CN101638222A - Preparation method of nano particles of metal oxide chemically modified by carboxylic acid - Google Patents
Preparation method of nano particles of metal oxide chemically modified by carboxylic acid Download PDFInfo
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- CN101638222A CN101638222A CN200910116861A CN200910116861A CN101638222A CN 101638222 A CN101638222 A CN 101638222A CN 200910116861 A CN200910116861 A CN 200910116861A CN 200910116861 A CN200910116861 A CN 200910116861A CN 101638222 A CN101638222 A CN 101638222A
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Abstract
The invention relates to a preparation method of nano particles of metal oxide chemically modified by carboxylic acid, comprising the following steps: chemically grafting carboxylic acid molecules onthe surfaces of nano particles of metal oxide by a solvent heat reaction; operating the solvent heat reaction of the nano particles of the metal oxide with carboxylic acid; then processing the nano particles by heat treatment after the reaction for removing physical adsorption; and obtaining the nano particles of the metal oxide, which is modified chemically by the carboxylic acid. The chemical reaction in a high-pressure kettle is operated at lower temperature; the dimensions and the crystal types of the nano particles are not influence by the reaction; and the obtained nano particles of themetal oxide have good dispersivity in an organic solvent. The preparation method has the following characteristics that the surfaces of the nano particles can contain a hydroxide radical or not; the carboxylic acid can be fatty acid or aromatic acid; the content of the carboxylic acid on the surfaces of the nano particles can be controlled by reaction conditions; and the preparation method has good applicability to the nano particles of the metal oxide, with simple equipment, convenient operation and good practical application prospect. The obtained nano particles of the metal oxide have largeapplication value in the fields of catalysts, optical materials, coating materials, photoelectric conversion materials, photovoltaic materials, organic and inorganic composite materials and the like.
Description
Technical field
The present invention relates to a kind of method of metal oxide nanoparticles being carried out chemical modification with carboxylic acid.
Background technology
Along with Materials science development, inorganic nanoparticles becomes the efficient functional materials that gets a good chance of because of its unique chemical and physicals.In the practical application, modification often need be carried out with organic molecule in the inorganic nanoparticles surface, main purpose comprises: prevent to reunite, its surface of functionalization, increase its dispersiveness or solvability in organic solvent, increase consistency of itself and organic materials etc. [referring to Acc.Chem.Res.2003,36,549-561; J.Mater.Chem.2005,15,3559-3592; C.R.Chimie 2003,6,1131-1151].Metal oxide nanoparticles has important application prospects in fields such as optics, magnetics, catalysis and photovoltaic cells.Yet the organic molecule modification on metal oxide nanoparticles surface and the method for functionalization are also very limited [referring to Monatsh Chem.2008,139,183-195; Acc.Chem.Res.2008,41,411-420].
Carboxylic acid is a kind of metal oxide nanoparticles surface-modifying agent commonly used.A kind of method is, in the metal oxide nanoparticles building-up process (as, sol-gel method) add carboxylic acid [referring to Angew.Chem.Int.Ed.2006,45,3414-3439; Chem.Rev.2005,105,1025-1102; J.Am.Chem.Soc.2007,129,6352-6353; Eur.J.Inorg.Chem.2008,980-987] carry out on-the-spot modification.There are many deficiencies in the method for on-the-spot modification: for example, in order to obtain stable crystallization material, often need carry out pyroprocessing (＞400 ℃) to modified product, cause the loss of nano grain surface properties-correcting agent; Though can acquire the nano particle of modification, the existence of properties-correcting agent makes crystallography characteristics, the shape and size of nano particle be subjected to very big influence, is difficult to realize finishing synchronously of modification and ad hoc structure growth; Be difficult to control the content of nano grain surface properties-correcting agent.Another kind method is that nano particle first synthesizing stable and that have a fixed structure carries out follow-up modification then; This method is comparatively desirable, the modification that can realize keeping ad hoc structure and performance.Traditional follow-up modification normally with metal oxide rice particle [referring to Chem.Eng.J.2006,119,71-81; Chem.Rev.2008,108.2064-2110; Colloids Surf.A:Physicochem.Eng.Aspects 2008,317,543-550] or nano-structure film [referring to: J.Phys.Chem.B 2006,110,15734-15741; J.Am.Chem.Soc.2007,129,4655-4665] be immersed in the organic solution of properties-correcting agent, the physical/chemical adsorption of modifier molecules is reached the purpose of modification by nano grain surface.Yet the desorption of properties-correcting agent often takes place in for want of stable chemical bond, the modified nanoparticles that this simply immersing obtains in actual applications; Simultaneously, because nano particle difficulties in dispersion or organic solvent in organic solvent can not be penetrated in the slit of nanometer aggregate effectively, be difficult for accomplishing the control of surface modification agent content.Therefore, foundation by the novel method of chemical bond grafting to the metal oxide nanoparticles surface, has important scientific meaning and using value with carboxylic acid molecules.
Summary of the invention
The invention provides a kind of preparation method of carboxylic acid-chemically modified metal oxide nanoparticles, be to utilize low-temperature solvent thermal response and thermal treatment to remove processes such as physical adsorption, realized the chemical modification of carboxylic acid, and the content of surface-modifying agent can be controlled by reaction conditions to the metal oxide nanoparticles surface.
The foregoing invention purpose is achieved through the following technical solutions:
A kind of preparation method of carboxylic acid-chemically modified metal oxide nanoparticles, it is characterized in that: earlier the nano particle of metal oxide and carboxyl acid modified dose of mixed solvent at alcohol-water are fully disperseed and dissolve, reinstall in the autoclave, place baking oven to react autoclave, temperature is 30～100 ℃ in the baking oven, and the reaction times is 6～72 hours; After question response is finished and naturally cooled to room temperature, take out the reactant in the autoclave, centrifugation obtains the crude product of modified nanoparticles; Crude product is heat-treated under nitrogen or other protection of inert gas after drying, removes the carboxylic acid molecules that contains in the crude product, promptly obtains carboxylic acid-chemically modified metal oxide nanoparticles; Thermal treatment temp T
AnBoiling point or sublimation temperature by carboxylic acid are determined, are enough to make carboxylic acid boiling or distillation to be volatilized away.
The weight ratio of described metal oxide nanoparticles and carboxylic acid is 1: 1～15, and the volume ratio of ethanol and water is 1: 3～4 in the mixed solvent of alcohol-water; Crude product was 50～80 ℃ of vacuum-dryings 10～24 hours; The heat treatment time of crude product is 30～60 minutes.
Described metal oxide nanoparticles is the TiO of surperficial hydroxyl
2Nano particle, surface be the TiO of hydroxyl not
2Or ZnO nano particle; The carboxyl mol ratio of metal oxide nanoparticles surface hydroxyl and carboxylic acid is 1: 0.5～30.
Described nano particle is TiO
2, ZnO, Al
2O
3, ZrO
2Or P25 nano particle.
Described carboxyl acid modified dose of selected fatty acid or aromatic acid, comprise and select parabromobenzoic acid (BBA) or dodecanoic acid (DA), butanic acid, n-caproic acid, 2 for use, 4-Sorbic Acid, Octadecane acid, 4-(4-aminophenyl) butyric acid or 4-(2, the 5-Dimethoxyphenyl) butyric acid.
The nano particle of metal oxide and carboxyl acid modified dose of mixed solvent at alcohol-water fully disperseed and when dissolving, adopt between acid or alkali conditioned reaction system pH=2～12.
Change weight ratio, temperature of reaction and the reaction times of carboxyl acid modified dose and nano particle, just can obtain the different chemical modification nano particle of surperficial carboxylic acid content.
The purposes of carboxylic acid-chemically modified metal oxide nanoparticles of the present invention, it is characterized in that: in organic solvent, have good dispersiveness and dispersion stabilization, be used to prepare catalyzer, optical material, coated material, photoelectric conversion material, solar cell material, organic-inorganic nanocomposite.
The purposes of described carboxylic acid-chemically modified metal oxide nanoparticles is characterized in that: utilize functional group to carry out follow-up chemical reaction at nano grain surface, obtain the metal oxide nanoparticles of further chemical modification; Further the nano particle of modification is used to prepare catalyzer, optical material, coated material, photoelectric conversion material, solar cell material, organic-inorganic nanocomposite.
The characteristics of the inventive method are: nano grain surface can contain hydroxyl (OH), also hydroxyl not; Carboxylic acid can be a lipid acid, also can be aromatic acid; The carboxylic acid that has other functional group in use obtains surface-functionalized nano particle during as properties-correcting agent; The carboxylic acid content of nano grain surface is controlled by reaction conditions; Chemical reaction in the autoclave carries out under lower temperature (30～100 ℃), and the size of nano particle and crystal formation are not subjected to the influence of this reaction; It is very little that chemical reaction in the autoclave is influenced by pH in pH=2～12 scopes; Has good universality for metal oxide nanoparticles.In addition, equipment simple (mainly being autoclave, retort furnace and whizzer), reaction conditions gentleness, easy and simple to handle that the inventive method is used have good actual application prospect; The metal oxide nanoparticles that obtains has good dispersiveness in organic solvent, have very big using value in fields such as catalysis, optical material, coated material, photoelectric conversion material, photovoltaic material, composite organic-inorganic materials.
Embodiment
Titanium dioxide (the TiO of embodiment 1. parabromobenzoic acids (BBA) modified surface hydroxyl
2-OH) nano particle.(1-1) TiO
2The preparation of-OH nano particle:
The mixture of 5ml Virahol and 12.5ml isopropyl titanate was added drop-wise in 10 minutes under room temperature in the 75ml salpeter solution (0.1M), and simultaneously with vigorous stirring, the white mixture that obtains was 80 ℃ of vigorous stirring gelations 8 hours; With 3# sand core funnel suction filtration, remove the not block aggregate of peptization; Filtrate benefit adds water to about 80ml, and changes in the tetrafluoroethylene inner liner stainless steel autoclave of 100ml; Autoclave naturally cools to room temperature in reaction under 200 ℃ after 12 hours in convection oven.(10000rpm 10min) separates nano particle, uses washing with alcohol (3 * 30ml) and centrifugation then by centrifugal.The TiO that obtains
2Nanoparticulate dispersed is in a certain amount of ethanol.
The TiO that scanning electronic microscope (SEM) and X-ray diffraction (XRD) analysis revealed obtain
2Nano particle diameter is 9～11nm, is mainly anatase phase, contains the brookite crystalline phase of minute quantity; Thermogravimetic analysis (TGA) (TGA) (span is 120～450 ℃) show this TiO
2Nano grain surface OH content is 3.12mmol/g.
(1-2) BBA modification TiO
2-OH nano particle:
In 30ml autoclave inner bag, add 0.82g BBA, 5.0ml TiO
2Alcohol dispersion liquid (solid content is 13.8mg/ml, and nano grain surface OH content is 3.12mmol/g) and 20.0ml deionized water, ultra-sonic dispersion 10 minutes obtains the OH/COOH mol ratio and is 1/19 reaction mixture.The autoclave that reactant is housed is placed convection oven, reacted 24 hours down in 100 ℃.The reaction finish after, treat that autoclave naturally cools to room temperature after, carry out centrifugal and washing with alcohol (10min), the nano particle of gained was 50 ℃ of vacuum-dryings 12 hours for 3 * 30ml, 10000rpm.In retort furnace,, promptly obtain the nano particle of BBA chemical modification with the thermal treatment 30 minutes under 250 ℃ and nitrogen protection of dried nano particle.
The sign of modified nanoparticles is as follows: infrared spectra (FT-IR) is at 1420cm
-1And 1513cm
-1Carboxylate salt (the COO at place
-) the eigen vibration peak shows that properties-correcting agent BBA is grafted to the surface of nano particle, 1680cm by chemical bond by bidentate chelating mode
-1(C=O) disappearance at peak shows that nano grain surface does not have the BBA of physical adsorption to place's carbonyl; Ultraviolet-visible (UV-vis) absorption spectrum shows the absorption that has occurred BBA at the 241nm place; XRD and SEM show that the size of autoclave reaction pair nano particle and crystal formation do not cause tangible influence; TGA (span is 350～600 ℃) shows that the content of nano grain surface BBA is 10.57%, and the surface hydroxyl percentage of grafting is 16.854%.TiO after the modification
2Nano particle has good dispersiveness and dispersion stabilization in organic solvents such as chloroform.
Titanium dioxide (the TiO of embodiment 2. dodecanoic acids (DA) modified surface hydroxyl
2-OH) nano particle.
(2-1) TiO
2The preparation of-OH nano particle: with embodiment 1.
(2-2) DA modification TiO
2-OH nano particle:
In 30ml autoclave inner bag, add 0.82g DA, 5.0ml TiO
2Alcohol dispersion liquid (solid content is 13.8mg/ml, and hydroxy radical content is 3.12mmol/g) and 20.0ml deionized water, ultra-sonic dispersion 10 minutes obtains the OH/COOH mol ratio and is 1/19 reaction mixture.The autoclave that reactant is housed is placed convection oven, reacted 24 hours down in 100 ℃.After question response is finished and is naturally cooled to room temperature, carry out centrifugal and washing with alcohol (10min), the nano particle of gained was 50 ℃ of vacuum-dryings 12 hours for 3 * 30ml, 21000rpm.In retort furnace,, promptly obtain the nano particle of DA chemical modification with the thermal treatment 30 minutes under 225 ℃ and nitrogen protection of dried nano particle.
The sign of modified nanoparticles is as follows: FT-IR composes at 1440cm
-1And 1520cm
-1Carboxylate salt (the COO at place
-) the eigen vibration peak shows that properties-correcting agent DA is grafted to the surface of nano particle, 1700cm by chemical bond by bidentate chelating mode
-1(C=O) disappearance at peak shows that nano grain surface does not have the DA of physical adsorption to place's carbonyl; TGA (span is 200～500 ℃) shows that the content of nano grain surface DA is 7.95%, and the surface hydroxyl percentage of grafting is 12.74%.TiO after the modification
2Nano particle has good dispersiveness and dispersion stabilization in organic solvents such as chlorobenzene.
Embodiment 3. parabromobenzoic acids (BBA) modified surface is the titanium dioxide (TiO of hydroxyl not
2) nano particle.
(3-1) TiO
2The preparation of-OH nano particle: with embodiment 1.
(3-2) TiO
2The preparation of nano particle:
Titanium dioxide (the TiO that will contain surface hydroxyl
2-OH) nano particle places retort furnace, in 450 ℃ of following thermal treatments 60 minutes, obtains the not titanium dioxide (TiO of hydroxyl of surface under air conditions
2) nano particle.XRD and this thermal treatment of SEM test shows are to TiO
2The size of nano particle and crystal formation do not cause tangible influence; TGA (span is 120～450 ℃) test result shows through TiO after this thermal treatment
2The residual volume of surface hydroxyl is 0.78mmol/g.
(3-3) BBA modification TiO
2Nano particle:
In 30ml autoclave inner bag, add 0.07g TiO
2, 0.82g BBA, 5.0ml ethanol and 20.0ml deionized water, ultra-sonic dispersion 10 minutes obtains TiO
2/ BBA weight ratio is 1/12 reaction mixture.The autoclave that reactant is housed is placed convection oven, reacted 24 hours down in 100 ℃.After question response is finished and is naturally cooled to room temperature, carry out centrifugal and washing with alcohol (10min), the nano particle of gained was 50 ℃ of vacuum-dryings 12 hours for 3 * 30ml, 10000rpm.In retort furnace,, promptly obtain the nano particle of BBA chemical modification with the thermal treatment 30 minutes under 250 ℃ and nitrogen protection of dried nano particle.
The sign of modified nanoparticles is as follows: FT-IR composes at 1420cm
-1And 1513cm
-1Carboxylate salt (the COO at place
-) the eigen vibration peak shows that properties-correcting agent BBA is grafted to the surface of nano particle, 1680cm by chemical bond by bidentate chelating mode
-1(C=O) disappearance at peak shows that nano grain surface does not have the BBA of physical adsorption to place's carbonyl; The UV-vis absorption spectrum shows the absorption that has occurred BBA at the 235nm place; XRD and SEM show that the size of autoclave reaction pair nano particle and crystal formation do not cause tangible influence; TGA (span is 350～600 ℃) shows that the content of nano grain surface BBA is 9.84%.TiO after the modification
2Nano particle has good dispersiveness and dispersion stabilization in organic solvents such as chloroform.
Embodiment 4. dodecanoic acids (DA) modified surface is the titanium dioxide (TiO of hydroxyl not
2) nano particle.
(4-1) TiO
2The preparation of-OH nano particle: with embodiment 1.
(4-2) TiO
2The preparation of nano particle: with embodiment 3.
(4-3) DA modification TiO
2Nano particle:
In 30ml autoclave inner bag, add 0.07g TiO
2, 0.82g DA, 5.0ml ethanol and 20.0ml deionized water, carried out ultra-sonic dispersion again 10 minutes, obtain TiO
2/ DA weight ratio is 1/12 reaction mixture.The autoclave that reactant is housed is placed convection oven, reacted 24 hours down in 100 ℃.After question response is finished and is naturally cooled to room temperature, carry out centrifugal and washing with alcohol (10min), the nano particle of gained was 50 ℃ of vacuum-dryings 12 hours for 3 * 30ml, 21000rpm.In retort furnace,, promptly obtain the nano particle of DA chemical modification with the thermal treatment 30 minutes under 225 ℃ and nitrogen protection of dried nano particle.
The sign of modified nanoparticles is as follows: FT-IR composes at 1440cm
-1And 1520cm
-1Carboxylate salt (the COO at place
-) the eigen vibration peak shows that properties-correcting agent DA is grafted to the surface of nano particle, 1700cm by chemical bond by bidentate chelating mode
-1(C=O) disappearance at peak shows that nano grain surface does not have the DA of physical adsorption to place's carbonyl; TGA (span is 200～500 ℃) shows that the content of nano grain surface DA is 10.44%.TiO after the modification
2Nano particle has good dispersiveness and dispersion stabilization in organic solvents such as chlorobenzene.
Embodiment 5. parabromobenzoic acids (BBA) modified zinc oxides (ZnO) nano particle.
(5-1) processing of ZnO nano particle:
Commodity zinc oxide nano (specification: 20～30nm,＞99.99%) (brilliant nano material technology company of sino-america joint-venture Hefei section.Network address: http://www.kmtcrystal.com; Address: Hefei City's 1125 mailbox; Postcode: 230031) in air in 450 ℃ of down heating 60 minutes, with the moisture content of removing surface adsorption etc.XRD and SEM show that this thermal treatment does not cause tangible influence to the size and the crystal formation of ZnO nano particle.
(5-2) BBA modification ZnO nano particle:
In 30ml autoclave inner bag, add 0.07g ZnO, 0.82g BBA, 5.0ml ethanol and 20.0ml deionized water, ultra-sonic dispersion 10 minutes obtains the ZnO/BBA weight ratio and is 1/12 reaction mixture.The autoclave that reactant is housed is placed convection oven, reacted 24 hours down in 100 ℃.After question response is finished and is naturally cooled to room temperature, carry out centrifugal and washing with alcohol (10min), the nano particle of gained was 50 ℃ of vacuum-dryings 12 hours for 3 * 30ml, 10000rpm.In retort furnace,, promptly obtain the nano particle of BBA chemical modification with the thermal treatment 30 minutes under 250 ℃ and nitrogen protection of dried nano particle.
The sign of modified nanoparticles is as follows: FT-IR composes at 1413cm
-1And 1547cm
-1Carboxylate salt (the COO at place
-) the eigen vibration peak shows that properties-correcting agent BBA is grafted to the surface of nano particle, 1680cm by chemical bond by the bridging mode
-1(C=O) disappearance at peak shows that nano grain surface does not have the BBA of physical adsorption to place's carbonyl; The UV-vis absorption spectrum shows the absorption that has occurred BBA at the 240nm place; XRD and SEM show that the size of autoclave reaction pair nano particle and crystal formation do not cause tangible influence; TGA (span is 350～600 ℃) shows that the content of nano grain surface BBA is 69.90%.ZnO nano particle after the modification has good dispersiveness and dispersion stabilization in organic solvents such as chlorobenzene.
Claims (10)
1, a kind of preparation method of carboxylic acid-chemically modified metal oxide nanoparticles, it is characterized in that: earlier metal oxide nanoparticles and carboxyl acid modified dose of mixed solvent at alcohol-water are fully disperseed and dissolve, reinstall in the autoclave, place baking oven to react autoclave, temperature is 30～100 ℃ in the baking oven, and the reaction times is 6～72 hours; After question response is finished and naturally cooled to room temperature, take out the reactant in the autoclave, centrifugation obtains the crude product of modified nanoparticles; Crude product is heat-treated under nitrogen or other protection of inert gas after drying, removes the carboxylic acid molecules that contains in the crude product, promptly obtains carboxylic acid-chemically modified metal oxide nanoparticles; Thermal treatment temp Tan is enough to make carboxylic acid boiling or distillation to be volatilized away by the boiling point of carboxylic acid or determining of sublimation temperature.
2, preparation method as claimed in claim 1 is characterized in that: the weight ratio of described metal oxide nanoparticles and carboxylic acid is 1: 1～15, and the volume ratio of ethanol and water is 1: 3～4 in the mixed solvent of alcohol-water; Crude product was 50～80 ℃ of vacuum-dryings 10～24 hours; The heat treatment time of crude product is 30～60 minutes.
3, preparation method as claimed in claim 1 is characterized in that: used metal oxide nanoparticles is the TiO of surperficial hydroxyl
2Nano particle, surface be the TiO of hydroxyl not
2Or ZnO nano particle; The carboxyl mol ratio of metal oxide nanoparticles surface hydroxyl and carboxylic acid is 1: 0.5～30.
4, preparation method as claimed in claim 1 is characterized in that: described nano particle is TiO
2, Fe
3O
4, ZnO, Al
2O
3, ZrO
2Or P25 nano particle.
5, preparation method as claimed in claim 1, it is characterized in that: described carboxyl acid modified dose of selected fatty acid or aromatic acid, comprise and select parabromobenzoic acid (BBA) or dodecanoic acid (DA), butanic acid, n-caproic acid, 2 for use, 4-Sorbic Acid, Octadecane acid, 4-(4-aminophenyl) butyric acid or 4-(2, the 5-Dimethoxyphenyl) butyric acid.
6, preparation method as claimed in claim 1 is characterized in that: the nano particle of metal oxide and carboxyl acid modified dose of mixed solvent at alcohol-water are fully disperseed and when dissolving, adopt between acid or alkali conditioned reaction system pH=2～12.
7, preparation method as claimed in claim 1 is characterized in that: change weight ratio, temperature of reaction and the reaction times of carboxyl acid modified dose and nano particle, just can obtain the different chemical modification nano particle of surperficial carboxylic acid content.
8, the purposes of the carboxylic acid-chemically modified metal oxide nanoparticles of method preparation as claimed in claim 1, it is characterized in that: in organic solvent, have good dispersiveness and dispersion stabilization, be used to prepare catalyzer, optical material, coated material, photoelectric conversion material, solar cell material, organic-inorganic nanocomposite.
9, preparation method as claimed in claim 1, it is characterized in that: with the carboxylic acid-chemically modified metal oxide nanoparticles that contains other functional group, and utilize on the modified nanoparticles surface carboxylic acid with functional group carry out follow-up chemical reaction, obtain the metal oxide nanoparticles of further chemical modification.
10, the purposes of the further modified metal-oxide nano particle of method preparation as claimed in claim 9, it is characterized in that: in organic solvent, have good dispersiveness and dispersion stabilization, be used to prepare catalyzer, optical material, coated material, photoelectric conversion material, solar cell material, organic-inorganic nanocomposite.
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| CN200910116861A CN101638222A (en) | 2009-05-25 | 2009-05-25 | Preparation method of nano particles of metal oxide chemically modified by carboxylic acid |
| CN200910205061.0A CN101792116B (en) | 2009-05-25 | 2009-10-24 | Method for preparing carboxylic acid-chemically modified metal oxide nanoparticles |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261098A (en) * | 2010-12-22 | 2013-08-21 | 3M创新有限公司 | Surface-modified zirconia nanoparticles |
| CN105948111A (en) * | 2016-04-21 | 2016-09-21 | 中国科学院生态环境研究中心 | Preparation method for titanium dioxide material with specific crystal face |
| CN110911570A (en) * | 2018-09-18 | 2020-03-24 | 浙江大学 | Quantum dot light-emitting device and preparation method thereof |
| CN111484755A (en) * | 2020-04-09 | 2020-08-04 | 行謇人工智能科技(上海)有限责任公司 | Lauric acid modified nano titanium dioxide and preparation method and application thereof |
| CN114989508A (en) * | 2022-06-07 | 2022-09-02 | 安徽蒙特尔电缆集团有限公司 | Aging-resistant cable and processing method thereof |
| WO2023213036A1 (en) * | 2022-05-06 | 2023-11-09 | 山东国瓷功能材料股份有限公司 | Surface-treated zirconium oxide nanopowder, zirconium oxide dispersion liquid, and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261098A (en) * | 2010-12-22 | 2013-08-21 | 3M创新有限公司 | Surface-modified zirconia nanoparticles |
| CN103261098B (en) * | 2010-12-22 | 2015-05-20 | 3M创新有限公司 | Surface-modified zirconia nanoparticles |
| US9139670B2 (en) | 2010-12-22 | 2015-09-22 | 3M Innovative Properties Company | Surface-modified zirconia nanoparticles |
| CN105948111A (en) * | 2016-04-21 | 2016-09-21 | 中国科学院生态环境研究中心 | Preparation method for titanium dioxide material with specific crystal face |
| CN105948111B (en) * | 2016-04-21 | 2017-06-16 | 中国科学院生态环境研究中心 | The preparation method of particular crystal plane titanic oxide material |
| CN110911570A (en) * | 2018-09-18 | 2020-03-24 | 浙江大学 | Quantum dot light-emitting device and preparation method thereof |
| CN110911570B (en) * | 2018-09-18 | 2021-11-19 | 浙江大学 | Quantum dot light-emitting device and preparation method thereof |
| CN111484755A (en) * | 2020-04-09 | 2020-08-04 | 行謇人工智能科技(上海)有限责任公司 | Lauric acid modified nano titanium dioxide and preparation method and application thereof |
| WO2023213036A1 (en) * | 2022-05-06 | 2023-11-09 | 山东国瓷功能材料股份有限公司 | Surface-treated zirconium oxide nanopowder, zirconium oxide dispersion liquid, and use |
| CN114989508A (en) * | 2022-06-07 | 2022-09-02 | 安徽蒙特尔电缆集团有限公司 | Aging-resistant cable and processing method thereof |
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