CN105696048A - Preparation method of hierarchical porous material - Google Patents
Preparation method of hierarchical porous material Download PDFInfo
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- CN105696048A CN105696048A CN201410697812.6A CN201410697812A CN105696048A CN 105696048 A CN105696048 A CN 105696048A CN 201410697812 A CN201410697812 A CN 201410697812A CN 105696048 A CN105696048 A CN 105696048A
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Abstract
The invention relates to a preparation method of a hierarchical porous material, and in particular to a two-step method, which conducts electrochemical oxidation on a precursor selected from gold, copper, silver, iron, nickel and other metals in a certain electrolyte, and then conducts electrochemical and light, electron beam, radiation, laser, heating and other methods for reduction. Compared with the prior art, the preparation method of the hierarchical porous material has the advantages of greenness, simpleness, easiness to implement, low cost of production and controllable porosity and pore size distribution of porous metal in the preparation process.
Description
Technical field
The invention belongs to technical field of material, more particularly to the preparation method of a kind of classifying porous material。
Background technology
Nano porous metal is the class novel nano structure material grown up this year, there is due to it the features such as specific surface area is big, density is little, flexible structure is adjustable, good penetrability so that porous material is widely used in the fields such as separation, catalysis, sensing, medicine, electrode, machinery。
A kind of common method preparing porous metals is de-alloyage and template。De-alloy approach generally to adopt specialty alloys as raw material, and alloy generally adopts metallurgical method to prepare, two kinds of electrochemical potentialses differ bigger metal and constitute。Control to dissolve metallic element relatively active in raw material by the method for electrolysis or chemical attack, thus producing pore space structure in raw material。The hole skeleton finally remained is made up of the metal of relative inertness in raw material。Template, technique relative complex, cost is high, it is difficult to realize industrialized production, and the pore structure of silver prepared by employing said method is single simultaneously, and is difficult to control to。
Summary of the invention
The present invention is directed to problems of the prior art, invent a kind of method preparing porous material being simply easily achieved。
For realizing foregoing invention content, the present invention realizes by the following technical solutions:
The preparation method of described classifying porous material, for adopting electrochemical method that metal material carries out oxidation processes in electrolyte, then carries out the prepared classifying porous material of reduction to the metal material after processing；
Described electrolyte contains cation that can be corresponding with described metal material and forms the anion of precipitation, and do not contain can with the metal cation of described metal material generation displacement reaction。
Described metal material is one or more the alloy in gold, silver, copper, zinc, ferrum, nickel, aluminum, magnesium, lead。
Containing the total mol concentration anion more than 1mM in described electrolyte, described anion is PO4 3-、S2-、CO3 2-, Cl-、Br-、I-In one or more, described electrolyte contains the molar concentration cation more than 1mM simultaneously, described cation is Na+、K+、H+In one or two or more。
Described method of reducing is one or more in electrochemical reduction, photoreduction, e-beam reduction, radiation reduction, laser reduction。
Metal material is carried out the detailed process of oxidation processes for described metal material for working electrode by described employing electrochemical method in electrolyte, with the one in platinum, graphite rod, silver, gold for electrode, silver/silver chloride, hydrargyrum/mercury oxide or saturated calomel are reference electrode, carry out electrochemicial oxidation with the solution containing the anion of cation formation precipitation that can be corresponding with described metal material for electrolyte。
Described classifying porous material is assembled, by metal nanoparticle, the one-level Porous materials aggregation that formed, and one-level Porous materials aggregation is again assembled and is connected with each other and formed；Described one-level Porous materials aggregation has one-level hole, between the one-level Porous materials aggregation again assembled, there is second hole；Obtained classifying porous material has graded porous structure, and the aperture in its one-level hole is 5-300nm, and the aperture of second hole is 0.5-5 μm。
When described reduction treatment is abundant, obtained classifying porous material is the corresponding porous metal material of described metal material；When described reduction treatment is insufficient, obtained classifying porous material is the composite of described metal material metal salt precipitate corresponding with described metal material or alkali precipitation。
In described prepared classifying porous material, the space stayed when one-level hole is by the nanoparticle aggregation of described metal material is constituted；The space that the aggregation that described second hole is formed by the nanoparticle aggregation of metal material stays when again assembling is constituted。
In described prepared classifying porous material, the diameter of metal material nanoparticle is 10-100nm, described nanoparticle aggregation formed aggregation be sized to 1-6 μm。
Compared with prior art, the preparation method of classifying porous material of the present invention has environmental protection, simplicity, easy to implement, production cost is low；And the aperture of porous metals and the advantage such as porosity distribution is controlled in preparation process。
Accompanying drawing illustrates:
Fig. 1 is the stereoscan photograph of the classifying porous silver of embodiment 2 preparation。
Detailed description of the invention:
Embodiment 1: the preparation Na containing 0.1M3PO4Solution and it can be used as electrolyte, magnesium sheet is as working electrode, platinized platinum is to electrode, hydrargyrum/mercuric oxide electrode is reference electrode, first under 2.5V (relative to reversible hydrogen electrode), carry out electrochemicial oxidation 2h, carry out electrochemical reduction 200s under-1.5V (relative to reversible hydrogen electrode) more afterwards and obtain porous magnesium。
Embodiment 2: prepare the solution of the NaBr containing 0.2M and it can be used as electrolyte, filamentary silver is as working electrode, platinized platinum is to electrode, silver/silver chloride electrode is reference electrode, first under 1.2V (relative to reversible hydrogen electrode), carry out electrochemicial oxidation 3h, carry out electrochemical reduction 250s under 0.12V (relative to reversible hydrogen electrode) more afterwards and obtain porous silver。
Embodiment 3: the preparation Na containing 0.3M3PO4Solution and it can be used as electrolyte, aluminium foil is as working electrode, platinized platinum is to electrode, saturated calomel electrode is reference electrode, first under 2.0V (relative to reversible hydrogen electrode), carry out electrochemicial oxidation 1h, carry out electrochemical reduction 150s under-1.0V (relative to reversible hydrogen electrode) more afterwards and obtain porous aluminum。
Embodiment 4: the preparation Na containing 0.4M2The solution of S also it can be used as electrolyte zine plate as working electrode, platinized platinum is to electrode, hydrargyrum/mercuric oxide electrode is reference electrode, first under 1.8V (relative to reversible hydrogen electrode), carry out electrochemicial oxidation 30min, carry out electrochemical reduction 100s under-1.3V (relative to reversible hydrogen electrode) more afterwards and obtain porous zinc。
Embodiment 5: the preparation Na containing 0.5M3PO4Solution and it can be used as electrolyte, iron plate is as working electrode, platinized platinum is to electrode, silver/silver chloride electrode, first under 2.6V (relative to reversible hydrogen electrode), carry out electrochemicial oxidation 1.5h, carry out electrochemical reduction 300s under-1.2V (relative to reversible hydrogen electrode) more afterwards and obtain porous iron。
Embodiment 6: the preparation Na containing 0.6M2The solution of S also it can be used as electrolyte, stereotype is as working electrode, platinized platinum is to electrode, hydrargyrum/mercuric oxide electrode is reference electrode, first under 2.0V (relative to reversible hydrogen electrode), carry out electrochemicial oxidation 2.5h, carry out electrochemical reduction 500s under-0.9V (relative to reversible hydrogen electrode) more afterwards and obtain porous lead。
Embodiment 7: the preparation Na containing 0.7M2CO3Solution and it can be used as electrolyte, copper sheet is as working electrode, platinized platinum is to electrode, hydrargyrum/mercuric oxide electrode is reference electrode, first under 1.5V (relative to reversible hydrogen electrode), carry out electrochemicial oxidation 4h, carry out electrochemical reduction 1000s under-1.4V (relative to reversible hydrogen electrode) more afterwards and obtain Porous Cu。
Fig. 1 is the stereoscan photograph of the porous silver according to embodiment 2 preparation, and the classifying porous silver as can be seen from the figure prepared by this method has loose structure, and the aperture in its one-level hole is 5-300nm, and the aperture of second hole is 0.5-5 μm。
Claims (9)
1. the preparation method of a classifying porous material, it is characterised in that: adopt electrochemical method that metal material carries out oxidation processes in electrolyte, then the metal material after processing is carried out the prepared classifying porous material of reduction；
Described electrolyte contains cation that can be corresponding with described metal material and forms the anion of precipitation, and do not contain can with the metal cation of described metal material generation displacement reaction。
2. the preparation method of classifying porous material as claimed in claim 1, it is characterised in that: described metal material is one or more the alloy in gold, silver, copper, zinc, ferrum, nickel, aluminum, magnesium, lead。
3. the preparation method of classifying porous material as claimed in claim 1 or 2, it is characterised in that: containing the total mol concentration anion more than 1mM in described electrolyte, described anion is PO4 3-、S2-、CO3 2-, Cl-、Br-、I-In one or more, containing the total mol concentration cation more than 1mM in described electrolyte, described cation is Na+、K+、H+In one or two or more。
4. the preparation method of classifying porous material as claimed in claim 1, it is characterised in that: described method of reducing is one or more in electrochemical reduction, photoreduction, e-beam reduction, radiation reduction, laser reduction。
5. the preparation method of classifying porous material as claimed in claim 1, it is characterized in that: metal material is carried out the detailed process of oxidation processes for described metal material for working electrode by described employing electrochemical method in electrolyte, with the one in platinum, graphite rod, silver, gold for electrode, silver/silver chloride, hydrargyrum/mercury oxide or saturated calomel are reference electrode, carry out electrochemicial oxidation with the solution containing the anion of cation formation precipitation that can be corresponding with described metal material for electrolyte。
6. the preparation method of classifying porous material as described in as arbitrary in claim 1-5, it is characterised in that: the one-level Porous materials aggregation formed assembled by described classifying porous material by metal nanoparticle, and one-level Porous materials aggregation is again assembled and is connected with each other and formed；Described one-level Porous materials aggregation has one-level hole, between the one-level Porous materials aggregation again assembled, there is second hole；
Obtained classifying porous material has graded porous structure, and the aperture in its one-level hole is 5-300nm, and the aperture of second hole is 0.5-5 μm。
7. the preparation method of the classifying porous material as described in as arbitrary in claim 1-5, it is characterised in that: when described reduction treatment is abundant, obtained classifying porous material is the corresponding porous metal material of described metal material；
When described reduction treatment is insufficient, obtained classifying porous material is the composite of described metal material metal salt precipitate corresponding with described metal material or alkali precipitation。
8. the preparation method of classifying porous material as claimed in claim 6, it is characterised in that: in described prepared classifying porous material, the space stayed when one-level hole is by the nanoparticle aggregation of described metal material is constituted；The space that the aggregation that described second hole is formed by the nanoparticle aggregation of metal material stays when again assembling is constituted。
9. the preparation method of classifying porous material as claimed in claim 8, it is characterised in that: in described prepared classifying porous material, the diameter of metal material nanoparticle is 10-100nm, described nanoparticle aggregation formed aggregation be sized to 1-6 μm。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410697812.6A CN105696048A (en) | 2014-11-27 | 2014-11-27 | Preparation method of hierarchical porous material |
| EP14894183.4A EP3231512B1 (en) | 2014-11-27 | 2014-12-19 | Preparation method of hierarchical porous material |
| PCT/CN2014/094286 WO2016082262A1 (en) | 2014-11-27 | 2014-12-19 | Hierarchical porous material and preparation method therefor |
| US14/900,440 US10052613B2 (en) | 2014-11-27 | 2014-12-19 | Hierarchical porous material and the preparation method thereof |
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| CN201410697812.6A CN105696048A (en) | 2014-11-27 | 2014-11-27 | Preparation method of hierarchical porous material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106563816A (en) * | 2016-10-26 | 2017-04-19 | 陕西科技大学 | Preparation method of wave absorbing material with nickel nanoparticles wrapped with porous carbon-loaded graphene |
| CN106910635A (en) * | 2017-02-24 | 2017-06-30 | 中国科学院合肥物质科学研究院 | A kind of orderly hole array anode tantalum foil for tantalum capacitor and preparation method thereof |
| CN107904645A (en) * | 2017-10-19 | 2018-04-13 | 天津大学 | A kind of anodized surface processing method for improving metal molybdenum foil surface-active |
| CN111020508A (en) * | 2019-12-23 | 2020-04-17 | 有研亿金新材料有限公司 | High-density fine-grain non-preferred-orientation W target and manufacturing method thereof |
| CN115229200A (en) * | 2022-07-26 | 2022-10-25 | 西安培华学院 | Preparation method of cubic porous silver micron material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106563816A (en) * | 2016-10-26 | 2017-04-19 | 陕西科技大学 | Preparation method of wave absorbing material with nickel nanoparticles wrapped with porous carbon-loaded graphene |
| CN106910635A (en) * | 2017-02-24 | 2017-06-30 | 中国科学院合肥物质科学研究院 | A kind of orderly hole array anode tantalum foil for tantalum capacitor and preparation method thereof |
| CN107904645A (en) * | 2017-10-19 | 2018-04-13 | 天津大学 | A kind of anodized surface processing method for improving metal molybdenum foil surface-active |
| CN107904645B (en) * | 2017-10-19 | 2019-10-11 | 天津大学 | A kind of anodized surface processing method improving metal molybdenum foil surface-active |
| CN111020508A (en) * | 2019-12-23 | 2020-04-17 | 有研亿金新材料有限公司 | High-density fine-grain non-preferred-orientation W target and manufacturing method thereof |
| CN115229200A (en) * | 2022-07-26 | 2022-10-25 | 西安培华学院 | Preparation method of cubic porous silver micron material |
| CN115229200B (en) * | 2022-07-26 | 2024-04-09 | 西安培华学院 | Preparation method of cube-shaped porous silver micrometer material |
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Application publication date: 20160622 |