CN109705839B - A kind of rare earth europium mesoporous hybrid light-emitting material functionalized with terpyridine derivatives, preparation method and application thereof - Google Patents

A kind of rare earth europium mesoporous hybrid light-emitting material functionalized with terpyridine derivatives, preparation method and application thereof Download PDF

Info

Publication number
CN109705839B
CN109705839B CN201811445133.4A CN201811445133A CN109705839B CN 109705839 B CN109705839 B CN 109705839B CN 201811445133 A CN201811445133 A CN 201811445133A CN 109705839 B CN109705839 B CN 109705839B
Authority
CN
China
Prior art keywords
terpyridine
preparation
functionalized
rare earth
derivative
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811445133.4A
Other languages
Chinese (zh)
Other versions
CN109705839A (en
Inventor
李恒
李亚娟
余旭东
庞雪蕾
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hebei University of Science and Technology
Original Assignee
Hebei University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hebei University of Science and Technology filed Critical Hebei University of Science and Technology
Priority to CN201811445133.4A priority Critical patent/CN109705839B/en
Publication of CN109705839A publication Critical patent/CN109705839A/en
Application granted granted Critical
Publication of CN109705839B publication Critical patent/CN109705839B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

本发明提供了一种三联吡啶衍生物功能化的稀土铕介孔杂化发光材料及其制备方法和应用,属于稀土介孔光化学传感材料技术领域。本发明通过原位合成的方法将三联吡啶衍生物共价键嫁接到介孔杂化材料中,得到三联吡啶衍生物功能化的介孔杂化材料;然后再通过配体交换反应得到三联吡啶衍生物功能化的稀土铕介孔杂化发光材料。本发明提供的制备方法使所得发光材料在分子的水平上实现了有机与无机基质之间的嫁接,且可操作性强,重现性好,无需催化剂等,成本低廉,且所得发光材料的机械性能和热稳定性好,特征发射强度大,对铜离子具有灵敏的选择性。

Figure 201811445133

The invention provides a rare earth europium mesoporous hybrid luminescent material functionalized with terpyridine derivatives, a preparation method and application thereof, and belongs to the technical field of rare earth mesoporous photochemical sensing materials. In the present invention, the covalent bond of the terpyridine derivative is grafted into the mesoporous hybrid material by the method of in-situ synthesis to obtain the functionalized mesoporous hybrid material of the terpyridine derivative; and then the terpyridine derivative is obtained through a ligand exchange reaction. Physically functionalized rare earth europium mesoporous hybrid luminescent materials. The preparation method provided by the invention enables the obtained luminescent material to realize grafting between organic and inorganic substrates at the molecular level, and has strong operability, good reproducibility, no catalyst, etc., low cost, and mechanical properties of the obtained luminescent material. It has good performance and thermal stability, high characteristic emission intensity and sensitive selectivity to copper ions.

Figure 201811445133

Description

Terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material and preparation method and application thereof
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)

1.一种三联吡啶衍生物功能化的稀土铕介孔杂化发光材料的制备方法,其特征在于,包括以下步骤:1. a preparation method of a terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material, is characterized in that, comprises the following steps: (1)在氮气保护条件下,将三联吡啶衍生物和氯化亚砜混合进行取代反应,得到酰氯中间体;所述三联吡啶衍生物为三联吡啶羧酸衍生物;所述三联吡啶羧酸衍生物为4'-对苯氧乙酸-2,2':6',2'三联吡啶、4'-对苯甲酸-2,2':6',2'三联吡啶、4'-邻苯氧乙酸-2,2':6',2'三联吡啶或4'-邻苯甲酸-2,2':6',2'三联吡啶;(1) Under nitrogen protection, the terpyridine derivative and thionyl chloride are mixed for substitution reaction to obtain an acid chloride intermediate; the terpyridine derivative is a terpyridine carboxylic acid derivative; the terpyridine carboxylic acid derivative The compounds are 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'-phthalic acid-2,2':6',2'terpyridine; (2)将所述酰氯中间体、有机溶剂、胺和有机硅烷偶联剂混合进行羧合反应,得到前驱体;所述有机硅烷偶联剂为3-氨丙基三乙氧基硅烷或3-氨丙基三甲氧基硅烷;(2) Mixing the acid chloride intermediate, organic solvent, amine and organosilane coupling agent for carboxylation reaction to obtain a precursor; the organosilane coupling agent is 3-aminopropyltriethoxysilane or 3-aminopropyltriethoxysilane - aminopropyltrimethoxysilane; (3)将所述前驱体、硅源、模板剂、水和盐酸混合后依次进行保温处理和水热反应,将所得水热反应产物中的模板剂去除,得到三联吡啶衍生物功能化介孔杂化材料;所述模板剂为P123;所述硅源为1,2-双(三乙氧基硅)乙烷;(3) After mixing the precursor, silicon source, template, water and hydrochloric acid, heat preservation treatment and hydrothermal reaction are performed in sequence, and the template agent in the obtained hydrothermal reaction product is removed to obtain a terpyridine derivative functionalized mesopore Hybrid material; the template agent is P123; the silicon source is 1,2-bis(triethoxysilyl)ethane; (4)将所述三联吡啶衍生物功能化介孔杂化材料和二元铕配合物在醇溶剂中进行配体交换反应,得到三联吡啶衍生物功能化的稀土铕介孔杂化发光材料。(4) The terpyridine derivative-functionalized mesoporous hybrid material and the binary europium complex are subjected to a ligand exchange reaction in an alcohol solvent to obtain a terpyridine derivative-functionalized rare-earth europium mesoporous hybrid light-emitting material. 2.根据权利要求1所述的制备方法,其特征在于,所述步骤(1)中三联吡啶衍生物和氯化亚砜的摩尔比为1:(100~300)。2. The preparation method according to claim 1, wherein the molar ratio of the terpyridine derivative to the thionyl chloride in the step (1) is 1:(100~300). 3.根据权利要求1所述的制备方法,其特征在于,所述步骤(1)中取代反应的温度为60~75℃,时间为5~10h。3 . The preparation method according to claim 1 , wherein the temperature of the substitution reaction in the step (1) is 60-75° C., and the time is 5-10 h. 4 . 4.根据权利要求1所述的制备方法,其特征在于,所述步骤(2)中的有机溶剂包括氯仿、N,N-二甲基甲酰胺和四氢呋喃中的一种或几种;4. The preparation method according to claim 1, wherein the organic solvent in the step (2) comprises one or more of chloroform, N,N-dimethylformamide and tetrahydrofuran; 所述胺包括二乙胺、三乙胺、丁二胺和己二胺中的一种或几种;The amine includes one or more of diethylamine, triethylamine, butanediamine and hexamethylenediamine; 所述酰氯中间体、胺和有机硅烷偶联剂的摩尔比为1:(1~2):(1~1.5)。The molar ratio of the acid chloride intermediate, amine and organosilane coupling agent is 1:(1~2):(1~1.5). 5.根据权利要求1所述的制备方法,其特征在于,所述前驱体和硅源的摩尔比为0.95:0.05~0.98:0.02;5. preparation method according to claim 1, is characterized in that, the molar ratio of described precursor and silicon source is 0.95:0.05~0.98:0.02; 所述模板剂、水和盐酸的质量比为1:(7~8):(2~2.5);The mass ratio of described templating agent, water and hydrochloric acid is 1:(7~8):(2~2.5); 所述前驱体和模板剂的摩尔比为1:(0.016~0.018)。The molar ratio of the precursor and the templating agent is 1:(0.016~0.018). 6.根据权利要求1所述的制备方法,其特征在于,所述步骤(3)中保温处理的温度为35~40℃,时间为18~30h;6 . The preparation method according to claim 1 , wherein the temperature of the heat preservation treatment in the step (3) is 35-40° C., and the time is 18-30 h; 6 . 所述步骤(3)中水热反应的温度为90~110℃,时间为24~50h。In the step (3), the temperature of the hydrothermal reaction is 90-110° C., and the time is 24-50 h. 7.根据权利要求1所述的制备方法,其特征在于,所述步骤(4)中二元铕配合物包括Eu(NTA)3·2H2O、Eu(TTA)3·2H2O或Eu(DBM)3·2H2O;7 . The preparation method according to claim 1 , wherein in the step (4), the binary europium complex comprises Eu(NTA)3·2H2O, Eu(TTA)3·2H2O or Eu(DBM)3 . 7 . 2H2O; 所述三联吡啶衍生物功能化介孔杂化材料和二元铕配合物的摩尔比为1:(0.8~1.5)。The molar ratio of the terpyridine derivative functionalized mesoporous hybrid material and the binary europium complex is 1:(0.8-1.5). 8.根据权利要求1所述的制备方法,其特征在于,所述步骤(4)中配体交换反应的温度为60~75℃,时间为10~15h。8 . The preparation method according to claim 1 , wherein the temperature of the ligand exchange reaction in the step (4) is 60-75° C., and the time is 10-15 h. 9 . 9.权利要求1~8任意一项所述制备方法制备的三联吡啶衍生物功能化的稀土铕介孔杂化发光材料。9. The rare earth europium mesoporous hybrid light-emitting material functionalized with a terpyridine derivative prepared by the preparation method according to any one of claims 1 to 8. 10.权利要求9所述的三联吡啶衍生物功能化的稀土铕介孔杂化发光材料在铜离子识别中的应用。10 . The application of the rare earth europium mesoporous hybrid luminescent material functionalized with a terpyridine derivative according to claim 9 in the identification of copper ions. 11 .
CN201811445133.4A 2018-11-29 2018-11-29 A kind of rare earth europium mesoporous hybrid light-emitting material functionalized with terpyridine derivatives, preparation method and application thereof Active CN109705839B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811445133.4A CN109705839B (en) 2018-11-29 2018-11-29 A kind of rare earth europium mesoporous hybrid light-emitting material functionalized with terpyridine derivatives, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811445133.4A CN109705839B (en) 2018-11-29 2018-11-29 A kind of rare earth europium mesoporous hybrid light-emitting material functionalized with terpyridine derivatives, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109705839A CN109705839A (en) 2019-05-03
CN109705839B true CN109705839B (en) 2021-08-31

Family

ID=66255311

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811445133.4A Active CN109705839B (en) 2018-11-29 2018-11-29 A kind of rare earth europium mesoporous hybrid light-emitting material functionalized with terpyridine derivatives, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109705839B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110330660B (en) * 2019-06-11 2021-07-20 河北科技大学 Preparation method and application of rare earth europium hybrid luminescent material with aluminum ion sensing performance
CN111521601B (en) * 2020-04-22 2022-01-25 中国科学院宁波材料技术与工程研究所 Application of ratio-type fluorescent polymer hydrogel in seafood freshness detection
CN112375090B (en) * 2020-11-25 2022-04-15 广西民族师范学院 Preparation method and application of copper complex with one-dimensional trapezoidal chain structure
CN114539447B (en) * 2021-12-29 2023-06-09 西北工业大学重庆科创中心 A self-calibrating ratio temperature probe based on europium metal polymer and its preparation method
CN115466404B (en) * 2022-09-16 2023-07-07 贵州师范大学 Preparation and application of homonuclear rare earth coordination polymer white light material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101220266A (en) * 2008-01-24 2008-07-16 同济大学 Preparation method of a β-diketone functionalized rare earth mesoporous hybrid luminescent material
CN106010502A (en) * 2015-11-24 2016-10-12 河北科技大学 Preparation method of rare earth mesoporous hybrid luminescent material with fluorine ion sensing properties

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101220266A (en) * 2008-01-24 2008-07-16 同济大学 Preparation method of a β-diketone functionalized rare earth mesoporous hybrid luminescent material
CN106010502A (en) * 2015-11-24 2016-10-12 河北科技大学 Preparation method of rare earth mesoporous hybrid luminescent material with fluorine ion sensing properties

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A Recoverable Ruthenium Aqua Complex Supported on Silica Particles: An Efficient Epoxidation Catalyst;Ferrer Ingrid等;《CHEMISTRY-A EUROPEAN JOURNAL》;20170323;第23卷(第17期);第15279页 *
Copper(II) complexes of pentadentate 17-membered macrocyclic diamidodiamines with N, O or S as additional donors;Herman GG等;《ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS》;20030731;第59卷;第4099页 *
Synthesis, characterization, and luminescence properties of the ternary europium complex covalently bonded to mesoporous SBA-15;Chunyun Peng等;《JOURNAL OF PHYSICAL CHEMISTRY B》;20050818;第109卷(第32期);第M294页 *

Also Published As

Publication number Publication date
CN109705839A (en) 2019-05-03

Similar Documents

Publication Publication Date Title
CN109705839B (en) A kind of rare earth europium mesoporous hybrid light-emitting material functionalized with terpyridine derivatives, preparation method and application thereof
CN112898965B (en) Preparation and use method of a ratiometric fluorescent probe for visual discrimination detection
CN105219376B (en) Bicolor Eu-MOFs/CDs fluorescent material as well as preparation and application thereof
CN106866445B (en) Eu/Zr-MOF fluorescent materials with blue and red double transmittings and its ratio fluorescent detection application
WO2023185543A1 (en) Preparation and detection methods for dual-channel visualized multicolor fluorescent probe
CN110229348B (en) A kind of Er3+/Tm3+-MOFs fluorescent material with blue light up-conversion and preparation method thereof
CN109678897B (en) A kind of Nd compound luminescent material containing phenanthroline and modified carboxylic acid ligand and preparation method thereof
CN104071769A (en) Method for preparing fluorescent carbon point by virtue of chemical oxidation method, fluorescent carbon point and application of fluorescent carbon point
CN110066401B (en) Red fluorescent rare earth europium coordination polymer and its preparation method and application
CN108947766B (en) A kind of fluorine-containing tetraphenylethylene compound and its preparation method and use
CN111234252B (en) Cadmium-organic supermolecule fluorescent polymer and preparation method and application thereof
CN106565966A (en) Europium-based coordination polymer nanosphere and preparation method and application thereof
CN101792664A (en) Method for preparing hybrid mesoporous luminescent material of calixarene and functionalized rare earth
CN101671557B (en) Preparation method of clay base fluorescent probe
JP3932323B2 (en) Organic group-modified silicate composite with improved emission intensity
CN115028188A (en) An organic cuprous halide material for high-efficiency ammonia gas fluorescence detection and its preparation and application
CN110551291B (en) Porous interpenetrating zinc-organic supramolecular polymer and its preparation method and application
CN1315724C (en) Process for preparing mesopore silicon dioxide material
CN109232654B (en) A kind of Eu/Tb-TCP-COOH complex luminescent material and its preparation method and application
CN105017304A (en) Preparation method for multi-color luminous rare earth complex functionalized polyhedral oligomeric silsesquioxane
CN107099285A (en) A kind of green emitting hydrogel and preparation method
CN103864823B (en) A kind of Cu (I) coordination polymer green luminescent material and synthetic method thereof
CN101338190A (en) A method for surface coating of strontium aluminate long-lasting luminescent powder
CN106590631B (en) A kind of rare earth mixing with nano calcium citrate fluorescent powder and preparation method thereof
CN110330664B (en) A kind of Eu/Tb-BHM-COOH complex and its preparation method and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant