CN107758676A - A kind of method that double layer hollow nanometer manganous silicate is prepared based on shape stay in place form of ringing a bell - Google Patents
A kind of method that double layer hollow nanometer manganous silicate is prepared based on shape stay in place form of ringing a bell Download PDFInfo
- Publication number
- CN107758676A CN107758676A CN201711134136.1A CN201711134136A CN107758676A CN 107758676 A CN107758676 A CN 107758676A CN 201711134136 A CN201711134136 A CN 201711134136A CN 107758676 A CN107758676 A CN 107758676A
- Authority
- CN
- China
- Prior art keywords
- zif
- msio
- manganese
- bell
- double layer
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a kind of method for preparing double layer hollow nanometer manganous silicate based on shape stay in place form of ringing a bell.The nano-complex particles of ZIF 8 coated using the mesoporous silicon oxide of the forming core shell structure of ringing a bell of uniqueness are as template, using pore passage structure and the imidazate frameworks of the ZIF 8 labile feature under acid-base condition of wherein mesoporous silicon oxide, pass through ammonium ion (NH4 +) hydrolyze the hydroxide ion (OH for carrying out control system‑) rate of release and total concentration.Can finally be formed structural stability, there is high specific surface area (445.3m2/ g) double layer hollow nanometer manganous silicate nano particle.Double layer hollow Mn (the SiO that the present invention is prepared4) nano particle good dispersion, pattern, size uniformity, synthetic method craft is simple, economy, and repeatability is high.And the nano particle being prepared, ability biodegradable well is shown in simulated body fluid.It is with a wide range of applications in fields such as electronics, the energy, environment, life.
Description
Technical field：
The present invention relates to the preparation method and technique of double layer hollow manganous silicate nano particle, is specially rung a bell using unique
ZIF-8 (the hereinafter referred to as ZIF-8@mSiO of the mesoporous silicon oxide cladding of forming core shell structure2) nano-complex particle is as mould
Plate, using the pore passage structure and ZIF-8 imidazates framework of wherein mesoporous silicon oxide under acid-base condition labile feature,
Under 10~35 DEG C or 50~180 DEG C of temperature conditionss, pass through ammonium ion (NH4 +) hydrolyze the hydroxide ion for carrying out control system
(OH-) rate of release and total concentration.OH first-The outer layer Si-O keys of shell are converted on the surface of template to be formed silicate from
Son (SiO3 2-), and be partly into duct and reach inside shell, make its internal layer Si-O keys convert to form SiO3 2-；Due to kernel
ZIF-8 cushioning effects, OH-Progressively decompose ZIF-8 so that template surfaces externally and internally has sufficient space and the manganese ion (Mn in system2 +) react, through sustained response 4~48 hours, it can finally form the double layer hollow Mn (SiO of structural stability4) nano particle.
Background technology：
The primary chemical formula of manganous silicate is MnSiO3, it is primarily present in manganese ore in nature, and rich reserves.Cause
Its unique layered molecular structure and higher specific surface area, good research is shown in fields such as the energy, catalysis, environment
Value.However, from manganese ore isolated In Natural Silicate manganese complex process, and purity is relatively low, and limits it in each field
Extensive use.Therefore, the artificial synthesized simple manganous silicate with higher degree, well-formed and more high-specific surface area is with very
Strong Research Significance.
With the development of nanometer science and technology, nano material shows excellent performance in each field.In order to prepare
Manganous silicate nano material with high specific surface area, reported at present it is a variety of have different structure (including solid, nucleocapsid and in
Hollow structure) and composition (including different valence state and different metal element composition manganese and silicon containing hydrochlorate) manganous silicate nano particle system
Preparation Method.Such as template-precipitation method, self-assembly method, chemical deposition, hydro-thermal method, sol-gal process.
Wherein, the manganous silicate nano particle of hollow structure, because it has the good heat endurance of higher specific surface area,
The neighborhoods such as lithium ion battery, environmental catalysis, adsorbing separation and medicine delivery show huge application potential.For example, 2012
Year Song Weiguo team of chemistry institute of the Chinese Academy of Sciences (J.Mater.Chem., 2012,22,17222-17226), is mould using CNT
Plate, silica is grown in its surface self-organization, and formation has high specific surface area (649m under high-temperature calcination2/ g) it is more
Hole Silica Nanotube, then under hydrothermal conditions, manganous silicate nanotube is prepared, in environmental contaminants Adsorption
Excellent performance is shown with terms of catalytic degradation.Zeng Huachun in 2014 et al. is template using silica medicine ball,
Under high temperature hydrothermal condition, manganous silicate is changed into using the silicic acid of formation, being prepared has higher specific surface area
(316.1m2/ g) hollow structure manganous silicate nano particle (ACS Nano., 2014,8 (6), 6407-6416), show pair
Organic dyestuff has the ability of higher catalytic degradation.Recently, Shi Jian woodss team (J.Am.Chem.Soc.2016,138,9881-
9894), by the use of mesoporous silica nano-particle as template, be prepared has high specific surface area under hydrothermal conditions
(222.0m2/ g) hollow manganous silicate nano particle, in drug delivery system, show preferable biodegradability and
Cancer target diagnostic feature.Due to Hollow Nanoparticles in aqueous, there is good monodispersity, and be not easy to reunite, because
It is and of great interest.In order to synthesize the hollow manganous silicate nano particle with more high-specific surface area, more and more grind
Study carefully personnel and start to turn to and the structure of manganous silicate nano particle is designed and regulated and controled.However, but seldom have been reported that double layer hollow
Lot of challenges be present in the preparation method of manganous silicate nano particle, therefore, synthesis double layer hollow manganous silicate nano particle.
The content of the invention：
The present invention for it is current the problem of, propose based on ring a bell shape stay in place form prepare double layer hollow nanometer manganous silicate (with
Lower abbreviation Mn (SiO4)) method.Using the ZIF-8@mSiO of the forming core shell structure of ringing a bell of uniqueness2Nano-complex particle conduct
Template, using the pore passage structure and ZIF-8 imidazates framework of wherein mesoporous silicon oxide under acid-base condition labile feature,
Under low temperature or hot conditions, using basic chemical hydrolysis balance theory, pass through NH4 +Hydrolysis carrys out the OH of control system-Release
Speed and total concentration.OH first-The outer layer Si-O keys of shell are converted to form SiO on the surface of template3 2-, and be partly into
Duct is reached inside shell, makes its internal layer Si-O keys convert to form SiO3 2-；Due to the ZIF-8 cushioning effects of kernel, OH-Progressively divide
Solve ZIF-8 so that template surfaces externally and internally has sufficient space and the Mn in system2+React, through sustained response for a period of time after,
Double layer hollow Mn (the SiO of structural stability can finally be formed4) nano particle.
Technical scheme is as follows：
A kind of method for preparing double layer hollow nanometer manganous silicate based on shape stay in place form of ringing a bell, is comprised the following steps that：
By ZIF-8 (the hereinafter referred to as ZIF-8@mSiO of the forming core shell structure mesoporous silicon oxide cladding of ringing a bell prepared2)
Nano-complex particle template is distributed in deionized water, forms the sol dispersion that stable mass concentration is 0.2~2%
System；Metal manganese salt is dissolved in deionized water, and adds ammonia chloride crystal (NH4Cl) it is used for regulation system ammonium ion (NH4 +) hydrolysis rate.Then to manganese ion (Mn2+) add in solution 38% ammoniacal liquor (NH3·H2O the manganese ion complexing) formed
Thing, and it is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, in 10~35 DEG C or 50~180 DEG C of temperature strip
Under part, pass through NH4 +Hydrolysis carrys out the hydroxide ion (OH of control system-) rate of release and total concentration, through sustained response 4~
After 48 hours, the double layer hollow Mn (SiO of structural stability can be finally formed4) nano particle.Product is washed through centrifugation, deionization
After washing three times, it is dried in vacuo and produces sample.
Wherein, the described forming core shell structure ZIF-8@mSiO that ring a bell2The preparation method of template is：The ZIF-8 that will be prepared
It is 1 through volume ratio:9 methanol and deionized water stepwise adsorption decentralized processing, adjusted under agitation by sodium hydroxide (NaOH) solution
Section system is to alkalescent (pH=8~10)；The surfactant for weighing 50% weight of reactant ZIF-8 fixed feeding area amounts adds
Stirring reaction 0.5~1 hour into system；The butyl ester of silicic acid four (TEOS) is added into above-mentioned solution and to continue stirring 0.1~2 small
When, stewing process 0.5~48 hour, centrifugation, washing, vacuum drying, obtain final core shell structure ZIF-8@mSiO2It is nano combined
Thing template.
The described forming core shell structure ZIF-8@mSiO that ring a bell2The mass ratio that feeds intake of template and deionized water is：1:500~
10:500。
Described metal manganese salt mainly includes manganese chloride, manganese acetate and manganese sulfate.
Described metal manganese salt, ammonium chloride, the amount ratio of the material that feeds intake of ammoniacal liquor and deionized water are：0.5:15:105:
5000~3:60:105:5000.
In the synthetic method of the present invention, the reaction equation of general principle is as follows：
Mn2++SiO3 2-+O2(g)+OH-→Mn(SiO4)(s)+H2O(l) (3)
Compared with prior art, the present invention has following remarkable advantage：Under low temperature or hot conditions, pass through NH4 +Hydrolysis
Carry out the OH of control system-Rate of release and total concentration (equation 1), OH first-On the surface of template by the outer layer Si-O of shell
Key converts to form SiO3 2-(equation 2), and be partly into duct and reach inside shell, make its internal layer Si-O keys convert to be formed
SiO3 2-；Due to the ZIF-8 cushioning effects of kernel, OH-Progressively decompose ZIF-8 so that template surfaces externally and internally has sufficient space and body
Mn in system2+React, through sustained response for a period of time after, can finally be formed structural stability, have compared with high-ratio surface
Product (445.3m2/ g) double layer hollow Mn (SiO4) nano particle (equation 3).Wherein, the nano-complex mould of bell-shaped structure is shaken
Plate, surface provide enough Si-O keys, and under kernel ZIF-8 cushioning effect, template can be performed etching, final energy
It is enough to keep stable double layer hollow structure, collapsing or decomposing for template will not be caused.The double layer hollow manganous silicate being prepared is received
Rice grain, there is higher specific surface area than existing Hollow Nanoparticles, preferable application value will be shown in association area.
Double layer hollow Mn (the SiO that the present invention synthesizes4) nano particle pattern, size uniformity, good dispersion, synthetic method work
Skill is simple, and repeatability is high, and economy, toxicity is low, environment-friendly, and multivalent state can cause higher reactivity,
Further types of compound is produced, is with a wide range of applications in fields such as electronics, the energy, environment, life.
Brief description of the drawings：
Double layer hollow Mn (the SiO that Fig. 1 is prepared4) nano particle TEM figure.
Embodiment：
With reference to embodiment and accompanying drawing, the invention will be further described.
Ring a bell forming core shell structure ZIF-8@mSiO2The preparation of nano-complex
The 50mg ZIF-8 prepared are distributed in 20mL methanol, after saturation to be adsorbed, redisperse is stirred into 80mL water
Lower addition 0.2mL 1mol/L NaOH solutions are mixed, 0.2g CTAB is weighed and is added in system and stir 5min, 1.2mL is added dropwise
TEOS, and continue to stir 5min, stewing process 5min, centrifugation, washing, 40 DEG C of vacuum drying, forming core shell structure of ringing a bell is made
ZIF-8@mSiO2Nano material.
Embodiment 1
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；0.5mmol manganese chlorides are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 4h is reacted at 10 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 2
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；0.5mmol manganese acetates are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 4h is reacted at 10 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 3
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；0.5mmol manganese sulfates are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 4h is reacted at 10 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 4
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；By 3mmol manganese chlorides be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, react 4h at 10 DEG C, ultimately form stabilization,
Monodispersed double layer hollow manganous silicate nano particle, after centrifugation, deionized water washing three times, 40 DEG C are dried in vacuo and produce product
Sample.
Embodiment 5
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；By 3mmol manganese acetates be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, react 4h at 10 DEG C, ultimately form stabilization,
Monodispersed double layer hollow manganous silicate nano particle, after centrifugation, deionized water washing three times, 40 DEG C are dried in vacuo and produce product
Sample.
Embodiment 6
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；By 3mmol manganese sulfates be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, react 4h at 10 DEG C, ultimately form stabilization,
Monodispersed double layer hollow manganous silicate nano particle, after centrifugation, deionized water washing three times, 40 DEG C are dried in vacuo and produce product
Sample.
Embodiment 7
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；0.5mmol manganese chlorides are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 4h is reacted at 10 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 8
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；0.5mmol manganese acetates are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 4h is reacted at 10 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 9
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；0.5mmol manganese sulfates are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 4h is reacted at 10 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 10
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；By 3mmol manganese chlorides be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, react 4h at 10 DEG C, ultimately form stabilization,
Monodispersed double layer hollow manganous silicate nano particle, after centrifugation, deionized water washing three times, 40 DEG C are dried in vacuo and produce product
Sample.
Embodiment 11
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；By 3mmol manganese acetates be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, react 4h at 10 DEG C, ultimately form stabilization,
Monodispersed double layer hollow manganous silicate nano particle, after centrifugation, deionized water washing three times, 40 DEG C are dried in vacuo and produce product
Sample.
Embodiment 12
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；By 3mmol manganese sulfates be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, react 4h at 10 DEG C, ultimately form stabilization,
Monodispersed double layer hollow manganous silicate nano particle, after centrifugation, deionized water washing three times, 40 DEG C are dried in vacuo and produce product
Sample.
Embodiment 13
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；0.5mmol manganese chlorides are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 4h is reacted at 35 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 14
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；By 3mmol manganese chlorides be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, react 4h at 35 DEG C, ultimately form stabilization,
Monodispersed double layer hollow manganous silicate nano particle, after centrifugation, deionized water washing three times, 40 DEG C are dried in vacuo and produce product
Sample.
Embodiment 15
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；0.5mmol manganese chlorides are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 4h is reacted at 50 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 16
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；By 3mmol manganese chlorides be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, react 4h at 50 DEG C, ultimately form stabilization,
Monodispersed double layer hollow manganous silicate nano particle, after centrifugation, deionized water washing three times, 40 DEG C are dried in vacuo and produce product
Sample.
Embodiment 17
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；0.5mmol manganese chlorides are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 4h is reacted at 180 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 18
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；By 3mmol manganese chlorides be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 4h is reacted at 180 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 19
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；0.5mmol manganese chlorides are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 4h is reacted at 35 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 20
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；By 3mmol manganese chlorides be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, react 4h at 35 DEG C, ultimately form stabilization,
Monodispersed double layer hollow manganous silicate nano particle, after centrifugation, deionized water washing three times, 40 DEG C are dried in vacuo and produce product
Sample.
Embodiment 21
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；0.5mmol manganese chlorides are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 4h is reacted at 50 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 22
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；By 3mmol manganese chlorides be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, react 4h at 50 DEG C, ultimately form stabilization,
Monodispersed double layer hollow manganous silicate nano particle, after centrifugation, deionized water washing three times, 40 DEG C are dried in vacuo and produce product
Sample.
Embodiment 23
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；0.5mmol manganese chlorides are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 4h is reacted at 180 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 24
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；By 3mmol manganese chlorides be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 4h is reacted at 150 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 25
The forming core shell structure ZIF-8@mSiO that ring a bell that 25mg is prepared2Nano-complex particle template is distributed to 10mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.8% is formed；0.2mmol manganese acetates are dissolved in 10mL
In ionized water, and add 6mmol NH4Cl.Then to addition 0.6mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, react 4h at 10 DEG C, ultimately form stabilization,
Monodispersed double layer hollow manganous silicate nano particle, after centrifugation, deionized water washing three times, 40 DEG C are dried in vacuo and produce product
Sample, obtained sample TEM figures are shown in Fig. 1.
Characterized by testing, the specific surface area of material is about 445.3m2/g；Aperture is about 3nm, and the nanometer being prepared
Particle, biodegradable ability well is shown in simulated body fluid, can degrade within 4~6 hours about 50%.
Embodiment 26
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；0.5mmol manganese acetates are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 48h is reacted at 10 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 27
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；By 3mmol manganese acetates be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 48h is reacted at 10 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 28
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；0.5mmol manganese acetates are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 48h is reacted at 35 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 29
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；By 3mmol manganese acetates be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 48h is reacted at 35 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 30
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；0.5mmol manganese acetates are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 48h is reacted at 50 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 31
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；By 3mmol manganese acetates be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 48h is reacted at 50 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 32
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；0.5mmol manganese acetates are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 48h is reacted at 180 DEG C, is ultimately formed
Stable, monodispersed double layer hollow manganous silicate nano particle, product after centrifugation, deionized water washing three times, do by 40 DEG C of vacuum
It is dry to produce sample.
Embodiment 33
The forming core shell structure ZIF-8@mSiO that ring a bell that 50mg is prepared2Nano-complex particle template is distributed to 25mL and gone
In ionized water, the colloidal dispersion system that stable mass concentration is 0.2% is formed；By 3mmol manganese acetates be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 48h is reacted at 180 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 34
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；0.5mmol manganese acetates are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 48h is reacted at 10 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 35
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；By 3mmol manganese acetates be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 48h is reacted at 10 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 36
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；0.5mmol manganese acetates are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 48h is reacted at 35 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 37
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；By 3mmol manganese acetates be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 48h is reacted at 35 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 38
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；0.5mmol manganese acetates are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 48h is reacted at 50 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 39
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；By 3mmol manganese acetates be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 48h is reacted at 50 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Embodiment 40
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；0.5mmol manganese acetates are dissolved in 90mL
In ionized water, and add 15mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese of formation from
Sub- complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 48h is reacted at 180 DEG C, is ultimately formed
Stable, monodispersed double layer hollow manganous silicate nano particle, product after centrifugation, deionized water washing three times, do by 40 DEG C of vacuum
It is dry to produce sample.
Embodiment 41
The forming core shell structure ZIF-8@mSiO that ring a bell that 500mg is prepared2Nano-complex particle template is distributed to 25mL
In deionized water, the colloidal dispersion system that stable mass concentration is 2% is formed；By 3mmol manganese acetates be dissolved in 90mL go from
In sub- water, and add 60mmol NH4Cl.Then to addition 0.8mL NH in manganese ion solution3·H2O, by the manganese ion of formation
Complex compound is added to above-mentioned ZIF-8@mSiO2In sol system；After stirring, 48h is reacted at 180 DEG C, is ultimately formed steady
Fixed, monodispersed double layer hollow manganous silicate nano particle, product is after centrifugation, deionized water washing three times, 40 DEG C of vacuum drying
Produce sample.
Claims (4)
- A kind of 1. method that double layer hollow nanometer manganous silicate is prepared based on shape stay in place form of ringing a bell, it is characterised in that will prepare Ring a bell forming core shell structure mesoporous silicon oxide cladding ZIF-8 nano-complex particle templates be distributed in deionized water, shake The ZIF-8 of bell-shaped nuclear shell structure mesoporous coated with silica hereinafter referred to as ZIF-8@mSiO2, mass concentration is formed as 0.2~2% Colloidal dispersion system；Metal manganese salt is dissolved in deionized water, and adds ammonia chloride crystal；Manganese ion complex compound is formed then to the ammoniacal liquor that mass concentration is 38% is added in manganese ion solution, and is added to above-mentioned ZIF-8@mSiO2In sol system；Described metal manganese salt, ammonium chloride, the amount ratio of the material that feeds intake of ammoniacal liquor and deionized water are： 0.5:15:105:5000~3:60:105:5000；After stirring, under 10~35 DEG C or 50~180 DEG C of temperature conditionss, After sustained response 4~48 hours, the double layer hollow Mn (SiO of structural stability can be finally formed4) nano particle；Product pass through from After the heart, deionized water washing, it is dried in vacuo and produces sample.
- 2. according to the method for claim 1, it is characterised in that the described forming core shell structure ZIF-8@mSiO that ring a bell2Template Preparation method is：By the ZIF-8 prepared through volume ratio be 1:9 methanol and deionized water stepwise adsorption decentralized processing, pass through hydrogen Sodium hydroxide solution under agitation regulation system to pH=8~10；Weigh the table of 50% weight of reactant ZIF-8 fixed feeding area amounts Face activating agent is added to stirring reaction 0.5~1 hour in system；The butyl ester of silicic acid four is slowly added into above-mentioned solution and is persistently stirred Mix 0.1~2 hour, stewing process 0.5~48 hour, centrifugation, washing, vacuum drying, obtain final core shell structure ZIF-8@ mSiO2Nano-complex template.
- 3. according to the method for claim 1, it is characterised in that the described forming core shell structure ZIF-8@mSiO that ring a bell2Template with The mass ratio that feeds intake of deionized water is：1:500~10:500.
- 4. according to the method for claim 1, it is characterised in that described metal manganese salt includes manganese chloride, manganese acetate or sulphur Sour manganese,.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711134136.1A CN107758676B (en) | 2017-11-16 | 2017-11-16 | Method for preparing double-layer hollow nano manganese silicate based on bell-shaped structure template |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711134136.1A CN107758676B (en) | 2017-11-16 | 2017-11-16 | Method for preparing double-layer hollow nano manganese silicate based on bell-shaped structure template |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107758676A true CN107758676A (en) | 2018-03-06 |
| CN107758676B CN107758676B (en) | 2020-01-10 |
Family
ID=61279302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711134136.1A Active CN107758676B (en) | 2017-11-16 | 2017-11-16 | Method for preparing double-layer hollow nano manganese silicate based on bell-shaped structure template |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107758676B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110589894A (en) * | 2019-09-17 | 2019-12-20 | 北京化工大学 | Preparation method of hollow metal oxide nano material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060281961A1 (en) * | 2003-05-15 | 2006-12-14 | Prasad Yandapalli D | Functional transition metal silicates |
| CN101217194A (en) * | 2007-12-27 | 2008-07-09 | 上海交通大学 | A magnesium secondary battery anode material and the corresponding preparation method |
| US20090214407A1 (en) * | 2008-02-21 | 2009-08-27 | Reyes Sebastian C | Separation of carbon dioxide from nitrogen utilizing zeolitic imidazolate framework materials |
| CN101540392A (en) * | 2009-04-09 | 2009-09-23 | 西安建筑科技大学 | Method for preparing lithium-manganese silicate of cathode material of lithium-ion battery |
| CN101721372A (en) * | 2008-10-10 | 2010-06-09 | 陈东 | Gold shell coated hollow mesoporous silicon dioxide spheres, method for preparing same and application thereof in tumor treatment |
| CN105680045A (en) * | 2016-04-15 | 2016-06-15 | 山东大学 | Preparation method of high-stability amorphous manganous silicate |
| CN106517216A (en) * | 2016-11-03 | 2017-03-22 | 北京化工大学 | Biodegradable mesoporous carbon and silicon nano-sphere and method for preparing same |
| CN107021498A (en) * | 2017-06-07 | 2017-08-08 | 延边大学 | Hollow silicic acid manganese material and preparation method thereof |
-
2017
- 2017-11-16 CN CN201711134136.1A patent/CN107758676B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060281961A1 (en) * | 2003-05-15 | 2006-12-14 | Prasad Yandapalli D | Functional transition metal silicates |
| CN101217194A (en) * | 2007-12-27 | 2008-07-09 | 上海交通大学 | A magnesium secondary battery anode material and the corresponding preparation method |
| US20090214407A1 (en) * | 2008-02-21 | 2009-08-27 | Reyes Sebastian C | Separation of carbon dioxide from nitrogen utilizing zeolitic imidazolate framework materials |
| CN101721372A (en) * | 2008-10-10 | 2010-06-09 | 陈东 | Gold shell coated hollow mesoporous silicon dioxide spheres, method for preparing same and application thereof in tumor treatment |
| CN101540392A (en) * | 2009-04-09 | 2009-09-23 | 西安建筑科技大学 | Method for preparing lithium-manganese silicate of cathode material of lithium-ion battery |
| CN105680045A (en) * | 2016-04-15 | 2016-06-15 | 山东大学 | Preparation method of high-stability amorphous manganous silicate |
| CN106517216A (en) * | 2016-11-03 | 2017-03-22 | 北京化工大学 | Biodegradable mesoporous carbon and silicon nano-sphere and method for preparing same |
| CN107021498A (en) * | 2017-06-07 | 2017-08-08 | 延边大学 | Hollow silicic acid manganese material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIN BAE LEE ET AL.: "Canted antiferromagnetism on a nanodimensional spherical surface geometry: the case of MnCO3 small hollow nanospheres", 《PHYSICAL REVIEW B: CONDENSED MATTER AND MATERIALS PHYSICS》 * |
| SEUNG-HO YU ET AL.: "Hollow Nanostructured Metal Silicates with Tunable Properties for Lithium Ion Battery Anodes", 《ACS APPLIED MATERIALS & INTERFACES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110589894A (en) * | 2019-09-17 | 2019-12-20 | 北京化工大学 | Preparation method of hollow metal oxide nano material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107758676B (en) | 2020-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103500622B (en) | Magnetism inorganic nanoparticle/ordered mesopore silica nuclear shell composite microsphere and preparing method thereof | |
| CN102633307A (en) | Method for hydrothermally preparing mono-dispersed hollow magnetic nanometer particles | |
| CN107486157B (en) | Multi-walled carbon nanotube/metal organic framework composite material and preparation method | |
| CN102350281A (en) | Preparation method of fluorescent mesoporous silica-based core-shell nanoscale capsule | |
| CN107955180B (en) | Method for preparing core-shell structure nano composite based on controllable adsorption driving force | |
| Feng et al. | Synthesis of rattle-structured CuCo2O4 nanospheres with tunable sizes based on heterogeneous contraction and their ultrahigh performance toward ammonia borane hydrolysis | |
| CN104475078B (en) | Preparation method of nano rare-earth metal oxide/ carbon nano pipe composite catalyst | |
| CN103359773B (en) | A kind of preparation method of zinc oxide nano rod | |
| CN101433959A (en) | Method for preparing hollow nano gold powder material | |
| CN102602883A (en) | Preparation method of silica-coated iron oxide nano-core-shell structural material | |
| CN105834446B (en) | A kind of synthetic method of ultra-thin stratiform NiO CoOx nanometer sheets load NiCo nano compositions | |
| CN108453265A (en) | A kind of Silica Nanotube confinement nano nickel particles and preparation method thereof | |
| CN1935662A (en) | Nano crystal constructed porous copper oxide aggregate and its preparing method | |
| CN109529523A (en) | Molecular sieve core-mesoporous organosilicon hollow shell multi-stage porous composite material and preparation method | |
| CN111233048A (en) | Double-shell MnCo2O4Hollow nanosphere material and synthesis method thereof | |
| CN104528836A (en) | Method for regulating and controlling shape of alpha-Fe2O3/graphene composite material | |
| CN109174105A (en) | A kind of preparation method of magnetic catalyst derived from double MOFs | |
| CN103638988B (en) | Magnetic mesoporous material, and preparation method and application of magnetic mesoporous material | |
| CN105502421A (en) | Preparation method of zinc silicate hollow micron ball | |
| CN107416834B (en) | Method for preparing hollow molybdenum carbide nanospheres by using gas template | |
| Zhang et al. | Synthesis and fabrication of CNTs/Fe 3 O 4@ Pdop@ Au nanocables by a facile approach | |
| CN108440767A (en) | It is a kind of that nanometer Au is combined to the new method for preparing Au@MOF composite materials with porous MOF | |
| CN110842212A (en) | Superfine Pd tetrahedral nano material and preparation method and application thereof | |
| CN107758676A (en) | A kind of method that double layer hollow nanometer manganous silicate is prepared based on shape stay in place form of ringing a bell | |
| CN114348976A (en) | Preparation method of asymmetric hollow porous composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |