CN104399490A - Method for preparing double-component supported type Pd-based nano catalyst - Google Patents
Method for preparing double-component supported type Pd-based nano catalyst Download PDFInfo
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- CN104399490A CN104399490A CN201410712982.7A CN201410712982A CN104399490A CN 104399490 A CN104399490 A CN 104399490A CN 201410712982 A CN201410712982 A CN 201410712982A CN 104399490 A CN104399490 A CN 104399490A
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Abstract
The invention relates to a method for preparing a double-component supported type Pd-based nano catalyst. The method comprises the following steps: 1) firstly, uniformly stirring glycerol and a specific surfactant in a certain ratio under the inert atmosphere, adding Pd metal precursor salt and a precursor solution of a second component into a mixed solution, heating to appointed temperature, keeping the temperature for a certain time, and cooling to room temperature; 2) uniformly mixing an obtained nano particle solution with a carrier, and performing ultrasonic treatment; 3) centrifuging, washing and drying the mixed solution; 4) performing roasting reduction on a product under the hydrogen atmosphere, thereby obtaining the double-component supported Pd-based nano catalyst. The double-component supported Pd-based nano catalyst prepared by using the method is not only simple in process, low in preparation cost, uniform in granular particle size distribution, wide in catalysis application range, but also wide in applicability and easy in large-scale preparation.
Description
Technical field
The preparation method of a kind of pair of component loading type Pd base nano-catalyst and catalytic applications thereof, particularly relate to a kind of two component loading type Pd-Mn, Pd-Co nanocatalyst, and the preparation method of two component loading type Pd base nano-catalysts for aspects such as the liquid phase oxidation reaction of the electrochemical oxidation reactions of alcohols, C-C coupling reaction, olefin hydrogenation, alcohols, hydrogen peroxide synthetic reaction, the hydrogenation-dechlorination reaction of aqueous phase alkenyl halide and the synthetic reactions of vinyl acetate.
Background technology
Carried noble metal nanocatalyst enjoys the extensive concern of numerous researchers of industrial quarters and scientific research circle due to its good catalytic performance, and commercial Application is extensive.
The loaded catalyst of Pd base nano particle becomes focus at present in the research of catalysis and fuel-cell catalyst, especially the Pd base nano particle of the many components of support type, such as PdAu nano particle starts rapid rise in recent years in the catalytic applications research of the synthesis of the electrochemical oxidation reactions of methyl alcohol, hydrogen peroxide, the reaction such as oxidation, the synthesis of vinyl acetate, the hydrogenation-dechlorination of aqueous phase alkenyl halide of alcohols.But up to now, the method preparing carried noble metal nano particle mainly concentrates on infusion process, coprecipitation, ion-exchange and precipitation reducing process.The active constituent particle diameter of loaded catalyst prepared by traditional preparation method, component often skewness and be difficult to regulation and control, and metal dispersity is low, content of metal is large, the shortcoming such as easily to reunite, production cost is high.The invention provides one and prepare two component loading type Pd base nano-catalyst, the method for especially two component PdCo, PdMn catalyst.Component, decentralization, particle diameter, the loading of the method controlled catalytic agent particle.
Summary of the invention
The object of this invention is to provide the preparation method of the two component Pd base nano-catalyst of a kind of simple efficient, that process is green support type, especially PdCo, PdMn nanocatalyst.
For achieving the above object, the technical solution used in the present invention is:
A preparation method for pair component loading type Pd base nano-catalyst,
1) under an inert atmosphere, glycerine and specific surfactant are stirred, ethylene glycol and surfactant with volume ratio for 200: 1-1: 1; Then add in mixed liquor by the solution of two kinds of metal precursor, be warming up to 200 degree of-250 degree, under agitation constant temperature 30 minutes-120 minutes, then naturally cools to room temperature;
2) the upper strata nanoparticles solution obtained is mixed with carrier, ultrasonic 30 minutes-4 hours, mixed solution is centrifugal, washing, dry;
3) product in a hydrogen atmosphere, 300-400 degree, roasting reduction, 1-5 hour, can obtain two component loading type Pd base nano-catalyst.
The first noble metal of described catalyst nano-particles is Pd; The second metal, this metal is Co, Mn, and form two component nano particle, the mass percent of Equations of The Second Kind metal in catalyst granules is 0-99.5%.
Described noble metal precursor body is palladium, palladium bichloride; Described the second metal precursor is cobalt acetate, cobalt chloride or manganese acetate, manganese nitrate.
Described surfactant can be PVP, polyethylene glycol.
Described inert atmosphere is nitrogen or argon gas.
Described high-temperature roasting for carry out roasting reduction in containing hydrogen atmosphere, temperature at 300-400 degree, time 1-5h.
Described catalyst carrier is Carbon Materials, such as CNT, Graphene or carbon black, and loading is 0.01-40% (mass fraction).
Even if catalyst prepared by the present invention is when metal loading is higher, the decentralization of metal nanoparticle is still fine, not only even particle size distribution, and noble metal loadings controls accurately simple, and the particle diameter of many component particle, composition are controlled; Described loaded with nano catalyst be the two component particle particle diameter of PdCo, PdMn all at below 10nm, particle size range is 1-50nm, and prepared nano particle diameter is even, and metal loading is 0.01-40% (mass fraction).Catalyst prepared by the present invention can be used for the electrochemical oxidation reactions of alcohols, C-C coupling reaction, olefin hydrogenation, the liquid phase oxidation reaction of alcohols, hydrogen peroxide synthetic reaction, the hydrogenation-dechlorination reaction of aqueous phase alkenyl halide and the synthetic reaction of vinyl acetate.
Compared with prior art, the present invention has following characteristics:
1. the present invention utilizes glycerine and Surfactants mixed system first to synthesize in the liquid phase and obtains particle diameter, the uniform nanoparticles solution of component, then with carrier mix and blend or ultrasonic, building-up process is easy to operate, without the need to special installation, process repeatability is high and be beneficial to amplification, easily realizes extensive preparation.
2. the metal loading of the loaded catalyst of preparation controls easily, to be especially applicable to high loadings.
3. the loaded catalyst of preparation can be applied in multiple reaction, and the catalytic reactions such as the electrochemical oxidation reactions of such as alcohols, the liquid phase oxidation reaction of alcohols, hydrogen peroxide synthetic reaction are applied widely.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the two component nanocatalyst of PdCo (10wt%) of the carbon black loadings of embodiment 1 gained;
Detailed description of the invention
Embodiment 1
Getting 120mL glycerine alcohol joins in there-necked flask, then adds 0.5g polyethylene glycol, under room temperature under an argon atmosphere, is uniformly mixed.The cobalt nitrate of 1mmol is dissolved in the water of 10mL, the palladium of 1mmol is dissolved in 10mL acetone soln, both solution is joined in the mixed solution of glycerine, then heat up and be heated to 120 DEG C, constant temperature 30 minutes, was continuing to be warming up to 220 DEG C, this constant temperature 30 minutes.React complete, naturally cool to room temperature.The solution getting nano particle mixes with carrier carbon black, ultrasonic 1h, centrifugation, and washing, 60 degree of vacuum drying.Then, under H2 atmosphere, 350 degree of roastings 2 hours, obtain the two component nanoparticle catalyst of loading type Pd Co, as Fig. 1.
Claims (8)
1. a preparation method for two component loading type Pd base nano-catalyst, is characterized in that:
1) under an inert atmosphere, glycerine and specific surfactant are stirred, ethylene glycol and surfactant with volume ratio for 200: 1-1: 1; Then add in mixed liquor by the solution of two kinds of metal precursor, Pd: the second metal ratio is 1: 1-1: 100, be warming up to 200 degree of-250 degree, under agitation constant temperature 30 minutes-120 minutes, then naturally cools to room temperature;
2) nanoparticles solution obtained is mixed with carrier, ultrasonic 30 minutes-4 hours, mixed solution is centrifugal, washing, dry;
3) product in a hydrogen atmosphere, 300-400 degree, roasting reduction, 1-5 hour, can obtain two component loading type Pd base nano-catalyst.
2. according to preparation method according to claim 1, it is characterized in that: the noble metal of the particle of this catalyst can be Pd; The second metal is Co, Mn, and the mass percent of the second metal in catalyst granules can be 0.5-99.5%.
3. according to preparation method according to claim 1, it is characterized in that: described noble metal precursor body is palladium, palladium bichloride; Described the second metal precursor is cobalt acetate, cobalt chloride or manganese acetate, manganese nitrate.
4. according to preparation method according to claim 1, it is characterized in that: described surfactant can be PVP, polyethylene glycol.
5. according to preparation method according to claim 1, it is characterized in that: described inert atmosphere is nitrogen or argon gas.
6. according to preparation method according to claim 1, it is characterized in that: high temperature carries out roasting reduction in containing hydrogen atmosphere, temperature at 300-400 degree, time 1-5h.
7. according to preparation method according to claim 1, it is characterized in that: this catalyst carrier is Carbon Materials, such as CNT, Graphene or carbon black, loading is 0.01-40% (mass fraction).
8. may be used for the electrochemical oxidation reactions of alcohols, C-C coupling reaction, olefin hydrogenation, the liquid phase oxidation reaction of alcohols, hydrogen peroxide synthetic reaction, the hydrogenation-dechlorination reaction of aqueous phase alkenyl halide and the synthetic reaction of vinyl acetate according to the catalyst of preparation described in claim 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126830A (en) * | 2015-07-22 | 2015-12-09 | 安徽理工大学 | Graphene-supported palladium catalyst, preparation method and application thereof |
| CN106732563A (en) * | 2017-01-24 | 2017-05-31 | 厦门大学 | A kind of preparation method of palladium carbon catalyst |
| CN107159202A (en) * | 2017-04-01 | 2017-09-15 | 浙江工业大学 | A kind of supported palladium catalyst of additive Mn and preparation method and application |
-
2014
- 2014-11-27 CN CN201410712982.7A patent/CN104399490A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126830A (en) * | 2015-07-22 | 2015-12-09 | 安徽理工大学 | Graphene-supported palladium catalyst, preparation method and application thereof |
| CN105126830B (en) * | 2015-07-22 | 2017-11-17 | 安徽理工大学 | A kind of graphene-supported palladium catalyst and its preparation method and application |
| CN106732563A (en) * | 2017-01-24 | 2017-05-31 | 厦门大学 | A kind of preparation method of palladium carbon catalyst |
| CN106732563B (en) * | 2017-01-24 | 2019-11-01 | 厦门大学 | A kind of preparation method of palladium carbon catalyst |
| CN107159202A (en) * | 2017-04-01 | 2017-09-15 | 浙江工业大学 | A kind of supported palladium catalyst of additive Mn and preparation method and application |
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