CN113801149B - Rare earth luminescent material, preparation method thereof and ammonia gas sensing application - Google Patents
Rare earth luminescent material, preparation method thereof and ammonia gas sensing application Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000000463 material Substances 0.000 title claims abstract description 77
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 56
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 39
- 230000004044 response Effects 0.000 claims abstract description 35
- 239000003446 ligand Substances 0.000 claims abstract description 27
- 238000012360 testing method Methods 0.000 claims abstract description 22
- 230000000171 quenching effect Effects 0.000 claims abstract description 18
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims abstract description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
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- 239000000047 product Substances 0.000 claims description 4
- 239000011540 sensing material Substances 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
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- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 abstract description 3
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- -1 rare earth ion Chemical class 0.000 description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention discloses a novel rare earth ternary complex luminescent material, wherein the molecular formula of the complex is Eu (TPM) 3 (PBO) wherein TPM is 1, 1-trifluoro-5, 5-dimethyl-2, 4-hexanedione; wherein PBO is a neutral heterocyclic ligand 2- (2-pyridine) benzoxazole. The compound is prepared by coordination reaction of europium nitrate, three times of equivalent TPM and one time of equivalent PBO ligand. The luminescent material has good luminescent performance; the luminescent material has selective response to ammonia gas and high sensitivity, and after being placed in an atmosphere containing ammonia gas, the luminescent material quickly shows the sensing response characteristic of fluorescence quenching; the material has good solubility and stability, is easy to prepare into paper-based or quartz glass sheet-based fluorescent sensing films, also rapidly shows fluorescence quenching response which can be observed by naked eyes in an ammonia-containing atmosphere, shows rapid response and fluorescence sensing performance of sensitive identification, can flexibly manufacture test paper into various required specifications, and can be used as a portable fluorescent sensing test paper device for detecting ammonia.
Description
Technical Field
The invention relates to the technical field of rare earth luminescent materials, in particular to the field of fluorescence sensing application of luminescent materials.
Background
The rare earth ion has the characteristics of long fluorescence life, high quantum yield, narrow emission band, large stokes shift and the like due to the unique f electron layer structure, so that the luminescent complex has wide application prospect in aspects of fluorescent imaging and luminescent materials, particularly fluorescent sensors and fluorescent probes applied to the fields of biological systems and biomedicine.
At present, the problem of ammonia pollution in various environments is not neglected. Ammonia is a colorless gas having a strong irritating odor, and is lighter than air (specific gravity of 0.5), and the lowest concentration is perceived as 5.3ppm. Ammonia is an alkaline substance that has both corrosive and irritating effects on the skin tissue being contacted. Ammonia is easily absorbed into the lungs and enters the blood through the alveoli, combines with hemoglobin, and destroys the oxygen transport function. Symptoms such as lacrimation, pharyngalgia, dyspnea, headache, nausea, and debilitation can occur after a large amount of ammonia is inhaled in a short period, and pulmonary edema and respiratory distress syndrome can occur in serious cases (science and technology and enterprises, 2010 (03): 70.). To more clearly verify the harm and impact of low concentrations of ammonia in air on human health, experts monitored workers working in an indoor environment with 3-13 mg/cubic meter of ammonia and found that the urea and ammonia content in urine increased and the urea in blood increased significantly compared to healthy people who were not exposed to ammonia. In addition, the information of the influence of ammonia gas on chickens in chicken houses in chicken farms provided by experts can be used as a reference. Because a large amount of ammonia gas is generated in chicken manure, when the ammonia gas in the air of the chicken house reaches 20ppm (equivalent to 15.2 mg/cubic meter), the chicken manure lasts for more than 6 weeks, the pulmonary congestion, the edema and the appetite of chicken flocks are reduced, the egg productivity is reduced, and diseases are easy to infect; if 50ppm is reached, the chicken develops laryngeal oedema, necrotic bronchitis, pulmonary hemorrhage, reduced respiratory rate and death after several days. Therefore, the ammonia concentration in the air in the henhouse is required to be controlled to 20ppm or less (livestock ecological newspaper 2020, 41 (09): 1-6.). From this, we can see that the low concentration ammonia pollution in the indoor air is harmful to human and animal health. So that it is very important to detect it quickly and accurately.
Currently, many conventional detection techniques for determining ammonia/amine atmospheres in environments include spectrophotometry, ion chromatography, gas chromatography, and the like. However, these detection techniques have some drawbacks such as long analysis time, or expensive equipment, or complicated operation. Therefore, the detection of ammonia pollutants should be developed toward miniaturization, intellectualization, generalization, simplified treatment process, improved detection accuracy, etc. The fluorescent film sensing technology has the advantages of simple operation, good reproducibility, high sensitivity, high response speed, good selectivity, rich signal acquisition and the like, and is expected to meet the development direction of detection of ammonia and amine pollutants in the future (Gao, M.; et al, ACS Sensors, 2016, 1 (2): 179-184).
The europium complex has strong luminescence property, can form multiple coordination, and combines proper ligand, so that the europium complex has unique luminescence property (university chemistry, 2016,31 (07): 65-71.). Europium complexes have long been used as fluorescent materials, but they are currently rarely used in VOC detection. Therefore, the fluorescent sensor for developing the europium complex has wide development potential in detection. The europium complex is used as a fluorescent probe to be manufactured into a fluorescent thin film sensor, and the fluorescent thin film sensor is used for sensing and detecting environmental harmful gases such as ammonia gas and the like, and has great practical application value.
Disclosure of Invention
The invention aims to provide a rare earth complex luminescent material with selective response to ammonia gas and high sensitivity, a preparation method thereof and fluorescence sensing application. The europium complex luminescent material with good luminescence property and thermal stability is conveniently and cheaply prepared by the coordination reaction of europium ions and ligands in the solution, the red fluorescence luminescent intensity is high, the stability is good, and the fluorescent film prepared by the europium complex luminescent material has obvious fluorescence quenching effect on the response of ammonia gas, and can be used for detecting the ammonia gas in various environments.
One of the technical proposal of the invention is to provide a novel rare earth complex luminescent material which is prepared from Eu (NO 3 ) 3 Is obtained by coordination reaction with ligand in sequence, and the molecular structure is Eu (TPM) 3 (PBO) wherein TPM is 1, 1-trifluoro-5, 5-dimethyl-2, 4-hexanedione; wherein PBO is a neutral heterocyclic ligand 2- (2-pyridine) benzoxazole.
The rare earth complex luminescent material is monoclinic system, P2 1 The/c space group (No. 14), unit cell parameters are a= 11.0161 (9) a, b= 12.4025 (9) a, c= 28.562 (2) a, α=90°, β=90°, γ=90°, v= 3902.4 (5) a 3 ，Z=4，D C =1.589 g/cm 3 The crystal color of the material is nearly colorless; the material structure is represented by a mononuclear neutral complex, wherein Eu 3+ Is positioned in the coordination environment center, and chelates 3 trifluoromethyl and tert-butyl substituted beta-diketone ligands TPM and 1 neutral nitrogen-containing ligand PBO around, and the four ligands are uniformly distributed in Eu 3＋ Is formed around the periphery of (2); eu (Eu) 3+ The ion adopts an eight-coordination mode, and six coordination atoms O and two coordination atoms N form a dodecahedron configuration; the molecular structure is shown as formula (I):
（I）；
the rare earth complex luminescent material has the advantages that Eu atoms are positioned in the center of a coordination polyhedron, the ligand contains rigid benzene rings and aromatic heterocyclic rings, trifluoromethyl and tertiary butyl with great steric hindrance, the rigidity and stability of the whole molecule of the complex are enhanced, the compound can realize high-efficiency luminescence through an antenna effect, and the trifluoromethyl-containing beta-diketone ligand has good sensitization effect on europium ions. Under the excitation of ultraviolet light with different wavelengths, the luminescent material emits strong red light with the maximum emission peak of 610nm, and can be used as a red light photoluminescence material or a luminescent layer material in a multilayer electroluminescent device.
The second technical scheme of the invention provides fluorescent sensing application based on a rare earth complex luminescent material Eu (TPM) 3 (PBO). The rare earth complex luminescent material film has obvious and rapid fluorescence quenching response to ammonia in the environment, the red fluorescence intensity of the rare earth complex luminescent material film can be obviously reduced in a very short time after the rare earth complex luminescent material film is placed in the environment where ammonia exists, and the higher the ammonia concentration is, the stronger the quenching response effect is shown, so the rare earth complex luminescent material film can be applied as a fluorescence sensing material for detecting ammonia. After the paper-based fluorescent film of the rare earth complex luminescent material is placed in an environment where ammonia exists, the red fluorescent intensity of the paper-based fluorescent film can rapidly generate fluorescence quenching response, and the higher the ammonia concentration is, the stronger the quenching response effect is shown, and the fluorescent sensing performance of rapid response and sensitive identification is shown, so that the paper-based fluorescent film can be used as a portable fluorescent sensing test paper device for detecting ammonia.
The third technical proposal of the invention is to provide a rare earth complex luminescent material Eu (TPM) 3 (PBO) preparation method. The preparation method is realized by mixing europium nitrate with a solution of a ligand TPM and PBO to carry out coordination reaction, and finally separating out to obtain a crystal powder product. The specific implementation scheme comprises five steps:
(1) Eu (NO) at room temperature 3 ) 3 ·6H 2 O powder is dissolved in acetonitrile;
(2) Dissolving TPM and KOH powder in a mixed solvent of acetonitrile and a small amount of water at room temperature;
(3) Mixing the two solutions, and stirring to fully react to obtain a clear solution A;
(4) Dissolving PBO powder in acetonitrile at room temperature, adding the acetonitrile to the solution A, mixing and stirring to fully carry out coordination reaction to obtain light yellow turbid liquid;
(5) Filtering, performing reduced pressure rotary evaporation on the filtrate to dryness to obtain yellowish powder, performing suction filtration and washing with deionized water for several times, and then drying to obtain crystalline powder product; molar ratio Eu (NO) 3 ) 3 TPM, KOH, PBO are 1, 3 and 1.
The fourth technical proposal of the invention provides a luminescent material Eu (TPM) based on rare earth complex 3 A method for preparing a film-based fluorescent sensor device of (PBO). The preparation method is characterized by comprising Eu (TPM) 3 After dissolution of the (PBO) crystal powder, the solution is used to coat a cellulose film or a glass sheet. The specific implementation scheme comprises six steps:
(1) Eu (TPM) with a certain concentration is configured according to the mass concentration of the substance 3 (PBO) in methylene chloride;
(2) Eu (TPM) 3 Adding a proper amount of methylene dichloride solution of PMMA into the (PBO) solution, and mixing to obtain a uniform solution;
(3) Dip coating or the like of Eu (TPM) 3 Coating the mixed solution of (PBO) and PMMA on a cellulose film (namely test paper base paper) or a glass sheet, and drying to obtain the paper-based or glass-based film fluorescence sensing device.
The invention has the beneficial effects that firstly, the provided rare earth complex luminescent material Eu (TPM) 3 The (PBO) well combines an anionic beta-diketone ligand and a neutral PBO ligand light absorber, effectively improves the luminous efficiency and the thermal stability of the material through the synergistic effect of the two ligands, has strong narrow band red light emission characteristic under the excitation of ultraviolet to blue light, and provides technical support for the further application of the luminous material in the fields of organic electroluminescence and the like.
The invention has the beneficial effects that the provided rare earth complex luminescent material Eu (TPM) 3 Sensing of (PBO)The complex has good fluorescence performance, and a small amount of material powder can emit strong fluorescence, so that a small amount of fluorescent powder is needed in practical application, the application cost is reduced conveniently, and a doping way easy to operate is convenient for controlling the application cost; the sensing response characteristic of fluorescence quenching can be observed quickly after the material prepared by the same process is placed in an ammonia gas atmosphere; and the solubility and stability are good, so that the fluorescent material is convenient to use as a fluorescent sensing material.
The invention has the beneficial effects that the provided luminescent material Eu (TPM) based on the rare earth complex 3 The paper-based or glass-based fluorescent film (PBO) is used for ammonia sensing, the paper-based fluorescent film is as simple and convenient as a common gas detection test paper, when the paper-based fluorescent film is used in specific application, after being placed in an environment where ammonia exists for a short time, the film is irradiated by an ultraviolet light source, the red fluorescent intensity of the paper-based fluorescent film is rapidly reduced, and the higher the ammonia concentration is, the stronger quenching response effect is shown, and the fluorescent sensing performance of rapid response and sensitive identification is shown, so that the paper-based fluorescent film can be used as a portable fluorescent detection test paper device for detecting the ammonia; the fluorescent sensing film can be flexibly manufactured into various required shapes, has light weight, is very convenient to carry and easy to prepare, and provides technical support for further application of luminescent materials. Glass-based fluorescent films also have very similar sensing properties. And can be easily compounded with fluorescent reference substance to prepare the ratio-type sensing film. And the glass-based sensing film is very suitable for being integrated with an optical fiber device, and is easy to develop into a remote real-time online monitoring device.
The invention has the beneficial effects that the luminescent material Eu (TPM) based on the rare earth complex is prepared again 3 The (PBO) and the preparation method of the paper-based and glass-based fluorescent sensing films have the advantages of simple process, simple equipment, simple and easily obtained raw materials, low production cost, capability of obtaining a large number of products in a short time, easy popularization and the like.
Drawings
FIG. 1 rare earth complex luminescent material Eu (TPM) 3 Single crystal structure of (PBO) molecules.
Fig. 2.Rare earth complex luminescent material Eu (TPM) 3 A stacking map of (PBO) molecules within a cell and its surrounding space.
FIG. 3 rare earth complex luminescent material Eu (TPM) 3 An infrared absorption spectrum of (PBO) is shown with the abscissa representing wave number and the ordinate representing transmittance.
FIG. 4 rare earth complex luminescent material Eu (TPM) 3 Ultraviolet visible absorption spectrum of (PBO), with the abscissa representing wavelength and the ordinate representing absorbance.
FIG. 5 rare earth complex luminescent material Eu (TPM) 3 An emission spectrum of (PBO) crystalline powder, wherein the excitation wavelength is 365nm, and the maximum emission peak is 610 nm; the abscissa is wavelength and the ordinate is intensity.
FIG. 6 rare earth complex luminescent material Eu (TPM) 3 (PBO) paper-based film emission spectrum, excitation wavelength is 365nm, and maximum emission peak is 610 nm; the abscissa is wavelength and the ordinate is intensity.
FIG. 7 rare earth complex luminescent material Eu (TPM) 3 (PBO) emission spectrum of quartz glass base film, excitation wavelength is 365nm, and maximum emission peak is 610 nm; the abscissa is wavelength and the ordinate is intensity.
FIG. 8 rare earth complex luminescent material Eu (TPM) 3 A fluorescence emission spectrum (main peak) of the paper-based sensing film of (PBO) after response to different times in an ammonia atmosphere; the abscissa is wavelength and the ordinate is intensity.
FIG. 9 rare earth complex luminescent material Eu (TPM) 3 A fluorescence intensity change curve of the paper-based sensing film of (PBO) after responding to different times in an ammonia atmosphere; the abscissa is time and the ordinate is intensity.
FIG. 10 rare earth complex luminescent material Eu (TPM) 3 A fluorescence emission intensity change curve of the paper-based sensing film of (PBO) after responding in ammonia gas atmosphere with different concentrations; the abscissa is the concentration in ppm, and the ordinate is the ratio I of the initial luminous intensity to the luminous intensity of ammonia gas of a certain concentration after response 0 /I。
FIG. 11 rare earth complex luminescent material Eu (TPM) 3 Quartz glass sheet based sensing of (PBO)The film responds to fluorescent emission patterns (main peaks) after different times in an ammonia atmosphere; the abscissa is the wavelength, and the ordinate is the ratio I of the initial luminous intensity to the luminous intensity at a certain moment 0 /I。
Detailed Description
The implementation process and the material performance of the invention are illustrated by the examples:
example 1
Rare earth complex luminescent material Eu (TPM) 3 The Preparation of (PBO) can be achieved by the following steps:
1. 0.180g/0.4mmol europium nitrate is weighed and dissolved in 5mL acetonitrile solution, and the solution is stirred for 5min to be completely dissolved, so as to obtain colorless solution A;
2. weighing 0.2352g/1.2mmol of TPM and 0.0820g/1.2mmol of potassium hydroxide, mixing and dissolving in a mixed solvent of 5mL of acetonitrile and 1mL of water, and fully stirring for 5min to obtain colorless transparent solution B;
3. weighing 0.078g/0.4mmol of 2-PBO, dissolving in 5mL of acetonitrile solution, and stirring for 15min to obtain pale yellow solution C;
4. adding the solution B into the solution A, stirring thoroughly until white precipitate is generated, adding the solution C into the mixed solution, and stirring thoroughly to obtain light yellow turbid liquid;
5. filtering to obtain yellowish filtrate and precipitate, steaming the filtrate under reduced pressure until it is dry to obtain yellowish powder, vacuum filtering with deionized water, washing for several times, and drying to obtain white powder, weighing to obtain yield of 0.2438g, and calculating to obtain yield of about 54.17%.
Example 2
Rare earth complex luminescent material Eu (TPM) 3 The Preparation of (PBO) single crystals can be achieved by the following steps:
1. weighing 0.020g of powder synthesized according to the method of example 1;
2. the powder was dissolved in 10ml of dichloromethane, stirred at room temperature until clear, and then filtered;
3. placing the light filtrate obtained by filtration in a clean test tube, placing deionized water as a precipitator in the lower layer in the test tube in advance, and semi-sealing, standing and crystallizing;
4. after several days, a large number of light-colored crystals grow in the test tube, the crystals with the size of 0.49mm multiplied by 0.35mm multiplied by 0.20mm are taken out for X-ray single crystal diffraction test, and Eu (TPM) is obtained by analysis 3 (PBO) crystal structure. The crystal structure diagram is shown in fig. 1 and 2.
Example 3
Rare earth complex luminescent material Eu (TPM) 3 Preparation of paper-based fluorescent film of (PBO): weighing 0.0020g Eu (TPM) 3 (PBO); adding the mixture into 6ml of dichloromethane solution, and fully stirring to fully dissolve the mixture to obtain light-colored clear solution; the complex solution was slowly added to the dichloromethane solution of PMMA, and the solution was light-colored, clear and transparent. Then the solution is subjected to micro-spraying on a prepared test strip to prepare a sensitive surface for fluorescence sensing, and a ratio type fluorescent test paper (paper-based fluorescent film) is obtained after waiting for drying; the paper-based fluorescence sensing film has very sensitive response to ammonia gas, and fluorescence quenching can occur when a small amount of ammonia gas exists in the environment.
Example 4
Rare earth complex luminescent material Eu (TPM) 3 Preparation of paper-based fluorescent film of (PBO): weighing 0.0020g Eu (TPM) 3 (PBO); adding into 6ml of dichloromethane solution, stirring thoroughly to dissolve thoroughly and obtain light-colored clear solution, immersing cellulose film test strip prepared in advance into the solution, taking out after soaking thoroughly and uniformly, pressing to dry, air drying, waiting for drying to obtain portable fluorescent test paper (paper-based fluorescent film); the paper-based fluorescence sensing film has very sensitive response to ammonia gas, and fluorescence quenching can occur when a small amount of ammonia gas exists in the environment.
Example 5
Red fluorescent complex material Eu (TPM) 3 Preparation of quartz glass sheet-based fluorescent film of (PBO): weighing 0.0020g Eu (TPM) 3 (PBO); adding the mixture into 6ml of dichloromethane solution, and fully stirring to fully dissolve the mixture to obtain light-colored clear solution; the complex solution was slowly added to the dichloromethane solution of PMMA, and the solution was light-colored, clear and transparent. Spin coating (1200 rad/min) on a clean quartz plate, drying (70deg.C, 30 m)in), then placing the sample in ammonia atmosphere for response, and testing fluorescence spectrum. The fluorescence sensing film has very sensitive response to ammonia gas, and fluorescence quenching can occur when a small amount of ammonia gas exists in the environment.
Eu pair (TPM) 3 A series of performance tests were performed on the pure phase Powder of (PBO) and its film samples. The steady state fluorescence test of the film shows that Eu (TPM) 3 (PBO) can emit intense red fluorescence under the action of different excitation wavelengths. It can be seen that the material can be applied to luminescent materials in OLED devices. The fluorescence test of the ammonia VOC response of the material shows that the material has obvious fluorescence quenching type sensing response phenomenon in ammonia atmosphere. As can be seen from the time response curve, the material can rapidly generate fluorescence quenching response to ammonia within a few seconds, and the maximum effect of the fluorescence quenching response is basically reached within 1 minute. It can be seen that the material can also be applied to fluorescent sensing materials for ammonia gas detection. However, as can be seen from the concentration response curve, the linear curve response characteristic of the static quenching mechanism is shown when the ammonia concentration is low, and the complex probe and the ammonia response are close to reach saturation when the concentration is high, so that the linear characteristic is not shown any more. Specific emission spectra are shown in fig. 5, 6, 7, 8, 9, 10, and 11.
Claims (6)
1. A rare earth complex luminescent material, characterized in that: the structural formula of the luminescent material is Eu (TPM) 3 (PBO) wherein TPM is 1, 1-trifluoro-5, 5-dimethyl-2, 4-hexanedione; wherein PBO is a neutral heterocyclic ligand 2- (2-pyridine) benzoxazole; the rare earth complex luminescent material is monoclinic system, P2 1 Space group/c, unit cell parameters areα＝90°，β＝90°，γ＝90°，/>Z＝4，D C ＝1.589g/cm 3 The crystal color of the material is nearly colorless; the material structure is represented by mononuclear neutral coordinationA compound in which Eu is 3+ Is positioned in the coordination environment center, and chelates 3 trifluoromethyl and tert-butyl substituted beta-diketone ligands TPM and 1 neutral nitrogen-containing ligand PBO around, and the four ligands are uniformly distributed in Eu 3+ Is formed around the periphery of (2); eu (Eu) 3+ The ion adopts an eight-coordination mode, and six coordination atoms O and two coordination atoms N form a dodecahedron configuration; the molecular structure is shown as formula (I):
2. the method for preparing a rare earth complex luminescent material according to claim 1, comprising the steps of:
(1) Eu (NO) at room temperature 3 ) 3 ·6H 2 O powder is dissolved in acetonitrile;
(2) Dissolving TPM and KOH powder in a mixed solvent of acetonitrile and a small amount of water at room temperature;
(3) Mixing the two solutions, and stirring to fully react to obtain a clear solution A;
(4) Dissolving PBO powder in acetonitrile at room temperature, adding the acetonitrile to the solution A, mixing and stirring to fully carry out coordination reaction to obtain light yellow turbid liquid;
(5) Filtering, performing reduced pressure rotary evaporation on the filtrate to dryness to obtain yellowish powder, performing suction filtration and washing with deionized water for several times, and then drying to obtain crystalline powder product; molar ratio Eu (NO) 3 ) 3 TPM, KOH, PBO is 1:3:3:1.
3. An application of a paper-based rare earth complex fluorescent sensing film with sensitive and selective response to ammonia gas is characterized in that: the portable fluorescent sensing test paper device is applied to the convenient detection of ammonia gas; the paper-based rare earth complex fluorescent sensing film is prepared by mixing rare earth complex luminescent material Eu (TPM) 3 (PBO) is dissolved and then coated on the base paper of the test paper to prepare the test paper; after the paper-based rare earth complex fluorescence sensing film is placed in an environment with ammonia gas, the paper-based rare earth complex fluorescence sensing film has red fluorescenceThe intensity is rapidly reduced, and the higher the ammonia concentration is, the stronger the quenching response effect is, and the fluorescence sensing performance of rapid response and sensitive identification is shown; wherein the structural formula of the rare earth complex luminescent material is Eu (TPM) 3 (PBO) wherein TPM is 1, 1-trifluoro-5, 5-dimethyl-2, 4-hexanedione, wherein PBO is the neutral heterocyclic ligand 2- (2-pyridine) benzoxazole; the rare earth complex luminescent material is monoclinic system, P2 1 Space group/c, unit cell parameters areα＝90°，β＝90°，γ＝90°，/> Z＝4，D C ＝1.589g/cm 3 The crystal color of the material is nearly colorless; the material structure is represented by a mononuclear neutral complex, wherein Eu 3+ Is positioned in the coordination environment center, and chelates 3 trifluoromethyl and tert-butyl substituted beta-diketone ligands TPM and 1 neutral nitrogen-containing ligand PBO around, and the four ligands are uniformly distributed in Eu 3+ Is formed around the periphery of (2); eu (Eu) 3+ The ion adopts an eight-coordination mode, and six coordination atoms O and two coordination atoms N form a dodecahedron configuration; the molecular structure is shown as formula (I):
4. the use according to claim 3, wherein the method for preparing a paper-based rare earth complex fluorescent sensing film having a sensitive selective response to ammonia gas comprises the steps of:
(1) Eu (TPM) with a certain concentration is configured according to the mass concentration of the substance 3 (PBO) dichloromethane solution X;
(2) Adding a proper amount of methylene dichloride solution of PMMA into the solution X, and uniformly mixing to obtain a solution Y;
(3) And coating the solution Y on the base paper of the test paper in a dip-coating and micro-spraying mode, wherein the base paper of the test paper is a cellulose film, and drying to obtain the paper-based rare earth complex fluorescence sensing film.
5. An application of a rare earth complex doped polymer-based fluorescent sensing film with sensitive and selective response to ammonia gas is characterized in that: the sensitive film in the fluorescence sensor is applied to the detection of ammonia gas, and is convenient for the integrated utilization of an optical fiber system; the rare earth complex doped polymer-based fluorescent sensing film is prepared by mixing a fluorescent sensing material Eu (TPM) 3 (PBO) is dissolved and then mixed into polymethyl methacrylate to be coated; after the rare earth complex doped polymer-based fluorescence sensing film is placed in an environment where ammonia exists, the red fluorescence intensity of the film is rapidly weakened, and the higher the ammonia concentration is, the stronger the quenching response effect is shown, and the fluorescence sensing performance of rapid response and sensitive identification is shown; wherein the structural formula of the rare earth complex luminescent material is Eu (TPM) 3 (PBO) wherein TPM is 1, 1-trifluoro-5, 5-dimethyl-2, 4-hexanedione, wherein PBO is the neutral heterocyclic ligand 2- (2-pyridine) benzoxazole; the rare earth complex luminescent material is monoclinic system, P2 1 Space group/c, unit cell parameters are α＝90°，β＝90°，γ＝90°，/>Z＝4，D C ＝1.589g/cm 3 The crystal color of the material is nearly colorless; the material structure is represented by a mononuclear neutral complex, wherein Eu 3+ Is positioned in the coordination environment center, and chelates 3 trifluoromethyl and tert-butyl substituted beta-diketone ligands TPM and 1 neutral nitrogen-containing ligand PBO around, and the four ligands are uniformly distributed in Eu 3+ Is around (2)；Eu 3+ The ion adopts an eight-coordination mode, and six coordination atoms O and two coordination atoms N form a dodecahedron configuration; the molecular structure is shown as formula (I):
6. the method according to claim 5, wherein the rare earth complex Eu (TPM) is based on 3 The preparation method of the polymer-based doped fluorescent sensing film (PBO) comprises the following steps:
(1) Dissolving polymethyl methacrylate solid in dichloromethane at room temperature;
(2) Rare earth complex Eu (TPM) at room temperature 3 (PBO) powder is dissolved in dichloromethane;
(3) Mixing the two solutions, and stirring to fully and uniformly mix the two solutions to obtain a clear solution Z;
(4) And spin-coating the clear solution Z on a quartz plate at room temperature, and drying to obtain the rare earth complex doped polymer-based fluorescent sensing film.
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