CN113753904B - Porous silicon dioxide nanoring and preparation method thereof - Google Patents

Porous silicon dioxide nanoring and preparation method thereof Download PDF

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CN113753904B
CN113753904B CN202111181750.XA CN202111181750A CN113753904B CN 113753904 B CN113753904 B CN 113753904B CN 202111181750 A CN202111181750 A CN 202111181750A CN 113753904 B CN113753904 B CN 113753904B
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silicon dioxide
nanoring
control agent
solution
morphology
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CN113753904A (en
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张建安
袁玉昆
吴明元
吴庆云
杨建军
刘久逸
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Anhui University
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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
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • 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
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention discloses a porous silicon dioxide nanoring and a preparation method thereof. The preparation method has the advantages of simple process, low cost and mild reaction conditions, can realize the controllable preparation of the porous silicon dioxide nanoring, and can be popularized for industrial production.

Description

Porous silicon dioxide nanoring and preparation method thereof
Technical Field
The invention belongs to the technical field of nano silicon compounds, particularly relates to a preparation method of a porous silicon dioxide nanoring, and further relates to the porous silicon dioxide nanoring prepared by the preparation method.
Background
The nano-silica material has been widely applied in the fields of optics, electronics, biomedicine, bioseparation technology, biosensing technology, catalytic reaction and the like, and has various morphologies, such as nanospheres, nanosheets and the like, and nano-silica with different morphologies often has different properties, especially some nano-structures with special morphologies.
The nano annular silicon dioxide has large specific surface area and strong adsorption capacity, and can be widely applied to the fields of catalyst carriers, drug carriers and the like. However, due to the special morphology of the nanorings and the absence of suitable cyclic precursors, porous silica nanorings cannot be synthesized by chemical methods simply.
The existing silicon dioxide nano-ring is mainly prepared by a template method: one method is to disperse synthesized silicon dioxide hollow spheres on a plane to form an array, and then carry out ion etching to prepare nano-ring silicon dioxide, but the method needs an auxiliary means of ion etching and has low yield (ACS appl. Mater. Interfaces 2016,8, 10451-10458); the other method is to assemble silicon dioxide nano particles into annular nano particles by small molecule induction, but the nano rings prepared by the method have weak mechanical property, have high requirements on experimental parameters, are not suitable for regulation and control, and are not easy for industrial production (Langmuir 2018,34,26, 7751-7758).
Disclosure of Invention
In view of the above, the present invention needs to provide a method for preparing a porous silica nanoring, in which a cationic surfactant is used as a template, and a first morphology control agent and a second morphology control agent are used to control the growth direction of silica, so as to prepare the porous silica nanoring.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a porous silicon dioxide nanoring, which comprises the following steps:
preparing a template solution, wherein the template solution is an aqueous solution of a cationic surfactant;
providing a first morphology control agent, fully mixing the first morphology control agent with the template solution, and adjusting the pH value of the system to 2-13 to obtain a first micelle solution with lamellar micelles;
providing a second morphology control agent, and fully mixing the second morphology control agent with the first micelle solution to obtain a second micelle solution with cyclic micelles;
providing a silicon dioxide precursor, mixing the silicon dioxide precursor with the second micelle solution, and heating for reaction to obtain a porous silicon dioxide nanoring dispersion;
purifying the porous silica nanoring dispersion to obtain porous silica nanorings.
In the further scheme, the adding amount of the cationic surfactant in the template solution is 0.25-2.5wt%;
the cationic surfactant is selected from cationic emulsifiers.
Further, the cationic emulsifier is selected from one of alkyl quaternary ammonium salt, quaternary ammonium salt containing heteroatom, quaternary ammonium salt containing benzene ring, quaternary ammonium salt containing heterocycle and amine salt type cationic emulsifier.
In a further embodiment, the first morphology control agent is selected from one of a water-soluble salt, a water-soluble organic acid, an anionic emulsifier, and an anionic polymer, wherein the water-soluble salt contains ClO 4 - 、Cl - 、NO 3 - 、SO 4 2- Or SO 3 2- The water-soluble organic acid contains carboxylic, sulfonic, sulfinic or thiocarboxylic functional groups.
Further, the anionic emulsifier is selected from one of carboxylate type, sulfonate type and sulfate type;
the anionic polymer is selected from one of sodium polyacrylate, sodium polymethacrylate, sodium polystyrene sulfonate, anionic waterborne polyurethane and anionic polyacrylamide.
In a further embodiment, the pH of the system is in the range of 8 to 11.
In a further scheme, the second appearance control agent is an alcohol substance, and the dosage of the alcohol substance is 3-30wt%;
the alcohol substance is at least one selected from ethanol, glycol, glycerol, diethylene glycol, hydrophilic macromolecules containing hydroxyl groups and hydrophilic micromolecules containing hydroxyl groups.
In a further scheme, the silicon dioxide precursor is selected from one or a mixture of more than two of sodium silicate, methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and silane coupling agent.
In a further scheme, the temperature-rising reaction comprises the following specific steps: stirring and reacting for 1-36h at 20-85 ℃.
The invention further provides a porous silicon dioxide nanoring prepared by the preparation method of any one of the above methods, wherein the porous silicon dioxide nanoring has an inner diameter of 20-5000nm and an outer diameter of 500nm-10 μm.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the porous silicon dioxide nanoring takes the cationic surfactant as a template, adopts the first morphology control agent and the second morphology control agent, regulates and controls the growth of silicon dioxide in the template solution, and can directly induce the generation of the porous silicon dioxide nanoring.
The adopted raw materials are all commercial chemical reagents, can be directly obtained in the market, and have low cost; the preparation is carried out through simple chemical reaction, and the process is simple; can react at room temperature, has mild reaction conditions and is easy to realize industrial production.
In addition, the shape of the porous silicon dioxide nanoring can be regulated and controlled by adjusting the dosage of the silicon dioxide precursor, the cationic surfactant and the shape control agent, and the regulation and control mode is simple.
The obtained porous silicon dioxide nanoring can be widely applied to the fields of catalyst carriers, drug carriers, microwave absorption or sensor energy and has wide prospects.
Drawings
FIG. 1 is a flow chart of a method for preparing a porous silica nanoring according to a preferred embodiment of the present invention;
FIG. 2 is a TEM image of a porous silica nanoring obtained in example 1 of the present invention;
FIG. 3 is an SEM image of porous silica nanorings obtained in example 1 of the present invention;
FIG. 4 is an infrared spectrum of a porous silica nanoring obtained in example 1 of the present invention;
FIG. 5 is a graph showing a distribution of particle sizes of porous silica nanorings obtained in example 2 of the present invention;
FIG. 6 is an SEM photograph of porous silica nanorings obtained in example 2 of the present invention;
FIG. 7 is an SEM photograph of porous silica nanorings obtained in example 3 of the present invention;
FIG. 8 is an SEM image of porous silica nanorings obtained in example 4 of the present invention;
FIG. 9 is an SEM image of porous silica nanorings obtained in example 5 of the present invention.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The first aspect of the present invention discloses a method for preparing a porous silica nanoring, as specifically shown in fig. 1, comprising the steps of:
preparing a template solution, wherein the template solution is an aqueous solution of a cationic surfactant;
providing a first morphology control agent, fully mixing the first morphology control agent with the template solution, and adjusting the pH of the system to 2-13 to obtain a first micelle solution with lamellar micelles;
providing a second morphology control agent, and fully mixing the second morphology control agent with the first micelle solution to obtain a second micelle solution with cyclic micelles;
providing a silicon dioxide precursor, mixing the silicon dioxide precursor with the second micelle solution, and heating for reaction to obtain a porous silicon dioxide nanoring dispersion;
purifying the porous silica nanoring dispersion to obtain porous silica nanorings.
According to the method, a cationic surfactant is used as a template, a first shape control agent and a second shape control agent are used for regulating and controlling the growth method of silicon dioxide in a template solution, and a silicon dioxide precursor is directly induced to prepare the porous silicon dioxide nanoring. The preparation of the template solution is not particularly limited, and the template solution can be obtained by adding a cationic surfactant into deionized water and dissolving.
The raw materials adopted in the preparation method are all commercial chemical reagents, are simple and easy to obtain, and have low cost, the steps of the whole preparation process are simple, and the reaction conditions are mild.
In addition, in the preparation method, the shape and size of the nanorings can be adjusted by adjusting the dosage or the proportional relationship of the cationic surfactant, the first shape control agent, the second shape control agent and the silica precursor, so the preparation method is not particularly limited, and specifically, the size of the silica nanorings can be increased by increasing the dosage of the cationic surfactant and the shape control agent; the thickness of the ring wall can be increased by increasing the amount of silica precursor. In one or more embodiments of the present invention, the cationic surfactant is present in an amount of 0.25 to 2.5wt%, the first morphology control agent is present in an amount of 0.1 to 1.0wt%, the second morphology control agent is present in an amount of 3 to 30wt%, and the silica precursor is present in an amount of 1 to 10wt%, based on the amount of deionized water present in the template solution.
Cationic surfactant
The cationic surfactant described herein refers to a nitrogen-containing organic amine derivative, specifically a cationic emulsifier, and is generally a conventional raw material for preparing nano-silica by using a cationic surfactant template method, and is not particularly limited, and may be selected from one of alkyl quaternary ammonium salts, quaternary ammonium salts containing heteroatoms (such as oxygen atom, sulfur atom, and nitrogen atom), quaternary ammonium salts containing benzene ring, quaternary ammonium salts containing heterocycle, and amine salt type cationic emulsifiers, wherein the alkyl quaternary ammonium salts may be mentioned by dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, and octadecyl trimethyl ammonium chloride, the quaternary ammonium salts containing heteroatoms may be mentioned by hexadecyl hydroxypropyl dimethyl ammonium chloride, the benzyl quaternary ammonium salts containing benzene ring may be mentioned by octadecyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, the quaternary ammonium salts containing heterocycle may be mentioned by hexadecyl pyridine bromide, and the amine salt type cationic emulsifiers may be mentioned by rosin amine.
First morphology controlling agent
The first morphology control agent described herein functions to interact with the cationic surfactant to form a layerThe micelle is used for regulating the growth direction of the silicon dioxide, so the chemical structure of the first morphology control agent at least comprises one functional group which can interact with the cationic surfactant to form a lamellar micelle compound, and the modification can be specifically carried out according to the type of the cationic surfactant. In one or more embodiments of the present invention, the first morphology controlling agent is selected from one of a water-soluble salt, a water-soluble organic acid, an anionic emulsifier, an anionic polymer. Wherein the water-soluble salt contains ClO 4 - 、Cl - 、NO 3 - 、SO 4 2- Or SO 3 2- Specific examples thereof which may be mentioned are sodium sulfate, potassium sulfite or ammonium chloride; the water-soluble organic acid is an organic acid which contains carboxylic acid, sulfonic acid, sulfinic acid or thiocarboxylic acid functional groups and has certain solubility in water, and specific examples are vanillic acid and citric acid; the anionic emulsifier is selected from one of carboxylate type, sulfonate type and sulfate type, wherein the carboxylate type can be sodium oleate, the sulfonate type can be sodium hexadecyl sulfonate, and the sulfate type can be sodium dodecyl sulfate; the anionic polymer is selected from one of sodium polyacrylate, sodium polymethacrylate, sodium polystyrene sulfonate, anionic waterborne polyurethane and anionic polyacrylamide.
Second appearance controlling agent
The second morphology-controlling agent described herein functions to dissociate the portions of the micelle having a small curvature, thereby converting the lamellar micelle into a cyclic micelle. Therefore, the second morphology controlling agent is a compound containing an-OH functional group, which can act with the cationic surfactant to dissociate portions of the micelle having small curvature because of its hydrophilicity. Specific examples thereof include, but are not limited to, one or a mixture of two or more of ethanol, ethylene glycol, glycerol, diethylene glycol, a hydroxyl group-containing hydrophilic polymer, and a hydrophilic small molecule; preferably, the second morphology controlling agent is selected from at least one of ethanol and ethylene glycol in consideration of easy availability of raw materials and cost, mainly due to the simple structure of ethanol and ethylene glycol, which is easily removed at a later stage.
Silicon dioxide precursor
The silica precursor described herein may be obtained as silica by hydrolysis, condensation, etc., which is not particularly limited and may be a routine choice in the art, and specifically, there may be mentioned, but not limited to, one or a mixture of two or more of sodium silicate, methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, silane coupling agent.
Further, the reaction in the present invention may be carried out under acidic or basic conditions, but generally, since the pH affects the hydrolytic polycondensation reaction rate of the silica precursor, it is preferable that the system is adjusted to be basic in the production method, and more preferably, the pH is in the range of 8 to 11, thereby obtaining a preferable rate of the hydrolytic polycondensation reaction. The step of adjusting the pH is performed by adding an alkali solution conventionally in the art, and in one or more embodiments of the present invention, the specific step is to add an organic base or an inorganic base to the system to a pH of 8 to 11, and then stir for 3 to 24 hours, wherein the organic base specifically includes but is not limited to one of ethylenediamine, triethylamine, triethanolamine, tetraethylenepentamine, diethylenetriamine, triethylenetetramine, ammonia water, tris (hydroxymethyl) aminomethane, tetrahydroxyethylethylene diamine, tetrahydroxypropylethylenediamine, tetraethylethylenediamine, 1, 8-bisdimethylaminomethyl naphthalene, and imidazole, and the inorganic base specifically includes but is not limited to one of ammonia water, sodium hydroxide, and potassium hydroxide.
In a further aspect, after the silica precursor is added, a temperature-raising reaction is performed to hydrolyze and condense the silica precursor, the reaction rate can be adjusted by adjusting the reaction temperature, and the specific reaction time can be adjusted according to the amount of the added silica precursor and the reaction rate, in one or more embodiments of the present invention, the temperature-raising reaction specifically includes: the reaction is carried out for 1 to 36 hours under stirring at a temperature of between 20 and 85 ℃, preferably at a temperature of between 20 and 65 ℃, more preferably at a temperature of between 30 and 50 ℃.
In a second aspect of the present invention, there is provided a porous silica nanoring, which is prepared by the preparation method according to the first aspect of the present invention, and can realize the control of the morphology and size of the porous silica nanoring by adjusting the amount and the proportional relationship of the raw materials, in one or more embodiments of the present invention, the porous silica nanoring is a porous ring with an inner diameter of 20 to 5000nm and an outer diameter of 500nm to 10 μm, that is, silica is in a ring structure, and a porous channel structure is formed on the ring. The nano porous ring has special shape and can be widely used in the fields of catalyst carriers, drug carriers, microwave absorption, sensors and the like.
The technical solution of the present invention will be more clearly and completely described below with reference to specific embodiments.
Example 1
Weighing 0.5g of hexadecyl trimethyl ammonium bromide, adding the hexadecyl trimethyl ammonium bromide into 200mL of deionized water for dissolving, and mechanically stirring for 3 hours to form a uniform template solution;
adding 0.2g of sodium polyacrylate into the template solution, adjusting the pH of the system to be =8 by using ammonia water, mechanically stirring for 2 hours, and fully dissolving to obtain a first micelle solution with lamellar micelles;
adding 40mL of ethanol into the first micelle solution, stirring for 10min, adding 2g of tetraethoxysilane, heating to 40 ℃, and stirring for 12h to obtain a porous silicon dioxide nano-ring dispersion;
and purifying and spray drying the porous silicon dioxide nano-ring dispersoid to obtain the porous silicon dioxide nano-ring.
Example 2
Weighing 1.0g of hexadecyltrimethylammonium chloride, adding the hexadecyltrimethylammonium chloride into 200mL of deionized water for dissolving, and mechanically stirring for 3 hours to form a uniform template solution;
adding 0.5g of sodium dodecyl sulfate into the template solution, adjusting the pH value to be =9 by using triethylamine, mechanically stirring for 2h, and fully dissolving to obtain a first micelle solution with lamellar micelles;
adding 40mL of ethylene glycol into the first micelle solution, stirring for 5min, adding 4g of methyl orthosilicate, heating to 20 ℃, and stirring for 12h to obtain a porous silicon dioxide nanoring dispersion;
and purifying and spray drying the porous silicon dioxide nano-ring dispersoid to obtain the porous silicon dioxide nano-ring.
Example 3
Weighing 1.5g of dodecyl dimethyl benzyl ammonium chloride, adding into 200mL of deionized water for dissolving, and mechanically stirring for 3 hours to form a uniform template solution;
adding 1.0g of anionic polyacrylamide into the template solution, adjusting the pH to be =9 by using ammonia water, mechanically stirring for 2 hours, and obtaining a first micelle solution with lamellar micelles after complete dissolution;
adding 20mL of ethanol into the first micelle solution, stirring for 10min, adding 6g of sodium silicate, heating to 60 ℃, and stirring for 12h to obtain a porous silicon dioxide nanoring dispersion;
and purifying and freeze-drying the porous silicon dioxide nano-ring dispersion to obtain the porous silicon dioxide nano-ring.
Example 4
Weighing 1.0g of hexadecyltrimethylammonium chloride, adding the hexadecyltrimethylammonium chloride into 200mL of distilled water for dissolving, and mechanically stirring for 3h to form a uniform template solution;
adding 2.5g of sodium dodecyl sulfate into the template solution, adjusting the pH to be =10 by triethanolamine, mechanically stirring for 2 hours, and fully dissolving to obtain a first micelle solution with lamellar micelles;
adding 60mL of ethylene glycol into the first micelle solution, stirring for 10min, adding 10g of 3-aminopropyltriethoxysilane, heating to 65 ℃, and stirring for 1h to obtain a porous silicon dioxide nano-ring dispersion;
and purifying and spray-drying the obtained porous silicon dioxide nano-ring dispersoid to obtain the porous silicon dioxide nano-ring.
Example 5
Weighing 5.0g of dodecyl trimethyl ammonium chloride, adding into 200mL of deionized water for dissolving, and mechanically stirring for 3 hours to form a uniform template solution;
adding 2.0g of sodium polystyrene sulfonate into the template solution, adjusting the pH to be =11 by using sodium hydroxide, mechanically stirring for 2 hours, and obtaining a first micelle solution with lamellar micelles after complete dissolution;
adding 5mL of ethanol into the first micelle solution, stirring for 10min, adding 20g of ethyl orthosilicate, heating to 60 ℃, and stirring for 36h to obtain a porous silicon dioxide nanoring dispersion;
and purifying and spray drying the porous silicon dioxide nano-ring dispersoid to obtain the porous silicon dioxide nano-ring.
Example 6
Weighing 5.0g of dodecyl trimethyl ammonium chloride, adding the dodecyl trimethyl ammonium chloride into 200mL of deionized water for dissolving, and mechanically stirring for 3 hours to form a uniform template solution;
adding 2.0g of sodium polystyrene sulfonate into the template solution, adjusting the pH to be =11 by using sodium hydroxide, mechanically stirring for 2 hours, and obtaining a first micelle solution with lamellar micelles after complete dissolution;
adding 80ml of ethanol into the first micelle solution, stirring for 1 hour, adding 20g of tetraethoxysilane, heating to 40 ℃, and stirring for 10 hours to obtain a porous silicon dioxide nano-ring dispersion;
and purifying and spray drying the porous silicon dioxide nano-ring dispersoid to obtain the porous silicon dioxide nano-ring.
Test example
The porous silica nanorings prepared in examples 1 to 6 were subjected to the relevant characterization, and the test results are shown in the attached drawings.
Wherein, fig. 2 is a TEM image of the porous silica nanoring in example 1, and it can be seen from the figure that the silica is porous structure, the morphology is ring-shaped, and the ring width of the nanoring is about 70nm;
FIG. 3 is an SEM image of the porous silica nanorings of example 1, from which it can be seen that the silica morphology is ring-shaped;
FIG. 4 is an infrared spectrum of the porous silica nanoring powder of example 1, in which 3419cm is included -1 The absorption peak is-OH stretching vibration peak and bending vibration peak, 1063cm -1 The strong absorption peak is caused by the vibration of Si-O-Si, and is classified intoBelongs to the characteristic absorption peak of the porous silicon dioxide nano-ring, which shows that the nano-porous silicon dioxide nano-ring is successfully synthesized in the embodiment.
Fig. 5 is a particle size distribution diagram of the porous silica nanoring in example 2, and since the nanoring has a special shape, information on the ring width and distribution of the porous silica nanoring can be obtained from the result, as can be seen from the diagram, the peak value of the ring width of the porous silica nanoring is 72nm, and the average ring width is about 75 nm;
FIG. 6 is an SEM photograph of porous silica nanorings of example 2, from which it can be seen that the silica morphology is ring-shaped.
Fig. 7, 8 and 9 are SEM images of the porous silica nanorings of examples 3, 4 and 5, and it can be seen that the morphology of silica is ring-shaped, and the shape characteristics of the rings are different.
Other parallel embodiments
Example 7
The present example uses the same embodiment as example 1, except that: the cationic surfactant is octadecyl dimethyl benzyl ammonium chloride with better emulsifying performance.
Example 8
Weighing 1g of dioctadecyl dimethyl ammonium bromide, adding the weighed 1g of dioctadecyl dimethyl ammonium bromide into 200mL of deionized water for dissolving, and mechanically stirring for 3 hours to form a uniform template solution;
adding 0.2g of sodium polyacrylate into the template solution, adjusting the pH of the system to be =8 by using ammonia water, mechanically stirring for 2 hours, and fully dissolving to obtain a first micelle solution with lamellar micelles;
adding 40mL of ethanol into the first micelle solution, stirring for 10min, adding 2g of ethyl orthosilicate, heating to 40 ℃, and stirring for 12h to obtain a porous silicon dioxide nanoring dispersion;
and purifying and spray drying the porous silicon dioxide nano-ring dispersoid to obtain the porous silicon dioxide nano-ring.
Example 9
Weighing 0.5g of hexadecyl trimethyl ammonium bromide, adding the hexadecyl trimethyl ammonium bromide into 200mL of distilled water for dissolving, and mechanically stirring for 3 hours to form a uniform template solution;
adding 2g of sodium stearate into the template solution, adjusting the pH value to be =10 by using triethanolamine, mechanically stirring for 2 hours, and fully dissolving to obtain a first micelle solution with lamellar micelles;
adding 60mL of ethylene glycol into the first micelle solution, stirring for 10min, adding 10g of 3-aminopropyl triethoxysilane, heating to 65 ℃, and stirring for 1h to obtain a porous silicon dioxide nano ring dispersion;
and purifying and spray-drying the obtained porous silicon dioxide nano-ring dispersoid to obtain the porous silicon dioxide nano-ring.
Example 10
The present example employs the same embodiment as example 3, except that: the first morphology control agent is sodium dodecyl benzene sulfonate with better emulsifying property.
Example 11
The present example uses the same embodiment as example 1, except that: the first morphology controller is sodium sulfate.
Example 12
The present example uses the same embodiment as example 3, except that: the first morphology controlling agent is ammonium chloride.
Example 13
The present example uses the same embodiment as example 1, except that: the first morphology controller is vanillic acid.
Example 14
The present example uses the same embodiment as example 1, except that: the first morphology controlling agent is citric acid.
Example 15
The present example uses the same embodiment as example 1, except that: the second morphology controlling agent is butanol.
Example 16
The present example adopts the same embodiment as example 4, except that: the second morphology controlling agent is glycerol.
Example 17
The present example employs the same embodiment as example 6, except that: the second morphology control agent is ethylene acetal.
Example 18
The present example uses the same embodiment as example 1, except that: the second morphology control agent is isopropyl alcohol.
Example 19
The present example uses the same embodiment as example 1, except that: the second morphology controlling agent is hydroxymethyl cellulose.
Example 20
The present example uses the same embodiment as example 1, except that: the silicon dioxide precursor is methyl triethoxysilane.
Example 21
The present example uses the same embodiment as example 1, except that: the precursor of the silicon dioxide is bis- [ gamma- (triethoxy silicon) propyl ] -disulfide.
Example 22
The present example uses the same embodiment as example 1, except that: the silica precursor is 1, 2-bis (triethoxysilyl) ethane.
Example 23
In this example, the same embodiment as in example 2 was employed except that the temperature of the temperature-raising reaction was 20 ℃ and the reaction time was 24 hours.
Example 24
This example was carried out in the same manner as in example 3 except that the temperature of the temperature-raising reaction was 30 ℃ and the reaction time was 6 hours.
Example 25
This example was conducted in the same manner as example 4 except that the temperature of the temperature-raising reaction was 50 ℃ and the reaction time was 6 hours.
Example 26
In this example, the same embodiment as in example 2 was employed except that the temperature of the temperature-raising reaction was 75 ℃ and the reaction time was 6 hours.
Example 27
This example was carried out in the same manner as in example 6 except that the temperature of the temperature-raising reaction was 85 ℃ and the reaction time was 3 hours.
It was tested that examples 7-27 all produced porous silica having nanoring structures.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.

Claims (11)

1. A preparation method of a porous silicon dioxide nanoring is characterized by comprising the following steps:
preparing a template solution, wherein the template solution is an aqueous solution of a cationic surfactant;
providing a first morphology control agent, fully mixing the first morphology control agent with the template solution, and adjusting the pH value of the system to 2-13 to obtain a first micelle solution with lamellar micelles, wherein the chemical structure of the first morphology control agent at least comprises a functional group capable of interacting with a cationic surfactant to form a lamellar micelle compound;
providing a second morphology control agent, and fully mixing the second morphology control agent with the first micelle solution to obtain a second micelle solution with annular micelles, wherein the second morphology control agent is a hydrophilic compound containing-OH functional groups;
providing a silicon dioxide precursor, mixing the silicon dioxide precursor with the second micelle solution, and heating for reaction to obtain a porous silicon dioxide nano-ring dispersion;
purifying the porous silica nanoring dispersion to obtain porous silica nanorings.
2. The method according to claim 1, wherein the cationic surfactant is added to the template solution in an amount of 0.25 to 2.5wt%;
the cationic surfactant is selected from cationic emulsifiers.
3. The method according to claim 2, wherein the cationic emulsifier is one selected from the group consisting of alkyl quaternary ammonium salts, quaternary ammonium salts containing hetero atoms, quaternary ammonium salts containing benzene rings, and amine salt type cationic emulsifiers.
4. The method according to claim 1, wherein the first morphology-controlling agent is one selected from the group consisting of a water-soluble salt containing ClO, a water-soluble organic acid, an anionic emulsifier, and an anionic polymer 4 - 、Cl - 、NO 3 - 、SO 4 2- Or SO 3 2- The water-soluble organic acid contains carboxylic, sulfonic, sulfinic or thiocarboxylic functional groups.
5. The method according to claim 4, wherein the anionic emulsifier is selected from one of carboxylate type, sulfonate type and sulfate type;
the anionic polymer is selected from one of sodium polyacrylate, sodium polymethacrylate, sodium polystyrene sulfonate, anionic waterborne polyurethane and anionic polyacrylamide.
6. The method of claim 1, wherein the system has a pH in the range of 8 to 11.
7. The method according to claim 1, wherein the second morphology controlling agent is an alcohol in an amount of 3 to 30wt%;
the alcohol substance is at least one selected from hydrophilic macromolecules containing hydroxyl and hydrophilic micromolecules containing hydroxyl.
8. The method according to claim 7, wherein the hydrophilic small molecule containing hydroxyl groups is at least one selected from the group consisting of ethanol, ethylene glycol, glycerol, and diethylene glycol.
9. The method according to claim 1, wherein the silica precursor is one or a mixture of two or more selected from the group consisting of sodium silicate, methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, and silane coupling agent.
10. The preparation method according to claim 1, wherein the temperature-raising reaction comprises the following specific steps: stirring and reacting for 1-36h at 20-85 ℃.
11. A porous silica nanoring, which is a porous ring having an inner diameter of 20 to 5000nm and an outer diameter of 500nm to 10 μm, produced by the production method according to any one of claims 1 to 10.
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