CN108238605A - A kind of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon and preparation method thereof - Google Patents
A kind of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon and preparation method thereof Download PDFInfo
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- CN108238605A CN108238605A CN201810304288.XA CN201810304288A CN108238605A CN 108238605 A CN108238605 A CN 108238605A CN 201810304288 A CN201810304288 A CN 201810304288A CN 108238605 A CN108238605 A CN 108238605A
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- 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
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
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- 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
Abstract
A kind of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon and preparation method thereof, belongs to technical field of inorganic nano-material preparation.First by nano lamellar silica ultrasonic disperse in deionized water, white emulsion is obtained, melamine is then added under the conditions of 60~90 DEG C of waters bath with thermostatic control stirs 1~3h, adds water soluble nickel salt, dilute acid soln is added in after being dispersed with stirring uniformly, obtains green lotion；Green lotion is transferred in autoclave, 5 are placed in the condition that temperature is 160~200 DEG C~for 24 hours, and it is dry in 60~90 DEG C of baking oven after centrifugation after naturally ringing to room temperature after the completion of reaction, obtain three-dimensional flower-shaped alkali formula silicic acid nickel microballoon.The shortcomings that previous hard template is removed and wasted is overcome as reactant and the template of self assembly using stratiform silica in the present invention.Meanwhile in the case where expanding reaction system and short time high temperature reaction, uniform flower-shaped silicic acid nickel microballoon can still generate.For the present invention using one step hydro thermal method, easy to operate, short preparation period process is pollution-free, and cost of material used is relatively low, is suitble to mass production.
Description
Technical field
The invention belongs to technical field of inorganic nano-material preparation, and in particular to a kind of by the three of two-dimensional nano piece self assembly
Tie up flower-shaped alkali formula silicic acid nickel microballoon and preparation method thereof.
Background technology
Silicic acid nickel has excellent physicochemical properties in battery material, magnetisable material and catalyst carrier etc..
In recent years, these properties caused the attention of researcher, and silicic acid nickel is considered as a kind of very promising functional inorganic
Material.The property of nano material and application and the pattern and size of material have direct relationship, and at present for nanometer nickel salt
Research focuses primarily upon the one-dimensional field such as nanometer rods, nano wire, nanofiber, and three-dimensional structure is self-assembled into for two-dimensional nano piece
Research it is also seldom.Since the material of this class formation has the characteristic of high-ratio surface, high stability and Surface Permeability, and
Its part that is staggeredly stacked can accommodate a large amount of guest molecule or large-sized object so that flower-like microsphere material is in catalyst, electricity
Many technical fields such as pond, photoelectric material, magnetic science have important role chemical industry progress.
Prepared by the tradition of flower-like structure silicic acid nickel and its composite inorganic membranes is hard template method, hydro-thermal self-assembly method and colloidal sol
Gel method etc..Template reaction system is unstable, and particle diameter distribution is uneven, and a certain proportion of template object is usually contained in product
Matter influences the purity of substance.The hard template used is additionally needed, need to heat or chemically reacts removing template, can be increased in this way
Big workload.Meanwhile hard template cannot be reused, and cause greatly to waste.Sol-gal process will use metal organic alkoxide,
The more difficult preparation of this raw material and expensive.Hydro-thermal self-assembling technique is more effective and practical in current synthesis multidimensional structure
Technology is widely used in as a kind of most common method for preparing nano-hollow ball in the preparation of various nano materials,
Its application in the preparation of polymer nanocomposite hollow ball has correlative study report, and technology relative maturity.Before control
Drive the parameters such as body ratio, concentration, reaction temperature, you can obtain two-dimensional nano piece self assembly flower-like structure material.It has not yet to see
There is the method report that three-dimensional flower-shaped structure silicic acid nickel microballoon is prepared on a large scale under the conditions of no template.
Invention content
In order to overcome problems of the prior art, the purpose of the present invention is to provide a kind of three-dimensional flower-shaped alkali formula silicic acid
Nickel microballoon and preparation method thereof, the method for the present invention is simple for process, easily operated.It is not only able to obtain lamella by the present invention very thin
Flower-like nanometer silicic acid nickel microballoon, and the particle diameter distribution of nanoparticle is highly uniform.
A kind of method that three-dimensional flower-shaped alkali formula silicic acid nickel microballoon is prepared by hydro-thermal self-assembly method of the present invention, it is special
Sign is：First by nano lamellar silica ultrasonic disperse in deionized water, white emulsion is obtained, then at 60~90 DEG C
Melamine is added under the conditions of water bath with thermostatic control and stirs 1~3h, adds water soluble nickel salt, it is molten to add in diluted acid after being dispersed with stirring uniformly
Liquid obtains green lotion；Green lotion is transferred in autoclave, temperature be 160~200 DEG C condition place 5~
For 24 hours, it is dry in 60~90 DEG C of baking oven after centrifugation after naturally ringing to room temperature after the completion of reaction, it obtains of the present invention
Three-dimensional flower-shaped alkali formula silicic acid nickel microballoon.
Stratiform silica be connected by oxygen-octahedron by public oxygen atom formed have stringent two-dimensional structure,
The electronegative silicone hydroxyl of layer surface can be neutralized by proton, alkali metal ion, and bulk is stacked by electrostatic force.Above-mentioned anti-
Should under the conditions of, nickel ion and stratiform silicon dioxde reaction are simultaneously self-assembled into three-dimensional flower-shaped silicic acid nickel microballoon, the flower-like microsphere
Crystal form coincide with pdf card numbers 49-1859.The three-dimensional flower-shaped silicic acid nickel microballoon of ultrathin nanometer piece self assembly uniformly disperses, no group
Poly- phenomenon.
Further, the water soluble nickel salt described in previous methods is nickel nitrate, nickel chloride, nickel sulfate, nickel acetate or its water
Close one or more mixtures in object.
Further, the diluted acid described in previous methods is one or more mixtures in hydrochloric acid, sulfuric acid, nitric acid, dilute
A concentration of 0.5mol/L~5mol/L of acid.
Further, the weight ratio of the nano lamellar silica described in previous methods and deionized water is 1：250~
400。
Further, the weight ratio 1.6~2 of the melamine described in previous methods and nano lamellar silica：1.
Further, the water soluble nickel salt described in previous methods and the molal weight of melamine ratio 0.5~0.9：1.
Further, the pH of the green lotion of the addition dilute acid soln described in previous methods is 1~3.
It will be described in detail the present invention below：
In the present invention, the use of melamine is the environment in order to provide a pH stable to reaction, it is therefore an objective to allow nickel
Silicone hydroxyl between ion and silica nanometer layer reacts so that nisiloy hydrochlorate can uniformly strut stratiform silica
And self assembly reacts, and forms thin layer silicic acid nickel.The purpose handled before reaction with ultrasonic disperse is to make stock dispersion uniform, this
Also for silica nanometer layer can be advantageously promoted and nickel nitrate reacts.
Using stratiform silica as reactant and the template of self assembly in the present invention, we can be directly to reaction
Product is filtered acquisition, does not need to carry out the removal of template, the shortcomings that overcoming previous hard template removal and waste.Meanwhile
In the case where expanding reaction system and short time high temperature reaction, uniform flower-shaped silicic acid nickel microballoon can still generate, these
Advantage can save cost, conducive to fairly large preparation.The present invention is easy to operate using one step hydro thermal method, manufacturing cycle short across
Journey is pollution-free, and cost of material used is relatively low, is suitble to mass production.
Description of the drawings
Fig. 1 is that the SEM of nano lamellar silica schemes；
Fig. 2 is the XRD diagram of flower-shaped silicic acid nickel microballoon that the embodiment of the present invention 2 is prepared；
Fig. 3 is the SEM figures for the flower-shaped silicic acid nickel microballoon that the embodiment of the present invention 2 is prepared；
Fig. 4 is the TEM figures for the flower-shaped silicic acid nickel microballoon that the embodiment of the present invention 2 is prepared.
Specific embodiment
Embodiment 1：
0.2g nano lamellar silica is dispersed in 50mL deionized waters, ultrasonic disperse, makes it homodisperse, formed
White emulsion.Then 0.35g melamines are added in into finely dispersed nanosilica solution and maintain 80 DEG C of thermostatted waters
Bath after steady temperature stirs 2.5h, adds in the Nickelous nitrate hexahydrate of 0.6g, after nickel nitrate is completely dissolved, adds in 0.6mol/L
Hydrochloric acid solution adjust solution pH=2, solution to be mixed after mixing, in 180 DEG C of autoclaves of the sealing being put into,
The hydro-thermal reaction time is 5h.It is dry in 80 DEG C of baking oven after centrifugation after naturally ringing to room temperature after the completion of reaction, it obtains
The three-dimensional flower-shaped alkali formula silicic acid nickel microballoons of 0.32g.
Embodiment 2：
2g nano lamellar silica is dispersed in 500mL deionized waters, ultrasonic disperse, makes it homodisperse, formed
White emulsion.Then 3.5g melamines are added in into finely dispersed nanosilica solution and maintain 80 DEG C of thermostatted waters
Bath after steady temperature stirs 2.5h, adds in the Nickelous nitrate hexahydrate of 6g, after nickel nitrate is completely dissolved, adds in the salt of 5mol/L
Acid solution adjust solution pH=2, solution to be mixed after mixing, in 180 DEG C of autoclaves of the sealing being put into, hydro-thermal
Reaction time is 5h.It is dry in 80 DEG C of baking oven after centrifugation after naturally ringing to room temperature after the completion of reaction, obtain 3.2g flowers
Shape silicic acid nickel microballoon.The XRD diagram of obtained flower-like microsphere such as Fig. 2, the crystalline structure for the Figure 49-1859 that fits like a glove, microballoon pattern
As shown in scanning figure 3 and transmission plot 4.As seen from the figure, three-dimensional flower-shaped alkali formula silicic acid nickel microballoon has successfully been prepared in the present invention.
Embodiment 3：
0.2g nano lamellar silica is dispersed in 50mL deionized waters, ultrasonic disperse, makes it homodisperse, formed
White emulsion.Then 0.35g melamines are added in into finely dispersed nanosilica solution and maintain 80 DEG C of thermostatted waters
Bath, steady temperature stirring add in the nickel acetate of 0.4g, after nickel nitrate is completely dissolved, add in 0.6mol/L's not less than after 2h
Hydrochloric acid solution adjust solution pH=2, solution to be mixed after mixing, in 180 DEG C of autoclaves of the sealing being put into, water
The thermal response time is 10h.It is dry in 80 DEG C of baking oven after centrifugation after naturally ringing to room temperature after the completion of reaction, it obtains
The three-dimensional flower-shaped alkali formula silicic acid nickel microballoons of 0.33g.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair
Bright preferable embodiment, embodiments of the present invention are simultaneously not restricted to the described embodiments, it should be appreciated that people in the art
Member can be designed that a lot of other modifications and embodiment, these modifications and embodiment will be fallen in principle disclosed in the present application
Within scope and spirit.
Claims (8)
1. a kind of preparation method of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon, it is characterised in that：First by nano lamellar silica
Ultrasonic disperse in deionized water, obtains white emulsion, and melamine is then added under the conditions of 60~90 DEG C of waters bath with thermostatic control stirs
1~3h is mixed, adds water soluble nickel salt, dilute acid soln is added in after being dispersed with stirring uniformly, obtains green lotion；Green lotion is turned
Move on in autoclave, temperature be 160~200 DEG C condition place 5~for 24 hours, reaction after the completion of naturally ring to room temperature after,
It is dry in 60~90 DEG C of baking oven after centrifugation, obtain three-dimensional flower-shaped alkali formula silicic acid nickel microballoon of the present invention.
2. a kind of preparation method of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon as described in claim 1, it is characterised in that：It is water-soluble
Nickel salt is one or more mixtures in nickel nitrate, nickel chloride, nickel sulfate, nickel acetate or its hydrate.
3. a kind of preparation method of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon as described in claim 1, it is characterised in that：Diluted acid is
One or more mixtures in hydrochloric acid, sulfuric acid, nitric acid, a concentration of 0.5mol/L~5mol/L of diluted acid.
4. a kind of preparation method of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon as described in claim 1, it is characterised in that：Nanometer layer
The weight ratio of shape silica and deionized water is 1：250~400.
5. a kind of preparation method of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon as described in claim 1, it is characterised in that：Melamine
The weight ratio 1.6~2 of amine and nano lamellar silica：1.
6. a kind of preparation method of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon as described in claim 1, it is characterised in that：It is water-soluble
The molal weight of nickel salt and melamine ratio 0.5~0.9：1.
7. a kind of preparation method of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon as described in claim 1, it is characterised in that：It adds in dilute
The pH of the green lotion of acid solution is 1~3.
8. a kind of preparation method of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon, it is characterised in that：It is by claim 1~7 any one
Method described in is prepared.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439319A (en) * | 2018-12-28 | 2019-03-08 | 陕西师范大学 | A kind of preparation method of treasure maesa herb globular nanostructures luminescent material |
| CN110240169A (en) * | 2019-07-03 | 2019-09-17 | 山东科技大学 | A kind of three-dimensional petal-shaped alkali formula silicic acid nickel and preparation method thereof |
| CN111017940A (en) * | 2019-12-16 | 2020-04-17 | 山东科技大学 | Biomass-based three-dimensional petal-shaped basic nickel silicate catalyst |
| CN112209426A (en) * | 2020-10-23 | 2021-01-12 | 深圳市环保科技集团有限公司 | Basic zinc chloride and preparation method thereof |
| CN113479897A (en) * | 2021-07-16 | 2021-10-08 | 常州大学 | Method for preparing two-dimensional nanosheet silicate by using attapulgite and application thereof |
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| CN102397774A (en) * | 2010-09-10 | 2012-04-04 | 中国科学院合肥物质科学研究院 | Silicon dioxide/nickel composite hollow spheres and preparation method thereof |
| CN105129809A (en) * | 2015-10-12 | 2015-12-09 | 上海第二工业大学 | Sea-urchin-shaped nanometer nickel silicate hollow sphere and preparation method thereof |
| CN106185965A (en) * | 2016-07-19 | 2016-12-07 | 中国工程物理研究院化工材料研究所 | The method preparing hollow silicic acid nickel microsphere for template with silicon dioxide |
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| CN102397774A (en) * | 2010-09-10 | 2012-04-04 | 中国科学院合肥物质科学研究院 | Silicon dioxide/nickel composite hollow spheres and preparation method thereof |
| CN105129809A (en) * | 2015-10-12 | 2015-12-09 | 上海第二工业大学 | Sea-urchin-shaped nanometer nickel silicate hollow sphere and preparation method thereof |
| CN106185965A (en) * | 2016-07-19 | 2016-12-07 | 中国工程物理研究院化工材料研究所 | The method preparing hollow silicic acid nickel microsphere for template with silicon dioxide |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439319A (en) * | 2018-12-28 | 2019-03-08 | 陕西师范大学 | A kind of preparation method of treasure maesa herb globular nanostructures luminescent material |
| CN109439319B (en) * | 2018-12-28 | 2021-09-14 | 陕西师范大学 | Preparation method of hollow flower ball-shaped nano-structure luminescent material |
| CN110240169A (en) * | 2019-07-03 | 2019-09-17 | 山东科技大学 | A kind of three-dimensional petal-shaped alkali formula silicic acid nickel and preparation method thereof |
| CN111017940A (en) * | 2019-12-16 | 2020-04-17 | 山东科技大学 | Biomass-based three-dimensional petal-shaped basic nickel silicate catalyst |
| CN112209426A (en) * | 2020-10-23 | 2021-01-12 | 深圳市环保科技集团有限公司 | Basic zinc chloride and preparation method thereof |
| CN113479897A (en) * | 2021-07-16 | 2021-10-08 | 常州大学 | Method for preparing two-dimensional nanosheet silicate by using attapulgite and application thereof |
| CN113479897B (en) * | 2021-07-16 | 2023-10-24 | 常州大学 | Method for preparing two-dimensional nano sheet silicate by using attapulgite and application thereof |
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