CN106732771A - A kind of hydrophobic nano silicon ball loads the preparation method of palladium-based catalyst - Google Patents
A kind of hydrophobic nano silicon ball loads the preparation method of palladium-based catalyst Download PDFInfo
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- CN106732771A CN106732771A CN201611169851.4A CN201611169851A CN106732771A CN 106732771 A CN106732771 A CN 106732771A CN 201611169851 A CN201611169851 A CN 201611169851A CN 106732771 A CN106732771 A CN 106732771A
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- palladium
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
Abstract
The present invention discloses the preparation method that a kind of hydrophobic nano silicon ball loads palladium-based catalyst, comprises the following steps：（One）, prepare with hydrophobic grouping and reduction group nano silicon spheres；（Two）, nano silicon spheres and palladium salt react obtain hydrophobic nano silicon ball load palladium-based catalyst.In preparation method of the invention, reducing agent is scheduled on carrier surface by Si C keyings, Pd ions only can just be reduced into Pd atoms in carrier surface in solution, the Pd atoms of generation are due to surface energy higher, therefore it is easy to assemble to form loaded nano palladium particle in carrier surface, overcome general chemistry reducing process be difficult to the problem that is carried out in carrier hydrophobic surface and, the preparation process pyroprocess that hydrogen reducing is not used generally, the organic group of carrier surface can be effectively maintained, compared with rear engrafting method of the prior art, the present invention can easily adjust the addition of organic group, so as to effectively control the hydrophobic property of catalyst surface.
Description
Technical field
The present invention relates to metal catalyst technology field, and in particular to a kind of hydrophobic nano silicon ball loads palladium-based catalyst
Preparation method.
Background technology
Hydrophobic type metal supported catalyst is often obtained in the organic reaction for be related to water in catalysis and is catalyzed than hydrophilic
The more preferable reaction effect of agent.For reactant be nonpolar or low pole substrate and product is the organic reaction such as alkane of polarity
Hydrocarbon is oxidized to reaction of alcohol, ketone etc., and the absorption of non-polar substrates and the desorption of polarity are more beneficial for due to hydrophobic surface
Therefore the conversion ratio and selectivity of the type reaction can be effectively improved.Therefore the preparation of hydrophobic type metal carrying catalyst is subject to
The extensive concern of people.Hydrophobic type gold-supported is prepared with hydrophobic type carrier using the customary preparation methods of metal supported catalyst
Often there are some problems in metal catalyst.For high-temperature hydrogen reduction method, due to hydrophobic organic groups often non-refractory because
This is easy to destroy the hydrophobicity of catalyst；It is hydrophobic due to carrier surface for the reduction of chemical reduction method such as boron hydride
Type, therefore polar metal ion is difficult close to metal surface.Therefore reduction is frequently experienced in the position away from metal surface, generation
Metallic particles be difficult firmly to be supported on carrier surface.A kind of feasible method is to prepare metal supported catalyst first, then
Silicic acid anhydride is carried out to it by the method for rear grafting.Had been reported that in document and prepare Ru/ by the method for dipping-hydrogen reducing
SiO2Catalyst, then flows back and carries out hydrophobic treatment to it in toluene with trim,ethylchlorosilane, obtains contact angle and reaches 137o's
Ru/SiO2Catalyst.But the method is difficult to the precise control catalyst hydrophobicity to be reached.
The content of the invention
It is an object of the invention to provide the preparation method that a kind of hydrophobic nano silicon ball loads palladium-based catalyst, by positive silicon
Sour methyl esters and the method for silane coupler copolymerization prepare the nano silicon spheres with hydrophobic grouping and reduction group, can adjust organic
The addition of group, and then efficiently control the hydrophobic property of catalyst surface.
The present invention realizes that the technical scheme that above-mentioned technical purpose is used is：A kind of hydrophobic nano silicon ball load palladium base catalysis
The preparation method of agent, comprises the following steps：
（One）, prepare with hydrophobic grouping and reduction group nano silicon spheres；
（Two）, nano silicon spheres and palladium salt react obtain hydrophobic nano silicon ball load palladium-based catalyst.
As a kind of further optimization of the preparation method of hydrophobic nano silicon ball load palladium-based catalyst of the invention：Step
（One）In the nano silicon spheres of middle preparation, hydrophobic grouping is that mass content is 0.1- containing 1-12 the alkane or aromatic hydrocarbons of carbon atom
25wt%；Reduction group is that, containing the 2-6 alkene of carbon atom, content is 0.1-10wt%.
As a kind of further optimization of the preparation method of hydrophobic nano silicon ball load palladium-based catalyst of the invention：It is described
Step（One）The specific preparation method of middle nano silicon spheres is：Surfactant and organic phase are compounded into solution A, in solution A
Add ammoniacal liquor formed microemulsion, in microemulsion be added dropwise methyl silicate, containing organic group silane coupling agent A and containing also former base
The mixed solution of group silane coupler B, stirs 4-48h, obtains solution B, then to adding ethanol demulsification, centrifugation, institute in solution B
Obtain solid and add alcohol reflux washing, repeated washing is centrifuged 3-5 times, 20-60 DEG C of vacuum drying obtains nano silicon spheres powder.
As a kind of further optimization of the preparation method of hydrophobic nano silicon ball load palladium-based catalyst of the invention：It is described
The ratio between amount of each component material is in solution B：Methyl silicate：Surfactant：Organic phase：H2O：NH3H2O：Silane coupler
A：Silane coupler B=1:1:（5-20）:（10-20）:1:(0.01-0.4):(0.05-0.2).
As a kind of further optimization of the preparation method of hydrophobic nano silicon ball load palladium-based catalyst of the invention：It is described
Cosurfactant is additionally added in solution A, cosurfactant is n-butanol.
As a kind of further optimization of the preparation method of hydrophobic nano silicon ball load palladium-based catalyst of the invention：It is described
Amount of alcohol added is during demulsification operation：2-20 times of silicon source molal weight, amount of alcohol added is during washing operation：Silicon source mole matter
5-50 times of amount, silicon source is referred to.
As a kind of further optimization of the preparation method of hydrophobic nano silicon ball load palladium-based catalyst of the invention：It is described
Surfactant is NPE（NP-7）；Organic phase is n-hexane, hexamethylene or toluene；Silane coupling A
Structural formula with silane coupler B is as follows：
。
As a kind of further optimization of the preparation method of hydrophobic nano silicon ball load palladium-based catalyst of the invention：It is described
Step（Two）Specific method be：Nano silicon spheres powder is distributed in the mixed solvent of water and organic solvent composition, 20-80 DEG C
When, stirring reaction 0.5-24h is then proceeded to the ethanol solution that Pd compounds are added dropwise in system under nitrogen protection, after reaction terminates
Centrifugation, is washed 3-5 times using the mixed solvent of water or water and organic solvent, and 20-80 DEG C of vacuum drying 6-48h obtains palladium base catalysis
Agent.
As a kind of further optimization of the preparation method of hydrophobic nano silicon ball load palladium-based catalyst of the invention：It is described
Organic solvent in mixed solvent is the one kind or any mixture in methyl alcohol, ethanol, normal propyl alcohol, tetrahydrofuran or acetone.
As a kind of further optimization of the preparation method of hydrophobic nano silicon ball load palladium-based catalyst of the invention：It is described
Pd compounds are palladium bichloride, palladium or palladium nitrate, and the consumption of Pd compounds is：Make Pd mass fractions in catalyst are finally obtained
It is 0.1-15wt%.
Beneficial effect
One, the preparation of hydrophobic nano silicon ball of the present invention load palladium-based catalyst are carried out by two steps, are prepared first with thin
Water base group and the nano silicon spheres of reduction group, then the nano silicon spheres and palladium salt of preparation react obtaining hydrophobic nano silicon
Ball loads palladium-based catalyst.Reducing agent is scheduled on carrier surface by the process by Si-C keyings, and Pd ions are only being carried in solution
Body surface face can just be reduced into Pd atoms, the Pd atoms of generation due to surface higher can, therefore be easy in carrier table
Face assembles to form loaded nano palladium particle, overcomes the difficulty that general chemistry reducing process is difficult to be carried out in carrier hydrophobic surface
Topic.On the other hand, the preparation process pyroprocess that hydrogen reducing is not used generally, the organic group of carrier surface can be obtained
It is effectively maintained；
Secondly, in preparation method of the invention, the nano silicon spheres with hydrophobic grouping and reduction group are by methyl silicate
Prepared by the method with silane coupler copolymerization, compared with rear engrafting method of the prior art, the present invention can be adjusted easily
The addition of organic group, so as to effectively control the hydrophobic property of catalyst surface；
Thirdly, in preparation method of the invention, the reduction group for using is alkene, crucial in Wacker olefin carbonylations
Step is Pd2+Alkenyl is oxidized to carbonyl under water existence condition, and is reduced into zeroth order Pd in itself, therefore in water existence condition
Lower alkene can regard Pd as2+Reducing agent, and the alkoxy silane containing alkene is common silane coupling reagent, and raw material is easy
, and alkene is at typical condition more than other conventional reducing agent stabilizations, therefore the carrier for preparing has stability very high,
Harsh preservation condition need not be compared.
Brief description of the drawings
Fig. 1 is the electromicroscopic photograph of the catalyst that embodiment 21 is prepared in the present invention；
Fig. 2 is the water contact angle picture of the catalyst that embodiment 21 is prepared in the present invention.
Specific embodiment
Technical scheme is described further with specific embodiment below in conjunction with the accompanying drawings：
Embodiment 1
(1) NP-7, n-butanol and hexamethylene are stirred at room temperature lower being well mixed and obtain clear solution A,
(2) to be dropwise added dropwise in above-mentioned clear solution ammoniacal liquor formed microemulsion；
(3) 5.21g methyl silicates and phenyltrimethoxysila,e, VTES is well mixed to form mixing
Solution.It is stirred vigorously down, mixed solution is added dropwise in microemulsion.The reaction solution for ultimately forming（Solution B）Middle each component material
The ratio between amount be, methyl silicate：NP-7：N-butanol：Hexamethylene：H2O：NH3H2O：Phenyltrimethoxysila,e：Vinyl three
Ethyoxyl silicon=1:1:4.5:15:16:1:0.2:0.05 and at room temperature continue stir 12h.
(4) after adding the demulsification of 10mL ethanol, 50mL alcohol refluxs wash 3 removal surfactants, 50 DEG C of vacuum drying
The nano silicon spheres containing organic group and reduction group are obtained afterwards, and water contact angle is 156 °.
Embodiment 2-12
Change the addition of n-butanol, hexamethylene, water, phenyltrimethoxysila,e and VTES in embodiment 1
Amount, other conditions are constant to prepare dewatering nano silicon ball, as a result see the table below：
。
Embodiment 13-16
The amount of ethanol and the backflow ethanol of being demulsified in last handling process in change embodiment 1, and do not allow temperature to dry, other conditions
Constant preparation nano silicon spheres, as a result see the table below.From result, post-treatment condition is to preparing the hydrophobicity of material without obvious shadow
Ring.
。
Embodiment 17
No. 1 carrier 1.00g prepared in embodiment 1 is dispersed in the mixed solvent of 50mL second alcohol and waters.Wherein second alcohol and water
Volume ratio is 1:1.It is the palladium bichloride diluted hydrochloric acid aqueous solution of 0.5wt% to palladium mass fraction is added in above-mentioned system under nitrogen protection
10.6g, and continue to stir 8 h.Reaction washs solid 5 times after terminating through centrifugation, ethanol and water mixed solvent, vacuum 50oC is dried
12h obtains the palladium catalyst of nano silicon spheres load, and hydrophobic angle is 151o, labeled as Pd-1.
Embodiment 18-25
Change carrier, the composition of reaction dissolvent, the condition such as palladium source category and quality, other conditions and catalyst system in embodiment 17
With embodiment 17, reaction result see the table below standby process：
。
Embodiment 26-30
Ethanol water mixed solvent in embodiment 17 is changed to water and other organic solvents, other conditions with embodiment 17, as a result
Following table：
。
Embodiment 31-36
Using styrene, atmospheric hydrogenation generates the hydrogenation that ethylbenzene is used for investigating prepared catalyst as model reaction at room temperature
Can and be contrasted with business Pd/C catalyst.
0.20molL-1Palladium catalyst is added in the ethanol water of styrene, palladium addition ensures palladium and styrene mole
Than being 1:1000.Reaction system uses nitrogen displacement first, is then replaced with hydrogen, is finally passed through atmospheric hydrogen reaction 30min.Instead
Should result see the table below：
。
The above, is only presently preferred embodiments of the present invention, and any formal limitation is not made to the present invention, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any to be familiar with this professional technology people
Member, without departing from the scope of the present invention, when using the technology contents of the disclosure above make out it is a little change or repair
The Equivalent embodiments for equivalent variations are adornd, as long as being without departing from technical solution of the present invention content, according to technical spirit of the invention
Any simple modification, equivalent variations and the modification made to above example, still fall within the range of technical solution of the present invention.
Claims (10)
1. a kind of hydrophobic nano silicon ball loads the preparation method of palladium-based catalyst, it is characterised in that comprise the following steps：
（One）, prepare with hydrophobic grouping and reduction group nano silicon spheres；
（Two）, nano silicon spheres and palladium salt react obtain hydrophobic nano silicon ball load palladium-based catalyst.
2. hydrophobic nano silicon ball as claimed in claim 1 loads the preparation method of palladium-based catalyst, it is characterised in that：Step
（One）In the nano silicon spheres of middle preparation, hydrophobic grouping is that mass content is 0.1- containing 1-12 the alkane or aromatic hydrocarbons of carbon atom
25wt%；Reduction group is that, containing the 2-6 alkene of carbon atom, content is 0.1-10wt%.
3. hydrophobic nano silicon ball as claimed in claim 1 loads the preparation method of palladium-based catalyst, it is characterised in that：The step
Suddenly（One）The specific preparation method of middle nano silicon spheres is：Surfactant and organic phase are compounded into solution A, are added in solution A
Enter ammoniacal liquor formed microemulsion, in microemulsion be added dropwise methyl silicate, containing organic group silane coupling agent A and containing reduction group
The mixed solution of silane coupler B, stirs 4-48h, obtains solution B, then to the demulsification of addition ethanol, centrifugation, gained in solution B
Solid adds alcohol reflux washing, repeated washing is centrifuged 3-5 times, and 20-60 DEG C of vacuum drying obtains nano silicon spheres powder.
4. the preparation method of palladium-based catalyst is loaded such as claim 3 hydrophobic nano silicon ball, it is characterised in that：The solution B
The ratio between amount of middle each component material is：Methyl silicate：Surfactant：Organic phase：H2O：NH3H2O：Silane coupling A：Silicon
Alkane coupling agent B=1:1:（5-20）:（10-20）:1:(0.01-0.4):(0.05-0.2).
5. the preparation method of palladium-based catalyst is loaded such as claim 3 hydrophobic nano silicon ball, it is characterised in that：The solution A
In be additionally added cosurfactant, cosurfactant is n-butanol.
6. the preparation method of palladium-based catalyst is loaded such as claim 3 hydrophobic nano silicon ball, it is characterised in that：The demulsification behaviour
Amount of alcohol added is when making：2-20 times of silicon source molal weight, amount of alcohol added is during washing operation：The 5- of silicon source molal weight
50 times.
7. the preparation method of palladium-based catalyst is loaded such as claim 3 hydrophobic nano silicon ball, it is characterised in that：Live on the surface
Property agent be NPE（NP-7）；Organic phase is n-hexane, hexamethylene or toluene；Silane coupling A and silane
The structural formula of coupling agent B is as follows：
。
8. hydrophobic nano silicon ball as claimed in claim 1 loads the preparation method of palladium-based catalyst, it is characterised in that：The step
Suddenly（Two）Specific method be：Nano silicon spheres powder is distributed in the mixed solvent of water and organic solvent composition, 20-80 DEG C
When, stirring reaction 0.5-24h is then proceeded to the ethanol solution that Pd compounds are added dropwise in system under nitrogen protection, after reaction terminates
Centrifugation, is washed 3-5 times using the mixed solvent of water or water and organic solvent, and 20-80 DEG C of vacuum drying 6-48h obtains palladium base catalysis
Agent.
9. hydrophobic nano silicon ball as claimed in claim 8 loads the preparation method of palladium-based catalyst, it is characterised in that：It is described mixed
Organic solvent in bonding solvent is the one kind or any mixture in methyl alcohol, ethanol, normal propyl alcohol, tetrahydrofuran or acetone.
10. hydrophobic nano silicon ball as claimed in claim 8 loads the preparation method of palladium-based catalyst, it is characterised in that：It is described
Pd compounds are palladium bichloride, palladium or palladium nitrate, and the consumption of Pd compounds is：Make Pd mass fractions in catalyst are finally obtained
It is 0.1-15wt%.
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| CN109701538A (en) * | 2018-12-28 | 2019-05-03 | 华东理工大学 | A kind of synthetic method and its application of nano silicon spheres |
| CN112973788A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Process for catalytic selective oxidation of hydrocarbons |
| CN112973787A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Supported material and preparation method thereof |
| CN115739095A (en) * | 2022-11-16 | 2023-03-07 | 合肥飞木生物科技有限公司 | Preparation method and application of Ni-Co @ C carbon core-shell hydrophobic nanoparticle catalyst |
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