CN101011668A - Ordered organic-inorganic hybrid mesoporous silica, loaded nanogold material thereof and preparation methods thereof - Google Patents
Ordered organic-inorganic hybrid mesoporous silica, loaded nanogold material thereof and preparation methods thereof Download PDFInfo
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- CN101011668A CN101011668A CN 200710034454 CN200710034454A CN101011668A CN 101011668 A CN101011668 A CN 101011668A CN 200710034454 CN200710034454 CN 200710034454 CN 200710034454 A CN200710034454 A CN 200710034454A CN 101011668 A CN101011668 A CN 101011668A
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- organic
- thioether
- inorganic hybrid
- mesoporous silica
- ion liquid
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000010931 gold Substances 0.000 claims abstract description 56
- 150000003568 thioethers Chemical class 0.000 claims abstract description 53
- 229910052737 gold Inorganic materials 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 37
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 21
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 glyoxaline ion Chemical class 0.000 claims description 87
- 239000007788 liquid Substances 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229920001296 polysiloxane Polymers 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052740 iodine Inorganic materials 0.000 claims description 12
- 239000011630 iodine Substances 0.000 claims description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000944 Soxhlet extraction Methods 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- ZWRUINPWMLAQRD-UHFFFAOYSA-N n-Nonyl alcohol Natural products CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 125000000962 organic group Chemical group 0.000 abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 239000002608 ionic liquid Substances 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 239000013335 mesoporous material Substances 0.000 description 22
- 229910004298 SiO 2 Inorganic materials 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000002390 rotary evaporation Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 7
- 238000000605 extraction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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Abstract
The invention discloses ordered organic-inorganic hybrid mesoporous silicon dioxide, a loaded nano-gold material thereof and a preparation method thereof. In the presence of a neutral long-chain template agent, tetraethoxysilane is mixed with an imidazole ionic liquid organic functional siloxane precursor containing thioether, and the organic-inorganic hybrid mesoporous silica material containing thioether ionic liquid is synthesized at a certain temperature in one step. Then, hydroxyl groups rich on the surfaces of the pore channels are utilized to directly reduce chloroauric acid (HAuCl)4) And the thioether organic functional group of the organic group is used for stabilizing the reduced gold particles. The preparation process is simple, no reducing agent is needed, and the environment protection is facilitated. The prepared nano gold particles have the characteristics of small average particle size, uniform distribution and the like, and show good characteristics before catalytic applicationAnd (5) landscape.
Description
Technical field:
The present invention relates to a kind of orderly organic-inorganic hybrid mesoporous silica material and supported nano-gold particulate material and their preparation method.Specifically, relate to a kind of bridged bond type organic functional presoma that is embedded with the glyoxaline ion liquid that contains thioether at organic-inorganic hybrid mesoporous silica material hole wall and preparation method thereof, relate to a kind of nano Au particle and preparation method thereof that in this organic-inorganic hybrid mesoporous silica material duct, prepares.
Background technology:
Mesoporous SiO
2The supported nano-gold particulate material is owing to can satisfy the desired special construction character of many catalytic reactions, and therefore research in recent years increases day by day.But because SiO
2The isoelectric point lower (IEP ≈ 2) on surface is if adopt methods such as conventional deposition-precipitation method and coprecipitation to be difficult to prepare little, the finely dispersed nano Au particle of particle diameter.The preparation method who is carried on nano catalyst among the mesoporous SiO2 at present mainly contains: 1, immobilized method (J.Catal.1999,181:37-48), promptly, make it to strengthen, (generally use NaBH by additional reducing agent again with the effect of SiO2 carrier surface by containing the organic coordination compound of gold ion
4) or temperature-programmed calcination prepare the load type nano gold particle catalyst.Its process complexity requires harshness to reaction condition, and the cationic golden presoma that adopts costs an arm and a leg.2, SiO
2The carrier surface modification (Micropor.Mesopor.Mater.2003,58:201-211), by organic functional (usually uses-SH and-NH
2The function group) to the carrier surface modification, prepares nano Au particle through electronation then.This preparation process is simple, but because the skewness of organic functions group in carrier makes the size of gold particle and the distribution in the duct be difficult to control.These two kinds of methods are owing to above-mentioned reason will be hindered the application of mesoporous material in catalysis.Recently Shanghai Silicate Inst., Chinese Academy of Sciences reported a kind of in ordered mesoporous material the method (J.Solid.State.Chem.2006 of supported nano-gold, what 179:1049-1055), this method was used is that cationic gold complex is by high-temperature roasting reduction preparation nano Au particle.
Summary of the invention:
One of purpose of the present invention provides that a kind of to have an aperture big, and organic group is evenly distributed, and the surface has enriches the orderly organic-inorganic hybrid mesoporous silica material of hydroxyl.
Two of the object of the invention still has big hole body volume and the orderly organic-inorganic hybrid mesoporous silica loaded with nano gold copper-base alloy in aperture after providing a kind of supported nano-gold.
Three of purpose of the present invention provides a kind of simple, practical orderly organic-inorganic hybrid mesoporous silica preparation methods.
Four of purpose of the present invention provides the simple orderly organic-inorganic hybrid mesoporous silica supported nano-gold preparation methods of a kind of gold ion reduction reaction process.
The objective of the invention is to realize by following manner:
A kind of orderly organic-inorganic hybrid mesoporous silica material, the mesoporous silicon oxide hole wall is embedded with the glyoxaline ion liquid that contains thioether.
A kind of orderly organic-inorganic hybrid mesoporous silica loaded with nano gold copper-base alloy, be embedded with contain thioether the glyoxaline ion liquid mesoporous silicon oxide as carrier, nanometer Au is distributed in this mesoporous silicon oxide duct.
The particle diameter of nano Au particle is 1.2-3nm in the duct.
The present invention also provides a kind of orderly organic-inorganic hybrid mesoporous silica preparation methods: (1) is dissolved in surfactant in the deionized water, adjust pH 1.5-3.5, add the glyoxaline ion liquid organic functional polysiloxane precursor body that contains thioether then, under strong agitation, ethyl orthosilicate is added in the above-mentioned solution, stirred 20-24 hour, system is warmed up to 70-90 ℃, still aging 24-48 hour; (2) product after filtration, water washing is to there not being Cl
-, vacuum drying is removed surfactant with the absolute ethyl alcohol soxhlet extraction, promptly gets the organic-inorganic hybrid mesoporous silica material of the glyoxaline ion liquid that contains thioether in order.
The described glyoxaline ion liquid organic functional polysiloxane precursor body that contains thioether synthesizes: under the stirring at room mercaptoalkyl alcohol is dissolved in the absolute ethyl alcohol, adds iodine behind the mixing, stirred 20-24 hour; Evaporation desolventizes the back and adds t-butyl methyl ether, extracts iodine with solution of sodium bisulfite then, and evaporation desolventizes; In residue, add thionyl chloride again, stirring at room, evaporation removes volatile materials; Add 3-ethoxy silane propyl group-4 at last in residue, the two hydrogen imidazoles of 5-are at N
2Add hot reflux under the protection, vacuum is removed the glyoxaline ion liquid organic functional polysiloxane precursor body that volatile matter obtains containing thioether.
Described mercaptoalkyl alcohol is 9-sulfydryl-1 nonyl alcohol, 6-sulfydryl-1-propyl alcohol or 3-sulfydryl-1-propyl alcohol.
Orderly organic-inorganic hybrid mesoporous silica supported nano-gold preparation methods of the present invention is: adjust pH reaches 7.0-8.0 in chlorauric acid solution, dropwise add again in the organic-inorganic hybrid mesoporous silica material of the orderly glyoxaline ion liquid that contains thioether, stir, product after filtration, washing, drying, promptly.
Orderly organic-inorganic hybrid mesoporous silica loaded with nano gold copper-base alloy of the present invention, owing to contain the glyoxaline ion liquid organic functions group of thioether on the mesoporous silicon oxide hole wall, the nm of gold that can make has the advantages that particle diameter is little and be evenly distributed, and the nm of gold particle diameter generally can reach 1.5-2.4nm.And the prepared in reaction of required orderly organic-inorganic hybrid mesoporous silica loaded with nano gold copper-base alloy is simple.
Preparation method's concrete steps of the present invention are as follows:
1, under the stirring at room mercaptoalkyl alcohol of different chain length (HO-R-SH, R is for preferably containing the straight chained alkyl of 3-9 carbon) is dissolved in the absolute ethyl alcohol, adds iodine behind the mixing, stirred 20-24 hour.Rotary evaporation adds t-butyl methyl ether after removing solvent, uses solution of sodium bisulfite (10mg/mL) extraction unreacted iodine completely then, and rotary evaporation desolventizes.Add thionyl chloride again in residue, stir under the room temperature, rotary evaporation removes volatile materials.At last, add 3-ethoxy silane propyl group-4 in residue, the two hydrogen imidazoles of 5-are at N
2Add hot reflux 20-30 hour under the protection, vacuum is removed volatile matter and is got viscous liquid.
2, will gather oxireme ether-poly-propylene oxide ether-poly-oxireme ether triblock polymer surfactant (P123) is to be dissolved in the deionized water under 35 ℃ in temperature, add hydrochloric acid the pH value of solution value is transferred to 1.5-3.5, adding the above-mentioned the 1st then goes on foot in the viscous liquid that is synthesized, continue to stir 5 minutes, under strong agitation, ethyl orthosilicate (TEOS) is joined in the above-mentioned solution, stirred 20-24 hour, and be warmed up to 70-90 ℃, still aging 20-48 hour.
3, product after filtration, water washing is to there not being Cl
-, vacuum drying 12-24 hour, removed template agent (P123) in 48 hours with the absolute ethyl alcohol soxhlet extraction, obtain a kind of ion liquid orderly organic-inorganic hybrid mesoporous silica material that contains thioether; The molar content that contains the glyoxaline ion liquid of thioether in the gained earth silicon material is 2-10%.
4, at gold chloride (HAuCl
4) add sodium hydroxide solution in the solution, regulate pH=7.0-8.0, dropwise join again in the above-mentioned prepared Metaporous silicon dioxide material of the 3rd step, stirred 20-30 hour, product after filtration, water washing is to there not being Cl
-, at room temperature vacuum drying 12-24 hour, obtain the nano Au particle of orderly organic-inorganic hybrid mesoporous silica material duct internal burden type.
Preparation method of the present invention has following advantage compared with prior art:
1, it is big that He Cheng ordered mesoporous material has the aperture, and organic group is evenly distributed, and the surface has features such as the hydroxyl of enriching.
2, He Cheng ordered mesoporous material contains glyoxaline ion liquid and two kinds of function organic groups of thioether.The function organic group makes still have bigger pore volume and aperture behind the supported nano-gold in the mesoporous material hole wall.
3, gold ion reduction reaction process is simple, does not need additional reducing agent, helps environmental protection.
4, can prepare the nano Au particle that particle diameter is littler and be more evenly distributed in conjunction with ordered mesoporous material as the abundant hydroxyl in carrier and surface.
Mesoporous silicon oxide hole wall of the present invention is embedded with the glyoxaline ion liquid ((EtO) that contains thioether
3Si (CH
2)
3-C
3H
5N
2 +Cl
--R-S-S-R-C
3H
5N
2 +Cl
--(CH
2)
3Si (OEt)
3, R preferably contains the straight chained alkyl of 3-9 carbon), (the glyoxaline ion liquid organic functional polysiloxane precursor body that promptly contains thioether) do not see bibliographical information as yet,
Thioether functional group can be used for fixedly nano Au particle in this material of the present invention; In addition, this glyoxaline ion liquid that contains thioether is embedded in the orderly organic-inorganic hybrid mesoporous silica material, abundant surface hydroxyl is contained in its duct, gold ion can be reduced into gold particle, for organic-inorganic hybrid mesoporous silica material load nano Au particle provides a new way.Orderly organic-inorganic hybrid mesoporous silica loaded with nano gold copper-base alloy of the present invention has the little and feature such as be evenly distributed of average grain diameter, demonstrates good catalytic applications prospect.
Material of the present invention is in the presence of the agent of neutral long-chain template, ethyl orthosilicate mixes with a kind of glyoxaline ion liquid organic functional polysiloxane precursor body that contains thioether, at a certain temperature the synthetic Metaporous silicon dioxide material that contains the ion liquid hybrid inorganic-organic of thioether of a step.Utilize the abundant hydroxyl in surface, its duct directly to reduce gold chloride (HAuCl then
4), and the thioether organo-functional group in the organic group is used for the stable gold particle that is reduced.Preparation process of the present invention is simple, does not need additional reducing agent, helps environmental protection.
Description of drawings
Accompanying drawing is the high-resolution-ration transmission electric-lens figure (HRTEM) of the prepared sample of the present invention (molar content of organic functional group is 2%).
Picture specification:
Fig. 1, Fig. 2 represent the ordered mesoporous material pore passage structure, and scale is 20nm among the figure.
Fig. 3, Fig. 4 represent that golden nanometer particle is distributed in the ordered mesoporous material duct, and scale is 20nm among the figure.
Instrument model: JEM-2010, accelerating potential 200KV.
The result shows that the ordered mesoporous material aperture is 5-8nm among Fig. 1, Fig. 2,
The result shows that the mesoporous material aperture is 4-5nm among Fig. 3, Fig. 4, and the Au particle size is 1.2-2.4nm in the duct.
The specific embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1
1, under the stirring at room 5ml6-sulfydryl-1-hexanol is dissolved in the 20ml absolute ethyl alcohol, adds 13.8g iodine then, stirred 24 hours.Rotary evaporation desolventizes the back and adds the 30ml t-butyl methyl ether, and with the solution of sodium bisulfite extraction iodine of 10mg/ml, rotary evaporation desolventizes then.In residue, add the 5ml thionyl chloride again, stirring at room 24 hours, rotary evaporation removes volatile materials.At last; add 5ml 3-ethoxy silane propyl group-4 in residue, the two hydrogen imidazole ion liquids of 5-added hot reflux 24 hours under the N2 protection; vacuum is removed volatile matter and is got viscous liquid, promptly contains the glyoxaline ion liquid organic functional polysiloxane precursor body of thioether.
2, remain under 35 ℃ in temperature, 4.0g P123 is dissolved in 150ml 1.6M (M the is mol/l) hydrochloric acid solution makes the pH value of solution value reach 2.0, add the glyoxaline ion liquid organic functional polysiloxane precursor body that 0.7g contains thioether then.Continue to stir after 5 minutes, add 8.4g ethyl orthosilicate (TEOS), stirred 20 hours.System is warmed up to 80 ℃ again, still aging 24 hours.Product after filtration, water washing is to there not being Cl
-(detecting with the 0.1M liquor argenti nitratis ophthalmicus) 80 ℃ of vacuum drying 12 hours, uses absolute ethyl alcohol soxhlet extraction 48 hours, removes P123.Obtain containing the hybrid inorganic-organic SiO 2 mesoporous materials of the glyoxaline ion liquid of thioether.Through XRD, N
2Modern detecting such as absorption/desorption, TEM characterizes, and the specific area (BET) of the sample that obtains is 512m
2/ g, pore volume are 0.73cm
3/ g, average pore size is 6.5nm.
3, get the above-mentioned sample that makes of 0.5g, add the 20g deionized water, (mM is * 10 dropwise to add 25ml 2.4mM then
-3Mol/l) gold chloride (HAuCl
4) solution (with 1MNaOH the pH value being transferred to 7.0 in advance), stirring at room 24 hours.Product after filtration, water washing is to there not being Cl
-(detecting with the 0.1M liquor argenti nitratis ophthalmicus), vacuum drying at room temperature 12 hours obtains containing the nano Au particle of hybrid inorganic-organic SiO 2 mesoporous materials duct internal burden type of the glyoxaline ion liquid of thioether.The specific area of sample (BET) is 444m
2/ g, pore volume are 0.44cm
3/ g, average pore size is 4.0nm.The gold nanometer particle grain size for preparing is 1.2-2.4nm.
Embodiment 2
1, under the stirring at room 5ml 9-sulfydryl-1 nonyl alcohol is dissolved in the 20ml absolute ethyl alcohol, adds 13.8g iodine then, stirred 24 hours.Rotary evaporation desolventizes the back and adds the 30ml t-butyl methyl ether, and with the solution of sodium bisulfite extraction iodine of 15mg/ml, rotary evaporation desolventizes then.In residue, add the 5ml thionyl chloride again, stirring at room 24 hours, rotary evaporation removes volatile materials.At last; add 5ml 3-ethoxy silane propyl group-4 in residue, the two hydrogen imidazole ion liquids of 5-added hot reflux 24 hours under the N2 protection; vacuum is removed volatile matter and is got viscous liquid, promptly contains the glyoxaline ion liquid organic functional polysiloxane precursor body of thioether.
2, remain under 35 ℃ in temperature, 4.0g P123 is dissolved in the 150ml 1.6M hydrochloric acid solution makes the pH value of solution value reach 2.0, add the glyoxaline ion liquid organic functional polysiloxane precursor body that 0.7g contains thioether then.Continue to stir after 5 minutes, add 8.4g ethyl orthosilicate (TEOS), stirred 20 hours.System is warmed up to 80 ℃ again, still aging 20 hours.Product after filtration, water washing is to there not being Cl
-(detecting with the 0.1M liquor argenti nitratis ophthalmicus) 80 ℃ of vacuum drying 20 hours, uses absolute ethyl alcohol soxhlet extraction 48 hours.Obtain containing the hybrid inorganic-organic SiO 2 mesoporous materials of the glyoxaline ion liquid of thioether.The specific area (BET) of the sample that obtains is 550m
2/ g, pore volume are 0.80cm
3/ g, average pore size is 6.7nm.
3, get the above-mentioned sample that makes of 0.5g, add the 20g deionized water, dropwise add 25ml 2.4mM gold chloride (HAuCl then
4) solution (with 1MNaOH the pH value being transferred to 7.5 in advance), stirring at room 24 hours.Product after filtration, water washing is to there not being Cl
-(detecting) with the 0.1M liquor argenti nitratis ophthalmicus, vacuum drying at room temperature 12 hours obtains containing the nano Au particle of hybrid inorganic-organic SiO 2 mesoporous materials duct internal burden type of the glyoxaline ion liquid of thioether, and the specific area of sample (BET) is 425m
2/ g, pore volume are 0.50cm
3/ g, average pore size is 4.2nm.The gold nanometer particle grain size for preparing is 1.5-2.8nm.
Embodiment 3
1, under the stirring at room 5ml 3-sulfydryl-1-propyl alcohol is dissolved in the 20ml absolute ethyl alcohol, adds 13.8g iodine then, stirred 24 hours.Rotary evaporation desolventizes the back and adds the 30ml t-butyl methyl ether, and with the solution of sodium bisulfite extraction iodine of 15mg/ml, rotary evaporation desolventizes then.In residue, add the 5ml thionyl chloride again, stirring at room 24 hours, rotary evaporation removes volatile materials.At last, add 5ml 3-ethoxy silane propyl group-4 in residue, the two hydrogen imidazole ion liquids of 5-are at N
2Added hot reflux 24 hours under the protection, vacuum is removed volatile matter and is got viscous liquid, promptly contains the glyoxaline ion liquid organic functional polysiloxane precursor body of thioether.
2, remain under 35 ℃ in temperature, 4.0g P123 is dissolved in the 150ml 1.6M hydrochloric acid solution makes the pH value of solution value reach 2.0, add the glyoxaline ion liquid organic functional polysiloxane precursor body that 0.7g contains thioether then.Continue to stir after 5 minutes, add 8.4g ethyl orthosilicate (TEOS), stirred 20 hours.System is warmed up to 80 ℃ again, still aging 20 hours.Product after filtration, water washing is to there not being Cl
-(detecting with the 0.1M liquor argenti nitratis ophthalmicus) 80 ℃ of vacuum drying 20 hours, uses absolute ethyl alcohol soxhlet extraction 48 hours.Obtain containing the hybrid inorganic-organic SiO 2 mesoporous materials of the glyoxaline ion liquid of thioether.The specific area (BET) of the sample that obtains is 496m
2/ g, pore volume are 0.68cm
3/ g, average pore size is 6.1nm.
3, get the above-mentioned sample that makes of 0.5g, add the 20g deionized water, dropwise add 25ml 2.4mM gold chloride (HAuCl then
4) solution (with 1M NaOH the pH value being transferred to 7.5 in advance), stirring at room 24 hours.Product after filtration, water washing is to there not being Cl
-(detecting) with the 0.1M liquor argenti nitratis ophthalmicus, vacuum drying at room temperature 12 hours obtains containing the nano Au particle of hybrid inorganic-organic SiO 2 mesoporous materials duct internal burden type of the glyoxaline ion liquid of thioether, and the specific area of sample (BET) is 460m
2/ g, pore volume are 0.38cm
3/ g, average pore size is 3.6nm.The gold nanometer particle grain size for preparing is 1.4-2.5nm.
Embodiment 4
The glyoxaline ion liquid organic functional polysiloxane precursor body that contains thioether is with embodiment 1.
1, temperature remains on 35 ℃, 4.0g P123 is dissolved in the 150ml 1.6M hydrochloric acid solution make the pH value of solution value reach 2.0, adds the glyoxaline ion liquid organic functional polysiloxane precursor body that 2.15g contains thioether then.Continue to stir after 5 minutes, add 8.0g ethyl orthosilicate (TEOS), stirred 20 hours.System is warmed up to 80 ℃ again, still aging 20 hours.Product after filtration, water washing is to there not being Cl
-(detecting with the 0.1M liquor argenti nitratis ophthalmicus) 80 ℃ of vacuum drying 20 hours, uses absolute ethyl alcohol soxhlet extraction 48 hours.Obtain containing the hybrid inorganic-organic SiO 2 mesoporous materials of the glyoxaline ion liquid of thioether.The specific area (BET) of the sample that obtains is 510m
2/ g, pore volume are 0.71cm
3/ g, average pore size is 6.0nm.
2, get the above-mentioned sample that makes of 0.5g, add the 20g deionized water, dropwise add 25ml 3.0mM gold chloride (HAuCl then
4) solution (with 1MNaOH the pH value being transferred to 7.5 in advance), stirring at room 24 hours.Product after filtration, water washing is to there not being Cl
-(detecting) with the 0.1M liquor argenti nitratis ophthalmicus, vacuum drying at room temperature 12 hours obtains containing the nano Au particle of hybrid inorganic-organic SiO 2 mesoporous materials duct internal burden type of the glyoxaline ion liquid of thioether, and the specific area of sample (BET) is 430m
2/ g, pore volume are 0.36cm
3/ g, average pore size is 3.5nm.The gold nanometer particle grain size for preparing is 1.8-2.7nm.
Embodiment 5
The glyoxaline ion liquid organic functional polysiloxane precursor body that contains thioether is with embodiment 1.
1, temperature remains on 35 ℃, 4.0g P123 is dissolved in the 150ml 1.6M hydrochloric acid solution make the pH value of solution value reach 2.0, adds the glyoxaline ion liquid organic functional polysiloxane precursor body that 3.0g contains thioether then.Continue to stir after 5 minutes, add 7.8g ethyl orthosilicate (TEOS), stirred 20 hours.System is warmed up to 80 ℃ again, still aging 20 hours.Product after filtration, water washing is to there not being Cl
-(detecting with the 0.1M liquor argenti nitratis ophthalmicus) 80 ℃ of vacuum drying 20 hours, uses absolute ethyl alcohol soxhlet extraction 48 hours.Obtain containing the hybrid inorganic-organic SiO 2 mesoporous materials of the glyoxaline ion liquid of thioether.The specific area (BET) of the sample that obtains is 467m
2/ g, pore volume are 0.63cm
3/ g, average pore size is 5.6nm.
2, get the above-mentioned sample that makes of 0.5g, add the 20g deionized water, dropwise add 25ml 3.2mM gold chloride (HAuCl then
4) solution (with 1MNaOH the pH value being transferred to 7.5 in advance), stirring at room 24 hours.Product after filtration, water washing is to there not being Cl
-(detecting) with the 0.1M liquor argenti nitratis ophthalmicus, vacuum drying at room temperature 12 hours obtains containing the nano Au particle of hybrid inorganic-organic SiO 2 mesoporous materials duct internal burden type of the glyoxaline ion liquid of thioether, and the specific area of sample (BET) is 421m
2/ g, pore volume are 0.30cm
3/ g, average pore size is 3.2nm.The gold nanometer particle grain size for preparing is 1.5-2.8nm.
Embodiment 6
The glyoxaline ion liquid organic functional polysiloxane precursor body that contains thioether is with embodiment 1.
1, remains under 35 ℃ in temperature, 4.0g P123 is dissolved in the 150ml 1.6M hydrochloric acid solution makes the pH value of solution value reach 2.0, add the glyoxaline ion liquid organic functional polysiloxane precursor body that 3.6g contains thioether then.Continue to stir after 5 minutes, add 7.6g ethyl orthosilicate (TEOS), stirred 20 hours.System is warmed up to 80 ℃ again, still aging 20 hours.Product after filtration, water washing is to there not being Cl
-(detecting with the 0.1M liquor argenti nitratis ophthalmicus) 80 ℃ of vacuum drying 20 hours, uses absolute ethyl alcohol soxhlet extraction 48 hours.Obtain containing the hybrid inorganic-organic SiO 2 mesoporous materials of the glyoxaline ion liquid of thioether.The specific area (BET) of the sample that obtains is 428m
2/ g, pore volume are 0.54cm
3/ g, average pore size is 5.1nm.
2, get the above-mentioned sample that makes of 0.5g, add the 20g deionized water, dropwise add 25ml 3.5mM chlorauric acid solution (with 1M NaOH the pH value being transferred to 7.5 in advance) then, stirring at room 24 hours.Product after filtration, water washing is to there not being Cl
-(detecting) with the 0.1M liquor argenti nitratis ophthalmicus, vacuum drying at room temperature 12 hours obtains containing the nano Au particle of hybrid inorganic-organic SiO 2 mesoporous materials duct internal burden type of the glyoxaline ion liquid of thioether, and the specific area of sample (BET) is 386m
2/ g, pore volume are 0.29cm
3/ g, average pore size is 3.0nm.The gold nanometer particle grain size for preparing is 1.5-3.0nm.
Claims (7)
1, a kind of orderly organic-inorganic hybrid mesoporous silica material, it is characterized in that: the mesoporous silicon oxide hole wall is embedded with the glyoxaline ion liquid that contains thioether.
2, a kind of orderly organic-inorganic hybrid mesoporous silica loaded with nano gold copper-base alloy is characterized in that: will be embedded with contain thioether the glyoxaline ion liquid mesoporous silicon oxide as carrier, nanometer Au is distributed in this mesoporous silicon oxide duct.
3, a kind of orderly organic-inorganic hybrid mesoporous silica loaded with nano gold copper-base alloy according to claim 2, it is characterized in that: the particle diameter of nano Au particle is 1.2-3nm in the duct.
4, a kind of orderly organic-inorganic hybrid mesoporous silica preparation methods: it is characterized in that: (1) is dissolved in surfactant in the deionized water, adjust pH 1.5-3.5, add the glyoxaline ion liquid organic functional polysiloxane precursor body that contains thioether then, under strong agitation, ethyl orthosilicate is added in the above-mentioned solution, stirred 20-24 hour, system is warmed up to 70-90 ℃, still aging 24-48 hour; (2) product after filtration, water washing is to there not being Cl
-, vacuum drying is removed surfactant with the absolute ethyl alcohol soxhlet extraction, promptly gets the organic-inorganic hybrid mesoporous silica material of the glyoxaline ion liquid that contains thioether in order.
5, a kind of ordered mesoporous silica dioxide preparation methods according to claim 4, it is characterized in that, synthesizing of the described glyoxaline ion liquid organic functional polysiloxane precursor body that contains thioether: under the stirring at room mercaptoalkyl alcohol is dissolved in the absolute ethyl alcohol, add iodine behind the mixing, stirred 20-24 hour; Evaporation desolventizes the back and adds t-butyl methyl ether, extracts iodine with solution of sodium bisulfite then, and evaporation desolventizes; In residue, add thionyl chloride again, stirring at room, evaporation removes volatile materials; At last, add 3-ethoxy silane propyl group-4 in residue, the two hydrogen imidazoles of 5-are at N
2Add hot reflux under the protection, vacuum is removed the glyoxaline ion liquid organic functional polysiloxane precursor body that volatile matter obtains containing thioether.
6, the preparation method of a kind of ordered mesoporous silica dioxide material according to claim 5 and load gold nano particle thereof, described mercaptoalkyl alcohol is 9-sulfydryl-1 nonyl alcohol, 6-sulfydryl-1-propyl alcohol or 3-sulfydryl-1-propyl alcohol.
7, a kind of orderly organic-inorganic hybrid mesoporous silica supported nano-gold preparation methods is: adjust pH reaches 7.0-8.0 in chlorauric acid solution, dropwise add again in the organic-inorganic hybrid mesoporous silica material of the orderly glyoxaline ion liquid that contains thioether, stir, product after filtration, washing, drying, promptly.
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