CN115505387B - Toy safety detection material and preparation method thereof - Google Patents
Toy safety detection material and preparation method thereof Download PDFInfo
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- CN115505387B CN115505387B CN202211188345.5A CN202211188345A CN115505387B CN 115505387 B CN115505387 B CN 115505387B CN 202211188345 A CN202211188345 A CN 202211188345A CN 115505387 B CN115505387 B CN 115505387B
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- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000001514 detection method Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims description 11
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000012300 argon atmosphere Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000011824 nuclear material Substances 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- RCPKXZJUDJSTTM-UHFFFAOYSA-L calcium;2,2,2-trifluoroacetate Chemical compound [Ca+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F RCPKXZJUDJSTTM-UHFFFAOYSA-L 0.000 claims description 8
- FAOLWJARFWBHJV-UHFFFAOYSA-K erbium(3+);2,2,2-trifluoroacetate Chemical compound [Er+3].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F FAOLWJARFWBHJV-UHFFFAOYSA-K 0.000 claims description 8
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
- OJOZHRCRUJKPIJ-UHFFFAOYSA-N magnesium;2,2,2-trifluoroacetic acid Chemical compound [Mg].OC(=O)C(F)(F)F OJOZHRCRUJKPIJ-UHFFFAOYSA-N 0.000 claims description 8
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000011258 core-shell material Substances 0.000 claims description 6
- 230000005284 excitation Effects 0.000 claims description 6
- 230000001502 supplementing effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 239000002159 nanocrystal Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 238000007689 inspection Methods 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 abstract description 33
- 229920003023 plastic Polymers 0.000 abstract description 9
- 239000004033 plastic Substances 0.000 abstract description 9
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910001451 bismuth ion Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- C09K11/7704—Halogenides
- C09K11/7705—Halogenides with alkali or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Organic Chemistry (AREA)
- Biophysics (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to a material for detecting safety of toys, in particular to a material for detecting phthalic acid in plastic toys. A toy safety detection material is a scintillating luminescent material, and has the following molecular formula: caClF@MgClF and Er. The amino groups on the surface of the toy safety detection material can effectively adsorb phthalate, so that the detection sensitivity is improved.
Description
Technical Field
The invention relates to a material for detecting safety of toys, in particular to a material for detecting phthalic acid in plastic toys.
Background
Phthalate has the functions of plasticizer and softening. To enhance the performance of the toy, phthalate salts may be added to the product. However, exceeding phthalate in the product may not only cause harm to the body of the child and affect the normal growth of the child, but also bring considerable loss to the interests of the toy manufacturer and the enterprises upstream and downstream thereof. Therefore, control and detection of phthalate salts in toy products is very important.
The existing detection Method of phthalate in toy plastic products is EN 14372 children product safety requirement and test Method (European standard, soxhlet extraction Method is adopted), CPSC-CH-C1001-09.3 phthalate test standard operation program (American standard, dissolution solidification Method is adopted), HEALTH CANADA Method C34 phthalate test (Canadian standard, dissolution Method is adopted), GB/T22048 toy and phthalate test in children polyvinyl chloride plastic (Chinese standard, soxhlet extraction Method is adopted). These methods have problems of slow response, complicated detection process, poor detection limit, and the like.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide the CaClF@MgCl F: er scintillation luminescent material which can rapidly and accurately detect phthalate in a plastic toy.
In order to achieve the above purpose, the present invention adopts the following technical scheme: a toy safety detection material is a scintillating luminescent material, and has the following molecular formula: caClF@MgClF and Er.
Preferably, the detection material is amino modified CaClF@MgCF, er scintillating luminescent material, and green light is emitted under the condition of X-ray excitation; the ratio of Ca to Mg is 1:1; the Er ion doping concentration was 6%.
The detection material is used for detecting the content of phthalate in the toy.
The preparation method of the toy safety detection material comprises the steps of preparing a precursor, preparing CaClF core materials and preparing CaClF@MgCl F: er core-shell materials.
Preferably, the preparation method comprises the following steps:
(1) Dissolving calcium carbonate in deionized water, adding ethanol and trifluoroacetic acid, stirring, supplementing an ethanol solution at intervals, and drying in a water bath to obtain a precursor of calcium trifluoroacetate;
(2) Dissolving magnesium carbonate in deionized water, adding ethanol and trifluoroacetic acid, stirring, supplementing an ethanol solution at intervals, and drying in a water bath to obtain a precursor of magnesium trifluoroacetate;
(3) Dissolving erbium oxide in deionized water and trifluoroacetic acid, carrying out circulating reflux stirring, and then drying in a water bath to obtain a precursor of erbium trifluoroacetate;
(4) Adding calcium trifluoroacetate into the mixed solution of oleic acid and octadecene, and preserving the temperature for 30-45 minutes under the protection of nitrogen or argon atmosphere;
(5) Adding trichloroacetic acid into the solution in the step (4), preserving heat for 30-50 minutes under the protection of nitrogen or argon atmosphere and under the condition of 110-150 o ℃, then heating to 300-320 o ℃ and preserving heat for 60-120 minutes;
(6) After the reaction in the step (5) is finished and naturally cooled to room temperature, centrifuging the mixture of ethanol and residual acetone to obtain a nuclear material, and dispersing the nuclear material in cyclohexane for later use;
(7) Adding magnesium trifluoroacetate and erbium trifluoroacetate into the mixed solution of oleic acid and octadecene, and preserving the temperature for 30-45 minutes under the protection of nitrogen or argon atmosphere.
(8) After the solution in the step (7) is cooled to room temperature, adding the nuclear nanocrystalline cyclohexane solution obtained in the step (6), and preserving the temperature for 30-40 minutes under the protection of nitrogen or argon atmosphere; then adding trichloroacetic acid and amino, and preserving the temperature for 10-15 minutes; then heating to 300-320 o ℃ and preserving the temperature for 60-90 minutes.
(9) And (3) after the reaction in the step (8) is finished and naturally cooled to room temperature, centrifuging by using ethanol to obtain core-shell nanocrystals, and then washing by using a mixed solution of acetone and ethanol to obtain CaClF@MgCl F: er.
Preferably, in the step (9), the mixture of acetone and ethanol is used for washing, wherein the volume ratio of the mixture of acetone and ethanol is 1:3. The amino group is oleylamine.
The toy safety detection material adopting the technical scheme belongs to a scintillating luminescent material, and emits bright green light under the condition of X-ray excitation. The material is dispersed in an acetone solution, phthalate with different contents is added, the scintillation luminescence intensity is changed, and the material can be applied to the detection of phthalate by fitting a relation curve between Er 3+ luminescence intensity and phthalate content and fitting a standard curve. The amino on the surface of the toy safety detection material can effectively adsorb phthalate, so that the detection sensitivity is improved; the carboxyl in the phthalate can specifically quench the scintillation luminous intensity of Er 3+, and has good accuracy; the X-ray has very deep penetrability and can be used for detecting the inside of the plastic toy.
Drawings
FIG. 1 is a transmission electron microscope image of CaClF@MgCl F: er material.
FIG. 2 is a diagram of scintillation luminescence spectrum of CaClF@MgCl F: er material under X-ray excitation.
FIG. 3 is a plot of scintillation luminescence intensity versus Er ion concentration for CaClF@MgCl F: er material.
FIG. 4 is a plot of scintillation luminescence intensity versus phthalate concentration for an acetone solution of the CaClF@MgCl F: er material.
FIG. 5 is a plot of scintillation luminescence intensity versus phthalate concentration for an acetone solution of the CaClF@MgCl F: er material.
FIG. 6 is a graph of scintillation luminescence intensity of an acetone solution of CaClF@MgCl F: er material versus iron, manganese, zinc, bismuth and copper ions.
FIG. 7 is a plot of scintillation luminescence intensity of an Er material acetone solution versus phthalate concentration for CaClF@MgCl F with no amino modification on the surface.
FIG. 8 is a comparative example NaYF 4: up-conversion luminescence intensity of Yb/Er versus phthalate concentration.
Detailed Description
The invention is further illustrated by the following examples and experiments.
A toy safety detection material is a scintillating luminescent material, and has the following molecular formula: caClF@MgClF and Er. The scintillating luminescent material is used for detecting the content of phthalate in the toy and emitting green light under the condition of X-ray excitation.
The preparation method of the toy safety detection material comprises the following steps:
Preparation of the precursor
(1) 2MM calcium carbonate is dissolved in 10ml of deionized water, then 5 ml of ethanol and 5 ml of trifluoroacetic acid are added, stirring is carried out for 6-12 hours at the temperature of 60 o ℃, 1-2 ml of ethanol solution is supplemented every 0.5 hour, and then drying is carried out in an 80 o C water bath kettle, so as to obtain the precursor of calcium trifluoroacetate.
(2) 5 MM magnesium carbonate is dissolved in 15 ml deionized water, then 10 ml ethanol and 10 ml trifluoroacetic acid are added, stirring is carried out for 12-24 hours at 70 o C, 2-3 ml of ethanol solution is supplemented every 0.5 hour, and then drying is carried out in an 80 o C water bath kettle, thus obtaining the precursor of magnesium trifluoroacetate.
(3) 1 Mmol of erbium oxide is dissolved in 10 ml of deionized water and 20 ml of trifluoroacetic acid, and the mixture is stirred for 6 to 10 hours under the condition of 80 o ℃ in a circulating reflux way, and then dried in an 80 o ℃ water bath kettle, so as to obtain the precursor of the erbium trifluoroacetate.
Preparation of CaClF Nuclear Material
(4) 0.5 Mmol of calcium trifluoroacetate is added into a mixture of 150 ml of oleic acid and 20 ml of octadecene, and the mixture is kept for 30 to 45 minutes under the protection of nitrogen or argon atmosphere and under the condition of 11 to 150 o ℃ in the presence of water.
(5) Adding 0.5 millimole trichloroacetic acid into the solution in the step (4), preserving the temperature for 30-50 minutes under the protection of nitrogen or argon atmosphere and under the condition of 110-150 o ℃, then rapidly heating to 300-320 o ℃ and preserving the temperature for 60-120 minutes.
(6) And (3) after the reaction in the step (5) is finished and naturally cooled to room temperature, centrifuging the mixture of ethanol and residual acetone to obtain a nuclear material, and dispersing the nuclear material in 2 milliliters of cyclohexane for later use.
Preparation of CaClF@MgCl F: er core-shell material
(7) 0.9 Mmol of magnesium trifluoroacetate and 0.1 mmol of erbium trifluoroacetate are added into a mixed solution of 15 ml of oleic acid and 20ml of octadecene, and the mixture is kept for 30 to 45 minutes under the conditions of nitrogen or argon atmosphere and 120 o ℃ under the condition of high temperature.
(8) After the solution in the step (7) is cooled to room temperature, adding the nuclear nanocrystalline cyclohexane solution obtained in the step (6), preserving heat for 30-40 minutes under the protection of nitrogen or argon atmosphere and under the condition of 80 o ℃, then adding 1 millimole of trichloroacetic acid and 15 milliliters of oleylamine, preserving heat for 10-15 minutes under the condition of 120 o ℃, then quickly heating to 300-320 o ℃ and preserving heat for 60-90 minutes.
(9) And (3) after the reaction in the step (8) is finished and naturally cooled to room temperature, centrifuging by using ethanol to obtain core-shell nanocrystals, and washing 3-5 times by using an acetone-ethanol mixed solution with the volume ratio of 1:3 to obtain CaClF@MgCl F: er.
The atomic emission spectrum analysis result shows that the ratio of Ca to Mg in the CaClF@MgCl F: er material is 1:1, and the doping concentration of Er ions is 6%. As shown in figure 1, the average grain diameter of the CaClF@MgCl F Er material is about 6 nanometers, and the dispersion and uniformity are good. The dispersibility is good, so that the interaction between the particle surface and the object to be detected is improved, and the detection sensitivity is improved.
The scintillation luminescence is derived from the 4f-4f transition of Er 3+ ions, the doping concentration is improved, the energy capture efficiency of activated ions on incident photons is improved, the scintillation luminescence intensity is improved, however, er 3+ ions have rich excited state energy levels, high concentration can cause non-radiative cross relaxation, luminescence is not facilitated, and therefore, the proper doping concentration of activated ions needs to be searched. As shown in FIG. 3, when the ion doping concentration of Er 3+ is increased from 2 mol% to 6mol%, the scintillation light-emitting intensity is gradually increased, and when the ion doping concentration is further increased, the scintillation light-emitting intensity starts to be weakened, which indicates that the optimal doping concentration is about 6mol% in the system designed by the invention.
In order to verify that the material designed by the invention can be used for detecting phthalate, caClF@MgCl F: er is dissolved in acetone and divided into a plurality of equal parts, then phthalate with different concentrations is respectively added, and finally, the change rule of the fluorescence intensity is represented by an X-ray spectrometer. As shown in fig. 4, the scintillation light emission intensity decreased approximately linearly as the phthalate concentration gradually increased from 0.01 to 0.1 micromoles per liter. As shown in fig. 5, the scintillation light intensity decreased approximately exponentially as the phthalate concentration gradually increased from 0.2 to 3 μmoles per liter. These data demonstrate that the CaClF@MgCl F: er material can be well applied to phthalate detection in a wide range.
In order to further verify that the CaClF@MgCF Er material designed by the invention can be applied to detection of phthalate in plastic products, powder samples of qualified plastic products on the market are added while the phthalate is added, and the change rule is basically consistent with the results of fig. 4 and 5. This demonstrates that the CaClF@MgCF: er material can be applied to the detection of phthalate in plastic products.
In order to verify the accuracy of the CaClF@MgCl F: er material for phthalate detection, the influence rule of the CaClF@MgCl F: er material by different metal ions in the solution is further analyzed. As shown in FIG. 6, different metal ions such as iron, manganese, zinc, bismuth and copper ions are added into a CaClF@MgCl F: er material dispersed solution, the scintillation luminous intensity is basically unchanged, and the fact that the metal ions do not influence the 4f-4f transition performance of Er3+ ions is high in accuracy.
In order to verify the importance of surface-coated oleylamine, caClF@MgCF: er materials were obtained without oleylamine on the surface by removing the oleylamine solvent during the preparation process, and further analyzed for their phthalate detection performance. As shown in fig. 7, the scintillation light emission intensity gradually decreased with increasing phthalate concentration from 0.01 to 0.1 micromoles per liter, but the magnitude of the decrease was significantly reduced. It is shown that oleylamine is advantageous for improving the adsorption of particles to phthalate, thereby improving the detection sensitivity.
For comparison, the usual up-conversion luminescent material NaYF 4 was used: yb/Er, the detection effect of the Yb/Er on phthalate is analyzed. Under 980 nm laser excitation conditions, naYF 4: the Yb/Er material shows stronger up-conversion luminescence. As shown in fig. 8, the up-conversion luminescence intensity of er3+ ion is less varied and irregular with increasing phthalate in the solution.
Claims (5)
1. A toy safety detection material is characterized in that the detection material is an oleylamine modified CaClF@MgCl F Er scintillating luminescent material; wherein, the ratio of Ca to Mg is 1:1; the doping concentration of Er ions is 6%;
the preparation method of the detection material comprises the following steps:
(1) Dissolving calcium carbonate in deionized water, adding ethanol and trifluoroacetic acid, stirring, supplementing an ethanol solution at intervals, and drying in a water bath to obtain a precursor of calcium trifluoroacetate;
(2) Dissolving magnesium carbonate in deionized water, adding ethanol and trifluoroacetic acid, stirring, supplementing an ethanol solution at intervals, and drying in a water bath to obtain a precursor of magnesium trifluoroacetate;
(3) Dissolving erbium oxide in deionized water and trifluoroacetic acid, carrying out circulating reflux stirring, and then drying in a water bath to obtain a precursor of erbium trifluoroacetate;
(4) Adding calcium trifluoroacetate into the mixed solution of oleic acid and octadecene, and preserving the temperature for 30-45 minutes under the protection of nitrogen or argon atmosphere;
(5) Adding trichloroacetic acid into the solution in the step (4), preserving heat for 30-50 minutes under the protection of nitrogen or argon atmosphere and under the condition of 110-150 o ℃, then heating to 300-320 o ℃ and preserving heat for 60-120 minutes;
(6) After the reaction in the step (5) is finished and naturally cooled to room temperature, centrifuging the mixture of ethanol and residual acetone to obtain a nuclear material, and dispersing the nuclear material in cyclohexane for later use;
(7) Adding magnesium trifluoroacetate and erbium trifluoroacetate into the mixed solution of oleic acid and octadecene, and preserving the temperature for 30-45 minutes under the protection of nitrogen or argon atmosphere;
(8) After the solution in the step (7) is cooled to room temperature, adding the nuclear nanocrystalline cyclohexane solution obtained in the step (6), and preserving the temperature for 30-40 minutes under the protection of nitrogen or argon atmosphere; then trichloroacetic acid and oleylamine are added, and the temperature is kept for 10-15 minutes; then heating to 300-320 o ℃ and preserving heat for 60-90 minutes;
(9) And (3) after the reaction in the step (8) is finished and naturally cooled to room temperature, centrifuging by using ethanol to obtain core-shell nanocrystals, and then washing by using a mixed solution of acetone and ethanol to obtain the oleylamine modified CaClF@MgCl F: er.
2. A toy safety inspection material according to claim 1, wherein green light is emitted under X-ray excitation.
3. Use of a toy safety detection material according to claim 1 for detecting the phthalate salt content of a toy.
4. The method for preparing the toy safety detection material according to claim 1, wherein the preparation method comprises the following steps:
(1) Dissolving calcium carbonate in deionized water, adding ethanol and trifluoroacetic acid, stirring, supplementing an ethanol solution at intervals, and drying in a water bath to obtain a precursor of calcium trifluoroacetate;
(2) Dissolving magnesium carbonate in deionized water, adding ethanol and trifluoroacetic acid, stirring, supplementing an ethanol solution at intervals, and drying in a water bath to obtain a precursor of magnesium trifluoroacetate;
(3) Dissolving erbium oxide in deionized water and trifluoroacetic acid, carrying out circulating reflux stirring, and then drying in a water bath to obtain a precursor of erbium trifluoroacetate;
(4) Adding calcium trifluoroacetate into the mixed solution of oleic acid and octadecene, and preserving the temperature for 30-45 minutes under the protection of nitrogen or argon atmosphere;
(5) Adding trichloroacetic acid into the solution in the step (4), preserving heat for 30-50 minutes under the protection of nitrogen or argon atmosphere and under the condition of 110-150 o ℃, then heating to 300-320 o ℃ and preserving heat for 60-120 minutes;
(6) After the reaction in the step (5) is finished and naturally cooled to room temperature, centrifuging the mixture of ethanol and residual acetone to obtain a nuclear material, and dispersing the nuclear material in cyclohexane for later use;
(7) Adding magnesium trifluoroacetate and erbium trifluoroacetate into the mixed solution of oleic acid and octadecene, and preserving the temperature for 30-45 minutes under the protection of nitrogen or argon atmosphere;
(8) After the solution in the step (7) is cooled to room temperature, adding the nuclear nanocrystalline cyclohexane solution obtained in the step (6), and preserving the temperature for 30-40 minutes under the protection of nitrogen or argon atmosphere; then trichloroacetic acid and oleylamine are added, and the temperature is kept for 10-15 minutes; then heating to 300-320 o ℃ and preserving heat for 60-90 minutes;
(9) And (3) after the reaction in the step (8) is finished and naturally cooled to room temperature, centrifuging by using ethanol to obtain core-shell nanocrystals, and then washing by using a mixed solution of acetone and ethanol to obtain the oleylamine modified CaClF@MgCl F: er.
5. The method for producing a toy safety inspection material according to claim 4, wherein in the step (9), the toy safety inspection material is washed with a mixed solution of acetone and ethanol in a volume ratio of 1:3.
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