CN108751209B - Preparation method and application of chain-shaped nano silicon dioxide - Google Patents
Preparation method and application of chain-shaped nano silicon dioxide Download PDFInfo
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Abstract
The invention discloses a preparation method and application of chain-shaped nano silicon dioxide, firstly, poly diallyl dimethyl ammonium chloride is dissolved in a mixed solvent of water and ethanol to prepare a low-concentration solution; then adding tetraethyl silicate and ammonia water into the system respectively, and hydrolyzing the tetraethyl silicate to form a chain-shaped silicon dioxide dispersion liquid; and drying the obtained mixed solution to remove water, and performing heat treatment to obtain chain-shaped nano silicon dioxide powder. The nano silicon dioxide is different from common spherical nano silicon dioxide, has a longer chain structure, and has special advantages and a larger application prospect in the aspects of nano catalyst loading, polymer reinforcing filler, pollutant removal and the like as a novel nano structure unit compared with isotropic spherical nano silicon dioxide.
Description
Technical Field
The invention relates to a preparation method and application of chain-shaped nano silicon dioxide, belonging to the technical field of nano materials.
Background
The nano silicon dioxide is an inorganic chemical material, commonly called white carbon black, is a nano material with the largest output in the world at present, is nontoxic, tasteless and pollution-free, and is environment-friendly. The nano silicon dioxide is amorphous white powder (an agglomerate thereof) in appearance, has a particle size ranging from 1 to 100 nanometers, and has a spherical microstructure and a flocculent and reticular quasi-granular structure. Due to the quantum tunnel effect, the quantum size effect and the volume effect of the nano-scale silicon dioxide, the free permeation function is generated, so that a space network structure is formed, the mechanical strength, toughness, wear resistance, aging resistance and other properties of the high polymer material can be greatly improved, and the nano-scale silicon dioxide still has high strength, stability and the like at high temperature. The nano silicon dioxide is mainly used in many fields such as electronic packaging materials, resin composite materials, plastics, coatings, rubbers, pigments (dyes), ceramics, glass fiber reinforced plastic products, drug carriers, antibacterial materials, cosmetics, novel materials and the like. Researchers have made a lot of researches on the directions of preparation, surface modification, material compounding, anisotropic regulation and the like of nano silicon dioxide.
At present, the preparation method of the nano silicon dioxide is divided into a physical method and a chemical method. 1) Physical method: physical methods are generally referred to as mechanical pulverization methods. The superfine product with the grain size of 1-5 microns can be obtained by crushing the aggregate of the silicon dioxide by a super jet mill or a high-energy ball mill. The method has the advantages of simple process, high energy consumption, easy impurity introduction, difficult control of powder characteristics, wider particle size distribution and low preparation efficiency. 2) The chemical method comprises the following steps: the nano-silica prepared by the chemical method has high purity and uniform particle size distribution, and mainly comprises a Chemical Vapor Deposition (CVD) method, an ion exchange method, a liquid phase method, a precipitation method, a microemulsion method, a Sol-Gel (Sol-Gel) method and the like, wherein the Stober method is one of the most main chemical methods for preparing the nano-silica at present, namely the precipitation method taking sodium silicate and inorganic acid as raw materials and the Sol-Gel method taking silicic acid vinegar and the like as raw materials, and the nano-silica prepared by the method is usually spherical nano-particles with the diameter of 20-1000 nanometers.
The non-spherical nano particles, also called anisotropic nano particles, have unique morphology and property characteristics, and have great application advantages in the directions of improving material catalytic properties and optical properties, molecular targeted recognition, biological material engineering, solid surfactants and the like. At present, some patents for preparing various types of non-spherical nano-silica have been reported, for example, geqingmin and the like adopt a hydrothermal method to prepare a spongy porous nano-silica film (CN 107051373A); royal orchid et al obtain silica nanosheets (CN106040279A) by heat-acid activation of kaolin; zhuyan et al discloses a preparation method of luminescent silica nanorods (CN 106587082A).
Disclosure of Invention
The invention aims to provide a preparation method and application of chain-shaped nano silicon dioxide, and a silicon dioxide nano material with larger specific surface area and higher dispersion stability in a polymer system is obtained.
The invention relates to a preparation method of chain-shaped nano silicon dioxide, which comprises the steps of firstly dissolving poly (diallyl dimethyl ammonium chloride) in a mixed solvent of water and ethanol to prepare a low-concentration solution; then adding tetraethyl silicate and ammonia water into the system respectively, and hydrolyzing the tetraethyl silicate to form a chain-shaped silicon dioxide dispersion liquid; and drying the obtained mixed solution to remove water, and performing heat treatment to obtain chain-shaped nano silicon dioxide powder.
The preparation method of the chain-shaped nano silicon dioxide comprises the following steps:
adding 15-35ml of ethanol into a three-neck flask, then adding 15-35ml of 500-10000mg/L polydiallyldimethylammonium chloride aqueous solution, stirring at 10-50 ℃, then sequentially adding 1-5ml of tetraethyl silicate and 0.05-2ml of ammonia water, and carrying out heat preservation reaction for 2-8 h; and after the reaction is finished, centrifuging the reaction solution, washing with deionized water and ethanol in sequence, and drying to obtain the chain-shaped nano silicon dioxide.
The centrifugation treatment was centrifugation at 12000 rpm.
The ammonia water is analytically pure.
The tetraethyl silicate was reagent grade, 98%.
The molecular weight of the polydiallyldimethylammonium chloride is 200000-500000.
The application of the chain-shaped nano silicon dioxide prepared by the invention is that the chain-shaped nano silicon dioxide is used as a carrier to load a nano catalyst. Preferably, the chain-shaped nano silicon dioxide is used as a carrier to prepare the chain-shaped SiO2The preparation process of the/Ag nano composite catalyst comprises the following steps:
dispersing 100mg of chain-like nano silicon dioxide and 1g of polyvinylpyrrolidone (PVP) into 45ml of deionized water, carrying out constant temperature water bath at 30 ℃, and slowly adding 0.1-1.0ml of 0.2mol/L AgNO3The solution is dripped within 40min, the stirring reaction is continued for 4h, and then 0.02-0.5g of Diethanolamine (DEA) is added, the temperature is adjusted to 45 ℃, and the constant temperature water bath is carried out for 12 h; after the reaction is finished, the obtained product is centrifuged for 10min by a centrifuge at 12000rpm, and then is washed by water and ethanol in sequence and dried to prepare the chain SiO2The Ag/nano composite catalyst.
The application of the chain-shaped nano-silica prepared by the invention is that the chain-shaped nano-silica is added into a polymer matrix to be used as a reinforcing filler. The polymer matrix is polyolefin, polyurethane or polyacrylate and the like, and the addition mass of the chain-shaped nano silicon dioxide is 0.1-5% of the mass of the polymer matrix.
Compared with the prior art, the invention has the beneficial effects that:
the nano silicon dioxide is different from common spherical nano silicon dioxide, has a longer chain structure, and has special advantages and a larger application prospect in the aspects of nano catalyst loading, polymer reinforcing filler, pollutant removal and the like as a novel nano structure unit compared with isotropic spherical nano silicon dioxide.
Drawings
FIG. 1 is a transmission electron microscope image of the chain-like nano-silica obtained in example 1, and it can be seen that the product is a chain-like structure, uniform in morphology, and about several hundred nanometers in length.
FIG. 2 is a transmission electron micrograph of the chain-like nano-silica obtained in example 2. The chain particle size was coarser than in example 1.
FIG. 3 is a transmission electron micrograph of the chain-like nano-silica obtained in example 3.
FIG. 4 is a transmission electron micrograph of the chain-like nano-silica obtained in example 4.
FIG. 5 is a transmission electron micrograph of the chain-like nano-silica obtained in example 5.
FIG. 6 is a transmission electron microscope image of the chain-like nano-silica obtained in example 6. It can be speculated from fig. 5 that a relatively uniform and regular profile can be obtained at a low rotation speed within a certain range.
FIG. 7 is a view showing the chain SiO obtained in example 72Transmission electron microscope picture of/Ag nano composite catalyst.
FIG. 8 is a diagram showing the spherical SiO obtained in example 82Transmission electron microscope picture of/Ag nano composite catalyst.
FIG. 9 shows a chain SiO obtained in example 72Ultraviolet absorption peak spectrogram of trifluralin catalyzed and reduced by/Ag composite nano catalyst and spherical SiO obtained in example 82the/Ag composite nano catalyst is used for catalyzing and reducing the trifluralin ultraviolet absorption peak spectrogram. As can be seen from FIG. 9, the spherical SiO22ml of trifluralin with the concentration of 100ppm is completely reduced in 54min by the Ag composite nano catalyst; and chain form SiO22ml of trifluralin with the concentration of 100ppm can be completely reduced by the Ag composite nano catalyst in 16min, and the catalytic activity of the Ag composite nano catalyst is obviously higher than that of spherical SiO2the/Ag composite nano catalyst. In the electron micrograph with silver loaded from above, the silver-loaded particles were smallerMore uniform chain form of SiO2the/Ag composite nano catalyst has better catalytic performance theoretically, which is consistent with the result obtained by actual test.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples, which are provided for implementation on the premise of the technical solution of the present invention, and give detailed implementation modes and specific operation procedures, but the scope of the present invention is not limited to the following examples.
Example 1:
the preparation process of the chain-shaped nano-silica in this example is as follows:
adding 35ml of ethanol into a three-neck flask, then adding 15ml of 1000mg/L poly (diallyldimethylammonium chloride) aqueous solution, and stirring at 30 ℃; adding 1ml of tetraethyl silicate into a three-neck flask, then adding 1ml of ammonia water (analytically pure), and reacting for 8 hours under the condition of heat preservation; and after the reaction is finished, centrifuging the reaction solution at 12000rpm for 15min, washing the reaction solution for 2 times by using deionized water, washing the reaction solution for 1 time by using ethanol, and drying the reaction solution to obtain the chain-shaped nano silicon dioxide.
Fig. 1 is a transmission electron microscope image of the chain-like nano-silica obtained in the embodiment, and it can be seen that the product is a chain-like structure, the morphology is uniform, and the length is about several hundred nanometers.
Example 2:
the preparation process of the chain-shaped nano-silica in this example is as follows:
adding 35ml of ethanol into a three-neck flask, then adding 15ml of 5000mg/L polydiallyldimethylammonium chloride aqueous solution, and stirring at 30 ℃; adding 1ml of tetraethyl silicate into a three-neck flask, then adding 1ml of ammonia water (analytically pure), and reacting for 8 hours under the condition of heat preservation; and after the reaction is finished, centrifuging the reaction solution at 12000rpm for 15min, washing the reaction solution for 2 times by using deionized water, washing the reaction solution for 1 time by using ethanol, and drying the reaction solution to obtain the chain-shaped nano silicon dioxide.
Fig. 2 is a transmission electron microscope image of the chain-like nano-silica obtained in the present example. The chain particle size was coarser than in example 1.
Example 3:
the preparation process of the chain-shaped nano-silica in this example is as follows:
adding 35ml of ethanol into a three-neck flask, then adding 15ml of 1000mg/L poly (diallyldimethylammonium chloride) aqueous solution, and stirring at 30 ℃; adding 1ml of tetraethyl silicate into a three-neck flask, then adding 0.5ml of ammonia water (analytically pure), and carrying out heat preservation reaction for 8 hours; and after the reaction is finished, centrifuging the reaction solution at 12000rpm for 15min, washing the reaction solution for 2 times by using deionized water, washing the reaction solution for 1 time by using ethanol, and drying the reaction solution to obtain the chain-shaped nano silicon dioxide.
FIG. 3 is a transmission electron microscope image of the chain-like nano-silica obtained in the present embodiment.
Example 4:
the preparation process of the chain-shaped nano-silica in this example is as follows:
adding 35ml of ethanol into a three-neck flask, then adding 15ml of 1000mg/L poly (diallyldimethylammonium chloride) aqueous solution, and stirring at 30 ℃; adding 1ml of tetraethyl silicate into a three-neck flask, then adding 0.1ml of ammonia water (analytically pure), and carrying out heat preservation reaction for 8 hours; and after the reaction is finished, centrifuging the reaction solution at 12000rpm for 15min, washing the reaction solution for 2 times by using deionized water, washing the reaction solution for 1 time by using ethanol, and drying the reaction solution to obtain the chain-shaped nano silicon dioxide.
Fig. 4 is a transmission electron microscope image of the chain-like nano-silica obtained in the present embodiment.
It can be seen from examples 1, 3 and 4 that the particle size slightly decreased and the number of branches decreased as the concentration of ammonia was decreased.
Example 5:
the preparation process of the chain-shaped nano-silica in this example is as follows:
adding 35ml of ethanol into a three-neck flask, then adding 15ml of 1000mg/L poly (diallyldimethylammonium chloride) aqueous solution, stirring at 30 ℃, and mechanically stirring at the rotating speed of 400 r/min; adding 1ml of tetraethyl silicate into a three-neck flask, then adding 1ml of ammonia water (analytically pure), and reacting for 8 hours under the condition of heat preservation; and after the reaction is finished, centrifuging the reaction solution at 12000rpm for 15min, washing the reaction solution for 2 times by using deionized water, washing the reaction solution for 1 time by using ethanol, and drying the reaction solution to obtain the chain-shaped nano silicon dioxide.
FIG. 5 is a transmission electron microscope image of the chain-like nano-silica obtained in the present example.
Example 6:
the preparation process of the chain-shaped nano-silica in this example is as follows:
adding 35ml of ethanol into a three-neck flask, then adding 15ml of 1000mg/L poly (diallyldimethylammonium chloride) aqueous solution, stirring at 30 ℃, and mechanically stirring at the rotating speed of 200 r/min; adding 1ml of tetraethyl silicate into a three-neck flask, then adding 1ml of ammonia water (analytically pure), and reacting for 8 hours under the condition of heat preservation; and after the reaction is finished, centrifuging the reaction solution at 12000rpm for 15min, washing the reaction solution for 2 times by using deionized water, washing the reaction solution for 1 time by using ethanol, and drying the reaction solution to obtain the chain-shaped nano silicon dioxide.
Fig. 6 is a transmission electron microscope image of the chain-like nano-silica obtained in the present embodiment. In combination with example 5, it is speculated that a relatively uniform and regular topography can be obtained at low rotational speeds within a certain range.
Example 7:
chain SiO in this example2The preparation of the/Ag nano composite catalyst material is as follows:
100mg of self-made nano silicon dioxide material (chain-shaped nano silicon dioxide regulated and controlled by 1000mg/L PDDA solution) and 1g of polyvinylpyrrolidone (PVP) are dispersed in 45ml of deionized water. Transferring the dispersion into a three-neck flask, and carrying out constant-temperature water bath at 30 ℃. Then 0.5ml of 0.2mol/L AgNO is slowly added into the bottle3The solution was added dropwise over 40min and stirring was continued for 4 h. Subsequently, 0.1g of Diethanolamine (DEA) was added, the temperature was adjusted to 45 ℃ and a constant temperature water bath was carried out for 12 hours. After the reaction is finished, the obtained product is centrifuged for 10min at 1200rpm of a centrifuge, and then washed 3 times by water and 3 times by ethanol. The product is dried to prepare the composite nano catalyst- -chain SiO2the/Ag composite nano catalyst.
Preparing 2mg/ml chain-shaped regulating SiO2Ag composite nano catalyst A1 liquid, 100ppm trifluralin methanol solution B liquid and 0.1mol/L diethanolamine aqueous solution C liquid. The experimental mixture ratio is trifluralin and SiO2The Ag nano catalyst is diethanolamine 2:5:0.1, namely methanol and water 2.1: 5. Wherein the diethanolamine is prepared for use.
Mixing with 2.1ml of water and 5ml of methanolAs a blank solution, 3 baselines were measured on UV-vis. Then, 2mlB solution and 5ml C solution were taken, and 0.1ml A1 solution (chain SiO)2the/Ag composite nano catalyst dispersion liquid) is quickly and uniformly mixed, then the mixture is quickly added into UV-vis to test the absorption peak value of the trifluralin, and meanwhile, timing is started, and the absorption peak value is measured every 2min until the trifluralin is completely degraded.
Example 8:
spherical SiO in this example2The preparation method of the/Ag composite nano catalyst comprises the following steps:
adding 35ml of ethanol into a three-neck flask, stirring at 30 ℃, and mechanically stirring at the rotating speed of 200 r/min; adding 1ml of tetraethyl silicate into a three-neck flask, then adding 1ml of ammonia water (analytically pure), and reacting for 8 hours under the condition of heat preservation; and after the reaction is finished, centrifuging the reaction solution at 12000rpm for 15min, washing the reaction solution for 2 times by using deionized water, then washing the reaction solution for 1 time by using ethanol, and drying the reaction solution to obtain the spherical nano silicon dioxide.
100mg of self-made spherical nano silicon dioxide material and 1g of polyvinylpyrrolidone (PVP) are dispersed in 45ml of deionized water. Transferring the dispersion into a three-neck flask, and carrying out constant-temperature water bath at 30 ℃. Then 0.5ml of 0.2mol/L AgNO is slowly added into the bottle3The solution was added dropwise over 40min and stirring was continued for 4 h. Subsequently, 0.1g of Diethanolamine (DEA) was added, the temperature was adjusted to 45 ℃ and a constant temperature water bath was carried out for 12 hours. After the reaction is finished, the obtained product is centrifuged for 10min at 1200rpm of a centrifuge, and then washed 3 times by water and 3 times by ethanol. The product is dried to prepare the composite nano catalyst-spherical SiO2the/Ag composite nano catalyst.
Preparing 2mg/ml spherical SiO2Ag composite nano catalyst A2 liquid, 100ppm trifluralin methanol solution B liquid and 0.1mol/L diethanolamine aqueous solution C liquid. The experimental mixture ratio is that trifluralin: SiO 22The Ag nano catalyst is diethanolamine 2:5:0.1, namely methanol and water 2.1: 5. Wherein the diethanolamine is prepared for use.
A blank solution was prepared by mixing 2.1ml of water and 5ml of methanol, and 3 baselines were measured on UV-vis. Then, 2mlB solution and 5ml C solution were added, and 0.1ml A2 solution (spherical SiO)2Ag composite nano catalyst dispersion liquid), quickly mixing them uniformly, then making them pass throughQuickly adding the trifluralin into UV-vis, testing the absorption peak value of the trifluralin, simultaneously starting timing, and testing the absorption peak value every 2min until the trifluralin is completely degraded.
Example 9:
the PVA film in this example was prepared as follows:
2.0g of PVA (pure) is added into a beaker, 30ml of deionized water is added, and the mixture is heated in a constant-temperature water bath at 90 ℃ for 2 hours under the condition of stirring. And after complete dissolution, performing ultrasonic treatment for 5min, pouring the mixture into an evaporation pan, and putting the evaporation pan into an oven to dry for 8h at the temperature of 60 ℃ to obtain a PVA film sample I.
2.0g of PVA (pure) was added to a beaker, 30ml of deionized water and 0.04g (2% by weight) of the spherical nano-silica prepared in example 8 were added, and the mixture was heated in a thermostatic water bath at 90 ℃ for 2 hours while stirring. And (3) after complete dissolution, performing ultrasonic treatment for 5min, pouring into an evaporation pan, and putting the evaporation pan into an oven to dry for 8h at the temperature of 60 ℃ to obtain a PVA film sample II.
2.0g of PVA (pure) was added to a beaker, 30ml of deionized water and 0.04g (2% by weight) of the chain-like nano-silica prepared in example 4 were added, and the mixture was heated in a constant temperature water bath at 90 ℃ for 2 hours while stirring. And after complete dissolution, performing ultrasonic treatment for 5min, pouring the mixture into an evaporation pan, and putting the evaporation pan into an oven to dry for 8h at the temperature of 60 ℃ to obtain a PVA film sample III.
Table 1 shows the results of the tensile strength tests of samples one, two and three obtained in example 9. It can be seen that the addition of the chain-like nano-silica enhances the elongation at break, tensile stress at break, tensile strength and tensile stress at yield of the PVA film.
TABLE 1
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. The application of chain-shaped nano silicon dioxide is characterized in that:
preparing chain SiO by using the chain nano silicon dioxide as a carrier2The Ag nano composite catalyst is used for catalyzing and reducing trifluralin;
the chain-shaped nano silicon dioxide is prepared by the method comprising the following steps:
firstly, dissolving poly (diallyldimethylammonium chloride) in a mixed solvent of water and ethanol to prepare a low-concentration solution; then adding tetraethyl silicate and ammonia water into the system respectively, and hydrolyzing the tetraethyl silicate to form a chain-shaped silicon dioxide dispersion liquid; drying the obtained mixed solution to remove water, and performing heat treatment to obtain chain-shaped nano silicon dioxide powder; the method specifically comprises the following steps:
adding 15-35ml of ethanol into a three-neck flask, then adding 15-35ml of 500-10000mg/L polydiallyldimethylammonium chloride aqueous solution, stirring at 10-50 ℃, then sequentially adding 1-5ml of tetraethyl silicate and 0.05-2ml of ammonia water, and carrying out heat preservation reaction for 2-8 h; after the reaction is finished, centrifuging the reaction solution, washing with deionized water and ethanol in sequence, and drying to obtain chain-shaped nano silicon dioxide;
the molecular weight of the polydiallyldimethylammonium chloride is 200000-500000.
2. Use according to claim 1, characterized in that:
the centrifugation treatment was centrifugation at 12000 rpm.
3. The application of chain-shaped nano silicon dioxide is characterized in that: adding the chain-shaped nano silicon dioxide into a polymer matrix to be used as a reinforcing filler;
the polymer matrix is polyolefin, polyurethane or polyacrylate;
the chain-shaped nano silicon dioxide is prepared by the method comprising the following steps:
firstly, dissolving poly (diallyldimethylammonium chloride) in a mixed solvent of water and ethanol to prepare a low-concentration solution; then adding tetraethyl silicate and ammonia water into the system respectively, and hydrolyzing the tetraethyl silicate to form a chain-shaped silicon dioxide dispersion liquid; drying the obtained mixed solution to remove water, and performing heat treatment to obtain chain-shaped nano silicon dioxide powder; the method specifically comprises the following steps:
adding 15-35ml of ethanol into a three-neck flask, then adding 15-35ml of 500-10000mg/L polydiallyldimethylammonium chloride aqueous solution, stirring at 10-50 ℃, then sequentially adding 1-5ml of tetraethyl silicate and 0.05-2ml of ammonia water, and carrying out heat preservation reaction for 2-8 h; after the reaction is finished, centrifuging the reaction solution, washing with deionized water and ethanol in sequence, and drying to obtain chain-shaped nano silicon dioxide;
the molecular weight of the polydiallyldimethylammonium chloride is 200000-500000;
the added mass of the chain-shaped nano silicon dioxide is 0.1-5% of the mass of the polymer matrix.
4. Use according to claim 3, characterized in that:
the centrifugation treatment was centrifugation at 12000 rpm.
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