CN113620303B - Method for preparing porous nano silicon dioxide pellets under neutral condition - Google Patents
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Abstract
The invention relates to the technical field of inorganic material synthesis, and provides a method for preparing porous nano silicon dioxide pellets under a neutral condition, which comprises the following steps: the method comprises three steps of formation of imidazole ionic liquid micelles, deposition of silicon dioxide and calcination of silicon spheres. Compared with the traditional sol-gel method, the method of the invention has the advantages that: the porous nano silicon dioxide spheres are prepared in a neutral aqueous phase system by using a catalytic system of imidazole ionic liquid and multiple weak acid radicals, and the preparation method has the advantages of high efficiency, simplicity, greenness and low consumption. The porous nano silicon dioxide spheres with uniform dispersion, high mechanical strength, controllable particle size and adjustable specific surface area are obtained by adopting the method.
Description
Technical Field
The invention relates to the technical field of inorganic material synthesis, in particular to a method for preparing porous nano silicon dioxide spheres under a neutral condition.
Background
Mesoporous Silica Nanospheres (MSNs) have the advantages of high specific surface area, large pore size, easy surface functionalization and the like, are receiving more and more attention, and are widely applied to various fields such as catalyst carriers, separation materials, biomedicines and the like. For example, the MSNs can be used for loading catalysts or enzymes, and can be used for solving the problem of recycling the catalysts or enzymes for multiple times in the chemical production process. MSNs also have excellent biocompatibility, chemical inertness and diffusion-controlled drug release mechanisms, and can be used to develop new drug release systems. The surface of the silicon dioxide contains abundant silicon hydroxyl, and the silicon dioxide can be used as a stationary phase carrier of the high performance liquid chromatography through bonding or modification.
Ordered mesoporous silicas are generally prepared by a surfactant-directed process under basic, acidic or neutral conditions. The silica precursor is first hydrolyzed and bound to the head group of the surfactant by electrostatic forces or hydrogen bonding interactions to form a liquid-crystalline mesophase. The mesophase transformation then takes place during hydrolysis and condensation of the silica species. The interaction between the surfactant and the silica precursor, as well as the hydrolysis and condensation rates of the silica, are largely dependent on the pH of the reaction system, directly affecting the formation and morphology of the mesophase. For example, in the preparation method of the multilevel mesoporous silica nanoparticle with the patent number of 201310568967.5, a long-chain ionic liquid surfactant is used as a template agent, organic small-molecule amine is used as an alkali source, tetraalkyl silicate is used as a silicon source, and deionized water is used as a water source, so that uniform spherical nanoparticles are obtained, the size can be accurately regulated within the range of 20-200 nm, and the pore size distribution of silica is wide. But it needs to use organic amine as alkali source for shaping and aging, and the obtained material has low strength and can cause environmental pollution.
Under alkaline or acidic conditions, the charged silica precursor and the oppositely charged surfactant form a strong interaction (S) + –I - Or S - –I + ) And is favorable for highly ordered mesoporous structure. Mesoporous Silica Nanospheres (MSNs) with regular pore canals and shapes are easy to synthesize. Weaker hydrogen bonding interactions (S) between the nonionic surfactant and the low charge silica precursor under neutral conditions 0 –I 0 ) Usually resulting in flexibility in the morphology and outer shape of the mesoporous silica. Under neutral conditions, the silica precursor Si (OH) is present 4-x O x- The negatively charged moieties bind to ionic or nonionic surfactants through weak electrostatic forces and hydrogen bonding interactions. Therefore, under neutral conditions, the conventional porous silica is easily controlled in the micron order, and it is difficult to obtain the nano-scale porous silica.
Disclosure of Invention
The invention aims to overcome at least one of the defects of the prior art, and the nano-porous silica material with uniform particle size and controllable size is synthesized by using the ionic liquid containing imidazole groups and multi-weak acid radical ions which can form micelles under a neutral condition. The invention prepares the porous silicon dioxide material by a simple method, and can provide a brand new thought for synthesizing MSNs materials. The purpose of the invention is realized based on the following technical scheme:
in one aspect of the present invention, there is provided a method for preparing porous nano silica spheres under a neutral condition, comprising the steps of:
s1, forming imidazole ionic liquid micelles: dispersing imidazole ionic liquid in water, and stirring to form micelle;
s2, silicon dioxide deposition: adding polybasic weak acid radical ions into the solution obtained in the step S1, adjusting the pH of the solution to be neutral, then adding a silicon dioxide precursor into the solution, and depositing under stirring and heating conditions to form silicon dioxide pellets;
s3, calcining silicon dioxide: and (3) centrifugally collecting the silica spheres obtained in the step (S2), drying, calcining at high temperature, and removing imidazole ionic liquid to obtain porous silica spheres.
Preferably, the imidazole ionic liquid in step S1 has the following structural formula:
wherein R is 1 Is (CH) 2 ) a CH 3 A is 0 to 5; r is 2 Is (CH) 2 ) b CH 3 B is 7 to 18; y is - Is Cl - ，BF 4 - ，H 2 PO 4 - ，NO 3 - ，PF 6 -，TFSI - ，FSI - And N (CN) 2 - One or more combinations thereof.
Preferably, the concentration of the imidazole ionic liquid in the aqueous solution in step S1 is 1 to 500mM.
Preferably, the polybasic weak acid radical in the step S2 is one or more of borate, carbonate, phosphate and sulfite, and the silica precursor is tetraethyl orthosilicate or tetramethyl orthosilicate.
Preferably, the concentration of the polybasic weak acid radical in the step S2 is 2-100mM.
Preferably, the reagent added in the step of adjusting the pH of the solution to neutrality in step S2 is: one or more of boric acid, carbonic acid, phosphoric acid, sulfurous acid, nitrous acid and acetic acid.
Preferably, the silica precursor is added in step S2 in one or more of a one-time addition manner, a slow dropwise addition manner, and a batch-wise equal addition manner.
Preferably, the rotation speed of the stirring in the step S2 is 80-300rpm, the heating temperature is 25-95 ℃, and the deposition time is 10-240min.
Preferably, the calcination in step S3 is carried out at a temperature of 400-1000 ℃ for 2-10h.
In another aspect of the invention, there is provided a porous nanosilica pellet, made according to any of the methods described above.
Preferably, the particle size of the porous nano-silica spheres is 20-5000nm.
Compared with the traditional sol-gel method, the method can achieve at least one of the following beneficial effects:
1. the invention uses the imidazole ionic liquid and the multi-component weak acid radical ion catalytic system, realizes the preparation of the nano-scale porous silicon dioxide by a simple method under the condition of neutral water phase, does not use extra surfactant and catalyst, and has the advantages of green and low consumption. The porous nano silicon dioxide spheres with controllable particle size and adjustable specific surface area are obtained, and have uniform dispersion and high mechanical strength.
2. The method does not need acid and alkali or other organic solvents, has simple post-treatment, is more environment-friendly and has low energy consumption.
3. The invention has simple process, does not need alkali forming aging, and can increase the strength of the material.
Drawings
FIG. 1 is a schematic diagram of self-assembly of 1-dodecyl-3-methylimidazolium chloride micelles;
FIG. 2 is an SEM image of silica microspheres prepared in example 1;
FIG. 3 is a BET curve of the silica microspheres prepared in example 1;
FIG. 4 is an SEM image of silica microspheres prepared in example 2;
FIG. 5 is a BET curve of the silica microspheres prepared in example 2;
FIG. 6 is an SEM image of silica microspheres prepared in example 3;
FIG. 7 is a BET plot of the silica microspheres prepared in example 3.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The following examples are all commercially available from laboratory instruments and reagents.
Example 1
Formation of imidazole ionic liquid micelles: weighing 1.720g of 1-dodecyl-3-methylimidazolium chloride (with the concentration of about 40 mM) and adding the 1-dodecyl-3-methylimidazolium chloride into 150mL of water for stirring, so that the 1-dodecyl-3-methylimidazolium chloride self-assembles to form micelles, and the schematic diagram is shown in figure 1;
0.123g of trisodium phosphate (concentration about 5 mM) is weighed into the above solution, and the pH of the solution is adjusted to 7.0 by adding an appropriate amount of phosphoric acid; 3.3mL of tetraethyl orthosilicate is added into the solution at one time, stirred at 25 ℃ and 150rpm for reaction for 120min, white precipitate is separated out, centrifuged at 8000rpm, and the product is dried in an oven at 80 ℃ and calcined in a muffle furnace at 600 ℃ for 4h to obtain the porous silicon dioxide pellets.
The interaction between imidazole group and phosphate radical can make the silicon dioxide grow on the micelle formed by imidazole ionic liquid, the size of the prepared uniformly dispersed small sphere is about 60nm (figure 2), the BET experiment shows that the pore diameter is about 0.38nm, and the specific surface area is about 378m 2 In terms of/g (FIG. 3).
Example 2
Formation of imidazole ionic liquid micelles: weighing 1.720g of 1-dodecyl-3-methylimidazole chloride salt (the concentration is about 40 mM) and adding the 1-dodecyl-3-methylimidazole chloride salt into 150mL of water for stirring, so that the 1-dodecyl-3-methylimidazole chloride salt is self-assembled into a micelle;
0.246g of trisodium phosphate (concentration about 10 mM) is weighed into the above solution, and the pH of the solution is adjusted to 7.0 by adding a suitable amount of phosphoric acid; 3.3mL of tetraethyl orthosilicate is slowly dripped into the solution, stirred at 60 ℃ and 150rpm for reaction for 120min, white precipitate is separated out, the product is centrifuged at 8000rpm, dried in an oven at 80 ℃ and calcined in a muffle furnace at 600 ℃ for 4h to obtain the porous silicon dioxide pellets.
The interaction between imidazole group and phosphate radical can make silicon dioxide grow on micelle formed by imidazole ionic liquid, the size of the prepared uniformly dispersed small sphere is about 260nm (figure 4), and BET experiment shows that the pore diameter is about 2.23nm, and the specific surface area is about 570m 2 In terms of/g (FIG. 5).
Example 3
Formation of imidazole ionic liquid micelles: weighing 1.720g of 1-dodecyl-3-methylimidazole chloride salt (the concentration is about 40 mM) and adding the 1-dodecyl-3-methylimidazole chloride salt into 150mL of water for stirring, so that the 1-dodecyl-3-methylimidazole chloride salt is self-assembled into a micelle;
0.246g of trisodium phosphate (concentration about 10 mM) is weighed into the above solution, and the pH of the solution is adjusted to 7.0 by adding an appropriate amount of phosphoric acid; 3.3mL of tetraethyl orthosilicate is added into the solution in 2 steps in equal amount (1.1 mL is added in every 2h for 3 times), the solution is stirred and reacted at 95 ℃ and 150rpm for 120min, white precipitate is separated out, the product is centrifuged at 8000rpm, dried in an oven at 80 ℃ and calcined in a muffle furnace at 600 ℃ for 4h to obtain the porous silica spheres.
The interaction between imidazole group and phosphate radical can make the silicon dioxide grow on the micelle formed by imidazole ionic liquid, the size of the prepared uniformly dispersed small sphere is about 550nm (figure 6), the BET experiment shows that the pore diameter is about 1.96nm, and the specific surface area is about 812m 2 In terms of/g (FIG. 7).
Example 4
Formation of imidazole ionic liquid micelles: 0.510g of 1-octyl-3-methylimidazolium hexafluorophosphate (with the concentration of about 10 mM) is weighed and added into 150mL of water to be stirred, so that the mixture is self-assembled to form micelles;
weighing 0.095g of sodium sulfite (with the concentration of about 5 mM) into the solution, and adding a proper amount of sulfurous acid to adjust the pH of the solution to 7.0; adding 3.3mL of tetramethyl orthosilicate into the solution in 3 batches in equal amount, stirring and reacting at 40 ℃ and 300rpm for 20min, separating out white precipitate, centrifuging at 8000rpm, drying the product in an oven at 80 ℃, and calcining in a muffle furnace at 400 ℃ for 10h to obtain the porous silica spheres.
The interaction between imidazole group and sulfite can make silicon dioxide grow on the micelle formed by imidazole ionic liquid, the size of the prepared uniformly dispersed small ball is about 100nm, the BET experiment shows that the pore diameter is about 1.65nm, and the specific surface area is about 730m 2 /g。
Example 5
Formation of imidazole ionic liquid micelles: 1.183g of 1-hexadecyl-3-methylimidazolium tetrafluoroborate (with the concentration of about 20 mM) is weighed and added into 150mL of water to be stirred, so that the micelle is formed by self-assembly;
weighing 1.144g of sodium borate (with the concentration of about 20 mM) into the solution, and adding a proper amount of boric acid to adjust the pH of the solution to 7.0; 3.3mL of tetramethyl orthosilicate is added into the solution at one time, the mixture is stirred at 100rpm for 180min at 80 ℃, white precipitate is separated out, the mixture is centrifuged at 8000rpm, and the product is dried in an oven at 80 ℃ and calcined in a muffle furnace at 1000 ℃ for 2h to obtain the porous silicon dioxide pellets.
The interaction between imidazole group and borate can make silicon dioxide grow on micelle formed by imidazole ionic liquid, the size of the prepared uniformly dispersed small sphere is about 710nm, BET experiment shows that the pore diameter is about 2.02nm, and the specific surface area is about 750m 2 /g。
Example 6
Formation of imidazole ionic liquid micelles: weighing 6.716g of 1-tetradecyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide salt (the concentration is about 80 mM) into 150mL of water, and stirring to enable the 1-tetradecyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide salt to self-assemble into micelles;
0.794g of sodium carbonate (concentration: about 50 mM) was weighed into the above solution, and a suitable amount of hydrochloric acid was added to adjust the pH of the solution to 7.0; 3.3mL of tetraethyl orthosilicate is slowly dripped into the solution, stirred at 70 ℃ and 150rpm for reaction for 120min, white precipitate is separated out, the product is centrifuged at 8000rpm, dried in an oven at 80 ℃ and calcined in a muffle furnace at 500 ℃ for 6h to obtain the porous silicon dioxide pellets.
Interaction between imidazole groups and nitriteThe action can make the silicon dioxide grow on the micelle formed by the imidazole ionic liquid, the size of the prepared uniformly dispersed globule is about 150nm, the BET experiment shows that the pore diameter is about 0.85nm, and the specific surface area is about 580m 2 /g。
Comparative example 1
The procedure of example 1 was repeated except that 1-dodecyl-3-methylimidazolium chloride was replaced with 1-hexyl-3-methylimidazolium chloride. Experiments show that the ionic liquid can not form micelles, the size of the finally obtained silica spheres is about 5nm, the dispersity is poor, the silica spheres are uneven and serious in aggregation, and the silica spheres with regular shapes can not be obtained, so that the formation of the imidazole ionic liquid micelles has great influence on the dispersity and size of the obtained silica spheres.
Comparative example 2
Removing step S1, a step of forming ionic liquid micelles in advance, that is: 1-dodecyl-3-methylimidazolium chloride, trisodium phosphate and tetraethyl orthosilicate were added to 150mL of an aqueous solution and stirred, an appropriate amount of phosphoric acid was added to adjust the pH of the solution to 7.0, and then the solution was heated and stirred to effect deposition, with the experimental parameters being the same as in example 1. The size of the finally obtained silicon dioxide spheres is about 30 mu m, the dispersity is poor, and the nano-scale silicon dioxide spheres cannot be obtained; indicating that the one-pot reaction has a large influence on the size of the resulting silica spheres.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (6)
1. A method for preparing porous nano silicon dioxide pellets under neutral conditions is characterized by comprising the following steps:
s1, forming imidazole ionic liquid micelles: dispersing imidazole ionic liquid in water, and stirring to form micelle;
s2, silicon dioxide deposition: adding polybasic weak acid radical ions into the solution obtained in the step S1, adjusting the pH of the solution to be neutral, then adding a silicon dioxide precursor into the solution, and depositing under stirring and heating conditions to form silicon dioxide pellets;
s3, calcining silicon dioxide: centrifugally collecting the silicon dioxide pellets obtained in the step S2, drying and calcining at high temperature to remove imidazole ionic liquid to obtain porous silicon dioxide pellets;
the structural formula of the imidazole ionic liquid in the step S1 is as follows:
wherein R is 1 Is (CH) 2 ) a CH 3 A is 0 to 5; r 2 Is (CH) 2 ) b CH 3 B is 8 to 18; y is - Is Cl - ，BF 4 - ，H 2 PO 4 - ，NO 3 - ，PF 6 -，TFSI - ，FSI - And N (CN) 2 - One or more combinations of (a);
the concentration of the imidazole ionic liquid in the aqueous solution in the step S1 is 1-500mM;
in the step S2, the multi-component weak acid radical is one or a combination of more of borate, carbonate, phosphate and sulfite, and the silicon dioxide precursor is tetraethyl orthosilicate or tetramethyl orthosilicate;
the concentration of the polybasic weak acid radical in the step S2 is 2-100mM.
2. The method for preparing porous nano silica spheres under neutral conditions as claimed in claim 1, wherein the reagent added in the step of adjusting the pH of the solution to be neutral in the step S2 is: one or more of boric acid, carbonic acid, phosphoric acid, sulfurous acid, nitrous acid and acetic acid.
3. The method for preparing porous nano silica spheres under neutral conditions as claimed in claim 1, wherein the silica precursor is added in step S2 in any combination of one or more of one-time addition, slow dropwise addition and batch-wise addition.
4. The method for preparing porous nano silica spheres under the neutral condition of claim 1, wherein the stirring speed in the step S2 is 80-300rpm, the heating temperature is 20-100 ℃, and the deposition time is 10-240min.
5. The method for preparing porous nano silica spheres under the neutral condition of claim 1, wherein the calcining temperature in the step S3 is 400-1000 ℃ and the calcining time is 2-10h.
6. Porous nanosilica beads, obtainable by a process according to any of claims 1 to 5.
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