CN113620303B - Method for preparing porous nano silicon dioxide pellets under neutral condition - Google Patents
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- CN113620303B CN113620303B CN202110966197.4A CN202110966197A CN113620303B CN 113620303 B CN113620303 B CN 113620303B CN 202110966197 A CN202110966197 A CN 202110966197A CN 113620303 B CN113620303 B CN 113620303B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000007935 neutral effect Effects 0.000 title claims abstract description 20
- 239000008188 pellet Substances 0.000 title claims abstract description 13
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 61
- 239000002608 ionic liquid Substances 0.000 claims abstract description 30
- 239000000693 micelle Substances 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 230000008021 deposition Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 229910021426 porous silicon Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 150000005837 radical ions Chemical class 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000008346 aqueous phase Substances 0.000 abstract 1
- 230000003993 interaction Effects 0.000 description 11
- 239000011148 porous material Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 7
- 125000002883 imidazolyl group Chemical group 0.000 description 7
- WREWAMXVXPPKQU-UHFFFAOYSA-N 1-dodecyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[NH+]1CN(C)C=C1 WREWAMXVXPPKQU-UHFFFAOYSA-N 0.000 description 6
- OPXNHKQUEXEWAM-UHFFFAOYSA-M 1-dodecyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCN1C=C[N+](C)=C1 OPXNHKQUEXEWAM-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- -1 small-molecule amine Chemical class 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000001488 sodium phosphate Substances 0.000 description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 4
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 4
- 235000019801 trisodium phosphate Nutrition 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- AEZLAQZYZLLTIV-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-methyl-3-tetradecylimidazol-1-ium Chemical class FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.CCCCCCCCCCCCCCN1C=C[N+](C)=C1 AEZLAQZYZLLTIV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- NKRASMXHSQKLHA-UHFFFAOYSA-M 1-hexyl-3-methylimidazolium chloride Chemical group [Cl-].CCCCCCN1C=C[N+](C)=C1 NKRASMXHSQKLHA-UHFFFAOYSA-M 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013267 controlled drug release Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
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- B82Y40/00—Manufacture or treatment of nanostructures
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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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