CN107366011A - A kind of nano porous copper load ultrafine copper oxide nanowire composite and its preparation method and application - Google Patents
A kind of nano porous copper load ultrafine copper oxide nanowire composite and its preparation method and application Download PDFInfo
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- CN107366011A CN107366011A CN201710583967.0A CN201710583967A CN107366011A CN 107366011 A CN107366011 A CN 107366011A CN 201710583967 A CN201710583967 A CN 201710583967A CN 107366011 A CN107366011 A CN 107366011A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
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- 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
- C22C1/02—Making non-ferrous alloys by melting
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/001—Amorphous alloys with Cu as the major constituent
Abstract
The present invention loads ultrafine copper oxide nanowire composite and its preparation method and application for a kind of nano porous copper.The material is bar, including noncrystal substrate, the nano porous copper that is covered on noncrystal substrate and the ultrafine copper oxide nano wire for being supported on nano porous copper surface；Described noncrystal substrate is CuxZryAlzAlloying component, wherein x, y, z are atomic percent, 45≤x≤50,45≤y≤50,5≤z≤10, and x+y+z=100；Wherein 85~135 μm of nano porous copper thickness, tough 118~138nm of bandwidth, 30~100nm of aperture size, 4~10 μm, wide 5~15nm of nanometer line length, every 20~30 nano wire clusters are into a branch of.Invention first of the invention builds cupric oxide nano line on nano-grade size matrix.Nanometer wire cupric oxide is combined closely with nanoporous copper metallic face, makes the material of preparation more efficiently photocatalytically degradating organic dye.
Description
Technical field：
The present invention relates to copper oxide material technical field, specifically a kind of nano porous copper load ultrafine copper oxide is received
Rice noodles composite and its preparation method and application.
Background technology：
In recent years because industrialization and population increase, various environmental problems particularly aquatile systemic contamination have become
Urgent problem to be solved in the world.Advanced oxidation technology (AOP) can be with various slightly solubility organic substances in fast degradation sewage.
AOP includes ozonisation, photocatalysis and Fenton methods.Photocatalysis is a relatively new interdisciplinary fields.Semiconductor light is urged
It is turned to cost benefit and green technology and provides a kind of new way for the depollution of environment and solar energy conversion.In various semiconductors
In, cupric oxide (CuO) possesses narrower energy gap (about 1.2eV) because it is p-type semiconductor material, has good electricity
Chemism, huge application potential is shown in terms of photocatalytically degradating organic dye.
First technology, publication number CN106115763A " a kind of preparation method of the spherical hierarchical organization material of cupric oxide " should
In patent, the product of preparation is cupric oxide nano powder, needs to calcine 2~5 hours at 400~600 DEG C in preparation process.
Substantial amounts of energy is not only consumed, and increases preparation cost.Before the powder sample is used for catalytic degradation organic dyestuff, contain
The methyl orange solution of the catalysis material need to stir 30 minutes in the dark could carry out illumination.Material handling processes are made to become more
It is complicated.Powder sample is easily mutually blocked and accumulated, and reduces catalytic efficiency.And it is not easy to reclaim after application, it is likely that draw
Send out secondary pollution.
First technology, publication number CN106629813A " a kind of supported porous cupric oxide nano line composite of foam copper and
Its preparation method and application ", in the patent, with reference to anodizing and calcine technology in foam copper superficial growth cupric oxide nano
Line.Matrix used this method is foam copper, has micron order bore hole size.Bore hole size is larger and can not regulate and control.And then synthesize
Cupric oxide nano line it is thicker, diameter about 200nm, poor toughness, easy fracture, property of the material as photocatalytic degradation agent will be influenceed
Energy and efficiency.
The content of the invention：
The purpose of the present invention is not easily recycled easily to reunite for powder visible light catalytic material in current techniques, it is likely that
Cause secondary pollution；Cupric oxide nano line is thicker in the supported porous cupric oxide nano line composite of foam copper, and easy fracture etc. is no
A kind of foot, there is provided nano porous copper load ultrafine copper oxide nanowire composite and its preparation method and application.The material bag
Include noncrystal substrate nano porous copper composite bar and be supported on the ultrafine copper oxide nano wire on its surface.Its preparation method be by
De- alloying technology is combined with anode oxidation process, by controlling de- alloying technology parameter to make zirconium, aluminium element in amorphous bar
Selective removal, the copper of remaining relative inertness form that pore space structure is controllable, the nanometer of noncrystal substrate support is more from combining
Hole copper composite bar, anode oxidation process and calcine technology then are used, ultra-fine oxygen is grown in nanoporous copper metallic face
Change copper nano-wire.Nano wire prepared by the present invention is finer and closely woven than what is reported at present, flexible, in photocatalytically degradating organic dye
Field shows the structure and performance advantage of uniqueness.
The technical scheme is that：
A kind of nano porous copper loads ultrafine copper oxide nanowire composite, and the material is bar, including noncrystal substrate,
The nano porous copper that is covered on noncrystal substrate and the ultrafine copper oxide nano wire for being supported on nano porous copper surface；Described
Noncrystal substrate is CuxZryAlzAlloying component, wherein x, y, z are atomic percent, 45≤x≤50,45≤y≤50,5≤z≤
10, and x+y+z=100；Wherein 85~135 μm of nano porous copper thickness, tough 118~138nm of bandwidth, aperture size 30~
100nm, 4~10 μm, wide 5~15nm of nanometer line length, every 20~30 nano wire clusters are into a branch of.
The preparation method of described nano porous copper load ultrafine copper oxide nanowire composite, is comprised the following steps that：
The first step, prepare non-crystaline amorphous metal bar
According to target composition weighs pure Cu, pure Zr and pure Al；Melting in vacuum arc melting furnace is put into after cleaning Cu- is made
Zr-Al alloy pigs, it is placed in after polishing, cleaning in quartz test tube, quartz test tube is put into vacuum gets rid of with solid in induction coil in machine
It is fixed, induction melting is carried out under high-purity argon gas protection, the molten metal of melting is blown into copper mold, its solidification is formed non-crystaline amorphous metal
Bar；Wherein：Melting and get rid of band vacuum be 9 × 10-4Pa；It is 0.5~2.0MPa to blow casting pressure；Copper mold bore dia be 1~
3mm；The obtained a diameter of 0.9~2.9mm of Ф of non-crystaline amorphous metal coupon, length are 30~70mm；
Second step, de- alloy treatment prepare nanoporous copper metal
Non-crystaline amorphous metal bar obtained in the previous step is placed in HF corrosive liquids and soaked 1~3 day, obtains nano porous copper gold
Category；Corrosion temperature is 298K constant temperature, and HF corrosive liquids concentration is 0.05~0.5M；
3rd step, anodic oxidation prepare nano porous copper load ultrafine copper oxide nanowire composite
Using platinum electrode as negative electrode, nanoporous copper metal made from previous step carries out anode as dc source anode
Oxidation, makes its Surface Creation Kocide SD nano wire, obtains nano porous copper and loads ultra-fine Kocide SD nanowire composite；
Obtained composite is placed in vacuum drying chamber and calcines 1.0~3.0h in 50~150 DEG C, is born so as to which nano porous copper be made
Carry ultrafine copper oxide nanowire composite；
Wherein, in anodic oxidation reactionses, electrolyte be 0.1~0.6M of concentration KOH solution, 0.5~10mA of current density
cm-2, 5~180min of reaction time, 20~30 DEG C of reaction temperature.
Described pure Cu, pure Zr and pure Al purity are that mass fraction is 99.99%.
The application of described nano porous copper load ultrafine copper oxide nanowire composite, it is organic for photocatalytic degradation
Dyestuff.
Described organic dyestuff is preferably rhodamine B, the one or more in methyl orange and methylene blue.
Above-mentioned a kind of nano porous copper load ultrafine copper oxide nanowire composite and its preparation method and application, it is used
To raw material and equipment obtained by known approach, operating procedure used is those skilled in the art institute energy
Grasp.
The present invention's is that substantive distinguishing features are：
(1) visible light catalytic material for preparing of the present invention be bar samples, and continuously the support of pore structure makes its tool on matrix
There is abundant porosity, avoid the shortcomings that dusty material is easily reunited, and use easily recovery later, be recycled recycling.
In current techniques, grown mostly using foam copper as matrix and aoxidize copper nano-wire, and commercialized foam copper ligament/hole
Hole size is micron order, and size fixation can not regulate and control.And then the cupric oxide nano line grown is thicker, diameter about 200nm, and
Crisp easy fracture.And this patent, using nanoporous copper metal as matrix, ligament/bore hole size is nanoscale and controllable, Jin Ersheng
Ultra-fine cupric oxide nano line is grown, a diameter of 5~15nm is fine and closely woven and flexible, substantially increases photocatalytic degradation efficiency.
(2) in current techniques, de- alloy is often carried out with amorphous alloy ribbon, and this patent is then with non-crystaline amorphous metal bar
De- alloy is carried out, anode oxidation process is applied on the basis of de- alloying technology, is visited on the basis of de- alloying technology parameter
Rope goes out anode oxidation process parameter.And then the technological parameter used in the present invention is a series of overall supporting perfect adaptations.
Compared with existing technology, beneficial effects of the present invention are as follows：
(1) present invention prepares a kind of nano porous copper with the method that anode oxidation process is combined using de- alloy technology and born
Ultrafine copper oxide nanowire composite is carried, the preparation method is not yet reported at present.The present invention prepares one kind using this method
Novel nano porous material with high efficiency photocatalysis degradating organic dye, including nano porous metal and it is supported on its surface
Cupric oxide nano line.Wherein de- alloy can prepare it is thick 85~135 μm, tough 118~138nm of bandwidth, aperture size 30~
100nm nanoporous copper metal.Long 4~10 μm, wide 5~15nm cupric oxide is prepared on its surface followed by anodic oxidation
Nano wire.
(2) invention first builds cupric oxide nano line on nano-grade size matrix.Nanometer wire cupric oxide and nanometer are more
Hole copper metallic face is combined closely, and makes the material of preparation more efficiently photocatalytically degradating organic dye.
(3) with publication number CN106629813A using foam copper as matrix phase ratio, nanoporous copper metal ligament/bore hole size
It can regulate and control.It is thus more fine and closely woven flexible in the cupric oxide nano line of its superficial growth, be advantageous to infiltration and the ion of solution
Transmission diffusion, increases light transmittance and light absorbs, increases the avtive spot of reaction, so as to be advantageous to photocatalytic degradation rapidly and efficiently
Ground is carried out.The degradation efficiency that the structure is used as photocatalytically degradating organic dye can improve more than 15 times.
Brief description of the drawings：
Fig. 1：The stereoscan photograph of the nano porous copper metal cross section prepared in embodiment 1.
Fig. 2：The stereoscan photograph of the nanoporous copper metallic face prepared in embodiment 1.
Fig. 3：The ESEM of the nano porous copper load ultrafine copper oxide nanowire composite prepared in embodiment 1 shines
Piece.
Fig. 4：The energy spectrum analysis of the nano porous copper load ultrafine copper oxide nanowire composite prepared in embodiment 1
Figure.
Embodiment
Embodiment 1
Select alloying component Cu50Zr45Al5, the atomic percent according to each element in subject alloy：Cu is 50at.%, Zr
For 45at.%, Al 5at.%, weigh high-purity copper sheet (6.425g), zirconium grain (8.302g) that mass fraction is 99.99% and
Aluminium flake (0.273g) obtains foundry alloy raw material 15g；Foundry alloy raw material is placed in vacuum arc melting furnace and (is put into before melting
99.9wt% pure titanium grain is as oxygen scavenging material), melt back 4 times is (to ensure the uniform of alloy under high-purity argon gas protection
Property), each 40s or so.Cool to room temperature with the furnace, that is, obtain Cu50Zr45Al5Alloy pig.
Take 2~3g of alloy pig after polishing cleaning to be placed in quartz test tube, quartz test tube is put into vacuum and got rid of in band machine and is felt
Answer in coil and fix, induction melting is carried out under high-purity argon gas protection and under certain pressure difference by the Cu of melting50Zr45Al5Gold
Category liquid is blown into copper mold, makes it quickly solidify to form non-crystaline amorphous metal bar；Pressure needed for blowing casting is 1.0MPa, vacuum 9.0
×10-4Pa, copper mold bore dia are 2mm, the obtained a diameter of Ф 2mm of non-crystaline amorphous metal coupon, length 40mm；
By Cu obtained in the previous step50Zr45Al5Amorphous coupon cuts into length and is 10mm stub, and is thrown with abrasive paper for metallograph
Light is to both ends horizontal, using the 0.05M HF solution of argon gas deoxygenation as corrosive liquid, by the Cu of well cutting50Zr45Al5Amorphous coupon
It is put into 0.05M HF and freely takes off alloy 1 day in 298k constant temperature, nanoporous copper metal is made.Fig. 1, Fig. 2 are this implementation respectively
The stereoscan photograph of obtained nano porous copper cross section and surface in example.It can be seen that there are certain thickness (~85 μm)
Nano porous copper (NPC) tubular layer be uniformly covered on inside amorphous bulk (BMG) matrix on.NPC has uniform, double
Three-dimensional (3D) nanoporous pattern of continuous ligament/pore space structure.Aperture size is 45nm, ligament width 118nm.By Fig. 1
Illustration can be seen that nano porous copper tubular layer and the amorphous bulk of inside are combined closely, and not be layered.
Using platinum electrode as negative electrode, the nano porous metal cleaning prepared, it is used as anode to carry out electrochemistry oxygen after drying
Change, experiment condition is concentration of electrolyte 0.5M KOH, current density 10mA cm-2, reaction time 10min, 20 DEG C of reaction temperature；
Reacted product is cleaned with deionized water, obtains the ultra-fine Kocide SD nano wire composite wood of nano porous copper Metal Supported
Material；
The ultra-fine Kocide SD nanowire composite of obtained nano porous copper Metal Supported is placed in vacuum drying chamber
2.0h is calcined in 60 DEG C, ultrafine copper oxide nanowire composite is loaded so as to which nano porous copper be made.Fig. 3 is in the present embodiment
The stereoscan photograph of the nano porous copper load ultrafine copper oxide nanowire composite of preparation.It is observed that cupric oxide is received
Rice noodles are closely supported on nanoporous copper metallic face, 5 μm, wide 10nm of nanometer line length, and every 20~30 nano wire clusters are into one
Beam.Fig. 4 is the energy spectrum analysis figure of the nano porous copper load ultrafine copper oxide nanowire composite prepared in the present embodiment.Knot
Fruit shows only copper and oxygen element, it was demonstrated that nanoporous copper metallic face constructs ultrafine copper oxide nano wire.
Nano porous copper load ultrafine copper oxide nanowire composite carries out photocatalytic degradation made from the present embodiment
The experimentation of organic dyestuff is as follows：
Photocatalytic degradation experiment is carried out from organic dyestuff rhodamine B, solution is by 8ml 15mg L-1Rhodamine B and
3ml20wt.%H2O2Oxidant forms, and using 500W xenon lamp as light source, the distance between xenon lamp and the solution that is degraded is
10cm, intensity of illumination are 100mW cm-2.During experiment, obtained nano porous copper Metal Supported ultrafine copper oxide nano wire is answered
Condensation material is immersed in solution, investigates the test case of solution after dyestuff degraded different time, and the relative absorbency of wherein dyestuff leads to
Ultraviolet-visible spectrophotometer (Lambda-750PerkinElmer) is crossed to be tested.Using obtained compound in the present embodiment
After material is degraded 0,1,2,5,7 minute to organic dyestuff rhodamine B respectively, contrasted from the relative absorbency of solution, at any time
Between extend to 7 minutes, dyestuff is degradable.The material carries out circulation degradation experiment, finds to congruent, different batches dyestuffs
The degradation rate of (weekly 60 minutes) is still more than 98.5% after degrading 5 weeks." a kind of foam copper is born with publication number CN106629813A
In load porous copper oxide nanowire composite and its preparation method and application " patent, received with the supported porous cupric oxide of foam copper
Rice noodles composite is that photocatalytic degradation material is compared, and not only required effective contact area is by original 9cm-2It is reduced to
0.66cm-2, and degradation time was brought up to 7 minutes by original 60 minutes, and catalytic efficiency greatly improves.Illustrate the present embodiment institute
Composite processed has the performance of extraordinary photocatalytically degradating organic dye, the performance have benefited from nano porous metal ligament/
Bore hole size is controllable, and the cupric oxide nano line of load is extremely fine and closely woven flexible, thus forms multi-stage nano loose structure
Advantage.
Embodiment 2
Select alloying component Cu50Zr45Al5, the atomic percent according to each element in subject alloy：Cu is 50at.%, Zr
For 45at.%, Al 5at.%, weigh high-purity copper sheet (6.425g), zirconium grain (8.302g) that mass fraction is 99.99% and
Aluminium flake (0.273g) obtains foundry alloy raw material 15g；Foundry alloy raw material is placed in vacuum arc melting furnace and (is put into before melting
99.9wt% pure titanium grain is as oxygen scavenging material), melt back 4 times is (to ensure the uniform of alloy under high-purity argon gas protection
Property), each 40s or so.Cool to room temperature with the furnace, that is, obtain Cu50Zr45Al5Alloy pig.
Take 2~3g of alloy pig after polishing cleaning to be placed in quartz test tube, quartz test tube is put into vacuum and got rid of in band machine and is felt
Answer in coil and fix, induction melting is carried out under high-purity argon gas protection and under certain pressure difference by the Cu of melting50Zr45Al5Gold
Category liquid is blown into copper mold, makes it quickly solidify to form non-crystaline amorphous metal bar；Pressure needed for blowing casting is 1.0MPa, vacuum 9.0
×10-4Pa, copper mold bore dia are 2mm, the obtained a diameter of Ф 2mm of non-crystaline amorphous metal coupon, length 40mm；
By Cu obtained in the previous step50Zr45Al5Amorphous coupon cuts into length and is 10mm stub, and is thrown with abrasive paper for metallograph
Light is to both ends horizontal, using the 0.05M HF solution of argon gas deoxygenation as corrosive liquid, by the Cu of well cutting50Zr45Al5Amorphous coupon
It is put into 0.05M HF and freely takes off alloy 2 days in 298k constant temperature, nanoporous copper metal is made.The μ of thickness 110 of NPC tubular layers
M, NPC aperture size are 60nm, ligament width 128nm.
Using platinum electrode as negative electrode, the nanoporous copper metal prepared carries out electrochemical oxidation as anode, tests bar
Part is concentration of electrolyte 1M KOH, current density 5mA cm-2, reaction time 10min, 20 DEG C of reaction temperature；By reacted production
Thing is cleaned with deionized water, is obtained nano porous copper and is loaded ultra-fine Kocide SD nanowire composite；
Obtained nano porous copper is loaded into ultra-fine Kocide SD nanowire composite, is placed in vacuum drying chamber in 60
DEG C calcining 2.0h, so as to be made nano porous copper load ultrafine copper oxide nanowire composite.10 μm of line length of nanometer, it is wide
15nm, every 20~30 nano wire clusters are into a branch of.
Nano porous copper load ultrafine copper oxide nanowire composite carries out photocatalytic degradation made from the present embodiment
The experimentation of organic dyestuff is as follows：
Photocatalytic degradation experiment is carried out from organic dyestuff rhodamine B, methyl orange, solution is by 4ml 15mg L-1Luo Dan
Bright B, 4ml 15mg L-1Methyl orange and 4ml 20wt.%H2O2Oxidant forms, using 500W xenon lamp as light source, xenon
Distance between lamp and the solution that is degraded is 10cm, and intensity of illumination is 100mW cm-2.During experiment, obtained sample is immersed into solution
In, the test case of solution, the relative absorbency of wherein dyestuff pass through UV-vis spectroscopy after investigation dyestuff degraded different time
Photometer (Lambda-750PerkinElmer) is tested.Using obtained composite in the present embodiment respectively to organic
After mixed dye is degraded 0,1,2,5,7 minute, contrasted from the relative absorbency of solution, 60 minutes are extended to the time, contaminated
Expect degradable.The material carries out circulation degradation experiment, finds (weekly 60 after being degraded 5 weeks to congruent, different batches dyestuff
Minute) degradation rate still be more than 98%, illustrate that there is the made composite of the present embodiment good photocatalytic degradation to have engine dyeing
The performance of material.
Embodiment 3
Select alloying component Cu50Zr45Al5, the atomic percent according to each element in subject alloy：Cu is 50at.%, Zr
For 45at.%, Al 5at.%, weigh high-purity copper sheet (6.425g), zirconium grain (8.302g) that mass fraction is 99.99% and
Aluminium flake (0.273g) obtains foundry alloy raw material 15g；Foundry alloy raw material is placed in vacuum arc melting furnace and (is put into before melting
99.9wt% pure titanium grain is as oxygen scavenging material), melt back 4 times is (to ensure the uniform of alloy under high-purity argon gas protection
Property), each 40s or so.Cool to room temperature with the furnace, that is, obtain Cu50Zr45Al5Alloy pig.
Take 2~3g of alloy pig after polishing cleaning to be placed in quartz test tube, quartz test tube is put into vacuum and got rid of in band machine and is felt
Answer in coil and fix, induction melting is carried out under high-purity argon gas protection and under certain pressure difference by the Cu of melting50Zr45Al5Gold
Category liquid is blown into copper mold, makes it quickly solidify to form non-crystaline amorphous metal bar；Pressure needed for blowing casting is 1.0MPa, vacuum 9.0
×10-4Pa, copper mold bore dia are 2mm, the obtained a diameter of Ф 2mm of non-crystaline amorphous metal coupon, length 40mm；
By Cu obtained in the previous step50Zr45Al5Amorphous coupon cuts into length and is 10mm stub, and is thrown with abrasive paper for metallograph
Light is to both ends horizontal, using the 0.05M HF solution of argon gas deoxygenation as corrosive liquid, by the Cu of well cutting50Zr45Al5Amorphous coupon
It is put into 0.05M HF and freely takes off alloy 3 days in 298k constant temperature, nanoporous copper metal is made.The μ of thickness 135 of NPC tubular layers
M, NPC aperture size are 72nm, ligament width 138nm.
Using platinum electrode as negative electrode, the nanoporous copper metal prepared carries out electrochemical oxidation as anode, tests bar
Part is concentration of electrolyte 0.5M KOH, current density 5mA cm-2, reaction time 10min, 20 DEG C of reaction temperature；Will be reacted
Product is cleaned with deionized water, is obtained nano porous copper and is loaded ultra-fine Kocide SD nanowire composite；
Obtained nano porous copper is loaded into ultra-fine Kocide SD nanowire composite, is placed in vacuum drying chamber in 60
DEG C calcining 2.0h, so as to be made nano porous copper load ultrafine copper oxide nanowire composite.8 μm, wide 5nm of line length of nanometer,
Every 20~30 nano wire clusters are into a branch of.
Nano porous copper load ultrafine copper oxide nanowire composite carries out photocatalytic degradation made from the present embodiment
The experimentation of organic dyestuff is as follows：
Photocatalytic degradation experiment is carried out from organic dyestuff rhodamine B, methyl orange and methylene blue, solution is by 3ml 15mg
L-1Rhodamine B, 3ml 15mg L-1Methyl orange, 3ml 15mg L-1Methylene blue and 4ml 20wt.%H2O2Oxidant
Composition, using 500W xenon lamp as light source, the distance between xenon lamp and the solution that is degraded is 10cm, intensity of illumination 100mW
cm-2.During experiment, obtained sample is immersed in solution, the test case of solution after dyestuff degraded different time is investigated, wherein contaminating
The relative absorbency of material is tested by ultraviolet-visible spectrophotometer (Lambda-750PerkinElmer).Use this reality
Apply in example after obtained composite degrades 0,1,2,5,7 minute to organic mixed dye respectively, by the relative absorbency of solution
Contrast is understood, extends to 60 minutes with the time, dyestuff is degradable.The material carries out circulation degradation experiment, find to it is congruent,
The degradation rate of (weekly 60 minutes) is still 100% after the dyestuff of different batches is degraded 5 weeks, illustrates the made composite wood of the present embodiment
Performance of the material with good photocatalytically degradating organic dye.
Comparative example 1：
The corrosive liquid selection sulfuric acid or hydrochloric acid (0.5M H of de- alloy2SO4Or 0.5M HCl), other conditions with embodiment 1,
Products therefrom detects through micro- Electronic Speculum, not it is observed that obvious nano-porous structure.
Comparative example 2：
In anodized, concentration of electrolyte 1M KOH, current density 20mA cm are selected-2, reaction time 5min,
10 DEG C of reaction temperature, for other conditions with embodiment 1, gained sample surfaces do not generate cupric oxide nano line, and face checking.
Comparative example 3：
In anodized, concentration of electrolyte 0.05M KOH, current density 5mA cm are selected-2, the reaction time
5min, 10 DEG C of reaction temperature, with embodiment 1, gained sample surfaces only generate short and small and scattered distribution cupric oxide and received other conditions
Rice noodles.
Above comparative example is to implement the case of failure, arbitrarily change preparation parameter of the present invention can lead to not to obtain it is tough
The good nano-porous materials of band/hole pattern, or the nano porous copper load ultrafine copper oxide nano wire composite wood prepared
Material does not reach preferable performance requirement etc..
According to the selection of presoma alloying component, the corrosive liquid must select hydrofluoric acid solution to reach good de- conjunction
Golden effect, selecting other solution to be caused for corrosive liquid, de- alloy cannot get nano-porous structure or ligament/hole is uneven；
During anodized, reasonable selection anodic oxidation experiment parameter is needed, otherwise the cupric oxide nano linear dimension of sample surfaces load
Short and small and distribution is scattered, or even surface can not generate cupric oxide nano line, not reach preferable photocatalytically degradating organic dye
Effect.
Unaccomplished matter of the present invention is known technology.
Claims (4)
1. a kind of nano porous copper loads ultrafine copper oxide nanowire composite, it is characterized in that the material is bar, including it is non-
Brilliant matrix, the nano porous copper being covered on noncrystal substrate and the ultrafine copper oxide nanometer for being supported on nano porous copper surface
Line；Described noncrystal substrate is CuxZryAlzAlloying component, wherein x, y, z are atomic percent, 45≤x≤50,45≤
Y≤50,5≤z≤10, and x+y+z=100；Wherein 85 ~ 135 μm of nano porous copper thickness, tough bandwidth 118 ~
138 nm, the nm of aperture size 30 ~ 100,4 ~ 10 μm of nanometer line length, wide 5 ~ 15 nm, every 20 ~ 30 nano wire clusters are into a branch of；
Described nano porous copper load ultrafine copper oxide nanowire composite is made by following methods, is comprised the following steps：
The first step, prepare non-crystaline amorphous metal bar
According to target composition weighs pure Cu, pure Zr and pure Al；Melting in vacuum arc melting furnace is put into after cleaning Cu-Zr-Al is made
Alloy pig, it is placed in after polishing, cleaning in quartz test tube, quartz test tube is put into vacuum gets rid of fixation in induction coil in band machine,
High-purity argon gas protection is lower to carry out induction melting, and the molten metal of melting is blown into copper mold, its solidification is formed non-crystaline amorphous metal bar；
Wherein：Melting and get rid of band vacuum be 9 × 10-4Pa；It is 0.5 ~ 2.0 MPa to blow casting pressure；Copper mold bore dia is 1 ~ 3 mm；
The obtained a diameter of mm of Ф 0.9 ~ 2.9 of non-crystaline amorphous metal coupon, length are 30 ~ 70 mm；
Second step, de- alloy treatment prepare nanoporous copper metal
Non-crystaline amorphous metal bar obtained in the previous step is placed in HF corrosive liquids and soaked 1 ~ 3 day, obtains nanoporous copper metal；Corrosion
Temperature is 298 K constant temperature, and HF corrosive liquids concentration is 0.05 ~ 0.5 M；
3rd step, anodic oxidation prepare nano porous copper load ultrafine copper oxide nanowire composite
Using platinum electrode as negative electrode, nanoporous copper metal made from previous step carries out anodic oxidation as dc source anode,
Make its Surface Creation Kocide SD nano wire, obtain nano porous copper and load ultra-fine Kocide SD nanowire composite；Will system
The composite obtained is placed in vacuum drying chamber calcines 1.0 ~ 3.0 h in 50 ~ 150 DEG C, surpasses so as to which nano porous copper load be made
Thin cupric oxide nano line composite；
Wherein, in anodic oxidation reactionses, electrolyte be the M of concentration 0.1 ~ 0.6 KOH solution, the mA cm of current density 0.5 ~ 10-2,
The min of reaction time 5 ~ 180,20 ~ 30 DEG C of reaction temperature.
2. the preparation method of nano porous copper load ultrafine copper oxide nanowire composite as claimed in claim 1, it is special
The purity levied as described pure Cu, pure Zr and pure Al is that mass fraction is 99.99%.
3. the application of nano porous copper load ultrafine copper oxide nanowire composite as claimed in claim 1, it is characterized in that
For photocatalytically degradating organic dye.
4. the application of nano porous copper load ultrafine copper oxide nanowire composite as claimed in claim 3, it is characterized in that
Described organic dyestuff is preferably rhodamine B, the one or more in methyl orange and methylene blue.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108295854A (en) * | 2018-01-30 | 2018-07-20 | 河北工业大学 | A kind of multi-stage porous nano porous copper load nano cuprous oxide wire composite material and preparation method |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103343253A (en) * | 2013-07-03 | 2013-10-09 | 河北工业大学 | Method for preparing nano-porous copper |
| CN104831197A (en) * | 2015-04-30 | 2015-08-12 | 河北工业大学 | Preparation method for nanometer porous copper silver |
| CN105543531A (en) * | 2016-01-04 | 2016-05-04 | 武汉理工大学 | Dealloying method for preparing micron nano-porous copper block body |
| CN106629813A (en) * | 2017-01-11 | 2017-05-10 | 河北工业大学 | Foam copper-supported porous copper oxide nanowire composite material and preparation method and application thereof |
| CN107326209A (en) * | 2017-07-05 | 2017-11-07 | 北京科技大学 | The preparation method of noble metal and magnesium-yttrium-transition metal nano wire and mesh nanometer material |
-
2017
- 2017-07-18 CN CN201710583967.0A patent/CN107366011B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103343253A (en) * | 2013-07-03 | 2013-10-09 | 河北工业大学 | Method for preparing nano-porous copper |
| CN104831197A (en) * | 2015-04-30 | 2015-08-12 | 河北工业大学 | Preparation method for nanometer porous copper silver |
| CN105543531A (en) * | 2016-01-04 | 2016-05-04 | 武汉理工大学 | Dealloying method for preparing micron nano-porous copper block body |
| CN106629813A (en) * | 2017-01-11 | 2017-05-10 | 河北工业大学 | Foam copper-supported porous copper oxide nanowire composite material and preparation method and application thereof |
| CN107326209A (en) * | 2017-07-05 | 2017-11-07 | 北京科技大学 | The preparation method of noble metal and magnesium-yttrium-transition metal nano wire and mesh nanometer material |
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| CN108193255B (en) * | 2018-01-30 | 2019-09-06 | 河北工业大学 | A kind of supported porous cuprous nano piece composite material and preparation method of nano porous copper |
| CN108597892A (en) * | 2018-04-28 | 2018-09-28 | 河北工业大学 | A kind of nano porous copper load copper-based oxide composite of morphology controllable and preparation method and application |
| CN108597892B (en) * | 2018-04-28 | 2019-12-27 | 河北工业大学 | Nano-porous copper-loaded copper-based oxide composite material with controllable morphology as well as preparation method and application thereof |
| CN110714196A (en) * | 2018-07-12 | 2020-01-21 | 南京理工大学 | Copper hydroxide nanobelt/nano porous copper composite material and application thereof |
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| CN112164597B (en) * | 2020-09-28 | 2022-05-27 | 桂林理工大学 | Copper oxide nano array electrode, copper oxide nano array non-solid water system flexible energy storage device and preparation method thereof |
| CN115475618A (en) * | 2022-10-17 | 2022-12-16 | 南京工程学院 | Preparation method of polygonal prism-shaped quaternary photocatalyst based on combustible amorphous strips |
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