CN109014238A - A kind of method of low temperature liquid phase synthesized high-performance metal material - Google Patents
A kind of method of low temperature liquid phase synthesized high-performance metal material Download PDFInfo
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- CN109014238A CN109014238A CN201810831613.8A CN201810831613A CN109014238A CN 109014238 A CN109014238 A CN 109014238A CN 201810831613 A CN201810831613 A CN 201810831613A CN 109014238 A CN109014238 A CN 109014238A
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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Abstract
The present invention relates to a kind of methods of low temperature liquid phase synthesized high-performance metal material, belong to Materials Science and Engineering technology and chemical field.Metal material prepared by the present invention includes: the materials such as one or more the monatomic of metallic element composition such as chemically synthesized Ti, V, Cr, Mn, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt and Au, diatomic, polyatom, elementide or superfine nano particle in low temperature liquid phase environment.
Description
Technical field
The present invention relates to low temperature liquid phases to synthesize monatomic metal, diatomic, polyatom, elementide or superfine nano particle
The method of contour performance materials belongs to Materials Science and Engineering technology and chemical field.
Background technique
Metal is as important inorganic substances, more than 2/3rds of periodic table of elements element species, possesses abundant and enables
The physicochemical characteristics that people is fascinated.Many metal materials have been widely used for catalysis, electronics, optical imagery, information storage, pass
Sense, medicine and other fields.Study surface, the performance of metal material and its size, shape, sufficiently with a series of physical parameter such as structure
Closely bound up, accurate control relevant parameter is most important during preparing high-performance metal materials.Particularly, metallic atom is made
For the active site of very multiple types catalytic reaction process, its effective rate of utilization how is improved, to improve activity and reduce
The cost of large-scale application is always the key problem of material science and catalytic field.With traditional nanometer grade gold metal catalyst
It compares, the metallic catalyst of atom level dispersion can not only significantly improve metallic atom as the effective of catalytic reaction activity site
Utilization rate also tends to have better catalytic selectivity, stability and anti-poisoning energy to realize higher specific mass activity
Power.Therefore, the high-performance metal materials of the dispersion of large scale preparation atom level or superfine nano structure, the catalysis for obtaining superelevation are living
Property, close to 100% catalytic efficiency and the circulation approach of green, to realize low cost, efficient green catalyst simultaneously
Large-scale use is put into, there is important scientific meaning and economic value.
In view of the higher surface free energy of atom level dispersed metal and activity, at this stage to impregnate calcining approach as representative
Preparation method, effective metal load capacity is general very limited (< 1.0wt%), how large scale preparation high metal load capacity
Atom level dispersed metal catalyst be still related fields problem urgently to be resolved.Solution synthesis is received as large scale preparation metal
The conventional method of meter Jing Ti, it is extremely difficult to obtain atom level dispersed metal to effectively inhibit forming core.Traditional method is all
Forming core is controlled by infinitely reducing the method for solution concentration, not only reliability is lower, and yield also can not be promoted significantly.Consider
To temperature as Chemical Kinetics and thermodynamic (al) important parameter is influenced, reduce temperature can be obviously improved nucleating potential barrier from
And effectively inhibit to be nucleated, to improve the concentration of monodispersed metallic atom in solution, and further effectively it is adsorbed on different
Or else carrier surface is obtained with the monodispersed metallic atom composite material of substrate surface.Therefore, the present invention is proposed and is realized low
Temperature inhibits the energy barrier of liquid phase synthesis forming core and growth, so that the one or more metallic element compositions of large scale preparation is single former
The method and technique of the structures performance function material such as son, diatomic, polyatom, elementide or ultrafine metal nanoparticles.
Summary of the invention
Technical scheme is as follows, a kind of method of low temperature liquid phase synthesized high-performance metal material, including following step
It is rapid:
(1) the metallic precursor solution A that suitable solvent configuration molar concentration is 0.001-1.0mol/L is chosen, before described
Drive body be soluble metallic compound, the metal include Ti, V, Cr, Mn, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, W,
Any one or more of elements such as Re, Os, Ir, Pt and Au, the metal material include one or more metallic elements
The structures such as the monatomic of composition, diatomic, polyatom, elementide or ultrafine metal nanoparticles；The solvent include water,
Ethyl alcohol, ethylene glycol, acetone, chloroform, ether, tetrafluoro hydrogen mutters, any one or more of dimethylformamide or formaldehyde by than
Example mixes；
(2) liquid phase synthesis redox reaction system is selected, comprising: electronation, photo-reduction and ultrasound reduction.Its
In, reducing agent includes NaBH4,KBH4,N2H4,N2H5OH, formaldehyde, formic acid, ascorbic acid, Na2SO3,K2SO3,H2C2O4, ultraviolet
Any one or more of light, visible light, full light and ultrasonic wave；The redox reaction solvent includes water, ethyl alcohol, second two
Alcohol, acetone, chloroform, ether, tetrafluoro hydrogen mutters, any one or more of dimethylformamide or formaldehyde mix in proportion；
(3) under ultra-low temperature surroundings, metallic precursor solution A prepared by step (1) is added to described in step (2)
In reducing agent solution, synthetic product dispersion liquid sufficiently can be obtained after reaction；The temperature controlling range of the reaction process be-
120-0 DEG C, stirring rate control is 100-5000rpm；Or at low ambient temperatures, by body before the metal of above-mentioned steps (1) preparation
Liquid solution A is placed in photo-reduction or ultrasonic reducing environment, synthetic product dispersion liquid sufficiently can be obtained after reaction.It is described to react
The temperature controlling range of journey is -120 DEG C -0 DEG C, and stirring rate control is 100-5000rpm；
(4) at low ambient temperatures, by the monatomic, double of one or more metallic elements composition of above-mentioned steps (3) preparation
It is centrifuged or is filtered by vacuum, room after the stirring of the materials homogeneous dispersion such as atom, polyatom, elementide or ultrafine metal nanoparticles
Corresponding high performance material can be obtained after temperature is dry.The temperature controlling range of the reaction process is -120-0 DEG C, when stirring
Between control be 10-600min, stirring rate control be 100-5000rpm；
The method that the present invention proposes low temperature liquid phase synthesized high-performance material, simple process operation are easy, and utilize low temperature environment
The thermodynamics and kinetics behavior chemically reacted in control solution is applicable in effectively adjust the nucleation and growth of metallic atom
In one or more metallic element groups such as Ti, V, Cr, Mn, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt and Au
At the materials such as monatomic, diatomic, polyatom, elementide or ultrafine metal nanoparticles.
Detailed description of the invention
Fig. 1 is that the scanning of the atom level dispersion Ag composite material of titanium dioxide (P25) load of the method for the present invention preparation is saturating
Penetrate electron microscope picture.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is described in more detail.
Embodiment 1
The Ag of atom level dispersion1/TiO2The preparation of composite material.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the AgNO of 0.02M3Reaction solution A and
N containing 5.0M2H5Titanium dioxide P25 support dispersion (the 2.5mg ml of OH reducing agent-1).Then, by above-mentioned solution and dispersion liquid
It is placed in cryogenic box, is cooled to subzero 60 DEG C and keeps the temperature 30 minutes.It is controlled with syringe pump, by 5ml AgNO3Reaction solution A with
0.5ml min-1Rate be added dropwise in the reduction agent carrier mixed dispersion liquid of 125mL.Mixing liquid is under the conditions of subzero 60 DEG C
Continue after being stirred to react 2h, is recycled and cleaned using cryogenic vacuum suction filtration, and in natural drying at room temperature.It can be obtained atom
The Ag of grade dispersion1/TiO2Composite material.
Embodiment 2
The Ag of atom level dispersion1/TiO2The preparation of composite material.
Firstly, muttering mixed solution as anti-icing fluid configuration using the water of volume ratio 1:9/tetrafluoro hydrogen: the AgNO of 0.05M3React molten
Liquid A and NaBH containing 5.0M4Titanium dioxide P25 support dispersion (the 5mg ml of reducing agent-1).Then, by above-mentioned solution and dispersion
Liquid is placed in cryogenic box, is cooled to subzero 60 DEG C and is kept the temperature 30 minutes.It is controlled with syringe pump, by 5ml AgNO3Reaction solution A is straight
It connects and is directly mixed with 125mL reduction agent carrier mixed dispersion liquid.Mixing liquid continues to be stirred to react 2h under the conditions of subzero 60 DEG C
Afterwards, it is recycled and is cleaned using cryogenic vacuum suction filtration, and in natural drying at room temperature.It can be obtained the Ag of atom level dispersion1/
TiO2Composite material.
Embodiment 3
The Ag of atom level dispersion1/TiO2The preparation of composite material.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the AgNO of 0.05M3Reaction solution A and
5mg ml-1Titanium dioxide P25 support dispersion.Then, above-mentioned solution and dispersion liquid are placed in cryogenic box, are cooled to subzero
45 DEG C and heat preservation 60 minutes.Introduce ultraviolet light AgNO3Solution A, light application time continue 2h, by the AgNO after reaction3Solution A
It is mixed with the support dispersion of 125mL.After mixing liquid continues to be stirred to react 2h under the conditions of subzero 45 DEG C, cryogenic vacuum is utilized
Suction filtration is recycled and is cleaned, and in natural drying at room temperature.It can be obtained the Ag of atom level dispersion1/TiO2Composite material.
Embodiment 4
The Ag/TiO of sub-nanometer cluster or superfine nano structure2The preparation of composite material.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the AgNO of 0.2M3Reaction solution A and
2.5mg ml-1Titanium dioxide P25 support dispersion.Then, above-mentioned solution and dispersion liquid are placed in cryogenic box, are cooled to zero
Lower 30 DEG C and heat preservation 60 minutes.By 5ml AgNO3Reaction solution A is mixed with the support dispersion of 125mL, is stirred and is introduced ultrasound
Dispersion.Ultrasonic time continues 2h, and control temperature condition is minus 30 DEG C.Recycle using cryogenic vacuum suction filtration later simultaneously clear
It washes, and in natural drying at room temperature.It can be obtained the Ag/TiO of sub-nanometer cluster or superfine nano structure2Composite material
Embodiment 5
The Ag of atom level dispersion1/MnO2The preparation of composite material.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the AgNO of 0.02M3Reaction solution A and
N containing 5.0M2H5The MnO of OH reducing agent2Nanometer powder support dispersion (2.5mg ml-1).Then, by above-mentioned solution and dispersion liquid
It is placed in cryogenic box, is cooled to subzero 60 DEG C and keeps the temperature 30 minutes.It is controlled with syringe pump, by 5ml AgNO3Reaction solution A with
0.5ml min-1Rate be added dropwise in the reduction agent carrier mixed dispersion liquid of 125mL.Mixing liquid is under the conditions of subzero 60 DEG C
Continue after being stirred to react 2h, is recycled and cleaned using cryogenic vacuum suction filtration, and in natural drying at room temperature.It can be obtained atom
The Ag of grade dispersion1/MnO2Composite material.
Embodiment 6
The Ag of atom level dispersion1/CeO2The preparation of composite material.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the AgNO of 0.02M3Reaction solution A and
N containing 5.0M2H5The CeO of OH reducing agent2Nanometer powder support dispersion (2.5mg ml-1).Then, by above-mentioned solution and dispersion liquid
It is placed in cryogenic box, is cooled to subzero 60 DEG C and keeps the temperature 30 minutes.It is controlled with syringe pump, by 5ml AgNO3Reaction solution A with
0.5ml min-1Rate be added dropwise in the reduction agent carrier mixed dispersion liquid of 125mL.Mixing liquid is under the conditions of subzero 60 DEG C
Continue after being stirred to react 2h, is recycled and cleaned using cryogenic vacuum suction filtration, and in natural drying at room temperature.It can be obtained atom
The Ag of grade dispersion1/CeO2Composite material.
Embodiment 7
The Ag of atom level dispersion1/SnO2The preparation of composite material.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the AgNO of 0.02M3Reaction solution A and
N containing 5.0M2H5The SnO of OH reducing agent2Nanometer powder support dispersion (2.5mg ml-1).Then, by above-mentioned solution and dispersion liquid
It is placed in cryogenic box, is cooled to subzero 60 DEG C and keeps the temperature 30 minutes.It is controlled with syringe pump, by 5ml AgNO3Reaction solution A with
0.5ml min-1Rate be added dropwise in the reduction agent carrier mixed dispersion liquid of 125mL.Mixing liquid is under the conditions of subzero 60 DEG C
Continue after being stirred to react 2h, is recycled and cleaned using cryogenic vacuum suction filtration, and in natural drying at room temperature.It can be obtained atom
The Ag of grade dispersion1/SnO2Composite material.
Embodiment 8
The Au of atom level dispersion1Ag1/SnO2The preparation of composite material.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the AgNO of 0.01M3With 0.01M's
HAuCl4Mixed reaction solution A and N containing 5.0M2H5The SnO of OH reducing agent2Nanometer powder support dispersion (2.5mg ml-1).It connects
, above-mentioned solution and dispersion liquid are placed in cryogenic box, subzero 60 DEG C is cooled to and keeps the temperature 30 minutes.It is controlled with syringe pump, it will
5ml AgNO3Reaction solution A is with 0.5ml min-1Rate be added dropwise in the reduction agent carrier mixed dispersion liquid of 125mL.It mixes
After liquid continues to be stirred to react 2h under the conditions of subzero 60 DEG C, is recycled and cleaned using cryogenic vacuum suction filtration, and in room temperature
It spontaneously dries.It can be obtained the Au of atom level dispersion1Ag1/SnO2Composite material.
Embodiment 9
The AuAg/TiO of sub-nanometer cluster2The preparation of composite material.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the AgNO of 0.02M3With 0.02M's
HAuCl4Mixed reaction solution A and N containing 5.0M2H5The TiO of OH reducing agent2Nanometer powder support dispersion.It then, will be above-mentioned molten
Liquid and dispersion liquid are placed in cryogenic box, are cooled to subzero 60 DEG C and are kept the temperature 30 minutes.It is controlled with syringe pump, by 5ml AgNO3Instead
Answer solution A with 0.5ml min-1Rate be added dropwise in the reduction agent carrier mixed dispersion liquid of 125mL.Mixing liquid is subzero 60
Continue after being stirred to react 2h under the conditions of DEG C, is recycled and cleaned using cryogenic vacuum suction filtration, and in natural drying at room temperature.?
Obtain the AuAg/TiO of sub-nanometer cluster2Composite material.
Embodiment 10
The preparation of AuAg superfine nano granular materials.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the AgNO of 0.05M3With 0.05M's
HAuCl4Mixed reaction solution A and 5.0M N2H5The reducing agent solution of OH.Then, above-mentioned solution and dispersion liquid are placed in cryogenic box
In, it is cooled to subzero 30 DEG C and keeps the temperature 30 minutes.It is controlled with syringe pump, by 5ml AgNO3Reaction solution A is with 0.5ml min-1's
Rate is added dropwise to the reducing agent solution of 125mL.After mixing liquid continues to be stirred to react 2h under the conditions of subzero 30 DEG C, low temperature is utilized
Vacuum filtration is recycled and is cleaned, and in natural drying at room temperature.It can be obtained AuAg superfine nano granular materials.
Embodiment 11
The Pd of atom level dispersion1/TiO2The preparation of composite material.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the K of 0.02M2PdCl4Reaction solution A
With N containing 5.0M2H5Titanium dioxide P25 support dispersion (the 2.5mg ml of OH reducing agent-1).Then, by above-mentioned solution and dispersion
Liquid is placed in cryogenic box, is cooled to subzero 60 DEG C and is kept the temperature 30 minutes.It is controlled with syringe pump, by 5ml K2PdCl4Reaction solution A
With 0.5ml min-1Rate be added dropwise in the reduction agent carrier mixed dispersion liquid of 125mL.Mixing liquid is in subzero 60 DEG C of conditions
Under continue after being stirred to react 2h, recycled and cleaned using cryogenic vacuum suction filtration, and in natural drying at room temperature.It can be obtained original
The Pd of sub- grade dispersion1/TiO2Composite material.
Embodiment 12
The preparation of the Pd/ mesoporous carbon MC composite material of sub-nanometer cluster or superfine nano structure.
Firstly, being configured by anti-icing fluid of the water of volume ratio 3:7/ethyl alcohol mixed solution: the K of 0.5M2PdCl4Reaction solution A and
5mg ml-1Mesoporous carbon MC support dispersion.Then, above-mentioned solution and dispersion liquid are placed in cryogenic box, are cooled to subzero 20
DEG C and keep the temperature 30 minutes.By 5ml l K2PdCl4Reaction solution A is mixed with the support dispersion of 125mL, is stirred and is introduced ultrasound
Dispersion.Ultrasonic time continues 2h, and control temperature condition is minus 30 DEG C.Recycle using cryogenic vacuum suction filtration later simultaneously clear
It washes, and in natural drying at room temperature.It can be obtained the Pd/ mesoporous carbon MC composite material of sub-nanometer cluster or superfine nano structure.
Embodiment 13
The Pt of atom level dispersion1/TiO2The preparation of composite material.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the H of 0.02M2PtCl6Reaction solution A
With N containing 5.0M2H5Titanium dioxide P25 support dispersion (the 2.5mg ml of OH reducing agent-1).Then, by above-mentioned solution and dispersion
Liquid is placed in cryogenic box, is cooled to subzero 60 DEG C and is kept the temperature 30 minutes.It is controlled with syringe pump, by 5ml H2PtCl6Reaction solution A
With 0.5ml min-1Rate be added dropwise in the reduction agent carrier mixed dispersion liquid of 125mL.Mixing liquid is in subzero 60 DEG C of conditions
Under continue after being stirred to react 2h, recycled and cleaned using cryogenic vacuum suction filtration, and in natural drying at room temperature.It can be obtained original
The Pt of sub- grade dispersion1/TiO2Composite material.
Embodiment 14
The Au of atom level dispersion1/TiO2The preparation of composite material.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the HAuCl of 0.02M4Reaction solution A
With N containing 5.0M2H5Titanium dioxide P25 support dispersion (the 2.5mg ml of OH reducing agent-1).Then, by above-mentioned solution and dispersion
Liquid is placed in cryogenic box, is cooled to subzero 60 DEG C and is kept the temperature 30 minutes.It is controlled with syringe pump, by 5ml HAuCl4Reaction solution A
With 0.5ml min-1Rate be added dropwise in the reduction agent carrier mixed dispersion liquid of 125mL.Mixing liquid is in subzero 60 DEG C of conditions
Under continue after being stirred to react 2h, recycled and cleaned using cryogenic vacuum suction filtration, and in natural drying at room temperature.It can be obtained original
The Au of sub- grade dispersion1/TiO2Composite material.
Embodiment 15
The preparation of the Au/ carbon nanotube CNTs composite material of sub-nanometer cluster or superfine nano structure.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:1/ethyl alcohol mixed solution: the HAuCl of 0.2M4Reaction solution A and
5mg ml-1Carbon nanotube CNT support dispersion.Then, above-mentioned solution and dispersion liquid are placed in cryogenic box, are cooled to subzero
30 DEG C and heat preservation 30 minutes.By 10ml HAuCl4Reaction solution A is mixed with the support dispersion of 125mL, is stirred and is introduced ultrasound
Dispersion.Ultrasonic time continues 2h, and control temperature condition is minus 30 DEG C.Recycle using cryogenic vacuum suction filtration later simultaneously clear
It washes, and in natural drying at room temperature.It can be obtained the Pd/ mesoporous carbon MC composite material of sub-nanometer cluster or superfine nano structure.
Embodiment 16
The Ru of atom level dispersion1/TiO2The preparation of composite material.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the RuCl of 0.02M3Reaction solution A and
N containing 5.0M2H5Titanium dioxide P25 support dispersion (the 2.5mg ml of OH reducing agent-1).Then, by above-mentioned solution and dispersion liquid
It is placed in cryogenic box, is cooled to subzero 60 DEG C and keeps the temperature 30 minutes.It is controlled with syringe pump, by 5ml RuCl3Reaction solution A with
0.5ml min-1Rate be added dropwise in the reduction agent carrier mixed dispersion liquid of 125mL.Mixing liquid is under the conditions of subzero 60 DEG C
Continue after being stirred to react 2h, is recycled and cleaned using cryogenic vacuum suction filtration, and in natural drying at room temperature.It can be obtained atom
The Ru of grade dispersion1/TiO2Composite material.
Embodiment 17
The Rh of atom level dispersion1/TiO2The preparation of composite material.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the C of 0.02M6H9O6Rh reaction solution A
With N containing 5.0M2H5Titanium dioxide P25 support dispersion (the 2.5mg ml of OH reducing agent-1).Then, by above-mentioned solution and dispersion
Liquid is placed in cryogenic box, is cooled to subzero 60 DEG C and is kept the temperature 30 minutes.It is controlled with syringe pump, by 5ml C6H9O6Rh reaction solution A
With 0.5ml min-1Rate be added dropwise in the reduction agent carrier mixed dispersion liquid of 125mL.Mixing liquid is in subzero 60 DEG C of conditions
Under continue after being stirred to react 2h, recycled and cleaned using cryogenic vacuum suction filtration, and in natural drying at room temperature.It can be obtained original
The Rh of sub- grade dispersion1/TiO2Composite material.
Embodiment 18
The Ir of atom level dispersion1/TiO2The preparation of composite material.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the HIrCl of 0.02M6Reaction solution A
With N containing 5.0M2H5Titanium dioxide P25 support dispersion (the 2.5mg ml of OH reducing agent-1).Then, by above-mentioned solution and dispersion
Liquid is placed in cryogenic box, is cooled to subzero 60 DEG C and is kept the temperature 30 minutes.It is controlled with syringe pump, by 5ml HIrCl6Reaction solution A
With 0.5ml min-1Rate be added dropwise in the reduction agent carrier mixed dispersion liquid of 125mL.Mixing liquid is in subzero 60 DEG C of conditions
Under continue after being stirred to react 2h, recycled and cleaned using cryogenic vacuum suction filtration, and in natural drying at room temperature.It can be obtained original
The Ir of sub- grade dispersion1/TiO2Composite material.
Embodiment 19
The W of atom level dispersion1/TiO2The preparation of composite material.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the WCl of 0.02M6Reaction solution A and
N containing 5.0M2H5Titanium dioxide P25 support dispersion (the 2.5mg ml of OH reducing agent-1).Then, by above-mentioned solution and dispersion liquid
It is placed in cryogenic box, is cooled to subzero 60 DEG C and keeps the temperature 30 minutes.It is controlled with syringe pump, by 5ml WCl6Reaction solution A with
0.5ml min-1Rate be added dropwise in the reduction agent carrier mixed dispersion liquid of 125mL.Mixing liquid is under the conditions of subzero 60 DEG C
Continue after being stirred to react 2h, is recycled and cleaned using cryogenic vacuum suction filtration, and in natural drying at room temperature.It can be obtained atom
The Rh of grade dispersion1/TiO2Composite material.
Embodiment 20
The Mo of atom level dispersion1/TiO2The preparation of composite material.
Firstly, being configured by anti-icing fluid of the water of volume ratio 1:9/ethyl alcohol mixed solution: the MoCl of 0.02M5Reaction solution A and
N containing 5.0M2H5Titanium dioxide P25 support dispersion (the 2.5mg ml of OH reducing agent-1).Then, by above-mentioned solution and dispersion liquid
It is placed in cryogenic box, is cooled to subzero 60 DEG C and keeps the temperature 30 minutes.It is controlled with syringe pump, by 10ml MoCl5Reaction solution A with
0.5ml min-1Rate be added dropwise in the reduction agent carrier mixed dispersion liquid of 125mL.Mixing liquid is under the conditions of subzero 60 DEG C
Continue after being stirred to react 2h, is recycled and cleaned using cryogenic vacuum suction filtration, and in natural drying at room temperature.It can be obtained atom
The Rh of grade dispersion1/TiO2Composite material.
Technical solution of the present invention is described in detail in above-described embodiment.It is apparent that the present invention is not limited being retouched
The embodiment stated.Based on the embodiments of the present invention, those skilled in the art can also make a variety of variations accordingly, but appoint
What is equal with the present invention or similar variation shall fall within the protection scope of the present invention.
Claims (4)
1. a kind of method of low temperature liquid phase synthesized high-performance metal material, which comprises the following steps:
(1) the metallic precursor solution A that preparation molar concentration is 0.001-1.0mol/L, the metal precursor are soluble
Metallic compound, the metal include in Ti, V, Cr, Mn, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt and Au
It is any one or more of, the solvent of the solution include water, ethyl alcohol, ethylene glycol, acetone, chloroform, ether, tetrafluoro hydrogen mutter, two
Any one or more of methylformamide or formaldehyde mix in proportion；
(2) liquid phase synthesis redox reaction system is selected, the reaction system includes: electronation, photo-reduction and ultrasound
Reduction.Wherein, reducing agent includes NaBH4,KBH4,N2H4,N2H5OH, formaldehyde, formic acid, ascorbic acid, Na2SO3,K2SO3,
H2C2O4, any one or more of ultraviolet light, visible light, full light and ultrasonic wave；The solvent of the redox reaction includes
Water, ethyl alcohol, ethylene glycol, acetone, chloroform, ether, tetrafluoro hydrogen mutters, any one or more of dimethylformamide or formaldehyde by
Ratio mixes；
(3) under ultra-low temperature surroundings, by step (1) prepare metallic precursor solution A, introduce step (2) described in photo-reduction,
It in ultrasonic reducing environment or is added in the solution of chemical reduction reaction described in step (2), original sufficiently can be obtained after reaction
The metal material dispersion liquid of sub- grade dispersion；
(4) at low ambient temperatures, will step (3) preparation atom level dispersion metal material homogeneous dispersion stirring after be centrifuged or
Vacuum filtration obtains corresponding high-performance metal materials after dry.
2. the method according to claim 1, wherein metal material described in step (1) includes one or more
The monatomic of metallic element composition, diatomic, polyatom, elementide or ultrafine metal nanoparticles structure.
3. the method according to claim 1, wherein addition can load in step (3) described ultra-low temperature surroundings
The support dispersion of resulting material, range of reaction temperature are -120 DEG C -0 DEG C, stirring rate 100-5000rpm.
4. the method according to claim 1, wherein in step (4) described low temperature environment, range of reaction temperature
It is -120 DEG C -0 DEG C, mixing time control is 10-600min, stirring rate 100-5000rpm.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101530796A (en) * | 2009-04-11 | 2009-09-16 | 泰山医学院 | Catalyst for catalytic oxidation of CO at low temperature and preparation method thereof |
| CN102553579A (en) * | 2011-05-27 | 2012-07-11 | 中国科学院福建物质结构研究所 | Preparation method of high-dispersity supported nano metal catalyst |
| CN103192090A (en) * | 2013-04-11 | 2013-07-10 | 贵研铂业股份有限公司 | Liquid-phase preparation method of monodisperse spherical gold, platinum and palladium alloy powder |
| US20160010229A1 (en) * | 2013-02-26 | 2016-01-14 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for synthesizing bimetal catalyst particles made of platinum and of another metal and use thereof in an electrochemical hydrogen production method |
| CN106334555A (en) * | 2016-11-15 | 2017-01-18 | 烟台大学 | High-activity and high-stability supported nanometer gold catalyst, preparation and application method |
| CN106914237A (en) * | 2017-02-28 | 2017-07-04 | 清华大学 | A kind of monoatomic preparation method of metal |
-
2018
- 2018-07-26 CN CN201810831613.8A patent/CN109014238A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101530796A (en) * | 2009-04-11 | 2009-09-16 | 泰山医学院 | Catalyst for catalytic oxidation of CO at low temperature and preparation method thereof |
| CN102553579A (en) * | 2011-05-27 | 2012-07-11 | 中国科学院福建物质结构研究所 | Preparation method of high-dispersity supported nano metal catalyst |
| US20160010229A1 (en) * | 2013-02-26 | 2016-01-14 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for synthesizing bimetal catalyst particles made of platinum and of another metal and use thereof in an electrochemical hydrogen production method |
| CN103192090A (en) * | 2013-04-11 | 2013-07-10 | 贵研铂业股份有限公司 | Liquid-phase preparation method of monodisperse spherical gold, platinum and palladium alloy powder |
| CN106334555A (en) * | 2016-11-15 | 2017-01-18 | 烟台大学 | High-activity and high-stability supported nanometer gold catalyst, preparation and application method |
| CN106914237A (en) * | 2017-02-28 | 2017-07-04 | 清华大学 | A kind of monoatomic preparation method of metal |
Non-Patent Citations (1)
| Title |
|---|
| 钭启升: "低温化学法合成单晶氧化锌纳米带", 《材料研究学报》 * |
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