CN104556071A - Porous silica preparation method and application of porous silica - Google Patents
Porous silica preparation method and application of porous silica Download PDFInfo
- Publication number
- CN104556071A CN104556071A CN201410843300.6A CN201410843300A CN104556071A CN 104556071 A CN104556071 A CN 104556071A CN 201410843300 A CN201410843300 A CN 201410843300A CN 104556071 A CN104556071 A CN 104556071A
- Authority
- CN
- China
- Prior art keywords
- porous silica
- preparation
- porous
- silicon
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides a porous silica preparation method which comprises steps as follows: 1), water glass is taken as a raw material, and a silica ball core is prepared after ion exchange, seed crystal preparation and particle growth; 2), a template agent and a silicon source are added into the silica ball core, the mixture is mixed and stirred, and a porous shell layer is grown on the silica ball core; 3), a particle containing the silica ball core and the porous shell layer are subjected to filtering, washing, drying, calcination or organic solvent extraction, and a porous silica particle is prepared. By means of the porous silica preparation method, the porous silica particle with very high specific surface area, good chemical activity and adsorption characteristic can be prepared, can be applied to the field of chemical-mechanical polishing solution abrasive, chemical catalysts, medicine carriers and the like and is applicable to large-scale industrial production.
Description
Technical field
The invention belongs to field of inorganic nano-material preparation, relate to a kind of preparation method and application thereof of porous silica, be specifically related to a kind of preparation method being applicable to the porous silica silicon grain of industrial scale operation.
Background technology
Porous silica silicon grain has nucleocapsid structure as one, particle diameter can reach nano level particle, comprises solid ball part and porous crust part.Because of it, to have specific surface area large, excellent adsorption, and chemically reactive is comparatively strong, advantages such as bio-compatibility is good and be applied to multiple different field.These fields mainly comprise chemically machinery polished, chemical industry catalysis, drug controlled release, sensor etc.At present, porous silica silicon grain contains a large amount of silicone hydroxyl mainly through rich surface, easily with the silane coupling agent generation condensation reaction containing organic group, in particle, introduce various different organic group by this method and carry out modification, its range of application can be extended to broader field.
As a kind of novel nano particulate material had a extensive future, the synthesis of porous silica is prepared into the large obstacle for limiting its application, finds a kind of cheap and to be suitable for again mass-produced synthesis preparation method be a current large problem in the urgent need to address.The people such as Stober make solvent with alcohols, and ammonia makes catalyzer, be hydrolyzed the method for then assembling and prepare the adjustable silica sphere of particle diameter, but the starting material of costliness make it and are not suitable for industrial production by making tetraethyl orthosilicate.Simultaneously, in order to prepare the silica dioxide granule containing pore passage structure, normally occur to act synergistically with the amphiphilic species such as tensio-active agent and silicon source material and form rod-shaped micelle in the solution, then silicon-dioxide grows at micellar surface, progressively forms the spheroid with pore passage structure.But mostly the present stage preparation of porous silica is with surfactants as template, and select organosilicon to do silicon source, complete under stober system, these class methods are not suitable for a large amount of production.Therefore, be necessary to carry out further research and exploitation to the synthesis preparation of porous silica.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of preparation method and application thereof of porous silica, for solving in prior art the problem of preparation method lacking the industrial production demand that is applicable to, low production cost, the simple porous silica of good performance of production technique.
For achieving the above object and other relevant objects, the invention provides a kind of preparation method of porous silica, comprise the steps:
1) take water glass as raw material, after ion-exchange, JZPD capsule, particle growth, obtained silicon-dioxide ball;
Preferably, described water glass is industrial waterglass (Na
2omSiO
2nH
2o).
Wherein, described modulus m is the molar ratio of silicon oxide and sodium oxide, and m is 2-4; Modulus n is the number of Bound moisture.
Preferably, the concentration of described water glass is 1-10%.
Preferably, described ion-exchange refers to and water glass is prepared silicic acid after ion exchange resin generation ion-exchange.
More preferably, described silicic acid of preparing is the water glass solution of 1-10% by concentration, after ion exchange resin generation ion-exchange, prepares the silicate solution that concentration is 1-10%.
Preferably, described JZPD capsule refers to and is at high temperature polymerized generation crystal seed by preparing silicic acid after ion-exchange.
More preferably, described JZPD capsule condition is: temperature of reaction: 70-100 DEG C; Alr mode: Keep agitation; Churning time: 0.5-12h; PH value: 7-12; Adjust ph reagent: the NaOH aqueous solution.
More preferably, the particle diameter of the crystal seed of described preparation is 0.1-5nm.
Preferably, described particle growth refers to drip in crystal seed prepares silicic acid through ion-exchange, makes crystal seed further growth.
More preferably, described particle growth condition is: temperature of reaction: 70-100 DEG C; The drop rate of silicic acid: 500-1000mL/h; PH value: 7-12; Adjust ph reagent: the NaOH aqueous solution; Alr mode: Keep agitation; Churning time: 6-24h.
The particle diameter that described particle finally grows depends on the concentration of crystal seed and the addition of silicic acid.
Described silicic acid drop rate and solution evaporation speed are consistent.
Preferably, the particle diameter of described silicon-dioxide ball is at 50-500nm.
Preferably, the form of described silicon-dioxide ball is colloidal sol (colloidal solution).
2) in step 1) in obtained silicon-dioxide ball, add template, and add silicon source, after mix and blend, thus grow porous crust on silicon-dioxide ball;
Preferably, described template is structure directing agent.
More preferably, described structure directing agent is tensio-active agent.
Optimally, described tensio-active agent is selected from cetyl trimethylammonium bromide (CTAB), octadecyl trimethoxysilane (C
18tMS) any one in.Described tensio-active agent take water as solvent.
More preferably, the mass percent concentration of described structure directing agent is 0.1-20%.
Preferably, described silicon source is the silicic acid that water glass is prepared through ion-exchange.
More preferably, the mol ratio of described structure directing agent and silicic acid is: 0.01-0.5:1.
More preferably, the reaction conditions of described growth porous crust is: silicic acid drop rate: 1-20ml/min; Temperature of reaction: 80-100 DEG C; Churning time: 20-30h.
Preferably, the thickness of described porous crust is 10-100nm.
3) following arbitrary step preparation is selected from:
A, by step 2) in the obtained particle comprising silicon-dioxide ball and porous crust, through repeating to filter, after washing, dry, calcining, obtained porous silica silicon grain;
Preferably, centrifuging is filtered into described in.
More preferably, described centrifugal rotational speed is 8000-15000r/min; Centrifugation time is 1-2 minute.
Preferably, described washing is the precipitation after centrifuging be scattered in water to carry out supersound washing.
More preferably, the described supersound washing time is 1-3min.Optimally, the described supersound washing time is 1min.
Preferably, the multiplicity of described filtration and washing is 2-3 time.
Preferably, described drying mode is in drying in oven, and described bake out temperature is 110-130 DEG C, and drying time is 0.5-1.5 hour.
More preferably, described bake out temperature is 120 DEG C, and drying time is 1 hour.
Preferably, described calcining manners is two-section calcining method.Described two-section calcining method can remove the tensio-active agent in porous silica silicon grain.
More preferably, the reaction conditions of described two-section calcining method is: first paragraph temperature of reaction: 150-300 DEG C, reaction times: 0.5-1.0h, temperature rise rate: 1-50 DEG C/min; Second segment temperature of reaction: 400-600 DEG C, the reaction times: 2-6h; Temperature rise rate: 1-50 DEG C/min.
Optimally, the reaction conditions of described two-section calcining method is: first paragraph temperature of reaction: 200-250 DEG C, reaction times: 0.5h, temperature rise rate: 5-30 DEG C/min; Second segment temperature of reaction: 450-550 DEG C, the reaction times: 4h; Temperature rise rate: 5-30 DEG C/min.
B, by step 2) in the obtained particle comprising silicon-dioxide ball and porous crust, through organic solvent extraction, obtained porous silica silicon grain.
Preferably, described organic solvent extracting is taken as: the mixing solutions precipitation after centrifuging being scattered in hydrochloric acid and ethanol carries out supersound washing, and after repeating filtration, washing, the supernatant liquid after centrifugal becomes colorless, by sedimentation and filtration, dry.
More preferably, described centrifugal rotational speed is 8000-15000r/min; Centrifugation time is 1-2 minute.
More preferably, the mass ratio of described hydrochloric acid and ethanol is 1:4-6.Optimally, the mass ratio of described hydrochloric acid and ethanol is 1:5.
More preferably, the described supersound washing time is 4-6min.Optimally, the described supersound washing time is 5min.
More preferably, the multiplicity of described filtration and washing is 2-3 time.
Preferably, described drying mode is in drying in oven, and described bake out temperature is 110-130 DEG C, and drying time is 0.5-1.5 hour.
More preferably, described bake out temperature is 120 DEG C, and drying time is 1 hour.
The present invention further discloses and adopts a kind of porous silica silicon grain that in the present invention, method is obtained, and for the purposes in chemical mechanical polishing liquid abrasive material, chemical catalyst, pharmaceutical carrier.
A kind of porous silica silicon grain that in the present invention, method obtains is the nuclear-shell structure type spherical comprising solid ball and porous crust.The particle diameter of described porous silica silicon grain is 30-600nm, and specific surface area is 300-1000m
2/ g.
As mentioned above, the preparation method of a kind of porous silica provided by the invention, ion exchange method is adopted to prepare silicon-dioxide ball, then structure directing agent is made with tensio-active agent, add silicic acid interaction and produce duct, grow porous crust, thus prepare the nuclear-shell structure type spherical comprising solid ball and porous crust.This kind of method is prepared porous silica silicon grain and is possessed high specific surface area, good chemically reactive and characterization of adsorption, can be applicable to chemical mechanical polishing liquid abrasive material, chemical catalyst, and the field such as pharmaceutical carrier.
In addition, in the preparation method of porous silica silicon grain provided by the invention, cheap water glass is adopted to make starting material, greatly reduce the cost of manufacture of porous silica silicon grain, adopt ion exchange method growth particle, can directly apply mechanically the existing equipment of industrial product and production technique, without the need to developing new instrument and supplies, effectively save manpower and physical resources, and reduced production cost, meet industrial demand.
Embodiment
Set forth the present invention further below in conjunction with specific embodiment, should be understood that these embodiments are only not used in for illustration of the present invention and limit the scope of the invention.
Below by way of specific specific examples, embodiments of the present invention are described, those skilled in the art the content disclosed by this specification sheets can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this specification sheets also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
The reagent used in following examples and instrument, all can commercially obtain.
Embodiment 1
The preparation process of porous silica silicon grain is as follows:
(1) be raw material with water glass, obtaining silicic acid by ion-exchange, is alkaline environment in pH value, prepares crystal seed, particle growth, prepare 80nm silicon-dioxide ball with high temperature polymerization under temperature of reaction 100 DEG C, silicic acid drop rate 1000ml/h condition.
(2) get the colloidal solution 50mL of above-mentioned 80nm silicon-dioxide ball, the solution 15mL added containing CTAB 0.6g mixes, and adds active silicic acid 110mL at 100 DEG C with 20ml/min speed, stirs 24h, thus grow porous crust on silicon-dioxide ball.Wherein, the mol ratio of CTAB and active silicic acid is 0.06:1.
(3) solution of the particle of silicon-dioxide ball and porous crust will be comprised, after filtration, washing, dry, obtain porous silica silicon grain after calcining.Wherein, calcining adopts two-section calcining method, and reaction conditions is: first paragraph temperature of reaction: 250 DEG C, the reaction times: 0.5h, temperature rise rate: 30 DEG C/min; Second segment temperature of reaction: 550 DEG C, the reaction times: 4h; Temperature rise rate: 30 DEG C/min.
Adopt DLS dynamic light scattering to measure the particle diameter of solid ball and porous silica silicon grain the porous silica silicon grain of acquisition, and adopt BET nitrogen adsorption method to measure the specific surface area of particle.Result is as shown in table 1.
Embodiment 2
The preparation process of porous silica silicon grain is as follows:
(1) take water glass as raw material, obtaining silicic acid by ion-exchange, is alkaline environment in pH value, prepares crystal seed, particle growth with high temperature polymerization under temperature of reaction 100 DEG C, silicic acid drop rate 1000ml/h condition, again after ultrafiltration and concentration, prepare 80nm silicon-dioxide ball.
(2) get the colloidal solution 50mL of above-mentioned 80nm silicon-dioxide ball, the solution 15mL added containing CTAB 0.6g mixes, and adds active silicic acid 150mL at 100 DEG C with 20ml/min speed, stirs 24h, thus grow porous crust on silicon-dioxide ball.Wherein, the mol ratio of CTAB and active silicic acid is 0.04:1.
(3) solution of the particle of silicon-dioxide ball and porous crust will be comprised, after filtration, washing, dry, obtain porous silica silicon grain after calcining.Wherein, calcining adopts two-section calcining method, and reaction conditions is: first paragraph temperature of reaction: 250 DEG C, the reaction times: 0.5h, temperature rise rate: 30 DEG C/min; Second segment temperature of reaction: 550 DEG C, the reaction times: 4h; Temperature rise rate: 30 DEG C/min.
Adopt DLS dynamic light scattering to measure the particle diameter of solid ball and porous silica silicon grain the porous silica silicon grain of acquisition, and adopt BET nitrogen adsorption method to measure the specific surface area of particle.Result is as shown in table 1.
Embodiment 3
The preparation process of porous silica silicon grain is as follows:
(1) take water glass as raw material, obtaining silicic acid by ion-exchange, is alkaline environment in pH value, prepares crystal seed, particle growth with high temperature polymerization under temperature of reaction 100 DEG C, silicic acid drop rate 1000ml/h condition, again after ultrafiltration and concentration, prepare 80nm silicon-dioxide ball.
(2) get the colloidal solution 50mL of above-mentioned 80nm silicon-dioxide ball, the solution 15mL added containing CTAB 0.8g mixes, and adds active silicic acid 110mL at 100 DEG C with 20ml/min speed, stirs 24h, thus grow porous crust on silicon-dioxide ball.Wherein, the mol ratio of CTAB and active silicic acid is 0.08:1.
(3) solution of the particle of silicon-dioxide ball and porous crust will be comprised, after filtration, washing, dry, obtain porous silica silicon grain after calcining.Wherein, calcining adopts two-section calcining method, and reaction conditions is: first paragraph temperature of reaction: 250 DEG C, the reaction times: 0.5h, temperature rise rate: 30 DEG C/min; Second segment temperature of reaction: 550 DEG C, the reaction times: 4h; Temperature rise rate: 30 DEG C/min.
Adopt DLS dynamic light scattering to measure the particle diameter of solid ball and porous silica silicon grain the porous silica silicon grain of acquisition, and adopt BET nitrogen adsorption method to measure the specific surface area of particle.Result is as shown in table 1.
Embodiment 4
The preparation process of porous silica silicon grain is as follows:
(4) take water glass as raw material, obtaining silicic acid by ion-exchange, is alkaline environment in pH value, prepares crystal seed, particle growth with high temperature polymerization under temperature of reaction 70 DEG C, silicic acid drop rate 500ml/h condition, again after ultrafiltration and concentration, prepare 50nm silicon-dioxide ball.
(5) get the colloidal solution 50mL of above-mentioned 50nm silicon-dioxide ball, add containing C
18the solution 15mL of TMS 0.6g mixes, and adds active silicic acid 110mL at 70 DEG C with 1ml/min speed, stirs 30h, thus grow porous crust on silicon-dioxide ball.Wherein, C
18the mol ratio of TMS and active silicic acid is 0.06:1.
(6) solution of the particle of silicon-dioxide ball and porous crust will be comprised, after filtration, washing, dry, obtain porous silica silicon grain after calcining.Wherein, calcining adopts two-section calcining method, and reaction conditions is: first paragraph temperature of reaction: 200 DEG C, the reaction times: 0.5h, temperature rise rate: 5 DEG C/min; Second segment temperature of reaction: 450 DEG C, the reaction times: 4h; Temperature rise rate: 5 DEG C/min.
Adopt DLS dynamic light scattering to measure the particle diameter of solid ball and porous silica silicon grain the porous silica silicon grain of acquisition, and adopt BET nitrogen adsorption method to measure the specific surface area of particle.Result is as shown in table 1.
Embodiment 5
The preparation process of porous silica silicon grain is as follows:
(7) take water glass as raw material, obtaining silicic acid by ion-exchange, is alkaline environment in pH value, prepares crystal seed, particle growth with high temperature polymerization under temperature of reaction 100 DEG C, silicic acid drop rate 1000ml/h condition, again after ultrafiltration and concentration, prepare 500nm silicon-dioxide ball.
(8) get the colloidal solution 50mL of above-mentioned 500nm silicon-dioxide ball, add containing C
18the solution 15mL of TMS 0.6g mixes, and adds active silicic acid 110mL at 100 DEG C with 20ml/min speed, stirs 20h, thus grow porous crust on silicon-dioxide ball.Wherein, C
18the mol ratio of TMS and active silicic acid is 0.06:1.
(9) solution of the particle of silicon-dioxide ball and porous crust will be comprised, after filtration, washing, dry, obtain porous silica silicon grain after calcining.Wherein, calcining adopts two-section calcining method, and reaction conditions is: first paragraph temperature of reaction: 250 DEG C, the reaction times: 0.5h, temperature rise rate: 20 DEG C/min; Second segment temperature of reaction: 550 DEG C, the reaction times: 4h; Temperature rise rate: 20 DEG C/min.
Adopt DLS dynamic light scattering to measure the particle diameter of solid ball and porous silica silicon grain the porous silica silicon grain of acquisition, and adopt BET nitrogen adsorption method to measure the specific surface area of particle.Result is as shown in table 1.
The particle diameter of table 1 porous silica silicon sample and specific surface area thereof
| Project | Particle diameter (nm) | Specific surface area (m 2/g) |
| Ball 1-3 | 78 | 83 |
| Embodiment 1 | 102 | 720 |
| Embodiment 2 | 114 | 711 |
| Embodiment 3 | 144 | 834 |
| Ball 4 | 50 | 102 |
| Embodiment 4 | 90 | 911 |
| Ball 5 | 500 | 38 |
| Embodiment 5 | 508 | 423 |
Result as can be seen from table 1, in the process preparing porous silica silicon grain, all can increase the thickness of shell by the consumption increasing silicic acid and tensio-active agent.From embodiment 1-3 data, increase silicic acid consumption, because particle diameter increases, specific surface area decline to a certain degree can be caused, and the consumption increasing tensio-active agent can significantly improve specific surface area.
In sum, the preparation method of a kind of porous silica provided by the invention, can prepare and possess high specific surface area, the porous silica silicon grain of good chemically reactive and characterization of adsorption, can be applicable to chemical mechanical polishing liquid abrasive material, chemical catalyst, and the field such as pharmaceutical carrier, and be applicable to the demand of large-scale commercial production.So the present invention effectively overcomes various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (10)
1. a preparation method for porous silica, comprises the steps:
1) take water glass as raw material, after ion-exchange, JZPD capsule, particle growth, obtained silicon-dioxide ball;
2) in step 1) in obtained silicon-dioxide ball, add template, and add silicon source, after mix and blend, thus grow porous crust on silicon-dioxide ball;
3) following arbitrary step preparation is selected from:
A) by step 2) in the obtained particle comprising silicon-dioxide ball and porous crust, through repeating to filter, after washing, dry, calcining, obtained porous silica silicon grain;
B) by step 2) in the obtained particle comprising silicon-dioxide ball and porous crust, through organic solvent extraction, obtained porous silica silicon grain.
2. the preparation method of a kind of porous silica according to claim 1, is characterized in that, step 1) in, described JZPD capsule condition is: temperature of reaction: 70-100 DEG C; Alr mode: Keep agitation; Churning time: 0.5-12h; PH value: 7-12; Adjust ph reagent: the NaOH aqueous solution.
3. the preparation method of a kind of porous silica according to claim 1, is characterized in that, step 1) in, described particle growth condition is: temperature of reaction: 70-100 DEG C; The drop rate of silicic acid: 500-1000mL/h; PH value: 7-12; Adjust ph reagent: the NaOH aqueous solution; Alr mode: Keep agitation; Churning time: 6-24h.
4. the preparation method of a kind of porous silica according to claim 1, is characterized in that, step 2) in, described template is structure directing agent; The mass percent concentration of described structure directing agent is 0.1-20%; Described silicon source is the silicic acid that water glass is prepared through ion-exchange; The mol ratio of described structure directing agent and silicic acid is: 0.01-0.5:1.
5. the preparation method of a kind of porous silica according to claim 1, is characterized in that, step 2) in, the reaction conditions of described growth porous crust is: silicic acid drop rate: 1-20ml/min; Temperature of reaction: 80-100 DEG C; Churning time: 20-30h.
6. the preparation method of a kind of porous silica according to claim 1, is characterized in that, step 3) in, described preparation process A) also to comprise any one of following condition or multinomial:
I) be filtered into centrifuging described in, described centrifugal rotational speed is 8000-15000r/min, and centrifugation time is 1-2 minute;
II) described washing is the precipitation after centrifuging be scattered in water to carry out supersound washing, and the described supersound washing time is 1-3min;
III) multiplicity of described filtration and washing is 2-3 time;
IV) described drying mode is in drying in oven, and described bake out temperature is 110-130 DEG C, and drying time is 0.5-1.5 hour;
V) described calcining manners is two-section calcining method; The reaction conditions of described two-section calcining method is: first paragraph temperature of reaction: 150-300 DEG C, the reaction times: 0.5-1.0h, temperature rise rate: 1-50 DEG C/min; Second segment temperature of reaction: 400-600 DEG C, the reaction times: 2-6h; Temperature rise rate: 1-50 DEG C/min.
7. the preparation method of a kind of porous silica according to claim 1, it is characterized in that, step 3) in, described preparation process B) described in organic solvent extracting be taken as: the mixing solutions precipitation after centrifuging being scattered in hydrochloric acid and ethanol carries out supersound washing, after repeating filtration, washing, supernatant liquid after centrifugal becomes colorless, by sedimentation and filtration, dry.
8. the preparation method of a kind of porous silica according to claim 7, is characterized in that, described organic solvent extraction also to comprise any one of following condition or multinomial:
I) described centrifugal rotational speed is 8000-15000r/min; Centrifugation time is 1-2 minute;
II) mass ratio of described hydrochloric acid and ethanol is 1:4-6;
III) the described supersound washing time is 4-6min;
IV) multiplicity of described filtration and washing is 2-3 time;
V) described drying mode is in drying in oven, described bake out temperature is 110-130 DEG C, and drying time is 0.5-1.5 hour.
9. a porous silica silicon grain, is obtained by preparation method described in claim arbitrary in claim 1-8.
10. a kind of porous silica silicon grain according to claim arbitrary in claim 1-8 is used for the purposes in chemical mechanical polishing liquid abrasive material, chemical catalyst, pharmaceutical carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410843300.6A CN104556071B (en) | 2014-12-29 | 2014-12-29 | A kind of preparation method and applications of porous silica |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410843300.6A CN104556071B (en) | 2014-12-29 | 2014-12-29 | A kind of preparation method and applications of porous silica |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104556071A true CN104556071A (en) | 2015-04-29 |
| CN104556071B CN104556071B (en) | 2017-01-04 |
Family
ID=53073278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410843300.6A Active CN104556071B (en) | 2014-12-29 | 2014-12-29 | A kind of preparation method and applications of porous silica |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104556071B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517217A (en) * | 2016-11-16 | 2017-03-22 | 嘉兴昊特新材料科技有限公司 | Preparation method of core-shell type silica sol |
| CN107140650A (en) * | 2017-04-07 | 2017-09-08 | 河南大学 | A kind of silica nanometer surfactant and preparation method thereof |
| CN107321313A (en) * | 2016-09-22 | 2017-11-07 | 武汉大学 | A kind of Surface porous core shell structure silica gel microball and its preparation method and application |
| CN111777074A (en) * | 2020-06-15 | 2020-10-16 | 冷水江三A新材料科技有限公司 | Preparation method of silicon dioxide for calcium ion efficient adsorbent |
| CN112473669A (en) * | 2020-11-30 | 2021-03-12 | 山西大学 | Low-temperature low-pressure direct hydrogenation catalyst for coal-based 1, 4-butynediol and preparation method thereof |
| CN114605923A (en) * | 2022-03-22 | 2022-06-10 | 深圳清华大学研究院 | Large-size silicon edge polishing solution and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435373A (en) * | 2002-12-05 | 2003-08-13 | 复旦大学 | Mesoporous material with three-D communicating pore structure and preparing process thereof |
| CN1715184A (en) * | 2004-06-28 | 2006-01-04 | 中国科学院理化技术研究所 | The preparation method of sphericity mesoporous silicon dioxide |
| CN101028927A (en) * | 2007-01-23 | 2007-09-05 | 吉林大学 | Production of porous silica with adjustable specific area and hydrothermal stability |
| CN101205067A (en) * | 2007-12-17 | 2008-06-25 | 李永兆 | Micro-spherical silica gel used for 20 to 100 micron liquid-phase chromatogram and method for making same |
| CN101704527A (en) * | 2009-12-15 | 2010-05-12 | 南开大学 | Monodisperse mesoporous silica nano-particle with controllable appearance and synthesis method thereof |
| CN101837983A (en) * | 2009-03-18 | 2010-09-22 | 中国石油天然气股份有限公司 | Method for synthesizing macroporous netlike spherical silicon dioxide material having mesoscopic structure |
| CN101993086A (en) * | 2010-12-20 | 2011-03-30 | 纪志勇 | Preparation method of mono-disperse silicon dioxide micro-spheres |
| CN102320612A (en) * | 2011-05-26 | 2012-01-18 | 东北师范大学 | Preparation method and application of fluorescence mesoporous silica nano-particle |
| CN102951648A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | Preparation method of nano silicon dioxide |
| CN103145133A (en) * | 2013-03-17 | 2013-06-12 | 上虞市佳和化工有限公司 | Preparation method of silicon sol |
| CN103449450A (en) * | 2013-08-29 | 2013-12-18 | 华南理工大学 | Preparation method of hollow mesoporous silica material |
-
2014
- 2014-12-29 CN CN201410843300.6A patent/CN104556071B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435373A (en) * | 2002-12-05 | 2003-08-13 | 复旦大学 | Mesoporous material with three-D communicating pore structure and preparing process thereof |
| CN1715184A (en) * | 2004-06-28 | 2006-01-04 | 中国科学院理化技术研究所 | The preparation method of sphericity mesoporous silicon dioxide |
| CN101028927A (en) * | 2007-01-23 | 2007-09-05 | 吉林大学 | Production of porous silica with adjustable specific area and hydrothermal stability |
| CN101205067A (en) * | 2007-12-17 | 2008-06-25 | 李永兆 | Micro-spherical silica gel used for 20 to 100 micron liquid-phase chromatogram and method for making same |
| CN101837983A (en) * | 2009-03-18 | 2010-09-22 | 中国石油天然气股份有限公司 | Method for synthesizing macroporous netlike spherical silicon dioxide material having mesoscopic structure |
| CN101704527A (en) * | 2009-12-15 | 2010-05-12 | 南开大学 | Monodisperse mesoporous silica nano-particle with controllable appearance and synthesis method thereof |
| CN101993086A (en) * | 2010-12-20 | 2011-03-30 | 纪志勇 | Preparation method of mono-disperse silicon dioxide micro-spheres |
| CN102320612A (en) * | 2011-05-26 | 2012-01-18 | 东北师范大学 | Preparation method and application of fluorescence mesoporous silica nano-particle |
| CN102951648A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | Preparation method of nano silicon dioxide |
| CN103145133A (en) * | 2013-03-17 | 2013-06-12 | 上虞市佳和化工有限公司 | Preparation method of silicon sol |
| CN103449450A (en) * | 2013-08-29 | 2013-12-18 | 华南理工大学 | Preparation method of hollow mesoporous silica material |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107321313A (en) * | 2016-09-22 | 2017-11-07 | 武汉大学 | A kind of Surface porous core shell structure silica gel microball and its preparation method and application |
| CN107321313B (en) * | 2016-09-22 | 2019-10-25 | 武汉大学 | A kind of Surface porous core-shell structure silica gel microball and its preparation method and application |
| CN106517217A (en) * | 2016-11-16 | 2017-03-22 | 嘉兴昊特新材料科技有限公司 | Preparation method of core-shell type silica sol |
| CN106517217B (en) * | 2016-11-16 | 2018-11-23 | 嘉兴昊特新材料科技有限公司 | A kind of preparation method of hud typed silica solution |
| CN107140650A (en) * | 2017-04-07 | 2017-09-08 | 河南大学 | A kind of silica nanometer surfactant and preparation method thereof |
| CN111777074A (en) * | 2020-06-15 | 2020-10-16 | 冷水江三A新材料科技有限公司 | Preparation method of silicon dioxide for calcium ion efficient adsorbent |
| CN112473669A (en) * | 2020-11-30 | 2021-03-12 | 山西大学 | Low-temperature low-pressure direct hydrogenation catalyst for coal-based 1, 4-butynediol and preparation method thereof |
| CN114605923A (en) * | 2022-03-22 | 2022-06-10 | 深圳清华大学研究院 | Large-size silicon edge polishing solution and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104556071B (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104556071A (en) | Porous silica preparation method and application of porous silica | |
| CN106279694B (en) | Nanometer cage-type silsesquioxane coupling agent and the method for preparing hybrid silica aeroge | |
| CN103193237B (en) | Mesoporous silica with yolk-shell structure and preparation method thereof | |
| CN104030294B (en) | A kind of preparation method of mesoporous silicon oxide coated single-walled carbon nano tube | |
| CN101804324B (en) | Modified molecular sieve with high selectivity to ammonia nitrogen in waste water and preparation method thereof | |
| CN103626188B (en) | Silica dioxide granule and preparation method thereof | |
| CN103771429A (en) | Method using co-template agent to synthesizing porous spherical silica | |
| CN107416849A (en) | A kind of method for preparing monodisperse nano silicon dioxide particle | |
| CN105271261A (en) | Hydrophobic silica aerogel pellets and preparation method thereof | |
| CN102557049A (en) | Method for producing silica particles | |
| CN103896284B (en) | A kind of monodisperse silica nano particle and preparation method thereof | |
| CN102951648B (en) | Preparation method of nano silicon dioxide | |
| CN109574507A (en) | A kind of nano-level sphere bioactivity glass and preparation method thereof | |
| CN109455730A (en) | A kind of preparation method of preparing spherical SiO 2 nano particle | |
| CN103252234B (en) | A kind of nuclear shell structure nano Catalysts and its preparation method and application | |
| CN103848427B (en) | A kind of high dispersive precipitated silica and preparation method thereof | |
| CN108821296A (en) | A kind of preparation method of mesoporous spherical nano Sio 2 particle | |
| CN102583404A (en) | Mesoporous silicon dioxide nanometer particle and preparation method | |
| CN103214026B (en) | Preparation method of CaO/ZnO core-shell structure nanometer material | |
| CN109559882A (en) | Amphiphilic hydroxyl magnetic bead and its preparation method and application | |
| CN103601201A (en) | Monodispersed mesoporous silica nanoparticles and synthetic method thereof | |
| CN102602959A (en) | Preparation method of pure nano-silicon ZSM-5 zeolite | |
| CN101746766A (en) | Method for preparing monodisperse silicon dioxide sphere by using blue algae as template | |
| CN109455727A (en) | A kind of micro-nano compound particle and its mechanical load are embedded in preparation process | |
| CN107572494B (en) | Preparation of hollow hydroxyapatite and application of hollow hydroxyapatite in drug carrier |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |