CN114574189B - Design and material preparation method of nano temperature probe with high sensitivity - Google Patents
Design and material preparation method of nano temperature probe with high sensitivity Download PDFInfo
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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
- C09K11/7766—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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- 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
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- 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
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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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
- G01K11/20—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using thermoluminescent materials
Abstract
The invention relates to a design and material preparation method of a nano temperature probe with high sensitivity. The nano temperature probe is made of NaYF 4 The main matrix is doped with a core-shell nano structure of specific rare earth ions, and the crystal nucleus is NaYF 4 Yb/Er/Ce, and the middle isolation layer is NaYF 4 The outer shell layer is NaYF 4 Yb/Tm. The core-shell structured nanoparticle is prepared by adopting a coprecipitation method. The nano-temperature fluorescent probe prepared by the invention can detect the Er from the crystal nucleus at the same time under the condition of infrared light excitation 3+ Green light and outer shell layer Tm 3+ Dual mode emission of blue light. As the temperature (303K-443K) increases, the crystal nucleus Er 3+ Green thermal decay, outer shell Tm 3+ The blue light is thermally enhanced, the luminous intensity ratio of the blue light to the green light is greatly improved, the luminous intensity ratio of the blue light and the green light is used as a temperature measurement parameter, and the relative sensitivity of temperature detection can reach 9.86% K at most ‑1 。
Description
Technical Field
The invention relates to the field of solid luminescent materials, in particular to a design and material preparation method of a nano temperature probe with high sensitivity.
Background
Accurate and real-time temperature detection has great significance for industrial application and scientific research. Conventional contact temperature probes require direct contact with the test object for sufficient heat exchange,there are great limitations in the field of micro-zone temperature measurement. In recent years, research and development personnel develop a novel luminous intensity ratio technology for non-contact temperature measurement, so that the temperature measurement sensitivity and the spatial resolution are improved. The technology utilizes the relation that the intensity ratio of different emission peaks of the fluorescent material changes along with the temperature to measure the temperature, wherein the rare earth up-conversion luminescent material is widely researched as a fluorescent temperature probe due to low toxicity, excellent physical and chemical stability, narrow-band emission and unique luminescent performance. The traditional rare earth up-conversion fluorescence temperature probe generally adopts a thermal coupling energy level of a single luminescence center to detect the temperature, such as Er 3+ Green light emission energy level of (2) 2 H 11/2 And 4 S 3/2 ，(Geitenbeek,R.G.,Prins,P.T.,Albrecht,W.,van Blaaderen,A.,Weckhuysen,B.M.,&Meijerink,A.(2017).NaYF 4 :Er 3+ ,Yb 3+ /SiO 2 Core/Shell Upconverting Nanocrystals for Luminescence Thermometry up to 900K.The Journal of Physical Chemistry C,121 (6), 3503-3510). Theoretically, the layout of the thermal coupling energy levels is in a thermal equilibrium state and accords with the Boltzmann distribution rule, so the thermal coupling energy gap is generally between 200 and 2000cm -1 Within the range. This results in the rare earth fluorescent temperature probe based on thermal coupling property that two emission peaks are too close, the electron phonon coupling effect is enhanced at high temperature, and spectra may overlap to generate temperature measurement errors. In addition, the sensitivity of the temperature probe is positively correlated with the thermal coupling energy level difference, the sensitivity value is limited by the thermal coupling energy level difference, and the relative sensitivity value is generally lower, so that the temperature probe is not beneficial to the application in the aspect of fine temperature measurement.
Disclosure of Invention
Based on the problems, the invention provides a design and material preparation of a nano temperature probe with high sensitivity, and aims to overcome the defects of a single-luminescence center thermal coupling fluorescent probe by using Er 3+ Green thermal decay and Tm 3+ The blue light thermal enhancement two different luminescent properties are integrated in a single core-shell nanoparticle, so that the preparation of the high-sensitivity temperature probe is realized. The material has Er under the irradiation of a commercial 980nm Laser Diode (LD) 3+ Green emission and Tm 3+ Blue light emissionWherein Er is 3+ The crystal nucleus area is positioned in the nanoparticle, is influenced by thermal quenching, and green light is weakened along with the temperature rise; tm (Tm) 3+ Located in the nanoparticle shell layer, tm, is enhanced by ligand phonon-assisted energy transfer with increasing temperature 3+ Blue light is continuously enhanced. Er (Er) 3+ Green light and Tm 3+ The blue light emission and the temperature show a strong dependence relationship with opposite brightness change trend, so that the high-sensitivity temperature measurement application can be realized through the change relationship of the luminous intensity ratio of the blue light emission and the temperature.
The aim of the invention is achieved by the following technical scheme.
A nano temperature probe with high sensitivity is a core-shell structure nanoparticle which is formed by hexagonal phase NaYF 4 The main matrix and the doped specific rare earth ions are combined.
Further, the rare earth ion doped in the crystal nucleus area is Yb/Er/Ce, and the rare earth ion doped in the shell layer is Yb/Tm.
Further, the core-shell structure nano particles are respectively green light emission crystal nuclei NaYF from inside to outside 4 Yb/Er/Ce, inert isolation layer NaYF 4 And a blue light emitting outer shell layer NaYF 4 Yb/Tm; the chemical expression of the core-shell structure nanoparticle is NaYF 4 :Yb/Er/Ce@NaYF 4 @NaYF 4 :Yb/Tm。
Wherein NaYF 4 The Yb/Er/Ce green light emitting crystal nucleus has the functions of responding green light emission under the irradiation of commercial 980nm LD and weakening the light emitting brightness with the temperature rise; inert isolation layer NaYF 4 For blocking unnecessary energy crosstalk between the green light emitting core and the blue light emitting crust layer; blue light emitting outer shell layer NaYF 4 Yb/Tm is effective in response to blue light emission under 980nm LD irradiation and in that the luminescence brightness increases with increasing temperature.
Further, green light emitting nuclei NaYF 4 Yb/Er/Ce rare earth ion Yb 3+ 、Er 3+ 、Ce 3+ The molar concentration of (2) is 10-30mol%, 1-4mol% and 0-6mol%, respectively; blue light emitting outer shell layer NaYF 4 Yb/Tm rare earth ion Yb 3+ And Tm 3+ The molar concentration of (2) is 9 to 69mol% and 0.5 to 2mol%, respectively.
Preferably, the green light emits nuclei NaYF 4 Yb/Er/Ce rare earth ion Yb 3+ 、Er 3+ 、Ce 3+ The molar concentration of (2) is 20mol%, 2mol% and 4mol%, respectively; blue light emitting outer shell layer NaYF 4 Yb/Tm rare earth ion Yb 3+ And Tm 3+ The molar concentration of (2) was 49mol% and 1mol%, respectively.
Further, the green light emitting nucleus has a diameter of 18.93nm, the inert isolation layer has a thickness of 0-8.67nm, and the blue light emitting outer shell layer has a thickness of 6.17nm.
Preferably, the inert isolation layer has a thickness of 3.49nm.
The invention provides a preparation method of a nano temperature probe with high sensitivity, which is prepared by adopting a coprecipitation method. The method comprises the following steps:
(1) Weighing acetate rare earth according to mole fraction, including salt Y (CH 3 COO) 3 、Yb(CH 3 COO) 3 、Er(CH 3 COO) 3 And Ce (CH) 3 COO) 3 Oleic acid and octadecene are used as reaction solvents, and the temperature is kept at 120-160 ℃ for 40-90 minutes to form rare earth oleic acid complexes; cooling to 40-60deg.C, adding NH-containing solution 4 F and NaOH are reacted for 30-60 minutes; after heating to 100 ℃, vacuumizing to remove residual methanol and water vapor; heating to 280-310 ℃ under the protection of argon gas for reaction for 80-100 minutes to obtain NaYF 4 Yb/Er/Ce crystal nucleus nano particles;
(2) Y (CH) was weighed according to mole fraction 3 COO) 3 Oleic acid and octadecene are used as reaction solvents, and the temperature is kept at 120-160 ℃ for 40-90 minutes to form rare earth oleic acid complexes; cooling to 70-90deg.C, adding the obtained NaYF obtained in step (1) 4 A cyclohexane solution of Yb/Er/Ce nano particles, and preserving the temperature for 30-60 minutes; cooling to 40-60deg.C, adding NH 4 F and NaOH are reacted for 30-60 minutes; after heating to 100 ℃, vacuumizing to remove residual methanol and water vapor; heating to 280-310 ℃ under the protection of argon gas for reaction for 80-100 minutes to obtain NaYF 4 :Yb/Er/Ce@NaYF 4 Core-shell structured nanoparticles;
(3) Weighing acetate rare earth according to mole fraction, including salt Y (CH 3 COO) 3 、Yb(CH 3 COO) 3 And Tm (CH) 3 COO) 3 Oleic acid and octadecene are used as reaction solvents, and the temperature is kept at 120-160 ℃ for 40-90 minutes to form rare earth oleic acid complexes; cooling to 70-90deg.C, adding the obtained NaYF obtained in step (2) 4 :Yb/Er/Ce@NaYF 4 A cyclohexane solution of the nano particles, and preserving the temperature for 30-60 minutes; cooling to 40-60deg.C, adding NH 4 F and NaOH are reacted for 30-60 minutes; after heating to 100 ℃, vacuumizing to remove residual methanol and water vapor; heating to 280-310 ℃ under the protection of argon gas for reaction for 80-100 minutes, cooling to room temperature, centrifugally washing with cyclohexane and ethanol for several times, and drying at 60 ℃ to obtain the core-shell nano particles NaYF 4 :Yb/Er/Ce@NaYF 4 @NaYF 4 Yb/Tm, namely the nano temperature probe.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The nano temperature probe is a core-shell structure nano particle, green light and blue light can be integrated into a single nano particle, so that the non-uniformity of mechanical mixing on a microscopic scale is avoided, the feasibility of serving as the nano temperature probe is ensured, and meanwhile, the mutual interference between luminous layers is avoided; by integrating Er in a single nanoparticle 3+ Green thermo-decay luminescence and Tm 3+ Different luminous characteristics (303K-443K) of the blue light thermal enhancement luminescence can greatly improve the thermosensitive characteristic of the luminous intensity ratio; ce (Ce) 3+ As adjusting ions, the relative emission intensity of the green light and the blue light of the nano probe can be well balanced, and the conversion of the luminescence color from green light emission at room temperature to high Wen Xialan light emission is realized. The luminous intensity ratio of the two is used as a temperature measurement parameter, and the highest temperature sensitivity can reach 9.86% K -1 。
(2) The nano temperature probe temperature measuring material has the advantages of simple preparation process, low cost, strong luminous brightness and stable photochemical property. Compared with the traditional single-light-emitting center fluorescent temperature probe, the fluorescent probe has higher temperature sensitivity, can realize rapid and accurate temperature measurement, and is hopeful to be developed into a novel fluorescent temperature probe device.
Drawings
FIG. 1 is a schematic diagram of a design of a nano-temperature probe with high sensitivity according to the present invention.
FIG. 2 is a NaYF prepared in example 1 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 @NaYF 4 XRD diffraction pattern of Yb/Tm (49/1 mol%) core-shell structure nanoparticles;
FIG. 3 is a NaYF prepared in example 1 4 Yb/Er/Ce (20/2/4 mol%) crystalline core nanoparticle and NaYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 Core-shell structured nanoparticles and NaYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 @NaYF 4 Transmission electron microscopy images and particle size distribution diagrams of Yb/Tm (49/1 mol%) core-shell structure nano particles;
FIG. 4 is a NaYF prepared in example 1 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 @NaYF 4 Yb/Tm (49/1 mol%) core-shell structure nanoparticle temperature fluorescence emission spectrum;
FIG. 5 is a NaYF prepared in example 1 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 @NaYF 4 Luminous intensity ratio and temperature sensitivity of Yb/Tm (49/1 mol%) core-shell structure nano-particles;
FIG. 6 is a NaYF prepared in example 2 4 :Yb/Er/Ce(20/2/x mol％)@NaYF 4 @NaYF 4 Yb/Tm (49/1 mol%) (x=0, 2,4, 6) temperature sensitivity map of core-shell structured nanoparticles;
FIG. 7 is a NaYF prepared in example 3 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 @NaYF 4 Temperature sensitivity diagram of Yb/Tm (x/1 mol%) (x= 9,29,49,69) core-shell structured nanoparticle;
FIG. 8 is a NaYF with different inert spacer thicknesses prepared in example 4 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 @NaYF 4 Temperature sensitivity diagram of Yb/Tm (49/1 mol%) core-shell structured nanoparticle.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples and drawings, but the following examples are only for enhancing the description of the technical solution of the present invention, and should not be construed as any limitation on the scope of the claimed invention.
It is noted that unless otherwise indicated, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.
The design schematic diagram of the nano temperature probe is shown in fig. 1. The fluorescent temperature probe is a core-shell structure nanoparticle doped with specific rare earth ions, and the main component of the fluorescent temperature probe is hexagonal phase NaYF 4 Green light emitting crystal nuclei NaYF from inside to outside 4 Yb/Er/Ce, inert isolation layer NaYF 4 And a blue light emitting outer shell layer NaYF 4 :Yb/Tm。
Example 1
The core-shell structured nanoparticle prepared in this example is composed of hexagonal phase NaYF 4 The main matrix is formed by doping rare earth ions with specific concentrations in different nanometer regions (the doped ions of a crystal nucleus region are Yb/Er/Ce and the doped ions of an outer shell layer are Yb/Tm), and the method specifically comprises the following steps:
(1) First step, naYF 4 Synthesis of Yb/Er/Ce (20/2/4 mol%) crystal nucleus nano-particles. The acetate rare earth with total amount of 0.4mmol is weighed according to a specific mole fraction, and comprises salt Y (CH) 3 COO) 3 (74％)、Yb(CH 3 COO) 3 (20％)、Er(CH 3 COO) 3 (2%) and Ce (CH) 3 COO) 3 (4%). Oleic acid and octadecene are used as reaction solvents, and the temperature is kept at 150 ℃ for 60 minutes to form rare earth oleic acid complexes; cooling to 50deg.C, adding 6mL containing 1.6mmol NH 4 F, reacting a methanol solution of 1mmol of NaOH for 40 minutes; after heating to 100 ℃, vacuumizing to remove residual methanol and water vapor; the reaction was carried out for 90 minutes at 300℃under the protection of argon, and then cooled to room temperature, and then washed with cyclohexane and ethanol by centrifugation several times, and dispersed in 4mL of cyclohexane.
(2) Second step, naYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 Synthesis of core-shell structured nanoparticles. The total amount was weighed to be 0 in a specific mole fraction.2mmol of Y (CH) 3 COO) 3 . Oleic acid and octadecene are used as reaction solvents, and the temperature is kept at 150 ℃ for 60 minutes to form rare earth oleic acid complexes; cooling to 80deg.C, adding 2mL of a solution containing NaYF 4 A cyclohexane solution of Yb/Er/Ce (20/2/4 mol%) nano particles, and preserving the heat for 30 minutes; cooling to 50deg.C, adding 3mL of a solution containing 0.8mmol NH respectively 4 F, reacting for 40 minutes with a methanol solution of 0.5mmol of NaOH; after heating to 100 ℃, vacuumizing to remove residual methanol and water vapor; the reaction was carried out for 90 minutes at 300℃under the protection of argon, and then cooled to room temperature, and then washed with cyclohexane and ethanol by centrifugation several times, and dispersed in 2mL of cyclohexane.
(3) Third step, naYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 @NaYF 4 Synthesis of Yb/Tm (49/1 mol%) core-shell structured nanoparticles. The acetate rare earth with total amount of 0.2mmol is weighed according to a specific mole fraction, and comprises salt Y (CH) 3 COO) 3 (50％)、Yb(CH 3 COO) 3 (49%) and Tm (CH) 3 COO) 3 (1%). Oleic acid and octadecene are used as reaction solvents, and the temperature is kept at 150 ℃ for 60 minutes to form rare earth oleic acid complexes; cooling to 80deg.C, adding 2mL of a solution containing NaYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 A cyclohexane solution of the nano particles, and preserving the temperature for 30 minutes; cooling to 50deg.C, adding 3mL of a solution containing 0.8mmol NH respectively 4 F, reacting for 40 minutes with a methanol solution of 0.5mmol of NaOH; after heating to 100 ℃, vacuumizing to remove residual methanol and water vapor; heating to 300 ℃ under the protection of argon gas for reaction for 90 minutes, cooling to room temperature, centrifugally washing with cyclohexane and ethanol for several times, and drying at 60 ℃ to obtain the core-shell structure nanoparticle.
FIG. 2 is a NaYF prepared in example 1 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 @NaYF 4 XRD diffraction pattern of Yb/Tm (49/1 mol%) core-shell structure nanoparticle, diffraction peak and standard card JCPDS:16-0334 (beta-NaYF) 4 ) The diffraction peaks were consistent, indicating that the core-shell structured nanoparticle prepared in example 1 was a pure phase hexagonal phase structure.
FIG. 3 is a NaYF prepared in example 1 4 Yb/Er/Ce (20/2/4 mol%) crystalline core nanoparticle and NaYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 Core-shell structured nanoparticles and NaYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 @NaYF 4 Transmission electron microscopy images and particle size distribution diagrams of Yb/Tm (49/1 mol%) core-shell structure nano particles; the transmission electron microscope result shows that the core-shell nano particles are of an epitaxially grown core-shell structure and are uniformly distributed. Wherein the diameter of the crystal nucleus is about 18.93nm, the diameter of the core-shell structure sample is about 25.91nm, and the diameter of the core-shell structure sample is about 38.26nm, namely the thickness of the inert spacing layer is 3.49nm, and the thickness of the blue light emitting outer shell layer is 6.17nm.
The fluorescence spectrum results of FIG. 4 show NaYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 @NaYF 4 Yb/Tm (49/1 mol%) core-shell nanoparticle detects Er under 980nm LD excitation 3+ 540nm green characteristic emission and Tm 3+ 450nm blue characteristic emission of (b), er as the temperature increases from 303K to 447K 3+ The emission intensity drops sharply and Tm 3+ The emission intensity of the light source is rapidly increased, the light emitting color is gradually changed from green to blue, and the ratio of the light emitting intensity of the light source and the light emitting intensity of the light source is used as a temperature measuring parameter, so that the highest temperature measuring relative sensitivity K is 9.86% -1 As shown in fig. 5.
Example 2
The core-shell structured nanoparticle prepared in this example is composed of hexagonal phase NaYF 4 The host matrix is doped with Ce with different concentrations in the crystal nucleus area 3+ Regulating and controlling optimal Ce 3+ Doping to achieve higher sensitivity. The method specifically comprises the following steps:
first step, naYF 4 Synthesis of Yb/Er/Ce (20/2/x mol%) (x=0, 2,4, 6) crystal nucleus nanoparticles. The acetate rare earth with total amount of 0.4mmol is weighed according to a specific mole fraction, and comprises salt Y (CH) 3 COO) 3 ((78-x)％)、Yb(CH 3 COO) 3 (20％)、Er(CH 3 COO) 3 (2%) and Ce (CH) 3 COO) 3 (x%). Oleic acid and octadecene are used as reaction solvents, and the temperature is kept at 150 ℃ for 60 minutes to form rare earth oleic acid complexes; cooling to 50deg.C, adding 6mL containing 1.6mmol NH 4 F, reacting a methanol solution of 1mmol of NaOH for 40 minutes; after heating to 100 ℃, vacuumizing to remove residual methanol and water vapor; heating under the protection of argonThe reaction was carried out at 300℃for 90 minutes, followed by cooling to room temperature, washing with cyclohexane and ethanol by centrifugation several times, and dispersing in 4mL of cyclohexane.
The subsequent operations are the same as those of the step (2) and the step (3) of the example 1, and finally NaYF is prepared 4 :Yb/Er/Ce(20/2/xmol％)@NaYF 4 @NaYF 4 Yb/Tm (49/1 mol%) (x=0, 2,4, 6) core-shell structured nanoparticles.
FIG. 6 is a NaYF prepared in example 2 4 :Yb/Er/Ce(20/2/x mol％)@NaYF 4 @NaYF 4 Temperature sensitivity contrast map of Yb/Tm (49/1 mol%) (x=0, 2,4, 6) core-shell structured nanoparticle, ce inside the nucleus 3+ When the doping concentration is 4mol%, the temperature sensitivity of the core-shell structure nanoparticle is highest.
Example 3
The core-shell structured nanoparticle prepared in this example is composed of hexagonal phase NaYF 4 The main matrix keeps the crystal nucleus area component unchanged and doped with ion Yb/Er/Ce (20/2/4 mol percent), and the Yb in the outermost shell layer is regulated 3+ To achieve higher sensitivity. The method specifically comprises the following steps:
the previous two-step operation was the same as step (1) and step (2) of example 1.
Third step, naYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 @NaYF 4 Synthesis of Yb/Tm (x/1 mol%) (x= 9,29,49,69) core-shell structured nanoparticles. The acetate rare earth with total amount of 0.2mmol is weighed according to a specific mole fraction, and comprises salt Y (CH) 3 COO) 3 ((99-x)％)、Yb(CH 3 COO) 3 (x%) and Tm (CH) 3 COO) 3 (1%). Oleic acid and octadecene are used as reaction solvents, and the temperature is kept at 150 ℃ for 60 minutes to form rare earth oleic acid complexes; cooling to 80deg.C, adding 2mL of a solution containing NaYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 A cyclohexane solution of the nano particles, and preserving the temperature for 30 minutes; cooling to 50deg.C, adding 3mL of a solution containing 0.8mmol NH respectively 4 F, reacting for 40 minutes with a methanol solution of 0.5mmol of NaOH; after heating to 100 ℃, vacuumizing to remove residual methanol and water vapor; heating to 300 ℃ under the protection of argon gas for reaction for 90 minutes, cooling to room temperature, and centrifugally washing with cyclohexane and ethanolAnd drying at 60 ℃ after several times to obtain the core-shell structure nanoparticle.
FIG. 7 is a NaYF prepared in example 3 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 @NaYF 4 Temperature sensitivity contrast plot of Yb/Tm (x/1 mol%) (x= 9,29,49,69) core-shell structured nanoparticle, outermost shell Yb 3+ The temperature sensitivity of the core-shell structured nanoparticle is highest when the doping concentration is 49 mol%.
Example 4
The core-shell structured nanoparticle prepared in this example is composed of hexagonal phase NaYF 4 The main matrix keeps the compositions of the crystal nucleus area and the outermost shell layer unchanged (the doped ions of the crystal nucleus area are Yb/Er/Ce, the doped ions of the outer shell layer are Yb/Tm), and the NaYF of the middle layer is regulated and controlled 4 To achieve optimal relative sensitivity, comprising in particular the steps of:
the first step is the same as step (1) of example 1.
Second step, naYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 Synthesis of core-shell structured nanoparticles. The total amount of x mmol (x= 0,0.2,0.4) of Y (CH) is weighed out in a specific molar fraction 3 COO) 3 . Oleic acid and octadecene are used as reaction solvents, and the temperature is kept at 150 ℃ for 60 minutes to form rare earth oleic acid complexes; cooling to 80deg.C, adding 2mL of a solution containing NaYF 4 A cyclohexane solution of Yb/Er/Ce (20/2/4 mol%) nano particles, and preserving the heat for 30 minutes; cooling to 50deg.C, adding 3mL of a solution containing 0.8mmol NH respectively 4 F, reacting for 40 minutes with a methanol solution of 0.5mmol of NaOH; after heating to 100 ℃, vacuumizing to remove residual methanol and water vapor; the reaction was carried out for 90 minutes at 300℃under the protection of argon, and then cooled to room temperature, and then washed with cyclohexane and ethanol by centrifugation several times, and dispersed in 2mL of cyclohexane.
Third, the procedure is the same as in step (3) of example 1.
FIG. 8 is NaYF prepared in example 4 4 :Yb/Er/Ce(20/2/4mol％)@xNaYF 4 @NaYF 4 Temperature sensitivity contrast of Yb/Tm (49/1 mol%) (x=0, 3.49,8.67 nm) core-shell structured nanoparticles, indicating intermediate shell NaYF 4 The thickness of (c) affects the temperature of the core-shell nanoparticleThe sensitivity of the probe, which most preferably has a thickness of 3.49nm.
Example 5
The core-shell structured nanoparticle prepared in this example is composed of hexagonal phase NaYF 4 The main matrix is formed by doping rare earth ions with specific concentrations in different nanometer regions (the doped ions of a crystal nucleus region are Yb/Er/Ce and the doped ions of an outer shell layer are Yb/Tm), and the method specifically comprises the following steps:
(1) First step, naYF 4 Synthesis of Yb/Er/Ce (20/2/4 mol%) crystal nucleus nano-particles. The acetate rare earth with total amount of 0.4mmol is weighed according to a specific mole fraction, and comprises salt Y (CH) 3 COO) 3 (74％)、Yb(CH 3 COO) 3 (20％)、Er(CH 3 COO) 3 (2%) and Ce (CH) 3 COO) 3 (4%). Oleic acid and octadecene are used as reaction solvents, and the temperature is kept at 160 ℃ for 40 minutes to form rare earth oleic acid complexes; cooling to 60 ℃ and adding 6mL containing 1.6mmol NH 4 F, reacting 1mmol of NaOH in methanol for 30 minutes; after heating to 100 ℃, vacuumizing to remove residual methanol and water vapor; the reaction was carried out at 310℃for 80 minutes under the protection of argon, then cooled to room temperature, and then washed with cyclohexane and ethanol by centrifugation several times, and dispersed in 4mL of cyclohexane.
(2) Second step, naYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 Synthesis of core-shell structured nanoparticles. A total of 0.2mmol of Y (CH) was weighed out in a specified molar fraction 3 COO) 3 . Oleic acid and octadecene are used as reaction solvents, and the temperature is kept at 160 ℃ for 40 minutes to form rare earth oleic acid complexes; cooling to 90deg.C, adding 2mL of a solution containing NaYF 4 A cyclohexane solution of Yb/Er/Ce (20/2/4 mol%) nano particles, and preserving the heat for 30 minutes; cooling to 60 ℃ and adding 3mL of the mixture containing 0.8mmol of NH respectively 4 F, reacting for 30 minutes with a methanol solution of 0.5mmol of NaOH; after heating to 100 ℃, vacuumizing to remove residual methanol and water vapor; the reaction was carried out at 310℃for 80 minutes under the protection of argon, then cooled to room temperature, and then washed with cyclohexane and ethanol by centrifugation several times, and dispersed in 2mL of cyclohexane.
(3) Third step, naYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 @NaYF 4 Yb/Tm (49/1 mol%) core-shell nanoparticleAnd (5) synthesizing. The acetate rare earth with total amount of 0.2mmol is weighed according to a specific mole fraction, and comprises salt Y (CH) 3 COO) 3 (50％)、Yb(CH 3 COO) 3 (49%) and Tm (CH) 3 COO) 3 (1%). Oleic acid and octadecene are used as reaction solvents, and the temperature is kept at 160 ℃ for 40 minutes to form rare earth oleic acid complexes; cooling to 90deg.C, adding 2mL of a solution containing NaYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 A cyclohexane solution of the nano particles, and preserving the temperature for 30 minutes; cooling to 60 ℃ and adding 3mL of the mixture containing 0.8mmol of NH respectively 4 F, reacting for 30 minutes with a methanol solution of 0.5mmol of NaOH; after heating to 100 ℃, vacuumizing to remove residual methanol and water vapor; heating to 310 ℃ under the protection of argon gas for reaction for 80 minutes, cooling to room temperature, centrifugally washing with cyclohexane and ethanol for several times, and drying at 60 ℃ to obtain the core-shell structure nanoparticle.
Example 6
The core-shell structured nanoparticle prepared in this example is composed of hexagonal phase NaYF 4 The main matrix is formed by doping rare earth ions with specific concentrations in different nanometer regions (the doped ions of a crystal nucleus region are Yb/Er/Ce and the doped ions of an outer shell layer are Yb/Tm), and the method specifically comprises the following steps:
first step, naYF 4 Synthesis of Yb/Er/Ce (20/2/4 mol%) crystal nucleus nano-particles. The acetate rare earth with total amount of 0.4mmol is weighed according to a specific mole fraction, and comprises salt Y (CH) 3 COO) 3 (74％)、Yb(CH 3 COO) 3 (20％)、Er(CH 3 COO) 3 (2%) and Ce (CH) 3 COO) 3 (4%). Oleic acid and octadecene are used as reaction solvents, and the temperature is kept at 120 ℃ for 90 minutes to form rare earth oleic acid complexes; cooling to 40 ℃ and adding 6mL containing 1.6mmol NH 4 F, reacting a methanol solution of 1mmol of NaOH for 60 minutes; after heating to 100 ℃, vacuumizing to remove residual methanol and water vapor; the reaction was carried out for 100 minutes at 280℃under the protection of argon, and after cooling to room temperature, the reaction mixture was centrifuged and washed several times with cyclohexane and ethanol, and dispersed in 4mL of cyclohexane.
(2) Second step, naYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 Synthesis of core-shell structured nanoparticles. A total of 0.2mmol of Y (CH) was weighed out in a specified molar fraction 3 COO) 3 . Oleic acid and octadecene are used as reaction solvents, and the temperature is kept at 120 ℃ for 90 minutes to form rare earth oleic acid complexes; cooling to 70deg.C, adding 2mL of a solution containing NaYF 4 A cyclohexane solution of Yb/Er/Ce (20/2/4 mol%) nano particles, and preserving the heat for 60 minutes; cooling to 40deg.C, adding 3mL of a solution containing 0.8mmol NH respectively 4 F, reacting for 60 minutes by using a methanol solution of 0.5mmol of NaOH; after heating to 100 ℃, vacuumizing to remove residual methanol and water vapor; the reaction was carried out for 100 minutes at 280℃under the protection of argon, and after cooling to room temperature, the reaction mixture was centrifuged and washed several times with cyclohexane and ethanol, and dispersed in 2mL of cyclohexane.
(3) Third step, naYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 @NaYF 4 Synthesis of Yb/Tm (49/1 mol%) core-shell structured nanoparticles. The acetate rare earth with total amount of 0.2mmol is weighed according to a specific mole fraction, and comprises salt Y (CH) 3 COO) 3 (50％)、Yb(CH 3 COO) 3 (49%) and Tm (CH) 3 COO) 3 (1%). Oleic acid and octadecene are used as reaction solvents, and the temperature is kept at 120 ℃ for 90 minutes to form rare earth oleic acid complexes; cooling to 70deg.C, adding 2mL of a solution containing NaYF 4 :Yb/Er/Ce(20/2/4mol％)@NaYF 4 A cyclohexane solution of the nano particles, and preserving heat for 60 minutes; cooling to 40deg.C, adding 3mL of a solution containing 0.8mmol NH respectively 4 F, reacting for 60 minutes by using a methanol solution of 0.5mmol of NaOH; after heating to 100 ℃, vacuumizing to remove residual methanol and water vapor; heating to 280 ℃ under the protection of argon gas for reaction for 100 minutes, cooling to room temperature, centrifugally washing with cyclohexane and ethanol for several times, and drying at 60 ℃ to obtain the core-shell structure nanoparticle.
Claims (2)
1. The preparation method of the nano temperature probe with high sensitivity is characterized by comprising the following steps:
(1) Y (CH) was weighed according to mole fraction 3 COO) 3 、Yb(CH 3 COO) 3 、Er(CH 3 COO) 3 And Ce (CH) 3 COO) 3 Heat-insulating in reaction solvent to form complex, then adding NH-containing catalyst 4 F and NaOH, and vacuumizing to remove residual methanol and waterSteam, and then reacts under the protection of argon to obtain NaYF 4 Yb/Er/Ce crystal nucleus nano particles;
(2) Y (CH) was weighed according to mole fraction 3 COO) 3 Heat-insulating in a reaction solvent to form a complex, and adding a catalyst containing NaYF obtained in the step (1) 4 Cyclohexane solution of Yb/Er/Ce nano particles, then NH is added 4 F and NaOH, vacuumizing to remove residual methanol and water vapor, and reacting under the protection of argon to obtain NaYF 4 :Yb/Er/Ce@NaYF 4 Core-shell structured nanoparticles;
(3) Y (CH) was weighed according to mole fraction 3 COO) 3 、Yb(CH 3 COO) 3 And Tm (CH) 3 COO) 3 Heat-insulating in a reaction solvent to form a complex, and adding a catalyst containing NaYF obtained in the step (2) 4 :Yb/Er/Ce@NaYF 4 The cyclohexane solution of nanoparticles is then added with NH 4 F and NaOH, vacuumizing to remove residual methanol and water vapor, reacting under the protection of argon, cooling to room temperature, centrifugally washing with cyclohexane and ethanol, and drying to obtain the core-shell nano particles NaYF 4 :Yb/Er/Ce@NaYF 4 @NaYF 4 Yb/Tm, namely the nano temperature probe;
NaYF 4 Yb/Er/Ce rare earth ion Yb 3+ 、Er 3+ 、Ce 3+ The molar concentration of (2) is 10-30mol%, 1-4mol% and 0-6mol%, respectively; naYF 4 Yb/Tm rare earth ion Yb 3+ 、Tm 3+ The molar concentration of (2) is 9 to 69mol% and 0.5 to 2mol%, respectively;
the reaction solvent in the steps (1), (2) and (3) is a mixed solvent of oleic acid and octadecene;
the temperature of the heat preservation in the steps (1), (2) and (3) is 120-160 ℃, and the heat preservation time is 40-90 minutes;
the addition of steps (1), (2) and (3) contains NH 4 F and NaOH are reacted for 30-60 minutes at the temperature of 40-60 ℃;
the temperature of the reaction carried out under the protection of argon in the steps (1), (2) and (3) is 280-310 ℃, and the reaction time is 80-100 minutes;
the step (2) of adding the catalyst containing the NaYF obtained in the step (1) 4 A cyclohexane solution of Yb/Er/Ce nano particles, and the adding of the step (3) contains NaYF obtained in the step (2) 4 :Yb/Er/Ce@NaYF 4 The cyclohexane solution of the nano particles is added after the temperature of the complex is reduced to 70-90 ℃, and then the temperature is kept for 30-60 minutes.
2. The nano temperature probe with high sensitivity prepared by the preparation method of claim 1, which is characterized in that the nano temperature probe is a core-shell structure nano particle; the core-shell structure nanoparticle is formed by hexagonal phase NaYF 4 The main matrix is formed by doping specific rare earth ions in a combined way; the core-shell nano particles are respectively green light emission crystal nuclei NaYF from inside to outside 4 Yb/Er/Ce, inert isolation layer NaYF 4 And a blue light emitting outer shell layer NaYF 4 Yb/Tm, the chemical expression of the core-shell structure nanoparticle is NaYF 4 :Yb/Er/Ce@NaYF 4 @NaYF 4 Yb/Tm; the green light emitting crystal nucleus NaYF 4 Yb/Er/Ce rare earth ion Yb 3+ 、Er 3+ 、Ce 3+ The molar concentration of (2) is 10-30mol%, 1-4mol% and 0-6mol%, respectively; blue light emitting outer shell layer NaYF 4 Yb/Tm rare earth ion Yb 3+ 、Tm 3+ The molar concentration of (2) is 9 to 69mol% and 0.5 to 2mol%, respectively.
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| Synthesis of NaYF4:20% Yb3+,2% Er3+,2% Ce3+@NaYF4 nanorods and their size dependent uptake efficiency under flow condition;Dongmei Qiu et al.;Journal of Rare Earths;第40卷;第1519-1526页 * |
| Temperature-dependent upconversion luminescence multicolor tuning and temperature sensing of multifunctional β-NaYF4:Yb/Er@β-NaYF4:Yb/Tm microcrystals;Dandan Ju et al.;CrystEngComm;第23卷;第3892-3900页 * |
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