CN111087032A - Silicon oxide and magnesium oxide composite material and synthesis method thereof - Google Patents

Silicon oxide and magnesium oxide composite material and synthesis method thereof Download PDF

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Publication number
CN111087032A
CN111087032A CN201811239877.0A CN201811239877A CN111087032A CN 111087032 A CN111087032 A CN 111087032A CN 201811239877 A CN201811239877 A CN 201811239877A CN 111087032 A CN111087032 A CN 111087032A
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composite material
silica
synthesizing
material according
magnesium oxide
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范峰
凌凤香
张会成
王少军
杨春雁
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Abstract

The invention discloses a silicon oxide and magnesium oxide composite material and a synthesis method thereof. The synthesis method comprises the steps of mixing magnesium oxide with an alcohol solvent, adding a buffer solution and a silicon source, stirring, standing, washing, drying, and finally performing heat treatment to obtain the silicon oxide/magnesium oxide composite material. The silicon oxide/magnesium oxide composite material provided by the invention has a core-shell structure, the shell layer is stably coated and is not easy to fall off, and the synthesis method is simple and easy.

Description

Silicon oxide and magnesium oxide composite material and synthesis method thereof
Technical Field
The invention belongs to the field of synthesis of porous inorganic materials, and particularly relates to a silicon oxide-containing composite material and a synthesis method thereof.
Background
The material with a core-shell structure is an important novel material, and is characterized in that a certain material is used as a core phase, and a layer of material of the same kind or different kinds grows on the outer surface of the core phase to form a shell layer, so that a composite structure similar to an eggshell form is formed. The core-shell material has a unique structure, so that the core-shell material has the advantages which are not possessed by a single-structure material, and has good application prospects in the fields of chemical industry, environmental protection and optics. But because of its unique and complex structure, the synthesis difficulty is far higher than that of common materials, mainly its structure is difficult to control, and its structure control and functionalization still need further research.
The magnesium oxide is an environment-friendly water treatment agent, and has the advantages of high activity, strong adsorption capacity, easiness in storage, no corrosiveness, safety, harmlessness and the like. The preparation of a nano-structure magnesium oxide hollow spherical shell and the research on nickel ion adsorption performance (functional material, 42 vol. in 2011), discloses magnesium oxide which has a strong adsorption effect on nickel ions, but the performance of the magnesium oxide hollow spherical shell needs to be strengthened.
CN103007847A discloses a composite particle based on magnetic nano immobilized laccase and ionic liquid, a preparation method thereof and application thereof in removing pollutants in water. Firstly, magnetic gamma-Fe is prepared2O3A nanoparticle; then, the nano magnetic particles are used as a core phase, tetraethoxysilane and silane coupling agent are used as silicon sources, and a sol-gel method is utilized to prepare the nano core-shell type magnetic silicon dioxide with the surface amino functionalized; then, magnetic nano immobilized laccase and ionic liquid composite particles are prepared through a series of functional operations and can be applied to treatment for removing pollutants in water.
CN105036070A discloses a gold nanorod-silicon dioxide core-shell structure nanomaterial, a preparation method and application thereof, wherein the preparation method comprises the steps of preparing a chiral gold nanorod shoulder-side assembly body, and taking the assembly body as a core; and then coating the chiral gold nanorod side-by-side assembly body with a silicon dioxide shell layer in an alcohol-water system to prepare the functional material with the shell layer structure.
CN102160985A discloses a magnetic silica microsphere with core-shell structure and surface anisotropic dual-functional groups and a preparation method thereof, wherein the preparation method comprises the steps of firstly preparing superparamagnetic microspheres as iron oxide cores by a solvothermal method; then coating a layer of silicon dioxide on the iron oxide by using a sol-gel method to obtain a material with a core-shell structure; then, the material is functionalized, and finally the magnetic silica core-shell material with high magnetic responsiveness and surface bifunctional groups is obtained.
CN101885493A discloses a method for synthesizing a ZSM-5/β core-shell type molecular sieve, which comprises the steps of treating a core-phase ZSM-5 molecular sieve to enable the surface of the core-phase ZSM-5 molecular sieve to adsorb β nano crystals, then adding other raw materials, and carrying out hydrothermal crystallization reaction to obtain the ZSM-5/β core-shell type zeolite molecular sieve.
CN106475134A discloses a core-shell catalyst with hydrotalcite as shell/molecular sieve as core, its preparation and application, the preparation process is mixing hydrogen type molecular sieve with deionized water, ultrasonic processing to make A solution; mixing nitrate, ammonium salt and deionized water to prepare a solution B; then mixing the solution A and the solution B, and dropwise adding ammonia water to prepare a solution C; and then stirring the solution C at a high temperature to finally obtain the molecular sieve with the shape of the core-shell structure, wherein the molecular sieve is used as a core and the petal-shaped hydrotalcite is used as a shell. Can be used for the catalytic reaction of m-dinitrobenzene hydrogenation to synthesize m-phenylenediamine.
In summary, some core-shell structure materials and preparation methods thereof have been disclosed in the prior art, but the materials obtained by the currently disclosed preparation methods have some defects, and the preparation methods are relatively complex and have high cost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a silicon oxide/magnesium oxide composite material and a synthesis method thereof. The silicon oxide/magnesium oxide composite material provided by the invention has a core-shell structure, the shell layer is stably coated and is not easy to fall off, and the synthesis method is simple and easy.
The invention provides a silicon oxide/magnesium oxide composite material, which takes magnesium oxide as a core layer and silicon oxide as a shell layer, wherein the diameter of the core layer is 0.5-3 mu m; the thickness of the shell layer is 10-100 nm; the specific surface area is 5-25 m2/g。
The second aspect of the invention provides a synthesis method of a silicon oxide/magnesium oxide composite material, which comprises the following steps:
(1) mixing magnesium oxide and a micromolecular alcohol solvent, and adding a pH buffer solution after uniformly mixing;
(2) adding a silicon source into the material obtained in the step (1) under the condition of stirring, uniformly mixing, and then standing;
(3) and (3) washing, drying and thermally treating the material obtained in the step (2) to obtain the silicon oxide/magnesium oxide composite material.
In the synthesis method of the silicon oxide/magnesium oxide composite material, the magnesium oxide is common magnesium oxide, and the particle size range of the magnesium oxide is 0.5-3 mu m; the magnesium oxide is subjected to a purification treatment prior to use, which is carried out by purification means known in the art, such as washing with water or a solvent, the selection of which is well known to those skilled in the art, in order to remove the impurities adsorbed in the zeolite.
In the method for synthesizing the silicon oxide/magnesium oxide composite material, the magnesium oxide is preferably prepared by the following method: mixing magnesium salt, ammonia water and water, uniformly mixing, putting into a reaction kettle for treatment, and separating, washing and drying to obtain the magnesium oxide.
In the method, the magnesium salt is magnesium chloride hexahydrate or magnesium nitrate hexahydrate.
In the method, the concentration of the ammonia water is 25 wt%.
In the method, the mass ratio of the magnesium salt, the ammonia water and the water is 1: 2-11: 0.5 to 1.6, preferably 1: 3-10: 0.6 to 1.5.
In the method, the treatment temperature is 100-170 ℃, and preferably 110-160 ℃; the treatment time is 4-20 h, preferably 5-18 h.
In the above-described process, the separation and washing are conventional procedures well known to those skilled in the art. If the separation is carried out by filtration, washing is generally referred to as washing with deionized water. Usually comprises a plurality of separation and washing operations, generally 1 to 6 times. The drying condition is generally drying for 5-15 h at 100-140 ℃.
In the method for synthesizing the silicon oxide/magnesium oxide composite material, the micromolecular alcohol solvent in the step (1) is C2-C4 alcohol, and specifically can be one or more of ethanol, propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, propylene glycol and butanediol.
In the synthesis method of the silicon oxide/magnesium oxide composite material, the mass ratio of the micromolecular alcohol solvent to the magnesium oxide in the step (1) is 5-40: 1, preferably 10 to 30: 1.
in the synthesis method of the silicon oxide/magnesium oxide composite material, the mixing treatment in the step (1) can adopt any means capable of realizing full mixing, such as one or more of stirring and ultrasonic treatment, preferably adopts a stirring and ultrasonic treatment combined mode, more preferably adopts a method of firstly stirring and then mixing in ultrasonic, the frequency of the ultrasonic is 15KHz-10MHz, and the power is 20-100W/L according to the volume of the solution. The stirring time is 0.1-2 h, preferably 0.2-1.8 h; the ultrasonic time is 1-6 h, preferably 2-5 h.
In the synthesis method of the silicon oxide/magnesium oxide composite material, the pH value of the pH buffer solution in the step (1) is 4-6, and preferably 4.5-5.8. The pH buffer may be one or more of sodium dihydrogen phosphate-citric acid pH buffer, sodium acetate pH buffer, potassium hydrogen phthalate-sodium hydroxide pH buffer, preferably sodium dihydrogen phosphate-citric acid pH buffer. The method of formulating the pH buffer is well known to those skilled in the art and can be carried out by methods known in the art.
In the synthesis method of the silicon oxide/magnesium oxide composite material, the mass ratio of the pH buffer solution to the magnesium oxide in the step (1) is 7-33: 1, preferably 8 to 32: 1.
in the method for synthesizing the silicon oxide/magnesium oxide composite material, an auxiliary agent can be added in the step (1), wherein the auxiliary agent comprises one or more of tween-20, tween-60 and tween-80; the mass ratio of the auxiliary agent to the micromolecular alcohols is 1: 5-40, preferably 1: 10 to 30.
In the method for synthesizing the silicon oxide/magnesium oxide composite material, the silicon source in the step (2) is one or more of methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate, and preferably ethyl orthosilicate.
In the synthetic method, the mass ratio of the silicon source in the step (2) to the magnesium oxide in the step (1) is 0.1-1.5: 1, preferably 0.15 to 1.45: 1.
in the method for synthesizing the silicon oxide/magnesium oxide composite material, the silicon source is added in the step (2) under the condition of 45-80 ℃, preferably 50-70 ℃.
In the method for synthesizing the silicon oxide/magnesium oxide composite material, in the step (2), a silicon source is added under the stirring condition, the stirring speed is 100-300 r/min, preferably 120-280 r/min, the stirring is continued for a period of time after the silicon source is dripped, and the stirring speed is 10-60 r/min, preferably 20-50 r/min; the stirring time is 1-10 h, preferably 2-9 h.
In the synthesis method of the silicon oxide/magnesium oxide composite material, the standing condition in the step (2) is as follows: the temperature is 25-40 ℃, and preferably 25-35 ℃; the time is 5-24 h, preferably 6-20 h.
In the method for synthesizing the silica/magnesia composite material according to the present invention, the separation and washing in step (3) are conventional procedures well known to those skilled in the art. If the separation is carried out by filtration, washing is generally referred to as washing with deionized water. Usually, the method comprises more than one separation and washing operation, and the number of the separation and washing operations is generally 1-6. The drying condition is generally drying for 5-15 h at 100-140 ℃.
In the synthesis method of the silicon oxide/magnesium oxide composite material, the heat treatment temperature in the step (3) is 180-300 ℃, and preferably 200-280 ℃; the heat treatment time is 1-6 h, preferably 2-5 h.
The silicon oxide-magnesium oxide composite material provided by the invention can be used for treating heavy metal ion wastewater in the field of water pollution prevention and control.
Compared with the prior art, the silicon oxide/magnesium oxide composite material and the synthesis method thereof provided by the invention have the following advantages:
(1) the silicon oxide/magnesium oxide composite material provided by the invention is a composite material with a core-shell structure, and the shell layer of the composite material is stably coated and is not easy to fall off.
(2) According to the method for synthesizing the silicon oxide/magnesium oxide composite material, the pH buffer solution is used for providing protons for silicon source hydrolysis, the concentration of the protons in a synthesis system can be kept unchanged by adding the pH buffer solution, the hydrolysis speed of an organic silicon source can be kept constant, the particle size of silicon oxide particles is kept consistent at all reaction time points, and further, the shell layer of the core-shell structure formed by uniformly covering the outer surface of magnesium oxide with the silicon oxide particles with uniform particle sizes is dense and ordered, so that the generated core-shell structure composite material is not easy to damage. The problems that in the prior art, the size of the obtained silicon oxide particles is not uniform, so that the accumulated silicon oxide shell layer is loose and easy to damage, and the finally formed core-shell structure composite material is unstable in structure are solved.
(3) In the method for synthesizing the silicon oxide/magnesium oxide composite material, the operation of adding the silicon source in the step (2) is particularly important for controlling the stirring condition, the stirring process needs to be carried out in a limited mode, the stirring speed is controlled to ensure the hydrolysis speed of the organic silicon source, the phenomenon that the organic silicon source is hydrolyzed too fast due to too fast stirring to generate large-particle silicon oxide particles which cannot be adsorbed by the outer surface of magnesium oxide and are not beneficial to generating a shell structure is avoided, and a mechanical mixture of magnesium oxide and large-particle silicon oxide is easily generated.
(4) In the synthesis method of the silicon oxide/magnesium oxide composite material, the auxiliary agent is added and used in combination with other means such as pH buffer solution and a silicon source adding control mode, so that a shell layer is formed, the shell layer distribution is ensured to be more uniform, mesoporous channels can be formed in the silicon oxide shell layer, and the transmission of substances can be accelerated.
Drawings
FIG. 1 is a TEM photograph of a synthesized sample of example 2.
FIG. 2 is a TEM photograph of a synthesized sample of comparative example 1.
Detailed Description
The synthesis of the analcime of the present invention is described in detail below by way of specific examples, but is not limited thereto.
The structural characteristics and the sizes of the composite materials in the embodiments and the comparative examples are characterized and tested by a transmission electron microscope, and the surface area is characterized and tested by a physical adsorption instrument.
Example 1: preparation of buffers of different pH
preparation of buffer solution at pH 4.5: 18g of sodium acetate and 9.8mL of glacial acetic acid are taken and diluted by adding distilled water until the total volume is 1000 mL.
preparation of pH4.8 buffer: mixing 19.96g of sodium dihydrogen phosphate with 99.8mL of distilled water to form solution A; mixing 10.14g of citric acid with 101.4mL of distilled water to form solution B; and mixing the solution A and the solution B to obtain a buffer solution.
preparation of pH5.0 buffer: mixing 20.6g of sodium dihydrogen phosphate with 103mL of distilled water to form solution A; mixing 9.7g of citric acid with 97mL of distilled water to form solution B; and mixing the solution A and the solution B to obtain a buffer solution.
preparation of pH5.2 buffer: 21.44g of sodium dihydrogen phosphate is mixed with 107.2mL of distilled water to form solution A; mixing 9.28g of citric acid with 92.8mL of distilled water to form solution B; and mixing the solution A and the solution B to obtain a buffer solution.
preparation of pH5.6 buffer: mixing 23.2g of sodium dihydrogen phosphate with 116mL of distilled water to form solution A; mixing 8.4g of citric acid with 84mL of distilled water to form solution B; and mixing the solution A and the solution B to obtain a buffer solution.
Example 2
10g of magnesium chloride hexahydrate, 40mL of distilled water and 12mL of ammonia water (the mass concentration is 25%) are taken and stirred for 1 hour; then the mixture is put into a reaction kettle for treatment for 6 hours at the temperature of 130 ℃; then washing the solid product with distilled water for 4 times until the solid product is neutral, and drying the solid product at 120 ℃ for 12 hours to obtain magnesium oxide;
taking 1.7g of the magnesium oxide, putting the magnesium oxide into 38mL of ethanol, stirring for 0.5h, then carrying out ultrasonic treatment for 3.2h, wherein the frequency of ultrasonic waves is 1MHz, and the power is 50W/L according to the volume of the solution; then placing the mixture into a water bath at 60 ℃, adding 56mL of buffer solution with pH4.8, dropwise adding 0.9 mL of ethyl orthosilicate under the stirring condition of 120 r/min, stirring the mixture for 5 hours at the speed of 20 r/min after the dropwise adding is finished, and then placing the mixture into a water bath at 30 ℃ for standing for 12 hours; subjecting the obtainedWashing the product with distilled water for 4 times to neutrality, drying at 120 deg.C for 12 hr, and heat treating at 260 deg.C for 3 hr to obtain SiO2The magnesium oxide composite material has the obtained sample number CL1, the properties of the sample are shown in Table 1, and the TEM photograph of the sample CL1 is shown in FIG. 1. As can be seen from fig. 1, the obtained sample has a core-shell structure.
Example 3
10g of magnesium chloride hexahydrate, 24mL of distilled water and 6mL of ammonia water (the mass concentration is 25%) are taken and stirred for 0.2 h; then the mixture is put into a reaction kettle for treatment for 10 hours at the temperature of 110 ℃; then washing the solid product with distilled water for 4 times until the solid product is neutral, and drying the solid product at 120 ℃ for 12 hours to obtain magnesium oxide;
2g of the magnesium oxide is taken and placed in 20mL of ethanol to be stirred for 0.2h, and then ultrasonic treatment is carried out for 2h, the frequency of ultrasonic waves is 15KHz, and the power is 100W/L according to the volume of the solution; then placing the mixture into a water bath at 70 ℃, adding 16mL of buffer solution with pH of 5.0, and dropwise adding 0.3mL of tetraethoxysilane under the stirring condition of 280 revolutions per minute; stirring at the speed of 50 r/min for 2h after the dropwise addition is finished, and standing in a water bath at the temperature of 25 ℃ for 6 h; washing the obtained product with distilled water for 4 times to neutrality, drying at 120 deg.C for 12h, and treating at 280 deg.C for 2h to obtain SiO2The magnesium oxide composite material obtained has sample number CL2, and the properties of the sample are shown in Table 1.
Example 4
10g of magnesium chloride hexahydrate, 85mL of distilled water and 15mL of ammonia water (the mass concentration is 25%) are taken and stirred for 1.8 h; then the mixture is put into a reaction kettle for treatment for 2 hours at 160 ℃; then washing the solid product with distilled water for 4 times until the solid product is neutral, and drying the solid product at 120 ℃ for 12 hours to obtain magnesium oxide;
2g of the magnesium oxide is taken and placed in 60mL of propanol to be stirred for 1.8h, and then ultrasonic treatment is carried out for 5h, wherein the frequency of ultrasonic waves is 10MHz, and the power is 20W/L according to the volume of the solution; then placing the mixture into a water bath at 50 ℃, adding 64mL of buffer solution with pH5.2, and dropwise adding 2.9 mL of tetraethoxysilane under the stirring condition of 120 revolutions per minute; stirring at the speed of 20 r/min for 9h after the dropwise addition is finished, and standing in a water bath at the temperature of 35 ℃ for 20 h; washing the obtained product with distilled water for 4 times to neutrality, drying at 120 deg.C for 12h, and treating at 220 deg.C for 3h to obtain SiO2The magnesium oxide composite material is obtained, the obtained sample is numbered CL 3, and the properties of the sample are shown in Table 1.
Example 5
Taking 12g of magnesium nitrate hexahydrate, 45mL of distilled water and 9mL of ammonia water (the mass concentration is 25 percent), and stirring for 1 h; then the mixture is put into a reaction kettle for treatment for 5 hours at the temperature of 140 ℃; then washing the solid product with distilled water for 4 times until the solid product is neutral, and drying the solid product at 120 ℃ for 12 hours to obtain magnesium oxide;
putting 1.25g of the magnesium oxide into 37mL of butanol, adding 2.4g of Tween-80, stirring for 0.5h, and then carrying out ultrasonic treatment for 3h, wherein the frequency of ultrasonic waves is 1MHz, and the power is 50W/L according to the volume of the solution; then placing the mixture into a water bath at 55 ℃, adding 50mL of buffer solution with pH5.6, and then dropwise adding 1mL of tetraethoxysilane into the mixture while stirring at the speed of 240 revolutions per minute; then stirring the mixture for 5 hours at the speed of 30 r/min, and standing the mixture in a water bath at the temperature of 35 ℃ for 12 hours; washing the obtained product with distilled water for 4 times to neutrality, drying at 120 deg.C for 12h, and treating at 270 deg.C for 4h to obtain SiO2Magnesium oxide composite, sample No. CL 4.
Example 6
Taking 10g of magnesium nitrate hexahydrate, 350mL of distilled water and 11mL of ammonia water (the mass concentration is 25 percent), and stirring for 1 h; then the mixture is put into a reaction kettle for 6.5 hours at the temperature of 120 ℃; then washing the solid product with distilled water for 4 times until the solid product is neutral, and drying the solid product at 120 ℃ for 12 hours to obtain magnesium oxide;
putting 1.4g of the magnesium oxide into 33 mL of ethanol, adding 2.1g of Tween-60, stirring for 1h, and then carrying out ultrasonic treatment for 2.5h, wherein the frequency of ultrasonic waves is 1MHz, and the power is 50W/L according to the volume of the solution; then placing the mixture into a water bath at 60 ℃, adding 50mL of buffer solution with pH4.5, and then dropwise adding 0.7 mL of tetraethoxysilane while stirring at the speed of 270 r/min; then stirring the mixture for 5 hours at the speed of 30 r/min, and standing the mixture in a water bath at the temperature of 30 ℃ for 12 hours; washing the obtained product with distilled water for 4 times to neutrality, drying at 120 deg.C for 12h, and treating at 230 deg.C for 2.5h to obtain SiO2Magnesium oxide composite, sample No. CL 5.
Comparative example 1
According to the material proportion of example 2, 10g of magnesium chloride hexahydrate, 40mL of distilled water and 12mL of ammonia water (mass concentration is 25%) are taken and stirred for 1 h; then the mixture is put into a reaction kettle for treatment for 6 hours at the temperature of 130 ℃; then washing the solid product with distilled water for 4 times until the solid product is neutral, and drying the solid product at 120 ℃ for 12 hours to obtain magnesium oxide;
taking 1.7g of the magnesium oxide, putting the magnesium oxide into 38mL of ethanol, stirring for 0.5h, then carrying out ultrasonic treatment for 3.2h, wherein the frequency of ultrasonic waves is 1MHz, and the power is 50W/L according to the volume of the solution; then placing the mixture in a water bath at 60 ℃, adding 56mL of hydrochloric acid solution with the pH value of 4.8, dropwise adding 0.9 mL of ethyl orthosilicate under the stirring condition of 120 r/min, stirring the mixture for 5 hours at the speed of 20 r/min after the dropwise adding is finished, and then placing the mixture in a water bath at 30 ℃ for standing for 12 hours; the obtained product was washed 4 times with distilled water to neutrality, dried at 120 ℃ for 12 hours, heat-treated at 260 ℃ for 3 hours, and obtained sample No. CL 7.
Comparative example 2
According to the material proportion of example 2, 10g of magnesium chloride hexahydrate, 40mL of distilled water and 12mL of ammonia water (mass concentration is 25%) are taken and stirred for 1 h; then the mixture is put into a reaction kettle for treatment for 6 hours at the temperature of 130 ℃; then washing the solid product with distilled water for 4 times until the solid product is neutral, and drying the solid product at 120 ℃ for 12 hours to obtain magnesium oxide;
taking 1.7g of the magnesium oxide, putting the magnesium oxide into 38mL of ethanol, stirring for 0.5h, then carrying out ultrasonic treatment for 3.2h, wherein the frequency of ultrasonic waves is 1MHz, and the power is 50W/L according to the volume of the solution; then placing the mixture into a water bath at 60 ℃, adding 56mL of buffer solution with pH4.8, dropwise adding 0.9 mL of ethyl orthosilicate under the stirring condition of 120 r/min, stirring the mixture for 5 hours at the speed of 2 r/min after the dropwise adding is finished, and then placing the mixture into a water bath at 30 ℃ for standing for 12 hours; the obtained product was washed 4 times with distilled water to neutrality, dried at 120 ℃ for 12 hours, heat-treated at 260 ℃ for 3 hours, and obtained sample No. CL 7.
Comparative example 3
According to the material proportion of example 2, 10g of magnesium chloride hexahydrate, 40mL of distilled water and 12mL of ammonia water (mass concentration is 25%) are taken and stirred for 1 h; then the mixture is put into a reaction kettle for treatment for 6 hours at the temperature of 130 ℃; then washing the solid product with distilled water for 4 times until the solid product is neutral, and drying the solid product at 120 ℃ for 12 hours to obtain magnesium oxide;
taking 1.7g of the magnesium oxide, putting the magnesium oxide into 38mL of ethanol, stirring for 0.5h, then carrying out ultrasonic treatment for 3.2h, wherein the frequency of ultrasonic waves is 1MHz, and the power is 50W/L according to the volume of the solution; then placing the mixture into a water bath at 60 ℃, adding 56mL of buffer solution with pH4.8, dropwise adding 0.9 mL of ethyl orthosilicate under the stirring condition of 120 r/min, stirring the mixture for 5h at the speed of 470 r/min after the dropwise adding is finished, and then placing the mixture into a water bath at 30 ℃ for standing for 12 h; the obtained product was washed 4 times with distilled water to neutrality, dried at 120 ℃ for 12 hours, heat-treated at 260 ℃ for 3 hours, and obtained sample No. CL 8.
Stability evaluation test:
in order to further verify the stability of the structure of the samples obtained in the above examples and comparative examples, the samples were subjected to ultrasonic treatment for 24 hours, the frequency of the ultrasonic wave was 10MHz, and the power was 100W/L based on the volume of the solution. Through tests, the shell layer of the sample obtained in the example 2-6 is not dropped after ultrasonic treatment, which shows that the sample prepared by the invention has very stable structure, the shell layer is combined with the core very tightly, and the sample is not easy to be damaged by external force.
TABLE 1 physicochemical Properties of samples obtained in examples and comparative examples
Figure DEST_PATH_IMAGE002

Claims (26)

1. The composite material takes magnesium oxide as a core layer and takes silicon oxide as a shell layer.
2. The silica/magnesia composite material according to claim 1, characterized in that: in the composite material, the diameter of a nuclear layer is 0.5-3 mu m; the thickness of the shell layer is 10-200 nm.
3. The silica/magnesia composite material according to claim 1, characterized in that: the specific surface area of the composite material is 10-30 m2/g。
4. A synthesis method of a silicon oxide/magnesium oxide composite material comprises the following steps:
(1) mixing magnesium oxide and a micromolecular alcohol solvent, and adding a pH buffer solution after uniformly mixing;
(2) adding a silicon source into the material obtained in the step (1) under the condition of stirring, uniformly mixing, and then standing;
(3) and (3) washing, drying and thermally treating the material obtained in the step (2) to obtain the silicon oxide/magnesium oxide composite material.
5. A method for synthesizing a silica/magnesia composite material according to claim 4, characterized in that: the particle size range of the magnesium oxide is 0.5-3 mu m.
6. A method for synthesizing a silica/magnesia composite material according to claim 4, characterized in that: the magnesium oxide is prepared by the following method: mixing magnesium salt, ammonia water and water, uniformly mixing, putting into a reaction kettle for treatment, and separating, washing and drying to obtain the magnesium oxide.
7. A method for synthesizing a silica/magnesia composite material according to claim 6, characterized in that: the magnesium salt is magnesium chloride hexahydrate or magnesium nitrate hexahydrate.
8. A method for synthesizing a silica/magnesia composite material according to claim 6, characterized in that: the mass ratio of the magnesium salt to the ammonia water to the water is 1: 2-11: 0.5 to 1.6, preferably 1: 3-10: 0.6 to 1.5.
9. A method for synthesizing a silica/magnesia composite material according to claim 6, characterized in that: the concentration of the ammonia water is 25 wt%.
10. A method for synthesizing a silica/magnesia composite material according to claim 6, characterized in that: the treatment temperature is 100-180 ℃, and preferably 110-170 ℃; the treatment time is 4-20 h, preferably 5-18 h.
11. A method for synthesizing a silica/magnesia composite material according to claim 4, characterized in that: the small molecular alcohol solvent in the step (1) is C2-C4 alcohol.
12. A method for synthesizing a silica/magnesia composite material according to claim 4 or 11, characterized in that: the micromolecular alcohol solvent in the step (1) is one or more of ethanol, propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, propylene glycol and butanediol.
13. A method for synthesizing a silica/magnesia composite material according to claim 4, characterized in that: in the step (1), the mass ratio of the micromolecular alcohol solvent to the magnesium oxide is 5-40: 1, preferably 10 to 30: 1.
14. a method for synthesizing a silica/magnesia composite material according to claim 4, characterized in that: the mixing treatment in the step (1) adopts one or more of stirring and ultrasonic treatment, preferably adopts a combined mode of stirring and ultrasonic treatment, and more preferably adopts a method of firstly stirring and then ultrasonically mixing.
15. A method of synthesizing a silica/magnesia composite material according to claim 12, characterized in that: the frequency of the ultrasonic wave is 15KHz-10MHz, the power is 20-100W/L according to the volume of the solution, and the stirring time is 0.1-2 h, preferably 0.2-1.8 h; the ultrasonic time is 1-6 h, preferably 2-5 h.
16. A method for synthesizing a silica/magnesia composite material according to claim 4, characterized in that: the pH value of the pH buffer solution in the step (1) is 4-6, and preferably 4.5-5.8.
17. A method of synthesizing a silica/magnesia composite material according to claim 4 or 14, characterized in that: the pH buffer solution in the step (1) is one or more of sodium dihydrogen phosphate-citric acid pH buffer solution, sodium acetate pH buffer solution and potassium hydrogen phthalate-sodium hydroxide pH buffer solution, and is preferably sodium dihydrogen phosphate-citric acid pH buffer solution.
18. A method for synthesizing a silica/magnesia composite material according to claim 4, characterized in that: the mass ratio of the pH buffer solution to the magnesium oxide in the step (1) is 7-33: 1, preferably 8 to 32: 1.
19. a method for synthesizing a silica/magnesia composite material according to claim 4, characterized in that: and (2) adding an auxiliary agent in the step (1), wherein the auxiliary agent comprises one or more of tween-20, tween-60 and tween-80.
20. A method of synthesizing a silica/magnesia composite material as defined in claim 17 wherein: the mass ratio of the auxiliary agent to the micromolecular alcohols is 1: 5-40, preferably 1: 10 to 30.
21. A method for synthesizing a silica/magnesia composite material according to claim 4, characterized in that: the silicon source in the step (2) is one or more of methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate, and preferably ethyl orthosilicate.
22. A method for synthesizing a silica/magnesia composite material according to claim 4, characterized in that: the mass ratio of the silicon source in the step (2) to the magnesium oxide in the step (1) is 0.1-1.5: 1, preferably 0.15 to 1.45: 1.
23. a method for synthesizing a silica/magnesia composite material according to claim 4, characterized in that: the condition for adding the silicon source in the step (2) is that the silicon source is added at the temperature of 45-80 ℃, preferably 50-70 ℃.
24. A method for synthesizing a silica/magnesia composite material according to claim 4, characterized in that: adding a silicon source under the stirring condition in the step (2), wherein the stirring speed is 100-300 r/min, preferably 120-280 r/min, and stirring is continued for a period of time after the silicon source is dropwise added, wherein the stirring speed is 10-60 r/min, preferably 20-50 r/min; the stirring time is 1-10 h, preferably 2-9 h.
25. A method for synthesizing a silica/magnesia composite material according to claim 4, characterized in that: the standing condition in the step (2) is as follows: the temperature is 25-40 ℃, and preferably 25-35 ℃; the time is 5-24 h, preferably 6-20 h.
26. A method for synthesizing a silica/magnesia composite material according to claim 4, characterized in that: the heat treatment temperature in the step (3) is 180-300 ℃, and preferably 200-280 ℃; the heat treatment time is 1-6 h, preferably 2-5 h.
CN201811239877.0A 2018-10-24 2018-10-24 Silicon oxide and magnesium oxide composite material and synthesis method thereof Pending CN111087032A (en)

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