CN108193255A - A kind of supported porous cuprous nano piece composite material of nano porous copper and preparation method thereof - Google Patents
A kind of supported porous cuprous nano piece composite material of nano porous copper and preparation method thereof Download PDFInfo
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- CN108193255A CN108193255A CN201810088988.XA CN201810088988A CN108193255A CN 108193255 A CN108193255 A CN 108193255A CN 201810088988 A CN201810088988 A CN 201810088988A CN 108193255 A CN108193255 A CN 108193255A
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- cuprous
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- 239000010949 copper Substances 0.000 title claims abstract description 120
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000005275 alloying Methods 0.000 claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 36
- 239000000956 alloy Substances 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 35
- 239000000975 dye Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 239000005300 metallic glass Substances 0.000 claims description 26
- 230000008018 melting Effects 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 20
- 238000012360 testing method Methods 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 8
- 229940043267 rhodamine b Drugs 0.000 claims description 8
- 230000006698 induction Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 229940095054 ammoniac Drugs 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 3
- 229940012189 methyl orange Drugs 0.000 claims description 3
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 3
- 241000282887 Suidae Species 0.000 claims description 2
- 229910004349 Ti-Al Inorganic materials 0.000 claims description 2
- 229910004692 Ti—Al Inorganic materials 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 229910013868 M2SO4 Inorganic materials 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000010936 titanium Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 20
- 230000015556 catabolic process Effects 0.000 description 14
- 238000006731 degradation reaction Methods 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 10
- 210000003041 ligament Anatomy 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 7
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 7
- 229940112669 cuprous oxide Drugs 0.000 description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- -1 Methylene Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003491 array Methods 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
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- B01J35/647—
-
- B01J35/651—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/11—Making amorphous alloys
-
- 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
-
- 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
A kind of supported porous cuprous nano piece composite material of nano porous copper, which is bar, including noncrystal substrate, the nano porous copper being covered on noncrystal substrate and the cuprous nanometer sheet of porous oxidation for being supported on nano porous copper surface；The noncrystal substrate is CuxZryTizAlwAlloying component, wherein x, y, z, w are atomic percent, 45≤x≤50,20≤y≤25,25≤z≤30,5≤w≤10 and x+y+z+w=100；Wherein 80~140 μm of nano porous copper thickness, tough 110~140nm of bandwidth, 40~100nm of aperture size；Nanometer sheet 50~90nm of thickness, nanometer length of a film 30~80nm, wide 5~10nm, the nano aperture size in nanometer sheet is 1~4nm.Preparation process of the present invention is simple, short preparation period；Prepared composite material possesses good mechanical integrity and thermal stability, is recycled recycling, and economic benefit is improved.
Description
Technical field：
The present invention relates to cuprous oxide field of material technology, specifically a kind of supported porous oxidation of nano porous copper is sub-
Copper nanosheet composite material and preparation method thereof.
Background technology：
Cuprous oxide is a kind of p-type narrow band gap (2.17eV) semi-conducting material, active electron-hole pair system, because
This shows good catalytic activity, shows very big application potential in photocatalytically degradating organic dye etc..Many institutes
Known, the degradation property of catalyst is often depending on its effective surface area and porosity.Therefore nanosizing and porous, are to carry
The effective ways of high cuprous Photocatalytic Degradation Property.
First technology, publication number CN102965711B " the anodic oxidation two-step methods of cuprous nano flaky powder material
Preparation method " is that substrate grows cuprous oxide nano-sheet powder in copper foil surface using copper foil in the patent.Due to copper foil base
Copy for the record or for reproduction body reduces the adequacy of reaction, increases reaction solution and the transmission range of internal nanometer sheet without porous structure.This
Outside, the cuprous nano piece average diameter of preparation is larger, it is easy to come off from matrix, the machinery for affecting the composite material is complete
Whole property.
First technology, publication number CN106229462A " the three-D nano-porous cuprous nano-chip arrays type lithiums of copper/two dimensional oxidation
Ion battery cathode and one one-step preparation method ", in the patent, need by cuprous nano piece obtained under vacuum into
Row is dry to avoid being aoxidized, and illustrates unstable using cuprous nano piece made from this method.In addition it is made under vacuum condition
Standby cuprous nano piece increases experimental cost, is unfavorable for marketing.
Invention content：
The purpose of the present invention is used easily to reunite in use for cuprous nano piece in current techniques
Later the deficiencies of being not easily recycled and easily being aoxidized provides a kind of nano porous copper supported porous cuprous nano piece composite wood
Material and preparation method thereof.The material includes noncrystal substrate nano porous copper composite bar and the porous oxidation for being supported on its surface
Cuprous nanometer sheet.Preparation method is first to be heat-treated amorphous bar, removes the residual stress inside amorphous bar.Then
A kind of supported porous cuprous nano piece composite material of nano porous copper is made using de- alloying technology and anode oxidation process
(wherein 80~140 μm of nano porous copper thickness, tough 110~140nm of bandwidth, 40~100nm of aperture size；Nanometer sheet thickness 50
~90nm, nanometer length of a film 30~80nm, wide 5~10nm.It distributed the nano aperture of a large amount of 1~4nm scales in nanometer sheet).
Rodlike composite material prepared by the present invention has the specific surface area of bigger and more active sites compared to what is reported at present
Point, and nanometer sheet is not easily to fall off.Use easily recycling later, is recycled recycling.The composite material has in photocatalytic degradation
Machine dye field occupies unique structure and performance advantage.
The technical scheme is that：
A kind of supported porous cuprous nano piece composite material of nano porous copper, which is bar, including non-
Brilliant matrix, the nano porous copper being covered on noncrystal substrate and the cuprous nanometer of porous oxidation for being supported on nano porous copper surface
Piece；The noncrystal substrate is CuxZryTizAlwAlloying component, wherein x, y, z, w are atomic percent, 45≤x≤50,20≤
Y≤25,25≤z≤30,5≤w≤10 and x+y+z+w=100；Wherein 80~140 μm of nano porous copper thickness, tough bandwidth 110
~140nm, 40~100nm of aperture size；Nanometer sheet 50~90nm of thickness, nanometer length of a film 30~80nm, wide 5~10nm, nanometer
The nano aperture size of on piece is 1~4nm.
The preparation method of the supported porous cuprous nano piece composite material of the nano porous copper, including walking as follows
Suddenly：
The first step prepares non-crystaline amorphous metal bar
According to target ingredient weighs pure Cu, pure Zr, pure Ti and pure Al；Melting in vacuum arc melting furnace is put into after cleaning to be made
Cu-Zr-Ti-Al alloy pigs, polishing, cleaning are placed in quartz test tube, and quartz test tube is put into vacuum gets rid of the line of induction in band machine
It is fixed in circle, induction melting is carried out under high-purity argon gas protection, molten metal liquid is blown into copper mold, forms its solidification non-
Peritectic alloy bar；Wherein：Melting and get rid of band vacuum degree be 9 × 10-4Pa；It is 0.5~2.0MPa to blow casting pressure；Copper mold bore dia is
1~3mm；A diameter of 0.9~the 2.9mm of Ф of non-crystaline amorphous metal coupon obtained, length are 30~70mm；
Non-crystaline amorphous metal bar is heat-treated by second step
Non-crystaline amorphous metal bar obtained in the previous step is placed in tube furnace, in the case of logical argon gas, with 2~4 DEG C of min-1
Speed from 25 DEG C of temperature programmings to 150 DEG C, after constant temperature keeps 1~3h, then with 10 DEG C of min-1Speed program be warming up to 200
DEG C, constant temperature takes out after keeping 1~3h；
Third walks, and de- alloy treatment prepares nanoporous copper metal
Non-crystaline amorphous metal bar obtained in the previous step is placed in HF corrosive liquids and is impregnated 1~3 day, obtains nano porous copper gold
Belong to；Corrosion temperature be 298K constant temperature, a concentration of 0.01~0.05M of HF corrosive liquids；Then in the H of 0.1~0.25M2SO4In solution
It impregnates 60~90 seconds；
4th step, anodic oxidation prepare the supported porous cuprous nano piece composite material of nano porous copper
Using platinum electrode as cathode, previous step passes through H2SO4The nanoporous copper metal that solution impregnates is as DC power supply sun
Pole carries out anodic oxidation.Composite material obtained is placed in drying box in 100~200 DEG C of dry 1~2h, it is more to obtain nanometer
The supported porous cuprous nano piece composite material of hole copper；
Wherein, in anodic oxidation reactions, mixed solution of the electrolyte for sodium hydroxide and sulfate of ammoniac, in mixed solution,
A concentration of 0.5~the 1.2M, NaOH and (NH of NaOH4)2SO4Molar ratio be 3:1；10~40mA of current density cm-2, during reaction
Between 30~90min, 20~30 DEG C of reaction temperature.
The pure Cu, pure Zr, pure Ti and pure Al purity be mass fraction be 99.99%.
The application of the supported porous cuprous nano piece composite material of the nano porous copper, has for photocatalytic degradation
Engine dyeing material.
The organic dyestuff is preferably rhodamine B, one or more in methyl orange and methylene blue.
Above-mentioned supported porous cuprous nano piece composite material of a kind of nano porous copper and preparation method thereof, it is used
Raw material and equipment are obtained by well known approach, and operating procedure used is that those skilled in the art can grasp
's.
The present invention substantive distinguishing features be：
(1) cuprous nano piece obtained in current techniques, surface do not have a nanoscale hole hole structure, and present invention system
It distributed the hole of a large amount of Nano grades in the nanometer sheet obtained, form a kind of supported porous cuprous nano piece of nano porous copper
Composite material.Therefore the specific surface area of material is improved, provides more reactivity sites.High-specific surface area, fine and close oxygen
Changing cuprous nanometer sheet makes it occupy unique structure and performance advantage in photocatalytically degradating organic dye field.
(2) in current techniques, de- alloy is often carried out with alloy thin band, nano porous copper obtained it is easily cracked and
It is broken, and then prepared cuprous nano piece is made to come off from nanoporous Copper substrate.And this patent with alloy bar material into
The de- alloy of row can not only realize the self-supporting of material, but also nanometer sheet is completely embedded with nanoporous Copper substrate.This patent leads to
Residual stress inside Overheating Treatment technique removal non-crystaline amorphous metal bar, further such that nanometer sheet and nanoporous Copper substrate are tight
Close connection, is easily recycled after use, is recycled recycling.This patent is by heat treatment process, de- alloying technology and anodic oxygen chemical industry
Skill, which is combined, explores a whole set of novel preparation process for preparing the cuprous oxide composite material with mechanical integrity.
(3) in current techniques, cuprous nano piece obtained is easily oxidized, and needs to be done under vacuum
It is dry to ensure stability.And cuprous oxide produced by the present invention has good stability, need to only dry in air.Section
About cost, is conducive to marketing.
Compared with existing technology, beneficial effects of the present invention are as follows：
(1) present invention prepares a kind of extremely stable and cuprous nano piece with nano-porous structure answer for the first time
Bar is closed, including noncrystal substrate, the nano porous copper being covered on noncrystal substrate and is supported on the more of nano porous copper surface
Hole cuprous nano piece.Wherein de- alloy can prepare 80~140 μm of thickness, tough 110~140nm of bandwidth, aperture size 40
The nanoporous copper metal of~100nm.50~90 μm of thickness is prepared on its surface followed by anodizing technology, long by 30~
The cuprous nanometer sheet of porous oxidation of 80nm, wide 5~10nm.It distributed the big nano aperture taken measurements as 1~4nm in nanometer sheet,
The composite material can efficiently photocatalytically degradating organic dye.
(2) heat treatment process, de- alloy technology and anode oxidation process are dexterously combined together preparation one by the present invention
The kind supported porous cuprous nano piece composite bar of nano porous copper, the preparation process is simple, short preparation period；Prepared
Composite material possesses good mechanical integrity and thermal stability, is recycled recycling, and economic benefit is improved.
(3) compared with the spongy cuprous nano pieces of publication number CN102965711B, the oxidation prepared by the present invention is sub-
Copper nanometer sheet average-size is more tiny, and nanometer sheet is tightly combined with matrix.And it is receiving for 1~4nm to be covered with size in nanometer sheet
Metre hole.Therefore possess the porosity of more horn of plenty and more reactivity sites.Be conducive to the infiltration of solution and the biography of ion
Defeated diffusion increases light transmittance and light absorption, is quickly and efficiently carried out so as to be conducive to photocatalytic degradation.The structure is used as photocatalysis
The degradation efficiency of degradating organic dye can improve 20 times or more.
Description of the drawings：
Fig. 1：The energy spectrum analysis figure of the nano porous copper prepared in embodiment 1.
Fig. 2：The stereoscan photograph of the nano porous copper prepared in embodiment 1.
Fig. 3：The XRD spectrum of the supported porous cuprous nano piece of nano porous copper prepared in embodiment 1.
Fig. 4：The stereoscan photograph of the supported porous cuprous nano piece of nano porous copper prepared in embodiment 1.
Specific embodiment
Embodiment 1
Select alloying component Cu50Zr20Ti25Al5, the atomic percent according to each element in subject alloy：Cu is
50at.%, Zr 20at.%, Ti 25at.%, Al 5at.% weigh the high-purity copper sheet that mass fraction is 99.99%
(7.525g), zirconium grain (4.321g), titanium grain (2.835g) and aluminium flake (0.32g) obtain master alloy raw material 15g；By master alloy raw material
It is placed in vacuum arc melting furnace and (the pure titanium grain of 99.9wt% is put into before melting as oxygen scavenging material), under high-purity argon gas protection
Melt back 4 times (ensure the uniformity of alloy), each 40s or so.Cool to the furnace room temperature to get to
Cu50Zr20Ti25Al5Alloy pig.
2~3g of alloy pig after polishing cleaning is taken to be placed in quartz test tube, quartz test tube is put into vacuum and got rid of in band machine and is felt
It answers in coil and fixes, induction melting is carried out under high-purity argon gas protection and under certain pressure difference by melting
Cu50Zr20Ti25Al5Molten metal is blown into copper mold, it is made quickly to solidify to form non-crystaline amorphous metal bar；Blowing pressure needed for casting is
1.0MPa, vacuum degree are 9.0 × 10-4Pa, copper mold bore dia be 2mm, a diameter of Ф 2mm of non-crystaline amorphous metal coupon obtained, length
For 40mm；
By Cu obtained in the previous step50Zr20Ti25Al5Non-crystaline amorphous metal bar cuts into the stub that length is 10mm.It is put
In tube furnace, in the case of logical argon gas, with 2 DEG C of min-1Speed from 25 DEG C of temperature programmings to 150 DEG C, constant temperature keeps 3h
Afterwards, then with 10 DEG C of min-1Speed program be warming up to 200 DEG C, constant temperature takes out after keeping 1h.
Non-crystaline amorphous metal bar obtained in the previous step is placed in 0.05M HF solution and takes off alloy treatment 1 day, be made ligament with
The nano porous copper of uniform pore diameter.Fig. 1 is the energy spectrum analysis figure of the nano porous copper prepared in the present embodiment, it was demonstrated that in 0.05M
Nanoporous copper metal is successfully prepared after taking off the alloy suitable time under HF.Fig. 2 is the nanoporous prepared in the present embodiment
The stereoscan photograph of copper, it may be determined that nano porous copper obtained has uniform, co-continuous ligament/pore space structure three-dimensional
(3D) nanoporous pattern.90 μm, ligament width 120nm, aperture size 50nm of nano porous copper thickness.Then in 0.1M
H2SO4It is impregnated 90 seconds in solution.
Using platinum electrode as cathode, the nano porous copper prepared cleans, carries out electrochemical oxidation as anode after drying,
Experiment condition is the mixed solution that electrolyte is sodium hydroxide and sulfate of ammoniac, in mixed solution, a concentration of 0.6M of NaOH,
(NH4)2SO4A concentration of 0.2M.Current density 10mA cm-2, reaction time 30min, 20 DEG C of reaction temperature；Spent after taking-up from
Sub- water cleaning, is placed in drying box, in 100 DEG C of dry 2h, it is compound obtaining the supported porous cuprous nano piece of nano porous copper
Material；Fig. 3 is the XRD spectrum of the supported porous cuprous nano piece of the nano porous copper prepared in the present embodiment, it was demonstrated that made
The porous nano-sheet obtained is cuprous oxide.Fig. 4 is the supported porous cuprous nano piece of the nano porous copper prepared in embodiment
Stereoscan photograph, it is observed that one layer of cuprous nano piece of covering neat fine and close in nanoporous copper metal,
Wherein nanometer sheet thickness 60nm, nanometer length of a film 50nm, wide 6nm.Pass through the supported porous cuprous nano piece of nano porous copper
Transmission electron microscope photo is we can observe that the pore size in nanometer sheet is 2nm.
The supported porous cuprous nano piece composite material of the nano porous copper made from the present embodiment carries out photocatalysis drop
The experimentation for solving organic dyestuff is as follows：
Organic dyestuff rhodamine B is selected to carry out photocatalytic degradation experiment, solution is by 7ml 15mg L-1Rhodamine B and
3ml20wt.%H2O2Oxidant forms, and using the xenon lamp of 500W as light source, the distance between xenon lamp and the solution that is degraded is
10cm, intensity of illumination are 100mW cm-2.It is during experiment, the supported porous cuprous nano piece of nano porous copper obtained is compound
Material is immersed in solution, investigates the test case of solution after dyestuff degradation different time, and the relative absorbency of wherein dyestuff passes through
Ultraviolet-visible spectrophotometer (Lambda-750PerkinElmer) is tested.Use composite wood obtained in the present embodiment
Material respectively to organic dyestuff rhodamine B degradation 0,1,2,3, after five minutes, by solution relative absorbency compare it is found that at any time
5 minutes are extended to, dyestuff is degradable.The material carries out cycle degradation experiment, finds to drop congruent, different batches dyestuff
The degradation rate for (each recycling 5min) after 5 cycles of solution is still more than 98.6%.Illustrate that the made composite material of the present embodiment has
The performance of good photocatalytically degradating organic dye, it is copper-based which has benefited from the regulatable nanoporous of composite material in itself
The structural advantage of body and the cuprous nanometer sheet of porous oxidation, while also have benefited from the good self-supporting of material and mechanical integrity,
So that the cuprous nanometer sheet of porous oxidation is connect well during the reaction with nanoporous Copper substrate.
Embodiment 2
Select alloying component Cu50Zr20Ti25Al5, the atomic percent according to each element in subject alloy：Cu is
50at.%, Zr 20at.%, Ti 25at.%, Al 5at.% weigh the high-purity copper sheet that mass fraction is 99.99%
(7.525g), zirconium grain (4.321g), titanium grain (2.835g) and aluminium flake (0.32g) obtain master alloy raw material 15g；By master alloy raw material
It is placed in vacuum arc melting furnace and (the pure titanium grain of 99.9wt% is put into before melting as oxygen scavenging material), under high-purity argon gas protection
Melt back 4 times (ensure the uniformity of alloy), each 40s or so.Cool to the furnace room temperature to get to
Cu50Zr20Ti25Al5Alloy pig.
2~3g of alloy pig after polishing cleaning is taken to be placed in quartz test tube, quartz test tube is put into vacuum and got rid of in band machine and is felt
It answers in coil and fixes, induction melting is carried out under high-purity argon gas protection and under certain pressure difference by melting
Cu50Zr20Ti25Al5Molten metal is blown into copper mold, it is made quickly to solidify to form non-crystaline amorphous metal bar；Blowing pressure needed for casting is
1.0MPa, vacuum degree are 9.0 × 10-4Pa, copper mold bore dia be 2mm, a diameter of Ф 2mm of non-crystaline amorphous metal coupon obtained, length
For 40mm；
By Cu obtained in the previous step50Zr20Ti25Al5Non-crystaline amorphous metal bar cuts into the stub that length is 10mm.It is put
In tube furnace, in the case of logical argon gas, with 4 DEG C of min-1Speed from 25 DEG C of temperature programmings to 150 DEG C, constant temperature keeps 1h
Afterwards, then with 10 DEG C of min-1Speed program be warming up to 200 DEG C, constant temperature takes out after keeping 2h.
Non-crystaline amorphous metal bar obtained in the previous step is placed in 0.05M HF solution and takes off alloy treatment 2 days, be made ligament with
The nano porous copper of uniform pore diameter.Nano porous copper obtained has uniform, co-continuous ligament/pore space structure three-dimensional (3D)
Nanoporous pattern.100 μm, ligament width 120nm, aperture size 60nm of nano porous copper thickness.Then in 0.2M
H2SO4It is impregnated 70 seconds in solution.
Using platinum electrode as cathode, the nano porous copper prepared cleans, carries out electrochemical oxidation as anode after drying,
Experiment condition is the mixed solution that electrolyte is sodium hydroxide and sulfate of ammoniac, in mixed solution, a concentration of 0.9M of NaOH,
(NH4)2SO4A concentration of 0.3M.Current density 40mA cm-2, reaction time 60min, 25 DEG C of reaction temperature；Spent after taking-up from
Sub- water cleaning, is placed in drying box, in 100 DEG C of dry 1h, it is compound obtaining the supported porous cuprous nano piece of nano porous copper
Material；Cuprous nano piece thickness 80nm, nanometer length of a film 70nm, wide 8nm.Pore size in nanometer sheet is 1.5nm.
The supported porous cuprous nano piece composite material of the nano porous copper made from the present embodiment carries out photocatalysis drop
The experimentation for solving organic dyestuff is as follows：
Organic dyestuff rhodamine B and methylene blue is selected to carry out photocatalytic degradation experiment, solution is by 5ml 15mg L-1Sieve
Red bright B, 2ml 20mg L-1Methylene blue and 3ml 40wt.%H2O2Oxidant forms, using the xenon lamp of 500W as light
Source, the distance between xenon lamp and the solution that is degraded are 10cm, and intensity of illumination is 100mW cm-2.During experiment, by nanoporous obtained
The supported porous cuprous nano piece composite material of copper is immersed in solution, investigates the test feelings of solution after dyestuff degradation different time
The relative absorbency of condition, wherein dyestuff is surveyed by ultraviolet-visible spectrophotometer (Lambda-750PerkinElmer)
Examination.Using composite material obtained in the present embodiment respectively to organic dyestuff rhodamine B degradation 0,1,2,3, after five minutes, by molten
The relative absorbency of liquid is compared it is found that extending to 5 minutes at any time, dyestuff is degradable.The material carries out cycle degradation experiment,
It was found that the degradation rate for (each recycling 5min) after 5 cycles of degrading to congruent, different batches dyestuff is still more than 98%.It says
The bright made composite material of the present embodiment has the performance of good photocatalytically degradating organic dye.
Embodiment 3
Select alloying component Cu50Zr20Ti25Al5, the atomic percent according to each element in subject alloy：Cu is
50at.%, Zr 20at.%, Ti 25at.%, Al 5at.% weigh the high-purity copper sheet that mass fraction is 99.99%
(7.525g), zirconium grain (4.321g), titanium grain (2.835g) and aluminium flake (0.32g) obtain master alloy raw material 15g；By master alloy raw material
It is placed in vacuum arc melting furnace and (the pure titanium grain of 99.9wt% is put into before melting as oxygen scavenging material), under high-purity argon gas protection
Melt back 4 times (ensure the uniformity of alloy), each 40s or so.Cool to the furnace room temperature to get to
Cu50Zr20Ti25Al5Alloy pig.
2~3g of alloy pig after polishing cleaning is taken to be placed in quartz test tube, quartz test tube is put into vacuum and got rid of in band machine and is felt
It answers in coil and fixes, induction melting is carried out under high-purity argon gas protection and under certain pressure difference by melting
Cu50Zr20Ti25Al5Molten metal is blown into copper mold, it is made quickly to solidify to form non-crystaline amorphous metal bar；Blowing pressure needed for casting is
1.0MPa, vacuum degree are 9.0 × 10-4Pa, copper mold bore dia be 2mm, a diameter of Ф 2mm of non-crystaline amorphous metal coupon obtained, length
For 40mm；
By Cu obtained in the previous step50Zr20Ti25Al5Non-crystaline amorphous metal bar cuts into the stub that length is 10mm.It is put
In tube furnace, in the case of logical argon gas, with 3 DEG C of min-1Speed from 25 DEG C of temperature programmings to 150 DEG C, constant temperature keeps 2h
Afterwards, then with 10 DEG C of min-1Speed program be warming up to 200 DEG C, constant temperature takes out after keeping 1h.By last obtained non-crystaline amorphous metal
Strip, which is placed in 0.05M HF solution, takes off alloy treatment 3 days, and ligament and the nano porous copper of uniform pore diameter is made.Nanometer obtained
Porous Cu has uniform, co-continuous ligament/pore space structure three-dimensional (3D) nanoporous pattern.100 μ of nano porous copper thickness
M, ligament width 140nm, aperture size 80nm.Then in 0.25M H2SO4It is impregnated 90 seconds in solution.
Using platinum electrode as cathode, electrochemical oxidation is carried out as anode after the nano porous copper cleaning got ready, drying, in fact
The condition of testing is the mixed solution that electrolyte is sodium hydroxide and sulfate of ammoniac, in mixed solution, a concentration of 1.2M, (NH of NaOH4)2SO4A concentration of 0.4M.Current density 20mA cm-2, reaction time 90min, 20 DEG C of reaction temperature；Deionized water is used after taking-up
Cleaning, is placed in drying box, in 150 DEG C of dry 1h, obtaining the supported porous cuprous nano piece composite wood of nano porous copper
Material；Cuprous nano piece thickness 90nm, nanometer length of a film 80nm, wide 10nm.Pore size in nanometer sheet is 4nm.
The supported porous cuprous nano piece composite material of the nano porous copper made from the present embodiment carries out photocatalysis drop
The experimentation for solving organic dyestuff is as follows：
Organic dyestuff rhodamine B and methyl orange is selected to carry out photocatalytic degradation experiment, solution is by 8ml 15mg L-1Luo Dan
Bright B, 1ml 20mg L-1Methyl orange and 1ml 40wt.%H2O2Oxidant forms, using the xenon lamp of 500W 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, nano porous copper obtained is born
It carries the cuprous nanosheet composite material of porous oxidation to immerse in solution, investigates the test case of solution after dyestuff degradation different time,
Wherein the relative absorbency of dyestuff is tested by ultraviolet-visible spectrophotometer (Lambda-750PerkinElmer).Make
With composite material obtained in the present embodiment respectively to organic dyestuff rhodamine B degradation 0,1,2,3, after five minutes, by the phase of solution
Absorptivity is compared it is found that extending to 5 minutes at any time, dyestuff is degradable.The material carries out cycle degradation experiment, discovery pair
Congruent, different batches dyestuffs degrade 5 degradation rates for (each recycling 5min) after recycling still more than 97.8%.Illustrate this
The made composite material of embodiment has the performance of good photocatalytically degradating organic dye.
Comparative example 1：
The non-crystaline amorphous metal bar of gained is directly carried out to de- alloy without Overheating Treatment, other conditions are the same as embodiment 1, gained
Cuprous oxide easily come off, mechanical integrity is destroyed.
Comparative example 2：
In heat treatment, with 20 DEG C of min-1Speed from 25 DEG C of temperature programmings to 300 DEG C, after constant temperature keeps 5h, then with
20min-1Speed program be warming up to 400 DEG C, constant temperature takes out band after keeping 0.5h.Other conditions take off alloy with embodiment 1
Still there is crackle appearance on the nano porous copper surface obtained afterwards.
Comparative example 3：
In anodized, electrolyte is selected as 0.05M NaOH, current density 50mA cm-2, the reaction time
100min, 10 DEG C of reaction temperature, other conditions do not have hole with embodiment 1, gained cuprous nano piece surface.
More than comparative example is to implement the case of failure, and arbitrarily change preparation parameter of the present invention can lead to not obtain tough
The good nano porous copper of band/hole pattern or the cuprous nanometer sheet of porous oxidation etc..
Heat treatment is had to pass through before the non-crystaline amorphous metal bar obtained is carried out de- alloy；Heat is carried out to non-crystaline amorphous metal bar
During processing, Temperature Programmed Processes cannot be changed arbitrarily, and the effect of removal internal residual stress is otherwise not achieved.At anodic oxidation
During reason, anodic oxidation experiment parameter need to be reasonably selected, otherwise the cuprous nano piece effect of nano porous copper Surface Creation is not
Ideal, and then photocatalytically degradating organic dye performance is had an impact.
Unaccomplished matter of the present invention is known technology.
Claims (5)
1. a kind of supported porous cuprous nano piece composite material of nano porous copper, it is characterized in that the composite material is bar,
Including noncrystal substrate, the nano porous copper being covered on noncrystal substrate and the porous oxidation Asia for being supported on nano porous copper surface
Copper nanometer sheet；The noncrystal substrate is CuxZryTizAlwAlloying component, wherein x, y, z, w are atomic percent, 45≤x
≤ 50,20≤y≤25,25≤z≤30,5≤w≤10 and x+y+z+w=100；Wherein nanoporous
80 ~ 140 μm of layers of copper thickness, tough 110 ~ 140 nm of bandwidth, 40 ~ 100 nm of aperture size；50 ~ 90 nm of nanometer sheet thickness, nanometer sheet
Long 30 ~ 80 nm, wide 5 ~ 10 nm, the nano aperture size in nanometer sheet is 1 ~ 4 nm.
2. the preparation method of the supported porous cuprous nano piece composite material of nano porous copper as described in claim 1,
It is characterized as including the following steps：
The first step prepares non-crystaline amorphous metal bar
According to target ingredient weighs pure Cu, pure Zr, pure Ti and pure Al；Melting in vacuum arc melting furnace is put into after cleaning, Cu- is made
Zr-Ti-Al alloy pigs, polishing, cleaning are placed in quartz test tube, and quartz test tube is put into vacuum gets rid of in band machine in induction coil
It is fixed, induction melting is carried out under high-purity argon gas protection, molten metal liquid is blown into copper mold, its solidification is made to form amorphous conjunction
Golden bar；Wherein：Melting and get rid of band vacuum degree be 9 × 10-4Pa；It is 0.5 ~ 2.0 MPa to blow casting pressure；Copper mold bore dia is 1
~3 mm；A diameter of 0.9 ~ 2.9 mm of Ф of non-crystaline amorphous metal coupon obtained, length are 30 ~ 70 mm；
Non-crystaline amorphous metal bar is heat-treated by second step
Non-crystaline amorphous metal bar obtained in the previous step is placed in tube furnace, in the case of logical argon gas, with 2 ~ 4 DEG C of min-1Speed
Degree is from 25 DEG C of temperature programmings to 150 DEG C, after constant temperature keeps 1 ~ 3 h, then with 10 DEG C of min-1Speed program be warming up to 200 DEG C, it is permanent
Temperature is taken out after keeping 1 ~ 3 h；
Third walks, and de- alloy treatment prepares nanoporous copper metal
Non-crystaline amorphous metal bar obtained in the previous step is placed in HF corrosive liquids and is impregnated 1 ~ 3 day, obtains nanoporous copper metal；Corrosion
Temperature be 298 K constant temperature, a concentration of 0.01 ~ 0.05 M of HF corrosive liquids；Then in the H of 0.1 ~ 0.25 M2SO4In solution impregnate 60 ~
90 seconds；
4th step, anodic oxidation prepare the supported porous cuprous nano piece composite material of nano porous copper
Using platinum electrode as cathode, previous step passes through H2SO4The nanoporous copper metal that solution impregnates as DC power supply anode,
Carry out anodic oxidation；Composite material obtained is placed in drying box in 100 ~ 200 DEG C of dry 1 ~ 2 h, obtains nano porous copper
Supported porous cuprous nano piece composite material；
Wherein, in anodic oxidation reactions, mixed solution of the electrolyte for sodium hydroxide and sulfate of ammoniac, in mixed solution, NaOH's
A concentration of 0.5 ~ 1.2 M, NaOH and (NH4)2SO4Molar ratio be 3:1；10 ~ 40 mA cm of current density-2, the reaction time 30 ~
90 min, 20 ~ 30 DEG C of reaction temperature.
3. the preparation method of the supported porous cuprous nano piece composite material of nano porous copper as claimed in claim 2, institute
The purity of pure Cu, pure Zr, pure Ti and pure Al stated are that mass fraction is 99.99%.
4. the application of the supported porous cuprous nano piece composite material of nano porous copper as described in claim 1, feature
To be used for photocatalytically degradating organic dye.
5. the application of the supported porous cuprous nano piece composite material of nano porous copper as claimed in claim 4, feature
It is rhodamine B for the organic dyestuff, it is one or more in methyl orange and methylene blue.
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| CN115212896B (en) * | 2022-07-26 | 2023-07-14 | 河北工业大学 | Nano-porous copper-loaded hepta copper tetrasulfide@cuprous oxide nanowire cluster composite material and preparation method and application thereof |
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