CN100556543C - A kind of orderly organic-inorganic hybrid mesoporous silica and loaded with nano gold copper-base alloy and their preparation method - Google Patents
A kind of orderly organic-inorganic hybrid mesoporous silica and loaded with nano gold copper-base alloy and their preparation method Download PDFInfo
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- CN100556543C CN100556543C CNB2007100344540A CN200710034454A CN100556543C CN 100556543 C CN100556543 C CN 100556543C CN B2007100344540 A CNB2007100344540 A CN B2007100344540A CN 200710034454 A CN200710034454 A CN 200710034454A CN 100556543 C CN100556543 C CN 100556543C
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Abstract
The invention discloses a kind of orderly organic-inorganic hybrid mesoporous silica and loaded with nano gold copper-base alloy and their preparation method.In the presence of the agent of neutral long-chain template, ethyl orthosilicate and a kind of glyoxaline ion liquid organic functional siloxanes that contains thioether be logical to be driven body and mixes, and a step is synthesized the Metaporous silicon dioxide material of the ion liquid hybrid inorganic-organic that contains thioether at a certain temperature.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 is simple, does not need additional reducing agent, helps environmental protection.The nano Au particle for preparing has the little and feature such as be evenly distributed of average grain diameter, demonstrates good catalytic applications prospect.
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 5ml 6-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-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 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-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 makes the pH value of solution value reach 2.0 in the 150ml1.6M hydrochloric acid solution, 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 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 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 makes the pH value of solution value reach 2.0 in the 150ml1.6M hydrochloric acid solution, 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 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 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 make the pH value of solution value reach 2.0 in the 150ml1.6M hydrochloric acid solution, 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 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 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 makes the pH value of solution value reach 2.0 in the 150ml1.6M hydrochloric acid solution, 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 (6)
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 imidazole ion liquid that contains thioether: (EtO)
3Si (CH
2)
3-C
3H
5N
2 +Cl
--R-S-S-R-C
3H
5N
2 +Cl
--(CH
2)
3Si (OEt)
3, R contains the straight chained alkyl of 3-9 carbon.
2, a kind of orderly organic-inorganic hybrid mesoporous silica material according to claim 1 is characterized in that: with hole wall be embedded with contain thioether the imidazole 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 material 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 the poly-oxireme ether of surfactant-poly-propylene oxide ether-poly-oxireme ether triblock polymer in the deionized water, adjust pH 1.5-3.5, add the imidazole 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 imidazole ion liquid that contains thioether in order;
Synthesizing of the described imidazole ion liquid organic functional polysiloxane precursor body that contains thioether: 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; 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 imidazole ion liquid organic functional polysiloxane precursor body that volatile matter obtains containing thioether;
Described mercaptoalkyl alcohol HO-R-SH, R is the straight chained alkyl that contains 3-9 carbon.
5, a kind of orderly organic-inorganic hybrid mesoporous silica preparation methods according to claim 4, described mercaptoalkyl alcohol is 9-sulfydryl-1 nonyl alcohol, 6-sulfydryl-1-hexanol or 3-sulfydryl-1-propyl alcohol.
6, 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 imidazole ion liquid that contains thioether, stir, product after filtration, washing, drying, promptly.
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| CN102198929B (en) * | 2010-03-22 | 2013-05-01 | 中国科学院理化技术研究所 | Hollow silicon dioxide sub-microsphere with nanoscale precious metal and silicon dioxide kernel and preparation method thereof |
| CN101940946B (en) * | 2010-08-24 | 2012-09-05 | 厦门大学 | Preparation method for propylene epoxidation catalyst |
| CN102814195B (en) * | 2011-06-09 | 2014-05-28 | 中国石油化工股份有限公司 | Load type acidic ionic liquid catalyst and preparation method and application thereof and preparation method of ethyl acetate and methyl oleate |
| WO2014055274A1 (en) * | 2012-10-01 | 2014-04-10 | Dow Global Technologies Llc | Ionic liquid grafted mesoporous silica compositions for polar gas/non-polar gas and olefin/paraffin separations |
| CN103007290B (en) * | 2012-12-13 | 2014-01-01 | 东南大学 | Nano-carrier particle controllable in drug release and preparation method thereof |
| CN108109899A (en) * | 2017-12-07 | 2018-06-01 | 东南大学 | A kind of preparation method for enhancing laser desorption ionization composite nanoparticle |
| CN109752536B (en) * | 2018-12-04 | 2022-03-15 | 浙江工业大学 | Optical probe based on gold nanoparticle efficient assembly structure and preparation and application thereof |
| CN110170326B (en) * | 2019-05-08 | 2020-06-05 | 北京化工大学 | High-dispersion supported noble metal catalytic material and preparation method thereof |
| CN113185705B (en) * | 2021-05-21 | 2022-05-13 | 深圳市光与生物科技有限公司 | Organic-inorganic hybrid material for single molecule detection and preparation method thereof |
-
2007
- 2007-02-15 CN CNB2007100344540A patent/CN100556543C/en active Active
Non-Patent Citations (3)
| Title |
|---|
| Nonionic triblock and star diblock copolymerandoligomericsurfactant syntheses of highlyordered,hydrothermallystlabe,mesoporous silica structures. Dongyuan Zhao et al.J. AM. CHEM. SOC.,Vol.120 No.24. 1998 * |
| Preparation and stabilization of gold nanoparticles formed byin situ reduction of aqueous chloroaurate ions withinsurface-modified mesoporous silica. Anirban Ghosh et al.Microporous and Mesoporous Materials,Vol.58 . 2003 * |
| Synthesis of Gold Nanoparticles Modified with IonicLiquidBased On the Imidazolium Cation. Hideaki Itoh et al.J. AM. CHEM. SOC.,Vol.126 No.10. 2004 * |
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