CN115108822A - Photo-thermal regulation ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ Method for producing aerogels - Google Patents
Photo-thermal regulation ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ Method for producing aerogels Download PDFInfo
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- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
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- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 38
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- 239000000203 mixture Substances 0.000 claims description 26
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- 238000003756 stirring Methods 0.000 claims description 22
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- 239000006185 dispersion Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000000352 supercritical drying Methods 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
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- -1 aluminum ion Chemical class 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
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- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 150000000918 Europium Chemical class 0.000 claims description 7
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- 150000003751 zinc Chemical class 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 150000002924 oxiranes Chemical class 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 229910002706 AlOOH Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 27
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- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
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- 230000005284 excitation Effects 0.000 description 4
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
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Abstract
The invention belongs to the field of preparation processes of multifunctional nano porous materials, and relates to a photothermal regulation and control type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ A method for preparing aerogel. By mixing gamma-AlOOH nano fiber and rare earth Eu 3+ Is embedded in ZnAl 2 O 4 In the matrix, finally preparing the photothermal regulation ceramic nanofiber reinforced ZnAl by means of a thermodynamic strengthening technology 2 O 4 :Eu 3+ An aerogel. The method has the advantages of simple raw materials and process, low energy consumption, and simple preparation processThe prepared ceramic fluorescent aerogel has the characteristics of high mechanical strength, high heat insulation property, high luminous efficiency and the like, provides a strong material basis for realizing the application of the photothermal regulation ceramic aerogel material in the photothermal sensing field, and has positive practical and production significance.
Description
Technical Field
The invention belongs to the field of preparation processes of multifunctional nano porous materials, and relates to a photothermal regulation and control type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ A preparation method of aerogel.
Background
The silica aerogel in the aerogel material is a solid material with the lowest density and the best heat insulation performance at present, a continuous three-dimensional network structure is arranged in the silica aerogel, the diameters of solid phases and pores are both nano-scale, the porosity can reach 80-99.8 percent, and the specific surface area can reach 1000m 2 A density as low as 2.8kg/m 3 The thermal conductivity at room temperature is below 12 mW/m.K. The silica aerogel has the characteristics of good heat insulation performance, small density, high temperature resistance and the like, and has great application potential in the aspects of heat, acoustics, optics and the like. However, pure silica aerogel generally has problems of low strength, large brittleness and the like, and most of it is in the form of powder or small block, and it is difficult to be directly used in various engineering fields such as energy, building, military and the like. Therefore, research and development of novel composite silicon aerogel integrating excellent heat insulation performance, mechanical performance and optical performance, and solving of the problem of poor comprehensive performance of pure silicon dioxide aerogel are always the key contents of research.
The prior nano-fiber ceramic aerogel becomes an ideal material for heat insulation due to high porosity, large surface area, low density, low thermal conductivity and good thermal oxidation resistance, and the structure of the nano-fiber ceramic aerogel comprises a plurality of entangled nano-fibers with the diameters of 100 and 300nm and the lengths of 20-150 mu m, so that the brittleness problem can be effectively overcome, and the heat resistance can be greatly improved. E.g. by mixing SiO with Yang et al 2 The combination of nanofibers and aluminoborate matrix to make superelastic ceramic nanofiber aerogel with layered structure has high thermal insulation and mechanical properties (Yang, Science Advances, 2018). Fluorescent aerogels have recently become particularly attractive for new designs for practical solid state lighting and for widespread use in advanced sensors and smart materials/devices due to specific optical properties and intuitive luminescence changes. For example, Niederberger and colleagues by doping Eu 3+ And Tb 3+ Synthesize luminescent Y 2 O 3 Aerogel shows adjustable color emission from red to green (Niederberger, ACS Nano,2016), but its fluorescence efficiency is poor, production cost is high, and further industrialization is impossible. Although thermal management and light regulation aerogel materials have been studied extensively, photothermal regulation integrated aerogel materials have not been studied yet. Therefore, the invention selects a semiconductor ZnAl with excellent optical performance 2 O 4 The material is used as a fluorescence main body, a silicon source is used as a bonding agent, and gamma-AlOOH nano fiber and rare earth Eu are mixed 3+ Is embedded in ZnAl 2 O 4 In the matrix, finally preparing the photothermal regulation ceramic nanofiber reinforced ZnAl by means of a thermodynamic strengthening technology 2 O 4 :Eu 3+ The aerogel has high heat insulation property, high mechanical strength and fluorescence property, and has great research significance in the field of photo-thermal sensing regulation.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a photothermal regulation type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ The preparation method of the aerogel has the advantages of simple raw materials and process and low energy consumption, and the prepared ceramic fluorescent aerogel has the characteristics of high mechanical strength, high heat insulation property, high luminous efficiency and the like, provides a strong material basis for realizing the application of the photothermal regulation and control ceramic aerogel material in the photothermal sensing field, and has positive practical and production significance.
The technical scheme of the invention is as follows: photo-thermal regulation ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ The preparation method of the aerogel comprises the following specific steps:
(1) fully dissolving trivalent aluminum salt in a certain amount of deionized water to obtain an aluminum ion solution;
(2) slowly dropwise adding the alkaline solution into the aluminum ion solution obtained in the step (1), stirring and adding the alkaline solution, and adjusting the pH of the solution to obtain Al (OH) 3 A sol system;
(3) the Al (OH) obtained in the step (2) 3 Pouring the sol into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction to obtain the gamma-AlOOH nano fiberA vitamin dispersion liquid;
(4) mixing divalent zinc salt, trivalent aluminum salt, trivalent europium salt and alcohol solvent, and stirring uniformly to obtain ZnAl 2 O 4 A sol system;
(5) adding the gamma-AlOOH nano-fiber dispersion liquid obtained in the step (3) into ZnAl obtained in the step (4) 2 O 4 Adding a silicon source serving as a binder into the sol after uniformly stirring, and stirring to obtain the photothermal regulation type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3 + A sol system;
(6) adding the epoxide into the step (5), stirring and gelling to obtain the photothermal regulation type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ Wet gel;
(7) carrying out solvent replacement and aging on the wet gel obtained in the step (6);
(8) performing supercritical drying on the wet gel subjected to solvent replacement and aging in the step (7) to obtain the photothermal regulation type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ An aerogel precursor;
(9) ZnAl obtained in the step (8) 2 O 4 :Eu 3+ Sintering the aerogel precursor in an air furnace to obtain the photothermal regulation ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ An aerogel.
Preferably, the trivalent aluminum salt in the step (1) is AlCl 3 ·6H 2 O or Al (NO) 3 ) 3 ·9H 2 One or a mixture of O; the molar ratio of the trivalent aluminum salt to the deionized water is 0.01-0.03: 1.
preferably, the alkaline solution in the step (2) is one or a mixture of an ammonia water solution, a sodium hydroxide solution or a hydrazine hydrate solution; the dropping speed of the alkaline solution is 1-3 mL/min; adjusting the pH value of the solution to 3.5-5.5.
Preferably, the temperature of the hydrothermal reaction in the step (3) is 120-260 ℃, and the reaction time is 6-30 h;
preferably, the divalent zinc salt in the step (4) is ZnCl 2 Or Zn (NO) 3 ) 2 ·6H 2 One or a mixture of O; trivalent aluminum salt is AlCl 3 ·6H 2 O or Al (NO) 3 ) 3 ·9H 2 One or a mixture of O; the europium salt being EuCl 3 ·6H 2 O or Eu (NO) 3 ) 3 ·6H 2 One or a mixture of O; the alcohol solvent is one or mixture of ethanol, isopropanol or methanol; the molar ratio of the divalent zinc salt to the trivalent aluminum salt to the europium salt to the alcohol solvent is 1: (1-3): (0.02-0.10): (10-30).
Preferably, the silicon source in the step (5) is one or a mixture of tetraethyl orthosilicate and tetramethyl orthosilicate; Gamma-AlOOH nano-fiber dispersion liquid and ZnAl 2 O 4 The volume ratio of the sol system is (0.2-1.2): 1; the mass ratio of the gamma-AlOOH nano-fiber dispersion liquid to the silicon source is (3.5-5.5): 1; the temperature of the re-stirring is 20-60 ℃, and the stirring time is 0.5-2.5 h.
Preferably, the epoxide in the step (6) is one or a mixture of propylene oxide, epichlorohydrin or ethylene oxide; the molar ratio of the epoxide to the trivalent aluminum salt is (6-14): 1, stirring the mixture at the temperature of 20-60 ℃ until gel is formed.
Preferably, the replacement solvent in the step (7) is one or a mixture of ethanol, diethyl ether, methanol or n-hexane; the time of solvent replacement and aging is 12-60 h, the temperature is 30-70 ℃, and the replacement liquid is replaced every 4-20 h.
Preferably, the drying mode in the step (8) is carbon dioxide or ethanol supercritical drying: when ethanol is subjected to supercritical drying, the pressure in the kettle is 6-10 Mpa, the reaction temperature is 250-275 ℃, the drying time is 2.5-6.5 h, and the pressure relief speed is 3-9L/min; carbon dioxide is used as a drying medium, the pressure in the kettle is 8-12 Mpa, the reaction temperature is 45-50 ℃, the drying time is 7-13 h, and the pressure relief speed is 3-9L/min.
Preferably, the sintering temperature in the step (9) is 800-1200 ℃, the sintering heat preservation time is 1-3 h, and the heating rate is 1-5 min/DEG C.
Has the advantages that:
the method of the invention and the photothermal regulation prepared by the methodCeramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ Aerogel materials have the following characteristics:
(1) simple process and low energy consumption. Adopts a hydrothermal method and a one-step sol-gel method, simultaneously introduces gamma-AlOOH nano-fiber, divalent zinc salt, trivalent aluminum salt and europium salt, and prepares the photothermal regulation type ceramic nano-fiber reinforced ZnAl through subsequent supercritical drying and thermodynamic strengthening processes 2 O 4 :Eu 3+ An aerogel material.
(2) The material has the structural characteristics of high porosity, high ratio, uniform particles and the like, and also has the performance advantages of high temperature resistance, high mechanical strength, spectrum regulation and control and the like, so that the material has positive significance for realizing the application of the aerogel material in the field of photo-thermal sensing.
Drawings
FIG. 1 is a photo-thermal controlled ceramic nanofiber reinforced ZnAl prepared in example 1 2 O 4 :Eu 3+ Physical photographs of aerogel materials.
FIG. 2 shows ZnAl reinforced by photothermal control ceramic nanofibers prepared in examples 1 to 5 2 O 4 :Eu 3+ Fluorescence emission spectra of aerogel materials.
FIG. 3 is a ZnAl reinforced ceramic nanofiber prepared in example 1 2 O 4 :Eu 3+ The pore size of the aerogel material is shown in the figure.
Detailed Description
The invention is further illustrated by the following examples without restricting the scope of protection thereto.
Example 1
(1) Mixing AlCl 3 ·6H 2 O and deionized water according to a molar ratio of 0.01: 1, when AlCl is mixed uniformly 3 ·6H 2 After the O is completely dissolved, slowly dropwise adding ammonia water solution at 1mL/min, adjusting the pH of the solution to 5, and adding the prepared Al (OH) 3 And placing the sol in a 100mL polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 200 ℃ for 12h to obtain the gamma-AlOOH nanofiber dispersion liquid.
(2) Zn (NO) 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O、Eu(NO 3 ) 3 ·6H 2 O and isopropanol in a molar ratio of 1: 2: 0.02: 10 are evenly mixed to obtain ZnAl 2 O 4 Collosol, namely mixing the gamma-AlOOH nano-fiber dispersion liquid obtained in the step (1) with ZnAl 2 O 4 The sol and tetraethyl orthosilicate are mixed according to a volume ratio of 1: 1 and a mass ratio of 4: 1, and uniformly stirring the mixture for 1.5 hours at the temperature of 30 ℃ to obtain the photothermal regulation and control type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ A sol system. Then reacting propylene oxide with Al (NO) 3 ) 3 ·9H 2 O is mixed according to a molar ratio of 8: 1 adding the photo-thermal regulation ceramic nano fiber reinforced ZnAl obtained by the method 2 O 4 :Eu 3+ In the sol system, the mixture is evenly stirred at 30 ℃ and poured into a mould to react until gel is formed.
(3) The photothermal regulation type ceramic nano fiber obtained in the step (2) is reinforced with ZnAl 2 O 4 :Eu 3+ The wet gel is subjected to solvent replacement, aging and supercritical drying to obtain the photothermal regulation type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ And (3) an aerogel precursor. The aging temperature is 30 ℃, the solvent replacement solution is an ethanol solution, the replacement time is 36h, and the solution is replaced every 12 h. CO 2 2 The supercritical drying pressure is 10Mpa, the drying time is 8h, the drying temperature is 50 ℃, and the pressure release speed is 6L/min.
(4) The photothermal regulation type ceramic nano fiber obtained in the step (3) is reinforced with ZnAl 2 O 4 :Eu 3+ Carrying out high-temperature heat treatment on the aerogel precursor to obtain the photothermal regulation type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ An aerogel. The sintering temperature is 1200 ℃, the heating speed is 2 ℃/min, the heat preservation time is 1h, and the sample is named AZE-1. The prepared photothermal regulation ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ The material graph of the aerogel AZE-1 is shown in figure 1, and it can be known from the graph that the photothermal modulation ceramic fluorescent aerogel has a complete block shape and certain mechanical strength, and the compressive strength is 1.8 MPa; the sample AZE-1 had a density of 0.189g/cm 3 The thermal conductivity of the material is 0.042W/m.K; FIG. 2 is a fluorescence spectrum of a sample, from whichThe sample AZE-1 respectively emits 590nm, 614nm, 649nm and 690nm red light under the excitation of 465nm blue light, and fig. 3 is a drawing showing that the sample AZE-1 is a mesoporous material, and the drawing shows that the sample AZE-1 belongs to the mesoporous material and has a specific surface area of 43.6cm 3 /g。
Example 2
(1) Mixing Al (NO) 3 ) 3 ·9H 2 O and deionized water according to a molar ratio of 0.03: 1, when Al (NO) is present after uniform mixing 3 ) 3 ·9H 2 After the O is completely dissolved, slowly dropwise adding a hydrazine hydrate solution at a rate of 2mL/min, adjusting the pH of the solution to 3.5, and adding the prepared Al (OH) 3 And (3) placing the sol in a 100mL polytetrafluoroethylene reaction kettle, and carrying out hydrothermal treatment at 260 ℃ for 6h to obtain the gamma-AlOOH nanofiber dispersion liquid.
(2) Reacting ZnCl 2 、Al(NO 3 ) 3 ·9H 2 O、EuCl 3 ·6H 2 O and ethanol are mixed according to a molar ratio of 1: 1: 0.06: 20 are evenly mixed to obtain ZnAl 2 O 4 Collosol, namely mixing the gamma-AlOOH nano-fiber dispersion liquid obtained in the step (1) with ZnAl 2 O 4 The sol and the tetramethyl orthosilicate are respectively mixed according to a volume ratio of 0.4: 1 and the mass ratio of 3.5: 1, uniformly mixing, and uniformly stirring for 2.5 hours at the temperature of 20 ℃ to obtain the photothermal regulation and control type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ A sol system. Then reacting propylene oxide with Al (NO) 3 ) 3 ·9H 2 O is mixed according to a molar ratio of 6: 1 adding the photo-thermal regulation ceramic nano fiber reinforced ZnAl obtained by the method 2 O 4 :Eu 3+ In the sol system, the mixture is evenly stirred at the temperature of 20 ℃ and poured into a mould to react until gel is formed.
(3) The photothermal regulation type ceramic nano fiber obtained in the step (2) is reinforced with ZnAl 2 O 4 :Eu 3+ The wet gel is subjected to solvent replacement, aging and supercritical drying to obtain the photothermal regulation and control type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ And (3) an aerogel precursor. The aging temperature is 50 ℃, the solvent replacement solution is an ether solution, the replacement time is 12 hours, and the solution is replaced every 4 hours. CO 2 2 The supercritical drying pressure is 8Mpa, the drying time is 13h, the drying temperature is 45 ℃, and the pressure release speed is 4L/min.
(4) The photothermal regulation type ceramic nano fiber obtained in the step (3) is reinforced with ZnAl 2 O 4 :Eu 3+ Carrying out high-temperature heat treatment on the aerogel precursor to obtain the photothermal regulation type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ An aerogel. The sintering temperature is 1100 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 1.5 h. The sample was named AZE-2 and the density of the resulting material was 0.152g/cm 3 Specific surface area of 63.5cm 3 The specific material has the following characteristics of a specific volume, a specific surface area, a substrate, a specific surface area, a substrate.
Example 3
(1) Mixing Al (NO) 3 ) 3 ·9H 2 O and deionized water according to a molar ratio of 0.015: 1, when Al (NO) is present after uniform mixing 3 ) 3 ·9H 2 After the O is completely dissolved, slowly dropwise adding sodium hydroxide solution at 1.5mL/min, adjusting the pH of the solution to 4, and adding the prepared Al (OH) 3 And placing the sol in a 100mL polytetrafluoroethylene reaction kettle, and carrying out hydrothermal treatment at 120 ℃ for 30h to obtain the gamma-AlOOH nanofiber dispersion liquid.
(2) Adding Zn (NO) 3 ) 2 ·6H 2 O、AlCl 3 ·6H 2 O、Eu(NO 3 ) 3 ·6H 2 O and methanol in a molar ratio of 1:
1.5: 0.04: 15 are evenly mixed to obtain ZnAl 2 O 4 Collosol, namely mixing the gamma-AlOOH nano-fiber dispersion liquid obtained in the step (1) with ZnAl 2 O 4 The sol and the tetramethyl orthosilicate are respectively mixed according to the volume ratio of 0.8: 1 and a mass ratio of 4.5: 1, uniformly mixing, and uniformly stirring for 1.5h at 40 ℃ to obtain the photothermal regulation and control type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ A sol system. Then reacting epichlorohydrin with AlCl 3 ·6H 2 O is mixed according to a molar ratio of 10: 1 adding the photo-thermal regulation ceramic nano fiber reinforced ZnAl obtained by the method 2 O 4 :Eu 3+ In the sol system, the mixture is evenly stirred at 40 ℃ and poured into a mould to react until gel is formed.
(3) Regulating and controlling the photo-heat obtained in the step (2)ZnAl reinforced by ceramic nano-fiber 2 O 4 :Eu 3+ The wet gel is subjected to solvent replacement, aging and supercritical drying to obtain the photothermal regulation type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ And (3) an aerogel precursor. The aging temperature is 60 ℃, the solvent replacement solution is a normal hexane solution, the replacement time is 48 hours, and the solution is replaced every 10 hours. Ethanol supercritical drying pressure of 9Mpa, drying time of 2.5h, drying temperature of 250 deg.C, and pressure release speed of 8L/min.
(4) The photothermal regulation type ceramic nano fiber obtained in the step (3) is reinforced with ZnAl 2 O 4 :Eu 3+ Carrying out high-temperature heat treatment on the aerogel precursor to obtain the photothermal regulation type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ An aerogel. The sintering temperature is 1000 ℃, the heating rate is 4 ℃/min, and the heat preservation time is 1.25 h. The sample was named AZE-3, and the density of the resulting material was 0.126g/cm 3 The specific surface area is 82.9cm 3 The pressure strength is 0.9MPa, the thermal conductivity of the material is 0.031W/m.K, and as shown in figure 2, sample AZE-3 emits 590nm, 614nm, 649nm and 690nm red light under excitation of 465nm blue light.
Example 4
(1) Mixing AlCl 3 ·6H 2 O and deionized water according to a molar ratio of 0.02: 1, when AlCl is mixed uniformly 3 ·6H 2 After the O is completely dissolved, slowly dropwise adding sodium hydroxide solution at a rate of 3mL/min, adjusting the pH of the solution to 5.5, and obtaining Al (OH) 3 And placing the sol in a 100mL polytetrafluoroethylene reaction kettle, and carrying out hydrothermal treatment at 140 ℃ for 24h to obtain the gamma-AlOOH nanofiber dispersion liquid.
(2) Adding Zn (NO) 3 ) 2 ·6H 2 O、AlCl 3 ·6H 2 O、EuCl 3 ·6H 2 O and isopropanol in a molar ratio of 1: 3: 0.08: 25 are evenly mixed to obtain ZnAl 2 O 4 Sol, namely mixing the gamma-AlOOH nanofiber dispersion liquid obtained in the step (1) with ZnAl 2 O 4 The sol and the tetramethyl orthosilicate are respectively mixed according to the volume ratio of 1.2: 1 and the mass ratio of 5.5: 1, uniformly mixing, and uniformly stirring for 0.5h at 60 ℃ to obtain the photothermal regulation and control type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ A sol system. Then mixing ethylene oxide with AlCl 3 ·6H 2 O is mixed according to a molar ratio of 14: 1 adding the photo-thermal regulation ceramic nano fiber reinforced ZnAl obtained by the method 2 O 4 :Eu 3+ In the sol system, the mixture is evenly stirred at 60 ℃ and poured into a mould to react until gel is formed.
(3) The photothermal regulation type ceramic nano fiber obtained in the step (2) is reinforced with ZnAl 2 O 4 :Eu 3+ The wet gel is subjected to solvent replacement, aging and supercritical drying to obtain the photothermal regulation type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ And (3) an aerogel precursor. The aging temperature is 40 ℃, the solvent replacement solution is a normal hexane solution, the replacement time is 60 hours, and the solution is replaced every 20 hours. The supercritical drying pressure of ethanol is 8Mpa, the drying time is 4h, the drying temperature is 260 ℃, and the pressure release speed is 9L/min.
(4) The photothermal regulation type ceramic nano fiber obtained in the step (3) is reinforced with ZnAl 2 O 4 :Eu 3+ Carrying out high-temperature heat treatment on the aerogel precursor to obtain the photothermal regulation and control type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ An aerogel. The sintering temperature is 900 ℃, the heating rate is 1 ℃/min, and the heat preservation time is 2 h. The sample was named AZE-4, and the density of the resulting material was 0.113g/cm 3 The specific surface area is 102.7cm 3 The specific material has the following characteristics of a specific structure, a specific structure and a specific weight, wherein the specific structure is shown in figure 2, a specific structure is shown in the specification, the specific structure is AZE-4, and the specific structure can be used for realizing the specific structure.
Example 5
(1) Mixing AlCl 3 ·6H 2 O and deionized water according to a molar ratio of 0.025: 1, when AlCl is mixed uniformly 3 ·6H 2 After the O is completely dissolved, slowly dropwise adding an ammonia water solution at 2.5mL/min, adjusting the pH of the solution to 4.5, and adding the prepared Al (OH) 3 And placing the sol in a 100mL polytetrafluoroethylene reaction kettle, and carrying out hydrothermal treatment at 220 ℃ for 10h to obtain the gamma-AlOOH nanofiber dispersion liquid.
(2) Reacting ZnCl 2 、AlCl 3 ·6H 2 O、Eu(NO 3 ) 3 ·6H 2 O and ethanol are mixed according to a molar ratio of 1: 2.5: 0.10: 30 are evenly mixed to obtain ZnAl 2 O 4 Collosol, namely mixing the gamma-AlOOH nano-fiber dispersion liquid obtained in the step (1) with ZnAl 2 O 4 The sol and tetraethyl orthosilicate are mixed according to a volume ratio of 0.6: 1 and the mass ratio of 5: 1, and uniformly mixing and stirring for 1h at 50 ℃ to obtain the photothermal regulation type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ A sol system. Then mixing propylene oxide with AlCl 3 ·6H 2 O is mixed according to a molar ratio of 12: 1 adding the photo-thermal regulation ceramic nano fiber reinforced ZnAl obtained by the method 2 O 4 :Eu 3+ In the sol system, the mixture is evenly stirred at 50 ℃ and poured into a mould to react until gel is formed.
(3) The photothermal regulation type ceramic nano fiber obtained in the step (2) is reinforced with ZnAl 2 O 4 :Eu 3+ The wet gel is subjected to solvent replacement, aging and supercritical drying to obtain the photothermal regulation type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ And (3) an aerogel precursor. The aging temperature is 20 ℃, the solvent replacement solution is n-hexane solution, the replacement time is 24 hours, and the solution is replaced every 6 hours. CO 2 2 The supercritical drying pressure is 12Mpa, the drying time is 7h, the drying temperature is 45 ℃, and the pressure release speed is 7L/min.
(4) The photothermal regulation type ceramic nano fiber obtained in the step (3) is reinforced with ZnAl 2 O 4 :Eu 3+ Carrying out high-temperature heat treatment on the aerogel precursor to obtain the photothermal regulation type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ An aerogel. The sintering temperature is 800 ℃, the heating rate is 3 ℃/min, and the heat preservation time is 3 h. The sample was named AZE-5 and the density of the resulting material was 0.107g/cm 3 The specific surface area is 123.5cm 3 The material has thermal conductivity of 0.027W/m.K and compression strength of 0.25MPa, and as shown in figure 2, sample AZE-5 emits red light of 590nm, 614nm, 649nm and 690nm under excitation of blue light of 465 nm.
FIG. 2 shows a photo-thermal control type ZnAl reinforced ceramic nanofiber 2 O 4 :Eu 3+ Fluorescence emission spectra of aerogel examples 1-5 under 465nm excitation, as can be seen from the figureThe fluorescence intensity gradually increases with the increase in sintering temperature.
Claims (10)
1. Photo-thermal regulation ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ The preparation method of the aerogel comprises the following specific steps:
(1) dissolving trivalent aluminum salt in a certain amount of deionized water to obtain an aluminum ion solution;
(2) dropwise adding the alkaline solution into the aluminum ion solution obtained in the step (1), stirring and adding the alkaline solution, and adjusting the pH of the solution to obtain Al (OH) 3 A sol system;
(3) the Al (OH) obtained in the step (2) 3 Pouring the sol into a reaction kettle, and carrying out hydrothermal reaction to obtain a gamma-AlOOH nanofiber dispersion liquid;
(4) mixing divalent zinc salt, trivalent aluminum salt, trivalent europium salt and alcohol solvent, and stirring uniformly to obtain ZnAl 2 O 4 A sol system;
(5) adding the gamma-AlOOH nano-fiber dispersion liquid obtained in the step (3) into ZnAl obtained in the step (4) 2 O 4 Adding a silicon source serving as a binder into the sol after uniformly stirring, and stirring to obtain the photothermal regulation type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ A sol system;
(6) adding the epoxide into the step (5), stirring and gelling to obtain the photothermal regulation type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ Wet gel;
(7) carrying out solvent replacement and aging on the wet gel obtained in the step (6);
(8) performing supercritical drying on the wet gel subjected to solvent replacement and aging in the step (7) to obtain the photothermal regulation type ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ An aerogel precursor;
(9) ZnAl obtained in the step (8) 2 O 4 :Eu 3+ Sintering the aerogel precursor in an air furnace to obtain the photothermal regulation ceramic nanofiber reinforced ZnAl 2 O 4 :Eu 3+ An aerogel.
2. The method according to claim 1, wherein the trivalent aluminum salt in step (1) is AlCl 3 ·6H 2 O or Al (NO) 3 ) 3 ·9H 2 O or a mixture thereof; the molar ratio of the trivalent aluminum salt to the deionized water is 0.01-0.03: 1.
3. the method according to claim 1, wherein the alkaline solution in step (2) is one or a mixture of an aqueous ammonia solution, a sodium hydroxide solution or a hydrazine hydrate solution; the dropping speed of the alkaline solution is 1-3 mL/min; adjusting the pH value of the solution to 3.5-5.5.
4. The method according to claim 1, wherein the hydrothermal reaction in step (3) is carried out at a temperature of 120 to 260 ℃ for 6 to 30 hours.
5. The method according to claim 1, wherein the divalent zinc salt in the step (4) is ZnCl 2 Or Zn (NO) 3 ) 2 ·6H 2 One or a mixture of O; trivalent aluminum salt is AlCl 3 ·6H 2 O or Al (NO) 3 ) 3 ·9H 2 One or a mixture of O; the europium salt being EuCl 3 ·6H 2 O or Eu (NO) 3 ) 3 ·6H 2 O or a mixture thereof; the alcohol solvent is one or mixture of ethanol, isopropanol or methanol; the molar ratio of the divalent zinc salt to the trivalent aluminum salt to the europium salt to the alcohol solvent is 1: (1-3): (0.02-0.10): (10-30).
6. The method according to claim 1, wherein the silicon source in step (5) is tetraethyl orthosilicate or tetramethyl orthosilicate or a mixture thereof; Gamma-AlOOH nano-fiber dispersion liquid and ZnAl 2 O 4 The volume ratio of the sol system is (0.2-1.2): 1; the mass ratio of the gamma-AlOOH nano-fiber dispersion liquid to the silicon source is (3.5-5.5): 1; the temperature of the re-stirring is 20-60 ℃, and the stirring is carried outThe stirring time is 0.5-2.5 h.
7. The process according to claim 1, wherein the epoxide in step (6) is one or a mixture of propylene oxide, epichlorohydrin and ethylene oxide; the molar ratio of the epoxide to the trivalent aluminum salt is (6-14): 1, stirring the mixture at the temperature of 20-60 ℃ until gel is formed.
8. The method according to claim 1, wherein the substitution solvent in the step (7) is one or a mixture of ethanol, diethyl ether, methanol or n-hexane; the time of solvent replacement and aging is 12-60 h, the temperature is 30-70 ℃, and the replacement liquid is replaced every 4-20 h.
9. The method according to claim 1, wherein the drying in step (8) is supercritical drying with carbon dioxide or ethanol: when ethanol is subjected to supercritical drying, the pressure in the kettle is 6-10 Mpa, the reaction temperature is 250-275 ℃, the drying time is 2.5-6.5 h, and the pressure relief speed is 3-9L/min; carbon dioxide is used as a drying medium, the pressure in the kettle is 8-12 Mpa, the reaction temperature is 45-50 ℃, the drying time is 7-13 h, and the pressure relief speed is 3-9L/min.
10. The method according to claim 1, wherein the sintering temperature in step (9) is 800-1200 ℃, the sintering holding time is 1-3 h, and the temperature rise rate is 1-5 min/° C.
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