CN106010502A - Preparation method of rare earth mesoporous hybrid luminescent material with fluorine ion sensing properties - Google Patents
Preparation method of rare earth mesoporous hybrid luminescent material with fluorine ion sensing properties Download PDFInfo
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Abstract
Belonging to the technical field of preparation of rare earth mesoporous optical chemosensing materials, the invention in particular relates to a preparation method of a rare earth mesoporous hybrid luminescent material with fluorine ion sensing properties. The method includes: covalently grafting an o-phenanthroline imidazole derivative ligand molecule to an inorganic mesoporous main skeleton, then introducing rare earth ions to synthesize a highly ordered rare earth mesoporous fluorine ion sensing material with stable chemical and thermal properties. The method provided by the invention has mild experimental conditions, the whole preparation system has the advantages of easy construction, simple operation, and easily controllable conditions, and the prepared product has stable quality and regular appearance.
Description
Technical field
The invention belongs to the preparing technical field of rare earth mesoporous optochemical sensor material, be specifically related to one and have
The system of the rare earth mesoporous hybridisation luminescent material of the adjacent Féraud beautiful jade imdazole derivatives functionalization of fluorine ion sensing performance
Preparation Method.
Background technology
Fluorion is widely present in nature with the form of fluoride, and with nerve gas, Drinking Water,
The uranium refinement of nuclear weapon, dental caries preventing and treating, osteoporotic clinical diagnosis etc. are closely related.Therefore, design is closed
The fluorion fluorescence chemical sensor that one-tenth is swift in response, susceptiveness is high is increasingly subject to people's attention.Sending out
Luminescent material field, rare earth compounding is high, right owing to having fluorescence lifetime length, light high color purity, luminous efficiency
Ligand modified do not affect the features such as central ion transmitting and be widely used in the identification of fluorion.But, pure dilute
Light stability and the heat stability of soil organic coordination compound are bad, therefore limit their use.And mesoporous material
Material, as a kind of excellent host material, has bigger pore volume, high specific surface area, orderly and adjustable
Pore passage structure, and modifiable inner surface, catalysis, adsorb and separate, nanomaterial assembly and
The various fields such as senser element have wide practical use.Although research worker also explores new constantly
Technology of preparing, but up to now, also not rare earth mesoporous miscellaneous about adjacent Féraud beautiful jade hydroxy derivatives functionalization
Change the synthetic technology report of luminescent material.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of has the rare earth mesoporous miscellaneous of fluorine ion sensing performance
Changing the preparation method of luminescent material, it will pass through altogether containing the rare earth compounding of adjacent Féraud beautiful jade imdazole derivatives
Valence link is grafted onto in inorganic mesoporous SBA-15 material of main part, thus achieves organic and nothing in the level of molecule
Grafting between machine substrate, has prepared luminous excellent, and has the rare earth mesoporous miscellaneous of sensitive response to fluorion
Formed material, and the performances such as its luminescence, optochemical sensor are studied.
For solving above-mentioned technical problem, the present invention is practiced by the following technical solutions:
The preparation method of a kind of rare earth mesoporous hybridisation luminescent material with fluorine ion sensing performance of the present invention, bag
Include following steps:
A, the synthesis of intermediate: neighbour's Féraud beautiful jade imdazole derivatives organic molecule is dissolved in organic solvent,
It is placed in flask, then the organic solvent dissolved with organo silane coupling agent is instilled in flask, control flask
The reaction temperature of interior solution is 60～75 DEG C, whole solution back flow reaction 10 in a nitrogen atmosphere～16 hours,
Remove organic solvent with Rotary Evaporators, obtain thick product, then with column chromatography use dichloromethane/
Methanol, as eluent, obtains the silicone intermediate that adjacent Féraud beautiful jade imdazole derivatives is modified；Wherein: adjacent
Féraud beautiful jade imdazole derivatives is 1:(1～1.3 with the mol ratio of organo-silicon coupling agent)；Methylene chloride/methanol
Ratio is (10～100): 1；
B, the synthetic reaction of the adjacent Féraud functional mesoporous SBA-15 of beautiful jade imdazole derivatives: by the neighbour of step a gained
The silicone intermediate of Féraud beautiful jade imdazole derivatives modification is mixed homogeneously with tetraethyl orthosilicate；Is lived in P123 surface
Property agent add in deionized water, stirring is allowed to dissolve, and adds and is uniformly mixed under hydrochloric acid, room temperature condition；
In whipping process, the silicone intermediate of dropping tetraethyl orthosilicate and adjacent Féraud beautiful jade imdazole derivatives modification
Mixed liquor, maintains the temperature at and stirs 18～30 hours at 35～40 DEG C；Wherein, adjacent Féraud beautiful jade imdazole derivatives changes
Property the mol ratio of silicone intermediate and tetraethyl orthosilicate be 0.95:0.05～0.98:0.02；P123 surface activity
The mass ratio of agent, deionized water and hydrochloric acid is 1:(7～8): (2～2.5)；
C, hydrothermal synthesis reaction: by step b | products therefrom is placed in the stainless steel reaction that politef is lining
In still, crystallization 24～50 hours under 90～110 DEG C of temperature conditionss；
D, filtration washing: be washed with deionized step c products therefrom the most neutral, dry, obtain the mould that do not eliminates
The white powder of plate agent；
E, the removal of template: step d products therefrom is used in apparatus,Soxhlet's ethanol extraction 18～28 little
Time, it is dried to obtain white powder；
F, the synthesis of rare earth mesoporous fluorine ion sensing material: be dissolved in ethanol solution by rare-earth salts, then will
Step e products therefrom is added thereto, and adds in said mixture by the ethanol solution of beta-diketon again after 2～6 hours,
Being stirred at reflux 10～15 hours under the conditions of 60～75 DEG C, the pressed powder finally given is collected by filtration, and uses second
Alcohol washs, vacuum drying, obtains required product；Wherein, rare-earth salts and step e products therefrom and beta-diketon
Mol ratio be 1:(1～3): (1～3).
Preferably, described in described step a, adjacent Féraud beautiful jade imdazole derivatives is 2-(2-hydroxyl)-imidazoles
[4,5-f]-1,10-neighbour's Féraud beautiful jade, 2-(3-hydroxyl)-imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade or 2-(4-hydroxyl)-imidazoles
[4,5-f]-1,10-neighbour's Féraud beautiful jade, 2-(2-sulfydryl)-imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade, 2-(3-sulfydryl)-imidazoles
Any one in [4,5-f]-1,10-neighbour's Féraud beautiful jade or 2-(4-sulfydryl)-imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade.
Preferably, organo-silicon coupling agent described in described step a is the silica-based propyl isocyanate of triethoxy, 3-
Any one in r-chloropropyl trimethoxyl silane or 3-aminopropyl trimethoxy silane.
Preferably, organic solvent described in described step a is anhydrous pyridine, oxolane, nitrogen, nitrogen-
In dimethylformamide or chloroform any one.
Preferably, rare-earth salts described in described step f is europium nitrate, Terbium nitrate (Tb(NO3)3), Europium chloride or terbium chloride
In any one.
Preferably, the beta-diketon described in described step f is thenoyltrifluoroacetone, dibenzoyl first
Any one in alkane, β-naphthoyltrifluoroacetone or hexafluoroacetylacetone.
Preferably, it is vacuum dried temperature described in described step f and is 55-65 DEG C.Optimum vacuum baking temperature is
60℃。
Preferably, the preparation side of the described rare earth mesoporous hybridisation luminescent material with fluorine ion sensing performance
Method, including step in detail below:
By 1mmol 2-(2-sulfydryl)-imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade is dissolved in 20mL anhydrous pyridine, is placed in burning
In Ping, then the 5ml anhydrous pyridine solution dissolved with the silica-based propyl isocyanate of 1mmol triethoxy is dropwise added
Entering, in control flask, the reaction temperature of solution is 75 DEG C, and whole solution back flow reaction 12 in a nitrogen atmosphere is little
Time, rotary evaporation removes organic solvent, then uses methylene chloride/methanol (60:1) conduct with column chromatography
Eluent, obtains 2-(2-sulfydryl)-imidazoles [4,5-f]-1, the silicone intermediate that 10-neighbour's Féraud beautiful jade is modified.Weigh
1.0g Pluronic P123 surfactant adds 7.5g deionized water and the hydrochloric acid 30g of 2mol/L, and heating is stirred
Mix and be allowed to dissolve.In whipping process, slowly dropping TEOS and the mixed liquor of calixarenes intermediate, mole
Ratio is 0.97:0.03, stirs 26 hours at 38 DEG C.It is then placed in the rustless steel that politef is lining
In reactor, crystallization 45 hours under the conditions of 100 DEG C, it is washed with deionized product the most neutral, at 60 DEG C
Lower drying, obtains the white powder of non-template agent removing.Then, apparatus,Soxhlet's is used dehydrated alcohol extraction
25 hours, it is dried to obtain white powder samples.Finally, 1mmol europium chloride is dissolved in ethanol solution,
It is subsequently adding the white powder of above-mentioned 3mmol, again by the second of 1mmol dibenzoyl methane after reacting two hours
Alcoholic solution adds in said mixture, stirring reaction 13 hours under the conditions of 70 DEG C.The solid finally given
Powder filter is collected, and uses dehydrated alcohol cyclic washing, is vacuum dried, obtains material requested under the conditions of 60 DEG C.
The present invention compared with prior art has the beneficial effect that
The rare earth mesoporous fluorine of the adjacent Féraud beautiful jade imdazole derivatives functionalization 1. prepared by the inventive method from
Sub-sensing material, rare earth ion characteristic emission intensity is big, and produces without organic and inorganic is separated, thus gram
Take small molecule emitter material mechanicalness and the weakness of stability deficiency, and it is regular to obtain surface, is situated between
See orderly mesoporous nano luminescent material.
The rare earth mesoporous fluorion of the adjacent Féraud beautiful jade imdazole derivatives functionalization 2. prepared by the inventive method
Sensing material, has sensitive selectivity to fluorion.
3. mild condition needed for the inventive method, workable, favorable reproducibility, and products obtained therefrom quality is steady
Fixed.Without additive, catalyst etc., economical, with low cost.
Accompanying drawing explanation
Fig. 1 is the dilute of the embodiment of the present invention 1 gained 2-(2-hydroxyl)-imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade functionalization
The small angle X-ray diffraction spectrogram of the mesoporous fluorine ion sensing material of soil.
Fig. 2 is the dilute of the embodiment of the present invention 1 gained 2-(2-hydroxyl)-imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade functionalization
The fluorescence emission spectrogram of the mesoporous fluorine ion sensing material of soil.
Fig. 3 is the dilute of the embodiment of the present invention 1 gained 2-(2-hydroxyl)-imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade functionalization
Soil mesoporous fluorine ion sensing material add fluorion time fluorescence titration curve and matched curve.
Detailed description of the invention
Below by embodiment, the invention will be further described, but protection scope of the present invention is not limited
In these embodiments.
Embodiment 1
1mmol 2-(2-hydroxyl)-imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade is dissolved in 20mL anhydrous tetrahydrochysene furan
In muttering, be placed in flask, then by dissolved with the silica-based propyl isocyanate of 1mmol triethoxy 5ml without
Water tetrahydrofuran solution is added dropwise over, and in control flask, the reaction temperature of solution is 70 DEG C, and whole solution exists
Back flow reaction 15 hours under nitrogen atmosphere, rotary evaporation removes organic solvent, then adopts with column chromatography
By methylene chloride/methanol (50:1) as eluent, obtaining 2-(2-hydroxyl)-imidazoles [4,5-f]-1,10-is adjacent
The silicone intermediate that Féraud beautiful jade is modified.Weigh 1.0g P123 surfactant add 7.5g deionized water and
The hydrochloric acid 30g of 2mol/L, heated and stirred is allowed to dissolve.In whipping process, slowly drip tetraethyl orthosilicate
The mixed liquor of the silicone intermediate modified with adjacent Féraud beautiful jade imdazole derivatives, mol ratio is 0.97:0.03,
Stir 24 hours at 35 DEG C.It is then placed in the stainless steel cauldron that politef is lining,
Crystallization 48 hours under the conditions of 100 DEG C.It is washed with deionized product to neutral.Dry at 60 DEG C,
White powder to non-template agent removing.Then, in apparatus,Soxhlet's, use dehydrated alcohol extraction 24 hours, dry
Dry obtain white powder samples.Finally, 1mmol rare earth europium nitrate is dissolved in ethanol solution, then adds
Enter the white powder of above-mentioned 3mmol, again by the ethanol of 1mmol thenoyltrifluoroacetone after reacting three hours
Solution adds in said mixture, stirring reaction 12 hours under the conditions of 65 DEG C.The solid finally given
Powder filter is collected, and uses dehydrated alcohol cyclic washing, is vacuum dried, obtains material requested under the conditions of 60 DEG C.
Embodiment 2
1mmol2-(3-hydroxyl)-imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade is dissolved in 20mL anhydrous tetrahydrochysene furan
In muttering, it is placed in flask, then by anhydrous for the 10ml dissolved with 1.1mmol 3-r-chloropropyl trimethoxyl silane
Tetrahydrofuran solution is added dropwise over, and in control flask, the reaction temperature of solution is 65 DEG C, and whole solution is at nitrogen
Back flow reaction 12 hours under gas atmosphere, rotary evaporation removes organic solvent, then uses two with column chromatography
Chloromethanes/methanol (60:1), as eluent, obtains 2-(3-hydroxyl)-imidazoles [4,5-f]-1,10-neighbour's Féraud
The silicone intermediate that beautiful jade is modified.Weigh 1.0g P123 surfactant add 7.5g deionized water and
The hydrochloric acid 30g of 2mol/L, heated and stirred is allowed to dissolve.In whipping process, slowly drip positive silicic acid second
The mixed liquor of the silicone intermediate of ester and adjacent Féraud beautiful jade imdazole derivatives modification, mol ratio is 0.965:
0.035, stir 26 hours.It is then placed in the stainless steel cauldron that politef is lining, at 100 DEG C
Under the conditions of crystallization 40 hours.It is washed with deionized product to neutral.Dry at 60 DEG C, obtain not
The white powder of template agent removing.Then, in apparatus,Soxhlet's, use dehydrated alcohol extraction 20 hours, be dried
Obtain white powder samples.Finally, 1mmol rare earth Terbium nitrate (Tb(NO3)3) is dissolved in ethanol solution, then adds
Enter the white powder of above-mentioned 3mmol, again by 1mmol thenoyltrifluoroacetone after reacting two hours
Ethanol solution adds in said mixture, stirs 12 hours under the conditions of 60 DEG C.The solid finally given
Powder filter is collected, and uses dehydrated alcohol cyclic washing, is vacuum dried, obtains material requested under the conditions of 65 DEG C.
Embodiment 3
By 1mmol 2-(2-sulfydryl)-imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade is dissolved in 20mL anhydrous pyridine,
It is placed in flask, then by the 5ml anhydrous pyridine solution dissolved with 1mmol 3-aminopropyl trimethoxy silane dropwise
Adding, in control flask, the reaction temperature of solution is 75 DEG C, whole solution back flow reaction 12 in a nitrogen atmosphere
Hour, rotary evaporation removes organic solvent, then uses methylene chloride/methanol (60:1) to make with column chromatography
For eluent, obtain 2-(2-sulfydryl)-imidazoles [4,5-f]-1, the silicone intermediate that 10-neighbour's Féraud beautiful jade is modified.Weigh
1.0g Pluronic P123 surfactant adds 7.5g deionized water and the hydrochloric acid 30g of 2mol/L, and heating is stirred
Mix and be allowed to dissolve.In whipping process, slowly dropping tetraethyl orthosilicate and adjacent Féraud beautiful jade imdazole derivatives are modified
The mixed liquor of silicone intermediate, mol ratio is 0.97:0.03, stirs 26 hours at 38 DEG C.Then
Put in the stainless steel cauldron that politef is lining, crystallization 45 hours under the conditions of 100 DEG C.Spend
Ionized water washed product is to neutral.Dry at 60 DEG C, obtain the white powder of non-template agent removing.Then,
In apparatus,Soxhlet's, use dehydrated alcohol extraction 25 hours, be dried to obtain white powder samples.Finally, will
1mmol europium chloride is dissolved in ethanol solution, is subsequently adding the white powder of above-mentioned 3mmol, reacts two
Again the ethanol solution of 1mmol dibenzoyl methane is added in said mixture after hour, under the conditions of 70 DEG C
Stirring reaction 13 hours.The pressed powder finally given is collected by filtration, and uses dehydrated alcohol cyclic washing, 60 DEG C
Under the conditions of be vacuum dried, obtain material requested.
Embodiment 4
By 1mmol 2-(3-sulfydryl)-imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade is dissolved in 20mL anhydrous pyridine,
It is placed in flask, then by the 10ml anhydrous tetrahydrochysene furan dissolved with the silica-based propyl isocyanate of 1mmol triethoxy
Solution of muttering is added dropwise over, and in control flask, the reaction temperature of solution is 75 DEG C, and whole solution is in a nitrogen atmosphere
Back flow reaction 12 hours, rotary evaporation removes organic solvent, then uses methylene chloride/methanol with column chromatography
(65:1) as eluent, 2-(2-sulfydryl)-imidazoles [4,5-f]-1 is obtained, the siloxanes that 10-neighbour's Féraud beautiful jade is modified
Intermediate.Weigh 1.0g P123 surfactant and add 7.5g deionized water and the hydrochloric acid 30g of 2mol/L,
Heated and stirred is allowed to dissolve.In whipping process, slowly dropping tetraethyl orthosilicate and adjacent Féraud beautiful jade imidazole derivatives
The mixed liquor of the silicone intermediate that thing is modified, mol ratio is 0.98:0.02, stirs 26 hours at 38 DEG C.
It is then placed in the stainless steel cauldron that politef is lining, crystallization 36 hours under the conditions of 100 DEG C.
It is washed with deionized product to neutral.Dry at 65 DEG C, obtain the white powder of non-template agent removing.So
After, in apparatus,Soxhlet's, use dehydrated alcohol extraction 24 hours, be dried to obtain white powder samples.Finally,
1mmol terbium trichloride is dissolved in ethanol solution, is subsequently adding the white powder of above-mentioned 3mmol, reaction
Again the ethanol solution of 1mmol dibenzoyl methane is added in said mixture after three hours, 70 DEG C of conditions
Lower stirring reaction 12 hours.The pressed powder finally given is collected by filtration, and uses dehydrated alcohol cyclic washing,
It is vacuum dried under the conditions of 65 DEG C, obtains material requested.
Claims (9)
1. having a preparation method for the rare earth mesoporous hybridisation luminescent material of fluorine ion sensing performance, it is special
Levy is to comprise the following steps:
A, the synthesis of intermediate: neighbour's Féraud beautiful jade imdazole derivatives organic molecule is dissolved in organic solvent,
It is placed in flask, then the organic solvent dissolved with organo silane coupling agent is instilled in flask, control flask
The reaction temperature of interior solution is 60～75 DEG C, whole solution back flow reaction 10 in a nitrogen atmosphere～16 hours,
Remove organic solvent with Rotary Evaporators, obtain thick product, then with column chromatography use dichloromethane/
Methanol, as eluent, obtains the silicone intermediate that adjacent Féraud beautiful jade imdazole derivatives is modified；Wherein: adjacent
Féraud beautiful jade imdazole derivatives is 1:(1～1.3 with the mol ratio of organo-silicon coupling agent)；Methylene chloride/methanol
Ratio be (10～100): 1；
B, the synthetic reaction of the adjacent Féraud functional mesoporous SBA-15 of beautiful jade imdazole derivatives: by step a gained
The silicone intermediate of adjacent Féraud beautiful jade imdazole derivatives modification is mixed homogeneously with tetraethyl orthosilicate；By P123 surface
Activating agent adds in deionized water, and stirring is allowed to dissolve, and adds hydrochloric acid, and under room temperature condition, stirring mixing is all
Even；In whipping process, in the middle of the siloxanes of dropping tetraethyl orthosilicate and adjacent Féraud beautiful jade imdazole derivatives modification
The mixed liquor of body, maintains the temperature at and stirs 18～30 hours at 35～40 DEG C；Wherein, adjacent Féraud beautiful jade imidazole derivatives
Silicone intermediate and the mol ratio of tetraethyl orthosilicate that thing is modified are 0.95:0.05～0.98:0.02；P123 surface
The mass ratio of activating agent, deionized water and hydrochloric acid is 1:(7～8): (2～2.5)；
C, hydrothermal synthesis reaction: by step b | products therefrom is placed in the stainless steel reaction that politef is lining
In still, crystallization 24～50 hours under 90～110 DEG C of temperature conditionss；
D, filtration washing: be washed with deionized step c products therefrom the most neutral, dry, obtain the mould that do not eliminates
The white powder of plate agent；
E, the removal of template: step d products therefrom is used in apparatus,Soxhlet's ethanol extraction 18～28 little
Time, it is dried to obtain white powder；
F, the synthesis of rare earth mesoporous fluorine ion sensing material: be dissolved in ethanol solution by rare-earth salts, then will
Step e products therefrom is added thereto, and again the ethanol solution of beta-diketon is added said mixture after 2～6 hours
In, under the conditions of 60～75 DEG C, it being stirred at reflux 10～15 hours, the pressed powder finally given is collected by filtration,
With washing with alcohol, vacuum drying, obtain required product；Wherein, rare-earth salts and step e products therefrom and β
The mol ratio of-diketone is 1:(1～3): (1～3).
The rare earth mesoporous hybridisation luminescent material with fluorine ion sensing performance the most according to claim 1
Preparation method, it is characterized in that, adjacent Féraud beautiful jade imdazole derivatives described in described step a be 2-(2-hydroxyl)-
Imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade, 2-(3-hydroxyl)-imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade or 2-(4-hydroxyl)-
Imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade, 2-(2-sulfydryl)-imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade, 2-(3-sulfydryl)-
Any one in imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade or 2-(4-sulfydryl)-imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade.
The rare earth mesoporous hybridisation luminescent material with fluorine ion sensing performance the most according to claim 1
Preparation method, it is characterized in that, organo-silicon coupling agent described in described step a is the silica-based isocyanide of triethoxy
Any one in propyl propionate, 3-r-chloropropyl trimethoxyl silane or 3-aminopropyl trimethoxy silane.
A kind of rare earth mesoporous hybridisation with fluorine ion sensing performance the most according to claim 1 is sent out
The preparation method of luminescent material, is characterized in that, organic solvent described in described step a be anhydrous pyridine, four
Hydrogen furan, nitrogen, in nitrogen-dimethylformamide or chloroform any one.
A kind of rare earth mesoporous hybridisation with fluorine ion sensing performance the most according to claim 1 is sent out
The preparation method of luminescent material, is characterized in that, rare-earth salts described in described step f be europium nitrate, Terbium nitrate (Tb(NO3)3),
Any one in Europium chloride or terbium chloride.
A kind of rare earth mesoporous hybridisation with fluorine ion sensing performance the most according to claim 1 is sent out
The preparation method of luminescent material, is characterized in that, the beta-diketon described in described step f is thenoyl trifluoro
Any one in acetone, dibenzoyl methane, β-naphthoyltrifluoroacetone or hexafluoroacetylacetone.
A kind of rare earth mesoporous hybridisation with fluorine ion sensing performance the most according to claim 1 is sent out
The preparation method of luminescent material, is characterized in that, is vacuum dried temperature and is 55-65 DEG C described in described step f.
A kind of rare earth mesoporous hybridisation with fluorine ion sensing performance the most according to claim 7 is sent out
The preparation method of luminescent material, is characterized in that, being vacuum dried temperature described in described step f is 60 DEG C.
The rare earth mesoporous hybridisation luminescent material with fluorine ion sensing performance the most according to claim 1
Preparation method, it is characterized in that including step in detail below:
By 1mmol 2-(2-sulfydryl)-imidazoles [4,5-f]-1,10-neighbour's Féraud beautiful jade is dissolved in 20mL anhydrous pyridine, puts
In flask, then by dissolved with the silica-based propyl isocyanate of 1mmol triethoxy 5ml anhydrous pyridine solution by
Being added dropwise to, in control flask, the reaction temperature of solution is 75 DEG C, whole solution back flow reaction in a nitrogen atmosphere
12 hours, rotary evaporation removed organic solvent, then uses methylene chloride/methanol (60:1) with column chromatography
As eluent, obtain 2-(2-sulfydryl)-imidazoles [4,5-f]-1, the silicone intermediate that 10-neighbour's Féraud beautiful jade is modified.
Weigh 1.0g Pluronic P123 surfactant and add 7.5g deionized water and the hydrochloric acid 30g of 2mol/L,
Heated and stirred is allowed to dissolve.In whipping process, slowly dropping tetraethyl orthosilicate and adjacent Féraud beautiful jade imidazole derivatives
The mixed liquor of the silicone intermediate that thing is modified, mol ratio is 0.97:0.03, stirs 26 hours at 38 DEG C.
It is then placed in the stainless steel cauldron that politef is lining, crystallization 45 hours under the conditions of 100 DEG C,
It is washed with deionized product the most neutral, dries at 60 DEG C, obtain the white powder of non-template agent removing.So
After, in apparatus,Soxhlet's, use dehydrated alcohol extraction 25 hours, be dried to obtain white powder samples.Finally,
1mmol europium chloride is dissolved in ethanol solution, is subsequently adding the white powder of above-mentioned 3mmol, reaction
Again the ethanol solution of 1mmol dibenzoyl methane is added in said mixture after two hours, 70 DEG C of conditions
Lower stirring reaction 13 hours.The pressed powder finally given is collected by filtration, and uses dehydrated alcohol cyclic washing,
It is vacuum dried under the conditions of 60 DEG C, obtains material requested.
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| CN109705839A (en) * | 2018-11-29 | 2019-05-03 | 河北科技大学 | A kind of rare-earth europium hybrid mesoporous luminescent material of terpyridyl derivative functionalization and its preparation method and application |
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| CN109705839A (en) * | 2018-11-29 | 2019-05-03 | 河北科技大学 | A kind of rare-earth europium hybrid mesoporous luminescent material of terpyridyl derivative functionalization and its preparation method and application |
| CN109705839B (en) * | 2018-11-29 | 2021-08-31 | 河北科技大学 | Terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material and preparation method and application thereof |
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| CN106010502B (en) | 2019-03-01 |
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