CN104746178B - A kind of preparation method of the silicate double-layer hollow nanofiber with multilevel hierarchy - Google Patents
A kind of preparation method of the silicate double-layer hollow nanofiber with multilevel hierarchy Download PDFInfo
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- CN104746178B CN104746178B CN201310731852.3A CN201310731852A CN104746178B CN 104746178 B CN104746178 B CN 104746178B CN 201310731852 A CN201310731852 A CN 201310731852A CN 104746178 B CN104746178 B CN 104746178B
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- hollow nanofiber
- multilevel hierarchy
- silicate
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Abstract
The invention belongs to inorganic chemical synthesis method, and in particular to have the preparation method of the silicate double-layer hollow nanofiber of multilevel hierarchy.The present invention is using acetate as raw material, using ammoniacal liquor as complexing agent, using ammonium chloride as mineralizer, using silicon dioxide hollow nanofiber as sacrifice template, in closed reactor, the hydro-thermal reaction under the conditions of certain temperature, the silicate double-layer hollow nanofiber with multilevel hierarchy can be synthesized.A diameter of 300 to 600 nanometers of gained fiber.The material of this pattern not only has big specific surface area, and is easy to settle, and is easy to separate and recover recycling from solution.Operation is simple and reliable for this method, and controllability is strong, using raw material cheap and easy to get, and has universality, is laid a good foundation for the extensive use of silicate.
Description
Technical field
The invention belongs to inorganic chemical synthesis method, and in particular to have the silicate double-layer hollow Nanowire of multilevel hierarchy
The preparation of dimension.
Background technology
Silicate is easy to adjust, and has good heat endurance and change due to abundant raw material, crystal structure stabilization, component
The physicochemical property of stability and uniqueness is learned, it is had extensively in absorption, catalyst carrier, medicine controlled releasing, lithium electricity etc.
Application.In recent years, the micro-/ nano material of various nano materials, particularly multi-layer hollow with special construction and special appearance
Material, cause the extensive concern of people.The material of this class formation has the characteristics that low-density, high-ratio surface, excellent stability,
And its hollow parts can accommodate substantial amounts of guest molecule or large-sized object, and it is peculiar based on microcosmic can to produce some
The property of " parcel " effect so that multi-layer hollow micro/nano material is in many skills such as medicine, lithium electricity, catalysis and pollutant processes
There is important application in art field.Therefore, silicate nano material of the synthesis with multi-layer hollow structure has more extensive
Actual application prospect.
At present, the method for traditional synthetic method and document report can only all synthesize the individual layer silicate hollow ball of ball-type,
So that silicate is above restricted in application.Such as Britain《Chemical communication》(Chemical Communications) 2008
Page 2911 report hydro-thermal method synthetic silicic acid nickel hollow nano-sphere.Middle king is waited in Chinese patent by force forever（Publication number：
CN101659417A）On disclose method on preparing porous silicate hollow bead using template.When this individual layer
When silicate hollow ball is as the adsorbent of processing water pollutant or heavy metal, it is easily suspended in water, it is difficult to separate and recover
And recycling, so as to greatly limit their practical application.Electrostatic spinning technique is as preparing having for ultra-long nano fiber
Efficacious prescriptions method, it is the unique method for preparing continuous nano-fibre that fast development is got up in recent years, and equipment requirement is simple, operation
Simplicity, yield are high.For nanofiber diameter prepared by this method typically between tens to hundreds of nanometers, length is generally several
Hundred microns, net felt structure is macroscopically being normally behaved as, the material of this structure is easy to settle, and is easy to separate from solution.Institute
With, using electrostatic spinning technique prepare with multilevel hierarchy silicate double-layer hollow nanofiber absorption etc. field have it is non-
Often important actual application value.
The content of the invention
In view of this, there is provided a kind of technique is simple, and cost is relatively low and the silicate with universality with multilevel hierarchy
The preparation method of double-layer hollow nanofiber is actually necessary.
Technical scheme provided by the present invention is as follows：
A kind of synthetic method of the silicate double-layer hollow nanofiber with multilevel hierarchy, first, with tetraethyl orthosilicate,
Polyvinylpyrrolidone（PVP）, absolute ethyl alcohol be raw material, prepare with certain viscosity electrospinning precursor solution, utilize electrostatic
Spining technology prepares tetraethyl orthosilicate/PVP composite fibres, then obtains silicon dioxide hollow nanofiber by calcining.Again with second
Hydrochlorate is raw material, using ammoniacal liquor as complexing agent, using ammonium chloride as mineralizer, using electrospinning silicon dioxide hollow nanofiber as sacrificial mold
Plate, the silicate double-layer hollow nanofiber with multilevel hierarchy is prepared under hydrothermal conditions.Its operating procedure is as follows：
（1）At room temperature, PVP, by volume, tetraethyl orthosilicate are added after tetraethyl orthosilicate is well mixed with absolute ethyl alcohol
Proportioning with absolute ethyl alcohol is 1：6.25, PVP mass fraction is 9%.4 hours of magnetic agitation, treat that PVP is completely dissolved mixing
After uniform and static 2 hours, tetraethyl orthosilicate/PVP composite fibre is prepared using electrostatic spinning technique.
（2）By step（1）The composite fibre of gained is calcined 2 hours at 550 DEG C, and heating rate is 0.5 DEG C/min, is obtained
To silicon dioxide hollow nanofiber.
（3）At room temperature, acetate, ammoniacal liquor, ammonium chloride, silicon dioxide hollow nanofiber are added to the water, in 100-180
10 hours of constant temperature at DEG C.
（4）By step（3）It is target product after the washing of gained solid product after the reaction product of middle gained is cooled to room temperature
Double-deck silicate hollow Nano fiber in use with multilevel hierarchy.
In step（3）Described in acetate can be nickel acetate tetrahydrate, copper acetate dihydrate, four acetate hydrate magnesium etc..
In step（4）Described in wash, can be washed respectively at least 3 times with water and ethanol successively.
Compared to prior art, the system of the silicate double-layer hollow nanofiber provided by the present invention with multilevel hierarchy
Preparation Method has advantages below：
（1）The silicate double-layer hollow nanofiber of multilevel hierarchy synthesized by the present invention is easily isolated and recycled and repeated profit
With.
（2）The present invention has universality, can prepare various silicate double-layer hollows by changing different metal ions and receive
Rice fibre structure.
（3）The present invention has very strong controllability, can be by adjusting electrospinning condition, and the diameter of effective control fiber is big
It is small, and can be by adjusting the proportioning between raw material, the wall thickness of silicate hollow nano fiber synthesized by effective control.
（4）For building-up process by using the method for hydro-thermal, synthetic reaction device is simple, and reaction condition is gentle, therefore has
It is widely applied prospect.
Brief description of the drawings
Accompanying drawing 1 is the electron scanning micrograph of silicon dioxide hollow nanofiber；
Accompanying drawing 2 is the transmission electron microscope photo of silicon dioxide hollow nanofiber；
Accompanying drawing 3 is the electron scanning micrograph of obtained silicic acid nickel double-layer hollow nanofiber at 100 DEG C of temperature；
Accompanying drawing 4 is the transmission electron microscope photo of obtained silicic acid nickel double-layer hollow nanofiber at 100 DEG C of temperature；
Accompanying drawing 5 is the electron scanning micrograph of obtained cupric silicate double-layer hollow nanofiber at 140 DEG C of temperature；
Accompanying drawing 6 is the transmission electron microscope photo of obtained cupric silicate double-layer hollow nanofiber at 140 DEG C of temperature；
Accompanying drawing 7 is the electron scanning micrograph of obtained magnesium silicate double-layer hollow nanofiber at 180 DEG C of temperature；
Accompanying drawing 8 is the transmission electron microscope photo of obtained magnesium silicate double-layer hollow nanofiber at 180 DEG C of temperature；
Embodiment
Embodiment 1：
By 1.6 milliliters of tetraethyl orthosilicates and 10 milliliters of absolute ethyl alcohol magnetic agitations 10 minutes；By 0.95 gram of polyvinyl pyrrole
Alkanone（Molecular weight is 90000）Add in above-mentioned solution, at room temperature magnetic agitation 4 hours, and static 2 hours, that is, formed and spun
Silk solution；The spinning solution prepared is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, 0.6 millimeter of nozzle diameter, adjust
Whole nozzle is 15 degree with horizontal plane inclination angle, applies 9.5 kilovolts of DC voltage, solidification distance is 20 centimetres, obtains positive silicic acid second
Ester/PVP composite nano fiber；The composite nano fiber of gained is put into temperature programmed control stove and is heat-treated, heating rate
For 0.5 DEG C/min, in 2 hours of 550 DEG C of constant temperature, afterwards with body of heater natural cooling, target product is produced.Product is through X ray powder
Last diffraction and energy dispersion X-ray Spectral Identification is unbodied silica.Two can be proved by SEM
For the diameter of silicon oxide nanofiber in 200-500 nanometers, prepared dioxy can be proved by being characterized by transmission electron microscope
SiClx nanofiber is hollow-core construction, about 60 nanometers of wall thickness（Such as attached Fig. 1 and 2）.
Embodiment 2：
At room temperature, 0.0002 mole of nickel acetate tetrahydrate is dissolved into 10 ml deionized waters, is sufficiently stirred 5 points
Clock；0.2 milliliter of concentrated ammonia liquor and 0.002 mole of ammonium chloride are sequentially added in mixed solution, continue stirring 5 minutes；Will be above-mentioned
Mixed solution is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining；0.02 gram of hollow silica nanofiber is added again
Enter into reactor, be put into after reactor is sealed in baking oven, hydro-thermal reaction 10 hours at 100 DEG C.Naturally cool to room temperature
Afterwards, with deionized water and absolute ethyl alcohol, alternately washing for several times, centrifugally separating mixture, produces target product.Product is through X ray powder
Last diffraction and energy dispersion X-ray Spectral Identification is silicic acid nickel, and silicic acid nickel Nanowire can be proved by SEM
Dimension has a multilevel hierarchy, and fibre wall is made up of two-dimentional nanometer sheet, and fibre diameter passes through in 300-600 rans
Transmission electron microscope, which characterizes, can prove that prepared silicic acid nickel nanofiber has double-deck hollow-core construction, and specific surface area is
373m2/g（Such as accompanying drawing 3 and 4）.
Embodiment 3：
At room temperature, 0.0002 mole of copper acetate dihydrate is dissolved into 10 ml deionized waters, is sufficiently stirred 5 points
Clock；0 .2 milliliters concentrated ammonia liquor and 0.002 mole of ammonium chloride are sequentially added in mixed solution, continue stirring 5 minutes；Will be above-mentioned
Mixed solution is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining；0.02 gram of hollow silica nanofiber is added again
Enter into reactor, be put into after reactor is sealed in baking oven, hydro-thermal reaction 10 hours at 140 DEG C.Naturally cool to room temperature
Afterwards, with deionized water and absolute ethyl alcohol, alternately washing for several times, centrifugally separating mixture, produces target product.Product is through X ray powder
Last diffraction and energy dispersion X-ray Spectral Identification is cupric silicate, and cupric silicate Nanowire can be proved by SEM
Dimension has multilevel hierarchy, and fibre wall is made up of one-dimensional nanotube, and fibre diameter passes through in 300-600 rans
Transmission electron microscope, which characterizes, can prove that prepared cupric silicate nanofiber has double-deck hollow-core construction, and specific surface area is
541m2/g（Such as accompanying drawing 5 and 6）.
Embodiment 4：
At room temperature, 0.0002 mole of four acetate hydrate magnesium are dissolved into 10 ml deionized waters, are sufficiently stirred 5 points
Clock；0.2 milliliter of concentrated ammonia liquor and 0.002 mole of ammonium chloride are sequentially added in mixed solution, continue stirring 5 minutes；Will be above-mentioned
Mixed solution is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining；0.02 gram of hollow silica nanofiber is added again
Enter into reactor, be put into after reactor is sealed in baking oven, hydro-thermal reaction 10 hours at 180 DEG C.Naturally cool to room temperature
Afterwards, with deionized water and absolute ethyl alcohol, alternately washing for several times, centrifugally separating mixture, produces target product.Product is through X ray powder
Last diffraction and energy dispersion X-ray Spectral Identification is magnesium silicate, and magnesium silicate Nanowire can be proved by SEM
Dimension has a multilevel hierarchy, and fibre wall is made up of two-dimentional nanometer sheet, and fibre diameter passes through in 300-600 rans
Transmission electron microscope, which characterizes, can prove that prepared magnesium silicate nanofiber has double-deck hollow-core construction, and specific surface area is
632m2/g（Such as accompanying drawing 7 and 8）.
Claims (2)
1. a kind of preparation method of the silicate double-layer hollow nanofiber with multilevel hierarchy, it is characterised in that this method includes
Following steps：
(1) silicon dioxide hollow nanofiber is prepared：
By 1.6 milliliters of tetraethyl orthosilicates and 10 milliliters of absolute ethyl alcohol magnetic agitations 10 minutes；It is 90000 by 0.95 gram-molecular weight
Polyvinylpyrrolidone is added in above-mentioned solution, magnetic agitation 4 hours, and static 2 hours at room temperature, that is, it is molten to form spinning
Liquid；The spinning solution prepared is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, 0.6 millimeter of nozzle diameter, adjustment spray
Mouth and horizontal plane inclination angle are 15 degree, apply 9.5 kilovolts of DC voltage, and solidification distance is 20 centimetres, obtain tetraethyl orthosilicate/
PVP composite nano fiber；The composite nano fiber of gained is put into temperature programmed control stove and is heat-treated, heating rate is
0.5 DEG C/min, in 2 hours of 550 DEG C of constant temperature, afterwards with body of heater natural cooling, obtain silicon dioxide hollow nanofiber;
(2) the silicate double-layer hollow nanofiber with multilevel hierarchy is prepared：
At room temperature, 0.0002 mole of acetate is dissolved into 10 ml deionized waters, be sufficiently stirred 5 minutes；By 0.2 milliliter
Concentrated ammonia liquor and 0.002 mole of ammonium chloride are sequentially added in mixed solution, continue stirring 5 minutes；Above-mentioned mixed solution is shifted
Into the stainless steel cauldron of polytetrafluoroethyllining lining；Again by the hollow silica Nanowire of gained in 0.02 gram of step (1)
Dimension is added in reactor, is put into after reactor is sealed in baking oven, hydro-thermal reaction 10 hours at a temperature of 100-180 DEG C, i.e.,
There must be the silicate double-layer hollow nanofiber of multilevel hierarchy.
2. according to the preparation method described in claim 1, it is characterised in that in step (2), described acetate is four hydration second
Sour nickel or copper acetate dihydrate or four acetate hydrate magnesium.
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| CN108867028B (en) * | 2018-07-18 | 2021-03-26 | 吉林大学 | Preparation method of flexible silicate nanofiber membrane |
| CN108862292A (en) * | 2018-09-10 | 2018-11-23 | 江西师范大学 | A method of regulation silicon dioxide microsphere partial size |
| CN109360985B (en) * | 2018-12-05 | 2021-07-02 | 安徽师范大学 | Two-dimensional porous flaky cobalt silicate nanomaterial and preparation method thereof, lithium ion battery cathode and lithium ion battery |
| CN110559985A (en) * | 2019-09-20 | 2019-12-13 | 南京信息工程大学 | Magnetic silicate adsorbent and preparation method thereof |
| CN114957843B (en) * | 2022-02-10 | 2024-01-09 | 福州大学 | Preparation and application of antistatic EVA (ethylene-vinyl acetate) and EPDM (ethylene-propylene-diene monomer) composite foam material |
| CN116618048B (en) * | 2023-04-24 | 2024-01-12 | 陕西科技大学 | Preparation method and application of single-wall copper silicate nano Guan Guangfen ton catalyst |
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| JP3782993B2 (en) * | 2001-11-28 | 2006-06-07 | 国立大学法人名古屋大学 | Manufacturing method of hollow nanofiber |
| CN101659417A (en) * | 2008-08-28 | 2010-03-03 | 中国科学院合肥物质科学研究院 | Porous silicate nanometer hollow granule and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3782993B2 (en) * | 2001-11-28 | 2006-06-07 | 国立大学法人名古屋大学 | Manufacturing method of hollow nanofiber |
| CN101659417A (en) * | 2008-08-28 | 2010-03-03 | 中国科学院合肥物质科学研究院 | Porous silicate nanometer hollow granule and preparation method thereof |
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