CN101348254A - Preparation of hollow nanosilica white sphere - Google Patents
Preparation of hollow nanosilica white sphere Download PDFInfo
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- CN101348254A CN101348254A CNA2007100121580A CN200710012158A CN101348254A CN 101348254 A CN101348254 A CN 101348254A CN A2007100121580 A CNA2007100121580 A CN A2007100121580A CN 200710012158 A CN200710012158 A CN 200710012158A CN 101348254 A CN101348254 A CN 101348254A
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Abstract
The invention relates to a silicon oxide sphere particle, in particular to a method for preparing a hollow nano silicon oxide sphere. In a bionic system with room temperature approximately neutral, the three block copolymer F1127 is taken as a structure guiding agent, the mutual interactions between hydrolytic oil-soluble silica resources and the three block copolymer F1127 and inorganic electrolytes are controlled, the hollow spherical particle is obtained by steps of the preparation of polymer micelle, hydrolytic polymerization of silica resources, hydrothermal crystallization, drying and extraction of the structure guiding agent; the size of the spherical particle is continuously adjusted in the range of between 10 and 20nm, and the thickness of a shell wall is continuously adjusted in the range of between 4 and 10nm. The synthesized nano hollow sphere has the advantages of big specific surface, big hole capacity, uniform particle size and good dispersibility of the particle, a multi-level structure formed between nano hollow spheres and high mechanical stability and thermal stability, etc.
Description
Technical field
The present invention relates to the silicon oxide ball particle, specifically a kind of preparation method of hollow nanosilica white sphere.
Background technology
Nano material with hollow structure is the focus in present investigation of materials field.Use polymer micelle can form the polymkeric substance hollow structure of size of particles at 1～100nm.Yet most polymkeric substance hollow ball is all very unstable, will swelling under air, seriously limited its application in practice.The inorganic hollow nanometer ball of granular size between 1～100nm is a kind of functional materials with special construction, because it has large specific surface, high store content, favorable mechanical and thermostability, be subjected to the extensive concern in nanosecond science and technology fields, be with a wide range of applications in research fields such as nanometer confinement catalysis, targeted drug (gene) slowly-releasing, absorption, artificial cell, insulating material, photonic crystal, dielectric materials and medical diagnosis on disease treatments.At present, the preparation method of hollow nanosilica white sphere mainly is divided into " hard template method " and reaches " soft template method ", hard template method mainly is to adopt inorganic microspheres or polymer microballoon as hard template, by adopting layer-layer self-assembling technique or sol-gel method shell at its outside surface self-assembly one deck silicon oxide, (US Patent:7 094 369,2006 by thermal treatment or solvent extraction the hard template removal to be obtained the silicon oxide hollow ball at last; CN Patent:1 506 308,2004; 1 772 363A, 2006; Chemistry of Material, 1999,11 volumes, 3309-3314 page or leaf; Journal of AmericanChemical Society, calendar year 2001,123 volumes, 7723-7724 page or leaf; Advanced Materials, 2006,18 volumes, 801-806 page or leaf; Chemistry of Material, 2007,19 volumes, 1700-1703 page or leaf .) but this method needs suitable surface modification and functionalization, complex process, complex operation usually.Soft template method can be divided into emulsion template, show (CN Patent:1 944 251A, 2007 such as promoting agent vesicle mold; 1 607 176A, 2005; Advanced Materials, 2003,15 volumes, 1097-1100 page or leaf; Chemistry of Material, 2004,16 volumes, 5420-5426 page or leaf; Chemical Communications calendar year 2001, the 2028-2029 page or leaf; Chemistry Letters 2002, the 62-63 page or leaf; Nano Letters 2003,3 volumes, 609-612 page or leaf; Journal of AmericanChemical Society, 2006,128 volumes, 6320-6321 page or leaf; Advanced Materials, 2005,17 volumes, 2368-2371 page or leaf).Use soft template method method synthetic hollow ball to have the size distribution heterogeneity usually, shortcomings such as easy reunion.Lu high definitions etc. are at " american chemical proceedings " (Journal ofAmerican Chemical Society, 2006,128 volumes, the 6320-6321 page or leaf) reported that vesica that use mixed surfactant (cats product and fluorocarbon surfactant) forms is as template in the aqueous solution, preparation nano silicon oxide hollow ball, the pH value of reaction system is higher, and and there is the shortcoming be easy to reunite in the hollow ball size of formation about 200nm.Utilize above-mentioned two kinds of method synthetic hollow nanospheres size of particles usually greater than 100nm, be difficult to the inorganic hollow nanometer ball of compound particle size at 1～100nm; And also there is the granular size heterogeneity in the hollow nanospheres that obtains, is easy to shortcomings such as reunion.
Utilizing polymer micelle to combine with sol-gel technique is the effective ways of compound particle less than the silicon oxide hollow ball of 100nm.U.S.'s " american chemical proceedings " (Journal of American ChemicalSociety, 2007,129 volumes, the 1534-1535 page or leaf) reported silicon oxide hollow ball about using ABC type segmented copolymer compound particle size as 30nm, but this method steps is loaded down with trivial details, and whole synthesis cycle needs about 7 days time, wastes time and energy to be difficult for the industrialization amplification, and the hollow ball size distribution heterogeneity that obtains, there is aggregation phenomenon.
Summary of the invention
It is adjustable to the purpose of this invention is to provide a kind of size of particles, has hollow nanosilica white sphere of multilevel hierarchy and preparation method thereof.Overcome preparation process complexity, consuming time in the prior art, be difficult to obtain the shortcomings such as hollow nanosilica white sphere of particle less than 100nm.
For achieving the above object, the present invention is under the bionical system of room temperature nearly neutral (pH=6-8), with triblock copolymer F127 is structure directing agent, and the oily molten silicon source of control hydrolysis and the interaction between triblock polymer F127 and the inorganic electrolyte prepare by polymer micelle, silicon source hydrolytic polymerization, hydrothermal crystallizing, drying is deviate from steps such as structure directing agent, obtain the hollow sphere particle, its big I is adjustable continuously in 10～20nm scope; Shell thickness is continuously adjustable high-specific surface area, large pore volume hollow nanosilica white sphere in 5～10nm scope.
Specifically can operate as follows:
(1) polymer micelle prepares, and structure directing agent triblock copolymer F127 is dissolved in the inorganic salt solution of pH=6-8; Anionic concentration in the inorganic salt solution is between 0.005～0.1M;
(2) hydrolytic polymerization in silicon source: under agitation in the intrafascicular adding silicon of polymer latex source, stir and make mother liquor, the whipping temp scope is 12～40 ℃ in the building-up process, churning time 10～48h;
The mol ratio of each component is: triblock copolymer: inorganic salt: silicon source=(1～2.2): (504～2520): (100～353);
(3) hydrothermal crystallizing: the mother liquor that step (2) is made is at 60～120 ℃ of hydrothermal crystallizing 24～48h;
(4) drying:, wash drying at room temperature with massive laundering with the product pumping rate behind step (3) hydrothermal crystallizing;
(5) deviate from structure directing agent:, make product of the present invention with the middle 10～30h of backflow of dried product (the 1.0g product can adopt the 50-400mL ethanolic soln, contains 1-4g HCl in the ethanolic soln) in the tart ethanolic soln.
Prepared hollow nano silicon oxide ball particle, its granular size is adjustable continuously in 10～30nm scope; Shell thickness is adjustable continuously in 4～15nm scope, and specific surface area is at 600～1000m
2g
-1Between, pore volume is at 2.0～3.3cm
3g
-1Between.Structure directing agent is easy to remove by the mode of alcohol extraction, reaches the purpose of economic recovery.
Described structure directing agent for adopt poly-oxyethylene be hydrophilic section, poly-propylene oxide be hydrophobic section [(EO)
106(PO)
70(EO)
106] triblock copolymer F127;
Stating inorganic salt solution is the aqueous solution of SODIUM PHOSPHATE, MONOBASIC-disodium hydrogen phosphate buffer solution, inorganic electrolyte sodium acetate, sodium sulfate or yellow soda ash, and anion concentration is between 0.02～0.1M.
Described silicon source is the organosilane BTME[(MeO of ethane bridging)
3SiCH
2CH
2Si (OMe)
3] or methyl silicate TMOS[(MeO)
4Si].
The following advantage of preparation method's tool of the present invention:
1. adopting cheap, nontoxic, biodegradable neutral surface active agent is structure directing agent, helps environment protection; Structure directing agent removes by the mode of alcohol extraction easily, reaches the purpose of economic recovery; Energy consumption is low, is suitable for suitability for industrialized production;
2. mild condition is simple to operate, can obtain the hollow nanosilica white sphere of large specific surface and large pore volume in very big ratio range.
3. by changing proportioning raw materials, temperature of reaction, conditions such as the kind of inorganic electrolyte can realize the adjustable continuously of hollow nanosilica white sphere particulate size and shell thickness.
The material of the present invention's preparation has following advantage:
1. Zhi Bei material has high mechanical stability and thermostability; Synthesis condition gentleness of the present invention, synthetic method is simple, by changing proportioning raw materials, temperature of reaction, condition may command hollow ball particulate sizes (adjustable continuously in 10～20nm scope) such as the kind of inorganic electrolyte; Shell thickness (adjustable continuously in 5～10nm scope); Have advantages such as high mechanical stability and thermostability.
2. Zhi Bei material granule homogeneous grain diameter and good dispersity; Adopting non-ionic type triblock polymer F127 among the present invention is structure directing agent, by the oily molten silicon source of control hydrolysis and the interaction between triblock polymer F127 and the inorganic electrolyte, under the bionical condition of the nearly neutral of room temperature, synthesized and have large specific surface and (can reach 969m
2g
-1) and large pore volume (can reach 3.23cm
3g
-1) the hollow nanosilica white sphere; This material granule homogeneous grain diameter and good dispersity;
3. Zhi Bei material all has big specific surface and large pore volume, and quality is loose, also can form multilevel hierarchy between the hollow nanospheres;
4. organic group is evenly distributed in the middle of the shell wall in the middle of Zhi Bei the material, helps further functionalization.
5. Zhi Bei hollow nanosilica white sphere is with a wide range of applications in fields such as medicine (gene) slowly-releasing, catalysis, biological medicine, artificial cell, absorption and separation.
6. synthetic mechanism is the micelle-forming concentration (CMC) of adding reduction triblock copolymer polymkeric substance F127 in the aqueous solution by inorganic salt, form single micella, anionic existence can stop micellar further to be assembled, after adding the organosilicon source, silicon source hydrolytic polymerization is wrapped in the nano level silicon oxide shell of the outside formation of single micella, and after the high-temperature water thermal treatment, micella inwardly shrinks, the further polymerization of silicon oxide deviates to form the hollow nanosilica white sphere behind the polymkeric substance.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) photo among the embodiment 1;
Fig. 2 is the nitrogen adsorption-desorption isothermal curve among the embodiment 1;
Fig. 3 is transmission electron microscope (TEM) photo among the embodiment 6;
Fig. 4 is the nitrogen adsorption-desorption isothermal curve among the embodiment 6.
Embodiment
A kind of preparation method of hollow nanosilica white sphere, concrete preparation process is as follows:
1) the inorganic electrolyte dissolving with structure directing agent, water and different concns forms settled solution I;
2) under vigorous stirring, silicon source presoma is added in the solution I, behind the 10～48h that stirs the mixture under 12～40 ℃, mixture is changed in the reactor, in 60～120 ℃ of hydrothermal crystallizing 24～48h;
3) product after filtration, wash filtrate clarification back drying at room temperature;
4. the structure directing agent of products therefrom extracts 6h with the mixing solutions of ethanol and HCl in 60～70 ℃.The 1g product adds 200mL ethanol and 2g concentrated hydrochloric acid, makes product of the present invention.
Embodiment 1
Under 20 ℃ of stirrings, 0.8g F127 is dissolved in the NaH that 28mL concentration is 0.04M
2PO
4-Na
2HPO
4(pH=6.86) of buffered soln, treat solution clarification after, add 2.7g (MeO)
3SiCH
2CH
2Si (OMe)
3, and in 20 ℃ of aging 24h of stirring.The mother liquor that makes changes reactor in 100 ℃ of crystallization 24h.Product after filtration, after the washing, drying, with the mixing solutions of dehydrated alcohol and HCl in 70 ℃ of extraction 24h.Product after filtration, after the drying, obtain white block lightweight solid.
Adopt FEI Tecnai G respectively
2Spirit transmission electron microscope (TEM), the ASAP2020 specific surface analyser of U.S. Merck ﹠ Co., Inc characterizes sample.
Fig. 1 has provided transmission electron microscope (TEM) photo of products obtained therefrom in the present embodiment 1; TEM result shows that the product that obtains is a hollow nanospheres, uniform particle diameter, good dispersity; The hollow nanospheres size is 18nm, internal diameter 8nm, wall thickness 10nm.The BET specific surface area of material is 894m
2g
-1Pore volume is 2.40cm
3g
-1
Embodiment 2
Adopt the preparation process of embodiment 1, be, add 1.08g (MeO) with its difference
3SiCH
2CH
2Si (OMe)
3As the silicon source.Obtain white block lightweight solid.Characterizing method is the same.TEM result shows that the product that obtains is a hollow nanospheres, and uniform particle diameter is better dispersed; The hollow nanospheres size is 15nm, internal diameter 8nm, wall thickness 7nm.The BET specific surface area of material is 969m
2g
-1Pore volume is 2.91cm
3g
-1
Embodiment 3
Adopt the preparation process of embodiment 1, be, 0.8g F127 is dissolved in the NaH that 28mL concentration is 0.08M with its difference
2PO
4-Na
2HPO
4(pH=6.86) of buffered soln adds 3.78g (MeO)
3SiCH
2CH
2Si (OMe)
3As the silicon source.Obtain white block lightweight solid.Characterizing method is the same.TEM result shows that the product that obtains is a hollow nanospheres, and uniform particle diameter is better dispersed; The hollow nanospheres size is 9nm, internal diameter 4nm, wall thickness 5nm.The BET specific surface area of material is 788m
2g
-1Pore volume is 2.32cm
3g
-1
Embodiment 4
Adopt the preparation process of embodiment 1, be, 0.8g F127 is dissolved in the NaH that 28mL concentration is 0.08M with its difference
2PO
4-Na
2HPO
4(pH=6.86) of buffered soln adds 1.62g (MeO)
3SiCH
2CH
2Si (OMe)
3As the silicon source.Obtain white block lightweight solid.Characterizing method is the same.TEM result shows that the product that obtains is a hollow nanospheres, and uniform particle diameter is better dispersed; The hollow nanospheres size is 12nm, internal diameter 4nm, wall thickness 8nm.The BET specific surface area of material is 967m
2g
-1Pore volume is 3.23cm
3g
-1
Embodiment 5
Adopt the preparation process of embodiment 1, be, 0.8g F127 is dissolved in the NaH that 28mL concentration is 0.10M with its difference
2PO
4-Na
2HPO
4(pH=6.86) of buffered soln.Obtain white powder lightweight solid.Characterizing method is the same.TEM result shows that the product that obtains is a hollow nanospheres, and uniform particle diameter is better dispersed; The hollow nanospheres size is 13nm, internal diameter 6nm, wall thickness 7nm.The BET specific surface area of material is 734m
2g
-1Pore volume is 2.80cm
3g
-1
Embodiment 6
Adopt the preparation process of embodiment 1, be, 0.8g F127 is dissolved in 28mL distilled water, the 1.38g NaAc of adding (0.06M pH=7.92) with its difference.Obtain white block lightweight solid.Characterizing method is the same.TEM result shows that the product that obtains is a hollow nanospheres, and uniform particle diameter is dispersed fabulous; The hollow nanospheres size is 20nm, internal diameter 12nm, wall thickness 8nm.The BET specific surface area of material is 815m
2g
-1Pore volume is 2.41cm
3g
-1
Embodiment 7
Adopt the preparation process of embodiment 1, be, 0.8g F127 is dissolved in 28mL distilled water, the 0.89g Na of adding with its difference
2CO
3(0.03M pH=11.35).Obtain white block lightweight solid.Characterizing method is the same.TEM result shows that the product that obtains is a hollow nanospheres, and uniform particle diameter is dispersed relatively poor; The hollow nanospheres size is 11nm, internal diameter 5nm, wall thickness 6nm.The BET specific surface area of material is 575m
2g
-1Pore volume is 2.08cm
3g
-1
Embodiment 8
Adopt the preparation process of embodiment 1, be, 0.8g F127 is dissolved in 28mL distilled water, the 1.19g Na of adding with its difference
2SO
4(0.03M pH=5.80).Obtain white powder lightweight solid.Characterizing method is the same.TEM result shows that the product that obtains is a hollow nanospheres, and uniform particle diameter is better dispersed; The hollow nanospheres size is 16nm, internal diameter 8nm, wall thickness 8nm.The BET specific surface area of material is 908m
2g
-1Pore volume is 2.50cm
3g
-1
Embodiment 9
Adopt the preparation process of embodiment 1, be that with its difference the mother liquor that makes changes reactor in 60 ℃ of crystallization 24h.Obtain white powder lightweight solid.Characterizing method is the same.TEM result shows that the product that obtains is a hollow nanospheres, and uniform particle diameter is better dispersed; The hollow nanospheres size is 16nm, internal diameter 8nm, wall thickness 8nm.The BET specific surface area of material is 1038m
2g
-1Pore volume is 2.55cm
3g
-1
Embodiment 10
Adopt the preparation process of embodiment 1, be that with its difference the mother liquor that makes changes reactor in 120 ℃ of crystallization 24h.Obtain white block lightweight solid.Characterizing method is the same.TEM result shows that the product that obtains is a hollow nanospheres, and uniform particle diameter is better dispersed; The hollow nanospheres size is 22nm, internal diameter 10nm, wall thickness 12nm.The BET specific surface area of material is 699m
2g
-1Pore volume is 2.71cm
3g
-1
Embodiment 11
Adopt the preparation process of embodiment 1, be, stir aging 24h in 12 ℃ with its difference.Obtain white block lightweight solid.Characterizing method is the same.TEM result shows that the product that obtains is a hollow nanospheres, and particle diameter is than homogeneous, and is dispersed relatively poor; The hollow nanospheres size is 20nm, internal diameter 10nm, wall thickness 10nm.The BET specific surface area of material is 1125m
2g
-1Pore volume is 1.68cm
3g
-1
Embodiment 12
Adopt the preparation process of embodiment 1, be, stir aging 24h in 40 ℃ with its difference.Obtain white block lightweight solid.Characterizing method is the same.TEM result shows that the product that obtains is a hollow nanospheres, and uniform particle diameter is better dispersed; The hollow nanospheres size is 15nm, internal diameter 6nm, wall thickness 9nm.The BET specific surface area of material is 804m
2g
-1Pore volume is 1.88cm
3g
-1
Embodiment 13
Adopt the preparation process of embodiment 1, be, add 3.04g methyl silicate TMOS[(MeO) with its difference
4Si] as the silicon source.Obtain white block lightweight solid.Obtain white block lightweight solid.Characterizing method is the same.TEM result shows that the product that obtains is a hollow nanospheres, and uniform particle diameter is better dispersed; The hollow nanospheres size is 13nm, internal diameter 8nm, wall thickness 5nm.The BET specific surface area of material is 341m
2g
-1Pore volume is 1.95cm
3g
-1
Claims (5)
1. the preparation method of a hollow nanosilica white sphere is characterized in that: can operate as follows,
(1) polymer micelle prepares, and structure directing agent triblock copolymer F127 is dissolved in the inorganic salt solution of pH=6-8; Anionic concentration in the inorganic salt solution is 0.005～0.1M;
(2) hydrolytic polymerization in silicon source: under agitation in the intrafascicular adding silicon of polymer latex source, stir and make mother liquor, the whipping temp scope is 12～40 ℃ in the building-up process, churning time 10～48h;
The mol ratio of each component is: triblock copolymer: inorganic salt: silicon source=1～2.2: 504～2520: 100～353;
(3) hydrothermal crystallizing: the mother liquor that step (2) is made is at 60～120 ℃ of hydrothermal crystallizing 24～48h;
(4) drying: the product pumping rate with behind step (3) hydrothermal crystallizing washes drying at room temperature with water;
(5) deviate from structure directing agent:, make product of the present invention with the dried product 10～30h that in the tart ethanolic soln, refluxes.
2. according to the preparation method of the described hollow nanosilica white sphere of claim 1, it is characterized in that: described structure directing agent for adopt poly-oxyethylene be hydrophilic section, poly-propylene oxide be hydrophobic section [(EO)
106(PO)
70(EO)
106] triblock copolymer F127.
3. according to the preparation method of the described hollow nanosilica white sphere of claim 1, it is characterized in that: described inorganic salt solution is the aqueous solution of SODIUM PHOSPHATE, MONOBASIC-disodium hydrogen phosphate buffer solution, inorganic electrolyte sodium acetate, sodium sulfate or yellow soda ash, and anion concentration is 0.02～0.1M.
4. according to the preparation method of the described hollow nanosilica white sphere of claim 1, it is characterized in that: described silicon source is the organosilane BTME[(MeO of ethane bridging)
3SiCH
2CH
2Si (OMe)
3] or methyl silicate TMOS[(MeO)
4Si].
5. according to the preparation method of the described hollow nanosilica white sphere of claim 1, it is characterized in that: product reflux course 1.0g product in the tart ethanolic soln adopts the 50-400mL ethanolic soln in the described step 5), contains 1-4g HCl in the ethanolic soln.
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| CN102951638A (en) * | 2012-11-30 | 2013-03-06 | 上海大学 | Hydrothermal synthesis method for hollow carbon nanomaterials |
| CN103803556A (en) * | 2012-11-05 | 2014-05-21 | 中国科学院大连化学物理研究所 | Organic modified hydrophobic nano silica hollow ball and preparation method thereof |
| JP2017508694A (en) * | 2013-12-19 | 2017-03-30 | ザ ユニバーシティー オブ クイーンズランド | Method for synthesizing silica vesicle and use thereof |
| CN112262105A (en) * | 2018-06-15 | 2021-01-22 | 国立大学法人东北大学 | Method for producing core-shell porous silica particles |
| CN112744818A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Carbon-silicon oxide compound and preparation method thereof |
| CN114506849A (en) * | 2022-02-24 | 2022-05-17 | 山东国瓷功能材料股份有限公司 | Hollow silicon dioxide microparticle, preparation method thereof and obtained product |
| CN115196640A (en) * | 2022-07-08 | 2022-10-18 | 太原理工大学 | Coal gangue-based mesoporous silicon oxide material and preparation method thereof |
| CN115449255A (en) * | 2022-10-20 | 2022-12-09 | 浦诺菲新材料有限公司 | Modified silicon dioxide nano-particles and preparation method thereof, super-hydrophobic polyurethane coating liquid and super-hydrophobic automobile paint surface protective film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2747669B1 (en) * | 1996-04-22 | 1998-05-22 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF HOLLOW SILICA PARTICLES |
| US6334988B1 (en) * | 1998-08-21 | 2002-01-01 | The University Of Vermont And State Agricultural College | Mesoporous silicates and method of making same |
| CN1244492C (en) * | 2003-11-19 | 2006-03-08 | 中国科学院金属研究所 | Synthesis method of monodispersed nano-mesopore silicon dioxide material |
| CN1268545C (en) * | 2004-06-24 | 2006-08-09 | 华东理工大学 | Nano-silicon dioxide used for nanometer standard granule |
-
2007
- 2007-07-18 CN CN2007100121580A patent/CN101348254B/en not_active Expired - Fee Related
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| CN103803556A (en) * | 2012-11-05 | 2014-05-21 | 中国科学院大连化学物理研究所 | Organic modified hydrophobic nano silica hollow ball and preparation method thereof |
| CN103803556B (en) * | 2012-11-05 | 2016-03-23 | 中国科学院大连化学物理研究所 | A kind of dewatering nano silicon oxide hollow ball of organic decoration and preparation thereof |
| CN102951638B (en) * | 2012-11-30 | 2014-12-31 | 上海大学 | Hydrothermal synthesis method for hollow carbon nanomaterials |
| CN102951638A (en) * | 2012-11-30 | 2013-03-06 | 上海大学 | Hydrothermal synthesis method for hollow carbon nanomaterials |
| JP2017508694A (en) * | 2013-12-19 | 2017-03-30 | ザ ユニバーシティー オブ クイーンズランド | Method for synthesizing silica vesicle and use thereof |
| US11033507B2 (en) | 2013-12-19 | 2021-06-15 | The University Of Queensland | Method of synthesis of silica vesicles and use thereof |
| CN112262105B (en) * | 2018-06-15 | 2023-08-11 | 国立大学法人东北大学 | Method for producing core-shell porous silica particles |
| CN112262105A (en) * | 2018-06-15 | 2021-01-22 | 国立大学法人东北大学 | Method for producing core-shell porous silica particles |
| CN112744818A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Carbon-silicon oxide compound and preparation method thereof |
| CN112744818B (en) * | 2019-10-30 | 2022-08-12 | 中国石油化工股份有限公司 | Carbon-silicon oxide compound and preparation method thereof |
| CN114506849A (en) * | 2022-02-24 | 2022-05-17 | 山东国瓷功能材料股份有限公司 | Hollow silicon dioxide microparticle, preparation method thereof and obtained product |
| CN115196640A (en) * | 2022-07-08 | 2022-10-18 | 太原理工大学 | Coal gangue-based mesoporous silicon oxide material and preparation method thereof |
| CN115196640B (en) * | 2022-07-08 | 2023-05-12 | 太原理工大学 | Gangue-based mesoporous silica material and preparation method thereof |
| CN115449255A (en) * | 2022-10-20 | 2022-12-09 | 浦诺菲新材料有限公司 | Modified silicon dioxide nano-particles and preparation method thereof, super-hydrophobic polyurethane coating liquid and super-hydrophobic automobile paint surface protective film |
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