CN108238605B - Three-dimensional flower-shaped basic nickel silicate microsphere and preparation method thereof - Google Patents
Three-dimensional flower-shaped basic nickel silicate microsphere and preparation method thereof Download PDFInfo
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- CN108238605B CN108238605B CN201810304288.XA CN201810304288A CN108238605B CN 108238605 B CN108238605 B CN 108238605B CN 201810304288 A CN201810304288 A CN 201810304288A CN 108238605 B CN108238605 B CN 108238605B
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
Abstract
A three-dimensional flower-shaped basic nickel silicate microsphere and a preparation method thereof belong to the technical field of inorganic nano material preparation. Firstly, ultrasonically dispersing nano layered silicon dioxide in deionized water to obtain white emulsion, then adding melamine under the condition of a constant-temperature water bath at the temperature of 60-90 ℃, stirring for 1-3 hours, then adding water-soluble nickel salt, stirring uniformly, and then adding a dilute acid solution to obtain green emulsion; and transferring the green emulsion into a high-pressure reaction kettle, standing for 5-24 hours at the temperature of 160-200 ℃, naturally cooling to room temperature after the reaction is finished, centrifugally separating, and drying in an oven at the temperature of 60-90 ℃ to obtain the three-dimensional flower-shaped basic nickel silicate microspheres. The invention adopts the layered silicon dioxide as a reactant and a self-assembled template, and overcomes the defects of removal and waste of the conventional hard template. Meanwhile, under the conditions of enlarging a reaction system and carrying out high-temperature reaction in a short time, uniform flower-shaped nickel silicate microspheres can still be generated. The method adopts a one-step hydrothermal method, is simple and convenient to operate, short in preparation period, pollution-free in process, low in cost of used raw materials and suitable for batch production.
Description
Technical Field
The invention belongs to the technical field of inorganic nano material preparation, and particularly relates to a three-dimensional flower-shaped basic nickel silicate microsphere self-assembled by two-dimensional nano sheets and a preparation method thereof.
Background
Nickel silicate has excellent physicochemical properties in the aspects of battery materials, magnetic substances, catalyst support science and the like. These properties have attracted attention from researchers in recent years, and nickel silicate is considered to be a promising functional inorganic material. The property and application of the nano material have a direct relation with the shape and size of the material, but the current research on the nano nickel salt mainly focuses on the one-dimensional fields of nano rods, nano wires, nano fibers and the like, and the research on the self-assembly of two-dimensional nano sheets into a three-dimensional structure is still few. The material with the structure has the characteristics of high specific surface, high stability and surface permeability, and the staggered and stacked part can contain a large number of guest molecules or large-size guests, so that the flower-shaped microsphere material has important chemical development in a plurality of technical fields such as catalysts, batteries, photoelectric materials, magnetic science and the like.
The traditional preparation of the flower-like structure nickel silicate and the composite microspheres thereof is a hard template method, a hydrothermal self-assembly method, a sol-gel method and the like. The template method reaction system is unstable, the particle size distribution is not uniform, and the product often contains a certain proportion of template substances, which affects the purity of the substances. In addition, hard templates are required, and removal of the templates by heating or chemical reaction is required, which increases the workload. Meanwhile, the hard template cannot be reused, which causes great waste. The sol-gel process uses metal organic alkoxides, which are difficult and expensive to prepare. The hydrothermal self-assembly technology is an effective and practical technology in the synthesis of multidimensional structures at present, is widely applied to the preparation of various nano materials as the most common method for preparing the hollow nanospheres, has related research reports on the application of the hydrothermal self-assembly technology in the preparation of the hollow nanospheres, and is relatively mature in technology. The two-dimensional nanosheet self-assembled flower-like structure material can be obtained by controlling parameters such as precursor proportion, concentration, reaction temperature and the like. At present, no method for preparing the nickel silicate microspheres with the three-dimensional flower-like structures in a large scale under the template-free condition is reported.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide the three-dimensional flower-shaped basic nickel silicate microspheres and the preparation method thereof. The method can obtain ultrathin flake-shaped nano nickel silicate microspheres with very uniform particle size distribution.
The invention relates to a method for preparing three-dimensional flower-shaped basic nickel silicate microspheres by a hydrothermal self-assembly method, which is characterized by comprising the following steps of: firstly, ultrasonically dispersing nano layered silicon dioxide in deionized water to obtain white emulsion, then adding melamine under the condition of a constant-temperature water bath at the temperature of 60-90 ℃, stirring for 1-3 hours, then adding water-soluble nickel salt, stirring uniformly, and then adding a dilute acid solution to obtain green emulsion; and transferring the green emulsion into a high-pressure reaction kettle, standing for 5-24 hours at the temperature of 160-200 ℃, naturally cooling to room temperature after the reaction is finished, centrifugally separating, and drying in an oven at the temperature of 60-90 ℃ to obtain the three-dimensional flower-shaped basic nickel silicate microspheres.
The layered silicon dioxide is formed by connecting silicon-oxygen tetrahedrons through common oxygen atoms and has a strict two-dimensional structure, and silicon hydroxyl groups with negative electricity on the surface of the layer can be neutralized by protons and alkali metal ions and are stacked into blocks through electrostatic acting force. Under the reaction conditions, nickel ions react with the layered silicon dioxide and self-assemble into three-dimensional flower-shaped nickel silicate microspheres, and the crystal form of the flower-shaped microspheres is consistent with pdf card number 49-1859. The ultrathin nanosheet self-assembled three-dimensional flower-shaped nickel silicate microspheres are uniformly dispersed without agglomeration.
Further, the water-soluble nickel salt in the foregoing method is a mixture of one or more of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, or hydrates thereof.
Further, the dilute acid in the method is one or a mixture of hydrochloric acid, sulfuric acid and nitric acid, and the concentration of the dilute acid is 0.5-5 mol/L.
Further, the weight ratio of the nano layered silica to the deionized water in the foregoing method is 1: 250 to 400.
Further, the weight ratio of the melamine to the nano layered silica in the method is 1.6-2: 1.
further, the molar mass ratio of the water-soluble nickel salt to the melamine in the previous method is 0.5-0.9: 1.
further, the pH of the green emulsion added with the dilute acid solution in the method is 1-3.
The present invention will be described in detail below:
in the invention, the melamine is used for providing an environment with stable pH value for reaction, and the purpose is to enable the nickel ions to react with silicon hydroxyl groups between silicon dioxide nano layers, so that the nickel silicate can uniformly strut layered silicon dioxide and perform self-assembly reaction to form thin-layer nickel silicate. The purpose of the ultrasonic dispersion treatment before the reaction is to uniformly disperse the raw materials, and the purpose is to better promote the reaction between the silicon dioxide nano-layer and the nickel nitrate.
According to the invention, the layered silicon dioxide is used as a reactant and a self-assembled template, so that a reaction product can be directly filtered and collected without removing the template, and the defects of removing and wasting a hard template in the prior art are overcome. Meanwhile, under the conditions of enlarging a reaction system and carrying out high-temperature reaction in a short time, uniform flower-shaped nickel silicate microspheres can still be produced, and the advantages of saving the cost and being beneficial to large-scale preparation. The method adopts a one-step hydrothermal method, is simple and convenient to operate, short in preparation period, pollution-free in process, low in cost of used raw materials and suitable for batch production.
Drawings
FIG. 1 is an SEM image of nano-layered silica;
FIG. 2 is an XRD pattern of flower-like nickel silicate microspheres prepared in example 2 of the present invention;
FIG. 3 is an SEM image of flower-like nickel silicate microspheres prepared in example 2 of the present invention;
FIG. 4 is a TEM image of flower-like nickel silicate microspheres prepared in example 2 of the present invention.
Detailed Description
Example 1:
0.2g of nano-layered silicon dioxide is dispersed in 50mL of deionized water, and the mixture is dispersed by ultrasonic to be uniform to form white emulsion. And then adding 0.35g of melamine into the uniformly dispersed nano silicon dioxide solution, maintaining a constant temperature water bath at 80 ℃, stirring at a constant temperature for 2.5 hours, adding 0.6g of nickel nitrate hexahydrate, adding 0.6mol/L hydrochloric acid solution to adjust the pH value of the solution to be 2 after the nickel nitrate is completely dissolved, uniformly mixing the mixed solution, and putting the mixed solution into a sealed 180 ℃ high-pressure reaction kettle for 5 hours of hydrothermal reaction. After the reaction is finished, the temperature is naturally reduced to room temperature, centrifugal separation is carried out, and drying is carried out in an oven at the temperature of 80 ℃, so that 0.32g of three-dimensional flower-shaped basic nickel silicate microspheres are obtained.
Example 2:
2g of nano-layered silicon dioxide is dispersed in 500mL of deionized water, and the mixture is dispersed by ultrasonic to be uniform to form white emulsion. And then adding 3.5g of melamine into the uniformly dispersed nano silicon dioxide solution, maintaining a constant-temperature water bath at 80 ℃, stirring at a constant temperature for 2.5 hours, adding 6g of nickel nitrate hexahydrate, adding 5mol/L hydrochloric acid solution to adjust the pH value of the solution to be 2 after the nickel nitrate is completely dissolved, uniformly mixing the mixed solution, and putting the mixed solution into a sealed 180 ℃ high-pressure reaction kettle for 5 hours of hydrothermal reaction. After the reaction is finished, the temperature is naturally reduced to room temperature, centrifugal separation is carried out, and drying is carried out in an oven at the temperature of 80 ℃, so that 3.2g of flower-shaped nickel silicate microspheres are obtained. The XRD pattern of the obtained flower-shaped microspheres is shown in figure 2, which completely conforms to the crystal structure of figures 49-1859, and the morphology of the microspheres is shown in scan figure 3 and transmission figure 4. As can be seen from the figure, the three-dimensional flower-shaped basic nickel silicate microspheres are successfully prepared by the method.
Example 3:
0.2g of nano-layered silicon dioxide is dispersed in 50mL of deionized water, and the mixture is dispersed by ultrasonic to be uniform to form white emulsion. And then adding 0.35g of melamine into the uniformly dispersed nano silicon dioxide solution, maintaining a constant temperature water bath at 80 ℃, stirring at a constant temperature for not less than 2 hours, adding 0.4g of nickel acetate, adding 0.6mol/L hydrochloric acid solution to adjust the pH value of the solution to be 2 after the nickel nitrate is completely dissolved, uniformly mixing the mixed solution, and putting the mixed solution into a sealed high-pressure reaction kettle at 180 ℃, wherein the hydrothermal reaction time is 10 hours. After the reaction is finished, the temperature is naturally reduced to room temperature, centrifugal separation is carried out, and then drying is carried out in an oven at the temperature of 80 ℃, so as to obtain 0.33g of three-dimensional flower-shaped basic nickel silicate microspheres.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (8)
1. A preparation method of three-dimensional flower-shaped basic nickel silicate microspheres is characterized by comprising the following steps: firstly, ultrasonically dispersing nano layered silicon dioxide in deionized water to obtain white emulsion, then adding melamine under the condition of a constant-temperature water bath at the temperature of 60-90 ℃, stirring for 1-3 hours, then adding water-soluble nickel salt, stirring uniformly, and then adding a dilute acid solution to obtain green emulsion; and transferring the green emulsion into a high-pressure reaction kettle, standing for 5-24 hours at the temperature of 160-200 ℃, naturally cooling to room temperature after the reaction is finished, centrifugally separating, and drying in an oven at the temperature of 60-90 ℃ to obtain the three-dimensional flower-shaped basic nickel silicate microspheres.
2. The method for preparing three-dimensional flower-like basic nickel silicate microspheres according to claim 1, wherein the method comprises the following steps: the water-soluble nickel salt is one or more of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate or their hydrates.
3. The method for preparing three-dimensional flower-like basic nickel silicate microspheres according to claim 1, wherein the method comprises the following steps: the diluted acid is one or a mixture of hydrochloric acid, sulfuric acid and nitric acid, and the concentration of the diluted acid is 0.5-5 mol/L.
4. The method for preparing three-dimensional flower-like basic nickel silicate microspheres according to claim 1, wherein the method comprises the following steps: the weight ratio of the nano layered silicon dioxide to the deionized water is 1: 250 to 400.
5. The method for preparing three-dimensional flower-like basic nickel silicate microspheres according to claim 1, wherein the method comprises the following steps: the weight ratio of melamine to nano layered silica is 1.6-2: 1.
6. the method for preparing three-dimensional flower-like basic nickel silicate microspheres according to claim 1, wherein the method comprises the following steps: the molar mass ratio of the water-soluble nickel salt to the melamine is 0.5-0.9: 1.
7. the method for preparing three-dimensional flower-like basic nickel silicate microspheres according to claim 1, wherein the method comprises the following steps: the pH of the green emulsion added with the dilute acid solution is 1-3.
8. A three-dimensional flower-shaped basic nickel silicate microsphere is characterized in that: is prepared by the method of any one of claims 1 to 7.
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| 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 |
| CN112209426B (en) * | 2020-10-23 | 2022-08-05 | 深圳市环保科技集团股份有限公司 | Basic zinc chloride and preparation method 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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| 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 |
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