CN110508280A - The cupric oxide nano line and the preparation method and application thereof of the micro- texture foam copper of laser - Google Patents
The cupric oxide nano line and the preparation method and application thereof of the micro- texture foam copper of laser Download PDFInfo
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- CN110508280A CN110508280A CN201910844231.3A CN201910844231A CN110508280A CN 110508280 A CN110508280 A CN 110508280A CN 201910844231 A CN201910844231 A CN 201910844231A CN 110508280 A CN110508280 A CN 110508280A
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 57
- 239000010949 copper Substances 0.000 title claims abstract description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000006260 foam Substances 0.000 title claims abstract description 48
- 229960004643 cupric oxide Drugs 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002070 nanowire Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 238000000280 densification Methods 0.000 claims abstract description 3
- 230000000737 periodic effect Effects 0.000 claims abstract description 3
- 239000000975 dye Substances 0.000 claims description 8
- 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 6
- 229940012189 methyl orange Drugs 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 2
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [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 2
- 229940043267 rhodamine b Drugs 0.000 claims description 2
- 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 1
- 238000004140 cleaning Methods 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 description 23
- 230000003647 oxidation Effects 0.000 description 22
- 238000000034 method Methods 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 12
- 238000007146 photocatalysis Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000013532 laser treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000012876 topography Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002493 microarray Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 206010040844 Skin exfoliation Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The cupric oxide nano line and the preparation method and application thereof of the micro- texture foam copper of laser, is related to cupric oxide nano line.It by foam copper after hydrochloric acid, dehydrated alcohol and deionized water clean up, is dried up using compressed nitrogen, obtains clean foam copper；Using nanosecond laser texture technology, laser related processing parameters are adjusted, laser texturing is carried out with " matts " scan pattern on foam copper surface, forms surface periodic micro-structure；Foam copper after laser texturing is placed in heating plate, heated at constant temperature for a period of time after, be annealed to room temperature, obtain the cupric oxide nano line with micron and nanometer composite structure.The cupric oxide nano line of preparation has multistage porous structure, is evenly distributed and grows densification, large specific surface area, nano wire is kept upright growth without staggeredly, nanowire length is about 4~10 μm substantially；Cupric oxide nano line and the adhesive force at copper-based bottom significantly increase, and nano wire is not easily to fall off without cracking.It can be applied in photocatalytically degradating organic dye.
Description
Technical field
The present invention relates to cupric oxide nano lines, cupric oxide nano line more particularly, to a kind of micro- texture foam copper of laser and
Preparation method and application.
Background technique
Industrial wastewater is mainly derived from the process such as dyeing textile, packaging processing and leather manufacture, and that discharges is organic
For example unprocessed inflow rivers and lakes up to standard of waste water from dyestuff will pollute.Effluent part even contains phenyl ring, amido, azo group
The carcinogens such as group may generate irreversible injury to environment and ecology.Common wastewater treatment method has physical absorption
Method, electrochemical process, film biologic treating technique method etc..The high activity that photosensitive semiconductor inspires under the irradiation of sunlight is free
Base effectively degradating organic dye and without secondary pollution, this method can be increasingly becoming the main trend of processing organic dye waste water.
Copper oxide is a kind of typical p-type semiconductor material, and forbidden bandwidth is 1.2~2eV, have optical response range compared with
Greatly, the remarkable advantages such as non-toxic, at low cost.Cupric oxide nano cable architecture, specific surface area is bigger, and reactivity is higher, can have
Effect improves photocatalysis performance.In addition, foam copper, as a kind of new function material, multistage porous structure has more Large ratio surface
It accumulates and is conducive to fluid and pass through, have very big application potential in photocatalysis field.
Currently, the customary preparation methods of cupric oxide nano line include sol-gel method, hydro-thermal method, co-electrodeposition method and template
Method etc..However, most of photocatalysis nano material by chemical method preparation is due to its Morphological Features, there is be difficult to recycle, again
It is multiple that utilization rate is low, easily causes secondary pollution problems.Thermal oxidation method can make nanometer by control oxidization time and oxidizing temperature
Line is grown directly upon on copper-based bottom, a kind of method for being that step is simple, cost is relatively low and being prepared on a large scale cupric oxide nano line.
But this method is easy to fall off or the problems such as substrate is cracked there are still nano wire, limit in photocatalytic applications degradation efficiency and
The promotion of cyclic utilization rate.
Chinese patent CN201710021434.3 disclose a kind of supported porous cupric oxide nano line composite material of foam copper and
Preparation method and application, the composite material include foam Copper substrate, and are supported on the cupric oxide nano line on surface；Wherein oxygen
It is 8~12 μm, wide 150~250nm long to change copper nano-wire, nano wire is without cracking, and not easily to fall off, microcosmic upper nano wire has porous knot
Structure, bore dia are 2~4nm, and macroscopically nano wire radially distributes, and it is micro- that every 60~150 nano wires form a copper oxide
Popped rice；Load thickness of the copper oxide on matrix is 8~12 μm；Described matrix is foam copper, 0.9~1.0mm of thickness, tough bandwidth 70
~100 μm, 150~250 μm, purity 99.95wt.% of aperture, porosity 78~82%.Preparation method: the first step, anodic oxidation
Method synthesizes Kocide SD nano wire；Second step calcines porous oxidation copper nano-wire processed.Composite material has multistage porous structure,
The hole of entire three-dimensional structure is abundant, and light is suitble to penetrate, and is also suitble to ion transmission.
Summary of the invention
It is an object of the invention to for deficiency existing for current techniques, proposition can effectively increase specific surface area and enhancing is received
The adhesive force of rice noodles improves the catalytic degradation efficiency and recycling rate of waterused of photochemical catalyst, overcomes current conventional particles shape photocatalysis
Agent is difficult to recycle, a kind of preparation method of the cupric oxide nano line of the micro- texture foam copper of laser of easy secondary pollution problems.
Another object of the present invention is to provide the cupric oxide nano lines of the micro- texture foam copper of laser to have in photocatalytic degradation
Application in engine dyeing material.
The preparation method of the cupric oxide nano line of the micro- texture foam copper of laser, comprising the following steps:
1) it by foam copper after hydrochloric acid, dehydrated alcohol and deionized water clean up, is dried up, is obtained clean using compressed nitrogen
Net foam copper；
2) nanosecond laser texture technology is utilized, laser related processing parameters are adjusted, on foam copper surface with " matts "
Scan pattern carries out laser texturing, forms surface periodic micro-structure；
3) foam copper after laser texturing is placed in heating plate, heated at constant temperature for a period of time after, be annealed to room temperature, obtain
To the cupric oxide nano line with micron and nanometer composite structure.
In step 1), the aperture of the foam copper can be 110ppi, purity 99%.
In step 2), the wavelength of the nanosecond laser can be 1064nm, and pulsewidth can be 200ns, and repetition rate can be
20KHz；The laser power of laser can be 15~25W, and scanning speed can be 800~1500mm/s, and sweep span can be 0.05
~0.5mm.
In step 3), the heated at constant temperature, which can be placed in heating plate, carries out open heating, and the temperature of heated at constant temperature can
It is 400~600 DEG C, the time of heated at constant temperature can be 3~7h；It is preferred that the temperature of heated at constant temperature is 500 DEG C, the heated at constant temperature time is
5h；The annealing rate can be 5~10 DEG C/min.
The cupric oxide nano line of the micro- texture foam copper of laser prepared by the present invention has multistage porous structure, be evenly distributed and
Growth is fine and close, large specific surface area, and nano wire is kept upright growth without staggeredly, nanowire length is about 4~10 μm substantially；Together
When, cupric oxide nano line and the adhesive force at copper-based bottom significantly increase, and nano wire is not easily to fall off without cracking.
The cupric oxide nano line of the micro- texture foam copper of laser can be applied in photocatalytically degradating organic dye.It is described to have
At least one of the preferred methyl orange of engine dyeing material, rhodamine B and methylene blue etc..
The present invention carries out the micro- texture in surface to foam copper using foam copper as substrate, using nanosecond laser, forms microarray week
Phase body structure surface, then heated at constant temperature in heating plate is placed on using thermal oxidation method, prepare cupric oxide nano line.It will prepare
Sample be applied to degradation methyl orange solution photocatalytic applications.Compared with prior art, outstanding advantages of the invention are as follows:
1) using the foam copper of porous multi-polar structure as substrate, be conducive to fluid and pass through, and laminated structure is easier to recycle, and mentions
The reaction efficiency and recycling rate of waterused of high photocatalytically degradating organic dye.
2) content that sample surfaces oxygen element can be improved using laser processing technology, is effectively facilitated in growth course and is aoxidized
The raising of copper nano-wire length and density improves the degradation rate of photocatalytically degradating organic dye.With multistage porous structure, can have
Effect increases specific surface area and surface-active.
3) laser texturing foam copper surface micro-structure can further discharge thermal stress, enhance the attachment of cupric oxide nano line
Power improves the stability of photo-catalytic degradation of methyl-orange, can be used repeatedly.
4) preparation method is easy to operate, low in cost, and the size and pattern of easily controllable nano wire are conducive to extensive work
Industry production, the micro nano structure of self-supporting are easier to recycle, not only can solve conventional particles shape photochemical catalyst and be difficult to recycle, and easy two
The problems such as secondary pollution, and have many advantages, such as photocatalytic activity height, good cycling stability, have in photocatalysis field and widely answers
Use prospect.
Detailed description of the invention
Fig. 1 is cupric oxide nano line preparation method schematic diagram.
Fig. 2 is cupric oxide nano line surface topography map.In Fig. 2, (a) is direct oxidation group, scale 50um；It (b) is straight
Meet oxidation group, scale 2um；It (c) is laser texturing oxidation group, scale 50um；It (d) is laser texturing oxidation group, scale 2um.
Fig. 3 is the EDS spectrogram of each group sample.In Fig. 3, (a) is primary sample group；(b) it is not aoxidized for the micro- texture of laser
Group；It (c) is laser texturing oxidation group.
Fig. 4 is photo-catalytic degradation of methyl-orange result figure.In Fig. 4, label ■ indicates laser treatment oxidation group；▲ indicate straight
Connect oxidation group；● indicate no catalyst group.
Fig. 5 is the sample surface morphology figure after photocatalysis experiment.It (a) is laser treatment oxidation group；It (b) is direct oxidation
Group；Scale is 1um.
Fig. 6 is loop test result figure.
Specific embodiment
Following embodiment will the present invention is further illustrated in conjunction with attached drawing.
Referring to Fig. 1, the preparation method of the cupric oxide nano line of the micro- texture foam copper of laser of the present invention, including following step
It is rapid:
Foam copper is made as 25mm × 25mm × 0.5mm sample by step 1, after salt acid soak, with dehydrated alcohol and
Deionized water is cleaned, then is dried up to obtain clean foam copper sample with compressed nitrogen.
Step 2, using nanosecond optical fiber laser (wavelength 1064nm, repetition rate 20kHz, pulsewidth 200ns) in foam copper
Surface carries out the micro- texture of laser with " matts " scan pattern.Laser facula focal diameter is 35 μm, and output power 20W is swept
Retouching number is 20 times, obtains the foam copper sample with micro-structure.
The resulting sample of step 2 and the sample obtained by step 1 are all placed in heating plate by step 3.It will heating
Plate temperature is controlled at 500 DEG C, aoxidizes 5h in air.After the completion of heating, room temperature is annealed to the rate of 5 DEG C/min, is obtained straight
Connect oxidation group sample and laser treatment oxidation group sample.
The surface topography of two groups of samples is observed.(a) figure and (b) figure are original foam copper sample surface shape in Fig. 2
Looks figure.(a) figure can be seen that the skeleton of foam copper still retains completely in Fig. 2, and " lint shape " occurs after oxidation in surface
Nano wire.Though (b) figure can be more clearly visible that CuO NWs has growth in Fig. 2, nanowire growth direction is unordered staggeredly, is in
The case where weediness, surface is more sparse to lodge and is unevenly distributed, and length is about 0.5~2 μm, and there are partial exfoliations.Fig. 2
In in (c) figure and Fig. 2 (d) figure be the thermal oxide after laser pre-treated CuO NWs surface topography map.(c) figure indicates in Fig. 2
It is 0.1mm in laser scanning pitch, under conditions of scanning times 20 times, foam copper is processed into " groined type " micro array structure.
(d) figure can clearly see in Fig. 2, and CuO NWs is evenly distributed and grows densification, and nano wire is kept upright growth without handing over substantially
Mistake, length are about 4~10 μm, considerably longer compared with (b) figure in Fig. 2.
Using EDS to primary sample group, laser texturing does not aoxidize group and three groups of samples of laser texturing oxidation group carry out
Characterization.Test result shows that sample surfaces have tri- kinds of elements of C, Cu, O, but the relative mass percentage of each group sample exists
Difference.(a) figure is primary sample spectrogram in Fig. 3, wherein the relative mass percentage of C is the relative mass percentage of 3.05%, Cu
Than only having 0.15% for 96.80%, O, illustrate that copper is essential element, surface has extremely slight oxidation.(b) figure is in Fig. 3
The unoxidized sample spectrogram of laser texturing, wherein the relative mass percentage of O is improved to 14.88%, it is seen then that the micro- texture of laser
Process improve the degree of oxidation of sample surfaces.(c) figure is the cupric oxide nano line sample spectra obtained after laser texturing in Fig. 3
Figure, the relative mass percentage of O further increases at this time, reaches 32.68%.
Step 4 prepares the methyl orange solution of 40mg/L, and the hydrogenperoxide steam generator that the concentration of 1mL is 30% is added, will be molten
After liquid pH value is adjusted to 3, solution and sample are placed in photocatalytic reaction device.
Step 5 reaches adsorption equilibrium after the dark treatment of 1h, then under ultraviolet lamp (10W, 254nm) irradiation, often
It samples every 5min, is sampled after 1h every 10min, use ultraviolet-visible spectrophotometer (UV-Vis, Genesys 10S) after centrifugation
It is to measure its absorbance at 465nm in wavelength, records numerical value, calculates the efficiency of degradation methyl orange solution, each Therapy lasted 2h.
Step 6 is arranged under identical experiment condition without catalyst group, direct oxidation group and laser treatment oxidation group
Three groups of control experiments, and carry out parallel laboratory test.
Step 7 follow for five times to the cupric oxide nano line aoxidized after laser treatment under the same conditions
Ring test experiment.
Photo-catalytic degradation of methyl-orange experimental result is as shown in Figure 4.The experiment results show that in no condition that catalyst is added
Under, the degradation rate of methyl orange only reaches 63.1% after 1h.After the sample that directly thermal oxidation group is added, though degradation rate has
It improves but effect is not significant, the degradation rate after 1h is 68.4%.The degradation rate of cupric oxide nano line by the micro- texture of laser
Just reach 87% after 1h, the degradation rate after 2h reaches 97%.
Surface topography after photocatalysis is tested observe as shown in Figure 5.Nano wire warp in (a) figure of Fig. 5
After crossing experiment, though there is part bending surface topography uninfluenced, substantially without dropping situations；And the nano wire in (b) figure of Fig. 5
It then almost falls off, only surplus root.The cupric oxide nano line sample obtained after laser pre-treated is degraded by 5 circulations
After experiment, the degradation rate of methyl orange solution still can reach 96%, as shown in Figure 6 there is no being substantially reduced, it is seen that it is stablized
Good, the high recycling rate of property.
The present invention prepares cupric oxide nano line by substrate of foam copper, has multistage porous structure, can effectively increase and compare table
Area and surface-active；In conjunction with the micro- texture pretreatment of nanosecond laser, cupric oxide nano line length and density are significantly improved, is increased simultaneously
The strong adhesive force of nano wire, can be improved the degradation rate of photocatalytically degradating organic dye.Preparation method of the present invention is easy to operate, at
This is cheap, and the size and pattern of easily controllable nano wire are conducive to large-scale industrial production, and the micro nano structure of self-supporting is not
It only can solve conventional particles shape photochemical catalyst to be difficult to recycle, easy secondary pollution problems, and there is photocatalytic activity height, circulation
The advantages that stability is good is with a wide range of applications in photocatalysis field.
The above is only a specific embodiment of the present invention, but the design concept of the present invention is not limited to this, all to utilize this
Design makes a non-material change to the present invention, and should all belong to behavior that violates the scope of protection of the present invention.
Claims (10)
1. the preparation method of the cupric oxide nano line of the micro- texture foam copper of laser, it is characterised in that the following steps are included:
1) it by foam copper after hydrochloric acid, dehydrated alcohol and deionized water clean up, is dried up using compressed nitrogen, obtains cleaning
Foam copper；
2) nanosecond laser texture technology is utilized, laser related processing parameters are adjusted, on foam copper surface with " matts " scanning
Pattern carries out laser texturing, forms surface periodic micro-structure；
3) foam copper after laser texturing is placed in heating plate, heated at constant temperature for a period of time after, be annealed to room temperature, had
There is the cupric oxide nano line of micron and nanometer composite structure.
2. the preparation method of the cupric oxide nano line of the micro- texture foam copper of laser as described in claim 1, it is characterised in that in step
It is rapid 1) in, the aperture of the foam copper is 110ppi, purity 99%.
3. the preparation method of the cupric oxide nano line of the micro- texture foam copper of laser as described in claim 1, it is characterised in that in step
It is rapid 2) in, the wavelength of the nanosecond laser is 1064nm, pulsewidth 200ns, repetition rate 20KHz.
4. the preparation method of the cupric oxide nano line of the micro- texture foam copper of laser as described in claim 1, it is characterised in that in step
It is rapid 2) in, the laser power of laser is 15~25W, and scanning speed is 800~1500mm/s, sweep span is 0.05~
0.5mm。
5. the preparation method of the cupric oxide nano line of the micro- texture foam copper of laser as described in claim 1, it is characterised in that in step
It is rapid 3) in, the heated at constant temperature, which is placed in heating plate, carries out open heating, and the temperature of heated at constant temperature is 400~600 DEG C, permanent
The time of temperature heating is 3~7h.
6. the preparation method of the cupric oxide nano line of the micro- texture foam copper of laser as described in claim 1, it is characterised in that in step
It is rapid 3) in, the temperature of the heated at constant temperature is 500 DEG C, and the heated at constant temperature time is 5h.
7. the preparation method of the cupric oxide nano line of the micro- texture foam copper of laser as described in claim 1, it is characterised in that in step
It is rapid 3) in, the annealing rate be 5~10 DEG C/min.
8. cupric oxide nano prepared by the preparation method of the cupric oxide nano line of the micro- texture foam copper of laser as described in claim 1
Line, it is characterised in that it has multistage porous structure, is evenly distributed and grows densification, large specific surface area, nano wire is kept substantially
Vertical growth is without staggeredly, nanowire length is about 4~10 μm.
9. cupric oxide nano line as claimed in claim 8 is applied in photocatalytically degradating organic dye.
10. being applied described in claim 9, it is characterised in that the organic dyestuff is in methyl orange, rhodamine B and methylene blue
At least one.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112729625A (en) * | 2020-12-25 | 2021-04-30 | 厦门大学 | Laser texture bionic capacitive flexible pressure sensor and preparation method thereof |
| CN112892535A (en) * | 2021-03-05 | 2021-06-04 | 内蒙古大学 | Cu for VOC purificationxPreparation of O/Cu trans-photocatalytic material |
| US11756435B2 (en) | 2021-10-18 | 2023-09-12 | The 28Th Research Institute Of China Electronics Technology Group Corporation | Airspace network optimization method based on flight normality target |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108504984A (en) * | 2018-04-27 | 2018-09-07 | 厦门大学 | A kind of super-hydrophobic composite construction preparation method of cupric oxide nano line |
-
2019
- 2019-09-06 CN CN201910844231.3A patent/CN110508280A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108504984A (en) * | 2018-04-27 | 2018-09-07 | 厦门大学 | A kind of super-hydrophobic composite construction preparation method of cupric oxide nano line |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112729625A (en) * | 2020-12-25 | 2021-04-30 | 厦门大学 | Laser texture bionic capacitive flexible pressure sensor and preparation method thereof |
| CN112729625B (en) * | 2020-12-25 | 2022-02-08 | 厦门大学 | Laser texture bionic capacitive flexible pressure sensor and preparation method thereof |
| CN112892535A (en) * | 2021-03-05 | 2021-06-04 | 内蒙古大学 | Cu for VOC purificationxPreparation of O/Cu trans-photocatalytic material |
| US11756435B2 (en) | 2021-10-18 | 2023-09-12 | The 28Th Research Institute Of China Electronics Technology Group Corporation | Airspace network optimization method based on flight normality target |
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