CN110004314A - A kind of preparation method of the metallic copper containing three-dimensional porous structure - Google Patents
A kind of preparation method of the metallic copper containing three-dimensional porous structure Download PDFInfo
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- CN110004314A CN110004314A CN201810516102.7A CN201810516102A CN110004314A CN 110004314 A CN110004314 A CN 110004314A CN 201810516102 A CN201810516102 A CN 201810516102A CN 110004314 A CN110004314 A CN 110004314A
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- metallic copper
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000010949 copper Substances 0.000 title claims abstract description 57
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000012298 atmosphere Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 229910016553 CuOx Inorganic materials 0.000 claims abstract description 13
- 239000007858 starting material Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 16
- 239000013067 intermediate product Substances 0.000 claims description 15
- 239000011889 copper foil Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000003570 air Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910000085 borane Inorganic materials 0.000 claims description 5
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 9
- 230000007812 deficiency Effects 0.000 abstract description 4
- 210000003850 cellular structure Anatomy 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 11
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
Abstract
The present invention relates to metal porous frame structure material field, the preparation method of specially a kind of metallic copper containing three-dimensional porous structure.It using business copper as starting material, after it is impregnated the of short duration time in certain density acid solution, is cleaned and is dried with deionized water, be placed on and burn in boat, be put into Muffle furnace and be heat-treated under an oxygen-containing atmosphere, convert CuO for copper sheetx, later again by CuOxIt is put into tube furnace and is heat-treated under reducing atmosphere, to obtain the metallic copper of three-dimensional porous structure.To which the pore size of porous structure can be regulated and controled by changing the reaction temperature in heat treatment process.The present invention directly prepares the metallic copper containing three-dimensional porous structure as starting material using business copper, and surface mutually has a large amount of holes with body.It further can change the pore size of porous structure by regulating and controlling temperature variable, effectively realize the Effective Regulation to cellular structure metals copper preparation process, be able to solve the deficiency that introduces impurity in traditional preparation methods and can not directly synthesize on a large scale.
Description
Technical field
The present invention relates to metal porous frame structure material field, the system of specially a kind of metallic copper containing three-dimensional porous structure
Preparation Method, by heat treatment process, using commercial copper as starting material, copper oxide intermediate wood is prepared in heat treatment under an oxygen-containing atmosphere
Material.On this basis, the metallic copper containing three-dimensional porous structure is directly prepared by simple sequential reduction atmosphere heat treatment.
Background technique
Metallic copper electrocatalysis material has many advantages, such as efficient, at low cost, thermodynamic stability is high, environmental-friendly, is
Most competitive one of material, can be widely used in electro-catalysis HER, OER, carbon dioxide also in numerous electrocatalysis materials
Former basis material etc. has commercialization value well.Especially the metallic copper containing three-dimensional porous structure is due to its permeability
The advantages such as good, high-specific surface area, high porosity, dimensionally stable improve the number of active site in catalysis reaction.However tradition system
The method of the standby metallic copper containing three-dimensional porous structure is extremely limited, predominantly template and goes alloyage, and the one side of Shortcomings,
First is that need to introduce during the preparation process other it is solid liquid impurities, can not completely remove, influence the catalytic activity of matrix；Second is that should
Preparation method is complex steps, at high cost for realizing directly extensive synthesis.
Therefore, development free from admixture should be continued to introduce and the direct metallic copper containing three-dimensional porous structure of synthesis on a large scale of low cost
Preparation method.Impurity elimination Quality Research is very more in current related preparation method, but can take into account inexpensive directly extensive synthesis
Preparation method never come out, become and limit one of bottleneck of its practical application.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of metallic copper containing three-dimensional porous structure, it is able to solve for biography
Impurity can not be completely removed in controlling Preparation Method, the deficiency that low cost directly synthesizes on a large scale.
The technical scheme is that
A kind of preparation method of the metallic copper containing three-dimensional porous structure, using business copper as starting material, by it in acid solution
It after middle immersion, is cleaned and is dried with deionized water, be placed on and burn on boat, be put into Muffle furnace and be heat-treated in oxygen-containing atmosphere, obtained
Intermediate product CuOx, 0≤x < 2；It places into tube furnace, is heat-treated under reducing atmosphere later, to obtain containing three-dimensional porous
The metal of structure regulates and controls the pore size of porous structure by changing the reaction temperature in heat treatment process.
The starting material be various business copper foils, copper alloy, powder copper and its powder copper alloy it is one or two kinds of with
On.
In the acid solution, H+Molar concentration be 0.01~10M, be added H+Using conventional hydrochloric acid, sulfuric acid, hydrogen fluorine
Acid, nitric acid or phosphoric acid.
The intermediate product CuOxFor Cu, CuO and Cu2One or more of O.
The oxygen-containing atmosphere is purity oxygen, air or oxygen；Alternatively, oxygen-containing atmosphere be air and nitrogen, argon gas, ammonia,
Helium, hydrogen, hydrogen sulfide, borine, methane, acetylene, carbon monoxide, carbon dioxide, sulfur dioxide it is one such or two kinds with
On mixed gas, heat treatment temperature be 200~1500 DEG C between, the processing time be 15min~180h.
The intermediate product CuOxIt is heat-treated under reducing atmosphere, reducing atmosphere is hydrogen or ammonia or reducing atmosphere
For hydrogen, ammonia and nitrogen, argon gas, helium, hydrogen sulfide, borine, methane, acetylene, carbon monoxide, carbon dioxide, sulfur dioxide
One or more kinds of mixed gas, treatment temperature is between 150~1200 DEG C, and the processing time is 15min~180h.
The pore size distribution range of the porous structure is 1nm~100 μm, and porosity is 10~70%.
Design philosophy of the invention is as follows:
Room temperature electro-catalysis reduction carbon dioxide synthesis gas phase or liquid phase fuel are that conventional high-temperature reaction under high pressure is replaced to synthesize item
One of important way of part.Metal copper-based catalysts containing three-dimensional porous structure are due to its excellent selectivity of product, permeability
The advantages such as good, high-specific surface area, high porosity and dimensionally stable are the research emphasis in electro-catalysis reduction carbon dioxide field.So
And the preparation method that tradition prepares porous metal copper has the shortcomings that introduce impurity and can not directly synthesize on a large scale.The present invention
Heat-treating methods will only be passed through, on the basis of not introducing extraneous template or impurity, realize that step is simple, at low cost contains three
The preparation of cellular structure metals copper is tieed up, directly synthesis provides chance on a large scale for porous metal copper.
The invention has the advantages and beneficial effects that:
1, this invention address that solving to introduce impurity and step during tradition preparation metallic copper containing three-dimensional porous structure simultaneously
Rapid deficiency cumbersome, at high cost on the basis of not introducing additional template and impurity, is realized by simple heat treatment process
The preparation of simple, the at low cost metallic copper containing three-dimensional porous structure of step.
2, the present invention uses environmental-friendly, the simple synthetic method of step, is conducive to large-scale production.
3, the starting material that the present invention uses is resourceful for solid-state material, is easy to store, use.
4, material prepared of the present invention have excellent selectivity of product, good penetrability, high-specific surface area, high porosity and
The advantages such as dimensionally stable play considerable advantage in electro-catalysis reduction carbon dioxide field.
Detailed description of the invention
The XRD spectrum of 1 resulting materials of Fig. 1 embodiment；Wherein, abscissa is 2 θ of the angle of diffraction, and unit is angle；Ordinate
For diffraction peak intensity, arbitrary unit.
The SEM photograph of 1 resulting materials of Fig. 2 embodiment.
The XRD spectrum of 1 resulting materials of Fig. 3 embodiment；Wherein, abscissa is 2 θ of the angle of diffraction, and unit is angle；Ordinate
For diffraction peak intensity, arbitrary unit.
The SEM photograph of 1 resulting materials of Fig. 4 embodiment.
The XRD spectrum of 1 resulting materials of Fig. 5 embodiment；Wherein, abscissa is 2 θ of the angle of diffraction, and unit is angle；Ordinate
For diffraction peak intensity, unit is arbitrary unit.
The SEM photograph of 1 resulting materials of Fig. 6 embodiment.
The SEM photograph of 2 resulting materials of Fig. 7 embodiment.
The SEM photograph of 3 resulting materials of Fig. 8 embodiment.
The SEM photograph of 3 resulting materials of Fig. 9 embodiment.
Specific embodiment
In the specific implementation process, the present invention provides a kind of preparation method of metallic copper containing three-dimensional porous structure, with business
Copper is starting material, after it is impregnated the of short duration time in certain density acid solution, is cleaned and is dried with deionized water, put
It sets on burning boat, is put into Muffle furnace and is heat-treated in oxygen-containing atmosphere, obtain intermediate product CuOx, tube furnace is placed into later also
It is heat-treated under Primordial Qi atmosphere, to obtain the metallic copper containing three-dimensional porous structure.To by changing the reaction in heat treatment process
Temperature regulates and controls the pore size of the metallic copper containing three-dimensional porous structure, specific feature by the heat treatment process under different temperatures
It is:
1, starting material used is the one or more of various business copper foils, copper alloy, powder copper and its powder copper alloy.
2, in certain density acid solution used, H+Molar concentration be 0.01~10M, be added H+Using conventional salt
Acid, sulfuric acid, hydrofluoric acid, nitric acid or phosphoric acid etc..
3, copper is changed into CuOx, oxygen-containing atmosphere used include purity oxygen, air or oxygen, air and nitrogen, argon gas,
Ammonia, helium, hydrogen, hydrogen sulfide, borine, methane, acetylene, carbon monoxide, carbon dioxide, sulfur dioxide etc. it is one such or
Several mixed gas, treatment temperature be 150~1500 DEG C (preferably 300~1000 DEG C) between, the processing time for 15min~
180h (preferably 30min~10h).
4, the intermediate product CuOx(0≤x < 2) is Cu, CuO and Cu2One or more of O.
5, by above-mentioned prepared intermediate product CuOxBe heat-treated under reducing atmosphere, reducing atmosphere be hydrogen, ammonia or
Person's hydrogen, ammonia and other gases (nitrogen, argon gas, helium, hydrogen sulfide, borine, methane, acetylene, carbon monoxide, carbon dioxide,
Sulfur dioxide) one or more of mixed gas, treatment temperature is between 150~1200 DEG C (preferably 300~900 DEG C),
The processing time is 15min~180h (preferably 30min~10h).
In the following, in conjunction with the embodiments next, the present invention will be described in detail.
Embodiment 1
In the present embodiment, cut commercial copper foil be 1cm × 2cm size rectangle (in the present embodiment, the thickness of commercial copper foil
Degree is 0.25mm), it puts it into equipped with 15mL containing 0.65M (molar concentration) H+(in the present embodiment, H+Using HCl) aqueous solution
5~10s of middle immersion, is cleaned with deionized water and is dried in a nitrogen atmosphere, is put into Muffle furnace later by 900 DEG C of air gas
Atmosphere handles 0.5h, obtains shaggy intermediate product CuOx(0≤x < 2), is mainly made of CuO.Intermediate product is put into pipe
800 DEG C of ammonia atmospheres are carried out in formula furnace and handle 1h, obtain the metallic copper rich in three-dimensional porous structure.
As shown in Figure 1, the XRD diffraction maximum of starting material commercialization copper foil used；As shown in Fig. 2, starting material used is commercial
Copper foil surface is relatively smooth, and roughness is smaller；As shown in figure 3, intermediate product CuO usedxIt is made of cuprous oxide and copper oxide,
Its main phase is copper oxide；As shown in figure 4, intermediate product CuO usedxThere is striped in surface, and roughness increases；As shown in figure 5, rich
The high preferred orientation of the high preferred orientation of the metallic copper containing three-dimensional porous structure and presoma commercialization copper foil difference；As shown in fig. 6, rich
The pore size of the metallic copper containing three-dimensional porous structure is 1 μm~5 μm, porosity 31%.
Embodiment 2
In the present embodiment, cut commercial copper foil be 1cm × 2cm size rectangle (in the present embodiment, the thickness of commercial copper foil
Degree is 0.25mm), it puts it into equipped with 15mL containing 0.65M (molar concentration) H+(in the present embodiment, H+Using HCl) aqueous solution
5~10s of middle immersion, is cleaned with deionized water and is dried in a nitrogen atmosphere, is put into Muffle furnace later by 900 DEG C of air gas
Atmosphere handles 0.5h, obtains shaggy intermediate product CuOx(0≤x < 2), is mainly made of CuO.Intermediate product is put into pipe
600 DEG C of ammonia atmospheres are carried out in formula furnace and handle 1h, obtain the metallic copper rich in three-dimensional porous structure.
As shown in fig. 7, the pore size rich in three-dimensional porous structure metallic copper is 0.01 μm~5 μm, porosity 17%.
Embodiment 3
Cut commercial copper foil be 1cm × 2cm size rectangle (in the present embodiment, commercial copper foil with a thickness of
0.25mm), it puts it into equipped with 15mL containing 0.65M (molar concentration) H+(in the present embodiment, H+Using HCl) aqueous solution in soak
5~10s is steeped, is cleaned with deionized water and is dried in a nitrogen atmosphere, is put into Muffle furnace later by 900 DEG C of air atmospheres
0.5h is managed, shaggy intermediate product CuO is obtainedx(0≤x < 2), is mainly made of CuO.Intermediate product is put into tube furnace
It is middle to carry out 1000 DEG C of ammonia atmospheres processing 1h, obtain the metallic copper rich in three-dimensional porous structure.
As shown in figure 8, the pore size rich in three-dimensional porous structure metallic copper is 5 μm~20 μm, porosity 49%.Such as
Shown in Fig. 9, the even pore distribution rich in three-dimensional porous structure metallic copper.
Embodiment the result shows that, the present invention is directly prepared as starting material using business copper foil and is contained by heat treatment process
Mutually there are a large amount of holes in the metallic copper of three-dimensional porous structure, surface and body.Further it can change by regulating and controlling temperature variable
The pore size of porous structure is effectively realized to the Effective Regulation of cellular structure metals copper preparation process, is able to solve traditional system
The deficiency that introduces impurity in Preparation Method and can not directly synthesize on a large scale.
Claims (7)
1. a kind of preparation method of metallic copper containing three-dimensional porous structure, it is characterised in that: using business copper as starting material, by its
After being impregnated in acid solution, clean and dried with deionized water, is placed on burning boat, be put into Muffle furnace in oxygen-containing atmosphere at heat
Reason obtains intermediate product CuOx, 0≤x < 2；It places into tube furnace, is heat-treated under reducing atmosphere later, to be contained
The metal of three-dimensional porous structure regulates and controls the pore size of porous structure by changing the reaction temperature in heat treatment process.
2. the preparation method of the metallic copper described in accordance with the claim 1 containing three-dimensional porous structure, it is characterised in that: the starting material
Material is the one or more of various business copper foils, copper alloy, powder copper and its powder copper alloy.
3. the preparation method of the metallic copper described in accordance with the claim 1 containing three-dimensional porous structure, it is characterised in that: the acidity is molten
In liquid, H+Molar concentration be 0.01~10M, be added H+Using conventional hydrochloric acid, sulfuric acid, hydrofluoric acid, nitric acid or phosphoric acid.
4. the preparation method of the metallic copper described in accordance with the claim 1 containing three-dimensional porous structure, it is characterised in that: the intermediate production
Object CuOxFor Cu, CuO and Cu2One or more of O.
5. the preparation method of the metallic copper described in accordance with the claim 1 containing three-dimensional porous structure, it is characterised in that: described oxygenous
Atmosphere is purity oxygen, air or oxygen；Alternatively, oxygen-containing atmosphere is air and nitrogen, argon gas, ammonia, helium, hydrogen, hydrogen sulfide, boron
The one such or two or more mixed gas of alkane, methane, acetylene, carbon monoxide, carbon dioxide, sulfur dioxide, heat treatment
Temperature is between 200~1500 DEG C, and the processing time is 15min~180h.
6. the preparation method of the metallic copper described in accordance with the claim 1 containing three-dimensional porous structure, it is characterised in that: the intermediate production
Object CuOxBe heat-treated under reducing atmosphere, reducing atmosphere be hydrogen or ammonia or reducing atmosphere be hydrogen, ammonia and nitrogen,
The one or more of argon gas, helium, hydrogen sulfide, borine, methane, acetylene, carbon monoxide, carbon dioxide, sulfur dioxide
Mixed gas, treatment temperature are between 150~1200 DEG C, and the processing time is 15min~180h.
7. the preparation method of the metallic copper described in accordance with the claim 1 containing three-dimensional porous structure, it is characterised in that: the porous knot
The pore size distribution range of structure is 1nm~100 μm, and porosity is 10~70%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111041523A (en) * | 2020-01-02 | 2020-04-21 | 东莞理工学院 | Copper-doped titanium dioxide photoelectrode, preparation method thereof and application thereof in photoelectrocatalysis decomposition of water |
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| CN111676482A (en) * | 2020-06-13 | 2020-09-18 | 大连大学 | Electrode for electrochemical reduction of carbon dioxide and application thereof |
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