CN114736680B - Preparation method of titanium carbide quantum dot based on multi-metal ion synergistic coordination modification - Google Patents
Preparation method of titanium carbide quantum dot based on multi-metal ion synergistic coordination modification Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 109
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 58
- 230000004048 modification Effects 0.000 title claims abstract description 51
- 238000012986 modification Methods 0.000 title claims abstract description 51
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 38
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 150000002500 ions Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003223 protective agent Substances 0.000 claims abstract description 8
- 238000009830 intercalation Methods 0.000 claims abstract description 7
- 230000002687 intercalation Effects 0.000 claims abstract description 7
- 230000005496 eutectics Effects 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- LZCMQBRCQWOSHZ-UHFFFAOYSA-N 2-bromo-2,2-difluoroacetic acid Chemical compound OC(=O)C(F)(F)Br LZCMQBRCQWOSHZ-UHFFFAOYSA-N 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims 1
- 239000000138 intercalating agent Substances 0.000 claims 1
- 238000006862 quantum yield reaction Methods 0.000 abstract description 13
- 239000012467 final product Substances 0.000 abstract description 6
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 5
- 229910001431 copper ion Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- -1 gallium ions Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 230000009977 dual effect Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001432 tin ion Inorganic materials 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
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory 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
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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
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method of a titanium carbide quantum dot based on multi-metal ion synergistic coordination modification. Finally, adding an intercalation agent, a noble metal ion providing agent and a quantum dot protecting agent into the titanium carbide powder in sequence by a solvothermal method in an inert atmosphere to prepare a final product. The quantum dots prepared by the method have the advantages that the surfaces of the quantum dots are provided with multi-metal ion wavy layered directional arrangement. Meanwhile, the light-emitting performance of the quantum dots can be regulated and controlled through the synergistic effect between noble metal ions and cobalt or copper ions, so that the appearance of the quantum dots is kept regular. The quantum yield of the quantum dot material prepared by the method reaches more than 95%, and the quantum dot material can be widely applied to novel display fields such as virtual reality, wearable equipment, aerospace display devices, telemedicine cooperation and the like.
Description
Technical Field
The invention belongs to the field of preparation of novel display materials, and particularly relates to a preparation method of novel titanium carbide quantum dots for display based on multi-metal ion synergistic coordination modification.
Background
Quantum Dots (QDs) are microparticles composed of a limited number of atoms, all three dimensional sizes on the order of nanometers (1-10 nm). Due to quantum confinement effect, the quantum dots can emit fluorescence of different colors by controlling the composition of the quantum dots. The quantum dots have the unique advantages of changeable emission color, narrow emission linewidth, easy photoelectric excitation, good light stability, excellent solution processability and the like, so that the quantum dots are expected to realize the unprecedented luminescent material category, and the characteristics bring about the attention and research of the quantum dots in various application fields.
The excellent optical and electrical properties of quantum dots, such as high fluorescence efficiency, narrow emission spectrum, low cost, processability, and spectral tunability by quantum dot confinement effect, make the intensive development of quantum dot light emitting diodes (QLEDs) as the subject of next generation displays for quantum dot research. Titanium carbide has excellent photoelectric performance at present, is studied in the field of quantum dot research, and the characteristics of strong fluorescence, high stability and easy regulation are also focused. Meanwhile, the metal ion doping can achieve extremely strong modification effect on the quantum dot, and the titanium carbide serving as the MXene substance has a multilayer structure and rich surface functional groups, so that the connection of the metal ions can be enhanced, and the modification effect is enhanced.
For synthesizing quantum dots conforming to novel display applications, from the current patent report, the quantum dots are mainly made of traditional materials, for example: in the patent CN111647403a, the metal salt containing gallium ions, the lead halide-based precursor and the cesium-based precursor are mixed and stirred to form the perovskite quantum dot doped with gallium ions, so that the fluorescence quantum efficiency and stability of the quantum dot are improved, but the conventional stirring method is easy to cause uneven ion doping. In the patent CN103059872A, zn doped CdTe quantum dots are synthesized by a one-step hydrothermal method, so that the fluorescence efficiency is improved, but the fluorescence performance of the quantum dots is easily hindered by using zinc ion doping with a higher proportion. CN113680359a discloses a composite material with tin ion doped titanium carbide quantum dots, but the fluorescence effect of the quantum dots per se is poor. The quantum dots are prepared by adopting the traditional preparation process (stirring or hydrothermal method) in the modification process of introducing metal ions, so that uniform dispersion of the metal ions is difficult to realize. Meanwhile, the single metal ions have lower electron transition-recombination efficiency, and excessive single metal ions can even shield the self luminescence performance of the quantum dots. In view of the above, the existing metal ion doped quantum dot cannot meet the requirements of the novel display industry, and the quantum dot with adjustable research and development performance, high stability and good dispersibility has been unprecedented.
Disclosure of Invention
The invention aims to: aiming at the problems of insufficient utilization rate of metal ions, difficult morphology regulation and control, low stability and the like in the prior art, the invention provides a preparation method of novel titanium carbide quantum dots for display based on multi-metal ion synergistic coordination modification.
The technical scheme is as follows: according to the preparation method of the titanium carbide quantum dot based on the multi-metal ion synergistic coordination modification, the B acid and the L acid are firstly utilized to react to generate a eutectic solvent, and then a microwave high-pressure heating method is utilized to etch titanium aluminum carbide, so that the copper-or cobalt-modified accordion-shaped titanium carbide powder is obtained. Finally, adding an intercalation agent, a noble metal ion providing agent and a quantum dot protecting agent into the titanium carbide powder in sequence by a solvothermal method in an inert atmosphere to obtain the titanium carbide quantum dot which is coordinated and modified based on the cooperation of multiple metal ions.
The specific steps of the invention are as follows:
step 1, mixing the acid B and the acid L according to the mass ratio of 1:0.5-1:2, and heating to react to obtain a eutectic solvent;
step 2, mixing the prepared eutectic solvent with titanium aluminum carbide powder according to the mass ratio of 1:1-3:1, placing the mixture in a microwave reactor for reaction, washing the obtained precipitate, and drying to obtain the copper-or cobalt-modified accordion-shaped titanium carbide powder;
step 3, mixing a noble metal ion source and an organic solvent according to a mass ratio of 1:40-1:500, heating for reaction, cooling, and collecting the obtained liquid to prepare a noble metal ion provider;
and 4, uniformly mixing the copper or cobalt modified accordion-shaped titanium carbide powder prepared in the step 2 and the intercalation agent in an inert atmosphere, adding the noble metal ion providing agent prepared in the step 3, stirring, adding the quantum dot protecting agent, reacting at a high temperature, centrifuging, taking supernatant, and vacuum drying to obtain the multi-metal ion synergistic coordination modified titanium carbide quantum dot.
In step 1, the acid B is one of trifluoromethanesulfonic acid, trifluoroacetic acid and difluorobromoacetic acid, and the acid L is copper chloride or cobalt chloride.
Further, in the step 1, the temperature is raised to 150-200 ℃ and the reaction is carried out for 30-60 min.
Further, in the step 2, setting the microwave frequency range of the microwave reactor to be 300-1000 MHz, the reaction temperature to be 40-150 ℃ and the reaction time to be 24-72 h; the drying temperature is 60-80 ℃ and the drying time is 24-72 h.
In step 3, the noble metal ion source is chloroplatinic acid, chloroauric acid, palladium chloride, silver nitrate, and the organic solvent is acetone or toluene.
Further, in the step 3, the temperature is raised to 100-250 ℃ and the reaction is carried out for 1-2 h.
In step 4, the inert atmosphere is one of argon, helium and nitrogen, and the intercalation agent is one or more of dimethyl sulfoxide, tetramethyl ammonium hydroxide and tetraethyl ammonium hydroxide; the quantum dot protective agent is ammonia water or ammonium chloride.
Further, in the step 4, the mass ratio of the titanium carbide powder, the intercalation agent, the noble metal ion provider and the quantum dot protecting agent is 1:5:10:2-1:20:50:6.
Further, in the step 4, the stirring time is 24-72 h.
Further, in the step 4, the temperature of the vacuum drying is 60-80 ℃ and the time is 24-72 h.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
(1) The invention successfully prepares the novel eutectic solvent with the dual functions of the L acid and the B acid, and the eutectic solvent breaks through the preparation bottleneck of the traditional process of firstly etching and then doping the metal doped titanium carbide, so that the preparation of the titanium carbide and the loading of metal ions are simultaneously carried out in a single reaction vessel. First, fluorine ions and hydrogen ions in the eutectic solvent react with titanium aluminum carbide to consume aluminum atoms, and then, with the destruction of the eutectic solvent structure, metal ions are exposed to coordinate with functional groups on the surface of the titanium carbide. The process utilizes the consumption-coordination of the eutectic solvent to realize the automatic and continuous reaction. Simplify the preparation process, reduce the introduction of impurities and improve the yield.
(2) The titanium carbide obtained by utilizing the microwave high-pressure heating method has a multilayer structure, and copper or cobalt ions are directionally and wavedly arranged on the titanium carbide due to the magnetic action of microwaves on metal ions. By setting different microwave frequencies and adjusting the microwave wavelength, copper or cobalt ions with different intervals can be obtained, and then noble metal ions are distributed on gaps of the copper or cobalt ions. The preparation method simplifies the modification process, improves the dispersity of metal ions, ensures that different metal ions are uniformly distributed on the surface of the whole quantum dot, improves the doping effect, ensures that the luminous performance is more uniform, increases the fluorescence intensity, reduces the non-radiative recombination of the quantum dot, and prolongs the fluorescence life of the quantum dot.
(3) Compared with the common multi-metal element doped quantum dot, the quantum dot prepared by the invention adopts the wave-shaped distribution synergistic coordination modification of a plurality of metal ions, and the metal ions are uniformly distributed in layers, so that the synergistic effect of noble metal-copper or noble metal-cobalt can be excited to the maximum. Meanwhile, the loading capacity of various metal ions can be accurately regulated and controlled by adjusting the microwave frequency, so that various performances of the quantum dots can be further adjusted. The noble metal element can effectively improve the luminous efficiency of the quantum dot, and the load of cobalt or copper ions on the surface of titanium carbide can better fix the crystal lattice, thereby improving the stability of the quantum dot. According to the actual industrial application, the microwave frequency is required to be adjusted, so that the multi-functionalization of the quantum dot can be realized.
Drawings
FIG. 1 is a schematic diagram of the structure of a titanium carbide quantum dot (left) and a titanium carbide quantum dot (right) coordinated and modified based on the cooperation of multi-metal ions;
FIG. 2 is a TEM image of novel titanium carbide quantum dots for display based on the synergistic coordination modification of multi-metal ions prepared in example 1;
FIG. 3 is a fluorescence plot of the novel titanium carbide quantum dot for display based on the synergistic coordination modification of multi-metal ions prepared in example 1;
FIG. 4 is a fluorescence plot of the novel titanium carbide quantum dot for display based on the synergistic coordination modification of multi-metal ions prepared in example 2.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1:
1g of trifluoromethanesulfonic acid and 2g of copper chloride are mixed, heated to 150 ℃ and reacted for 30min to prepare the eutectic solvent.
3g of the eutectic solvent was mixed with 1.5g of titanium aluminum carbide powder, and the mixture was placed in a microwave reactor at a set frequency of 300MHz, reacted at 100℃for 28 hours, the obtained precipitate was washed, and the obtained product was dried at 60℃for 24 hours to prepare an accordion-like titanium carbide powder having copper modification.
0.1g of chloroplatinic acid was mixed with 20mL of acetone, heated to 100℃and reacted for 1 hour. After cooling, the obtained liquid was collected to prepare a noble metal ion-providing agent.
Under nitrogen atmosphere, 1g of the copper-modified accordion-like titanium carbide powder was mixed with 10mL of dimethyl sulfoxide, and then 20mL of noble metal ion-providing agent was added thereto and stirred for 24 hours. 4mL of ammonia water was added, the temperature was raised to 230℃and the reaction was carried out for 72 hours. Centrifuging to obtain supernatant, and vacuum drying at 60 ℃ for 30 hours to obtain the novel titanium carbide quantum dot for display based on the collaborative coordination modification of the multi-metal ions.
The quantum dot yield test was performed on the novel display quantum dot based on the multi-metal ion synergistic coordination modification prepared in example 1, and the result shows that the quantum yield is 96%; TEM morphology test is carried out on the novel display quantum dot based on the multi-metal ion synergistic coordination modification prepared in the embodiment 1, and as shown in fig. 2, the size of the quantum dot is 8.4nm multiplied by 3nm as can be seen from fig. 2; fluorescence spectrum test was performed on the novel display quantum dot based on the multi-metal ion synergistic coordination modification prepared in example 1, and as shown in fig. 3, the fluorescence emission peak of the quantum dot is 425nm.
Comparative example 1:
1g of p-toluenesulfonic acid and 2g of copper chloride were mixed, heated to 150 ℃ and reacted for 30min to prepare a eutectic solvent.
3g of the eutectic solvent was mixed with 1.5g of titanium aluminum carbide powder, and the mixture was placed in a microwave reactor at a set frequency of 300MHz, reacted at 100℃for 28 hours, the obtained precipitate was washed, and the obtained product was dried at 60℃for 24 hours to prepare an accordion-like titanium carbide powder having copper modification.
0.1g of chloroplatinic acid was mixed with 20mL of acetone, heated to 100℃and reacted for 1 hour. After cooling, the obtained liquid was collected to prepare a noble metal ion-providing agent.
Under nitrogen atmosphere, 1g of the copper-modified accordion-like titanium carbide powder was mixed with 10mL of dimethyl sulfoxide, and then 20mL of noble metal ion-providing agent was added thereto and stirred for 24 hours. 4mL of ammonia water was added, the temperature was raised to 230℃and the reaction was carried out for 72 hours. Centrifuging to obtain supernatant, and vacuum drying at 60 ℃ for 30 hours to obtain the novel titanium carbide quantum dot for display based on the collaborative coordination modification of the multi-metal ions.
The quantum dot yield test was performed on the novel display quantum dot based on the multi-metal ion synergistic coordination modification prepared in comparative example 1, and the result showed that the quantum yield was 23%; the quantum dots are nonuniform in size; the fluorescence emission peak of the quantum dot is 430nm. Compared with example 1, in comparative example 1, the triflic acid is replaced by the p-toluenesulfonic acid, under the condition of not changing other conditions, the quantum yield is greatly reduced, and the quantum dot size is different, because after changing the B acid, the reaction of the eutectic solvent and the titanium aluminum carbide cannot be synchronous with the coordination of metal ions, the reaction is not thoroughly carried out, and the appearance of the quantum dot is uneven and the performance is weakened.
Example 2:
1g of trifluoroacetic acid and 1g of copper chloride are mixed, the temperature is raised to 160 ℃, and the mixture is reacted for 40 minutes to prepare the eutectic solvent.
2g of the eutectic solvent was mixed with 1.3g of titanium aluminum carbide powder, and the mixture was placed in a microwave reactor at a set frequency of 400MHz, reacted at 70℃for 24 hours, the obtained precipitate was washed, and the obtained product was dried at 60℃for 48 hours to prepare an accordion-like titanium carbide powder having copper modification.
0.3g of chloroauric acid and 30mL of acetone are mixed evenly, heated to 110 ℃ and reacted for 1h. After cooling, the obtained liquid was collected to prepare a noble metal ion-providing agent.
Under an argon atmosphere, 1g of the copper-modified accordion-like titanium carbide powder was mixed with 15mL of dimethyl sulfoxide, and then 30mL of a noble metal ion-providing agent was added thereto and stirred for 30 hours. 4mL of ammonia water was added thereto, the temperature was raised to 350℃and the reaction was carried out for 34 hours. Centrifuging to obtain supernatant, and vacuum drying at 70deg.C for 30 hr to obtain the final product.
The novel display quantum dot based on the multi-metal ion synergistic coordination modification prepared in the example 2 is tested, and the result shows that the quantum yield is 97%; the quantum dot size is 8.1nm multiplied by 2.9nm; fluorescence spectrum test was performed on the novel display quantum dot based on the multi-metal ion synergistic coordination modification prepared in example 2, and as shown in fig. 4, the fluorescence emission peak of the quantum dot is 424nm.
Comparative example 2:
1g of trifluoroacetic acid and 1g of ferric chloride are mixed, the temperature is raised to 160 ℃, and the mixture is reacted for 40 minutes to prepare the eutectic solvent.
2g of the eutectic solvent was mixed with 1.3g of titanium aluminum carbide powder, and the mixture was placed in a microwave reactor at a set frequency of 400MHz, reacted at 70℃for 24 hours, the obtained precipitate was washed, and the obtained product was dried at 60℃for 48 hours to prepare an accordion-like titanium carbide powder having iron modification.
0.3g of chloroauric acid and 30mL of acetone are mixed evenly, heated to 110 ℃ and reacted for 1h. After cooling, the obtained liquid was collected to prepare a noble metal ion-providing agent.
Under an argon atmosphere, 1g of the iron-modified accordion-like titanium carbide powder was mixed with 15mL of dimethyl sulfoxide, and then 30mL of a noble metal ion-providing agent was added thereto and stirred for 30 hours. 4mL of ammonia water was added thereto, the temperature was raised to 350℃and the reaction was carried out for 34 hours. Centrifuging to obtain supernatant, and vacuum drying at 70deg.C for 30 hr to obtain the final product.
The quantum dot yield test was performed on the novel display quantum dot based on the multi-metal ion synergistic coordination modification prepared in comparative example 2, and the result showed that the quantum yield was 21%; the quantum dots are nonuniform in size; the fluorescence emission peak of the quantum dot is 415nm. Compared with example 2, in comparative example 2, copper chloride is replaced by ferric chloride, the quantum yield is greatly reduced under the condition of other conditions being unchanged, and the quantum dot size is different; this is probably due to the fact that after the L acid is changed, the eutectic solvent structure is changed, so that the formation of titanium carbide and the coordination process of iron ions are not fully reacted, the coordination of subsequent noble metal ions is blocked, and the synergism of the multi-metal ions cannot be exerted; meanwhile, other metal ions have poor modification effect on the titanium carbide quantum dots, so that the quantum dots have low performance.
Example 3:
1g of difluorobromoacetic acid and 1.5g of copper chloride were mixed, heated to 170℃and reacted for 50 minutes to prepare a eutectic solvent.
2.5g of the eutectic solvent was mixed with 1.6g of titanium aluminum carbide powder, and the mixture was placed in a microwave reactor, the frequency was set at 460MHz, reacted at 50℃for 35 hours, the obtained precipitate was washed, and the obtained product was dried at 60℃for 28 hours, to prepare an accordion-like titanium carbide powder having copper modification.
0.3g of palladium chloride and 30mL of acetone are uniformly mixed, the temperature is raised to 120 ℃, and the reaction is carried out for 2 hours. After cooling, the obtained liquid was collected to prepare a noble metal ion-providing agent.
Under helium atmosphere, 1.2g of the copper-modified accordion-like titanium carbide powder was mixed with 15mL of tetrabutylammonium hydroxide, and then 30mL of noble metal ion-providing agent was added thereto, followed by stirring for 30 hours. 5mL of ammonia water was added thereto, the temperature was raised to 500℃and the reaction was carried out for 24 hours. Centrifuging to obtain supernatant, and vacuum drying at 70deg.C for 40 hr to obtain the final product.
The novel display quantum dot based on the multi-metal ion synergistic coordination modification prepared in the example 3 is tested, and the result shows that the quantum yield is 95%; the quantum dot size is 8nm multiplied by 2.2nm; the fluorescence emission peak of the quantum dot is 425nm.
Comparative example 3:
1g of difluorobromoacetic acid and 1.5g of copper chloride were mixed, heated to 170℃and reacted for 50 minutes to prepare a eutectic solvent.
2.5g of the eutectic solvent was mixed with 1.6g of titanium aluminum carbide powder, and the mixture was placed in a microwave reactor, the frequency was set at 460MHz, reacted at 50℃for 35 hours, the obtained precipitate was washed, and the obtained product was dried at 60℃for 28 hours, to prepare an accordion-like titanium carbide powder having copper modification.
0.3g of ruthenium chloride was mixed with 30mL of acetone, heated to 120℃and reacted for 2 hours. After cooling, the obtained liquid was collected to prepare a noble metal ion-providing agent.
Under helium atmosphere, 1.2g of the copper-modified accordion-like titanium carbide powder was mixed with 15mL of tetrabutylammonium hydroxide, and then 30mL of noble metal ion-providing agent was added thereto, followed by stirring for 30 hours. 5mL of ammonia water was added thereto, the temperature was raised to 500℃and the reaction was carried out for 24 hours. Centrifuging to obtain supernatant, and vacuum drying at 70deg.C for 40 hr to obtain the final product.
The quantum dot yield test was performed on the novel display quantum dot based on the multi-metal ion synergistic coordination modification prepared in comparative example 3, and the result showed that the quantum yield was 43%; the fluorescence emission peak of the quantum dot is 415nm. Compared with example 3, in comparative example 3, palladium chloride is replaced by ruthenium chloride, and under the condition that other conditions are unchanged, the fluorescence efficiency of the quantum dots is greatly reduced; this may be due to the weak synergy between the multi-metal ions caused by the replacement of the noble metal ions, thereby degrading the quantum dot performance.
Example 4:
2g of trifluoromethanesulfonic acid and 1g of cobalt chloride are mixed, heated to 180 ℃ and reacted for 60min to prepare the eutectic solvent.
3g of the eutectic solvent was mixed with 2g of titanium aluminum carbide powder, and the mixture was placed in a microwave reactor at a set frequency of 500MHz, reacted at 40℃for 72 hours, the obtained precipitate was washed, and the obtained product was dried at 70℃for 72 hours to obtain an accordion-like titanium carbide powder having a cobalt modification.
0.4g of palladium chloride was mixed with 30mL of toluene, heated to 150℃and reacted for 2 hours. After cooling, the obtained liquid was collected to prepare a noble metal ion-providing agent.
Under a nitrogen atmosphere, 1.7g of the powder of the accordion-shaped titanium carbide with the cobalt modification was mixed with 20mL of tetramethylammonium hydroxide, and then 30mL of a noble metal ion-providing agent was added thereto and stirred for 55 hours. 4g of ammonium chloride was added, the temperature was raised to 370℃and the reaction was carried out for 64 hours. Centrifuging to obtain supernatant, and vacuum drying at 80deg.C for 50 hr to obtain novel titanium carbide quantum dot for display based on polymetallic ion synergistic coordination modification.
The novel display quantum dot based on the multi-metal ion synergistic coordination modification prepared in the example 4 is tested, and the result shows that the quantum yield is 95%; the quantum dot size is 8.2nm multiplied by 2.9nm; the fluorescence emission peak of the quantum dot is 425nm.
Example 5:
2g of trifluoroacetic acid and 1g of cobalt chloride are mixed, the temperature is raised to 200 ℃, and the mixture is reacted for 50 minutes, so that the eutectic solvent is prepared.
3g of the eutectic solvent was mixed with 1.5g of titanium aluminum carbide powder, and the mixture was placed in a microwave reactor at a set frequency of 860MHz, reacted at 60℃for 72 hours, the obtained precipitate was washed, and the obtained product was dried at 70℃for 35 hours to prepare an accordion-like titanium carbide powder having a cobalt modification.
0.4g of palladium chloride was mixed with 40mL of toluene, heated to 130℃and reacted for 2 hours. After cooling, the obtained liquid was collected to prepare a noble metal ion-providing agent.
Under helium atmosphere, 1.2g of the powder of the cobalt-modified accordion-shaped titanium carbide was mixed with 10mL of tetramethylammonium hydroxide, and then 40mL of noble metal ion-providing agent was added thereto, followed by stirring for 40 hours. 4mL of ammonia water was added thereto, the temperature was raised to 470℃and the reaction was continued for 36 hours. Centrifuging to obtain supernatant, and vacuum drying at 70deg.C for 40 hr to obtain the final product.
The novel display quantum dot based on the multi-metal ion synergistic coordination modification prepared in the example 5 is tested, and the result shows that the quantum yield is 96%; the quantum dot size was 8.2nm×3.1nm, and the fluorescence emission peak was 425nm.
Example 6:
2g of difluorobromoacetic acid and 1g of cobalt chloride are mixed, heated to 190 ℃ and reacted for 30min to prepare the eutectic solvent.
3g of the eutectic solvent was mixed with 1.8g of titanium aluminum carbide powder, and the mixture was placed in a microwave reactor at a set frequency of 1000MHz, reacted at 150℃for 48 hours, the obtained precipitate was washed, and the obtained product was dried at 80℃for 24 hours to prepare an accordion-like titanium carbide powder having a cobalt modification.
0.3g of silver nitrate was mixed with 40mL of toluene, heated to 130℃and reacted for 1.5h. After cooling, the obtained liquid was collected to prepare a noble metal ion-providing agent.
Under an argon atmosphere, 1.2g of the powder of the cobalt-modified accordion-like titanium carbide was mixed with 15mL of tetramethylammonium hydroxide, followed by adding 10mL of the noble metal ion-providing agent and stirring for 43 hours. 4g of ammonium chloride was added, the temperature was raised to 470℃and the reaction was carried out for 72 hours. Centrifuging to obtain supernatant, and vacuum drying at 80deg.C for 52 hr to obtain novel titanium carbide quantum dot for display based on polymetallic ion synergistic coordination modification.
The novel quantum dot for display, which is prepared in example 6 and is coordinated and modified based on the cooperation of multiple metal ions, is tested, and the result shows that the quantum yield is 95%; the quantum dot size was 8nm×2.9nm, and the fluorescence emission peak was 426nm.
From the above examples, the novel quantum dot for display based on the multi-metal ion synergistic coordination modification provided by the invention has the advantages of high quantum yield, uniform size distribution and high luminous purity, and is a good material for the novel display field.
Claims (9)
1. The preparation method of the titanium carbide quantum dot based on the multi-metal ion synergistic coordination modification is characterized by comprising the following steps:
step 1, mixing the acid B and the acid L according to the mass ratio of 1:0.5-1:2, and heating to react to obtain a eutectic solvent;
step 2, mixing the prepared eutectic solvent with titanium aluminum carbide powder according to the mass ratio of 1:1-3:1, placing the mixture in a microwave reactor for reaction, washing the obtained precipitate, and drying to obtain the copper-or cobalt-modified accordion-shaped titanium carbide powder;
step 3, mixing a noble metal ion source and an organic solvent according to a mass ratio of 1:40-1:500, heating for reaction, cooling, and collecting the obtained liquid to prepare a noble metal ion provider;
step 4, uniformly mixing the accordion-shaped titanium carbide powder with copper or cobalt modification prepared in the step 2 and an intercalation agent in an inert atmosphere, then adding the noble metal ion providing agent prepared in the step 3, stirring, adding a quantum dot protecting agent, reacting at a high temperature, centrifuging to obtain a supernatant, and vacuum drying to prepare the multi-metal ion synergistic coordination modified titanium carbide quantum dot;
the acid B is one of trifluoromethanesulfonic acid, trifluoroacetic acid and difluorobromoacetic acid, and the acid L is cupric chloride or cobalt chloride; the noble metal ion source is one of chloroplatinic acid, chloroauric acid, palladium chloride and silver nitrate; the quantum dot protective agent is ammonia water or ammonium chloride.
2. The preparation method of the titanium carbide quantum dot based on the multi-metal ion synergistic coordination modification, which is disclosed in claim 1, is characterized in that in the step 1, the temperature is raised to 150-200 ℃ and the reaction is carried out for 30-60 min.
3. The preparation method of the titanium carbide quantum dot based on the multi-metal ion synergistic coordination modification, which is characterized in that in the step 2, the microwave frequency range of a microwave reactor is set to be 300-1000 MHz, the reaction temperature is 40-150 ℃, and the reaction time is 24-72 h; the drying temperature is 60-80 ℃ and the drying time is 24-72 h.
4. The method for preparing the titanium carbide quantum dot based on the multi-metal ion synergistic coordination modification according to claim 1, wherein in the step 3, the organic solvent is acetone or toluene.
5. The preparation method of the titanium carbide quantum dot based on the multi-metal ion synergistic coordination modification, which is disclosed in claim 1, is characterized in that in the step 3, the temperature is raised to 100-250 ℃ and the reaction is carried out for 1-2 h.
6. The method for preparing the titanium carbide quantum dot based on the multi-metal ion synergistic coordination modification according to claim 1, wherein in the step 4, the inert atmosphere is one of argon, helium and nitrogen, and the intercalating agent is one or more of dimethyl sulfoxide, tetramethyl ammonium hydroxide and tetraethyl ammonium hydroxide.
7. The preparation method of the titanium carbide quantum dot based on the multi-metal ion synergistic coordination modification, according to claim 1, is characterized in that in the step 4, the mass ratio of the titanium carbide powder, the intercalation agent, the noble metal ion providing agent and the quantum dot protecting agent is 1:5:10:2-1:20:50:6.
8. The preparation method of the titanium carbide quantum dot based on the multi-metal ion synergistic coordination modification, which is disclosed in claim 1, is characterized in that in the step 4, the stirring time is 24-72 h.
9. The method for preparing the titanium carbide quantum dot based on the multi-metal ion synergistic coordination modification, which is disclosed in claim 1, is characterized in that in the step 4, the temperature of vacuum drying is 60-80 ℃ and the time is 24-72 h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1535860A (en) * | 1966-08-18 | 1968-08-09 | Texas Instruments Inc | Method for depositing titanium carbide and product obtained |
| CN106976917A (en) * | 2017-03-03 | 2017-07-25 | 陕西科技大学 | Sheet cobalt black two-dimensional layer carbonization titanium composite material and its two-step preparation |
| CN111250122A (en) * | 2020-01-23 | 2020-06-09 | 福建工程学院 | Ag/MXene/TiO modified by nano noble metal2Composite material and preparation method thereof |
| CN111785534A (en) * | 2020-06-08 | 2020-10-16 | 华中科技大学 | Method for immobilizing MXene by ionic liquid covalent bonding and product thereof |
| CN113042078A (en) * | 2021-03-15 | 2021-06-29 | 浙江工业大学 | Preparation method of modified MXene material with sulfonic group |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109764971B (en) * | 2019-01-14 | 2021-09-17 | 京东方科技集团股份有限公司 | Flexible temperature sensor, manufacturing method thereof and flexible equipment |
-
2022
- 2022-04-22 CN CN202210427790.6A patent/CN114736680B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1535860A (en) * | 1966-08-18 | 1968-08-09 | Texas Instruments Inc | Method for depositing titanium carbide and product obtained |
| CN106976917A (en) * | 2017-03-03 | 2017-07-25 | 陕西科技大学 | Sheet cobalt black two-dimensional layer carbonization titanium composite material and its two-step preparation |
| CN111250122A (en) * | 2020-01-23 | 2020-06-09 | 福建工程学院 | Ag/MXene/TiO modified by nano noble metal2Composite material and preparation method thereof |
| CN111785534A (en) * | 2020-06-08 | 2020-10-16 | 华中科技大学 | Method for immobilizing MXene by ionic liquid covalent bonding and product thereof |
| CN113042078A (en) * | 2021-03-15 | 2021-06-29 | 浙江工业大学 | Preparation method of modified MXene material with sulfonic group |
Non-Patent Citations (3)
| Title |
|---|
| A general Lewis acidic etching route for preparing MXenes with enhanced electrochemical performance in non-aqueous electrolyte;Youbing Li ，etc;《NATURE MATERiALS》;第19卷;894-899 * |
| Chemically Stabilized and Functionalized 2D-MXene with Deep Eutectic Solvents as Versatile Dispersion Medium;Jeonghui Kim，etc;《Adv. Funct. Mater.》;第31卷;2008722 * |
| Enhanced photocatalytic degradation of perfluorooctanoic acid by Ti3C2 MXene-derived heterojunction photocatalyst: Application of intercalation strategy in DESs;Haoran Song,etc;《Science of the Total Environment》;第746卷;141009 * |
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