CN112404448A - Low-temperature large-scale preparation method of three-dimensional reticular nano-structure metal foam material - Google Patents
Low-temperature large-scale preparation method of three-dimensional reticular nano-structure metal foam material Download PDFInfo
- Publication number
- CN112404448A CN112404448A CN201910793285.1A CN201910793285A CN112404448A CN 112404448 A CN112404448 A CN 112404448A CN 201910793285 A CN201910793285 A CN 201910793285A CN 112404448 A CN112404448 A CN 112404448A
- Authority
- CN
- China
- Prior art keywords
- solution
- nano
- agno
- temperature
- dimensional reticular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
Abstract
The invention discloses a low-temperature large-scale preparation method of a three-dimensional reticular nano-structure metal foam material, which comprises the following steps: in an ice-water bath, AgNO is added3、HAuCl4、K2PdCl4、K2PtCl6Mixing the single aqueous solution with glycerol under vigorous stirring, rapidly adding water and hydrazine to generate a suspension product under constant-temperature oscillation, and finally washing and freeze-drying; the adjustment and control of the porosity and the size of the foam-like nano structure are realized by adjusting the concentration. The general method provided by the invention has the advantages of simple device, mild conditions and easy realization of large-scale production.
Description
Technical Field
The invention relates to a preparation method of a three-dimensional reticular nano-structure metal foam material, in particular to a method capable of realizing low-temperature large-scale preparation under the condition of not using any template and surfactant.
Background
The three-dimensional reticular metal foam material with the nano structure has wide application in the technical fields of catalysis, Raman biomolecule detection, gas sensing, water purification, energy storage and the like, because the material has the characteristics of low density, high specific surface area, high gas permeability and the like, and simultaneously, the performance can be improved by reducing the size of a connector, forming a high-index surface, combining with other metals and the like. However, the three-dimensional net-shaped nanostructure reported internationally at present is mainly concentrated on metal oxides, and the common template method is not suitable for preparing the noble metal three-dimensional net-shaped nanostructure foam material.
In recent years, a number of methods for synthesizing a three-dimensional network nanostructure noble metal foam have been internationally reported, such as a dealloying method, a glucose reduction method under PH control, a reaction-limited aggregation method, and an emulsion synthesis method. These methods have disadvantages such as complicated preparation steps or are limited to a small number of kinds of noble metals. In particular, when the materials are synthesized in a hydrothermal severe environment, the surfactant is indispensable in the synthesis process and is difficult to expand into large-scale industrial production. One key step to achieve precise control of the nanostructure is to combine the advantages of rapid reduction of nanoparticle nucleation and growth, followed by slow assembly and thermally induced fusion. The invention provides a low-temperature large-scale preparation method of a three-dimensional reticular nano-structure metal foam material, which realizes the regulation and control of the porosity and the size of a foamy nano-structure by controlling reaction kinetics at low temperature and regulating the concentration of a reaction solution under the condition of no template and no surfactant. The general method provided by the invention is simple in device, can be carried out at low temperature, and is easy to realize large-scale production.
Disclosure of Invention
The invention aims to provide a universal low-temperature large-scale preparation method of a three-dimensional reticular nano-structure metal foam material. AgNO is added in ice-water bath3Mixing the solution with glycerol, and rapidly adding water and hydrazine into the mixed solution by adopting vigorous stirring; adding ethanol into the mixed solution, and aggregating the suspension by constant-temperature oscillation; shaking and washing the product with distilled water, and freeze-drying to obtain three-dimensional net-shaped nano porous Ag; when HAuCl is used4、K2PdCl4And K2PtCl6Solution replacement of AgNO3When the solution is used, the three-dimensional reticular nano-structure gold, palladium and platinum foam materials can be prepared respectively. The method is simple, rapid and economical.
In order to achieve the purpose, the invention provides the following technical scheme: at a certain concentrationAgNO3Mixing the solution with 6mL of glycerol, and placing the mixture in an ice-water bath at 0 ℃ to obtain a colorless and transparent mixed solution; in the process of violent stirring, 3mL of water and hydrazine are quickly added into the mixed solution, and the mixture is continuously stirred for 10min in an ice-water bath to form opaque gray suspension; under the action of continuous stirring, adding 5mL of ethanol into the mixed solution; transferring the suspension into a constant-temperature oscillator, gradually changing to be transparent, and simultaneously enabling yellow-gray spongy solids to be gathered and suspended in the solution; and (3) cleaning the floating objects by using distilled water, and freeze-drying to obtain a target product, namely the three-dimensional net-shaped nano porous Ag.
The best proposal is that the reaction mixed solution is required to be placed in an ice water bath at 0 ℃ when being prepared; AgNO3The optimal concentration range of the solution is 5-20 mM.
The best scheme is that the suspension is transferred into a constant temperature oscillator, the reaction temperature is constant at 60 ℃, the oscillation speed is 80 r/min, and the duration is 2 h.
The best scheme is that the final product is subjected to vacuum freeze drying for 12 hours.
When HAuCl is used4、K2PdCl4And K2PtCl6Solution replacement of AgNO3When the solution is used, the three-dimensional reticular nano-structure gold, palladium and platinum foam materials can be prepared respectively.
Compared with the reported preparation method, the preparation method has the following beneficial effects: the preparation method provided by the invention does not use a template and a surfactant, adopts a reaction mixed solution prepared in an ice-water bath at 0 ℃ to inhibit the rapid growth of crystal grains, and adopts a freeze drying method to avoid the damage of surface tension to a porous structure; the adjustment and control of the porosity and the size of the foam-like nano structure are realized by adjusting the concentration of the reaction solution. The preparation method is simple, rapid and economical, and is a universal low-temperature large-scale preparation method.
Drawings
FIG. 1 shows different AgNO's according to the invention3SEM and TEM pictures of the prepared product at concentration: (a)5mM, (b)10mM, (c)15mM and (d)20 mM. (d) The inset is the SAED pattern of the particles in the circle;
FIG. 2 is SEM picture of the three-dimensional reticular nano-structure gold, palladium and platinum foam material prepared in the invention.
Detailed Description
A method for preparing three-dimensional net-shaped nano porous metal is shown in figure 1, and different AgNO are shown in figure 13SEM and TEM pictures of Ag prepared at the concentration, and fig. 2 is SEM picture of gold, palladium and platinum. The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings.
Example 1
The preparation method of the three-dimensional reticular nano-structure foam Ag comprises the following steps: 5mM of AgNO3Mixing the solution with 6ml of glycerol, and placing the mixture in an ice-water bath at the temperature of 0 ℃ to obtain a colorless and transparent mixed solution; rapidly adding 3mL of water and hydrazine into the mixed solution under mechanical stirring at 250 revolutions per minute, and continuously stirring in an ice-water bath for 10min to form opaque gray suspension; under the action of continuous stirring, adding 5mL of ethanol into the mixed solution; transferring the suspension into a constant temperature oscillator at 60 ℃, wherein the oscillation speed is 80 r/min, the oscillation lasts for 2 hours, the suspension gradually becomes transparent, and meanwhile, yellow gray spongy solid is suspended in the solution; and (4) washing the suspended substance with distilled water, and carrying out vacuum freeze drying for 12h to obtain a final product.
Example 2
Mixing AgNO3The concentration of the aqueous solution was changed to 10mM, as in example 1.
Example 3
Mixing AgNO3The concentration of the aqueous solution was changed to 15mM, as in example 1.
Example 4
Mixing AgNO3The concentration of the aqueous solution was changed to 20mM, as in example 1.
FIG. 1 shows different AgNO3SEM and TEM pictures of the three-dimensional reticular nanostructure foam Ag prepared at the concentration. It can be seen that when AgNO is used3The concentration of the solution is lower than 5mM or higher than 20mM, and three-dimensional reticular nano-structure foam cannot be obtained. Too low a concentration results in an insufficient number density of nanoparticles to fuse with other nanoparticles during their activation time. Too high a concentration results in the formation of nanoparticle sizesToo large, eventually forming agglomerates of particles.
Example 5
The preparation method of the three-dimensional reticular nano-structure foam gold comprises the following steps: AgNO at a concentration of 5mM as in example 13The aqueous solution was changed to HAuCl at a concentration of 10mM4The aqueous solution was prepared under the same conditions as in example 1.
Example 6
The preparation method of the three-dimensional reticular nano-structure foam palladium comprises the following steps: AgNO at a concentration of 5mM as in example 13The aqueous solution was changed to a concentration of 10mM K2PdCl4The aqueous solution was prepared under the same conditions as in example 1.
Example 7
The preparation method of the three-dimensional reticular nano-structure foam palladium comprises the following steps: AgNO at a concentration of 5mM as in example 13The aqueous solution was changed to a concentration of 10mM K2PtCl6The aqueous solution was prepared under the same conditions as in example 1.
In fig. 2, (a-c) correspond to SEM pictures of three-dimensional reticulated nanostructure foam gold, palladium, and platinum products prepared in examples 5, 6, and 7, respectively. It can be clearly seen that the three-dimensional reticular porous structure is uniformly distributed, and a large number of nano particles with uniform size exist in the single connecting nano wire forming the network structure. Meanwhile, the preparation method provided by the invention is a general method. Particularly, the adjustment and control of the porosity and the size of the foam-like nano structure can be realized by adjusting the concentration of the reaction solution.
The technical solutions of the present invention or similar technical solutions designed by those skilled in the art based on the teachings of the technical solutions of the present invention are all within the scope of the present invention to achieve the above technical effects.
Claims (5)
1. A low-temperature large-scale preparation method of a three-dimensional reticular nano-structure metal foam material is characterized in that AgNO with a certain concentration is used3Mixing the solution with 6mL of glycerol, and placing the mixture in an ice-water bath at 0 ℃ to obtain a colorless and transparent mixed solution; during vigorous stirring, 3mL of water and rapidly added to the mixed solutionHydrazine, stirring continuously in ice water bath for 10min to form opaque gray suspension; under the action of continuous stirring, adding 5mL of ethanol into the mixed solution; transferring the suspension into a constant-temperature oscillator, gradually changing to be transparent, and simultaneously enabling yellow-gray spongy solids to be gathered and suspended in the solution; and (3) cleaning the floating objects by using distilled water, and freeze-drying to obtain a target product, namely the three-dimensional net-shaped nano porous Ag.
2. The method according to claim 1, wherein the reaction mixture solution is prepared by placing in an ice-water bath at 0 ℃; AgNO3The concentration range of the solution is 5-20 mM.
3. The process according to claim 1, wherein the suspension is transferred to a constant temperature oscillator at a constant reaction temperature of 60 ℃ and at an oscillation rate of 80 rpm for a duration of 2 h.
4. The method of claim 1, wherein the final product is lyophilized under vacuum for 12 h.
5. The method of claim 1, wherein the method is a general low-temperature large-scale method of preparation when HAuCl is used4、K2PdCl4And K2PtCl6Solution replacement of AgNO3When the solution is used, the three-dimensional reticular nano-structure gold, palladium and platinum foam materials can be prepared respectively, and large-scale production is easy to realize.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910793285.1A CN112404448A (en) | 2019-08-23 | 2019-08-23 | Low-temperature large-scale preparation method of three-dimensional reticular nano-structure metal foam material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910793285.1A CN112404448A (en) | 2019-08-23 | 2019-08-23 | Low-temperature large-scale preparation method of three-dimensional reticular nano-structure metal foam material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112404448A true CN112404448A (en) | 2021-02-26 |
Family
ID=74779873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910793285.1A Pending CN112404448A (en) | 2019-08-23 | 2019-08-23 | Low-temperature large-scale preparation method of three-dimensional reticular nano-structure metal foam material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112404448A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113245554A (en) * | 2021-04-21 | 2021-08-13 | 中山大学 | Silver porous material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003088A (en) * | 2006-12-08 | 2007-07-25 | 中国工程物理研究院激光聚变研究中心 | Organism single layer protecting metal-group foam material, and its preparing method |
| CN106670495A (en) * | 2015-11-06 | 2017-05-17 | 南京大学 | Preparation method of network-state Ag-Au-Pd trimetal porous material |
| CN107785558A (en) * | 2017-10-27 | 2018-03-09 | 重庆特瑞新能源材料有限公司 | A kind of preparation method of lithium iron phosphate/carbon composite positive pole |
| CN108202146A (en) * | 2017-12-29 | 2018-06-26 | 华中科技大学 | A kind of three-dimensional porous graphene package nano zero-valence carbon/carbon-copper composite material and preparation method |
| US20180311737A1 (en) * | 2015-11-30 | 2018-11-01 | The Regents Of The University Of California | Low-density interconnected metal foams and methods of manufacture |
-
2019
- 2019-08-23 CN CN201910793285.1A patent/CN112404448A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003088A (en) * | 2006-12-08 | 2007-07-25 | 中国工程物理研究院激光聚变研究中心 | Organism single layer protecting metal-group foam material, and its preparing method |
| CN106670495A (en) * | 2015-11-06 | 2017-05-17 | 南京大学 | Preparation method of network-state Ag-Au-Pd trimetal porous material |
| US20180311737A1 (en) * | 2015-11-30 | 2018-11-01 | The Regents Of The University Of California | Low-density interconnected metal foams and methods of manufacture |
| CN107785558A (en) * | 2017-10-27 | 2018-03-09 | 重庆特瑞新能源材料有限公司 | A kind of preparation method of lithium iron phosphate/carbon composite positive pole |
| CN108202146A (en) * | 2017-12-29 | 2018-06-26 | 华中科技大学 | A kind of three-dimensional porous graphene package nano zero-valence carbon/carbon-copper composite material and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 尹艳红等: "三维网状结构Ru/石墨烯/碳纳米管复合材料作为锂氧电池正极催化剂的性能", 《高等学校化学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113245554A (en) * | 2021-04-21 | 2021-08-13 | 中山大学 | Silver porous material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fang et al. | Mesocrystals: Syntheses in metals and applications | |
| Boyjoo et al. | Synthesis of micro and nano-sized calcium carbonate particles and their applications | |
| US10875098B2 (en) | Methods of controlling nanostructure formations and shapes | |
| Zhou et al. | Decahedral nanocrystals of noble metals: Synthesis, characterization, and applications | |
| Niu et al. | Seed-mediated growth of noble metal nanocrystals: crystal growth and shape control | |
| Ji et al. | Synthesis, growth mechanism, and applications of zinc oxide nanomaterials | |
| Tang et al. | PVP-assisted sonoelectrochemical growth of silver nanostructures with various shapes | |
| Yang et al. | Shaping particles by chemical diffusion and reaction | |
| CN108430676B (en) | Method for synthesizing metal nanoparticles in an aqueous environment without the use of shape-directing agents | |
| CN106141171B (en) | Hud typed superstructure nano material, its preparation method and application | |
| CN108356284B (en) | Preparation method of silver nanocubes | |
| Chang et al. | Electrochemical synthesis to convert a Ag film into Ag nanoflowers with high electrocatalytic activity | |
| CN105522168B (en) | Preparing method of cube platinum ruthenium core-shell nanocrystalline and product of preparing method | |
| CN104308175A (en) | Spheroidal gold particle and step-by-step rapid synthesis method thereof | |
| Wei et al. | PH controlled synthesis of high aspect-ratio gold nanorods | |
| Qiu et al. | Controllable synthesis of palladium nanoparticles via a simple sonoelectrochemical method | |
| CN112404448A (en) | Low-temperature large-scale preparation method of three-dimensional reticular nano-structure metal foam material | |
| CN109304477A (en) | A kind of high length-diameter ratio silver nanowires raw powder's production technology | |
| CN106670496A (en) | Preparation method of copper nanowires or copper nanoparticles | |
| CN109834292B (en) | Macroscopic large-area two-dimensional Janus nano gold film and preparation method and application thereof | |
| Jing et al. | Microorganism‐mediated, CTAC‐directed synthesis of SERS‐sensitive Au nanohorns with three‐dimensional nanostructures by Escherichia coli cells | |
| Deng et al. | A generic in situ seed-mediated size-control method in the case of cuprous oxide nanocubes and their antibacterial activities | |
| CN101380679A (en) | Method for preparing monodisperse superfine globular nickel powder using precursor complexes | |
| CN103752841B (en) | A kind of preparation method of copper nanoparticle | |
| Fu et al. | Single-crystal ZnO cup based on hydrothermal decomposition route |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210226 |
|
| WD01 | Invention patent application deemed withdrawn after publication |