG C.
After the completion of hydro-thermal reaction, product is washed with deionized to neutrality, is dried at 60 DEG C, obtains non-template agent removing
Light yellow powder.Then, light yellow powder is extracted 24 hours in Soxhlet extractor with dehydrated alcohol, is dried to obtain three pyrroles
The functional mesoporous hybrid material of piperidine derivatives is buff powder.
(4) by 0.8mmol binary europium complex Eu (DBM)3·2H2O is dissolved in ethanol solution, is then added above-mentioned
The buff powder of 0.8mmol is stirred at reflux 12 hours under the conditions of 70 DEG C, and finally obtained solid powder is collected by filtration,
With ethanol washing, to get 4'- to phenoxy acetic acid -2,2':6', the rare-earth europium of 2' terpyridyl functionalization is mesoporous miscellaneous for vacuum drying
Change luminescent material.
Embodiment 5
Other conditions and embodiment 1 are identical, and terpyridyl derivative is only replaced with 4'- para Toluic Acid -2,2':6', 2'
Terpyridyl obtains 4'- para Toluic Acid -2,2':6', the rare-earth europium hybrid mesoporous luminescent material of 2' terpyridyl functionalization.
Embodiment 6
Other conditions and embodiment 1 are identical, and terpyridyl derivative is only replaced with 4'- neighbour's phenoxy acetic acid -2,2':6',
2' terpyridyl obtains 4'- neighbour's phenoxy acetic acid -2,2':6', the hybrid mesoporous luminous material of the rare-earth europium of 2' terpyridyl functionalization
Material.
Embodiment 7
Other conditions and embodiment 1 are identical, and terpyridyl derivative is only replaced with 4'- o- benzoic acid -2,2':6', 2'
Terpyridyl obtains 4'- o- benzoic acid -2,2':6', the rare-earth europium hybrid mesoporous luminescent material of 2' terpyridyl functionalization.
Characterization is carried out to 2~7 products therefrom of embodiment according to the method in embodiment 1 and copper ion sensing capabilities are tested,
Acquired results and embodiment 1 are similar.
As can be seen from the above embodiments, preparation method provided by the invention makes gained luminescent material in the level of molecule
Organic grafting between inorganic matrix is realized, the mechanical performance and thermal stability of luminescent material, and operability are improved
By force, favorable reproducibility, it is low in cost without catalyst etc.；And the luminescent material surface being prepared is regular, and thermal stability is good,
There is sensitive selectivity to copper ion.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the rare-earth europium hybrid mesoporous luminescent material of terpyridyl derivative functionalization, which is characterized in that
The following steps are included:
(1) under the conditions of nitrogen protection, terpyridyl derivative and thionyl chloride is mixed and carry out substitution reaction, is obtained in acyl chlorides
Mesosome；The terpyridyl derivative is terpyridyl carboxylic acid derivates；
(2) acid chloride intermediate, organic solvent, amine and organo silane coupling agent are mixed and carries out carboxylic conjunction reaction, obtain forerunner
Body；
(3) isothermal holding and hydro-thermal reaction will be successively carried out after the presoma, silicon source, template, water and mixed in hydrochloric acid, by institute
The template removal in hydro-thermal reaction product is obtained, the functional mesoporous hybrid material of terpyridyl derivative is obtained；
(4) the functional mesoporous hybrid material of the terpyridyl derivative and binary europium complex are subjected to ligand in alcoholic solvent
Exchange reaction obtains the rare-earth europium hybrid mesoporous luminescent material of terpyridyl derivative functionalization.
2. preparation method according to claim 1, which is characterized in that the terpyridyl derivative packet in the step (1)
4'- is included to phenoxy acetic acid -2,2':6', 2' terpyridyl, 4'- para Toluic Acid -2,2':6', 2' terpyridyl, 4'- neighbour's benzene oxygen second
Acid -2,2':6', 2' terpyridyl or 4'- o- benzoic acid -2,2':6', 2' terpyridyl；
The molar ratio of the terpyridyl derivative and thionyl chloride is 1:(100~300).
3. preparation method according to claim 1, which is characterized in that the temperature of substitution reaction is 60 in the step (1)
~75 DEG C, the time is 5~10h.
4. preparation method according to claim 1, which is characterized in that the organic solvent in the step (2) include chloroform,
One or more of N,N-dimethylformamide and tetrahydrofuran；
The organo silane coupling agent includes 3- aminopropyl triethoxysilane or 3- aminopropyl trimethoxysilane；
The amine includes one or more of diethylamine, triethylamine, butanediamine and hexamethylene diamine；
The molar ratio of the acid chloride intermediate, amine and organo silane coupling agent is 1:(1~2): (1~1.5).
5. preparation method according to claim 1, which is characterized in that the silicon source in the step (3) is bis- (three second of 1,2-
Oxygroup silicon) ethane or ethyl orthosilicate；
The template is P123；
The molar ratio of the presoma and silicon source is 0.95:0.05~0.98:0.02；
The mass ratio of the template, water and hydrochloric acid is 1:(7~8): (2~2.5)；
The molar ratio of the presoma and template is 1:(0.016~0.018).
6. preparation method according to claim 1, which is characterized in that the temperature of isothermal holding is 35 in the step (3)
~40 DEG C, the time is 18~30h；
The temperature of hydro-thermal reaction is 90~110 DEG C in the step (3), and the time is 24~50h.
7. preparation method according to claim 1, which is characterized in that binary europium complex includes Eu in the step (4)
(NTA)3·2H2O、Eu(TTA)3·2H2O or Eu (DBM)3·2H2O；
The molar ratio of the functional mesoporous hybrid material of the terpyridyl derivative and binary europium complex is 1:(0.8~1.5).
8. preparation method according to claim 1, which is characterized in that the temperature of ligand exchange reaction in the step (4)
It is 60~75 DEG C, the time is 10~15h.
9. the rare-earth europium of the terpyridyl derivative functionalization of the preparation of preparation method described in claim 1~8 any one is mesoporous
Hybrid luminescent materials.
10. the rare-earth europium hybrid mesoporous luminescent material of terpyridyl derivative functionalization as claimed in claim 9 is known in copper ion
Application in not.
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| CN114539447A (en) * | 2021-12-29 | 2022-05-27 | 西北工业大学重庆科创中心 | Self-calibration ratio temperature probe based on europium metal polymer and preparation method thereof |
| CN114539447B (en) * | 2021-12-29 | 2023-06-09 | 西北工业大学重庆科创中心 | Self-calibration ratio temperature probe based on europium metal polymer and preparation method thereof |
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