CN104415753B - The method for directly synthesizing bimetal nano material - Google Patents
The method for directly synthesizing bimetal nano material Download PDFInfo
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- CN104415753B CN104415753B CN201310376329.3A CN201310376329A CN104415753B CN 104415753 B CN104415753 B CN 104415753B CN 201310376329 A CN201310376329 A CN 201310376329A CN 104415753 B CN104415753 B CN 104415753B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a kind of method prepared by bimetal nano material, with VO (acac)2、Pd(OAc)2, the pyrrolidones of N vinyl 2 be raw material, by the method for hydrogen reducing, at 60 DEG C, 50% acetic acid is used as solvent, one-step synthesis target material.The nano catalytic material that this method is synthesized is used for the reaction that benzene direct oxidation prepares phenol, and the good stability of the material is presented in gentle reaction condition.
Description
Technical field
The present invention relates to one kind with VO (acac)2、Pd(OAc)2, NVP be raw material, pass through gas
The method of reduction, under 0 DEG C~160 DEG C of reaction temperature, using aqueous acetic acid as solvent, one-step synthesis target material
Method.
Background technology
Phenol is the important chemical intermediate of a class, the epoch that will be terminated at ' cheap oil ', straight by benzene with high selectivity
Connect that to prepare phenol extremely important.At past 60 years, a series of homogeneous/heterogeneous catalytic process is developed, but break through
Existing cumene process is but very difficult.Benzene direct oxidation prepares the reaction that phenol is a dynamics Controlling, therefore, with conjunction
The catalyst (may is that several nanometers) of suitable size, while ensureing that its three-dimensional freedom is perhaps to improve catalytic efficiency and selectivity
Effective ways.In current existing report, hydroxylating has used H2,NH3, the co-conducer such as CO and ascorbic acid, and
These co-conducers are also more green.
As far as we know, higher phenol yield can be obtained using co-conducer.However, really challenge exists benzene hydroxylation
In being directly realized by the activation to molecular oxygen.In traditional palladium-catalyzed reaction, using aromatic compound as reaction substrate, tendency
In generation coupling reaction.For example, using H5PMo10V2O40With Pd (OAc)2As catalyst, the connection that yield is 10.4% can be obtained
Benzene, simultaneous selection may be up to 83.5%.It is strong using highly acid solvent TFA (trifluoroacetic acid) and TFAA (TFAA) mixing
Protonic solvent, is used bpym-Pd (OAc)2It is used as catalyst, Al (OTf)3As co-catalyst, reaction can be from coupling to hydroxyl
Certain transformation (phenol yield 3.8%, biphenyl yield 1.9%) occurs for change course.
In recent years, nano metal cluster show with traditional catalyst very big catalytic performance difference, and then receive extensively
Concern.Wherein, duplex metal nano granule even shows the effect of concerted catalysis well.For example, Au-Pd nano particles are in first
Good bimetallic synergy is shown in benzene oxidatoin and oxidation of alcohols, Pt-Co duplex metal nano granules are efficient expenses
Tropsch synthesis catalyst.But, as far as we know, using oxygen as oxidant, without using co-conducer or additive (for example
Heteropoly acid) and realize liquid-phase catalysis benzene hydroxylation reaction at present there is no literature reported on.But, it is used as oxidation using vanadium base heteropoly acid
Pd (0), can be oxidized to Pd (II), so as to realize the circulation of the reaction by agent.
Material preparation method described in this patent is without document report, and catalysis material of the same race is without document report.
The content of the invention
The purpose of the present invention is one class bimetal nano material preparation method of exploitation.
The bimetal nano material preparation method that the present invention is provided, with VO (acac)2、Pd(OAc)2, N- vinyl -2- pyrroles
Pyrrolidone is raw material, by the method for hydrogen reducing, under 0 DEG C~160 DEG C of reaction temperature, and the acetic acid using 50% is as molten
Agent, the method for one-step synthesis bimetal nano material.
The cladding metal synthesis material for being suitable for the present invention is the metals such as cadmium, vanadium, chromium, iron, manganese, cobalt, zinc, nickel, cerium, copper
Acetylacetonate compound.Core metal synthesis material is acetate, sulfate, the nitre of the metals such as platinum, silver, gold, palladium, rhodium, ruthenium, iridium
Hydrochlorate, halide.Surfactant is this Pan's series, TWEEN Series, quaternary ammonium salt series of surfactants, and these raw materials can be
In the market is bought.
In the present invention, cladding metal is with core metal mol ratio 5:1~200:Between 1, and preferably 10:1-30:1 it
Between.
The reaction medium for being adapted to the present invention is 20-80% aqueous acetic acid.
It is suitable for the reaction temperature of the present invention between 0 DEG C~160 DEG C, and preferably between 50 DEG C~140 DEG C.
The preparation method of the bimetal nano catalysis material of the catalysis benzene hydroxylation phenol of the present invention, uses common VO
(acac)2、Pd(OAc)2, NVP be raw material, reaction condition is gentle, and reaction yield is high, synthetic method letter
Just.
The nano catalytic material that this method is synthesized is used for the reaction that benzene direct oxidation prepares phenol, in gentle reaction bar
Part presents the good stability of the material.
Brief description of the drawings
The XRD powder diffractions of the resulting materials of Fig. 1 embodiments 1：PVP is coated on Pd (OAc)2, and then use 1.4MPa H2
6h is reduced at 60 DEG C.10%Pd-VOxPrepared by for example above-mentioned methods of NPs, VO (acac)2It is same to use PVP and H2Under these conditions
Processing.10%Pd-VOxThe composition of duplex metal nano granule can be characterized by XRD spectra, as shown in Figure 1.Three samples
In be the PdO seen at 2 θ=34 ° appearance.Appearance in 2 θ=40 ° can be attributed to Pd (111).It is interesting that VO
(acac)2Show 10%Pd-VOxThe similar XRD spectra of nano particle, and there is not PdO appearance, this also illustrates
10%Pd-VOxPd in sample is by having good dispersive property after hydrogen reducing.
Transmission electron microscope (TEM) figure of the resulting materials of Fig. 2 embodiments 1：10%Pd-VOxThe transmission electron microscope (TEM) of nano particle
Characterize and particle diameter distribution is as shown in Figure 2.Shown in figure, 10%Pd-VOxNano material has chi dispersed and homogeneous well
Very little, its average grain diameter is 7.2nm, and D50 is 7.21nm.
The x-ray photoelectron power spectrum of the resulting materials of Fig. 3 embodiments 1：The surface of Pd kinds is covered by vanadium, therefore, the sign hand
Section only has weaker peak value (scanning times=200) equally explanation Pd and is coated in catalyst.In 334.6eV and 339.9eV
The radiation signal that place is produced is 3d5/2 the and 3d3/2 regional Electronics generation by Pd (0), illustrates Pd (OAc)2Really by H2It is restored to
Pd(0).At the same time, Pd receives electron bombardment and generates electronics loss peak positioned at 345.5eV.
Embodiment
Following embodiment will more comprehensively be described to the present invention.
Embodiment 1
By 0.0530g (0.2mmol) VO (acac)2With 0.0045g (0.02mmol) Pd (OAc)2Added to dissolved with 0.11g
In (2mmol) PVP 6.8mL 50wt% acetic acid.Reactant is under the conditions of 0 DEG C, using 0.8MPa hydrogen reducing 4h, and then
To water miscible Pd-VOxNanocatalyst.Its structure is determined using TEM (concrete structure is as shown in Figure 2).
Reacted using obtained catalysis material for benzene hydroxylation, 0.78g benzene (10mmol) is added to 6.8mL nanometers
In grain solution, 0.5MPa O2Add in 50mL autoclaves and react, magnetic agitation, reaction temperature is 140 DEG C, keeps 5h, obtains benzene
Phenol yield is 5.3%.
Embodiment 2
By 0.1060g (0.2mmol) VO (acac)2With 0.0045g (0.02mmol) Pd (OAc)2Added to dissolved with 0.22g
In (2mmol) PVP 6.8mL 50wt% acetic acid.Reactant is under the conditions of 60 DEG C, using 0.8MPa hydrogen reducing 4h, and then
To water miscible Pd-VOxNanocatalyst.Its structure is determined using TEM (concrete structure is as shown in Figure 2).
Reacted using obtained catalysis material for benzene hydroxylation, 0.78g benzene (10mmol) is added to 6.8mL nanometers
In grain solution, 2MPa O2Add in 50mL autoclaves and react, magnetic agitation, reaction temperature is 140 DEG C, keeps 5h, obtains phenol
Yield is 2.8%.
Embodiment 3
By 0.0530g (0.2mmol) VO (acac)2With 0.0090g (0.02mmol) Pd (OAc)2Added to dissolved with 0.11g
In (2mmol) PVP 6.8mL 50wt% acetic acid.Reactant is under the conditions of 140 DEG C, using 1.4MPa hydrogen reducing 8h, and then
Obtain water miscible Pd-VOxNanocatalyst.Its structure is determined using TEM (concrete structure is as shown in Figure 2).
Reacted using obtained catalysis material for benzene hydroxylation, 0.78g benzene (10mmol) is added to 6.8mL nanometers
In grain solution, 1.4MPa O2Add in 50mL autoclaves and react, magnetic agitation, reaction temperature is 140 DEG C, keeps 5h, obtains benzene
Phenol yield is 6.0%.
Embodiment 4-10
Similar to embodiment 1, it is different from part and is：Surfactant used, cladding metal consumption, core metal are used
Amount, hydrogen reducing temperature, hydrogen reducing time, react the following result (table one) after terminating：
Table one
Embodiment 11-15
Similar to embodiment 1, it is different from part and is：Using different bimetal nano material concentrations, hydroxylating
Temperature, hydroxylating time, obtain following result (table two)：
Table two
The catalysis material that the inventive method is synthesized is reacted applied to benzene hydroxylation, and this is presented in gentle reaction condition
The good stability of material.
Claims (5)
1. a kind of method that liquid-phase catalysis benzene hydroxylation reaction prepares phenol, it is characterised in that：Using oxygen as oxidant, benzene
For raw material, bimetal nano material is catalyst, prepares phenol；
Wherein, the preparation method of the bimetal nano material is：Using acetic acid and water as solvent, with particles cladded by metallic compound, interior
Core metallic compound, surfactant are raw material, pass through reducing gas H2The method of reduction, in 0 DEG C~160 DEG C of reaction temperature
Next step synthesizes target bimetal nano material；
Particles cladded by metallic compound is vanadium acetylacetonate；Core metal compound is palladium；
The surfactant is selected from polyvinylpyrrolidone, bromide sixteen alkyls pyridine, hexadecyltrimethylammonium chloride, chlorine
More than one or both of octadecylpyridinium.
2. according to the method described in claim 1, it is characterised in that：The reaction medium of catalyst preparation is mass concentration 20-
80% aqueous acetic acid.
3. according to the method described in claim 1, it is characterised in that：Wherein, cladding metal for core metal atomic quantity 5~
200 times.
4. according to the method described in claim 1, it is characterised in that：
The particles cladded by metallic compound is with surfactant qualities ratio 1：25~25：Between 1.
5. according to the method described in claim 1, it is characterised in that：Reducing gas pressure is between 0.1-8MPa.
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| CN109603829B (en) * | 2018-12-12 | 2021-10-15 | 浙江工业大学 | Cu-Co bimetallic catalyst and preparation method and application thereof |
| CN111293323B (en) * | 2020-02-25 | 2023-03-07 | 安徽师范大学 | Porous platinum-palladium nano cubic material, preparation method thereof and application thereof in catalyzing methanol oxidation |
| CN116237060A (en) * | 2023-03-27 | 2023-06-09 | 吉林大学 | Wide-temperature sulfur-resistant CO oxidation catalyst and preparation method and application thereof |
Citations (2)
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| CN1381328A (en) * | 2001-04-18 | 2002-11-27 | 中国科学院化工冶金研究所 | Process for preparing superfine (nano) metal powder by hydrogen reduction of polyol |
| MX2008016440A (en) * | 2008-12-19 | 2010-06-21 | Ct Investig Y Estudios Del Ipn | Methanol- and carbon monoxide-resistant bimetallic electro catalysts applied in polymeric electrolyte fuel cells. |
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| CN103111308A (en) * | 2013-03-05 | 2013-05-22 | 北京大学 | Method for directly synthesizing Pt-Co bimetallic nanoparticles utilizing water phase and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381328A (en) * | 2001-04-18 | 2002-11-27 | 中国科学院化工冶金研究所 | Process for preparing superfine (nano) metal powder by hydrogen reduction of polyol |
| MX2008016440A (en) * | 2008-12-19 | 2010-06-21 | Ct Investig Y Estudios Del Ipn | Methanol- and carbon monoxide-resistant bimetallic electro catalysts applied in polymeric electrolyte fuel cells. |
Non-Patent Citations (1)
| Title |
|---|
| PtIr合金催化剂的制备极其电催化性能;杨伦权等;《功能材料》;20120815;第43卷(第15期);第1998-1999页 * |
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