CN113122254A - Fluorescent probe material and preparation method and application thereof - Google Patents
Fluorescent probe material and preparation method and application thereof Download PDFInfo
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- CN113122254A CN113122254A CN202110425084.3A CN202110425084A CN113122254A CN 113122254 A CN113122254 A CN 113122254A CN 202110425084 A CN202110425084 A CN 202110425084A CN 113122254 A CN113122254 A CN 113122254A
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002159 nanocrystal Substances 0.000 claims abstract description 104
- 239000011258 core-shell material Substances 0.000 claims abstract description 65
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 58
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 58
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000005642 Oleic acid Substances 0.000 claims abstract description 58
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 58
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 58
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 58
- 239000003446 ligand Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000001514 detection method Methods 0.000 claims abstract description 19
- 230000005284 excitation Effects 0.000 claims abstract description 17
- 159000000000 sodium salts Chemical class 0.000 claims description 37
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 33
- 239000011737 fluorine Substances 0.000 claims description 33
- 229910052731 fluorine Inorganic materials 0.000 claims description 33
- 150000001225 Ytterbium Chemical class 0.000 claims description 28
- 150000001621 bismuth Chemical class 0.000 claims description 28
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 24
- 239000011734 sodium Substances 0.000 claims description 23
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 150000000917 Erbium Chemical class 0.000 claims description 14
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 14
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 4
- 229940073609 bismuth oxychloride Drugs 0.000 claims description 4
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 4
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000000523 sample Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 claims description 4
- 238000001831 conversion spectrum Methods 0.000 claims description 3
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 abstract description 42
- 238000004020 luminiscence type Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000005281 excited state Effects 0.000 abstract description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- -1 ytterbium ions Chemical class 0.000 description 12
- 229910052769 Ytterbium Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000005264 electron capture Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000009182 swimming Effects 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 230000002354 daily effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- MIHRVCSSMAGKNH-UHFFFAOYSA-N ethylcarbamodithioic acid Chemical compound CCNC(S)=S MIHRVCSSMAGKNH-UHFFFAOYSA-N 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 230000002792 vascular Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention provides a fluorescent probe material and a preparation method and application thereof, belonging to the technical field of inorganic luminescent materials. The fluorescent probe material provided by the invention can emit 980nm up-conversion light under the condition of 1550nm laser excitation, the excitation light and the emission light are both located in a near infrared region, no background fluorescence is generated in the detection process, and the accuracy is high; moreover, oleic acid ligand contained on the surface of the core-shell nanocrystal can enable the core-shell nanocrystal to have good dispersibility in gasoline, the influence of lead ions on the surface of the core-shell nanocrystal can be promoted, and the lead ions can effectively capture Er3+Electrons on the excited state energy level of the ion, and then Er is reduced3+To Yb3+Energy transfer efficiency of (1), resulting in Yb3+The up-conversion luminescence intensity of the ions at 980nm is gradually reduced along with the increase of the concentration of the lead ions, and the method can be applied to quantitative detection of the lead content in the gasoline.
Description
Technical Field
The invention relates to the technical field of inorganic luminescent materials, in particular to a fluorescent probe material and a preparation method and application thereof.
Background
Lead ion (Pb)2+) Is obtained by the loss of two electrons of the outermost layer of lead atoms, usually blue in color, and is hydrated in an aqueous solution as the ion [ Cu (H)2O)4]2+Exist in the form of (1). Different salts containing lead ions are widely used in the fields of human daily life, biomedicine, industry and the like, mainly because the lead ions have a plurality of special functions. For example, lead ions have a bactericidal effect, and can be properly added into a swimming pool for disinfection, so that the water in the swimming pool is usually blue; lead sulfate is considered to be a very safe pesticide; the lead ions and connective tissues in the yam are greatly helpful for human development and have obvious curative effects on vascular system diseases. Lead is a metal element required by human bodies, and about 2-3 mg of lead is required to be taken from food every day by normal people. However, the wide use of lead ions causes pollution to the environment to a certain extent, and therefore, the quantitative detection technology of the content of lead ions has important scientific research value.
At present, the detection method of lead ions mainly comprises an ethylamino dithioformic acid spectrophotometry, an iodometry, an atomic absorption method, an ion chromatography, an electrochemical detection method, a colorimetric method and the like, and the detection technologies are complex and are difficult to realize real-time in-situ online detection. The fluorescent probe has the characteristics of non-contact, quick response, high spatial resolution and high accuracy, and is widely applied to detection of pH, temperature, pressure, biomolecules and the like. More importantly, the fluorescence detection method is simple and can realize rapid in-situ on-line detection. However, the excitation and emission wavelengths of the current probe materials for lead ion detection are both in the visible light range, the penetration depth is shallow, background fluorescence is easily generated, the interference signal is strong, and the detection accuracy is poor.
Disclosure of Invention
The invention aims to provide a fluorescent probe material and a preparation method and application thereof, wherein the excitation wavelength is 1550nm in a near infrared two-region mode, the emission wavelength is in a near infrared one-region mode, the central wavelength is 980nm, background fluorescence is not generated in the detection process, and the high accuracy is achieved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a fluorescent probe material, which comprises a core-shell nanocrystal and an oleic acid ligand coated on the surface of the core-shell nanocrystal, wherein the oleic acid ligand is electrostatically adsorbed on the surface of the core-shell nanocrystal; the composition of the core-shell nanocrystal is Na0.6K0.4BiaErbYb0.1F4@NaBicYbdF4Said Na0.6K0.4BiaErbYb0.1F4As a nucleus, the NaBicYbdF4Is a shell; wherein a is 0.5 to 0.7, b is 0.3 to 0.5, c is 0.7 to 0.9, and d is 0.1 to 0.3.
Preferably, the mass of the oleic acid ligand is 15-25% of the total mass of the core-shell nanocrystal and the oleic acid ligand.
The invention provides a preparation method of the fluorescent probe material in the technical scheme, which comprises the following steps:
mixing a first sodium salt, a potassium salt, a first bismuth salt, an erbium salt, a first ytterbium salt, a first fluorine source, first oleic acid, first oleylamine and a first solvent, and performing first growth to obtain a core nanocrystal;
mixing a second sodium salt, a second bismuth salt, a second ytterbium salt, a second fluorine source, second oleic acid, second oleylamine and a second solvent with the core nanocrystal to perform second growth to obtain a fluorescent probe material;
the molar ratio of the first sodium salt, the potassium salt, the first bismuth salt, the erbium salt, the first ytterbium salt and the first fluorine source is 0.6:0.4 (0.5-0.7) to 0.3-0.5) to 0.1: 4;
the molar ratio of the second sodium salt to the second bismuth salt to the second ytterbium salt to the second fluorine source is 1 (0.7-0.9) to 0.1-0.3) to 4;
the molar ratio of the first sodium salt to the second sodium salt is 0.6: 1.
Preferably, the first sodium salt and the second sodium salt independently comprise sodium nitrate or sodium chloride; the potassium salt comprises potassium carbonate; the first bismuth salt and the second bismuth salt independently comprise bismuth nitrate, bismuth chloride or bismuth oxychloride; the erbium salt comprises erbium nitrate or erbium chloride; the first ytterbium salt and the second ytterbium salt independently comprise ytterbium nitrate or ytterbium chloride.
Preferably, the first fluorine source and the second fluorine source are ammonium fluoride; the dosage ratio of the first fluorine source, the first oleic acid and the first oleylamine is (4-6) mmol, (5-10) mL, (1-2) mL.
Preferably, the dosage ratio of the second fluorine source, the second oleic acid and the second oleylamine is (4-6) mmol, (5-10) mL, (1-2) mL.
Preferably, the temperature of the first growth is 25-35 ℃ and the time is 30-60 min.
Preferably, the temperature of the second growth is 25-35 ℃ and the time is 60-90 min.
The invention provides an application of the fluorescent probe material in the technical scheme or the fluorescent probe material prepared by the preparation method in the technical scheme in quantitative detection of lead content in gasoline.
The invention provides a method for detecting lead content in gasoline, which comprises the following steps:
mixing gasoline containing different lead ion concentrations with a fluorescent probe material, detecting under the condition of 1550nm exciting light excitation, calculating integral intensity according to the obtained up-conversion spectrum, fitting a relation curve of the fluorescent integral intensity and the lead ion concentration, and obtaining the lead ion content in a gasoline sample according to the relation curve; the fluorescent probe material is the fluorescent probe material in the technical scheme or the fluorescent probe material prepared by the preparation method in the technical scheme.
The invention provides a fluorescent probe material, which comprises a core-shell nanocrystal and an oleic acid ligand coated on the surface of the core-shell nanocrystal, wherein the oleic acid ligand is electrostatically adsorbed on the surface of the core-shell nanocrystal; the composition of the core-shell nanocrystal is Na0.6K0.4BiaErbYb0.1F4@NaBicYbdF4Said Na0.6K0.4BiaErbYb0.1F4Is a core of saidNaBicYbdF4Is a shell; wherein a is 0.5 to 0.7, b is 0.3 to 0.5, c is 0.7 to 0.9, and d is 0.1 to 0.3. The fluorescent probe material provided by the invention can emit 980nm up-conversion light under the excitation condition of a 1550nm laser, the excitation wavelength of the fluorescent probe material is 1550nm, the emission wavelength (980nm) is in 1550nm, the center wavelength of the fluorescent probe material is 980nm, the excitation light and the emission light are both in a near-infrared region, no background fluorescence exists in the detection process, and the accuracy is high. In Na0.6K0.4BiF4In the host lattice, Er3+And Yb3+All occupy Bi3+Lattice site, the energy of incident photon is Er in the nuclear nanocrystalline3+Ion absorption, corresponding to4I15→4I13Further filling by a two-photon absorption process4I11Energy level at which the energy of the radiated photons is transferred to Yb after the electrons return to the ground state3+Further fill Yb3+Is/are as follows2F5/2Energy level, resulting in up-converted luminescence with a central wavelength at 980 nm. In addition, by doping a small amount of Yb in the shell layer3+Can increase Yb3+For Er3+Ion(s)4I11The probability of electron capture on the energy level, and thus the up-conversion luminous efficiency is improved.
The oleic acid ligand contained on the surface of the fluorescent probe material provided by the invention can enable the core-shell nanocrystal to have good dispersibility in gasoline, and is beneficial to enlarging the interaction area of lead ions in the gasoline and the surface of the core-shell nanocrystal, and after the lead ions in the gasoline are contacted with the surface of the core-shell nanocrystal, Er can be captured due to the excited state energy level of the lead ions3+Ion(s)4I11Electrons at the energy level, thereby reducing Yb3+The probability of electron capture of ions on the energy level is reduced, and the process reduces Er3+To Yb3+Energy transfer efficiency of (1), resulting in Yb3+The upconversion luminous intensity of ions at 980nm is gradually reduced along with the increase of the concentration of lead ions, and the fluorescent probe material designed by the invention has very high upconversion luminous intensity, so that the change amplitude of the fluorescent intensity along with the increase of the concentration of the lead ionsThe method is very obvious, and can well establish a relation curve of up-conversion luminescence intensity and lead ion concentration, and further be applied to quantitative detection of lead content in gasoline.
Drawings
FIG. 1 is an X-ray diffraction pattern of core-shell nanocrystals prepared in example 1 containing an oleic acid ligand;
FIG. 2 is a transmission electron micrograph of core-shell nanocrystals prepared in example 1 containing oleic acid ligands;
FIG. 3 is an upconversion spectrum of the core-shell nanocrystal with oleic acid ligand prepared in example 1 under the excitation condition of 1550nm laser;
FIG. 4 is an upconversion spectrum of the core nanocrystal with oleic acid ligand prepared in example 1 under 1550nm laser excitation;
FIG. 5 shows Yb in the shell layer of the core-shell nanocrystals prepared in examples 1 to 3 and comparative examples 1 to 23+A relation curve graph of ion doping concentration and up-conversion luminescence intensity;
FIG. 6 is a graph of fluorescence intensity of core-shell nanocrystals with oleic acid ligand prepared in example 1 as a function of lead ion concentration in cyclohexane solution;
FIG. 7 is a graph showing the effect of common metal ions in cyclohexane solution on the fluorescence intensity of the core-shell nanocrystals containing oleic acid ligand prepared in example 1;
FIG. 8 is a graph of fluorescence intensity of core-shell nanocrystals prepared in example 1 and containing oleic acid ligand as a function of lead ion concentration in commercial gasoline;
fig. 9 is a graph showing the relationship between the fluorescence intensity of the core-shell nanocrystal without an acidic ligand prepared in comparative example 1 and the concentration of lead ions in a cyclohexane solution.
Detailed Description
The invention provides a fluorescent probe material, which comprises a core-shell nanocrystal and an oleic acid ligand coated on the surface of the core-shell nanocrystal, wherein the oleic acid ligand is electrostatically adsorbed on the surface of the core-shell nanocrystal; the composition of the core-shell nanocrystal is Na0.6K0.4BiaErbYb0.1F4@NaBicYbdF4What is, what isThe above Na0.6K0.4BiaErbYb0.1F4As a nucleus, the NaBicYbdF4Is a shell; wherein a is 0.5 to 0.7, b is 0.3 to 0.5, c is 0.7 to 0.9, and d is 0.1 to 0.3.
The fluorescent probe material provided by the invention comprises core-shell nanocrystals, wherein the core-shell nanocrystals consist of Na0.6K0.4BiaErbYb0.1F4@NaBicYbdF4Said Na0.6K0.4BiaErbYb0.1F4As a nucleus, the NaBicYbdF4Is a shell; wherein a is 0.5-0.7, b is 0.3-0.5, c is 0.7-0.9, and d is 0.1-0.3; more preferably, a is 0.5, b is 0.4, c is 0.8, and d is 0.2.
The fluorescent probe material provided by the invention comprises an oleic acid ligand coated on the surface of the core-shell nanocrystal, and the oleic acid ligand is electrostatically adsorbed on the surface of the core-shell nanocrystal. In the invention, the mass of the oleic acid ligand is 15-25% of the total mass of the core-shell nanocrystal and the oleic acid ligand, and more preferably 20%.
The invention provides a preparation method of the fluorescent probe material in the technical scheme, which comprises the following steps:
mixing a first sodium salt, a potassium salt, a first bismuth salt, an erbium salt, a first ytterbium salt, a first fluorine source, first oleic acid, first oleylamine and a first solvent, and performing first growth to obtain a core nanocrystal;
mixing a second sodium salt, a second bismuth salt, a second ytterbium salt, a second fluorine source, second oleic acid, second oleylamine and a second solvent with the core nanocrystal to perform second growth to obtain a fluorescent probe material;
the molar ratio of the first sodium salt, the potassium salt, the first bismuth salt, the erbium salt, the first ytterbium salt and the first fluorine source is 0.6:0.4 (0.5-0.7) to 0.3-0.5) to 0.1: 4;
the molar ratio of the second sodium salt to the second bismuth salt to the second ytterbium salt to the second fluorine source is 1 (0.7-0.9) to 0.1-0.3) to 4;
the molar ratio of the first sodium salt to the second sodium salt is 0.6: 1.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The method comprises the steps of mixing a first sodium salt, a potassium salt, a first bismuth salt, an erbium salt, a first ytterbium salt, a first fluorine source, first oleic acid, first oleylamine and a first solvent, and performing first growth to obtain the core nanocrystal. In the present invention, the first sodium salt preferably includes sodium nitrate or sodium chloride; the potassium salt preferably comprises potassium carbonate; the first bismuth salt preferably comprises bismuth nitrate, bismuth chloride or bismuth oxychloride; the erbium salt preferably comprises erbium nitrate or erbium chloride; the first ytterbium salt preferably comprises ytterbium nitrate or ytterbium chloride. In the present invention, the molar ratio of the first sodium salt, the potassium salt, the first bismuth salt, the erbium salt, the first ytterbium salt and the first fluorine source is 0.6:0.4 (0.5 to 0.7): 0.3 to 0.5):0.1:4, preferably 0.6:0.4 (0.55 to 0.65): 0.35 to 0.45):0.1:4, more preferably 0.6:0.4:0.6:0.4:0.1: 4.
In the present invention, the first fluorine source is preferably ammonium fluoride; the dosage ratio of the first fluorine source, the first oleic acid and the first oleylamine is (4-6) mmol, (5-10) mL, (1-2) mL, more preferably (4.5-5.5) mmol, (6-8) mL, (1.5-1.8) mL, and further preferably 5mmol, 7mL and 1.6 mL. The first oleylamine is utilized to reduce the energy barrier of the growth of the nanocrystal, and the nucleation and growth of the nanocrystal are further promoted. According to the invention, the first oleic acid is utilized to improve the dispersibility of the core nanocrystal, so that the uniform growth of the shell layer in the second growth process is promoted, and the core-shell nanocrystal with good dispersibility is obtained.
In the present invention, the first solvent is preferably ethylene glycol; the volume ratio of the first solvent to the first oleic acid is preferably 5 (5-10), and more preferably 5 (6-8).
In the invention, the first sodium salt, potassium salt, first bismuth salt, erbium salt, first ytterbium salt, first fluorine source, first oleic acid, first oleylamine and the first solvent are preferably mixed by dissolving the first sodium salt, potassium salt, first bismuth salt, erbium salt and first ytterbium salt in the first solvent, stirring for 10-15 min, and then adding the first fluorine source, first oleic acid and first oleylamine to the obtained mixture. The stirring speed is not particularly limited in the invention, and the materials can be uniformly mixed according to the process well known in the field.
In the invention, the temperature of the first growth is preferably 25-35 ℃, the time is preferably 30-60 min, and more preferably 40-50 min; the first growth is preferably carried out under stirring conditions, and the rotation speed of the stirring is not particularly limited in the present invention, and the reaction can be smoothly carried out according to a process well known in the art.
In the first growth process, the first sodium salt, the potassium salt, the first bismuth salt, the erbium salt, the first ytterbium salt and the first fluorine source are subjected to low-temperature nucleation and high-temperature growth to obtain the core nanocrystal, and the first oleic acid is electrostatically adsorbed on the surface of the core nanocrystal.
After the first growth is completed, the present invention preferably performs centrifugal washing on the obtained product to obtain the core nanocrystal. In the invention, the washing reagent used for centrifugal washing is preferably a mixed solution of ethanol and cyclohexane, and the volume ratio of the ethanol to the cyclohexane is preferably 3: 1; the number of times of centrifugal washing is preferably 3-5 times. The first oleylamine on the surface of the core nanocrystal is removed by washing.
After obtaining the core nanocrystals, the present invention preferably disperses the core nanocrystals in cyclohexane for use.
After the core nanocrystal is obtained, a second sodium salt, a second bismuth salt, a second ytterbium salt, a second fluorine source, second oleic acid, second oleylamine and a second solvent are mixed with the core nanocrystal to perform second growth, so that the fluorescent probe material is obtained. In the present invention, the second sodium salt preferably includes sodium nitrate or sodium chloride; the second bismuth salt preferably comprises bismuth nitrate, bismuth chloride or bismuth oxychloride; the second ytterbium salt preferably comprises ytterbium nitrate or ytterbium chloride. In the invention, the molar ratio of the second sodium salt, the second bismuth salt, the second ytterbium salt and the second fluorine source is 1 (0.7-0.9): 0.1-0.3): 4, preferably 1 (0.75-0.85): 0.15-0.25): 4, and more preferably 1:0.8:0.2: 4. In the present invention, the molar ratio of the first sodium salt to the second sodium salt is 0.6: 1.
In the present invention, the second fluorine source is preferably ammonium fluoride; the dosage ratio of the second fluorine source, the second oleic acid and the second oleylamine is preferably (4-6) mmol, (5-10) mL, (1-2) mL, and more preferably (4.5-5.5) mmol, (5-10) mL, (1-2) mL. According to the invention, the second oleylamine is utilized to reduce the energy barrier of the growth of the nanocrystal, so that the nucleation and growth of the nanocrystal are promoted; the invention utilizes the second oleic acid to improve the dispersibility of the core-shell nanocrystal in gasoline, and is convenient for realizing the detection of lead ions in gasoline.
In the present invention, the second solvent is preferably ethylene glycol; the volume ratio of the second solvent to the second oleic acid is preferably 5 (5-10), and more preferably 5 (6-8).
In the present invention, the core nanocrystal is preferably used in the form of a dispersion, and the solvent used for the dispersion of the core nanocrystal is preferably cyclohexane; the concentration of the dispersion liquid of the core nanocrystal is not particularly limited, and the core nanocrystal can be sufficiently dispersed. The amount of the dispersion liquid of the core nanocrystal is not particularly limited, and the molar ratio of the first sodium salt to the second sodium salt can be satisfied.
In the invention, the process of mixing the second sodium salt, the second bismuth salt, the second ytterbium salt, the second fluorine source, the second oleic acid, the second oleylamine and the second solvent with the core nanocrystal is preferably to dissolve the second sodium salt, the second bismuth salt and the second ytterbium salt in the second solvent, stir for 10-20 min, then add the second oleic acid and the second oleylamine to the obtained mixture, stir for 30-60 min at room temperature (25-35 ℃), then add the core nanocrystal dispersion, continue to stir for 50-70 min, and then add the second fluorine source. The stirring speed is not particularly limited in the invention, and the materials can be uniformly mixed according to the process well known in the field.
In the invention, the temperature of the second growth is preferably 25-35 ℃, the time is preferably 60-90 min, and more preferably 70-80 min; the second growth is preferably carried out under stirring conditions. The stirring speed is not particularly limited in the invention, and the materials can be uniformly mixed according to the process well known in the field. In the second growth process, a second sodium salt, a second bismuth salt, a second ytterbium salt and a second fluorine source form nuclei on the surface of the core nanocrystal and grow to form a core-shell nanocrystal, and meanwhile, second oleic acid is electrostatically adsorbed on the surface of the core-shell nanocrystal.
After the second growth is completed, the obtained product is preferably subjected to centrifugal washing to form core-shell nanocrystals, so that the fluorescent probe material is obtained. In the invention, the washing reagent used for centrifugal washing is preferably a mixed solution of ethanol and cyclohexane, and the volume ratio of the ethanol to the cyclohexane is preferably 3: 1; the number of times of centrifugal washing is preferably 3-5 times. The second oleylamine on the surface of the core-shell nanocrystal is removed by washing.
The invention provides an application of the fluorescent probe material in the technical scheme or the fluorescent probe material prepared by the preparation method in the technical scheme in quantitative detection of lead content in gasoline. The method of the present invention is not particularly limited, and the method may be applied according to a method known in the art.
The invention provides a method for detecting lead content in gasoline, which comprises the following steps:
mixing gasoline containing different lead ion concentrations with a fluorescent probe material, detecting under the condition of 1550nm exciting light excitation, calculating integral intensity according to the obtained up-conversion spectrum, fitting a relation curve of the fluorescent integral intensity and the lead ion concentration, and obtaining the lead ion content in a gasoline sample according to the relation curve; the fluorescent probe material is the fluorescent probe material in the technical scheme or the fluorescent probe material prepared by the preparation method in the technical scheme.
In the invention, the dosage ratio of the gasoline to the fluorescent probe material is preferably 10mL (0.2-0.4) mg, and more preferably 10mL to 0.3 mg. The specific concentration of the lead ions with different concentrations is not specially limited, and the lead ions can be adjusted according to actual requirements.
The process of calculating the integrated intensity and fitting the fluorescence integrated intensity-lead ion concentration relation curve is not particularly limited in the present invention, and the process can be performed according to the process well known in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Containing oleic acid ligand Na0.6K0.4Bi0.5Er0.4Yb0.1F4@NaBi0.8Yb0.2F4The preparation method of the core-shell nanocrystal comprises the following steps:
(1) adding 0.6mmol of sodium nitrate, 0.2mmol of potassium carbonate, 0.5mmol of bismuth nitrate, 0.4mmol of erbium nitrate and 0.1mmol of ytterbium nitrate into 5mL of ethylene glycol, stirring for 10min, then adding 4mmol of ammonium fluoride, 10mL of oleic acid and 2mL of oleylamine, stirring for 40min at room temperature (30 ℃), centrifugally washing the obtained product for 3 times by using a mixed solution of ethanol and cyclohexane (volume ratio of 3:1), and obtaining Na0.6K0.4Bi0.5Er0.4Yb0.1F4Dispersing the nuclear nanocrystals in 5mL of cyclohexane for later use;
(2) adding 1mmol of sodium nitrate, 0.8mmol of bismuth nitrate and 0.2mmol of ytterbium nitrate into 5mL of ethylene glycol, stirring for 10min, then adding 10mL of oleic acid and 2mL of oleylamine, stirring for 40min at room temperature (30 ℃), then adding the nuclear nanocrystal dispersion obtained in the step (1), continuing stirring for 50min, then adding 4mmol of ammonium fluoride, continuing stirring for 70min at room temperature (30 ℃), centrifugally washing the obtained product for 3 times by using an ethanol and cyclohexane mixed solution (volume ratio is 3:1) to obtain Na containing an oleic acid ligand0.6K0.4Bi0.5Er0.4Yb0.1F4@NaBi0.8Yb0.2F4Core-shell nanocrystals (the mass of the oleic acid ligand is 20% of the total mass of the core-shell nanocrystals and the oleic acid ligand).
Example 2
The only difference from example 1 is: and (3) adding 0.1mmol of ytterbium nitrate in the step (2), namely, the doping concentration of ytterbium ions in the shell layer accounts for 10 mol%.
Example 3
The only difference from example 1 is: and (3) adding 0.3mmol of ytterbium nitrate in the step (2), namely, the doping concentration of ytterbium ions in the shell layer accounts for 30 mol%.
Comparative example 1
The only difference from example 1 is: and (3) adding 0mmol of ytterbium nitrate in the step (2), namely, the doping concentration of ytterbium ions in the shell layer accounts for 0 mol%.
Comparative example 2
The only difference from example 1 is: and (3) adding 0.4mmol of ytterbium nitrate in the step (2), namely, the doping concentration of ytterbium ions in the shell layer accounts for 40 mol%.
Comparative example 3
The only difference from example 1 is: the step of adding oleic acid is removed in the steps (1) and (2), and the oil-free acid ligand Na is obtained0.6K0.4Bi0.5Er0.4Yb0.1F4@NaBi0.8Yb0.2F4Core-shell nanocrystals.
Characterization and testing
1) For Na prepared in example 10.6K0.4Bi0.5Er0.4Yb0.1F4@NaBi0.8Yb0.2F4Performing powder X-ray diffraction test on the core-shell nanocrystals, wherein the results are shown in FIG. 1; as can be seen from FIG. 1, the diffraction peaks match well with standard PDF cards 27-1427 (lower vertical line in FIG. 1), indicating Na prepared in example 10.6K0.4Bi0.5Er0.4Yb0.1F4@NaBi0.8Yb0.2F4The core-shell nanocrystals are pure hexagonal phase.
2) The core-shell nanocrystals prepared in example 1 were subjected to transmission electron microscopy, and the results are shown in fig. 2; as can be seen from FIG. 2, Na prepared in example 10.6K0.4Bi0.5Er0.4Yb0.1F4@NaBi0.8Yb0.2F4The shape of the core-shell nanocrystal is uniform and the dispersibility is good.
3) Na prepared in example 1 was subjected to the excitation with a 1550nm laser (fluorescence spectrometer, laser power 800mW, and slit size of both incident and emergent light of 2mm)0.6K0.4Bi0.5Er0.4Yb0.1F4Core nanocrystal and Na0.6K0.4Bi0.5Er0.4Yb0.1F4@NaBi0.8Y0.2F4The core-shell nanocrystals are respectively subjected to luminescence property test, and the results are shown in fig. 3 and 4; as can be seen from FIG. 3, the core-shell nanocrystals showed strong near-infrared-one-region up-conversion luminescence with a center wavelength of 980 nm. As can be seen from comparison of FIGS. 3 and 4, the product of example 1 was compared with Na0.6K0.4Bi0.5Er0.4Yb0.1F4@NaBi0.8Y0.2F4Core-shell nanocrystals, Na0.6K0.4Bi0.5Er0.4Yb0.1F4The luminescence intensity of the core nanocrystal is obviously weaker, because the cladding of the shell layer enables the radiationless relaxation probability of the activated ions on the surface of the core-shell nanocrystal to be reduced, the luminescence intensity of the core-shell nanocrystal is stronger than that of the core nanocrystal, and the result shows that the product prepared in example 1 is the core-shell structure nanocrystal.
4) The core-shell nanocrystals prepared in examples 1 to 3 and comparative examples 1 to 2 were subjected to a luminescence property test under different ytterbium ion doping concentrations (excitation power is 0.5W, and slit widths of incident light and emergent light are both 2mm), and the results are shown in fig. 5; as can be seen from fig. 5, as the doping concentration of the ytterbium ion in the shell layer increases from 0 to 20 mol%, the upconversion luminescence intensity gradually increases, mainly because the energy transfer efficiency from the ytterbium ion to the erbium ion increases with the increase of the doping concentration of the ytterbium ion, whereas as the doping concentration of the ytterbium ion in the shell layer continues to increase to 40 mol%, the upconversion luminescence intensity gradually decreases instead, mainly because the higher doping concentration of the ytterbium ion increases the probability of radiationless relaxation between the active ions, resulting in the decrease of the upconversion luminescence intensity.
5) Lead ions (0. mu. mol/L, 0.1. mu. mol/L, 0.2. mu. mol/L, 0.3. mu. mol/L, 0.4. mu. mol/L, 0.5. mu. mol/L, 0.6. mu. mol/L, 0.7. mu. mol/L, 0.8. mu. mol/L, 0.9. mu. mol/L, 1.0. mu. mol/L) were added to the cyclohexane solution (0.1mg/mL) containing the core-shell nanocrystals prepared in example 1, respectively, and the luminescence intensities thereof (excitation power of 0.5W, both incident light and emergent light width of 2mm) were measured, respectively, and the results are shown in FIG. 6; as can be seen from FIG. 6, the lead ions are concentrated with the lead ionsIncrease in degree Yb3+The up-conversion luminescence intensity of ions at 980nm is obviously reduced, and the reduction amplitude is equal to that of Pb2+The ion concentrations are closely related; lithium ions, sodium ions, calcium ions, barium ions, iron ions or magnesium ions were added to the cyclohexane solution (0.1mg/mL) containing the core-shell nanocrystals prepared in example 1, respectively, and the luminescence intensity thereof was measured, and the cyclohexane solution (0.1mg/mL) was used as a control, and the results are shown in fig. 7; as can be seen from FIG. 7, Yb3+The upconversion luminescence intensity of the ion at 980nm is substantially unchanged; it is demonstrated that the core-shell nanocrystals prepared in example 1 can specifically recognize lead ions.
Application example
1) 0.3mg of the core-shell nanocrystals prepared in example 1 was added to 10mL of gasoline containing different lead ion concentrations (0. mu. mol/L, 0.1. mu. mol/L, 0.2. mu. mol/L, 0.3. mu. mol/L, 0.4. mu. mol/L, 0.5. mu. mol/L, 0.6. mu. mol/L, 0.7. mu. mol/L, 0.8. mu. mol/L, 0.9. mu. mol/L, 1.0. mu. mol/L), respectively, and the luminescence intensities (excitation power 0.5W, both incident light and emergent light slit widths 2mm) were measured, and the results are shown in FIG. 8; as can be seen from FIG. 8, Yb3+The up-conversion luminescence intensity of the ions at 980nm is obviously weakened along with the increase of the concentration of lead ions, which shows that the fluorescent probe material can be used for detecting the lead content in gasoline.
2) 0.3mg of the acid ligand free core-shell nanocrystals prepared in comparative example 3 was added to 10mL of cyclohexane containing different lead ion concentrations (0. mu. mol/L, 0.1. mu. mol/L, 0.2. mu. mol/L, 0.3. mu. mol/L, 0.4. mu. mol/L, 0.5. mu. mol/L, 0.6. mu. mol/L, 0.7. mu. mol/L, 0.8. mu. mol/L, 0.9. mu. mol/L, 1.0. mu. mol/L) and the emission intensity was measured under the excitation of a 1550nm laser, as shown in FIG. 9; as can be seen from FIG. 9, Yb3+The upconversion luminous intensity of ions at 980nm is basically equal to Pb2+The ion concentration is irrelevant, which shows that the oleic acid ligand coats the nanocrystal, so that the nanocrystal has excellent dispersibility in cyclohexane, the effect of lead ions on the surface of the nanocrystal can be promoted, and the detection effect of the lead ions is directly influenced.
The above results show that Na of the present invention0.6K0.4Bi0.5Er0.4Yb0.1F4@NaBi0.8Yb0.2F4The core-shell nanocrystal can effectively and quantitatively detect the content of lead ions in gasoline, and the detection mechanism is as follows: oleic acid ligand on the surface of the core-shell nanocrystal enables the nanocrystal to be well dispersed in gasoline, and the interaction between lead ions and the surface of the nanocrystal is facilitated, and Er can be reduced by the lead ions3+To Yb3+Energy transfer efficiency of (1), resulting in Yb3+The up-conversion luminescence intensity at 980nm is gradually reduced, so that the lead content is detected.
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. The fluorescent probe material is characterized by comprising a core-shell nanocrystal and an oleic acid ligand coated on the surface of the core-shell nanocrystal, wherein the oleic acid ligand is electrostatically adsorbed on the surface of the core-shell nanocrystal; the composition of the core-shell nanocrystal is Na0.6K0.4BiaErbYb0.1F4@NaBicYbdF4Said Na0.6K0.4BiaErbYb0.1F4As a nucleus, the NaBicYbdF4Is a shell; wherein a is 0.5 to 0.7, b is 0.3 to 0.5, c is 0.7 to 0.9, and d is 0.1 to 0.3.
2. The fluorescent probe material of claim 1, wherein the mass of the oleic acid ligand is 15-25% of the total mass of the core-shell nanocrystal and the oleic acid ligand.
3. The method for preparing a fluorescent probe material as claimed in claim 1 or 2, comprising the steps of:
mixing a first sodium salt, a potassium salt, a first bismuth salt, an erbium salt, a first ytterbium salt, a first fluorine source, first oleic acid, first oleylamine and a first solvent, and performing first growth to obtain a core nanocrystal;
mixing a second sodium salt, a second bismuth salt, a second ytterbium salt, a second fluorine source, second oleic acid, second oleylamine and a second solvent with the core nanocrystal to perform second growth to obtain a fluorescent probe material;
the molar ratio of the first sodium salt, the potassium salt, the first bismuth salt, the erbium salt, the first ytterbium salt and the first fluorine source is 0.6:0.4 (0.5-0.7) to 0.3-0.5) to 0.1: 4;
the molar ratio of the second sodium salt to the second bismuth salt to the second ytterbium salt to the second fluorine source is 1 (0.7-0.9) to 0.1-0.3) to 4;
the molar ratio of the first sodium salt to the second sodium salt is 0.6: 1.
4. The method of claim 3, wherein the first and second sodium salts independently comprise sodium nitrate or sodium chloride; the potassium salt comprises potassium carbonate; the first bismuth salt and the second bismuth salt independently comprise bismuth nitrate, bismuth chloride or bismuth oxychloride; the erbium salt comprises erbium nitrate or erbium chloride; the first ytterbium salt and the second ytterbium salt independently comprise ytterbium nitrate or ytterbium chloride.
5. The method of claim 3, wherein the first and second fluorine sources are ammonium fluoride; the dosage ratio of the first fluorine source, the first oleic acid and the first oleylamine is (4-6) mmol, (5-10) mL, (1-2) mL.
6. The preparation method of claim 3 or 5, wherein the amount ratio of the second fluorine source, the second oleic acid and the second oleylamine is (4-6) mmol, (5-10) mL, (1-2) mL.
7. The method according to claim 3, wherein the first growth is carried out at a temperature of 25 to 35 ℃ for 30 to 60 min.
8. The method of claim 3, wherein the second growth is carried out at a temperature of 25 to 35 ℃ for 60 to 90 min.
9. The fluorescent probe material of claim 1 or 2 or the fluorescent probe material prepared by the preparation method of any one of claims 3 to 8 is applied to quantitative detection of lead content in gasoline.
10. A method for detecting the lead content in gasoline is characterized by comprising the following steps:
mixing gasoline containing different lead ion concentrations with a fluorescent probe material, detecting under the condition of 1550nm exciting light excitation, calculating integral intensity according to the obtained up-conversion spectrum, fitting a relation curve of the fluorescent integral intensity and the lead ion concentration, and obtaining the lead ion content in a gasoline sample according to the relation curve; the fluorescent probe material is the fluorescent probe material as described in claim 1 or 2 or the fluorescent probe material prepared by the preparation method as described in any one of claims 3 to 8.
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