CN101785998A - Sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst and preparation method and application thereof - Google Patents
Sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to sulfydryl functionalized ordered mesoporous silicon-immobilize Au heterogeneous catalyst and a preparation method and application thereof. The preparation method is as follows: mixing surfactant, strong acid, water, ethyl orthosilicate and sulfhydryl silane under heating condition, continuously stirring the reactant mixture, filtering the reactant mixture to get white solid, and sequentially washing and drying the white solid to get a sulfydryl functionalized ordered mesoporous silicon carrier; mixing the carrier with ethanol and HAuCl4 solution, stirring for 24h under room temperature, pump filtering and washing the mixture, and vacuum drying overnight. In this way, the ordered mesoporous sulfydryl functionalized SBA-15-immobilize Au heterogeneous catalyst can be formed. The preparation process is simple and the heterogeneous catalyst prepared through the method has efficient and long-lasting catalytic activity, can improve the reaction speed, reduce the production cost and improve the quality of the product, and can be recycled for use, thereby reducing environment pollution.
Description
Technical field
The present invention relates to a kind of preparation technology and application thereof of order mesoporous heterogeneous catalysis, particularly a kind of preparation method of the order mesoporous mercapto-functionalized immobilized Au heterogeneous catalysis of SBA-15 and the application of cleaning alkynes hydration reaction in aqueous medium thereof.
Background technology
In recent years, carry out the important branch that organic synthesis becomes Green Chemistry with water to replace organic solvent.The alkynes hydration reaction is the important organic reaction of a class, and products therefrom is important organic synthesis intermediate.Tradition is used for the catalyst of alkynes hydration reaction mainly based on mercury, substitute and to have more supervirulent mercury though develop multiple organic Au complex recently, homogeneous catalyst exists all the time and is difficult to reuse, easily cause heavy metal pollution and improve problems such as reaction cost.Therefore develop the synthetic method of novel mesoporous heterogeneous catalysis, improve the catalytic performance of catalyst, have very important theory significance and industrial value.
In recent years, utilize the carrier of ordered mesoporous material as immobilized metallic catalyst, the cleaning organic synthesis that is implemented in the aqueous medium causes extensive concern gradually, wherein, the ordered mesoporous silicon material of functionalization especially is subjected to the attention of vast chemist because of the advantage of the decentralization of the characteristics raising active sites of its bigger serface, regular pore passage structure.
Summary of the invention
The invention reside in provides a kind of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis.
The present invention also provides the preparation method of above-mentioned sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis.
Another object of the present invention is to provide above-mentioned Application of Catalyst.
For achieving the above object, the preparation method comprises, ethyl orthosilicate, hydrosulphonyl silane and surfactant are carried out copolycondensation, gets precipitation after the ageing, and extraction is removed surfactant and obtained mercapto-functionalized ordered mesoporous silicon; With above-mentioned mercapto-functionalized ordered mesoporous silicon, HAuCl
4Solution and ethanol mix, and stirring, suction filtration and vacuum drying promptly get sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis.
Concrete preparation method comprises the steps:
1) surfactant and HCl being formulated as surfactant concentration is that 3.8～5.0mM, HCl concentration are the solution of 1.5～2.1M, mixes under 30～50 ℃ condition;
Add ethyl orthosilicate (TEOS), pre-polymerization 80～100min adds hydrosulphonyl silane again, mix and continue reaction 20～26h, and under 90～110 ℃ of conditions ageing 22～30h, get precipitation;
The mol ratio of ethyl orthosilicate and hydrosulphonyl silane is 10: 1～100: 1;
The mol ratio of the total content of silicon and surfactant is 1: 0.015～0.025 in ethyl orthosilicate and the hydrosulphonyl silane;
2) surfactant is removed in step 1) products therefrom washing back extraction, obtained mercapto-functionalized ordered mesoporous silicon.
3) under 20～35 ℃, with step 2) mercapto-functionalized ordered mesoporous silicon, the 0.09～0.15mol/L HAuCl of gained
4Solution and ethanol mix, and mercapto-functionalized ordered mesoporous silicon and the ratio of Au are 1g: 0.15～0.30mmol, with the ratio of ethanol be 1g: 6～12ml; Behind reaction 20～30h, get precipitation and washing drying, form sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis.
In the step 1), described surfactant is selected from P123.
In the step 1), described hydrosulphonyl silane is selected from 3-trimethoxy silicon n-pro-pyl mercaptan or 3-triethoxysilicane n-pro-pyl mercaptan.
Step 2) in, extraction is removed before the surfactant, and precipitation is carried out milled processed.Method of extraction is: the mixed solution with hydrochloric acid and ethanol extracts 20～32h under 70～90 ℃ of conditions; The mass volume ratio of solid and liquid is 1g: 800～1200mL;
In the mixed solution of described hydrochloric acid and ethanol, content of hydrochloric acid is 0.8～1.2mol/L, and the content of ethanol is 410～780g/L.
In the step 3), described HAuCl
4Solution is HAuCl
4The aqueous solution or ethanolic solution, the mass volume ratio of solid and liquid are 1g: 6.0～10mL; HAuCl in the liquid
4Be 0.09～0.15mol/L.
A kind of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis that said method obtains, specific area is 500～700m
2/ g has the two-dimentional hexagonal mesoporous structure of high-sequential, and pore volume is 0.4～0.8cm
3/ g; The aperture is 5.0～8.0nm.The supported quantity of Au is 0.019～0.025mmol/g.
Above-mentioned sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis can be applicable to the cleaning alkynes hydration reaction in the aqueous medium.The hydration reaction of phenylacetylene for example, this course of reaction can be represented by following formula:
In the alkynes hydration reaction of catalyst of the present invention in aqueous medium, has advantages of high catalytic activity.Its superior catalytic activity is mainly owing to following factors:
1, this sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis has regular orderly two-dimentional hexagonal mesoporous structure, the pore-size distribution of homogeneous, bigger specific area.These characteristics have guaranteed that the even dispersion in catalytic activity site, substrate fully contact with the activated centre.
2, the golden nanometer particle less (1-3nm) on this sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis, thereby have higher activity.
3, the alkynes hydration reaction generally needs acid to do co-catalyst, and this law is by HAuCl by the sulfydryl in the catalyst
4Oxidation generation-SO
3H guarantees to be reflected under enough sour environments to carry out like this, and-SO
3Enrichment around the active sites of H in carrier, thus the carrying out that reacts promoted.
Alkynes hydration reaction yield in sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis catalysis aqueous medium can reach 99%, selectivity can reach 100%.And still have catalytic efficiency preferably after can reusing 12 times, the reaction yield reaches 93%.
The heterogeneous catalysis duct of the present invention's preparation is unobstructed, and active sites is evenly distributed, and the reactivity height can overcome deficiency of the prior art; Even distribution, the substrate that can realize the catalytic activity site fully contact with the activated centre, can realize the recycling of catalyst again, finally realize the target of green catalysis.And the preparation method is simple, and cost is low.
Description of drawings
Fig. 1 is the little angle XRD figure of the immobilized Au heterogeneous catalysis of embodiment 1 gained sulfydryl function ordered mesoporous silicon;
Fig. 2 is the TEM figure of the immobilized Au heterogeneous catalysis of embodiment 1 gained sulfydryl function ordered mesoporous silicon;
Fig. 3 is the TEM figure after the immobilized Au heterogeneous catalysis of the sulfydryl function ordered mesoporous silicon of embodiment 1 gained corrodes with HF;
Fig. 4 applies mechanically number of times and yield for the immobilized Au heterogeneous catalysis of embodiment 1 gained sulfydryl function ordered mesoporous silicon.
The specific embodiment
Below in conjunction with drawings and the specific embodiments content of the present invention is further specified
A kind of preparation method of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis comprises the following steps:
1) with 1.0g P123 (EO
20PO
70EO
20) (0.17mmol), 8.0g H
2O and 31mL 2M HCl solution mix, in the folder hot jacket, stir 3h under 40 ℃ of conditions, add 9.5mmol ethyl orthosilicate (TEOS) then, after treating TEOS pre-polymerization 90min, add 3-trimethoxy silicon n-pro-pyl mercaptan (0.5mmol) again, continue to stir 24h, ageing 24h under 100 ℃ of conditions obtains the white solid powder after filtration washing, the vacuum drying;
2) above-mentioned material is ground with agate mortar, at last with HCl/C
2H
5OH extracts, and the mass volume ratio of solid and liquid is 1g: 1000mL; In the mixed solution of described hydrochloric acid and ethanol, content of hydrochloric acid is 1.0mol/L, and the content of ethanol is 750g/L.Products therefrom is mercapto-functionalized ordered mesoporous silicon, represents with SH-SBA-15.Little angle XRD figure as shown in Figure 1.
3) under 25 ℃, with 0.50g SH-SBA-15,1mL 0.1M HAuCl
4The aqueous solution and 5ml ethanol mix, and after continuing to stir 24h, mixed reactant is filtered, filter cake is through washing and after 60 ℃ of dry processing, form the immobilized Au heterogeneous catalysis of order mesoporous mercapto-functionalized SBA-15, wherein the content of Au is 0.019～0.025mmol/g.
By the product of BET method mensuration the foregoing description 1, the immobilized Au heterogeneous catalysis of sulfydryl function ordered mesoporous silicon (is called for short Au@SH/SO
3H-SBA-15) structural parameters are listed in table 1:
Table 1 Au@SH/SO
3The structural parameters of H-SBA-15
The little angle XRD figure (Fig. 1) of prepared sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis and TEM figure (Fig. 2) and as seen, prepared heterogeneous catalysis from the BET data all have orderly two-dimentional hexagonal mesoporous structure, pore-size distribution comparatively homogeneous, have bigger specific area.
A kind of preparation method of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis comprises the following steps:
1) with 0.9g P123 (EO
20PO
70EO
20) (0.16mmol), 8.0g H
2O and 31mL2M HCl solution mix, in the folder hot jacket, stir 3h under 40 ℃ of conditions, add (9.6mmol) ethyl orthosilicate (TEOS) then, after treating TEOS pre-polymerization 90min, add 3-trimethoxy silicon n-pro-pyl mercaptan (0.4mmol) again, continue to stir 22h, ageing 24h under 100 ℃ of conditions obtains the white solid powder after filtration washing, the vacuum drying;
2) above-mentioned material is ground with agate mortar, at last with HCl/C
2H
5OH extracts, and obtains mercapto-functionalized ordered mesoporous silicon; Represent with SH-SBA-15.The mass volume ratio of solid and liquid is 1g: 900mL; In the mixed solution of described hydrochloric acid and ethanol, content of hydrochloric acid is 1.1mol/L, and the content of ethanol is 750g/L.
3) under 25 ℃, with 0.45g SH-SBA-15,1mL 0.1M HAuCl
4The aqueous solution and 5ml ethanol mix, and after continuing to stir 24h, mixed reactant is filtered, filter cake is through washing and after 50 ℃ of dry processing, form the immobilized Au heterogeneous catalysis of order mesoporous mercapto-functionalized SBA-15, wherein the content of Au is 0.019～0.025mmol/g.。
A kind of preparation method of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis comprises the following steps:
1) with 1.1g P123 (EO
20PO
70EO
20) (0.19mmol), 9.0g H
2O and 31mL 2M HCl solution mix, in the folder hot jacket, stir 3h under 40 ℃ of conditions, add (9.7mmol) ethyl orthosilicate (TEOS) then, after treating TEOS pre-polymerization 90min, add 3-trimethoxy silicon n-pro-pyl mercaptan (0.3mmol) again, continue to stir 26h, ageing 24h under 100 ℃ of conditions obtains the white solid powder after filtration washing, the vacuum drying;
2) above-mentioned material is ground with agate mortar, at last with HCl/C
2H
5OH extracts, and obtains mercapto-functionalized ordered mesoporous silicon; Represent with SH-SBA-15.The mass volume ratio of solid and liquid is 1g: 800mL; In the mixed solution of described hydrochloric acid and ethanol, content of hydrochloric acid is 0.8mol/L, and the content of ethanol is 650g/L.Products therefrom is represented with SH-SBA-15.
3) under 25 ℃, with 0.6g SH-SBA-15,1mL 0.1M HAuCl
4The aqueous solution and 6.0ml ethanol mix, and after continuing to stir 24h, mixed reactant is filtered, filter cake is through washing and after 70 ℃ of vacuum drying treatment, form the immobilized Au heterogeneous catalysis of order mesoporous mercapto-functionalized SBA-15, wherein the content of Au is 0.019～0.025mmol/g.
The detailed process that embodiment 1 resulting sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis is used for the alkynes hydration reaction is as follows:
In having the 10ml round-bottomed flask of reflux condensing tube, add 0.25mmol alkynes, contain the catalyst of 0.010mmol Au; React 1.5h under 80 ℃ of conditions, products therefrom carries out product analysis by GC, active result such as table 2 after using the 10ml ethyl acetate extraction.
Reaction equation is:
The sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis of table 2. is to the catalytic activity table of alkynes hydration reaction in the aqueous medium
From the table data as can be seen, the order mesoporous mercapto-functionalized immobilized Au heterogeneous catalysis of SBA-15 catalyst alkynes hydration reaction in aqueous medium of preparation shows higher activity.
Remaining heterogeneous catalysis washs 2～4 times with ethyl acetate, deionized water, and 60～80 ℃ of following vacuum drying are reused next time, apply mechanically experiment, and its catalytic activity is seen Fig. 3.
As can be seen from Figure 4, repeat to apply mechanically 10 times after, sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis still has catalytic activity preferably, efficiency of pcr product is 92%.
Claims (9)
1. the preparation method of a sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis is characterized in that, this method comprises the following steps:
1) surfactant and HCl being formulated as surfactant concentration is that 3.8～5.0mmol/L, HCl concentration are the solution of 1.5～2.1mol/L, mixes under 30～50 ℃ condition;
Add ethyl orthosilicate pre-polymerization 80～100min, add hydrosulphonyl silane again, mix and continue reaction 20～26h, and under 90～110 ℃ of conditions ageing 22～30h, get precipitation;
The mol ratio of ethyl orthosilicate and hydrosulphonyl silane is 10: 1～100: 1;
The mol ratio of the total content of silicon and surfactant is 1: 0.015～0.025 in ethyl orthosilicate and the hydrosulphonyl silane;
2) surfactant is removed in step 1) products therefrom washing back extraction, obtained mercapto-functionalized ordered mesoporous silicon;
3) under 20～35 ℃, with step 2) mercapto-functionalized ordered mesoporous silicon, the HAuCl of gained
4Solution or alcohol mix, and mercapto-functionalized ordered mesoporous silicon and the ratio of Au are 1g: 0.15～0.30mmol;
Behind reaction 20～30h, get precipitation and washing drying, form sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis.
2. the preparation method of the described a kind of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis of claim 1 is characterized in that the surfactant described in the step 1) is P123.
3. the preparation method of the described a kind of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis of claim 1, it is characterized in that: the hydrosulphonyl silane described in the step 1) is selected from 3-trimethoxy silicon n-pro-pyl mercaptan or 3-triethoxysilicane n-pro-pyl mercaptan.
4. the preparation method of the described a kind of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis of claim 1 is characterized in that: step 2) extraction removes before the surfactant, and precipitation is carried out milled processed.
5. the preparation method of the described a kind of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis of claim 1 is characterized in that step 2) method of extraction is, extracts 20～32h with the mixed solution of hydrochloric acid and ethanol under 70～90 ℃ of conditions; The mass volume ratio of solid and liquid is 1g: 500～1000mL;
In the mixed solution of described hydrochloric acid and ethanol, content of hydrochloric acid is 0.8～1.2mol/L, and the content of ethanol is 410～780g/L.
6. the preparation method of the described a kind of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis of claim 1 is characterized in that, the described mercapto-functionalized ordered mesoporous silicon of step 3) is 1g: 6～12ml with ratio with ethanol.
7. the preparation method of the described a kind of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis of claim 1 is characterized in that the method for step 3) drying is vacuum drying, and dry temperature is 40～70 ℃.
8. a sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis is characterized in that, by the described method preparation of claim 1～7, specific area is 500～700m
2/ g has the two-dimentional hexagonal mesoporous structure of high-sequential, and pore volume is 0.4～0.8cm
3/ g; The aperture is 5.0～8.0nm, and the supported quantity of Au is 0.019～0.025mmol/g.
9. the described sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalysis of claim 8 application aspect the alkynes hydration reaction in the catalysis aqueous medium.
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