CN101785998B - 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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- CN101785998B CN101785998B CN2010101149689A CN201010114968A CN101785998B CN 101785998 B CN101785998 B CN 101785998B CN 2010101149689 A CN2010101149689 A CN 2010101149689A CN 201010114968 A CN201010114968 A CN 201010114968A CN 101785998 B CN101785998 B CN 101785998B
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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 catalyst, particularly a kind of preparation method of the order mesoporous mercapto-functionalized immobilized Au heterogeneous catalyst of SBA-15 and the application of cleaning alkynes hydration reaction in water 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 one type of important organic reaction, and products therefrom is important organic synthesis intermediate.The catalyzer that tradition is used for the alkynes hydration reaction is main with mercury mainly; Substitute and to have more supervirulent mercury though develop multiple organic Au title complex recently, homogeneous catalyst exists all the time and is difficult to reuse, be prone to cause heavy metal contamination and improve problems such as reaction cost.Therefore develop the compound method of novel mesoporous heterogeneous catalyst, improve the catalytic performance of catalyzer, have very important theory significance and commercial value.
In recent years; Utilize the carrier of ordered mesoporous material as immobilized metal catalyst; The cleaning organic synthesis that is implemented in the water medium causes extensive concern gradually; Wherein, the ordered mesoporous silicon material of functionalization especially receives the attention of vast chemist because of the advantage of the dispersity 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 catalyst.
The present invention also provides the preparation method of above-mentioned sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst.
Another object of the present invention is to provide above-mentioned Application of Catalyst.
For realizing above-mentioned purpose, the preparation method comprises, tetraethoxy, hydrosulphonyl silane and tensio-active agent are carried out copolycondensation, gets deposition after the ageing, and extraction is removed tensio-active agent 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 catalyst.
Concrete preparation method comprises the steps:
1) tensio-active agent and HCl being formulated as surfactant concentration is that 3.8～5.0mM, HCl concentration are the solution of 1.5～2.1M, under 30～50 ℃ condition, mixes;
Add tetraethoxy (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 deposition;
The mol ratio of tetraethoxy and hydrosulphonyl silane is 10: 1～100: 1;
The mol ratio of the total content of silicon and tensio-active agent is 1: 0.015～0.025 in tetraethoxy and the hydrosulphonyl silane;
2) tensio-active agent 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 alcoholic acid ratio be 1g: 6～12ml; Behind reaction 20～30h, get deposition and washing drying, form sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst.
In the step 1), described tensio-active agent is selected from P123.
In the step 1), described hydrosulphonyl silane is selected from 3-trimethoxy silicon n-propyl mercaptan or 3-triethoxysilicane n-propyl mercaptan.
Step 2) in, extraction is removed before the tensio-active agent, and deposition is carried out milled processed.Method of extraction is: under 70～90 ℃ of conditions, extract 20～32h with hydrochloric acid and alcoholic acid mixing solutions; The mass volume ratio of solid and liquid is 1g: 800～1200mL;
In described hydrochloric acid and the alcoholic acid mixing solutions, content of hydrochloric acid is 0.8～1.2mol/L, and alcoholic acid content is 410～780g/L.
In the step 3), described HAuCl
4Solution is HAuCl
4The aqueous solution or ethanolic soln, 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 catalyst that aforesaid method obtains, specific surface 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 catalyst can be applicable to the cleaning alkynes hydration reaction in the water medium.The hydration reaction of phenylacetylene for example, this reaction process can be represented by following formula:
In the alkynes hydration reaction of catalyzer of the present invention in water 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 catalyst has regular orderly two-dimentional hexagonal mesoporous structure, the pore size distribution of homogeneous, bigger specific surface area.These characteristics have guaranteed that the homodisperse in catalytic activity site, substrate fully contact with the active site.
2, the golden nanometer particle less (1-3nm) on this sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst, thereby have higher activity.
3, the alkynes hydration reaction generally needs acid to do co-catalyst, and this law is by HAuCl through the sulfydryl in the catalyzer
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 catalyst catalysis water 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 catalyst duct of the present invention's preparation is unobstructed, and active sites is evenly distributed, and reactive behavior is high, can overcome deficiency of the prior art; Uniform distribution, the substrate that can realize the catalytic activity site fully contact with the active site, can realize the recycle of catalyzer 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 catalyst of embodiment 1 gained sulfydryl function ordered mesoporous silicon;
Fig. 2 is the TEM figure of the immobilized Au heterogeneous catalyst of embodiment 1 gained sulfydryl function ordered mesoporous silicon;
Fig. 3 is the TEM figure after the immobilized Au heterogeneous catalyst 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 catalyst of embodiment 1 gained sulfydryl function ordered mesoporous silicon.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment content of the present invention is further specified
Embodiment 1
A kind of preparation method of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst 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 tetraethoxy (TEOS) then, treat TEOS pre-polymerization 90min after; Add 3-trimethoxy silicon n-propyl 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 materials 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 described hydrochloric acid and the alcoholic acid mixing solutions, content of hydrochloric acid is 1.0mol/L, and alcoholic acid content is 750g/L.Products therefrom is mercapto-functionalized ordered mesoporous silicon, representes with SH-SBA-15.Little angle XRD figure is 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 drying treatment; Form the immobilized Au heterogeneous catalyst 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 catalyst of sulfydryl function ordered mesoporous silicon (is called for short AuSH/SO
3H-SBA-15) structural parameter are listed in table 1:
Table 1 AuSH/SO
3The structural parameter of H-SBA-15
The little angle XRD figure (Fig. 1) of prepared sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst and TEM figure (Fig. 2) and visible, prepared heterogeneous catalyst from the BET data all have orderly two-dimentional hexagonal mesoporous structure, pore size distribution comparatively homogeneous, have bigger specific surface area.
A kind of preparation method of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst 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) tetraethoxy (TEOS) then, treat TEOS pre-polymerization 90min after; Add 3-trimethoxy silicon n-propyl 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 materials 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 described hydrochloric acid and the alcoholic acid mixing solutions, content of hydrochloric acid is 1.1mol/L, and alcoholic acid content 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 drying treatment; Form the immobilized Au heterogeneous catalyst of order mesoporous mercapto-functionalized SBA-15, wherein the content of Au is 0.019～0.025mmol/g.。
Embodiment 3
A kind of preparation method of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst comprises the following steps:
1) with 1.1g P123 (EO
20PO
70EO
20) (0.19mmol), 9.0g H
2O and 31mL 2 M HCl solution mix; In the folder hot jacket, stir 3h under 40 ℃ of conditions, add (9.7mmol) tetraethoxy (TEOS) then, treat TEOS pre-polymerization 90min after; Add 3-trimethoxy silicon n-propyl 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 materials 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 described hydrochloric acid and the alcoholic acid mixing solutions, content of hydrochloric acid is 0.8mol/L, and alcoholic acid content 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 catalyst 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 catalyst is used for the alkynes hydration reaction is following:
In having the 10ml round-bottomed flask of reflux condensing tube, add 0.25mmol alkynes, contain the catalyzer of 0.010mmol Au; React 1.5h under 80 ℃ of conditions, products therefrom with the 10ml ethyl acetate extraction after, carry out product analysis by GC, active result such as table 2.
Reaction formula is:
The sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst of table 2. is to the catalytic activity table of alkynes hydration reaction in the water medium
Data can find out that the order mesoporous mercapto-functionalized immobilized Au heterogeneous catalyst of SBA-15 catalyzer alkynes hydration reaction in water medium of preparation shows higher activity from table.
Remaining heterogeneous catalyst is with ETHYLE ACETATE, deionized water wash 2～4 times, and 60～80 ℃ of following vacuum-dryings 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 catalyst 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 catalyst is characterized in that, this method comprises the following steps:
1) tensio-active agent 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, under 30～50 ℃ condition, mixes;
Add tetraethoxy pre-polymerization 80～100min, add hydrosulphonyl silane again, mix and continue reaction 20～26h, and under 90～110 ℃ of conditions ageing 22～30h, get deposition;
The mol ratio of tetraethoxy and hydrosulphonyl silane is 10: 1～100: 1;
The mol ratio of the total content of silicon and tensio-active agent is 1: 0.015～0.025 in tetraethoxy and the hydrosulphonyl silane;
2) tensio-active agent 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, HAuCl4 solution and the ethanol mixing of gained, mercapto-functionalized ordered mesoporous silicon and the ratio of Au are 1g: 0.15～0.30mmol;
Behind reaction 20～30h, get deposition and washing drying, form sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst.
2. the preparation method of the described a kind of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst of claim 1 is characterized in that the tensio-active agent 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 catalyst of claim 1, it is characterized in that: the hydrosulphonyl silane described in the step 1) is selected from 3-trimethoxy silicon n-propyl mercaptan or 3-triethoxysilicane n-propyl mercaptan.
4. the preparation method of the described a kind of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst of claim 1 is characterized in that: step 2) extraction removes before the tensio-active agent, and deposition is carried out milled processed.
5. the preparation method of the described a kind of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst of claim 1 is characterized in that step 2) method of extraction is under 70～90 ℃ of conditions, to extract 20～32h with hydrochloric acid and alcoholic acid mixing solutions; The mass volume ratio of solid and liquid is 1g: 500～1000mL;
In described hydrochloric acid and the alcoholic acid mixing solutions, content of hydrochloric acid is 0.8～1.2mol/L, and alcoholic acid content is 410～780g/L.
6. the preparation method of the described a kind of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst of claim 1 is characterized in that, the said mercapto-functionalized ordered mesoporous silicon of step 3) with the alcoholic acid ratio be 1g: 6～12ml.
7. the preparation method of the described a kind of sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst of claim 1 is characterized in that step 3) exsiccant method is vacuum-drying, and the exsiccant temperature is 40～70 ℃.
8. a sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst is characterized in that, by each said method preparation of claim 1～7, specific surface 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 said sulfydryl functionalized ordered mesoporous silicon-immobilized Au heterogeneous catalyst of claim 8 application aspect the alkynes hydration reaction in the catalysis water medium.
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| CN102698788B (en) * | 2012-05-16 | 2014-04-16 | 浙江大学 | High-dispersion dual-functional catalyst for hydrogenating and deoxidizing phenol and preparation method of catalyst |
| CN102814197B (en) * | 2012-09-18 | 2014-05-07 | 济南大学 | Preparation method and application of retinervus luffae fructus-supported nanogold catalyst |
| CN102814196B (en) * | 2012-09-18 | 2014-05-07 | 济南大学 | Preparation method and application of dextrangel-supported nanogold catalyst |
| CN103772177B (en) * | 2014-01-07 | 2016-03-02 | 郑州大学 | A kind of preparation method of p-methoxy-acetophenone |
| CN106916179B (en) * | 2017-02-27 | 2018-08-28 | 苏州硒诺唯新新材料科技有限公司 | Functionalization material and its production technology and use |
| CN110627090A (en) * | 2018-06-25 | 2019-12-31 | 中国石油化工股份有限公司 | Preparation method and application of sulfydryl functionalized SBA molecular sieve |
| CN110449143B (en) * | 2019-04-16 | 2022-04-19 | 中华人民共和国镇江海关 | Multifunctional mixed-mode chromatographic stationary phase and preparation method thereof |
| CN111187388A (en) * | 2019-12-30 | 2020-05-22 | 广州奥松电子有限公司 | Novel ordered mesoporous organic-inorganic composite humidity-sensitive material and preparation method and application thereof |
| CN112007695B (en) * | 2020-09-23 | 2021-10-08 | 中国科学院大连化学物理研究所 | Sulfur-containing silane coupling agent modified gold catalyst for acetylene hydrochlorination |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101564687A (en) * | 2009-02-13 | 2009-10-28 | 仲恺农业工程学院 | In situ synthesis ultramicropore load platinum catalyst and solvent-free microwave hydrosilylation |
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| CN101564687A (en) * | 2009-02-13 | 2009-10-28 | 仲恺农业工程学院 | In situ synthesis ultramicropore load platinum catalyst and solvent-free microwave hydrosilylation |
Non-Patent Citations (2)
| Title |
|---|
| Sunyoung Park, et al.Direct Synthesis of Hydrogen Peroxide from Hydrogen and Oxygen over Palladium Catalyst Supported on SO3H-Functionalized SBA-15.《catalysis letters》.2009,第130卷 * |
| 李和兴等.特定结构光催化剂的制备及其构效关系.《催化学报》.2008,第29卷(第1期),91-98. * |
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