CN101875011A - TiO2 carrier-supported precious metal palladium as well as preparation method and application thereof - Google Patents
TiO2 carrier-supported precious metal palladium as well as preparation method and application thereof Download PDFInfo
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- CN101875011A CN101875011A CN2010101156659A CN201010115665A CN101875011A CN 101875011 A CN101875011 A CN 101875011A CN 2010101156659 A CN2010101156659 A CN 2010101156659A CN 201010115665 A CN201010115665 A CN 201010115665A CN 101875011 A CN101875011 A CN 101875011A
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- precious metal
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- palladium
- metal palladium
- tio
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Abstract
The invention relates to TiO2 carrier-supported precious metal palladium as well as a preparation method and application thereof. A supported type catalyst is obtained by regulating the pH value of water-soluble inorganic palladium salt, supporting to suspending P25TiO2 with an adsorptive method and filtering and roasting. The invention provides a new approach for supporting the palladium salt, improves the utilization rate of palladium and has low production cost and simple preparation method, and the obtained supported catalyst has high activity and higher economic benefit and can be recycled.
Description
Technical field
The present invention relates to a kind of novel load noble metal nano carrier material method.
Background technology
The Heck reaction is the reaction of the continuous C-C key of the important formation unsaturated double-bond of a class, has developed into a kind of increasingly extensive methodology of organic synthesis of using in the past more than 30 year gradually.This cross-coupling reaction is one of means important in the modern organic synthesis, it makes us can synthesize a series of aryl olefins, acetylene hydrocarbon compound efficiently, thereby is having important use to be worth aspect the preparation of household chemicals such as dyestuff, medicine, natural products, agricultural chemicals, Chinese cassia tree acid type spices and novel high polymer material.
For the Heck reaction, need the booster action of catalysis of transition metal palladium and organophosphorus ligand usually.Palladium catalyst is expensive and poisonous, service life is short, organic phosphine compound is hypertoxic to air-sensitive and can not reuse, and makes the Heck reaction not use deeply and widely industrial obtaining.Be carried on precious metals palladium catalyst inorganic in every way or the organic polymer carrier on, not only kept its catalytic activity but also be easy to separating and reclaiming.So how effectively loaded palladium catalyst becomes the research topic of a urgent need.
Summary of the invention
The objective of the invention is to: overcome the deficiency of above technology, a kind of TiO that can be recycled is provided
2The catalyst of supported palladium, the technology of the coupling of realization disactivation halogenated aryl hydrocarbon and alkene.
This out-phase palladium catalyst is by regulating the pH value of inorganic palladium saline solution, utilizing absorption method to load to P25 type TiO
2On, filter and roasting, obtain TiO
2The catalyst of supported palladium.
The preparation method of this out-phase palladium catalyst is at the PdCl that accurately regulates the pH value
2In the aqueous solution, add TiO
2, stirred 0.5～3 hour, suction filtration, 60 ℃ of dryings of vacuum 12 hours are ground, and under certain heating rate, are warming up to 500 ℃, and roasting 3 hours promptly gets TiO
2The catalyst of supported palladium.
This out-phase palladium catalyst is used and is mainly used in the Heck reaction, comprises purifying, separates each unit process.It is characterized in that in the DMF solvent under the condition of acetate or carbonate existence, halogeno-benzene and alkene were 100 ℃～140 ℃ reactions 10-24 hour, catalyst amount is 0.1% (molar percentage) of reactant.Reaction is cooled to room temperature after finishing, and the filtered and recycled different-phase catalyst recycles after the drying, and filtrate adds saturated aqueous common salt and ether, and extract and separate goes out organic facies, organic layer Na
2SO
4Drying, last silicagel column purifying promptly gets the Heck reactor product.Product yield is: 75%.Described acetate and carbonate are sylvite and sodium salt, optimization acid's sylvite.
The preparation of this different-phase catalyst is simple, and is active high, repeatedly reusable.After experimental results show that circulation 10 times, active significantly do not reduce.
The specific embodiment
The preparation of I, different-phase catalyst is got 50ml distilled water and is placed the 100ml beaker, adds 0.25g PdCl
2, stir.Drip the watery hydrochloric acid of 0.1mol/L then,, add 1.5g P25 type TiO until the pH of solution value about 1.5
2, continuing to stir after 3 hours, suction filtration is washed with distilled water in the filtrate with 1molL
-1AgNO
3Confirm no Cl
-, 60 ℃ of dry 12h of gained filter cake vacuum grind and to be placed in the Muffle furnace, with roasting 3h behind the 5 ℃/Min heating rate to 500 ℃, cool off naturally, promptly get this different-phase catalyst.
2, the heck coupling reaction of different-phase catalyst catalysis is existing is example with the preparation methyl cinnamate, and non-limiting examples is described below: in the 20ml reaction tube, add bromobenzene 0.054ml, methacrylate 0.053ml, different-phase catalyst catalyst 0.1g, potassium acetate 0.075g, DMF 2.5ml.Place 140 ℃ oil bath, magnetic agitation 24 hours.Reaction is cooled to room temperature after finishing, the filtered and recycled different-phase catalyst, and the filtrate static layering, extraction, organic facies saturated common salt water washing three times, further the silicagel column purifying promptly gets little yellow product methyl cinnamate, yield 75%.34 ℃-35 ℃ of product fusing points; δ
C(400MHz, CDCl
3) 51.6,117.9,127.9,128.3,128.9,129.2,130.3,134.4,144.8 and 167.3; M/z 162 (M
+, 65%), 161 (45), 131 (100), 117 (5), 103 (82) and 73 (91).
Claims (3)
1. TiO
2The preparation method of the different-phase catalyst of carrier load type precious metal palladium is characterized in that: at the PdCl that accurately regulates the pH value
2In the aqueous solution, add Degussa P25 type TiO
2, stirring 0.5～3 hour, suction filtration under certain heating rate, is warmed up to 500 ℃ of roastings 3 hours.
2. prepared TiO of the described method of claim 1
2The different-phase catalyst of carrier load type precious metal palladium.
3. described TiO of claim 1
2The different-phase catalyst of carrier load type precious metal palladium is used to prepare vinyl compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101156659A CN101875011A (en) | 2009-04-30 | 2010-01-29 | TiO2 carrier-supported precious metal palladium as well as preparation method and application thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910111604.2 | 2009-04-30 | ||
| CN200910111604 | 2009-04-30 | ||
| CN2010101156659A CN101875011A (en) | 2009-04-30 | 2010-01-29 | TiO2 carrier-supported precious metal palladium as well as preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101875011A true CN101875011A (en) | 2010-11-03 |
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ID=43017755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101156659A Pending CN101875011A (en) | 2009-04-30 | 2010-01-29 | TiO2 carrier-supported precious metal palladium as well as preparation method and application thereof |
Country Status (1)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6372347A (en) * | 1986-09-12 | 1988-04-02 | Central Res Inst Of Electric Power Ind | Oxidizing catalyst |
| CN1255405A (en) * | 1998-11-26 | 2000-06-07 | 北京大学 | Palladium catalyst with carrier of titanium oxide-alumina compound, and its preparing process and application |
| CN1709572A (en) * | 2005-04-29 | 2005-12-21 | 四川大学 | Aryl halide to olefin arylation carrying bimetallic catalyst, and its preparing method |
| CN1792433A (en) * | 2005-11-21 | 2006-06-28 | 厦门大学 | Microorganism reduced noble metal (S) modified TiO2 catalyst and its prepn. method |
-
2010
- 2010-01-29 CN CN2010101156659A patent/CN101875011A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6372347A (en) * | 1986-09-12 | 1988-04-02 | Central Res Inst Of Electric Power Ind | Oxidizing catalyst |
| CN1255405A (en) * | 1998-11-26 | 2000-06-07 | 北京大学 | Palladium catalyst with carrier of titanium oxide-alumina compound, and its preparing process and application |
| CN1709572A (en) * | 2005-04-29 | 2005-12-21 | 四川大学 | Aryl halide to olefin arylation carrying bimetallic catalyst, and its preparing method |
| CN1792433A (en) * | 2005-11-21 | 2006-06-28 | 厦门大学 | Microorganism reduced noble metal (S) modified TiO2 catalyst and its prepn. method |
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Application publication date: 20101103 |