CN103934468A - Supercritical hydrothermal synthesis method of nano metal or nano metal oxide particles - Google Patents
Supercritical hydrothermal synthesis method of nano metal or nano metal oxide particles Download PDFInfo
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- CN103934468A CN103934468A CN201410131897.1A CN201410131897A CN103934468A CN 103934468 A CN103934468 A CN 103934468A CN 201410131897 A CN201410131897 A CN 201410131897A CN 103934468 A CN103934468 A CN 103934468A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a supercritical hydrothermal synthesis method of nano metal or nano metal oxide particles. The method includes the following steps that soluble metal salt solution and alkali liquor (or a mixture of alkali liquor, reducing agent solution and organic ligands) are fully mixed to serve as reaction precursors of supercritical hydrothermal synthesis; the reaction precursors and preheated supercritical water are pressurized and pumped into a mixer through a high-pressure pump, after temperature is raised in a direct mixing mode, supercritical hydrothermal synthesis reaction is conducted; after a period of reaction, the obtained product is cooled, centrifuged and dried, and the nano metal or nano metal oxide particles are obtained. The nano metal or nano metal nano metal oxide particles produced through the method have the advantages of being small in particle size, good in dispersibility, high in purity and the like.
Description
[technical field]
The present invention relates to a kind of preparation method of nano particle, particularly relate to the supercritical water process for thermosynthesizing of a kind of nano metal or nano-metal-oxide particle.
[background technology]
Nano metal or nano-metal-oxide particle are important industrial products, compared with common metal or metal-oxide powder, there is more superior performance, as large specific area, interfacial effect, quantum effect and quantum tunneling effect etc., give it and be different from the various special performances of traditional material and special electricity, calorifics, magnetics, optics and mechanical property, be widely used in every field, as being used as catalyst, have the features such as particle diameter is little, specific surface large, the activated centre number of particle surface is many, catalytic efficiency is high, selectively strong; Aspect sensor, as the coating film of sensor, can greatly improve the selective and sensitivity of sensor; At battery industry, be expected to the negative material for high-performance chemical battery; For the colouring agent, tail gas clean-up material, slider material etc. of glass, pottery.
Traditional nanometer grain preparation method is divided into Physical and the large class of chemical method two.Physical comprises mechanical milling method and physical vaporous deposition, and its shortcoming is complex process equipment, yields poorly, and large-scale production difficulty is larger.Microemulsion method and spray pyrolysis etc. generally all will pass through high-temperature heat treatment, cause particle easily to be reunited, and occur particle misgrowth phenomenon.And conventional hydro-thermal method is longer reaction time, conventionally need several hours, even reaction time a couple of days, the unavoidable larger problem of germination.It is a kind of comparative maturity and industrial process that chemical electrolysis method is prepared nano-metal particle, but the metal dust obtaining conventionally need to pass through the techniques such as ball milling, sub-sieve again and just finally obtain ultra-fine metallic particles, and in electrolysis waste solution, contain a large amount of metal ions, discharge can cause the pollution of the wasting of resources and environment arbitrarily, thereby has restricted the large-scale application of the method.Liquid phase reduction is the nanometer grain preparation method comparatively enlivening in recent years, but the method need adopt the additive component of a large amount of organic solvents or severe toxicity conventionally, causes aborning severe contamination, and its application is very limited.Therefore, green, the efficient nano particle technology of preparing of exploration taking water as reaction medium is significant.
Supercritical water (Supercritical water, be called for short SCW) refers to that temperature and pressure is all higher than the water of the special state of its critical point (T=374.15 DEG C, P=22.12MPa).Supercritical water has the character of liquid and vaporous water concurrently, only has a small amount of hydrogen bond to exist in the water under this state, and dielectric constant is similar to organic solvent, has high diffusion coefficient and low viscosity.Overcritical hydrothermal synthesis reaction refers in airtight high-pressure reactor, using supercritical water as reaction medium, make that slaine is hydrolyzed in hydro-thermal medium, dehydration, and then nucleation, growth, the final reaction that forms the nanocrystal with certain particle size and crystal habit.In supercritical water, the nonpolarity gases such as reductive organic matter or hydrogen can with the miscible formation homogeneous reaction system of supercritical water, realize metal oxide and efficiently reduce, generate highly purified metal nanoparticle.Because reaction medium is supercritical water, course of reaction is carried out in airtight high-pressure bottle, thereby can not introduce other pollutant in course of reaction, is considered to a kind of fabrication technology of environmental protection.
[summary of the invention]
The object of this invention is to provide the supercritical water process for thermosynthesizing of a kind of nano metal or nano-metal-oxide particle, nano metal prepared by the method or nano-metal-oxide composition granule have that particle diameter is little, favorable dispersibility, purity advantages of higher.
For achieving the above object, the present invention is achieved by the following technical solutions:
The supercritical water process for thermosynthesizing of nano metal or nano-metal-oxide particle, comprises the steps:
1) adopt pure water to dissolve soluble metallic salt, obtain soluble metal salting liquid;
2) respectively the mixture of the soluble metal salting liquid obtaining and alkali lye or alkali lye, reducing agent and organic ligand is forced into supercritical pressure, and at normal temperatures both is carried out to premixed, obtain the pre-reaction material for overcritical hydrothermal synthesis reaction;
3) by step 2) pre-reaction material that obtains directly mixes with the supercritical water through preheating, be heated to supercriticality, go forward side by side in supercritical water thermal synthesis reactor and carry out overcritical hydrothermal synthesis reaction, after question response completes, product is carried out to cooling, step-down and collection, obtain product sample;
4) the product sample of gained is carried out to centrifugation, washing, dry, can obtain nano metal or nano-metal-oxide granular product.
The present invention further improves and is: soluble metallic salt is sulfate, nitrate or chlorate.
The present invention further improves and is: in the time of preparation soluble metal salting liquid, it is carried out to preheating to improve the solubility of soluble metallic salt.
The present invention further improves and is: the addition of the mixture of alkali lye or alkali lye, reducing agent and organic ligand should make pre-reaction material be neutral.
The present invention further improves and is: reducing agent is hydrogen or formic acid, and it reduces for the metal ion to high valence state.
The present invention further improves and is: in the molecule of organic ligand, contain carboxyl or the amido of polar functional group, it has heat endurance in supercritical water simultaneously.
The present invention further improves and is: organic ligand is ethylenediamine tetra-acetic acid.
The present invention further improves and is: supercritical water thermal synthesis reactor is batch (-type) supercritical water thermal synthesis reactor or continuous supercritical water thermal synthesis reactor.
The present invention further improves and is: in step 4), after pure water and absolute ethanol washing, carry out vacuum drying at 60 DEG C again.
Compared with prior art, advantage of the present invention is:
Nano metal prepared by the present invention or nano-metal-oxide particle have that particle diameter is little, good dispersion and purity high, and the nano metal obtaining or nano-metal-oxide can be used for additive or the electrode material etc. of effective catalyst, coloring agent.
[brief description of the drawings]
Fig. 1 is the FB(flow block) of the supercritical water process for thermosynthesizing of nano metal of the present invention or nano-metal-oxide particle.
Fig. 2 is the TEM figure of the nano oxidized copper products of gained in the invention process case 1.
Fig. 3 is the XRD figure of the nano oxidized copper products of gained in the embodiment of the present invention 1.
Fig. 4 is the TEM figure of gained Nanometer Copper product in the embodiment of the present invention 2.
Fig. 5 is the XRD figure of gained Nanometer Copper product in the embodiment of the present invention 2.
[detailed description of the invention]
Below in conjunction with the drawings and specific embodiments, the present invention is described in further details.
Referring to Fig. 1, the supercritical water process for thermosynthesizing of nano metal of the present invention or nano-metal-oxide particle, comprises the steps:
1) adopt pure water to dissolve soluble metallic salt, obtain soluble metal salting liquid, in the time of preparation soluble metal salting liquid, can carry out preheating to improve the solubility of soluble metallic salt to it.
2) respectively the mixture of the soluble metal salting liquid obtaining and alkali lye or alkali lye, reducing agent and organic ligand is forced into supercritical pressure, and at normal temperatures both is carried out to premixed, obtain the pre-reaction material for overcritical hydrothermal synthesis reaction; Wherein, the addition of the mixture of alkali lye or alkali lye, reducing agent and organic ligand should make pre-reaction material be neutral, reducing agent can be hydrogen or formic acid, it reduces for the metal ion to high valence state, in the molecule of organic ligand, contain carboxyl or the amido of polar functional group, it has heat endurance in supercritical water simultaneously, such as ethylenediamine tetra-acetic acid.
3) by step 2) pre-reaction material that obtains directly mixes with the supercritical water through preheating, be heated to supercriticality, go forward side by side in supercritical water thermal synthesis reactor and carry out overcritical hydrothermal synthesis reaction, after question response completes, product is carried out to cooling, step-down and collection, obtain product sample; Wherein, supercritical water thermal synthesis reactor is batch (-type) supercritical water thermal synthesis reactor or continuous supercritical water thermal synthesis reactor.
4) the product sample of gained is carried out to centrifugation, after pure water and absolute ethanol washing, at 60 DEG C, carry out again vacuum drying, can obtain nano metal or nano-metal-oxide granular product.
Wherein, above-mentioned soluble metallic salt is sulfate, nitrate or chlorate.
Embodiment 1:
The present embodiment, to adopt the thermal synthesis of copper sulphate supercritical water to prepare nano cupric oxide as example, describes the inventive method, comprises the following steps:
1) by CuSO
45H
2o crystal (Cu (NO
3)
2crystal or CuCl
2crystal) be dissolved in pure water, obtain copper sulphate (copper nitrate or the copper chloride) solution of 0.5mol/L;
2) adopt NaOH solution to regulate the pH value of copper sulphate (copper nitrate or copper chloride) solution neutral to approaching, the pre-reaction material using the mixture obtaining as overcritical hydrothermal synthesis reaction;
3) adopting high-pressure pump respectively by step 2) pre-reaction material generating is directly mixed into supercritical water thermal synthesis reactor with the pure water that is preheated to supercritical temperature, after a period of time in reaction time, (be conventionally less than 1min), collect through product cooling, step-down, adopt centrifugal separator to separate nano cupric oxide product, again through pure water and absolute ethyl alcohol cyclic washing, at 60 DEG C, carry out again, after vacuum drying, can obtaining nano cupric oxide product.
After testing, the granularity of the nano cupric oxide product obtaining is 20～100nm, and particle size were increases with reactant concentration conventionally, and increases and reduce with NaOH addition.
Referring to Fig. 2 and Fig. 3, Fig. 2 is the TEM figure of the nano oxidized copper products of gained in the invention process case 1; Fig. 3 is the XRD figure of the nano oxidized copper products of gained in the embodiment of the present invention 1.As can be seen from Figures 2 and 3, the nano cupric oxide particle that adopts supercritical water thermal synthesis technology to prepare is uniform elliposoidal structure; Can find out from XRD analysis collection of illustrative plates, product is made up of cupric oxide completely, does not have other impurity component.
Embodiment 2:
The present embodiment, to adopt the thermal synthesis of soluble copper salt supercritical water to prepare Nanometer Copper as example, describes the inventive method, comprises the following steps:
1) by CuSO
45H
2o crystal (Cu (NO
3)
2crystal or CuCl
2crystal) be dissolved in pure water, obtain copper sulphate (copper nitrate or the copper chloride) solution of 0.5mol/L;
2) copper sulphate (copper nitrate or the copper chloride) solution obtaining is fully mixed with the mixture of NaOH solution, formic acid solution and ethylenediamine tetra-acetic acid, as the pre-reaction material of overcritical hydrothermal synthesis reaction;
3) adopt high-pressure pump respectively by step 2) generate pre-reaction material directly mix with the pure water that is preheated to supercritical temperature after, enter supercritical water thermal synthesis reactor, after a period of time in reaction time, collect through product cooling, step-down, adopt centrifugal separator to separate Nanometer Copper product, again through pure water and absolute ethyl alcohol cyclic washing, at 60 DEG C, carry out again, after vacuum drying, can obtaining Nanometer Copper product.
After testing, the granularity of the Nanometer Copper product obtaining is 15～80nm, and particle size were increases with reactant concentration conventionally, increases and reduces with NaOH addition; Products therefrom is highly purified nano copper particle, oxygen-freeization copper or cuprous oxide impurity.
Referring to Fig. 4 and Fig. 5, Fig. 4 is the TEM figure of gained Nanometer Copper product in the embodiment of the present invention 2; Fig. 5 is the XRD figure of gained Nanometer Copper product in the embodiment of the present invention 2.As can be seen from Figure 4 and Figure 5, the nano copper particle particle diameter that adopts supercritical water thermal synthesis technology to prepare is evenly distributed, and particle dispersion is good.Can find out from XRD analysis collection of illustrative plates, product is made up of cupric oxide completely, does not have other impurity component; Can find out from XRD analysis collection of illustrative plates, product by pure Nanometer Copper form, very high purity.
Claims (9)
1. the supercritical water process for thermosynthesizing of nano metal or nano-metal-oxide particle, is characterized in that, comprises the steps:
1) adopt pure water to dissolve soluble metallic salt, obtain soluble metal salting liquid;
2) respectively the mixture of the soluble metal salting liquid obtaining and alkali lye or alkali lye, reducing agent and organic ligand is forced into supercritical pressure, and at normal temperatures both is carried out to premixed, obtain the pre-reaction material for overcritical hydrothermal synthesis reaction;
3) by step 2) pre-reaction material that obtains directly mixes with the supercritical water through preheating, be heated to supercriticality, go forward side by side in supercritical water thermal synthesis reactor and carry out overcritical hydrothermal synthesis reaction, after question response completes, product is carried out to cooling, step-down and collection, obtain product sample;
4) the product sample of gained is carried out to centrifugation, washing, dry, can obtain nano metal or nano-metal-oxide granular product.
2. the supercritical water process for thermosynthesizing of nano metal according to claim 1 or nano-metal-oxide particle, is characterized in that: soluble metallic salt is sulfate, nitrate or chlorate.
3. the supercritical water process for thermosynthesizing of nano metal according to claim 1 or nano-metal-oxide particle, is characterized in that: in the time of preparation soluble metal salting liquid, it is carried out to preheating to improve the solubility of soluble metallic salt.
4. the supercritical water process for thermosynthesizing of nano metal according to claim 1 or nano-metal-oxide particle, is characterized in that: the addition of the mixture of alkali lye or alkali lye, reducing agent and organic ligand should make pre-reaction material be neutral.
5. according to the supercritical water process for thermosynthesizing of the nano metal described in claim 1 or 4 or nano-metal-oxide particle, it is characterized in that: reducing agent is hydrogen or formic acid, and it reduces for the metal ion to high valence state.
6. according to the supercritical water process for thermosynthesizing of the nano metal described in claim 1 or 4 or nano-metal-oxide particle, it is characterized in that: in the molecule of organic ligand, contain carboxyl or the amido of polar functional group, it has heat endurance in supercritical water simultaneously.
7. the supercritical water process for thermosynthesizing of nano metal according to claim 6 or nano-metal-oxide particle, is characterized in that: organic ligand is ethylenediamine tetra-acetic acid.
8. the supercritical water process for thermosynthesizing of nano metal according to claim 1 or nano-metal-oxide particle, is characterized in that: supercritical water thermal synthesis reactor is batch (-type) supercritical water thermal synthesis reactor or continuous supercritical water thermal synthesis reactor.
9. the supercritical water process for thermosynthesizing of nano metal according to claim 1 or nano-metal-oxide particle, is characterized in that: in step 4), after pure water and absolute ethanol washing, carry out vacuum drying at 60 DEG C again.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410131897.1A CN103934468B (en) | 2014-04-02 | 2014-04-02 | The supercritical water process for thermosynthesizing of nano metal or metal oxide nano particles |
| PCT/CN2014/090721 WO2015149517A1 (en) | 2014-04-02 | 2014-11-10 | Supercritical hydrothermal synthesis method for metal or metal oxide nanoparticles |
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| CN201410131897.1A CN103934468B (en) | 2014-04-02 | 2014-04-02 | The supercritical water process for thermosynthesizing of nano metal or metal oxide nano particles |
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| CN103934468B CN103934468B (en) | 2016-03-30 |
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| CN104772470A (en) * | 2015-03-26 | 2015-07-15 | 太原理工大学 | Method for preparing heterogeneous crystal nucleus nanometer metal powder by near-and super-critical hydrothermal reduction |
| WO2015149517A1 (en) * | 2014-04-02 | 2015-10-08 | 西安交通大学 | Supercritical hydrothermal synthesis method for metal or metal oxide nanoparticles |
| CN109628164A (en) * | 2018-11-20 | 2019-04-16 | 太原理工大学 | A kind of overcritical hydro-thermal combustion method using nanometer fuel |
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