CN104556960B - Hierarchical-structured spherical opal and preparation method thereof - Google Patents
Hierarchical-structured spherical opal and preparation method thereof Download PDFInfo
- Publication number
- CN104556960B CN104556960B CN201510020743.XA CN201510020743A CN104556960B CN 104556960 B CN104556960 B CN 104556960B CN 201510020743 A CN201510020743 A CN 201510020743A CN 104556960 B CN104556960 B CN 104556960B
- Authority
- CN
- China
- Prior art keywords
- paligorskite
- globular protein
- pore canal
- multistage pore
- preparation
- 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.)
- Expired - Fee Related
Links
Abstract
The invention relates to a hierarchical-structured spherical opal and a preparation method thereof. The hierarchical-structured spherical opal is a microsphere with a multi-layer structure, which is self-assembled by silicon dioxide nanosheets, wherein the diameters of the silicon dioxide nanosheets are 0.5-1.5 microns; a pore structure is formed between the nanosheets in layers; communicated large structure is formed between the layers; the preparation method comprises the following steps: adopting a traditional surfactant (CTAB) as a template agent, and acid-activated palygorskite as a carbon source, stirring at 60 DEG C for 2-6 hours when the pH value of the system is 11-12.5; and carrying out hydrothermal reaction at 160-200 DEG C for 24-120 hours, washing and then removing a surfactant by thermal treatment, so as to obtain the hierarchical-structured spherical opal. According to the method, SiO2 in the opal is effectively utilized as the silicon source, so that the cost is reduced, and application of the opal is expanded.
Description
Technical field
The present invention relates to the synthetic method of a kind of multistage pore canal globular protein stone, belong to field of inorganic materials, tool
Body relates to a kind of method that nanoscale twins is self-assembly of multistage pore canal globular protein stone.
Background technology
Porous material is because it is catalysis, environmental protection, separation analysis, quasiconductor and opto-electronic device, biological doctor
The fields such as treatment have wide practical use, the focus that the most always researcher is paid close attention to.
At present, multi-stage artery structure preparing spherical SiO 2 Product formation method is broadly divided into two kinds, die version method
And soft template method.Hard template method is mainly with spherical carbon material, and polypropylene microsphere is that template is to synthesize multistage pore canal ball
Shape silicon dioxide, and soft template mainly uses surfactant to synthesize the preparing spherical SiO 2 of multilevel hierarchy.
Wherein to have pore structure adjustable for soft template method, the plurality of advantages such as morphology controllable and be widely used.Typical example
Son has: Kim use double end surfactant do the multistage silicon oxide vesicle material of templated synthesis (Science,
1998,282,1302)；It is a series of multistage that Yang etc. utilize polyethylene ball and block copolymer to do templated synthesis
Structural material (Science, 1998,282,2244)；Wang etc. use polyacrylic acid and cation surface activating
Agent is done hybrid template and is prepared for the monocrystalline silica dioxide granule (Chem.Mater., 2010,22,3829) of multilevel hierarchy.
Wu Lidong etc. use two-step method first to add appropriate polyvinylpyrrolidone (PVP) in sol-gel process and obtain
To silica dioxide granule, pseudo-brilliant transformation technology is then used to obtain multistage pore canal preparing spherical SiO 2 (CN
103130229 A).Said method generally uses tetraethyl orthosilicate or sodium silicate to be silicon source, and employs valency
The surfactant that lattice are high, synthesis cost is high, is unfavorable for industrialized production.
Therefore, cheap raw material such as mineral silicon source and traditional cationic surfactant how is utilized to synthesize
The crystallization product of multi-stage artery structure is a technical barrier urgently to be resolved hurrily.
Summary of the invention
The technical problem to be solved is for above-mentioned deficiency present in prior art, it is provided that
A kind of employing conventional surfactant (CTAB) is template, with the Paligorskite after acid activation for silicon source system
The method of standby multistage pore canal globular protein stone.
For solving above-mentioned technical problem, present invention provide the technical scheme that
Thering is provided a kind of multistage pore canal globular protein stone, described multistage pore canal globular protein stone is silicon dioxide
The microsphere of the multi-layer nano lamellar structure of nanometer sheet self assembly, silica nanometer sheet is a diameter of
15-30nm, microspherulite diameter is 0.5-1.5 μm, forms duct knot in every layer of nanoscale twins between nanometer sheet
Structure, forms the macropore structure of connection between nanoscale twins.
The preparation method step of multistage pore canal globular protein stone of the present invention is as follows:
1) Paligorskite after acid activation is prepared: by Paligorskite and hydrochloric acid solution 1:10-1:100 by volume
Mixing, process 2-12h, be washed with distilled water to after filtration without chloride ion, dry, grind obtain acid work
Paligorskite after change；
2) multistage pore canal globular protein stone is prepared: with step 1) Paligorskite after gained acid activation is as silicon
Source, adds in the water dissolved with surfactant cetyl trimethylammonium bromide, and regulation system pH value is
11-12.5, stirs 2-6h under the conditions of 60-80 DEG C, then in 160-200 DEG C of hydro-thermal reaction 24-120h,
Washing after-baking obtains multistage pore canal globular protein stone.
By such scheme, step 1) described Paligorskite Particle size requirements mesh number is more than 100 mesh.
By such scheme, step 1) concentration of described hydrochloric acid solution is 4-8mol/L.
By such scheme, step 2) Paligorskite after described acid activation and cetyl trimethylammonium bromide
Mass ratio is 1:2-4:1, and the Paligorskite after described acid activation with the mass volume ratio of water is
0.1-0.4g/10mL。
By such scheme, step 2) described regulation system pH value be use concentration be the hydrogen of 0.5mol/L
Sodium hydroxide solution regulates.
By such scheme, step 2) described Technology for Heating Processing be under 550 DEG C of temperature conditionss process 3-6h.
The beneficial effects of the present invention is: 1, present invention process is simple, overcomes prior art difficult point, with
Conventional surfactant CTAB is template, the crystallization product of synthesis multi-stage artery structure.2, effective
Utilize the SiO in Paligorskite2As silicon source, reduce cost, widen the application of Paligorskite.3, originally
The multistage pore canal globular protein stone granule of invention preparation is uniform, can be used for biological medicine, environmental conservation, work
The fields such as industry catalysis.
Accompanying drawing explanation
Fig. 1 is the TEM figure of the Paligorskite after the acid activation prepared by the embodiment of the present invention 1；
Fig. 2 is the XRD figure of the multistage pore canal globular protein stone prepared by embodiment 3；
Fig. 3 is the TEM figure of the multistage pore canal globular protein stone prepared by embodiment 3；
Fig. 4 is the field emission scanning electron microscope of the multistage pore canal globular protein stone prepared by embodiment 3
(FESEM) figure.
Detailed description of the invention
For making those skilled in the art be more fully understood that technical scheme, the most right
The present invention is described in further detail.
Paligorskite used by the embodiment of the present invention is the Paligorskite raw ore bought, and Paligorskite particle diameter is 200 mesh.
Embodiment 1
Paligorskite is mixed with the hydrochloric acid solution 1:10 by volume of 4M (mol/L), processes 2h, mistake
It is washed with deionized after filter to without chloride ion, after drying at a temperature of 60 DEG C overnight and grinding, obtains acid activation
After Paligorskite, standby.It is illustrated in figure 1 the transmission electron microscope picture of the Paligorskite after acid activation, by Fig. 1
There is many holes in Paligorskite after visible acid treatment, shows that acid treatment takes off Mg and makes its avtive spot increase.
Take 0.1gCTAB to be dissolved in 10mL water, after adding the above-mentioned acid activation of 0.4g after stirring 5min
Paligorskite, regulates with the sodium hydroxide solution of 0.5mol/L and stirs under the conditions of its pH value is 11.5,60 DEG C
2h, then in 160 DEG C of hydro-thermal reactions 72h, by a large amount of water and washing with alcohol and dry, then in 550 DEG C
Heat treatment 6h, i.e. obtains multistage pore canal globular protein stone.
Embodiment 2
Paligorskite is mixed with the hydrochloric acid solution 1:10 by volume of 4M, processes 10h, spend after filtration
Ionized water washing, to without chloride ion, obtains the Paligorskite after acid activation after drying and grinding, standby.
Take 0.2gCTAB to be dissolved in 10mL water, after adding the above-mentioned acid activation of 0.2g after stirring 5min
Paligorskite, regulates with the sodium hydroxide solution of 0.5mol/L and stirs under the conditions of its pH value is 11.5,60 DEG C
4h, then in 160 DEG C of hydro-thermal reactions 72h, by a large amount of water and washing with alcohol and dry, then in 550 DEG C
Heat treatment 6h, i.e. obtains multistage pore canal globular protein stone.
Embodiment 3
Paligorskite is mixed with the hydrochloric acid solution 1:10 by volume of 8M, processes 12h, spend after filtration
Ionized water washing, to without chloride ion, obtains the Paligorskite after acid activation after drying and grinding, standby.
Take 0.2gCTAB to be dissolved in 10mL water, after adding the above-mentioned acid activation of 0.2g after stirring 5min
Paligorskite, regulates with the sodium hydroxide solution of 0.5mol/L and stirs under the conditions of its pH value is 12.0,60 DEG C
6h, then in 200 DEG C of hydro-thermal reactions 120h, by a large amount of water and washing with alcohol and dry, then in 550 DEG C
Heat treatment 6h, i.e. obtains product.
Figure of description 2-4 is XRD, TEM and the FESEM figure of product prepared by the present embodiment respectively.
Fig. 2 is it can be seen that it has peak, characteristic peak to occur in 2 θ in big angle range is 21.775 and 35.785
Place, illustrates the silicon dioxide i.e. opal that it is crystallization.Fig. 3 can be seen that on product microcosmic as diameter
The microsphere of the multi-layer nano lamellar structure that the nanometer sheet of about 15-30nm assembles, in every layer of nanoscale twins
Forming pore passage structure between nanometer sheet, form the macropore structure of connection between nanoscale twins, Fig. 4 can see
Being spheroidal particle to product entirety pattern, size is 0.5-1.5 μm, and ball surface nanometer layer has
Pore passage structure.
Embodiment 4
Paligorskite is mixed with the hydrochloric acid solution 1:40 by volume of 8M, processes 2h, spend after filtration
Ionized water washing, to without chloride ion, obtains the Paligorskite after acid activation after drying and grinding, standby.
Take 0.2gCTAB to be dissolved in 10mL water, after adding the above-mentioned acid activation of 0.2g after stirring 5min
Paligorskite, regulates with the sodium hydroxide solution of 0.5mol/L and stirs under the conditions of its pH value is 12.5,80 DEG C
2h, then in 160 DEG C of hydro-thermal reactions 24h, by a large amount of water and washing with alcohol and dry, then in 550 DEG C
Heat treatment 6h, i.e. obtains multistage pore canal globular protein stone.
Embodiment 5
Paligorskite is mixed with the hydrochloric acid solution 1:60 by volume of 6M, processes 4h, spend after filtration
Ionized water washing, to without chloride ion, obtains the Paligorskite after acid activation after drying and grinding, standby.
Take 0.2gCTAB to be dissolved in 10mL water, after adding the above-mentioned acid activation of 0.1g after stirring 5min
Paligorskite, regulates with the sodium hydroxide solution of 0.5mol/L and stirs under the conditions of its pH value is 11.5,80 DEG C
4h, then in 200 DEG C of hydro-thermal reactions 24h, by a large amount of water and washing with alcohol and dry, then in 550 DEG C
Heat treatment 6h, i.e. obtains multistage pore canal globular protein stone.
Embodiment 6
Paligorskite is mixed with the hydrochloric acid solution 1:80 by volume of 8M, processes 6h, spend after filtration
Ionized water washing, to without chloride ion, obtains the Paligorskite after acid activation after drying and grinding, standby.
Take 0.1gCTAB to be dissolved in 10mL water, after adding the above-mentioned acid activation of 0.4g after stirring 5min
Paligorskite, regulates with the sodium hydroxide solution of 0.5mol/L and stirs under the conditions of its pH value is 11.5,80 DEG C
6h, then in 200 DEG C of hydro-thermal reactions 24h, by a large amount of water and washing with alcohol and dry, then in 550 DEG C
Heat treatment 6h, i.e. obtains multistage pore canal globular protein stone.
Embodiment 7
Paligorskite is mixed with the hydrochloric acid solution 1:100 by volume of 4M, processes 2h, spend after filtration
Ionized water washing, to without chloride ion, obtains the Paligorskite after acid activation after drying and grinding, standby.
Take 0.2gCTAB to be dissolved in 10mL water, after adding the above-mentioned acid activation of 0.1g after stirring 5min
Paligorskite, regulates stirring 2h under the conditions of its pH value is 11,60 DEG C with the sodium hydroxide solution of 0.5mol/L,
Then in 200 DEG C of hydro-thermal reactions 24h, by a large amount of water and washing with alcohol and dry, then at 550 DEG C of heat
Reason 3h, i.e. obtains multistage pore canal globular protein stone.
Embodiment 8
Paligorskite is mixed with the hydrochloric acid solution 1:100 by volume of 4M, processes 2h, spend after filtration
Ionized water washing, to without chloride ion, obtains the Paligorskite after acid activation after drying and grinding, standby.
Take 0.2gCTAB to be dissolved in 10mL water, after adding the above-mentioned acid activation of 0.2g after stirring 5min
Paligorskite, regulates with the sodium hydroxide solution of 0.5mol/L and stirs under the conditions of its pH value is 11.5,60 DEG C
2h, then in 200 DEG C of hydro-thermal reactions 24h, by a large amount of water and washing with alcohol and dry, then in 550 DEG C
Heat treatment 6h, i.e. obtains multistage pore canal globular protein stone.
Claims (7)
1. a multistage pore canal globular protein stone, it is characterised in that described multistage pore canal globular protein stone
For the microsphere of the multi-layer nano lamellar structure of silica nanometer sheet self assembly, silica nanometer sheet
A diameter of 15-30nm, microspherulite diameter is 0.5-1.5 μm, is formed in every layer of nanoscale twins between nanometer sheet
Pore passage structure, forms the macropore structure of connection between nanoscale twins.
2. the preparation method of a multistage pore canal globular protein stone, it is characterised in that step is as follows:
1) Paligorskite after acid activation is prepared: by Paligorskite and hydrochloric acid solution 1:10-1:100 by volume
Mixing, processes 2-12h, is washed with deionized to without chloride ion after filtration, dries, grinds and obtain acid
Paligorskite after activation；
2) multistage pore canal globular protein stone is prepared: with step 1) Paligorskite after gained acid activation is as silicon
Source, adds in the water dissolved with surfactant cetyl trimethylammonium bromide, and regulation system pH value is
11-12.5, stirs 2-6h under the conditions of 60-80 DEG C, then in 160-200 DEG C of hydro-thermal reaction 24-120h,
Washing after-baking obtains multistage pore canal globular protein stone.
The preparation method of multistage pore canal globular protein stone the most according to claim 2, its feature exists
In step 1) described Paligorskite Particle size requirements mesh number is more than 100 mesh.
The preparation method of multistage pore canal globular protein stone the most according to claim 2, its feature exists
In step 1) concentration of described hydrochloric acid solution is 4-8mol/L.
The preparation method of multistage pore canal globular protein stone the most according to claim 2, its feature exists
In step 2) Paligorskite after described acid activation is 1:2-4:1 with cetyl trimethylammonium bromide mass ratio,
Paligorskite after described acid activation is 0.1-0.4g/10mL with the mass volume ratio of water.
The preparation method of multistage pore canal globular protein stone the most according to claim 2, its feature exists
In step 2) described regulation system pH value be use concentration be 0.5mol/L sodium hydroxide solution regulation.
The preparation method of multistage pore canal globular protein stone the most according to claim 2, its feature exists
In step 2) described Technology for Heating Processing be under 550 DEG C of temperature conditionss process 3-6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510020743.XA CN104556960B (en) | 2015-01-16 | 2015-01-16 | Hierarchical-structured spherical opal and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510020743.XA CN104556960B (en) | 2015-01-16 | 2015-01-16 | Hierarchical-structured spherical opal and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104556960A CN104556960A (en) | 2015-04-29 |
| CN104556960B true CN104556960B (en) | 2017-01-11 |
Family
ID=53074148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510020743.XA Expired - Fee Related CN104556960B (en) | 2015-01-16 | 2015-01-16 | Hierarchical-structured spherical opal and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104556960B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106398652B (en) * | 2016-09-12 | 2019-08-02 | 中南大学 | A kind of silver-loaded silica nanometer sheet and preparation method thereof for heat accumulation |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101708853B (en) * | 2009-07-08 | 2013-03-27 | 济南大学 | Hollow silicon dioxide microsphere with different surface configurations and preparation method thereof |
| CN102390843B (en) * | 2011-08-02 | 2013-05-01 | 复旦大学 | Three-dimensional interconnected hierarchical-structured zeolite molecular sieve material and preparation method thereof |
| CN102304761B (en) * | 2011-08-23 | 2012-06-27 | 陕西科技大学 | Preparation method for non-close-packed opal photonic crystal |
| CN103130229B (en) * | 2011-11-30 | 2014-10-22 | 中国科学院大连化学物理研究所 | Multistage pore silica nano material and preparation method thereof |
-
2015
- 2015-01-16 CN CN201510020743.XA patent/CN104556960B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104556960A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tong et al. | Polymorphous ZnO complex architectures: selective synthesis, mechanism, surface area and Zn-polar plane-codetermining antibacterial activity | |
| Li et al. | A novel approach to hierarchical sphere-like ZnAl-layered double hydroxides and their enhanced adsorption capability | |
| Ramimoghadam et al. | Synthesis and characterization of ZnO nanostructures using palm olein as biotemplate | |
| Xu et al. | Efficient adsorption and photocatalytic degradation of Rhodamine B under visible light irradiation over BiOBr/montmorillonite composites | |
| CN104030335B (en) | A kind of homogeneous phase hydrothermal method that adopts prepares Sm (OH) 3the method of/ZnO nano mixture | |
| Cheng et al. | Synthesis of MCM-22 zeolite using rice husk as a silica source under varying-temperature conditions | |
| CN110193342A (en) | A kind of modified attapulgite earth adsorbing and preparation method thereof | |
| CN109942012B (en) | Nanoscale flaky boehmite and preparation method thereof | |
| Lu et al. | From structure evolution of palygorskite to functional material: A review | |
| Cai et al. | Template-free solvothermal synthesis of hierarchical boehmite hollow microspheres with strong affinity toward organic pollutants in water | |
| CN104607231A (en) | Carbon nitride photocatalyst with three-dimensional ordered macroporous structure and preparation method of carbon nitride photocatalyst | |
| Akpotu et al. | Effect of synthesis conditions on the morphology of mesoporous silica from elephant grass and its application in the adsorption of cationic and anionic dyes | |
| CN106622331B (en) | A kind of preparation method of high-specific surface area graphite phase carbon nitride photochemical catalyst | |
| Song et al. | Controlled synthesis of porous flower-like TiO2 nanostructure with enhanced photocatalytic activity | |
| CN104874385B (en) | A kind of TiO2Nanotube/SiO2Compound catalysis material of aeroge and preparation method thereof | |
| Song et al. | Self-assembled synthesis of urchin-like AlOOH microspheres with large surface area for removal of pollutants | |
| Pudukudy et al. | Synthesis, characterization, and photocatalytic performance of mesoporous α-Mn2O3 microspheres prepared via a precipitation route | |
| Pan et al. | A novel synthesis of micrometer silica hollow sphere | |
| Gu et al. | Preparation and characterization of highly photocatalytic active hierarchical BiOX (X= Cl, Br, I) microflowers for rhodamine B degradation with kinetic modelling studies | |
| Wang et al. | Size control of SBA-15 by tuning the stirring speed for the formation of CMK-3 with distinct adsorption performance | |
| CN104556960B (en) | Hierarchical-structured spherical opal and preparation method thereof | |
| CN110227515A (en) | Bi2MoO6/BiPO4P-n heterojunction photochemical catalyst, preparation method and applications | |
| Wang et al. | 3D hierarchical ZnOHF nanostructures: synthesis, characterization and photocatalytic properties | |
| CN105271374A (en) | Preparation method of stannic oxide microspheres of oriented connection microstructure | |
| Wang et al. | Needle-like calcium carbonate assisted self-assembly of mesostructured hollow silica nanotubes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170111 Termination date: 20180116 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |