CN101927188B - Ordered mesoporous organic metal Au (I) heterogeneous catalyst and preparation method and application thereof - Google Patents
Ordered mesoporous organic metal Au (I) heterogeneous catalyst and preparation method and application thereof Download PDFInfo
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- CN101927188B CN101927188B CN2009102475818A CN200910247581A CN101927188B CN 101927188 B CN101927188 B CN 101927188B CN 2009102475818 A CN2009102475818 A CN 2009102475818A CN 200910247581 A CN200910247581 A CN 200910247581A CN 101927188 B CN101927188 B CN 101927188B
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Abstract
The invention relates to an ordered mesoporous organic metal Au (I) heterogeneous catalyst and a preparation method and application thereof. The method comprises the following steps of: mixing and precipitating Au(tht)Cl and (EtO)3Si(CH2)PPh2 to obtain organic metal Au (I) silane; adding phenyl bridged organosilane and a surfactant to perform copolycondensation; aging the obtained product and taking precipitate; and removing the surfactant by extraction. The prepared ordered mesoporous organic metal Au (I) heterogeneous catalyst has a specific surface area of between 700 and 900 m<2>/g, a highly ordered two-dimensional hexagonal mesoporous structure and aperture of between 2.5 and 3.2nm, can be used for hydration reaction of alkyne in a water medium and can be repeatedly used for multiple times. The invention fulfills the aims of uniform distribution of catalytic active sites, full contact between a substrate and an active centre, cycling of the catalyst and environment-friendly catalysis.
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 ordered mesoporous organic metal Au (I) [Au (I)-PPh
2-PMO (Ph)] preparation method and the application of cleaning alkynes hydration reaction in aqueous medium thereof of heterogeneous catalysis.
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 catalyst 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 (I) complex recently, homogeneous catalyst exists all the time and is difficult to reuse, be prone to cause heavy metal pollution and improve problems such as reaction cost.
Organo-metallic catalyst is immobilized to order mesoporous organosilicon (PMO) carrier; Can utilize the decentralization of the characteristics raising active sites of its bigger serface, regular pore passage structure; Because carrier framework itself is rich in the hydrophobicity that organic group (like methyl, ethyl, phenyl etc.) can improve carrier, helps organic reactant and in aqueous medium, adsorb and diffusion in addition to active sites.Therefore to the PMO carrier, become one of heat subject of research recent years with organic metal is immobilized.At present solid support method is mainly the back grafting, promptly through coordinate bond with Organometallic complex to the PMO carrier of modifying functional group.But the method causes the obstruction in duct easily, and active sites can't evenly distribute, thereby reactivity is lower.
Summary of the invention
Of the present inventionly be to provide a kind of ordered mesoporous organic metal Au (I) heterogeneous catalysis.
Another object of the present invention is to provide above-mentioned Preparation of catalysts method.
The present invention also provides above-mentioned Application of Catalyst.
Be to realize that above-mentioned purpose, preparation method comprise, with AuCl (tht) Cl with (EtO)
3Si (CH
2) PPh
2Mixed deposition obtains organic metal Au (I) silane; Add an amount of phenyl bridging organosilan and surfactant again and carry out copolycondensation, get deposition after the ageing, surfactant is removed in extraction.
Be specially, the preparation method of a kind of ordered mesoporous organic metal Au (I) heterogeneous catalysis comprises the following steps:
1) be 1.5: 1～1: 6 Aul (tht) Cl (thiophane chlorauride) and (EtO) with mol ratio
3Si (CH
2) PPh
2(2-(diphenylphosphine) ethyl triethoxysilane) is dissolved in organic solvent and mixing; The mixed reactant volume is concentrated the back add precipitating reagent; Sediment is leached, washs; Promptly obtain organic metal Au (I) silane (two-[2-(diphenylphosphine) ethyl triethoxysilane] chloraurides are represented with 2-DPPAu (I) TS);
2) be that surfactant concentration is that 0.02～0.04M, HCl concentration are the solution of 0.3～1M with surfactant, HCl and water mixed preparing, under 40～60 ℃ condition, mix;
Add phenyl bridging organosilan, pre-polymerization 15～30 minutes adds step 1) gained organic metal Au (I) silane again, mix and continue reaction 10～20 hours, and under 80～100 ℃ of conditions ageing 16～48h, get deposition;
The mol ratio of phenyl bridging organosilan and organic metal Au (I) silane is 5: 1～100: 1;
The mol ratio of the total content of silicon and surfactant is 1: 0.2～0.4 in phenyl bridging organosilan and organic metal Au (I) silane;
3) with step 2) products therefrom washing back extraction removes surfactant, obtains ordered mesoporous carbon/metal (I) heterogeneous catalysis.
In the step 1), said precipitating reagent is preferably n-hexane or benzinum; Organic solvent is CH
2Cl
2Or toluene, be preferably CH
2Cl
2
Add before the precipitating reagent, the mixed reactant volume is concentrated into 1/10～1/3.
Step 2) in, described surfactant is selected from Brij 76 or P 123.In the step 3), extraction is removed before the surfactant, and deposition 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 390～785g/L.
A kind of ordered mesoporous organic metal Au (I) heterogeneous catalysis that said method obtains, specific area is 700～900m
2/ g has the two-dimentional hexagonal mesoporous structure of high-sequential, and pore volume is 0.4～0.9cm
3/ g; The aperture is 2.5～3.2nm.
Above-mentioned ordered mesoporous organic metal Au (I) heterogeneous catalysis can be applicable to the cleaning alkynes hydration reaction in the aqueous medium, the hydration reaction of phenylacetylene for example, and this course of reaction can be represented by following formula:
At Au (I)-PPh
2Alkynes hydration reaction yield in-PMO (Ph) the heterogeneous catalysis catalysis aqueous medium can reach 91%, selectivity can reach 100%.Than commercialization Au (PPh
3) Cl homogeneous catalyst activity exceeds 65%, and still having catalytic efficiency preferably after reusing 4 times, the reaction yield reaches 82%.
The heterogeneous catalysis duct of the present invention's preparation is unobstructed, and active sites is evenly distributed, and reactivity is high, 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 recycle of catalyst again, finally realize the target of green catalysis.And the preparation method is simple, and cost is low.
In the alkynes hydration reaction in aqueous medium, by Au (the I)-PPh of copolycondensation method preparation
2-PMO (Ph) have than homogeneous catalyst higher catalytic activity.Its superior catalytic activity is mainly owing to following factors:
Au (the I)-PPh of 1, copolycondensation method preparation
2-PMO (Ph) has regular orderly two-dimentional hexagonal mesoporous structure, the comparatively pore-size distribution, bigger specific area of homogeneous.These characteristics have guaranteed that the even dispersion in catalytic activity site, substrate fully contact with the activated centre.
2, the PMO carrier is because of the organic backbone of himself has high hydrophobicity, and when making organic reaction in the catalysis aqueous medium, organic substrates more is prone to the duct diffusion, thereby improves catalytic efficiency.
3, the alkynes hydration reaction need add inorganic acid, and bigger specific area makes enrichment around the active sites of inorganic acid in carrier, and in addition, silica itself also has certain acidity, thereby has promoted the carrying out of reaction.
Description of drawings
Fig. 1 is embodiment 1 product A u (I)-PPh
2The little angle XRD figure of-PMO (Ph);
Fig. 2 applies mechanically the graph of a relation of number of times and yield for embodiment 1 gained catalyst.
The specific embodiment
Below in conjunction with accompanying drawing and specific embodiment content of the present invention is further specified
1) 0.1mmol AuCl (tht) Cl is dissolved in 10ml CH
2Cl
2In, add 0.2mmol (EtO) then
3Si (CH
2) PPh
2, fully stir 1h, by the time solution concentration to being about 1ml, adds 15ml hexane (C
6H
4), the white solid of acquisition with hexane (2 * 5ml) washed twice, product be organic metal Au (I) silane.
2) with 0.40g Brij 76 (C
18H
37EO
10) (0.56mmol), 18.69g H
2O and 1.31ml 37% dense HCl solution mix, and in the folder hot jacket, stir 12h under 50 ℃ of conditions, add 2.2mmol phenyl bridging organosilan (EtO) then
3Si (C
6H
4) Si (EtO)
3(being BTESB), treat BTESB pre-polymerization 20min after, 0.2mmol adds the resulting organic metal Au of step 1) (I) silane again, continues to stir 12h, ageing 24h under 100 ℃ of conditions obtains the white solid powder after filtration washing, the vacuum drying;
3) 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 720g/L.
Products therefrom is with Au (I)-PPh
2-PMO (Ph) expression.Little angle XRD figure is as shown in Figure 1.Show that it has order mesoporous structure.
Measure through ICP, wherein contain the gold dollar element.
1) 0.2mmol AuCl (tht) Cl is dissolved in 10ml CH
2Cl
2In, add 0.4mmol (EtO) then
3Si (CH
2) PPh
2, fully stir 1h, by the time solution concentration to being about 1ml, adds 15ml hexane (C
6H
4), the white solid of acquisition with hexane (2 * 5ml) washed twice, product be organic metal Au (I) silane.
2) with 0.35g Brij 76 (C
18H
37EO
10) (0.49mmol), 18.69g H
2O and 1.31mL 37% dense HCl mix, and in the folder hot jacket, stir 12h under 50 ℃ of conditions, add 2.3mmol phenyl bridging organosilan (EtO) then
3Si (C
6H
4) Si (EtO)
3(being BTES), treat BTES pre-polymerization 20min after, add 0.1mmol step 1) gained organic metal Au (I) silane again, continue to stir 12h, ageing 24h under 100 ℃ of conditions obtains the white solid powder after filtration washing, the vacuum drying;
3) 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: 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 590g/L.Products therefrom is with Au (I)-PPh
2-PMO (Ph) expression.
1) 0.3mmol Au (tht) Cl is dissolved in 10ml CH
2Cl
2In, add 0.6mmol (EtO) then
3Si (CH
2) PPh
2, fully stir 1h, by the time solution concentration to being about 2ml, adds 15ml hexane (C
6H
4), the white solid of acquisition with hexane (2 * 5ml) washed twice, product be organic metal Au (I) silane.
2) with 0.45g Brij 76 (C
18H
37EO
10) (0.63mmol), 18.69g H
2O and 1.31ml 37% dense HCl mix, and in the folder hot jacket, stir 12h under 50 ℃ of conditions, add the phenyl bridging organosilan (EtO) of 2.2mmol then
3Si (C
6H
4) Si (EtO)
3(being BTES), treat BTES pre-polymerization 20min after, add 0.2mmol step 1) gained organic metal Au (I) silane again, continue to stir 12h, ageing 24h under 100 ℃ of conditions obtains the white solid powder after filtration washing, the vacuum drying;
3) 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: 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 650g/L.Products therefrom is with Au (I)-PPh
2-PMO (Ph) expression.
By the product of BET method mensuration the foregoing description 1, Au (I)-PPh
2The structural parameters of-PMO (Ph) heterogeneous catalysis are listed in table 1:
| Sample | Specific area (m 2/g) | Pore volume (cm 3/g) | Average pore size (nm) |
| Au(I)-PPh 2-PMO(Ph) | 892 | 0.69 | 3.1 |
And Au as shown in Figure 1 (I)-PPh
2The little angle XRD figure of-PMO (Ph); Can find out from BET data and XRD figure, prepared heterogeneous catalysis all have orderly two-dimentional hexagonal mesoporous structure, pore-size distribution comparatively homogeneous, have bigger specific area.
With embodiment 1 resulting Au (I)-PPh
2The detailed process that-PMO (Ph) heterogeneous catalysis is used for the alkynes hydration reaction is following: add 0.250m mol phenylacetylene, 50.0 μ mol H at the 10ml round-bottomed flask that has reflux condensing tube
2SO
4, contain the catalyst of 10.0 μ mol Au (I); React 7h under 100 ℃ of conditions, products therefrom with the 10ml ethyl acetate extraction after, carry out product analysis by GC.
With not immobilized Au (PPh
3) the Cl catalyst is tester, active result such as table 2.
Table 2.Au (I)-PPh
2-PMO (Ph) and the catalytic activity table of homogeneous catalyst to alkynes hydration reaction in the aqueous medium:
| Catalysts | Conv.(％) | Sel.(％) | ?Yield(％) |
| Au(I)-PPh 2-PMO(Ph) | 26 | 100 | ?26 |
| Au(PPh 3)Cl | 91 | 100 | ?91 |
[0053]Data can be found out from table, under identical reaction condition, and Au (I)-PPh
2-PMO (Ph) heterogeneous catalysis is than Au (PPh
3) Cl has higher catalytic activity, conversion ratio exceeds 65%.
Remaining heterogeneous catalysis is with ethyl acetate, deionized water washing 2～4 times, and 60～80 ℃ of following vacuum drying are reused next time, apply mechanically experiment, and its catalytic activity is seen Fig. 2.
As can be seen from Figure 2, repeat to apply mechanically four times after, Au (I)-PPh
2-PMO (Ph) heterogeneous catalysis still has catalytic activity preferably, and efficiency of pcr product is 82%.
Claims (6)
1. an ordered mesoporous organic metal Au (I) heterogeneous catalysis is characterized in that, specific area is 700～900m
2/ g has the two-dimentional hexagonal mesoporous structure of high-sequential, and pore volume is 0.4～0.9cm
3/ g; The aperture is 2.5～3.2nm; The preparation method comprises the following steps:
1) with mol ratio be 1.5: 1～1: 6 Au (tht) Cl with (EtO)
3Si (CH
2) PPh
2Be dissolved in organic solvent and mixing, the mixed reactant volume concentrated the back add precipitating reagent, sediment is leached, washs, promptly obtain organic metal Au (I) silane; Said precipitating reagent is n-hexane or benzinum;
2) be that surfactant concentration is that 0.02～0.04M, HCl concentration are the solution of 0.5～1M with surfactant, HCl and water mixed preparing, under 40～60 ℃ condition, mix;
Add phenyl bridging organosilan, pre-polymerization 15～30min adds step 1) gained organic metal Au (I) silane again, mix and continue reaction 10～20h, and under 80～100 ℃ of conditions ageing 20～32h, get deposition;
The mol ratio of phenyl bridging organosilan and organic metal Au (I) silane is 5: 1～100: 1;
The mol ratio of the total content of silicon and surfactant is 1: 0.2～0.4 in phenyl bridging organosilan and organic metal Au (I) silane; Described surfactant is selected from Brij 76;
3) with step 2) products therefrom washing back extraction removes surfactant, obtains ordered mesoporous organic metal Au (I) heterogeneous catalysis.
2. the described ordered mesoporous organic metal Au of claim 1 (I) heterogeneous catalysis is characterized in that, organic solvent described in the step 1) is CH
2Cl
2Or toluene.
3. the described ordered mesoporous organic metal Au of claim 1 (I) heterogeneous catalysis is characterized in that: the step 3) extraction is removed before the surfactant, and deposition is carried out milled processed.
4. the described ordered mesoporous organic metal Au of claim 1 (I) heterogeneous catalysis is characterized in that, the step 3) method of extraction does, under 70～90 ℃ of conditions, extracts 20～32h with the mixed solution of hydrochloric acid and ethanol; 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 390～785g/L;
5. the described ordered mesoporous organic metal Au of claim 1 (I) heterogeneous catalysis is characterized in that, adds before the precipitating reagent in the step 1), and the mixed reactant volume is concentrated into 1/10～1/3.
6. each said ordered mesoporous organic metal Au (I) heterogeneous catalysis application aspect the alkynes hydration reaction in the catalysis aqueous medium of claim 1～5.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962059A (en) * | 2006-11-21 | 2007-05-16 | 上海师范大学 | Heterogenous organic metal catalyst with three-dimensional mesoporous structure, preparation method and application thereof |
| CN100998951A (en) * | 2006-12-30 | 2007-07-18 | 上海师范大学 | Three-dimensional meso-hole structure non-homogeneous organic metal compound-silicon hydrid catalyst and its preparation method and application |
| CN101214452A (en) * | 2007-12-28 | 2008-07-09 | 上海师范大学 | Mesopore structure non-homogeneous phase organo-metallic catalyst and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962059A (en) * | 2006-11-21 | 2007-05-16 | 上海师范大学 | Heterogenous organic metal catalyst with three-dimensional mesoporous structure, preparation method and application thereof |
| CN100998951A (en) * | 2006-12-30 | 2007-07-18 | 上海师范大学 | Three-dimensional meso-hole structure non-homogeneous organic metal compound-silicon hydrid catalyst and its preparation method and application |
| CN101214452A (en) * | 2007-12-28 | 2008-07-09 | 上海师范大学 | Mesopore structure non-homogeneous phase organo-metallic catalyst and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Hexing Li, et al.Water-medium barbier reaction over a mesoporous Pd(II) organometallic catalyst immobilized on the ethyl-bridged PMOs.《The Journal of Physical chemistry C》.2008,第112卷(第16期),6366-6371. * |
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