CN106513052A - Preparation method of organic modified kaolin-loaded nano-palladium catalyst - Google Patents
Preparation method of organic modified kaolin-loaded nano-palladium catalyst Download PDFInfo
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- CN106513052A CN106513052A CN201611073313.5A CN201611073313A CN106513052A CN 106513052 A CN106513052 A CN 106513052A CN 201611073313 A CN201611073313 A CN 201611073313A CN 106513052 A CN106513052 A CN 106513052A
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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Abstract
The invention discloses a preparation method of an organic modified kaolin-loaded nano-palladium catalyst. The preparation method comprises dissolving raw kaolin and an organic modifying agent in a solvent, carrying out stirring at the room temperature, carrying out centrifugation, washing the precipitates three times by n-hexane, carrying out vacuum drying to obtain organic modified kaolin, adding the organic modified kaolin into an organic solvent, carrying out continuous stirring at the room temperature, adding a palladium chloride aqueous solution and an amino acid ligand into the mixture drop by drop along with continuous stirring to obtain a mixed solution, adding an alkaline solution into the mixed solution, adjusting solution pH to 7, then adding a reductant into the solution in batches, carrying out standing, carrying out centrifugalization precipitation, washing the precipitates orderly through distilled water and ethanol, and carrying out air drying to obtain the organic modified kaolin-loaded nano-palladium catalyst. The catalyst can stably carry the nano-palladium particles so that the heterogeneous organic modified kaolin-loaded nano-palladium catalyst has a high loading capacity, stable catalytic performances and strong applicability.
Description
Technical field
The present invention relates to a kind of method for preparing loaded nanometer palladium catalyst, and in particular to a kind of organically-modified Kaolin is born
The preparation method of nano Pd catalyst is carried, belongs to supported nano-gold metal catalyst preparing technical field.
Background technology
In recent years, supported nano-gold metal catalyst, especially Technique of Nano Pd, Au catalyst, are demonstrate,proved in many organic reactions
Bright is the heterogeneous catalysis of high selectivity.For example, the oxidation reaction of alcohols and aldehydes, the epoxidation reaction of propylene, acetylene
Hydrochlorination and carbon carbon coupling reaction.Common loaded nanometer palladium catalyst has：The palladium catalyst of active C load and in the recent period
The carbon nanotube loaded palladium catalyst of report；The palladium catalyst of macromolecule loading；The palladium chtalyst of inorganic, metal oxide load
Agent etc..And clay is utilized, such as you open up soil, Kaolin, and during as load carriers, palladium is poor with the binding ability of clay, preparation
Catalyst stability is low, and palladium load capacity does not reach catalytic reaction requirement all the time.Therefore the method for developing various modified clays, its
In again based on organically-modified method.But, for Kaolin, many organically-modified method of report is in Kaolin at present
Adsorption in terms of have some to be in progress, and have no remarkable break-throughs in terms of supported nano-gold metal catalyst.
The content of the invention
The invention provides a kind of preparation method of organically-modified kaoline loaded with nano palladium catalyst, efficiently can make
The loaded nanometer palladium catalyst of standby various stable loads.
As organic ligand can load nanoparticle palladium by coordinate bond, therefore, by being effectively modified to kaolinic,
Nanoparticle palladium can be stably loaded, higher, stable in the solution heterogeneous nanocatalyst of load capacity is obtained.
Realize that the method comprises the steps,
S1 is dissolved in Kaolin original soil, organically-modified reagent in solvent, obtains mixed liquor A；The Kaolin original soil is
Kaolin mineral products；Described organically-modified reagent is 3- aminocarbonyl propyl triethoxysilanes or phenyltrimethoxysila,e, or
Both add simultaneously；Described solvent is selected from normal hexane, pentane or hexamethylene；
S2 mixed liquor As at room temperature, stir 6-12 hours, are then centrifuged for, and the precipitation for obtaining is washed three times through normal hexane,
Vacuum drying 12 hours, obtains organically-modified Kaolin B；
The organically-modified Kaolin B of S3 are added in organic solvent, persistently stir 1 hour, then persistently stirring under room temperature
In, Deca palladium chloride aqueous solution and amino acid ligand obtain mixed liquor C.The ratio of Palladous chloride. and amino acid ligand is 1：(2～
4)；The organic solvent is tetrahydrofuran or chloroform；Described amino acid ligand is 1B；
Aqueous slkali, adjustment is added to add the pH value of the mixed liquor C of aqueous slkali to 7, then add in batches in S4 mixed liquor C
Reducing agent, finally stands 24 hours.Centrifugation is precipitated.Precipitation distilled water wash 4 times, washing with alcohol 2 times, air drying
12-24 hours, thus obtain organically-modified kaoline loaded nano Pd catalyst D.
Described aqueous slkali is sodium hydroxide or potassium hydroxide aqueous solution；
Described reducing agent is sodium borohydride aqueous solution.
Compared with prior art, the present invention has the advantages that.
The inventive method is by organically-modified kaolinic method so as to can stably load nanoparticle palladium, prepares
Go out the heterogeneous organically-modified kaoline loaded nano Pd catalyst of load capacity height, stable in catalytic performance, strong applicability, make to urge
Agent preparation cost is reduced, and raw material is easy to get, simple to operate, is suitable to apply in the industrial production.
Description of the drawings
Fig. 1 .1 are Pd/NH2, TEM (transmission electron microscope) figure of Ph@KL.
Fig. 1 .2 are Pd/NH2, the grain size distribution of the palladium nano-particles of Ph@KL.
Fig. 2 .1 are Pd/NH2TEM (transmission electron microscope) figure of@KL.
Fig. 2 .2 are 1wt%Pd/NH2The grain size distribution of the palladium nano-particles of@KL.
TEM (transmission electron microscope) figures of Fig. 3 .1 for Pd/Ph@KL.
Grain size distributions of Fig. 3 .2 for the palladium nano-particles of Pd/Ph@KL.
Specific embodiment
Embodiment 1
The present embodiment is by being changed collectively as organic with 3- aminocarbonyl propyl triethoxysilanes and phenyltrimethoxysila,e
Property reagent prepares organically-modified kaoline loaded with nano palladium catalyst.
The 3- aminocarbonyl propyl triethoxysilanes (APTES) of 1.2mmol, the benzene of 1.2mmol is added in 1g Kaolin original soils
Base trimethoxy silane, and 30mL normal hexane solvents are added, obtain mixed liquor A.Mixed liquor A is stirred at room temperature 6 hours.Then
Centrifugation, the solid for obtaining are washed three times through normal hexane, are vacuum dried 12 hours, are obtained organically-modified Kaolin, and be named as
NH2,Ph@KL.The organically-modified Kaolin NH of 0.97g2, Ph@KL are added in the tetrahydrofuran solution of 20mL, lasting under room temperature
Stirring 1 hour, then under continuous stirring, Deca PdCl2Aqueous solution (0.01M, 28.2mL) and 1B (0.03M,
1mL), obtain mixed liquid B.0.1M sodium hydrate aqueous solutions, adjustment solution ph to 7 is added in mixed liquid B.Then in batches
Add sodium borohydride aqueous solution (0.35M, 4.5mL).Last mixed liquor stands 24 hours, centrifugation precipitation.Precipitation is distilled
Water washing 4 times, washing with alcohol 2 times are dried in overnight air, obtain organically-modified kaoline loaded nano Pd catalyst, mark
It is designated as Pd/NH2,Ph@KL.Fig. 1 .1-1.2 are 3wt%Pd/NH2, TEM (transmission electron microscope) figures and palladium nano-particles of Ph@KL
Particle diameter distribution, table 1 are Kaolin (KL), NH2, Ph@KL, 3wt%Pd/NH2, the specific surface area and Pd actual negative carrying capacity of Ph KL
(atomic absorption spectrum AAS measure).
1 Kaolin of table (KL), NH2, Ph@KL, 3wt%Pd/NH2, the specific surface area and Pd actual negative carrying capacity of Ph KL
Embodiment 2
The present embodiment prepares organically-modified kaolinite by being used as organically-modified reagent with 3- aminocarbonyl propyl triethoxysilanes
Native loaded nanometer palladium catalyst.
The 3- aminocarbonyl propyl triethoxysilanes (APTES) of 1.2mmol are added in 1g Kaolin original soils, and just add 30mL
Hexane solvent, obtains mixed liquor A.Mixed liquor A is stirred at room temperature 6 hours.It is then centrifuged for, the solid for obtaining is washed through normal hexane
Wash three times, be vacuum dried 12 hours, obtain organically-modified Kaolin, and be named as NH2@KL.The organically-modified Kaolin of 0.97g
NH2@KL are added in the tetrahydrofuran solution of 20mL, persistently stir 1 hour, then under continuous stirring, Deca under room temperature
PdCl2Aqueous solution (0.01M, 9.3mL) and 1B (0.03M, 0.4mL), obtain mixed liquid B.Add in mixed liquid B
0.1M sodium hydrate aqueous solutions, adjustment solution ph to 7.Then sodium borohydride aqueous solution (0.35M, 4.5mL) is added in batches.
Last mixed liquor stands 24 hours, centrifugation precipitation.Precipitation distilled water wash 4 times, washing with alcohol 2 times, in overnight air
It is dried, obtains organically-modified kaoline loaded nano Pd catalyst, be labeled as Pd/NH2@KL.Fig. 2 is 1wt%Pd/NH2@KL
TEM (transmission electron microscope) figures and palladium nano-particles particle diameter distribution, table 2 be 1wt%Pd/NH2The specific surface area and Pd realities of@KL
Border load capacity.
2 3wt%Pd/NH of table2The specific surface area and Pd actual negative carrying capacity of@KL
Embodiment 3
The present embodiment by with phenyltrimethoxysila,e be used as organically-modified reagent prepare it is organically-modified kaoline loaded
Nano Pd catalyst.
The phenyltrimethoxysila,e of 1.2mmol is added in 1g Kaolin original soils, and adds 30mL normal hexane solvents, obtain
Mixed liquor A.Mixed liquor A is stirred at room temperature 6 hours.It is then centrifuged for, the solid for obtaining is washed three times through normal hexane, vacuum is done
Dry 12 hours, organically-modified Kaolin is obtained, and is named as Ph@KL.The organically-modified Kaolin Ph@KL of 0.97g are added to
In the tetrahydrofuran solution of 20mL, 1 hour, then under continuous stirring, Deca PdCl under room temperature, is persistently stirred2Aqueous solution
(0.01M, 28.2mL) and 1B (0.03M, 1mL), obtains mixed liquid B.0.1M sodium hydroxide water is added in mixed liquid B
Solution, adjustment solution ph to 7.Then sodium borohydride aqueous solution (0.35M, 4.5mL) is added in batches.Last mixed liquor stands
24 hours, centrifugation precipitation.Precipitation distilled water wash 4 times, washing with alcohol 2 times are dried in overnight air, obtain organic changing
The kaoline loaded nano Pd catalyst of property, is labeled as Pd/Ph@KL.TEM (transmission electron microscope) figures of the Fig. 3 for 3wt%Pd/Ph@KL
And the particle diameter distribution of palladium nano-particles, specific surface area and Pd actual negative carrying capacity of the table 3 for 3wt%Pd/Ph KL.
The specific surface area and Pd actual negative carrying capacity of 3 3wt%Pd/Ph KL of table
Claims (2)
1. a kind of preparation method of organically-modified kaoline loaded with nano palladium catalyst, it is characterised in that：Realize that the method includes
Following steps,
S1 is dissolved in Kaolin original soil, organically-modified reagent in solvent, obtains mixed liquor A；The Kaolin original soil is kaolinite
Native mineral products；Described organically-modified reagent is 3- aminocarbonyl propyl triethoxysilanes or phenyltrimethoxysila,e, or both
Add simultaneously；Described solvent is selected from normal hexane, pentane or hexamethylene；
S2 mixed liquor As at room temperature, stir 6-12 hours, are then centrifuged for, and the precipitation for obtaining is washed three times through normal hexane, vacuum
It is dried 12 hours, obtains organically-modified Kaolin B；
The organically-modified Kaolin B of S3 are added in organic solvent, are persistently stirred 1 hour under room temperature, then in persistently stirring, drop
Plus palladium chloride aqueous solution and amino acid ligand, obtain mixed liquor C；The organic solvent is tetrahydrofuran or chloroform；It is described
Amino acid ligand be 1B；
Aqueous slkali, adjustment is added to add the pH value of the mixed liquor C of aqueous slkali to 7, then add reduction in batches in S4 mixed liquor C
Agent, finally stands 24 hours；Centrifugation is precipitated；Precipitation distilled water wash 4 times, washing with alcohol 2 times, air drying 12-
24 hours, thus obtain organically-modified kaoline loaded nano Pd catalyst D；
Described aqueous slkali is sodium hydroxide or potassium hydroxide aqueous solution；
Described reducing agent is sodium borohydride aqueous solution.
2. the preparation method of a kind of organically-modified kaoline loaded with nano palladium catalyst according to claim 1, its feature
It is：The ratio of Palladous chloride. and amino acid ligand is 1：(2～4).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109453762A (en) * | 2018-10-23 | 2019-03-12 | 湖南大学 | A kind of preparation method and application of modified clay mine loaded palladium catalyst |
| CN111250117A (en) * | 2020-02-07 | 2020-06-09 | 新疆大学 | Supported mercury-free catalyst, preparation method thereof and application thereof in catalyzing hydrochlorination of acetylene |
| CN112517007A (en) * | 2020-12-11 | 2021-03-19 | 内蒙古师范大学 | Kaolin loaded nano-iron catalyst and application thereof in cross dehydrogenation coupling reaction |
| CN113480845A (en) * | 2021-07-16 | 2021-10-08 | 江西省铭新科技有限公司 | Regenerated PA plastic particle prepared from waste cloth and method thereof |
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| CN102847533A (en) * | 2012-10-12 | 2013-01-02 | 南京师范大学 | Microwave method for synthesizing attapulgite and palladium nanocomposite catalyst |
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| XIAOYU LI ET AL.: "Assembling strategy to synthesize palladium modified kaolin nanocomposites with different morphologies", 《SCIENTIFIC REPORTS》 * |
| YONG-SHENG BAO ET AL.: "Replacing Pd(OAc)2 with supported palladium nanoparticles in ortho-directed CDC reactions of alkylbenzenes", 《GREEN CHEMISTRY》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109453762A (en) * | 2018-10-23 | 2019-03-12 | 湖南大学 | A kind of preparation method and application of modified clay mine loaded palladium catalyst |
| CN109453762B (en) * | 2018-10-23 | 2021-09-07 | 湖南大学 | Preparation method and application of modified clay mineral supported palladium catalyst |
| CN111250117A (en) * | 2020-02-07 | 2020-06-09 | 新疆大学 | Supported mercury-free catalyst, preparation method thereof and application thereof in catalyzing hydrochlorination of acetylene |
| CN112517007A (en) * | 2020-12-11 | 2021-03-19 | 内蒙古师范大学 | Kaolin loaded nano-iron catalyst and application thereof in cross dehydrogenation coupling reaction |
| CN112517007B (en) * | 2020-12-11 | 2023-02-03 | 内蒙古师范大学 | Kaolin loaded nano-iron catalyst and application thereof in cross dehydrogenation coupling reaction |
| CN113480845A (en) * | 2021-07-16 | 2021-10-08 | 江西省铭新科技有限公司 | Regenerated PA plastic particle prepared from waste cloth and method thereof |
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