CN104746178A - Preparation method of silicate double-layer hollow nanometer fiber with multistage structure - Google Patents
Preparation method of silicate double-layer hollow nanometer fiber with multistage structure Download PDFInfo
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- CN104746178A CN104746178A CN201310731852.3A CN201310731852A CN104746178A CN 104746178 A CN104746178 A CN 104746178A CN 201310731852 A CN201310731852 A CN 201310731852A CN 104746178 A CN104746178 A CN 104746178A
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Abstract
The invention relates to a preparation method of a silicate double-layer hollow nanometer fiber with a multistage structure. The preparation method belongs to an inorganic chemical synthesis method. The preparation method comprises that acetate as a raw material, ammonium hydroxide as a complexing agent, ammonium chloride as a mineralizer and silica hollow nanometer fibers as sacrifice templates undergo a hydro-thermal reaction at a certain temperature in an enclosed reactor to produce the silicate double-layer hollow nanometer fibers with multistage structures. The silicate double-layer hollow nanometer fiber has the diameter of 300-600 nanometers. The silicate double-layer hollow nanometer fiber has a large specific surface area, can be precipitated easily and is convenient for separation from a solution, recovery and recycle. The preparation method has simple and reliable processes, has high controllability, adopts cheap and easily available raw materials, has universality and lays the foundation of wide application of silicate.
Description
Technical field
The invention belongs to inorganic chemical synthesis method, be specifically related to the preparation of the silicate double-layer hollow nanofiber with multilevel hierarchy.
Background technology
Silicate, because abundant raw material, crystal structure are stable, component is easy to adjustment, and has the physicochemical property of good heat endurance and chemical stability and uniqueness, makes it have a wide range of applications in absorption, catalyst carrier, medicine controlled releasing, lithium are electric etc.In recent years, the micro/nano material of the various nano material with special construction and special appearance, particularly multi-layer hollow, causes the extensive concern of people.The material of this class formation has the features such as low-density, high-ratio surface, excellent stability, and its hollow parts can hold a large amount of guest molecules or large-sized object, the character based on microcosmic " parcel " effect that some are peculiar can be produced, make multi-layer hollow micro/nano material have important application in many technical fields such as medicine, electric, the catalysis of lithium and pollutant process.Therefore, synthesize the silicate nano material with multi-layer hollow structure and have actual application prospect more widely.
At present, traditional synthetic method and the method for bibliographical information all can only synthesize the monolayer silicon hydrochlorate hollow ball of ball-type, and silicate is restricted in application.Such as, 2911 pages, Britain's " chemical communication " (Chemical Communications) 2008 reports water heat transfer silicic acid nickel hollow nano-sphere.Middle king waits by force the method disclosed on Chinese patent (publication number: CN101659417A) about adopting template synthesis porous silicate hollow bead forever.When the silicate hollow ball of this individual layer is as process water pollutant or the adsorbent of heavy metal, is easy to be suspended in water, is difficult to separation and recovery and recycling, thus greatly limit their practical application.Electrostatic spinning technique is as the effective ways preparing ultra-long nano fiber, and be the unique method preparing continuous nano-fibre that fast development is in recent years got up, and equipment requirement is simple, easy and simple to handle, productive rate is high.Nanofiber diameter prepared by this method is generally between tens to hundreds of nanometer, and length is generally hundreds of micron, and macroscopically generally showing as net felt structure, the material of this structure is easy to sedimentation, is convenient to be separated from solution.So utilizing electrostatic spinning technique to prepare the silicate double-layer hollow nanofiber with multilevel hierarchy has very important actual application value in fields such as absorption.
Summary of the invention
In view of this, provide a kind of technique simple, cost is lower and to have the preparation method with the silicate double-layer hollow nanofiber of multilevel hierarchy of universality real in necessary.
Technical scheme provided by the present invention is as follows:
A kind of synthetic method with the silicate double-layer hollow nanofiber of multilevel hierarchy, first, with ethyl orthosilicate, polyvinylpyrrolidone (PVP), absolute ethyl alcohol for raw material, preparation has the electrospinning precursor solution of certain viscosity, utilize electrostatic spinning technique to prepare ethyl orthosilicate/PVP composite fibre, then obtain silicon dioxide hollow nanofiber through calcining.Be raw material with acetate again, being complexing agent with ammoniacal liquor, take ammonium chloride as mineralizer, and with electrospinning silicon dioxide hollow nanofiber for sacrificing template, preparation has the silicate double-layer hollow nanofiber of multilevel hierarchy under hydrothermal conditions.Its operating procedure is as follows:
(1) under room temperature, add PVP after being mixed by ethyl orthosilicate with absolute ethyl alcohol, by volume, the proportioning of ethyl orthosilicate and absolute ethyl alcohol is the mass fraction of 1:6.25, PVP is 9%.Magnetic agitation 4 hours, dissolves completely until PVP and mixes and after static 2 hours, utilize electrostatic spinning technique to prepare the composite fibre of ethyl orthosilicate/PVP.
(2) by the roasting 2 hours at 550 DEG C of the composite fibre of step (1) gained, heating rate is 0.5 DEG C/min, obtains silicon dioxide hollow nanofiber.
(3) under room temperature, acetate, ammoniacal liquor, ammonium chloride, silicon dioxide hollow nanofiber are added to the water, constant temperature 10 hours at 100-180 DEG C.
(4), after the product of middle for step (3) gained being cooled to room temperature, after the washing of gained solid product, namely target product has the silicon bi-layer hydrochlorate hollow Nano fiber in use of multilevel hierarchy.
Described acetate can be nickel acetate tetrahydrate, copper acetate dihydrate, four acetate hydrate magnesium etc. in step (3).
Wash described in step (4), at least 3 times can be washed respectively with water and ethanol successively.
Compared to prior art, the preparation method with the silicate double-layer hollow nanofiber of multilevel hierarchy provided by the present invention has the following advantages:
(1) the silicate double-layer hollow nanofiber of the multilevel hierarchy synthesized by the present invention is easy to separation and recovery and recycling.
(2) the present invention has universality, by changing different metal ions, prepares various silicate double-layer hollow nanofibrous structures.
(3) the present invention has very strong controllability, can by regulating electrospinning condition, the effective diameter controlling fiber, and can by regulating the proportioning between raw material, the effective wall thickness controlling synthesized silicate hollow nano fiber.
(4) building-up process is by adopting the method for hydro-thermal, and synthetic reaction device is simple, and reaction condition is gentle, is therefore with a wide range of applications.
Accompanying drawing explanation
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 silicic acid nickel double-layer hollow nanofiber obtained at temperature 100 DEG C;
Accompanying drawing 4 is the transmission electron microscope photo of silicic acid nickel double-layer hollow nanofiber obtained at temperature 100 DEG C;
Accompanying drawing 5 is the electron scanning micrograph of cupric silicate double-layer hollow nanofiber obtained at temperature 140 DEG C;
Accompanying drawing 6 is the transmission electron microscope photo of cupric silicate double-layer hollow nanofiber obtained at temperature 140 DEG C;
Accompanying drawing 7 is the electron scanning micrograph of magnesium silicate double-layer hollow nanofiber obtained at temperature 180 DEG C;
Accompanying drawing 8 is the transmission electron microscope photo of magnesium silicate double-layer hollow nanofiber obtained at temperature 180 DEG C;
Detailed description of the invention
Embodiment 1:
By 1.6 milliliters of ethyl orthosilicates and 10 milliliters of absolute ethyl alcohol magnetic agitation 10 minutes; 0.95 gram of polyvinylpyrrolidone (molecular weight is 90000) is added in above-mentioned solution, stirs 4 hours in room temperature lower magnetic force, and static 2 hours, namely form spinning solution; The spinning solution prepared is added in the liquid storage pipe of device for spinning, carries out electrostatic spinning, nozzle diameter 0.6 millimeter, adjustment nozzle and horizontal plane inclination angle are 15 degree, apply the DC voltage of 9.5 kilovolts, solidification distance is 20 centimetres, obtains the composite nano fiber of ethyl orthosilicate/PVP; Be put in temperature programmed control stove by the composite nano fiber of gained and heat-treat, heating rate is 0.5 DEG C/min, 550 DEG C of constant temperature 2 hours, naturally cools afterwards, obtain target product with body of heater.Product is unbodied silica through X-ray powder diffraction and energy dispersion X-ray Spectral Identification.Can prove that silica nano fibrous diameter is in 200-500 nanometer by scanning electronic microscope, by transmission electron microscope characterize can prove prepared silica nano fibrous be hollow-core construction, wall thickness about 60 nanometer (as attached Fig. 1 and 2).
Embodiment 2:
Under room temperature, the nickel acetate tetrahydrate of 0.0002 mole is dissolved in 10 ml deionized water, fully stirs 5 minutes; The ammonium chloride of 0.2 milliliter of concentrated ammonia liquor and 0.002 mole is added in mixed solution successively, continues stirring 5 minutes; Above-mentioned mixed solution is transferred in teflon-lined stainless steel cauldron; Again 0.02 gram of hollow silica nanofiber is joined in reactor, after being sealed by reactor, put into baking oven, hydro-thermal reaction 10 hours at 100 DEG C.After naturally cooling to room temperature, alternately wash for several times with deionized water and absolute ethyl alcohol, centrifugally separating mixture, obtains target product.Product is silicic acid nickel through X-ray powder diffraction and energy dispersion X-ray Spectral Identification, can prove that silicic acid nickel nanofiber has multilevel hierarchy by scanning electronic microscope, fibre wall is made up of the nanometer sheet of two dimension, fibre diameter is at 300-600 ran, characterized by transmission electron microscope and can prove that prepared silicic acid nickel nanofiber has double-deck hollow-core construction, specific area is 373m
2/ g(is as accompanying drawing 3 and 4).
Embodiment 3:
Under room temperature, the copper acetate dihydrate of 0.0002 mole is dissolved in 10 ml deionized water, fully stirs 5 minutes; The ammonium chloride of 0 .2 milliliter concentrated ammonia liquor and 0.002 mole is added in mixed solution successively, continues stirring 5 minutes; Above-mentioned mixed solution is transferred in teflon-lined stainless steel cauldron; Again 0.02 gram of hollow silica nanofiber is joined in reactor, after being sealed by reactor, put into baking oven, hydro-thermal reaction 10 hours at 140 DEG C.After naturally cooling to room temperature, alternately wash for several times with deionized water and absolute ethyl alcohol, centrifugally separating mixture, obtains target product.Product is cupric silicate through X-ray powder diffraction and energy dispersion X-ray Spectral Identification, can prove that cupric silicate nanofiber has multilevel hierarchy by scanning electronic microscope, fibre wall is made up of the nanotube of one dimension, fibre diameter is at 300-600 ran, characterized by transmission electron microscope and can prove that prepared cupric silicate nanofiber has double-deck hollow-core construction, specific area is 541m
2/ g(is as accompanying drawing 5 and 6).
Embodiment 4:
Under room temperature, the four acetate hydrate magnesium of 0.0002 mole are dissolved in 10 ml deionized water, fully stir 5 minutes; The ammonium chloride of 0.2 milliliter of concentrated ammonia liquor and 0.002 mole is added in mixed solution successively, continues stirring 5 minutes; Above-mentioned mixed solution is transferred in teflon-lined stainless steel cauldron; Again 0.02 gram of hollow silica nanofiber is joined in reactor, after being sealed by reactor, put into baking oven, hydro-thermal reaction 10 hours at 180 DEG C.After naturally cooling to room temperature, alternately wash for several times with deionized water and absolute ethyl alcohol, centrifugally separating mixture, obtains target product.Product is magnesium silicate through X-ray powder diffraction and energy dispersion X-ray Spectral Identification, can prove that magnesium silicate nanofiber has multilevel hierarchy by scanning electronic microscope, fibre wall is made up of the nanometer sheet of two dimension, fibre diameter is at 300-600 ran, characterized by transmission electron microscope and can prove that prepared magnesium silicate nanofiber has double-deck hollow-core construction, specific area is 632m
2/ g(is as accompanying drawing 7 and 8).
Claims (2)
1. there is a preparation method for the silicate double-layer hollow nanofiber of multilevel hierarchy, it is characterized in that the method comprises the steps:
(1) silicon dioxide hollow nanofiber is prepared:
By 1.6 milliliters of ethyl orthosilicates and 10 milliliters of absolute ethyl alcohol magnetic agitation 10 minutes; 0.95 gram of polyvinylpyrrolidone (molecular weight is 90000) is added in above-mentioned solution, stirs 4 hours in room temperature lower magnetic force, and static 2 hours, namely form spinning solution; The spinning solution prepared is added in the liquid storage pipe of device for spinning, carries out electrostatic spinning, nozzle diameter 0.6 millimeter, adjustment nozzle and horizontal plane inclination angle are 15 degree, apply the DC voltage of 9.5 kilovolts, solidification distance is 20 centimetres, obtains the composite nano fiber of ethyl orthosilicate/PVP; Be put in temperature programmed control stove by the composite nano fiber of gained and heat-treat, heating rate is 0.5 DEG C/min, 550 DEG C of constant temperature 2 hours, naturally cools afterwards, obtain silicon dioxide hollow nanofiber with body of heater.
(2) preparation has the silicate double-layer hollow nanofiber of multilevel hierarchy:
Under room temperature, the acetate of 0.0002 mole is dissolved in 10 ml deionized water, fully stirs 5 minutes; The ammonium chloride of 0.2 milliliter of concentrated ammonia liquor and 0.002 mole is added in mixed solution successively, continues stirring 5 minutes; Above-mentioned mixed solution is transferred in teflon-lined stainless steel cauldron; Again the hollow silica nanofiber of gained in 0.02 gram of step (1) is joined in reactor, baking oven is put into after being sealed by reactor, in uniform temperature Water Under thermal response 10 hours, the silicate double-layer hollow nanofiber of multilevel hierarchy must be had.
2. according to preparation method according to claim 1, it is characterized in that in step (2), described acetate is nickel acetate tetrahydrate or copper acetate dihydrate or four acetate hydrate magnesium.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108867028A (en) * | 2018-07-18 | 2018-11-23 | 吉林大学 | A kind of preparation method of flexibility silicate nano tunica fibrosa |
| CN108862292A (en) * | 2018-09-10 | 2018-11-23 | 江西师范大学 | A method of regulation silicon dioxide microsphere partial size |
| CN109360985A (en) * | 2018-12-05 | 2019-02-19 | 安徽师范大学 | A kind of two dimension porous flake cobaltous silicate nano material and preparation method thereof, negative electrode of lithium ion battery, 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 |
| CN114957843A (en) * | 2022-02-10 | 2022-08-30 | 福州大学 | Preparation and application of antistatic EVA (ethylene-vinyl acetate copolymer) and EPDM (ethylene-propylene-diene monomer) composite foam material |
| CN116618048A (en) * | 2023-04-24 | 2023-08-22 | 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 |
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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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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108867028A (en) * | 2018-07-18 | 2018-11-23 | 吉林大学 | A kind of preparation method of flexibility silicate nano tunica fibrosa |
| CN108862292A (en) * | 2018-09-10 | 2018-11-23 | 江西师范大学 | A method of regulation silicon dioxide microsphere partial size |
| CN109360985A (en) * | 2018-12-05 | 2019-02-19 | 安徽师范大学 | A kind of two dimension porous flake cobaltous silicate nano material and preparation method thereof, negative electrode of lithium ion battery, 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 |
| CN114957843A (en) * | 2022-02-10 | 2022-08-30 | 福州大学 | Preparation and application of antistatic EVA (ethylene-vinyl acetate copolymer) and EPDM (ethylene-propylene-diene monomer) composite foam material |
| 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 |
| CN116618048A (en) * | 2023-04-24 | 2023-08-22 | 陕西科技大学 | Preparation method and application of single-wall copper silicate nano Guan Guangfen ton catalyst |
| 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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