CN109705839B - Terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material and preparation method and application thereof - Google Patents
Terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material and a preparation method and application thereof, belonging to the technical field of rare earth mesoporous photochemical sensing materials. According to the invention, a terpyridine derivative covalent bond is grafted into a mesoporous hybrid material by an in-situ synthesis method to obtain a terpyridine derivative functionalized mesoporous hybrid material; then ligand exchange reaction is carried out to obtain the terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material. The preparation method provided by the invention realizes grafting between organic and inorganic substrates on the molecular level of the obtained luminescent material, and has the advantages of strong operability, good reproducibility, no need of catalysts and the like, low cost, good mechanical property and thermal stability of the obtained luminescent material, high characteristic emission intensity and sensitive selectivity on copper ions.
Description
Technical Field
The invention relates to the technical field of rare earth mesoporous photochemical sensing materials, in particular to a terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material and a preparation method and application thereof.
Background
Copper is a micronutrient mineral which is essential to human body, is closely related to human health, is an important component of protein and enzyme in the body, participates in and activates a plurality of important enzymes, and has very important function for maintaining body health and normal operation of organs. The lack of copper in human body can cause anemia, arterial abnormality, brain disorder, etc., and the excessive copper content can cause liver cirrhosis, diarrhea, dyskinesia, sensory neuropathy, etc. Therefore, the design and synthesis of materials with selective recognition function for copper ions are of great significance.
The photochemical sensing material has the advantages of high sensitivity, real-time identification, convenience, rapidness and the like, so the photochemical sensing material is rapidly developed in cation identification. The rare earth complex, especially the rare earth europium complex, has the characteristics of narrow emission band, high color purity and long fluorescence life of the rare earth elements. Therefore, new types of rare earth fluorescence sensors are receiving increasing attention from researchers. At present, a large number of related documents are reported at home and abroad, and part of results are commercially applied.
However, most of the existing rare earth fluorescence chemical sensors are pure rare earth complex luminescent materials and have the defects of poor photo-thermal stability and poor mechanical property.
Disclosure of Invention
In view of the above, the present invention aims to provide a terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material, and a preparation method and an application thereof. The terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material provided by the invention has the advantages of good mechanical property, good thermal stability and very sensitive response to copper ions.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material is characterized by comprising the following steps:
(1) under the condition of nitrogen protection, mixing a terpyridine derivative and thionyl chloride for substitution reaction to obtain an acyl chloride intermediate; the terpyridine derivative is a terpyridine carboxylic acid derivative;
(2) mixing the acyl chloride intermediate, an organic solvent, amine and an organosilane coupling agent to carry out a carboxyl reaction to obtain a precursor;
(3) mixing the precursor, a silicon source, a template agent, water and hydrochloric acid, sequentially carrying out heat preservation treatment and hydrothermal reaction, and removing the template agent in the obtained hydrothermal reaction product to obtain a terpyridine derivative functionalized mesoporous hybrid material;
(4) and carrying out ligand exchange reaction on the terpyridine derivative functionalized mesoporous hybrid material and a binary europium complex in an alcohol solvent to obtain the terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material.
Preferably, the terpyridine derivative in the step (1) comprises 4 '-p-phenoxyacetic acid-2, 2':6',2' terpyridine, 4 '-p-benzoic acid-2, 2':6',2' terpyridine, 4 '-o-phenoxyacetic acid-2, 2':6',2' terpyridine or 4 '-o-benzoic acid-2, 2':6',2' terpyridine;
the molar ratio of the terpyridine derivative to the thionyl chloride is 1 (100-300).
Preferably, the temperature of the substitution reaction in the step (1) is 60-75 ℃, and the time is 5-10 h.
Preferably, the organic solvent in step (2) comprises one or more of chloroform, N-dimethylformamide and tetrahydrofuran;
the organosilane coupling agent comprises 3-aminopropyltriethoxysilane or 3-aminopropyltrimethoxysilane;
the amine comprises one or more of diethylamine, triethylamine, butanediamine and hexanediamine;
the mole ratio of the acyl chloride intermediate to the amine to the organosilane coupling agent is 1 (1-2) to 1-1.5.
Preferably, the silicon source in the step (3) is 1, 2-bis (triethoxy silicon) ethane or ethyl orthosilicate;
the template agent is P123;
the molar ratio of the precursor to the silicon source is 0.95: 0.05-0.98: 0.02;
the mass ratio of the template agent to the water to the hydrochloric acid is 1 (7-8) to 2-2.5;
the molar ratio of the precursor to the template is 1 (0.016-0.018).
Preferably, the temperature of the heat preservation treatment in the step (3) is 35-40 ℃, and the time is 18-30 h;
the temperature of the hydrothermal reaction in the step (3) is 90-110 ℃, and the time is 24-50 h.
Preferably, the binary europium complex in the step (4) comprises Eu (NTA)3·2H2O、Eu(TTA)3·2H2O or Eu (DBM)3·2H2O；
The molar ratio of the terpyridine derivative functionalized mesoporous hybrid material to the binary europium complex is 1 (0.8-1.5).
Preferably, the temperature of the ligand exchange reaction in the step (4) is 60-75 ℃, and the time is 10-15 h.
The invention provides a terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material prepared by the preparation method.
The invention provides application of a terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material in copper ion recognition.
The invention provides a preparation method of a terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material, which grafts terpyridine derivatives into the mesoporous hybrid material through an in-situ synthesis method to obtain the terpyridine derivative functionalized mesoporous hybrid material; then, ligand exchange reaction is carried out to ensure that the terpyridine derivative functionalized mesoporous hybrid material exchanges coordinated water molecules in the europium binary complex, thereby obtaining the terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material. The preparation method provided by the invention realizes grafting between organic and inorganic matrixes on the molecular level of the luminescent material, thereby improving the mechanical property and thermal stability of the luminescent material, and having strong operability, good reproducibility, no need of catalysts and the like, and low cost.
The invention provides the terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material prepared by the preparation method in the scheme, the luminescent material provided by the invention has a regular surface, is a mesoporous ordered nano mesoporous luminescent material, has excellent luminescent performance, large characteristic emission intensity and good thermal stability, overcomes the defects of insufficient mechanical property and stability of a pure rare earth complex luminescent material, and has excellent copper ion sensing performance and sensitive selectivity on copper ions. The embodiment result shows that the luminescent material provided by the invention can generate sensitive response to copper ions with the concentration of 0.2 mu M, and the fluorescence fitting curve obtained in the range of the copper ion concentration of 0.2 mu M-20 mu M has good linear relation.
Drawings
FIG. 1 is a transmission electron microscope image of a 4 '-p-phenoxyacetic acid-2, 2', 6',2' terpyridine functionalized rare earth europium mesoporous hybrid luminescent material obtained in example 1 of the present invention;
FIG. 2 is a solid fluorescence emission spectrum of a rare earth europium mesoporous hybrid luminescent material functionalized by 4 '-p-phenoxyacetic acid-2, 2':6',2' terpyridine obtained in example 1 of the present invention;
FIG. 3 is a thermogravimetric graph of a 4 '-p-phenoxyacetic acid-2, 2' -6 ',2' -terpyridine functionalized rare earth europium mesoporous hybrid luminescent material obtained in example 1 of the present invention;
FIG. 4 is a fluorescence titration curve of the 4 '-p-phenoxyacetic acid-2, 2', 6',2' terpyridine functionalized rare earth europium mesoporous hybrid luminescent material obtained in example 1 of the present invention when copper ions are added;
FIG. 5 is a fitting curve of the fluorescence titration results of the 4 '-p-phenoxyacetic acid-2, 2', 6',2' terpyridine functionalized rare earth europium mesoporous hybrid luminescent material obtained in example 1 of the present invention.
Detailed Description
The invention provides a preparation method of a terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material, which comprises the following steps:
(1) under the condition of nitrogen protection, mixing a terpyridine derivative and thionyl chloride for substitution reaction to obtain an acyl chloride intermediate; the terpyridine derivative is a terpyridine carboxylic acid derivative;
(2) mixing the acyl chloride intermediate, an organic solvent, amine and an organosilane coupling agent to carry out a carboxyl reaction to obtain a precursor;
(3) mixing the precursor, a silicon source, a template agent, water and hydrochloric acid, sequentially carrying out heat preservation treatment and hydrothermal reaction, and removing the template agent in the obtained hydrothermal reaction product to obtain a terpyridine derivative functionalized mesoporous hybrid material;
(4) and carrying out ligand exchange reaction on the terpyridine derivative functionalized mesoporous hybrid material and a binary europium complex in an alcohol solvent to obtain the terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material.
In the invention, terpyridine derivatives and thionyl chloride are mixed, and substitution reaction is carried out under the condition of nitrogen protection to obtain an acyl chloride intermediate. In the present invention, the terpyridine derivative is a terpyridine carboxylic acid derivative (L-COOH), preferably including 4 '-p-phenoxyacetic acid-2, 2':6',2' terpyridine, 4 '-p-benzoic acid-2, 2':6',2' terpyridine, 4 '-o-phenoxyacetic acid-2, 2':6',2' terpyridine or 4 '-o-benzoic acid-2, 2':6',2' terpyridine; the molar ratio of the terpyridine derivative to the thionyl chloride is preferably 1 (100-300), and more preferably 1 (150-250).
In the invention, the temperature of the substitution reaction is preferably 60-75 ℃, more preferably 65-75 ℃, and the time is preferably 5-10 hours, more preferably 6-8 hours. The invention preferably carries out the substitution reaction under the protection of nitrogen and under the reflux condition.
After the completion of the substitution reaction, in the present invention, it is preferable to remove thionyl chloride in the obtained substitution reaction solution to obtain an acid chloride intermediate (L-COCl). According to the invention, preferably, after the substitution reaction is finished, the thionyl chloride is removed by distilling for 20-30 min through a rotary evaporator, and the obtained acyl chloride intermediate (L-COCl) is a viscous red substance.
After obtaining the acyl chloride intermediate (L-COCl), the invention mixes the acyl chloride intermediate, organic solvent, amine and organosilane coupling agent for carboxylic reaction to obtain precursor (L-COOH-NH)2). In the invention, preferably, the acyl chloride intermediate is dissolved in an organic solvent, and then the amine and the organosilane coupling agent are sequentially added into the solution. In the present invention, the organic solvent preferably includes one or more of chloroform, N-dimethylformamide and tetrahydrofuran; the organosilane coupling agent preferably comprises 3-aminopropyltriethoxysilane or 3-aminopropyltrimethoxysilane; the amine preferably includes diethylamine, triethylamine,One or more of butanediamine and hexanediamine; the mole ratio of the acyl chloride intermediate, the amine and the organic silane coupling agent is preferably 1 (1-2) to 1-1.5, and more preferably 1 (1.5) to 1.2-1.3; the invention has no special requirement on the dosage of the organic solvent, and the carboxyl reaction can be smoothly carried out by using the dosage of the organic solvent which is well known to a person skilled in the art.
In the present invention, the temperature of the carboxylic acid polymerization reaction is preferably room temperature, and the time is preferably 2 hours. In the invention, the carboxylation reaction is preferably carried out under the stirring condition; the invention has no special requirement on the stirring rotating speed, and can ensure that the carboxylic polymerization reaction is smoothly carried out. During the carboxylation reaction, acyl chloride and amine are subjected to carboxylation reaction to generate amide.
After the carboxylation reaction is finished, the obtained carboxylation reaction liquid is preferably filtered, and the organic solvent in the filtrate is evaporated through rotary evaporation to obtain the precursor (L-COOH-NH)2)。
After the precursor is obtained, the precursor, a silicon source, a template agent, water and hydrochloric acid are mixed and then are subjected to heat preservation treatment and hydrothermal reaction in sequence, and the template agent in the obtained hydrothermal reaction product is removed to obtain the terpyridine derivative functionalized mesoporous hybrid material (L-COOH-MSNs). In the present invention, the templating agent is preferably P123; the silicon source is preferably 1, 2-bis (triethoxysilyl) ethane or tetraethoxysilane; in the invention, when the template agent is P123 and the silicon source is 1, 2-bis (triethoxy silicon) ethane, the obtained terpyridine derivative functionalized mesoporous hybrid material is a periodic mesoporous hybrid material (L-COOH-PMO).
In the present invention, the concentration of the hydrochloric acid is preferably 2 mol/L; the hydrochloric acid can play a role in adjusting the pH value of the solution and promoting hydrolysis and self-assembly.
In the invention, the molar ratio of the precursor to the silicon source is preferably 0.95: 0.05-0.98: 0.02; the mass ratio of the template agent to the water to the hydrochloric acid is preferably 1 (7-8) to 2-2.5, and more preferably 1 (7.3-7.5) to 2.2-2.3; the molar ratio of the precursor to the template is preferably 1: (0.016 to 0.018), preferably 1: (0.0168 to 0.0173).
The preparation method comprises the steps of preferably mixing a precursor and a silicon source to obtain a first mixed solution, dissolving a template in water, adding hydrochloric acid to obtain a second mixed solution, dropwise adding the first mixed solution into the second mixed solution at the temperature of 35-40 ℃ under the stirring condition, and after dropwise adding, carrying out heat preservation treatment on the mixed solution.
In the invention, the temperature of the heat preservation treatment is preferably 35-40 ℃, more preferably 36-38 ℃, and the time is preferably 18-30 hours, more preferably 20-25 hours; in the present invention, the heat-insulating treatment is preferably performed under stirring. The invention improves the condensation polymerization degree of the obtained mesoporous hybrid material through heat preservation treatment.
After the heat preservation treatment is finished, the mixed solution is subjected to hydrothermal reaction. In the invention, the temperature of the hydrothermal reaction is preferably 90-110 ℃, more preferably 95-105 ℃, and the time is preferably 24-50 h, more preferably 36-48 h. According to the invention, the hydrothermal reaction is preferably carried out in a stainless steel reaction kettle with a polytetrafluoroethylene lining, and the precursor and the silicon source are subjected to self-assembly through the hydrothermal reaction to obtain the mesoporous hybrid material.
After the hydrothermal reaction is finished, the hydrothermal reaction liquid is preferably filtered, and the filter cake is washed to be neutral by using deionized water and then dried to obtain a hydrothermal reaction product. The invention has no special requirement on the drying temperature, and can completely dry the filter cake.
After the hydrothermal reaction product is obtained, the template agent in the hydrothermal reaction product is removed. According to the invention, the template agent is preferably removed by Soxhlet extraction, the Soxhlet extraction agent is preferably ethanol, and the extraction time is preferably 18-28 h, more preferably 20-25 h.
After the Soxhlet extraction is finished, the product obtained by the Soxhlet extraction is preferably dried to obtain the terpyridine derivative functionalized mesoporous hybrid material. The invention has no special requirements on the drying temperature and time, and can completely dry the product after Soxhlet extraction. In the invention, the terpyridine derivative functionalized mesoporous hybrid material is light yellow powder.
After the terpyridine derivative functionalized mesoporous hybrid material is obtained, the inventionAnd carrying out ligand exchange reaction on the terpyridine derivative functionalized mesoporous hybrid material and a binary europium complex in an alcohol solvent to obtain the terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material. In the present invention, the binary europium complex preferably comprises Eu (NTA)3·2H2O、Eu(TTA)3·2H2O or Eu (DBM)3·2H2O (wherein, NTA: beta-naphthoyl trifluoroacetone, TTA: 2-thenoyltrifluoroacetone, DBM: dibenzoylmethane); the mole ratio of the terpyridine derivative functionalized mesoporous hybrid material to the binary europium complex is preferably 1: (0.8 to 1.5), and more preferably 1: 1.
In the present invention, the alcohol solvent is preferably methanol and/or ethanol; in the invention, preferably, the binary europium complex is dissolved in an alcohol solvent, and then the terpyridine derivative functionalized mesoporous hybrid material is added into the dissolving solution.
In the invention, the temperature of the ligand exchange reaction is preferably 60-75 ℃, more preferably 65-70 ℃, and the time is preferably 10-15 h, more preferably 12-13 h; the ligand exchange reaction is preferably carried out under stirring and refluxing conditions in the present invention. In the process of ligand exchange reaction, because the coordination capacity of the nitrogen atom of the terpyridine carboxylic acid is stronger than the coordination capacity of water molecules, the coordination water molecules in the binary europium complex are replaced by the terpyridine derivative functionalized mesoporous hybrid material, so that the mesoporous hybrid luminescent material is obtained.
After the ligand exchange reaction is finished, the ligand exchange reaction solution is preferably filtered, and the solid product obtained by filtering is washed and then dried in vacuum to obtain the terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material. In the present invention, the washing detergent is preferably ethanol; the temperature of the vacuum drying is preferably 55-65 ℃, and more preferably 60 ℃; the invention has no special requirement on the vacuum drying time, and can completely dry the washed product.
The invention provides a terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material prepared by the preparation method in the scheme. The luminescent material provided by the invention realizes grafting between organic and inorganic matrixes on the molecular level, has high mechanical property and thermal stability, has excellent copper ion sensing performance, and has sensitive selectivity on copper ions.
The invention also provides application of the terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material in copper ion identification. In the invention, the terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material has copper ion sensing performance, has high characteristic emission intensity and good luminescent effect, and the fluorescence signal of the terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material can be quenched by copper ions, and the larger the addition amount of the copper ions is, the worse the fluorescence signal is. The embodiment shows that the fluorescent signal and the copper ion concentration of the terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material have a good linear fitting relationship, and the luminescent material has a wide application prospect in copper ion identification.
The present invention provides a terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material, and a preparation method and an application thereof, which are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) 1mmol of 4 '-p-phenoxyacetic acid-2, 2', 6',2' terpyridine is dissolved in 15mL of thionyl chloride solvent, the solution is placed in a flask, the reaction temperature of the solution in the flask is controlled at 60 ℃, and the whole solution is refluxed and reacted for 8 hours under the nitrogen atmosphere. After the reaction is finished, distilling for 30 minutes, and removing thionyl chloride by using a rotary evaporator to obtain an acyl chloride intermediate (a viscous red substance L-COCl).
(2) 1mmol of L-COCl was dissolved in 20mL of chloroform, and then 2mmol of triethylamine and 1.2mmol of 3-aminopropyltriethoxysilane were added, followed by reaction for two hours under stirring at ordinary temperature. After the reaction is completed, a Buchner funnel is used for suction filtration, filtrate is left, a rotary evaporator is used for removing the organic solvent, and a precursor L-COOH-NH is obtained2。
(3) 2.0g of Pluronic P123 surfactant was weighed into 15g of deionized water and 60g of 2mol/L hydrochloric acid, and dissolved by heating and stirring. At room temperature, slowlySlowly dropwise adding 1, 2-bis (triethoxy silicon) ethane and precursor L-COOH-NH2The molar ratio of the 1, 2-bis (triethoxysilyl) ethane to the precursor is 0.94: 0.06 mol, total amount is 1mol, stirring for 24 hours. Then put into a stainless steel reaction kettle with a lining made of polytetrafluoroethylene and crystallized for 48 hours at the temperature of 100 ℃.
After the hydrothermal reaction was completed, the product was washed to neutrality with deionized water. Drying at 60 ℃ to obtain light yellow powder without removing the template agent. Then, extracting the light yellow powder with absolute ethyl alcohol in a Soxhlet extractor for 24 hours, and drying to obtain the terpyridine derivative functionalized mesoporous hybrid material which is light yellow powder.
(4) 0.8mmol of binary europium complex Eu (NTA)3·2H2Dissolving O in an ethanol solution, adding 0.8mmol of terpyridine derivative functionalized mesoporous hybrid material prepared in the step (3), stirring and refluxing for 12 hours at 70 ℃, filtering and collecting solid powder finally obtained, washing with ethanol, and drying in vacuum to obtain the 4 '-p-phenoxyacetic acid-2, 2':6',2' terpyridine functionalized rare earth europium mesoporous hybrid luminescent material.
The characterization result of the obtained 4 '-p-phenoxyacetic acid-2, 2', 6',2' terpyridine functionalized rare earth europium mesoporous hybrid luminescent material is as follows:
FIG. 1 is a transmission electron micrograph of the obtained europium mesoporous hybrid luminescent material, wherein (a) is a transmission electron micrograph along the [100] axis, and (b) is a transmission electron micrograph along the [110] axis; as can be seen from FIG. 1, the luminescent material prepared by the invention is a nano mesoporous luminescent material with regular surface and ordered mesoscopic structure.
FIG. 2 is a solid fluorescence emission spectrum of the obtained europium mesoporous hybrid luminescent material, wherein the attached drawing is a picture of the obtained europium mesoporous hybrid luminescent material taken under the irradiation of a 365nm ultraviolet lamp; according to the figure 2, the europium mesoporous hybrid luminescent material prepared by the invention has strong fluorescence emission intensity, and according to the attached figure, the europium mesoporous hybrid luminescent material can emit strong red fluorescence under the irradiation of a 365nm ultraviolet lamp.
FIG. 3 is a thermogravimetric curve analysis chart of the obtained europium mesoporous hybrid luminescent material; as can be seen from FIG. 3, the europium mesoporous hybrid luminescent material prepared by the invention has excellent thermal stability.
The copper ion sensing performance of the obtained 4 '-phenoxyacetic acid-2, 2', 6',2' terpyridine functionalized rare earth europium mesoporous hybrid luminescent material is tested:
the prepared europium mesoporous hybrid luminescent material is prepared into a solution of 1mg/mL, and a fluorescence titration experiment is carried out: adding Cu into europium mesoporous hybrid luminescent material solution2+Solution (Cu)2+The concentration range of the solution is 0-200 mu M), and a fluorescence spectrometer is adopted for carrying out fluorescence spectrum analysis;
the obtained fluorescence titration curve is shown in FIG. 4, and the internal attached drawing is a picture obtained by taking pictures under 365nm ultraviolet lamp before and after adding 200 μ M copper ions into 1mg/mL mesoporous hybrid luminescent material solution. As can be seen from FIG. 4, Cu was not added2+The fluorescence intensity of europium mesoporous hybrid luminescent material solution is very strong along with Cu2+Increasing concentration, gradually decreasing fluorescence intensity, Cu2+When the concentration reaches 200 mu M, the fluorescence signal is quenched; according to the attached diagram, before adding copper ions, the europium mesoporous hybrid luminescent material of the invention shows strong red fluorescence under the irradiation of a 365nm ultraviolet lamp, and after adding 200 μ M copper ions, the fluorescence signal is quenched.
Fitting according to the result of the fluorescence titration curve, wherein the obtained fitted curve is shown in FIG. 5; as can be seen from FIG. 5, the fluorescence intensity and Cu were observed in the range of 0.2. mu.M to 20. mu.M in the concentration of copper ions2+The concentration has a good linear relation (R is 0.99877), which shows that the mesoporous hybrid luminescent material prepared by the invention can effectively identify copper ions.
Example 2
(1) 1mmol of 4 '-p-phenoxyacetic acid-2, 2', 6',2' terpyridine is dissolved in 15mL of thionyl chloride solvent, the solution is placed in a flask, the reaction temperature of the solution in the flask is controlled to be 70 ℃, and the whole solution is refluxed and reacted for 8 hours under the nitrogen atmosphere. And after the reaction is finished, distilling for 30 minutes, and removing thionyl chloride by using a rotary evaporator to obtain a viscous red substance L-COCl.
(2) 1mmol of L-COCl was dissolved in 20mL of chloroform, and 2mmol of triethylamine was added, followed by1.2mmol of 3-aminopropyltriethoxysilane was added and reacted for two hours under stirring at room temperature. After the reaction is completed, a Buchner funnel is used for suction filtration, filtrate is left, a rotary evaporator is used for removing the organic solvent, and a precursor L-COOH-NH is obtained2。
(3) 2.0g of Pluronic P123 surfactant was weighed into 15g of deionized water and 60g of 2mol/L hydrochloric acid, and dissolved by heating and stirring. Slowly dripping 1, 2-bis (triethoxy silicon) ethane and a precursor L-COOH-NH at room temperature2The molar ratio of (1) to (3) is 0.93: 0.07, total amount is 1mol, stirring for 24 hours. Then put into a stainless steel reaction kettle with a lining made of polytetrafluoroethylene and crystallized for 40 hours at the temperature of 100 ℃.
And after the hydrothermal reaction is finished, washing the product to be neutral by using deionized water, and drying at 60 ℃ to obtain light yellow powder without removing the template agent. Then, extracting the obtained light yellow powder with absolute ethyl alcohol in a Soxhlet extractor for 24 hours, and drying to obtain the terpyridine derivative functionalized mesoporous hybrid material which is light yellow powder.
(4) 0.8mmol of binary europium complex Eu (NTA)3·2H2Dissolving O in an ethanol solution, adding the light yellow powder of 0.8mmol, stirring and refluxing for 12 hours at 70 ℃, filtering and collecting the finally obtained solid powder, washing with ethanol, and drying in vacuum to obtain the 4 '-p-phenoxyacetic acid-2, 2', 6',2' terpyridine functionalized rare earth europium mesoporous hybrid luminescent material.
Example 3
(1) Dissolving 1mmol of 4 '-p-phenoxyacetic acid-2, 2', 6',2' terpyridine in 15mL of thionyl chloride solvent, placing the solution in a flask, controlling the reaction temperature of the solution in the flask to be 60-75 ℃, and carrying out reflux reaction on the whole solution for 8 hours under the nitrogen atmosphere. And after the reaction is finished, distilling for 30 minutes, and removing thionyl chloride by using a rotary evaporator to obtain a viscous red substance L-COCl.
(2) 1mmol of L-COCl was dissolved in 20mL of chloroform, and then 2mmol of triethylamine and 1.2mmol of 3-aminopropyltriethoxysilane were added, followed by reaction for two hours under stirring at ordinary temperature. After the reaction was completed, the reaction mixture was filtered with a Buchner funnel, the filtrate was retained, and the organic matter was removed by a rotary evaporatorSolvent to obtain a precursor L-COOH-NH2。
(3) 2.0g of Pluronic P123 surfactant was weighed into 15g of deionized water and 60g of 2mol/L hydrochloric acid, and dissolved by heating and stirring. Slowly dripping 1, 2-bis (triethoxy silicon) ethane and a precursor L-COOH-NH at room temperature2The molar ratio of the mixed solution of (1) to (2) is 0.94: 0.06 mol, total amount is 1mol, stirring for 24 hours. Then put into a stainless steel reaction kettle with a lining made of polytetrafluoroethylene and crystallized for 48 hours at the temperature of 100 ℃.
And after the hydrothermal reaction is finished, washing the product to be neutral by using deionized water, and drying at 60 ℃ to obtain light yellow powder without removing the template agent. Then, extracting the obtained light yellow powder in a Soxhlet extractor for 24 hours by using absolute ethyl alcohol, and drying to obtain the terpyridine derivative functionalized mesoporous hybrid material which is light yellow powder.
(4) 0.8mmol of binary europium complex Eu (TTA)3·2H2Dissolving O in an ethanol solution, adding 0.8mmol of terpyridine derivative functionalized mesoporous hybrid material prepared in the step (3), stirring and refluxing for 12 hours at 70 ℃, filtering and collecting solid powder finally obtained, washing with ethanol, and drying in vacuum to obtain the 4 '-p-phenoxyacetic acid-2, 2':6',2' terpyridine functionalized rare earth europium mesoporous hybrid luminescent material.
Example 4
(1) Dissolving 1mmol of 4 '-p-phenoxyacetic acid-2, 2', 6',2' terpyridine in 15mL of thionyl chloride solvent, placing the solution in a flask, controlling the reaction temperature of the solution in the flask to be 60-75 ℃, and carrying out reflux reaction on the whole solution for 8 hours under the nitrogen atmosphere. And after the reaction is finished, distilling for 30 minutes, and removing thionyl chloride by using a rotary evaporator to obtain a viscous red substance L-COCl.
(2) 1mmol of L-COCl was dissolved in 20mL of chloroform, and then 2mmol of triethylamine and 1.2mmol of 3-aminopropyltriethoxysilane were added, followed by reaction for two hours under stirring at ordinary temperature. After the reaction is completed, a Buchner funnel is used for suction filtration, filtrate is left, a rotary evaporator is used for removing the organic solvent, and a precursor L-COOH-NH is obtained2。
(3) 2.0g Pluronic P123 surfactant was weighed out15g of deionized water and 60g of 2mol/L hydrochloric acid were added thereto, and the mixture was heated and stirred to dissolve. Slowly dripping 1, 2-bis (triethoxy silicon) ethane and a precursor L-COOH-NH at room temperature2The molar ratio of the mixed solution of (1) to (2) is 0.94: 0.06 mol, total amount is 1mol, stirring for 24 hours. Then put into a stainless steel reaction kettle with a lining made of polytetrafluoroethylene and crystallized for 48 hours at the temperature of 100 ℃.
And after the hydrothermal reaction is finished, washing the product to be neutral by using deionized water, and drying at 60 ℃ to obtain light yellow powder without removing the template agent. Then, extracting the light yellow powder in a Soxhlet extractor for 24 hours by using absolute ethyl alcohol, and drying to obtain the terpyridine derivative functionalized mesoporous hybrid material which is light yellow powder.
(4) 0.8mmol of binary europium complex Eu (DBM)3·2H2Dissolving O in an ethanol solution, adding the light yellow powder of 0.8mmol, stirring and refluxing for 12 hours at 70 ℃, filtering and collecting the finally obtained solid powder, washing with ethanol, and drying in vacuum to obtain the 4 '-p-phenoxyacetic acid-2, 2', 6',2' terpyridine functionalized rare earth europium mesoporous hybrid luminescent material.
Example 5
The other conditions are the same as the example 1, only the terpyridine derivative is replaced by 4 '-p-benzoic acid-2, 2':6',2' terpyridine, and the 4 '-p-benzoic acid-2, 2':6',2' terpyridine functionalized rare earth europium mesoporous hybrid luminescent material is obtained.
Example 6
Under the same other conditions as in example 1, only the terpyridine derivative is replaced by 4 '-o-phenoxyacetic acid-2, 2':6',2' terpyridine, so as to obtain the 4 '-o-phenoxyacetic acid-2, 2':6',2' terpyridine functionalized rare earth europium mesoporous hybrid luminescent material.
Example 7
The other conditions are the same as the example 1, only the terpyridine derivative is replaced by 4 '-o-benzoic acid-2, 2':6',2' terpyridine, and the 4 '-o-benzoic acid-2, 2':6',2' terpyridine functionalized rare earth europium mesoporous hybrid luminescent material is obtained.
The products obtained in examples 2 to 7 were characterized and tested for copper ion sensing performance according to the method in example 1, and the results were similar to those of example 1.
The preparation method provided by the invention realizes grafting between organic and inorganic matrixes on the molecular level, improves the mechanical property and thermal stability of the luminescent material, and has the advantages of strong operability, good reproducibility, no need of a catalyst and the like, and low cost; and the prepared luminescent material has regular surface, good thermal stability and sensitive selectivity to copper ions.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material is characterized by comprising the following steps:
(1) under the condition of nitrogen protection, mixing a terpyridine derivative and thionyl chloride for substitution reaction to obtain an acyl chloride intermediate; the terpyridine derivative is a terpyridine carboxylic acid derivative; the terpyridyl carboxylic acid derivative is 4 '-p-phenoxyacetic acid-2, 2':6',2' terpyridyl, 4 '-p-benzoic acid-2, 2':6',2' terpyridyl, 4 '-o-phenoxyacetic acid-2, 2':6',2' terpyridyl or 4 '-o-benzoic acid-2, 2':6',2' terpyridyl;
(2) mixing the acyl chloride intermediate, an organic solvent, amine and an organosilane coupling agent to carry out a carboxyl reaction to obtain a precursor; the organosilane coupling agent is 3-aminopropyltriethoxysilane or 3-aminopropyltrimethoxysilane;
(3) mixing the precursor, a silicon source, a template agent, water and hydrochloric acid, sequentially carrying out heat preservation treatment and hydrothermal reaction, and removing the template agent in the obtained hydrothermal reaction product to obtain a terpyridine derivative functionalized mesoporous hybrid material; the template agent is P123; the silicon source is 1, 2-bis (triethoxy silicon) ethane;
(4) and carrying out ligand exchange reaction on the terpyridine derivative functionalized mesoporous hybrid material and a binary europium complex in an alcohol solvent to obtain the terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material.
2. The preparation method of claim 1, wherein the molar ratio of the terpyridine derivative to the thionyl chloride in the step (1) is 1 (100-300).
3. The preparation method according to claim 1, wherein the temperature of the substitution reaction in the step (1) is 60 to 75 ℃ and the time is 5 to 10 hours.
4. The preparation method according to claim 1, wherein the organic solvent in the step (2) comprises one or more of chloroform, N-dimethylformamide and tetrahydrofuran;
the amine comprises one or more of diethylamine, triethylamine, butanediamine and hexanediamine;
the mole ratio of the acyl chloride intermediate to the amine to the organosilane coupling agent is 1 (1-2) to 1-1.5.
5. The preparation method according to claim 1, wherein the molar ratio of the precursor to the silicon source is 0.95: 0.05-0.98: 0.02;
the mass ratio of the template agent to the water to the hydrochloric acid is 1 (7-8) to 2-2.5;
the molar ratio of the precursor to the template is 1 (0.016-0.018).
6. The preparation method according to claim 1, wherein the temperature of the heat preservation treatment in the step (3) is 35-40 ℃ and the time is 18-30 h;
the temperature of the hydrothermal reaction in the step (3) is 90-110 ℃, and the time is 24-50 h.
7. The method according to claim 1, wherein the binary europium complex in step (4) comprises Eu (NTA) 3.2H 2O, Eu (TTA) 3.2H 2O, or Eu (DBM) 3.2H 2O;
the molar ratio of the terpyridine derivative functionalized mesoporous hybrid material to the binary europium complex is 1 (0.8-1.5).
8. The preparation method according to claim 1, wherein the temperature of the ligand exchange reaction in the step (4) is 60-75 ℃ and the time is 10-15 h.
9. The terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material prepared by the preparation method of any one of claims 1 to 8.
10. The use of rare earth europium mesoporous hybrid luminescent material functionalized by terpyridine derivatives as claimed in claim 9 in copper ion recognition.
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