CN106881087B - One kind cube skeletal porous silver and preparation method thereof - Google Patents
One kind cube skeletal porous silver and preparation method thereof Download PDFInfo
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- CN106881087B CN106881087B CN201510941199.2A CN201510941199A CN106881087B CN 106881087 B CN106881087 B CN 106881087B CN 201510941199 A CN201510941199 A CN 201510941199A CN 106881087 B CN106881087 B CN 106881087B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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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
Abstract
Microcosmic a kind of cube of skeletal porous silver is above cube structure, and its side length is 0.5~1.5 μm；The side of the cubic structure is made of porous silver；The aperture of the porous silver is 20~100nm.The preparation method of described cube of skeletal porous silver, first prepares cube skeleton silver halide with template to be a kind of, later removes template, electrochemical treatments is carried out finally by opposition quadrate bone frame silver halide, to obtain a cube method for skeletal porous silver.Compared with prior art, of the present invention cube of skeletal porous silver has hierarchical porous structure, and when being used as oxygen reduction catalyst, the centre bore of cube skeleton is conducive to the transmission in it of active material, hole on skeleton is conducive to the promotion of active surface area, to be conducive to hydrogen reduction catalysis reaction.The preparation method of described cube of skeletal porous silver is with environmentally protective, easy, easy to implement, production cost is low；And the aperture of porous metals and the advantages that controllable porosity distribution in preparation process.
Description
Technical field
The invention belongs to field of nano material preparation, more particularly to a kind of cube skeletal porous silver；
The invention further relates to the preparation methods of described cube of skeletal porous silver.
Background technique
A kind of novel nano structure material that nano porous metal is this year to grow up, since it has specific surface area
Greatly, the features such as density is small, flexible structure is adjustable, good penetrability, so that porous material is widely used in separation, catalysis, biography
The fields such as sense, medicine, electrode, machinery.Porous silver is due to its excellent physicochemical properties, in catalyst material, electronic ceramics
The fields such as material, antistatic material, biosensor material have wide practical use.
The common method for preparing porous metals is de- alloyage and template.But both methods technique is relative complex,
It is at high cost, it is difficult to realize industrialized production, while single using the pore structure of the silver of above method preparation, and be difficult to control.
Aiming at the problems existing in the prior art, we have invented a kind of classifying porous silver and a kind of preparation classifications being simply easily achieved
The method of porous silver, and applied for Chinese patent.By the classifying porous silver of this method preparation have excellent hydrogen reduction and
Hydrogen-peroxide reduction electro catalytic activity, but the pore size of the classifying porous silver is mainly nanoscale, there is only a small amount of micro-
The hole of meter level, when the classifying porous silver thickness of preparation is larger, porous structure is still unfavorable for reactive material in duct
Transmission, causes its active material that cannot make full use of.
Summary of the invention
The present invention aiming at the problems existing in the prior art, has invented one kind cube skeletal porous silver and preparation method thereof
To realize that foregoing invention content, the present invention are realized using following technical scheme:
It is the cube frame structure being surrounded by by the identical seamed edge of 12 length, seamed edge on described cube of skeleton is microcosmic
Side length is 0.5~1.5 μm；The seamed edge of the cubic structure is made of porous silver；The aperture of the porous silver is 20~100nm.
The aperture of the porous silver is preferably 50~80nm.
Steps are as follows for the preparation method of described cube of skeletal porous silver: first with template preparation using silver halide as the vertical of seamed edge
Quadrate bone frame silver halide, later removes template, electrochemical treatments is carried out finally by opposition quadrate bone frame silver halide, to be stood
Square skeletal porous silver.
The template of the template preparation cube skeleton silver halide is cubic crystal NaCl, NaBr, NaI, KCl, KBr, KI
One of.
The process that the opposition quadrate bone frame silver halide carries out electrochemical treatments is, using cube skeleton silver halide as work electricity
Pole is to electrode with one of platinum or graphite rod, and one of silver/silver chlorate, mercury/mercury oxide or saturation calomel are reference electricity
Pole, using the aqueous solution of NaOH or KOH as electrolyte.
During the electrochemical treatments, the electrochemical treatments current potential relative to reversible hydrogen electrode is -0.1V~-2V；
The electrochemical treatments time is 1s~100h.
The electrochemical treatments current potential is preferably -0.6V~-1.2V；The electrochemical treatments time be preferably 60s~
20h；The electrochemical treatments time optimal is 120s~8h.
Compared with prior art, the preparation method of of the present invention cube of skeletal porous silver has environmentally protective, easy, easy
It is low in implementation, production cost；And the aperture of porous metals and the advantages that controllable porosity distribution in preparation process, it is used as
When oxygen reduction catalyst, the centre bore of cube skeleton is conducive to the transmission in it of active material, and the hole on skeleton is conducive to
The promotion of active surface area, to be conducive to hydrogen reduction catalysis reaction.
Detailed description of the invention:
Fig. 1 a is the stereoscan photograph of cube skeleton silver chlorate prepared according to embodiment 1, and Fig. 1 b is according to embodiment 1
The transmission electron microscope photo of cube skeleton silver chlorate of preparation, Fig. 1 c is the bone of cube skeletal porous silver prepared according to embodiment 1
The transmission electron microscope photo of frame structure.
Fig. 2 is the oxygen reduction activity curve of cube skeletal porous silver prepared according to embodiment 1.
Specific embodiment
The present invention is described in detail below with reference to embodiment.Certain present invention is not limited in these specific implementations
Example.
The saturated aqueous solution of 3mL sodium chloride is added to by embodiment 1. to be prepared sodium chloride in 100mL dehydrated alcohol and stands
Cube, the ethyl alcohol that the ethanol solution of the silver nitrate of 100mL 0.01M is added to sodium chloride cube obtained above later are molten
In liquid, after reaction for 24 hours, reaction product is washed with water, reaction product is put into drying in convection oven and obtains a cube skeleton chlorination
Silver；Reaction product is coated on carbon paper, constant potential handles 30min at -0.8V again later, obtains a cube skeletal porous silver.
The saturated aqueous solution of 3mL sodium bromide is added to by embodiment 2. to be prepared sodium bromide in 100mL dehydrated alcohol and stands
Cube, the ethyl alcohol that the ethanol solution of the silver nitrate of 100mL 0.01M is added to sodium bromide cube obtained above later are molten
In liquid, after reacting 18h, reaction product is washed with water, reaction product is put into drying in convection oven and obtains a cube skeleton bromination
Silver；Reaction product is coated on carbon paper, constant potential handles 100h at -0.1V again later, obtains a cube skeletal porous silver.
The saturated aqueous solution of 3mL sodium iodide is added to by embodiment 3. to be prepared sodium iodide in 100mL dehydrated alcohol and stands
Cube, the ethyl alcohol that the ethanol solution of the silver nitrate of 100mL 0.01M is added to sodium iodide cube obtained above later are molten
In liquid, after reacting 12h, reaction product is washed with water, reaction product is put into drying in convection oven and obtains a cube skeleton iodate
Silver；Reaction product is coated on carbon paper, constant potential handles 20h at -2V again later, obtains a cube skeletal porous silver.
The saturated aqueous solution of 3mL potassium chloride is added to by embodiment 4. to be prepared potassium chloride in 100mL dehydrated alcohol and stands
Cube, the ethyl alcohol that the ethanol solution of the silver nitrate of 100mL 0.01M is added to potassium chloride cube obtained above later are molten
In liquid, after reaction for 24 hours, reaction product is washed with water, reaction product is put into drying in convection oven and obtains a cube skeleton chlorination
Silver；Reaction product is coated on carbon paper, constant potential handles 20min at -0.6V again later, obtains a cube skeletal porous silver.
The saturated aqueous solution of 3mL potassium bromide is added to by embodiment 5. to be prepared potassium bromide in 100mL dehydrated alcohol and stands
Cube, the ethyl alcohol that the ethanol solution of the silver nitrate of 100mL 0.01M is added to potassium bromide cube obtained above later are molten
In liquid, after reacting 18h, reaction product is washed with water, reaction product is put into drying in convection oven and obtains a cube skeleton bromination
Silver；Reaction product is coated on carbon paper, constant potential handles 2h at -1.2V again later, obtains a cube skeletal porous silver.
The saturated aqueous solution of 3mL potassium iodide is added to by embodiment 6. to be prepared potassium iodide in 100mL dehydrated alcohol and stands
Cube, the ethyl alcohol that the ethanol solution of the silver nitrate of 100mL 0.01M is added to potassium iodide cube obtained above later are molten
In liquid, after reacting 12h, reaction product is washed with water, reaction product is put into drying in convection oven and obtains a cube skeleton iodate
Silver；Reaction product is coated on carbon paper, constant potential handles 1s at -1.5V again later, obtains a cube skeletal porous silver.
The saturated aqueous solution of 3mL potassium bromide is added to by embodiment 7. to be prepared potassium bromide in 100mL dehydrated alcohol and stands
Cube, the ethyl alcohol that the ethanol solution of the silver nitrate of 100mL 0.01M is added to potassium bromide cube obtained above later are molten
In liquid, after reacting 18h, reaction product is washed with water, reaction product is put into drying in convection oven and obtains a cube skeleton bromination
Silver；Reaction product is coated on carbon paper, constant potential handles 5h at -1.7V again later, obtains a cube skeletal porous silver.
Fig. 1 a is the stereoscan photograph of cube skeleton silver chlorate prepared according to embodiment 1, and Fig. 1 b is according to embodiment 1
The transmission electron microscope photo of cube skeletal porous silver of preparation, Fig. 1 c is the bone of cube skeletal porous silver prepared according to embodiment 1
The transmission electron microscope photo of frame structure.As shown, the side length of cube skeleton silver chlorate and cube skeletal porous silver is 0.5~1.5 μ
m；The size of centre bore is 300-800nm, and the side of described cube of skeletal porous silver is made of porous silver；The hole of the porous silver is big
Small is 20~100nm.
Fig. 2 is the oxygen reduction activity curve of cube skeletal porous silver prepared according to embodiment 1.As seen from the figure, the catalysis
Agent has preferable oxygen reduction catalytic activity.
Claims (8)
1. a kind of cube skeletal porous silver, it is characterised in that: be by the identical seamed edge of 12 length on described cube of skeleton is microcosmic
The cube frame structure being surrounded by, seamed edge side length are 0.5~1.5 μm；The seamed edge of the cubic structure is by porous silver-colored structure
At；The aperture of the porous silver is 20~100 nm；
Described cube of skeletal porous silver is prepared by the following method to obtain: first being prepared with template using silver halide as cube of seamed edge
Skeleton silver halide, later removes template, electrochemical treatments is carried out finally by opposition quadrate bone frame silver halide, to obtain cube
Skeletal porous silver.
2. as described in claim 1 cube of skeletal porous silver, it is characterised in that: the aperture of the porous silver is 50~80 nm.
3. a kind of preparation method of any cube skeletal porous silver of claim 1,2, it is characterised in that: first use template legal system
It is standby later to remove template using silver halide as cube skeleton silver halide of seamed edge, it is carried out finally by opposition quadrate bone frame silver halide
Electrochemical treatments, to obtain a cube skeletal porous silver.
4. the preparation method of as claimed in claim 3 cube of skeletal porous silver, it is characterised in that: the template prepares cube bone
The template of frame silver halide is cubic crystal NaCl, NaBr, NaI, KCl, KBr, one of KI.
5. the preparation method of as claimed in claim 3 cube of skeletal porous silver, it is characterised in that: the opposition quadrate bone frame silver halide
The process for carrying out electrochemical treatments is, is to electricity with one of platinum or graphite rod using cube skeleton silver halide as working electrode
Pole, it is electrolysis with the aqueous solution of NaOH or KOH that one of silver/silver chlorate, mercury/mercury oxide or saturation calomel, which are reference electrode,
Liquid.
6. preparation method as claimed in claim 5, it is characterised in that: during the electrochemical treatments, relative to reversible
The electrochemical treatments current potential of hydrogen electrode is -0.1V~-2V；The electrochemical treatments time is the h of 1 s~100.
7. preparation method as claimed in claim 6, it is characterised in that: the electrochemical treatments current potential is -0.6 V~-1.2
V；The electrochemical treatments time is the h of 60 s~20.
8. preparation method as claimed in claim 7, it is characterised in that: the electrochemical treatments time is 120 s~8h.
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| CN108517540B (en) * | 2018-04-11 | 2020-01-21 | 东莞理工学院 | Porous silver and preparation method thereof, silver powder and application thereof |
| CN109261149A (en) * | 2018-07-30 | 2019-01-25 | 青岛科技大学 | The nano-porous silver of self-supporting and the preparation method of silver electrode |
| KR102316874B1 (en) * | 2021-01-28 | 2021-10-25 | 영남대학교 산학협력단 | Method of manufacturing porous hollow structure silver nanoparticles, porous hollow structure silver nanoparticles therefrom and polymer gel comprising the same |
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| DE1286757B (en) * | 1963-07-15 | 1969-01-09 | Erdoelchemie Gmbh | Process for the production of porous silver |
| CN101693197B (en) * | 2009-10-19 | 2011-06-22 | 山东大学 | Porous silver catalyzer and process for preparing same |
| CN102601380B (en) * | 2011-12-21 | 2015-05-20 | 中国科学院过程工程研究所 | Cubic copper powder and method for preparing same |
| CN104308172B (en) * | 2014-08-11 | 2016-08-17 | 常州大学 | A kind of method preparing the micro-nano metal of hollow cubic |
| CN104525937B (en) * | 2014-12-23 | 2016-08-24 | 吉林大学 | A kind of porous silver micro nano structure and pattern thereof and the controlled preparation method of size |
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