CN109772452A - A kind of superfine nano palladium catalyst and preparation method thereof based on high-molecular gel network - Google Patents
A kind of superfine nano palladium catalyst and preparation method thereof based on high-molecular gel network Download PDFInfo
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- CN109772452A CN109772452A CN201910019051.1A CN201910019051A CN109772452A CN 109772452 A CN109772452 A CN 109772452A CN 201910019051 A CN201910019051 A CN 201910019051A CN 109772452 A CN109772452 A CN 109772452A
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Abstract
The invention discloses a kind of superfine nano palladium catalyst and preparation method thereof based on high-molecular gel network.The catalyst is the catalyst of rich alkynes macromolecule loading, its palladium is uniformly fixed in the crosslinking points for the gel network that rich alkynes macromolecule is formed, and preparation method includes the following steps: palladium presoma being added in rich alkynes Polymer Solution, 15~20h is stood under the conditions of 10 DEG C~40 DEG C and obtains stable gel rubber material, then up to palladium catalyst after reducing agent reduction, washing, drying.Pd is effectively dispersed in gel network by the cross-linked network in the palladium catalyst, is allowed to catalytic activity and selectivity is more preferable, and stablize to air and steam.Should and preparation method is simple, mild condition, is easy to scale synthesis.
Description
Technical field
The present invention relates to palladium catalysts, and in particular to a kind of superfine nano palladium catalyst based on high-molecular gel network and
Preparation method.
Background technique
Noble metal catalyst is extremely important in modern industry, and many chemicals production links require gold
Metal catalyst.But with the development of modern industry, the demand of noble metal is growing, and the reserves of Precious Metals Resources are limited on the earth
Since Precious Metals Resources are rare and expensive.Traditional homogeneous catalyst, although having good catalytic activity and selection
Property, but be difficult to separate and recover.By taking Pd base catalyst as an example, in pharmaceutical chemistry, field of fine chemical, often with Pd (PPh3)4Etc. phosphorous
The catalyst of ligand realizes the production of chemicals.The recycling of catalyst, purification process is cumbersome and needs to consume a large amount of solvent, consumption
Take human and material resources, and ligand needed for catalyst itself is not also cheap, greatly limits the industrial application of this kind of catalyst.Cause
This, develop it is a kind of cheap, be readily synthesized and have and have a good application prospect with the nanocatalyst that homogeneous catalyst matches in excellence or beauty.
With the development of nanotechnology, nanoscale noble metal catalyst possesses good catalytic activity.With noble metal
Size reduction (forming nanometer even sub-nanometer particle), its specific surface area, surface defect, the fold of nano material increase, can
Significantly improve the activity and selectivity of catalyst.However, the nanoparticle of small size is prone to roll into a ball in catalytic reaction process
Poly- or loss, causes catalytic performance to decline.To solve the above problems, the research hotspot in the field, which is mainly concentrated in, passes through choosing
Select more suitable carrier and preparation method, and it is more excellent and have height to combine the modes such as addition auxiliary agent to design and prepare performance
The loaded noble metal catalyst of stability.But the preparation of this kind of catalyst generally requires the microstructure of carrier very high, conjunction
, low yield also relatively cumbersome at step, cost are also relatively high.
Summary of the invention
An object of the present invention is to provide for a kind of superfine nano palladium catalyst based on high-molecular gel network, should
Pd is effectively dispersed in gel network by the cross-linked network in palladium catalyst, is allowed to catalytic activity and selectivity is more preferable,
And air and steam are stablized.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of superfine nano palladium catalyst based on high-molecular gel network, the catalyst are rich alkynes macromolecule loadings
Catalyst, palladium are uniformly fixed in the crosslinking points for the gel network that rich alkynes macromolecule is formed.
Another object of the present invention is then to provide the above-mentioned superfine nano palladium catalyst system based on high-molecular gel network
Preparation Method, the preparation method is simple, mild condition, is easy to scale synthesis.
Specifically, before above-mentioned palladium catalyst preparation method is the following steps are included: be added palladium in rich alkynes Polymer Solution
Body is driven, 15~20h is stood under the conditions of 10 DEG C~40 DEG C and obtains stable gel rubber material, then through reducing agent reduction, washing, drying
Afterwards up to palladium catalyst.
Wherein, the macromolecule in the rich alkynes Polymer Solution is the modified polyvinyl alcohol of ynamine, and alkynyl grafting rate is 20
~80%；The concentration of the richness alkynes Polymer Solution is 30~100mg/mL, and solvent is water, N, N '-dimethyl formamide, diformazan
Sulfoxide, tetrahydrofuran, any one or more in 1,4- dioxane, in acetonitrile.
Specifically, the rich alkynes macromolecule preparation step is as follows: using N, the hydroxyl of N '-carbonyl dimidazoles activated polyethylene alcohol
Base, then reacted with ynamine, rich alkynes macromolecule can be arrived；Wherein, polyvinyl alcohol, N, the molar ratio of N '-carbonyl dimidazoles and ynamine
For 1:0.2~1.5:0.2~1.6.
As a preferred embodiment, the palladium presoma is sodium tetrachloropallate, tetrachloro-palladium potassium chlorate, palladium chloride, palladium acetate, three
Any one in fluoroacetic acid palladium, palladium nitrate.
As a preferred embodiment, the reducing agent is sodium borohydride, in hydrazine hydrate, sodium citrate, sodium ascorbate
It is one or more.
As a preferred embodiment, palladium presoma and the rich high molecular mass ratio of alkynes are 1:5~20.
As a preferred embodiment, the molar ratio of palladium presoma and reducing agent is 1:4~40.
Compared with prior art, the invention has the following advantages:
(1) rich alkynes macromolecule of the invention can gradually polymerize in the presence of Pd, and formation cross-linked network ultimately forms solidifying
Glue；Pd can be effectively dispersed in gel network by Pd meeting and polymer complex, cross-linked network simultaneously.Due to cross-linked network
Confinement effect, using Pd nano particle (PdNPs) uniform particle sizes of reducing agent preparation, size is in 1~4nm.
(2) Pd presoma is directly added to mixing containing rich alkynes macromolecule organic solvent or water and organic solvent by the present invention
It closes in solution, at 10 DEG C~40 DEG C, is not necessarily to other any catalyst, solution can form gel within a very short time.Solidifying
During gelatinization, Pd polymerize the alkynes in macromolecular chain, can be coordinated with Pd while forming crosslinking points, keep Pd equal
Even is fixed in gel network, and Pd reunites when can effectively avoid reduction preparation PdNPs, and effectively that PdNPs is immobilized
In macromolecule.The Pd catalyst obtained after drying process stablizes air and steam.
(3) preparation method of the present invention is simple, mild condition, is easy to scale synthesis, and the catalysis is lived with good catalysis
Property.
Detailed description of the invention
Fig. 1 is gel sample.
Fig. 2 is the sample of freeze-drying.
Fig. 3 is (0) -1 gel of Pd (II) -1 and Pd.
Fig. 4 is (0) -1 catalyst of Pd.
Fig. 5 is the SEM of (0) -1 catalyst of Pd.
Fig. 6 is the TEM of (0) -1 catalyst of Pd.
Fig. 7 is the SEM of (0) -2 catalyst of Pd.
Fig. 8 is the TEM of (0) -2 catalyst of Pd.
Specific embodiment
The invention will be further described with embodiment for explanation with reference to the accompanying drawing, and mode of the invention includes but not only limits
In following embodiment.
Any feature disclosed in this specification unless specifically stated can be equivalent or with similar purpose by other
Alternative features are replaced.That is, unless specifically stated, each feature is an example in a series of equivalent or similar characteristics
?.
Embodiment 1:
It is weighed into 400mg polyvinyl alcohol in reaction flask, 10mL DMF, heating stirring dissolution is added；Reaction solution is cooled to room
1.22g N is added portionwise after temperature, 413mg propargylamine is added after 3h is stirred at room temperature in N- carbonyl dimidazoles, continues to add after stirring 16h
Enter 4mL ammonium hydroxide quenching reaction；As shown in Fig. 2, precipitating obtains grafting rate by instilling in dehydrated alcohol after the concentration of gained mixed liquor
40% alkynyl functionalized polyvinyl alcohol (Alkyne-PVA), obtains light yellow product after vacuum drying.To the light yellow product into
Row detection obtains the infrared figure of alkynyl functionalized polyvinyl alcohol as shown in Figure 1.
5mg sodium tetrachloropallate is taken, 50 μ L deionized waters and 100 μ L DMF is dissolved in, obtains in mixed solution, thereto quickly
The above-mentioned Alkyne-PVA solution (solution concentration 50mg/mL) being prepared of 1mL is instilled, is uniformly mixed, stands and Pd is made
(II) -1 gel, as shown in Fig. 3 left figure；After being washed with deionized repeatedly, 5mL is added and contains the water-soluble of 6.5mg sodium borohydride
(0) -1 gel of Pd of black is sufficiently made in liquid after reaction, as shown in Fig. 3 right figure, repeatedly after washing, in 20mL deionized water
It impregnates for 24 hours, is freeze-dried (0) -1 catalyst of Pd that black is made, as shown in Figure 4.
(0) -1 catalyst of Pd obtained is detected, obtains the SEM of (0) -1 catalyst of Pd as shown in Figure 5 and as schemed
The TEM of (0) -1 catalyst of Pd shown in 6.By Fig. 5 it will be evident that (0) -1 catalyst of Pd is porous material, Fig. 6 can be obvious
Find out that the Pd nano particle diameter in gel rubber material between 1~4nm, and is uniformly dispersed.
Embodiment 2:
It is weighed into 400mg polyvinyl alcohol in reaction flask, 10mL DMF, heating stirring dissolution is added；Reaction solution is cooled to room
1.22g N is added portionwise after temperature, 413mg propargylamine is added after 3h is stirred at room temperature in N- carbonyl dimidazoles, continues to add after stirring 16h
Enter 4mL ammonium hydroxide quenching reaction；As shown in Fig. 2, precipitating obtains grafting rate by instilling in dehydrated alcohol after the concentration of gained mixed liquor
40% alkynyl functionalized polyvinyl alcohol (Alkyne-PVA), obtains light yellow product after vacuum drying.To the light yellow product into
Row detection obtains the infrared figure of alkynyl functionalized polyvinyl alcohol as shown in Figure 1.
10mg sodium tetrachloropallate is taken, is dissolved in 50 μ L deionized waters and 100 μ L DMF mixed solutions, is quickly instilled thereto
The above-mentioned Alkyne-PVA solution (solution concentration 50mg/mL) being prepared of 1mL is uniformly mixed, and stands and Pd (II) -2 is made
Gel.After being washed with deionized repeatedly, the aqueous solution that 5mL contains 13mg sodium borohydride is added, black sufficiently is made after reaction
(0) -2 gel of Pd, repeatedly washing after, impregnated in 20mL deionized water for 24 hours, be freeze-dried be made black Pd (0) -2 urge
Agent.
(0) -1 catalyst of Pd obtained is detected, obtains the SEM of (0) -2 catalyst of Pd as shown in Figure 7 and as schemed
The TEM of (0) -2 catalyst of Pd shown in 8.It can be seen that obtained (0) -2 catalyst of Pd is porous material, Pd nano particle
Partial size is between 1~4nm and is evenly distributed, also, compared with Example 1, and pattern, distribution are consistent.
Embodiment 3
It is weighed into 800mg polyvinyl alcohol in reaction flask, 20mL DMF, heating stirring dissolution is added；Reaction solution is cooled to room
486mg N is added portionwise after temperature, 83mg propargylamine is added after 3h is stirred at room temperature in N- carbonyl dimidazoles, continues to be added after stirring 16h
4mL ammonium hydroxide quenching reaction；It will be instilled in dehydrated alcohol after the concentration of gained mixed liquor, precipitating obtains 19% alkynyl functionalization of grafting rate
Polyvinyl alcohol (Alkyne-PVA), obtains light yellow product after vacuum drying.
8.86mg palladium chloride is taken, is dissolved in 100 μ L deionized waters and 200 μ L DMF mixed solutions, it is above-mentioned quickly to instill 2mL
In the solution of the made Alkyne-PVA of method, solution concentration 50mg/mL.It is uniformly mixed, stands and Pd (II) gel is made.It spends
After ion water washing is multiple, the aqueous solution that 7mL contains 19mg sodium borohydride is added, the Pd (0) that black is sufficiently made after reaction is solidifying
Glue repeatedly after washing, impregnates for 24 hours in 30mL deionized water, is freeze-dried Pd (0) catalyst that black is made.
Embodiment 4
It is weighed into 800mg polyvinyl alcohol in reaction flask, 20mL DMF, heating stirring dissolution is added；Reaction solution is cooled to room
486mg N is added portionwise after temperature, 83mg propargylamine is added after 3h is stirred at room temperature in N- carbonyl dimidazoles, continues to be added after stirring 16h
4mL ammonium hydroxide quenching reaction；It will be instilled in dehydrated alcohol after the concentration of gained mixed liquor, precipitating obtains 19% alkynyl functionalization of grafting rate
Polyvinyl alcohol (Alkyne-PVA), obtains light yellow product after vacuum drying.
7.5mg sodium tetrachloropallate is taken, is dissolved in 50 μ L deionized waters and 100 μ L DMF mixed solutions, is quickly instilled on 1mL
In the solution for stating the made Alkyne-PVA of method, solution concentration 100mg/mL is uniformly mixed, and stands and Pd (II) gel is made.
After being washed with deionized repeatedly, the aqueous solution that 10mL contains 225mg sodium citrate is added, black is made after heating sufficiently reaction
Pd (0) gel, repeatedly washing after, impregnated in 20mL deionized water for 24 hours, be freeze-dried be made black Pd (0) catalyst.
Can clearly be learnt by above embodiments, palladium catalyst grain diameter of the invention uniformly, size between 1~4nm,
Also, Pd presoma is directly added in the mixed solution containing rich alkynes macromolecule organic solvent or water and organic solvent by it,
At 10 DEG C~40 DEG C, other any catalyst are not necessarily to, solution can form gel within a very short time；In the process of gelation
In, Pd polymerize the alkynes in macromolecular chain, can be coordinated with Pd while forming crosslinking points, be fixed on Pd uniformly
In gel network, Pd reunites when avoiding reduction preparation PdNPs, effectively that PdNPs is immobilized in macromolecule.It is prepared
Method is simple, mild condition, is easy to scale synthesis, can be applicable.
Above-described embodiment is only the preferred embodiment of the present invention, should not be taken to limit protection scope of the present invention, but
It is all in body design thought of the invention and mentally make have no the change of essential meaning or polishing, the technology solved
Problem is still consistent with the present invention, should all be included within protection scope of the present invention.
Claims (9)
1. a kind of superfine nano palladium catalyst based on high-molecular gel network, which is characterized in that the catalyst is that rich alkynes is high
The catalyst of molecule load, palladium are uniformly fixed in the crosslinking points for the gel network that rich alkynes macromolecule is formed.
2. a kind of preparation method of superfine nano palladium catalyst described in claim 1, which comprises the following steps:
Palladium presoma is added in rich alkynes Polymer Solution, 15~20h is stood under the conditions of 10 DEG C~40 DEG C and obtains stable gel material
Material, then up to palladium catalyst after reducing agent reduction, washing, drying.
3. the preparation method of superfine nano palladium catalyst according to claim 2, which is characterized in that the richness alkynes macromolecule
Macromolecule in solution is the modified polyvinyl alcohol of ynamine, and alkynyl grafting rate is 20~80%.
4. the preparation method of superfine nano palladium catalyst according to claim 3, which is characterized in that the richness alkynes macromolecule
The concentration of solution is 30~100mg/mL, and solvent is water, N, N '-dimethyl formamide, dimethyl sulfoxide, tetrahydrofuran, Isosorbide-5-Nitrae-two
Any one or more in six ring of oxygen, in acetonitrile.
5. the preparation method of superfine nano palladium catalyst according to claim 4, which is characterized in that the richness alkynes macromolecule
Preparation step is as follows: using N, the hydroxyl of N '-carbonyl dimidazoles activated polyethylene alcohol, then reacts with ynamine, can arrive rich alkynes high score
Son；Wherein, the molar ratio of polyvinyl alcohol, N, N '-carbonyl dimidazoles and ynamine is 1:0.2~1.5:0.2~1.6.
6. according to the preparation method of superfine nano palladium catalyst described in claim 3~5 any one, which is characterized in that institute
It is any one in sodium tetrachloropallate, tetrachloro-palladium potassium chlorate, palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate for stating palladium presoma
Kind.
7. the preparation method of superfine nano palladium catalyst according to claim 6, which is characterized in that the reducing agent is boron
One of sodium hydride, hydrazine hydrate, sodium citrate, sodium ascorbate are a variety of.
8. the preparation method of superfine nano palladium catalyst according to claim 7, which is characterized in that palladium presoma and rich alkynes
High molecular mass ratio is 1:5~20.
9. the preparation method of superfine nano palladium catalyst according to claim 8, which is characterized in that palladium presoma and reduction
The molar ratio of agent is 1:4~40.
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| CN114540834A (en) * | 2022-02-22 | 2022-05-27 | 中国工程物理研究院材料研究所 | MXene-based catalyst and preparation method and application thereof |
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| CN114540834A (en) * | 2022-02-22 | 2022-05-27 | 中国工程物理研究院材料研究所 | MXene-based catalyst and preparation method and application thereof |
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Application publication date: 20190521 |