CN103830734A - Preparation method and use of silica/metal composite material - Google Patents
Preparation method and use of silica/metal composite material Download PDFInfo
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- CN103830734A CN103830734A CN201310589657.1A CN201310589657A CN103830734A CN 103830734 A CN103830734 A CN 103830734A CN 201310589657 A CN201310589657 A CN 201310589657A CN 103830734 A CN103830734 A CN 103830734A
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Abstract
The invention relates to a preparation method of a silica/metal composite material and belongs to the technical field of polymers for biological medicine. The preparation method comprises the following steps of carrying out catalytic hydrolysis on a silicon-containing compound in an organic template-containing solution under the alkaline condition to obtain porous silica containing the organic template, carrying out pumping filtration on the porous silica containing the organic template, carrying out washing, extraction and drying to obtain porous silica, mixing the porous silica and a metal salt aqueous solution by stirring to obtain a crude product, and heating the crude product in a reduction atmosphere in a tubular furnace to obtain the silica/metal composite material. The preparation method has simple processes and is environmentally friendly.
Description
Technical field
The invention belongs to biological medical polymer material technical field, be specifically related to a kind of for silicon dioxide/metallic composite and its preparation method and application.
Background technology
Silica nano material has high drug loading and controllable release ability as pharmaceutical carrier, having shown huge potential using value aspect the diagnosis of biomedical sector especially cancer and treatment, is expected to become pharmaceutical carrier of new generation.Mesoporous silicon oxide specific surface area by template synthesis is large, Stability Analysis of Structures, and good biocompatibility, can embedding sensitivity reagent, and for controlled transport and the release of medicine or bioactive molecule.In recent years, nanoscale precious metal (gold, platinum, palladium etc.) has obtained research widely as molecular targeted agents directed agents, but nanoparticle surface can be higher, easily reunites, thereby lose original activity and selectivity in preparation process.Therefore, urgent wish to prepare there is bigger serface, nano material that good dispersion keeps high stability simultaneously.Compound noble metal can be realized molecular targeted controllable sustained-release as the directed agents of targeted drug, therefore mesoporous silicon oxide and noble metal is compounded to form to molecular targeted agents study on the carrier significant.
The research of composite before comprises on precious metal material and inorganic carrier co-precipitation, inorganic carrier sputter noble metal etc., these methods can effectively form nano metal particles composite silicon dioxide carrier material, but noble metal nano particles is all generally the outer surface that is wrapped in silicon dioxide, can not well be scattered in mesoporous SiO 2, in medicament slow release process, cause medicine can not well be carried on silica surface, caused noble metal to come off in medicament slow release process simultaneously.
Summary of the invention
The object of the invention is for existing noble metal nano particles synthesis condition harshness, between granule, very easily reunite, functional mesoporous silicon dioxide synthesis technique complexity, solvent for use toxicity is high, and noble metal granule can not well be scattered in the drawbacks such as mesoporous silicon oxide composite inner, a kind of absorption property that ordered mesoporous silica dioxide is good that utilizes is provided, precious metal ion is adsorbed in the middle of silicon dioxide mesoporous, reach original position synthesis nano noble metal granule/ordered mesoporous silicon dioxide composite material and nano level noble metal granule is all scattered in to the preparation method of the functionalized nano mesoporous silicon oxide original position composite Nano metal particulate material in the middle of silicon dioxide mesoporous with ground in conjunction with calcine technology.
A technical scheme of the present invention provides a kind of preparation method of silicon dioxide/metallic composite: by silicon-containing compound catalyzing hydrolysis under the solution neutral and alkali condition that contains organic formwork agent, must contain the porous silica of organic formwork agent; By the porous silica sucking filtration, the washing that contain organic formwork agent, filter cake alcohol extraction, removes after extract to obtain porous silica; Porous silica is reacted with aqueous metal salt mix and blend, and sucking filtration, washing, be then placed in crude product heat treatment under reducing atmosphere and obtain silicon dioxide/metallic composite.
The preparation method that technique scheme provides according to the present invention, comprises following steps:
1) organic formwork agent is dissolved in solvent, adds the aqueous solution of alkali or alkali, rise to 20-95 DEG C of constant temperature and stir; After all dissolving, add silicon-containing compound, keep constant temperature stirring reaction 0.5-30 hour;
2) reactant liquor sucking filtration step 1) being obtained, filter cake solvent wash, filter cake adds ethanol to rise to 20-78 DEG C of constant temperature stirring 0.5-30 hour; Solution sucking filtration, filter cake solvent wash, 20-200 DEG C of dry 1-24 hour;
3) by step 2) product that obtains reacts 0.5-30 hour with an aqueous metal salt 20-95 DEG C mix and blend, reactant liquor sucking filtration, product washing; Then by crude product in tube furnace, under reducing atmosphere, be warming up to 200-1000 DEG C after heat preservation hot process 0.5-24 hour, obtain silicon dioxide/metallic composite.
The preparation method that technique scheme provides according to the present invention, in some embodiments, described silicon-containing compound is organo-silicon compound or inorganic silicon compound.
In other embodiment of the present invention, described organo-silicon compound are selected from ethyl orthosilicate, methyl silicate, 3-mercaptopropyl trimethoxysilane or 3-aminopropyl trimethoxysilane, and inorganic silicon compound is selected from alkali silicate or hydrated alkali metal silicate.
In other embodiment of the present invention, described alkali silicate is selected from Lithium metasilicate, sodium silicate, potassium silicate, rubidium silicate or cesium silicate.
In other embodiment of the present invention, described hydrated alkali metal silicate is selected from silicate hydrate lithium, hydrated sodium silicate, silicate hydrate potassium, silicate hydrate rubidium or silicate hydrate caesium.
The preparation method that technique scheme provides according to the present invention, in some embodiments, described organic formwork agent is organic cation surfactant, organic anion surfactant or organic non-ionic surface active agent, or the combination of organic cation surfactant and organic non-ionic surface active agent, or the combination of organic anion surfactant and organic non-ionic surface active agent.
In other embodiment of the present invention, described organic cation surfactant is selected from alkylamine salt, alkyl quaternary ammonium salts or heterocyclic cationic surfactant; Organic anion surfactant is selected from alkyl carboxylic acid salt, alkyl sulfonates, alkylsurfuric acid salt or alkyl phosphate salt analog anion surfactants; Organic non-ionic surface active agent is polyoxyethylene-type or polyhydric alcohol type.
In other embodiment of the present invention, described organic cation surfactant is selected from Dodecyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, Cetyltrimethylammonium bromide, Dodecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride or octadecyl trimethyl ammonium chloride; Organic anion surfactant is dodecyl sodium sulfate or sodium lauryl sulphate; Organic non-ionic surface active agent is Polyethylene Glycol.
In other embodiment of the present invention, described organic non-ionic surface active agent is selected from PEG-200, PEG-400, PEG-600, PEG-800, PEG-1000, PEG-1500, PEG-2000, PEG-4000, PEG-6000, PEG-8000, PEG-10000 or PEG-20000.
The preparation method that technique scheme provides according to the present invention, in some embodiments, described solvent is selected from water, methanol, ethanol, ethylene glycol, normal propyl alcohol, isopropyl alcohol, propylene glycol, n-butyl alcohol, sec-butyl alcohol, isobutanol, the tert-butyl alcohol or butanediol.
The preparation method that technique scheme provides according to the present invention, in some embodiments, described alkali is inorganic base.
In other embodiment of the present invention, described inorganic base is selected from ammonia, ammonium carbonate, ammonium bicarbonate, lithium carbonate, lithium acetate, Lithium hydrate, sodium bicarbonate, sodium carbonate, sodium acetate, sodium hydroxide, potassium bicarbonate, potassium carbonate, potassium acetate or potassium hydroxide.
The preparation method that technique scheme provides according to the present invention, in some embodiments, step 1) speed of agitator is 100-6000 rev/min.
In other embodiment of the present invention, step 1) speed of agitator is 100-2000 rev/min, and the response time is 1-20 hour.
The preparation method that technique scheme provides according to the present invention, in some embodiments, step 2) in filter cake add ethanol to rise to 40-78 DEG C of constant temperature to stir 1-24 hour; 50-150 after solvent wash DEG C of dry 1-24 hour for filter cake.
The preparation method that technique scheme provides according to the present invention, in some embodiments, described slaine is hydrochlorate, nitrate or the sulfate of gold, silver, platinum, cobalt, copper, ferrum, nickel or zinc.
In other embodiment of the present invention, described slaine is auric chloride, platinum chloride, gold chloride, chloroplatinic acid, platinum nitrate or silver nitrate.
The preparation method that technique scheme provides according to the present invention, in some embodiments, step 3) is by step 2) product that obtains reacts 0.5-12 hour with an aqueous metal salt 20-50 DEG C mix and blend.
The preparation method that technique scheme provides according to the present invention, in some embodiments, in step 3) reducing atmosphere gases used be hydrogen and the mixing of noble gas.
In other embodiment of the present invention, described noble gas is selected from nitrogen, argon or helium.
In other embodiment of the present invention, in reducing atmosphere, the shared volume ratio of hydrogen is 5%-40%.
The preparation method that technique scheme provides according to the present invention, in some embodiments, after step 3) is warming up to 200-1000 DEG C with the heating rate of 1-10 DEG C/min, heat preservation hot is processed 0.5-24 hour.
Another technical scheme of the present invention provides silicon dioxide/metallic composite prepared by a kind of method that technique scheme provides according to the present invention for preparing the application of target medicine carrier.
Unless clearly state in contrast, otherwise all scopes that the present invention quotes comprised end value.The scope that represents the shared volume ratio a of hydrogen as " the shared volume ratio of hydrogen is 5%-40% " is 5%≤a≤40%.
The term "or" that the present invention uses represents alternative, if suitable, they can be combined, and that is to say, term "or" comprises each listed independent alternative and their combination.For example, " noble gas is selected from nitrogen, argon or helium " represents that described noble gas can be the one in bisphenol-A, bisphenol AF or 1-methyl pyrocatechol, can be also its more than one combination.
The term " washing " that the present invention uses refers in particular to and washs with reaction dissolvent, as in the time that the solvent of organic formwork agent is methanol, by the porous silica sucking filtration that contains organic formwork agent and use methanol wash.
The present invention compared with prior art, has following beneficial effect:
1, one-step synthesis has been prepared functionalized nano ordered mesoporous silicon-dioxide material, does not need secondary load functional group, has simplified technique, does not need to use poisonous and harmful solvent, environmental friendliness;
2, utilize functional mesoporous earth silicon material GOLD FROM PLATING SOLUTION to be belonged to the absorption property of ion, can by metal with the form of complex be adsorbed onto its inner mesoporous in the middle of, obtain composite material precursor; Then utilize high-temperature calcination, inner metal is changed into and is dispersed in mesoporous central metal simple-substance by chemical combination state.
Brief description of the drawings
Fig. 1 is that the embodiment of the present invention 1 makes silica/platinum composite transmission electron microscope photo.
Fig. 2 is that the embodiment of the present invention 3 makes silicon dioxide/metal/composite material stereoscan photograph.
Detailed description of the invention
The following stated be the preferred embodiment of the present invention, what the present invention protected is not limited to following preferred implementation.It should be pointed out that on the basis of conceiving in these innovation and creation for a person skilled in the art, some distortion and the improvement made, all belong to protection scope of the present invention.
Embodiment 1
Under room temperature, 0.50g cetyl trimethyl ammonium bromide is dissolved in 200mL water, stirs, after fully dissolving, add 2mL2mol/L sodium hydrate aqueous solution, 80 DEG C of constant temperature stir.Add 2.0g ethyl orthosilicate and 0.5g3-mercaptopropyl trimethoxysilane to join in reactant liquor, with the rotating speed stirring reactions of 800 revs/min 1 hour, sucking filtration, distilled water cleans filtering residue.Crude product is placed in to 60 DEG C of 100mL ethanol and stirs 12 hours, sucking filtration, washing with alcohol filtering residue, 80 DEG C of dry 15h obtain white porous silica powder.
Get 0.1g porous silica powder powder and join in 50mL50mmol/L platinum nitrate solution, 40 DEG C are stirred sucking filtration after 1 hour, distilled water wash.Crude product is placed in to temperature programming tube furnace, in the nitrogen atmosphere that contains 20% hydrogen, is warming up to 800 DEG C with the heating rate of 2 DEG C/min, be incubated 8 hours, obtain ordered mesoporous silica dioxide/platinum composite.Its transmission electron microscope photo is shown in Fig. 1.
Embodiment 2
Under room temperature, 0.50g Cetyltrimethylammonium bromide is dissolved in 200mL water, stirs, after fully dissolving, add 2mL2mol/L ammonia aqueous solution, 70 DEG C of constant temperature stir.Add 2.0g ethyl orthosilicate and 0.5g3-aminopropyl trimethoxysilane to join in reactant liquor, with the rotating speed stirring reactions of 1100 revs/min 2 hours, sucking filtration, distilled water cleans filtering residue.Crude product is placed in to 65 DEG C of 100mL ethanol and stirs 8 hours, sucking filtration, washing with alcohol filtering residue, 80 DEG C of dry 10h obtain white porous silica powder.
Get 0.1g porous silica powder powder and join in 50mL50mmol/L platinum acid chloride solution, 20 DEG C are stirred sucking filtration after 0.5 hour, distilled water wash.Crude product is placed in to temperature programming tube furnace, in the nitrogen atmosphere that contains 30% hydrogen, is warming up to 1000 DEG C with the heating rate of 5 DEG C/min, be incubated 3 hours, obtain ordered mesoporous silica dioxide/platinum composite.
Embodiment 3
Under room temperature, 2g Dodecyl trimethyl ammonium chloride is dissolved in 200mL water, stirs, after fully dissolving, add 2mL2mol/L potassium hydroxide aqueous solution, 40 DEG C of constant temperature stir.Add 5.0g ethyl orthosilicate and 0.5g3-mercaptopropyl trimethoxysilane to join in reactant liquor, with the rotating speed stirring reactions of 900 revs/min 1.5 hours, sucking filtration, distilled water cleans filtering residue.Crude product is placed in to 70 DEG C of 100mL ethanol and stirs 20 hours, sucking filtration, washing with alcohol filtering residue, 150 DEG C of dry 1h obtain white porous silica powder.
Get 0.1g porous silica powder powder and join in 50mL50mmol/L chlorauric acid solution, 30 DEG C are stirred sucking filtration after 2 hours, distilled water wash.Crude product is placed in to temperature programming tube furnace, in the argon gas atmosphere that contains 40% hydrogen, is warming up to 700 DEG C with the heating rate of 10 DEG C/min, be incubated 5 hours, obtain ordered mesoporous silica dioxide/metal/composite material.Its stereoscan photograph is shown in Fig. 2.
Embodiment 4
Under room temperature, 2g hexadecyltrimethylammonium chloride is dissolved in 200mL water, stirs, after fully dissolving, add 2mL2mol/L aqueous sodium carbonate, 50 DEG C of constant temperature stir.Add 5.0g ethyl orthosilicate and 0.5g3-aminopropyl trimethoxysilane to join in reactant liquor, with the rotating speed stirring reactions of 1200 revs/min 0.5 hour, sucking filtration, distilled water cleans filtering residue.Crude product is placed in to 78 DEG C of 100mL ethanol and stirs 0.5 hour, sucking filtration, washing with alcohol filtering residue, 20 DEG C of dry 24h obtain white porous silica powder.
Get 0.1g porous silica powder powder and join in 50mL50mmol/L platinum chloride solution, 25 DEG C are stirred sucking filtration after 4 hours, distilled water wash.Crude product is placed in to temperature programming tube furnace, in the helium atmosphere that contains 10% hydrogen, is warming up to 600 DEG C with the heating rate of 3 DEG C/min, be incubated 4 hours, obtain ordered mesoporous silica dioxide/platinum composite.
Embodiment 5
Under room temperature, 0.7g octadecyl trimethyl ammonium chloride and 0.3g PEG-1000 are dissolved in 200mL water, stir, after fully dissolving, add 2mL2mol/L potassium acetate aqueous solution, 60 DEG C of constant temperature stir.Add 5.0g ethyl orthosilicate and 0.5g3-mercaptopropyl trimethoxysilane to join in reactant liquor, with the rotating speed stirring reactions of 1000 revs/min 4 hours, sucking filtration, distilled water cleans filtering residue.Crude product is placed in to 40 DEG C of 100mL ethanol and stirs 30 hours, sucking filtration, washing with alcohol filtering residue, 80 DEG C dry obtains white porous silica powder.
Get 0.1g porous silica powder powder and join in 50mL50mmol/L platinum nitrate solution, 20 DEG C are stirred sucking filtration after 10 hours, distilled water wash.Crude product is placed in to temperature programming tube furnace, in the argon gas atmosphere that contains 10% hydrogen, is warming up to 500 DEG C with the heating rate of 8 DEG C/min, be incubated 7 hours, obtain ordered mesoporous silica dioxide/platinum composite.
Embodiment 6
Under room temperature, 0.6g Dodecyl trimethyl ammonium chloride and 0.5g PEG-6000 are dissolved in 200mL water, stir, after fully dissolving, add 2mL2mol/L sodium bicarbonate aqueous solution, 80 DEG C of constant temperature stir.Add 5.0g ethyl orthosilicate and 0.5g3-aminopropyl trimethoxysilane to join in reactant liquor, with the rotating speed stirring reactions of 300 revs/min 10 hours, sucking filtration, distilled water cleans filtering residue.Crude product is placed in to 65 DEG C of 100mL ethanol and stirs 30 hours, sucking filtration, washing with alcohol filtering residue, 80 DEG C dry obtains white porous silica powder.
Get 0.1g porous silica powder powder and join in 50mL50mmol/L chlorogold solution, 50 DEG C are stirred sucking filtration after 2 hours, distilled water wash.Crude product is placed in to temperature programming tube furnace, in the argon gas atmosphere that contains 5% hydrogen, is warming up to 400 DEG C with the heating rate of 6 DEG C/min, be incubated 2 hours, obtain ordered mesoporous silica dioxide/metal/composite material.
Embodiment 7
Under room temperature, 1g hexadecyltrimethylammonium chloride is dissolved in 200mL water, stirs, after fully dissolving, add 2mL2mol/L ammonium carbonate solution, 20 DEG C of constant temperature stir.Add 5.0g ethyl orthosilicate and 0.5g3-aminopropyl trimethoxysilane to join in reactant liquor, with the rotating speed stirring reactions of 500 revs/min 3 hours, sucking filtration, distilled water cleans filtering residue.Crude product is placed in to 20 DEG C of 100mL ethanol and stirs 24 hours, sucking filtration, washing with alcohol filtering residue, 80 DEG C dry obtains white porous silica powder.
Get 0.1g porous silica powder powder and join in 50mL50mmol/L chlorogold solution, 60 DEG C are stirred sucking filtration after 1 hour, distilled water wash.Crude product is placed in to temperature programming tube furnace, in the argon gas atmosphere that contains 10% hydrogen, is warming up to 550 DEG C with the heating rate of 4 DEG C/min, be incubated 6 hours, obtain ordered mesoporous silica dioxide/metal/composite material.
Embodiment 8
Under room temperature, 1g hexadecyltrimethylammonium chloride is dissolved in 200mL water, stirs, after fully dissolving, add 2mL2mol/L sodium hydrate aqueous solution, 95 DEG C of constant temperature stir.Add 5.0g ethyl orthosilicate and 0.5g3-aminopropyl trimethoxysilane to join in reactant liquor, with the rotating speed stirring reactions of 400 revs/min 20 hours, sucking filtration, distilled water cleans filtering residue.Crude product is placed in to 65 DEG C of 100mL ethanol and stirs 30 hours, sucking filtration, washing with alcohol filtering residue, 80 DEG C dry obtains white porous silica powder.
Get 0.1g porous silica powder powder and join in 50mL50mmol/L chlorogold solution, 75 DEG C are stirred sucking filtration after 15 hours, distilled water wash.Crude product is placed in to temperature programming tube furnace, in the nitrogen atmosphere that contains 5% hydrogen, is warming up to 300 DEG C with the heating rate of 1 DEG C/min, be incubated 24 hours, obtain ordered mesoporous silica dioxide/metal/composite material.
Embodiment 1-8 has effectively solved that functional mesoporous silicon dioxide synthesis technique complexity, synthetic are toxic, nanoscale precious metal granule is difficult to obtain and nano-noble metal granule is difficult to the problem of disperseing, and has obtained that pattern is controlled, functional group is controlled, synthesis technique is simple, eco-friendly functional mesoporous earth silicon material.
Claims (24)
1. a preparation method for silicon dioxide/metallic composite, is characterized in that: by silicon-containing compound catalyzing hydrolysis under the solution neutral and alkali condition that contains organic formwork agent, must contain the porous silica of organic formwork agent; By the porous silica sucking filtration, the washing that contain organic formwork agent, filter cake alcohol extraction, removes after extract to obtain porous silica; Porous silica is reacted with aqueous metal salt mix and blend, and sucking filtration, washing, be then placed in crude product heat treatment under reducing atmosphere and obtain silicon dioxide/metallic composite.
2. preparation method according to claim 1, is characterized in that comprising following steps:
1) organic formwork agent is dissolved in solvent, adds the aqueous solution of alkali or alkali, rise to 20-95 DEG C of constant temperature and stir; After all dissolving, add silicon-containing compound, keep constant temperature stirring reaction 0.5-30 hour;
2) reactant liquor sucking filtration step 1) being obtained, filter cake solvent wash, filter cake adds ethanol to rise to 20-78 DEG C of constant temperature stirring 0.5-30 hour; Solution sucking filtration, filter cake solvent wash, 20-200 DEG C of dry 1-24 hour;
3) by step 2) product that obtains reacts 0.5-30 hour with an aqueous metal salt 20-95 DEG C mix and blend, reactant liquor sucking filtration, product washing; Then by crude product in tube furnace, under reducing atmosphere, be warming up to 200-1000 DEG C after heat preservation hot process 0.5-24 hour, obtain silicon dioxide/metallic composite.
3. preparation method according to claim 1 and 2, is characterized in that, described silicon-containing compound is organo-silicon compound or inorganic silicon compound.
4. preparation method according to claim 3, it is characterized in that, described organo-silicon compound are selected from ethyl orthosilicate, methyl silicate, 3-mercaptopropyl trimethoxysilane or 3-aminopropyl trimethoxysilane, and inorganic silicon compound is selected from alkali silicate or hydrated alkali metal silicate.
5. preparation method according to claim 4, is characterized in that, described alkali silicate is selected from Lithium metasilicate, sodium silicate, potassium silicate, rubidium silicate or cesium silicate.
6. preparation method according to claim 4, is characterized in that, described hydrated alkali metal silicate is selected from silicate hydrate lithium, hydrated sodium silicate, silicate hydrate potassium, silicate hydrate rubidium or silicate hydrate caesium.
7. preparation method according to claim 1 and 2, it is characterized in that, described organic formwork agent is organic cation surfactant, organic anion surfactant or organic non-ionic surface active agent, or the combination of organic cation surfactant and organic non-ionic surface active agent, or the combination of organic anion surfactant and organic non-ionic surface active agent.
8. preparation method according to claim 7, is characterized in that, described organic cation surfactant is selected from alkylamine salt, alkyl quaternary ammonium salts or heterocyclic cationic surfactant; Organic anion surfactant is selected from alkyl carboxylic acid salt, alkyl sulfonates, alkylsurfuric acid salt or alkyl phosphate salt analog anion surfactants; Organic non-ionic surface active agent is polyoxyethylene-type or polyhydric alcohol type.
9. preparation method according to claim 8, it is characterized in that, described organic cation surfactant is selected from Dodecyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, Cetyltrimethylammonium bromide, Dodecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride or octadecyl trimethyl ammonium chloride; Organic anion surfactant is dodecyl sodium sulfate or sodium lauryl sulphate; Organic non-ionic surface active agent is Polyethylene Glycol.
10. preparation method according to claim 9, it is characterized in that, described organic non-ionic surface active agent is selected from PEG-200, PEG-400, PEG-600, PEG-800, PEG-1000, PEG-1500, PEG-2000, PEG-4000, PEG-6000, PEG-8000, PEG-10000 or PEG-20000.
11. preparation methoies according to claim 2, is characterized in that, described solvent is selected from water, methanol, ethanol, ethylene glycol, normal propyl alcohol, isopropyl alcohol, propylene glycol, n-butyl alcohol, sec-butyl alcohol, isobutanol, the tert-butyl alcohol or butanediol.
12. preparation methoies according to claim 2, is characterized in that, described alkali is inorganic base.
13. preparation methoies according to claim 12, it is characterized in that, described inorganic base is selected from ammonia, ammonium carbonate, ammonium bicarbonate, lithium carbonate, lithium acetate, Lithium hydrate, sodium bicarbonate, sodium carbonate, sodium acetate, sodium hydroxide, potassium bicarbonate, potassium carbonate, potassium acetate or potassium hydroxide.
14. preparation methoies according to claim 2, is characterized in that, step 1) speed of agitator is 100-6000 rev/min.
15. preparation methoies according to claim 2, is characterized in that, step 1) speed of agitator is 100-2000 rev/min, and the response time is 1-20 hour.
16. preparation methoies according to claim 2, is characterized in that step 2) in filter cake add ethanol to rise to 40-78 DEG C of constant temperature to stir 1-24 hour; 50-150 after solvent wash DEG C of dry 1-24 hour for filter cake.
17. preparation methoies according to claim 1 and 2, is characterized in that, described slaine is hydrochlorate, nitrate or the sulfate of gold, silver, platinum, cobalt, copper, ferrum, nickel or zinc.
18. preparation methoies according to claim 17, is characterized in that, described slaine is auric chloride, platinum chloride, gold chloride, chloroplatinic acid, platinum nitrate or silver nitrate.
19. preparation methoies according to claim 2, is characterized in that, step 3) is by step 2) product that obtains reacts 0.5-12 hour with an aqueous metal salt 20-50 DEG C mix and blend.
20. preparation methoies according to claim 2, is characterized in that, in step 3) reducing atmosphere gases used be hydrogen and the mixing of noble gas.
21. preparation methoies according to claim 20, is characterized in that, described noble gas is selected from nitrogen, argon or helium.
22. preparation methoies according to claim 20, is characterized in that, in reducing atmosphere, the shared volume ratio of hydrogen is 5%-40%.
23. preparation methoies according to claim 2, is characterized in that, after step 3) is warming up to 200-1000 DEG C with the heating rate of 1-10 DEG C/min, heat preservation hot is processed 0.5-24 hour.
24. silicon dioxide/metallic composites of preparing according to the method described in claim 1-23 any one are for preparing the application of target medicine carrier.
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| CN108935516A (en) * | 2018-08-20 | 2018-12-07 | 黄河科技学院 | A kind of preparation method of heat-resistant composite antibacterial functional material |
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| CN112956603B (en) * | 2021-04-01 | 2021-10-12 | 联科华技术有限公司 | Monoatomic zinc additive capable of replacing feeding nano zinc oxide and preparation method thereof |
| CN114029051A (en) * | 2021-12-23 | 2022-02-11 | 浙江微通催化新材料有限公司 | Platinum dioxide catalyst and preparation method thereof |
| CN114433075A (en) * | 2021-12-29 | 2022-05-06 | 广东省科学院化工研究所 | Platinum catalyst and preparation method and application thereof |
| CN117159743A (en) * | 2023-08-07 | 2023-12-05 | 金三江(肇庆)硅材料股份有限公司 | Lubricating and drug-carrying difunctional silicon dioxide microsphere as well as preparation method and application thereof |
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