CN110714196A - Copper hydroxide nanobelt/nano porous copper composite material and application thereof - Google Patents
Copper hydroxide nanobelt/nano porous copper composite material and application thereof Download PDFInfo
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- CN110714196A CN110714196A CN201810763016.6A CN201810763016A CN110714196A CN 110714196 A CN110714196 A CN 110714196A CN 201810763016 A CN201810763016 A CN 201810763016A CN 110714196 A CN110714196 A CN 110714196A
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- 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
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/63—Treatment of copper or alloys based thereon
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/64—Treatment of refractory metals or alloys based thereon
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- 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
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Abstract
The invention discloses a copper hydroxide nano-belt/nano-porous copper composite material and application thereof, wherein the material is prepared by a method that nano-porous copper belt NP Cu is put into ammonium persulfate (NH) at the temperature of 293K-313K4)2S2O8And sodium hydroxide (soaking in NaOH mixed solution for 3-120 s, repeatedly cleaning with deionized water and absolute ethyl alcohol for multiple times, and air-drying to obtain the copper hydroxide nano-belt/nano-porous copper composite materialThe method controls the appearance of the copper hydroxide nano-belt/nano-porous copper composite material in time, the operation process is simple and controllable, and the prepared copper hydroxide nano-belt/nano-porous copper composite material has the advantages of high specific surface area, high porosity, high activity and the like, is used for degrading azo dyes, and obviously improves the treatment efficiency.
Description
Technical Field
The invention relates to the technical field of environmental protection and catalytic degradation, in particular to a copper hydroxide nanobelt/nano porous copper composite material and application thereof.
Background
The dye waste water discharged from textile, paper-making, leather, printing and other industries causes serious environmental pollution. The proportion of the azo dye in the dye is about 50 percent, so the method has very important theoretical value and engineering practical significance for economically and efficiently treating the wastewater containing the azo dye.
The method of degrading azo dyes in wastewater can be classified into physical, biological and chemical methods according to the composition, properties and treatment indexes of wastewater. The activated carbon adsorption method is a conventional physical process, but the pollutant is not completely degraded; the biological method is a sewage treatment technology for degrading and removing organic pollutants in sewage by utilizing the metabolism of microorganisms, and has the limitations of slow degradation rate and long reaction period; the chemical method only utilizes chemical substances to react with pollutants, but the application cost is higher. With the rapid development of nanotechnology, nanoporous metals show great application prospects in the aspect of azo dye degradation.
Disclosure of Invention
The invention aims to provide a copper hydroxide nanobelt/nano-porous copper composite material and application thereof.
The purpose of the invention is realized by the following steps:
a composite copper hydroxide nano-band/porous copper nanoparticles is prepared through putting the porous copper nanoparticles (NP Cu) in ammonium persulfate ((NH) at 293-313K4)2S2O8) Soaking the mixture in a mixed solution of sodium hydroxide (NaOH) for 3 to 120 seconds, and repeatedly cleaning the mixture for multiple times by using deionized water and absolute ethyl alcoholAnd then drying to obtain the copper hydroxide nano belt/nano porous copper composite material.
The preparation process of the nano-porous copper strip comprises the following steps: the titanium-copper-based amorphous alloy strip is placed into hydrofluoric acid with the temperature of 298K-333K and the concentration of 0.05 mol/L-0.2 mol/L for dealloying treatment for 4 h-12 h, and then is repeatedly cleaned by deionized water and absolute ethyl alcohol for multiple times and dried to obtain the nano porous copper strip.
Further, the titanium-copper based amorphous alloy has copper atom percentage of 20-60%, and the alloy includes but is not limited to the following elements: ti, Zr, Ni, Sn, Al, Zn, Au, Ag, Pd.
The preparation method comprises the following specific steps:
step 1, selecting raw materials according to the proportion of target alloy, placing the raw materials in a crucible, and placing the crucible in high vacuum (5 x 10)-3Pa), and repeatedly smelting for three to four times in order to ensure that the alloy can be uniformly mixed during smelting;
step 2, putting the smelted master alloy into a quartz tube, and obtaining a titanium-copper-based amorphous alloy strip by using a single copper roller melt-spinning quenching method;
step 3, a corrosive solution is selected to carry out dealloying treatment on the titanium-copper-based amorphous alloy to obtain a nano porous copper strip;
and 4, carrying out alkaline oxidation treatment on the nano porous copper strip to obtain the copper hydroxide nano strip/nano porous copper composite material.
Further, step 3 specifically comprises the following steps: and (3) under 313K, the titanium-copper-based amorphous alloy strip is placed into an HF solution for dealloying for 6 hours. After the dealloying is finished, repeatedly cleaning the sample by using deionized water and absolute ethyl alcohol until the HF solution is completely cleaned, and airing at room temperature to obtain a nano porous copper strip;
further, in step 4, the specific process of alkaline oxidation is as follows: treating at the room temperature of 298K by an alkaline oxidation method, and putting the obtained nano-porous copper strip into a container (NH)4)2S2O8The treatment time is 5s in the mixed solution of the deionized water and 10mol/L NaOH; after the alkaline oxidation process, the sample was repeatedly washed with deionized water and absolute ethanol until the sample was washedAnd completely cleaning the solution, airing at room temperature and storing to obtain the copper hydroxide nano-belt/nano-porous copper composite material.
An application of a copper hydroxide nanobelt/nano-porous copper composite material is that the copper hydroxide nanobelt/nano-porous copper composite material is taken, ultrasonically shaken and crushed into powder, the powder is put into a methyl orange solution bottle and is put into a shaking table with the shaking speed of 280rpm, and the powder is reacted for 60min under a 40W fluorescent lamp to complete degradation.
Furthermore, the copper hydroxide nano-belt/nano-porous copper composite material has a shape of a nano-belt.
Compared with the prior art, the invention has the following remarkable advantages: (1) the degradation rate of the copper hydroxide nanobelt/nano porous copper composite material on azo dyes reaches more than 98 percent; (2) in the process of decomposing the azo dye by the copper hydroxide nanobelt/nano porous copper composite material, the azo dye is decomposed into small molecules, no secondary pollutant harmful to the environment is generated, and the material is a green and environment-friendly material.
Drawings
FIG. 1 shows Ti in example40.6Zr9.4Cu40.6Ni6.3Sn3.1XRD pattern of amorphous thin ribbon.
FIG. 2 is an SEM image of an example, (a) is an SEM image of nano-porous copper after dealloying; (b) is SEM image of copper hydroxide nanometer belt/nanometer porous copper composite material treated by alkaline oxidation process.
FIG. 3 is a UV spectrum of the example.
Detailed Description
The following description is made in conjunction with the accompanying drawings and embodiments
Examples
(1) With Ti40.6Zr9.4Cu40.6Ni6.3Sn3.1As the starting alloy components, a mixture of starting alloy components having a raw material purity of 99.99% of Ti, 99.99% of Zr, 99.99% of Cu, 99.99% of Ni, and 99.99% of Sn was placed in a crucible, and the crucible was placed in a melting furnace. Firstly, the furnace chamber is vacuumized to ensure that the vacuum degree in the furnace chamber is 5 x 10-3Pa, then filling with argonGas, thereby ensuring that the alloy smelting can be carried out uniformly in the atmosphere protection of inert gas. In order to ensure that the alloy can be uniformly mixed, each alloy ingot is repeatedly smelted for 3 to 4 times.
(2) Putting the smelted mother alloy into a quartz tube, putting the quartz tube into melt-spinning equipment, melting the alloy by induction heating, and finally spraying the melted alloy onto a copper roller rotating at high speed by using high-pressure argon to form Ti with the thickness of 30 mu m and the width of 1mm40.6Zr9.4Cu40.6Ni6.3Sn3.1Amorphous thin bands and characterization of the amorphous structure by XRD.
(3) Under 313K, the titanium-copper base amorphous alloy strip is put into 60mL of 0.2mol/L HF solution for dealloying for 6 h. And after the dealloying is finished, repeatedly cleaning the sample by using deionized water and absolute ethyl alcohol until the HF solution is completely cleaned, and airing at room temperature to obtain the nano porous copper strip.
(4) The resulting nanoporous copper strips were loaded at room temperature 298K with a solution containing 0.913g (NH)4)2S2O8In a mixed solution of 22mL of deionized water and 8mL of 10mol/L NaOH, the treatment time is 5 s. And after the alkaline oxidation method, repeatedly cleaning the sample by using deionized water and absolute ethyl alcohol until the solution is completely cleaned, airing at room temperature and storing to obtain the copper hydroxide nanobelt/nano porous copper composite material. The sample surface was observed by SEM.
And ultrasonically vibrating the prepared copper hydroxide nano-belt/nano-porous copper composite material into powder, putting the powder into azo dye for fading, selecting 20mg/L Methyl Orange (MO) as the azo dye, and comparing the azo dye with porous copper powder with the same mass, wherein the result shows that the degradation efficiency of the copper hydroxide nano-belt/nano-porous copper composite material is highest under the same condition.
FIG. 1 is Ti40.6Zr9.4Cu40.6Ni6.3Sn3.1The XRD patterns of the amorphous alloy precursor after dealloying and after the alkaline oxidation method show that a wide and dispersive diffuse scattering peak appears in the pattern when the diffraction angle is between 40 and 50 degrees from the XRD of the titanium-copper base amorphous alloy precursor, and the sample is the amorphous alloy. DealloyingThe XRD chart treated by the alkaline oxidation method shows that the amorphous crystallization has obvious crystallization peak, and compared with PDF card, Cu and Cu can be known to be formed2O,Cu(OH)2。
FIG. 2 is SEM images of the dealloyed nanoporous copper (a) and the copper hydroxide nanoribbon/nanoporous copper composite material (b) treated by the alkaline oxidation method, and it can be found that the surface and the inside of the dealloyed nanoporous copper have a three-dimensional through porous structure; after the alkaline oxidation treatment, copper hydroxide grows on the surface of the nano-porous copper.
FIG. 3 shows that 10mg of copper hydroxide nanobelt/nanoporous copper composite material and nanoporous copper are respectively ultrasonically shaken and crushed into powder, the powder is put into a bottle filled with 5mL of 20mg/L methyl orange solution (MO), the bottle is put into a shaking table with the shaking speed of 280rpm, and the bottle reacts for 60min under a 40W fluorescent lamp to complete degradation. FIG. 3 shows the degradation effect of the two solutions in a pair, according to the formula eta ═ A0-A)/A0X 100% (wherein A)0The original absorbance of methyl orange at the maximum absorption wavelength, and A the absorbance of the degraded solution at the maximum absorption wavelength) to obtain that the degradation efficiency of the two materials to the methyl orange solution (MO) is 98.5% (5s) and 72.26% (NP Cu), so that the copper hydroxide nano-belt/nano-porous copper composite material can improve the efficiency of degrading azo dyes.
Claims (9)
1. The copper hydroxide nano-belt/nano-porous copper composite material is characterized by being prepared by the following method, placing a nano-porous copper belt into a mixed solution of ammonium persulfate and sodium hydroxide for soaking for 3-120 s at the temperature of 293K-313K, repeatedly washing with deionized water and absolute ethyl alcohol for multiple times, and then drying to obtain the copper hydroxide nano-belt/nano-porous copper composite material.
2. The copper hydroxide nanoribbon/nanoporous copper composite material according to claim 1, wherein the nanoporous copper strip is prepared by the following process: the titanium-copper-based amorphous alloy strip is placed into hydrofluoric acid with the temperature of 298K-333K and the concentration of 0.05 mol/L-0.2 mol/L for dealloying treatment for 4 h-12 h, and then is repeatedly cleaned by deionized water and absolute ethyl alcohol for multiple times and dried to obtain the nano porous copper strip.
3. The copper hydroxide nanoribbon/nanoporous copper composite material according to claim 1, wherein the titanium-copper based amorphous alloy comprises copper in an atomic percentage of 20 to 60%, and the alloy comprises but is not limited to the following elements: ti, Zr, Ni, Sn, Al, Zn, Au, Ag, Pd.
4. The copper hydroxide nanoribbon/nanoporous copper composite material according to claim 1, wherein the titanium-copper based amorphous alloy is Ti40.6Zr9.4Cu40.6Ni6.3Sn3.1。
5. The copper hydroxide nanoribbon/nanoporous copper composite material according to claim 1, wherein the preparation method comprises the following specific steps:
step 1, selecting raw materials according to the proportion of target alloy, placing the raw materials in a crucible, and placing the crucible in high vacuum (5 x 10)-3Pa), and repeatedly smelting for three to four times in order to ensure that the alloy can be uniformly mixed during smelting;
step 2, putting the smelted master alloy into a quartz tube, and obtaining a titanium-copper-based amorphous alloy strip by using a single copper roller melt-spinning quenching method;
step 3, a corrosive solution is selected to carry out dealloying treatment on the titanium-copper-based amorphous alloy to obtain a nano porous copper strip;
and 4, carrying out alkaline oxidation treatment on the nano porous copper strip to obtain the copper hydroxide nano strip/nano porous copper composite material.
6. The copper hydroxide nanoribbon/nanoporous copper composite material according to claim 5, wherein the specific process of step 3 is as follows: and (3) under 313K, the titanium-copper-based amorphous alloy strip is placed into an HF solution for dealloying for 6 hours. And after the dealloying is finished, repeatedly cleaning the sample by using deionized water and absolute ethyl alcohol until the HF solution is completely cleaned, and airing at room temperature to obtain the nano porous copper strip.
7. The copper hydroxide nanoribbon/nanoporous copper composite material according to claim 5, wherein in the step 4, the alkaline oxidation is performed as follows: treating at the room temperature of 298K by an alkaline oxidation method, and putting the obtained nano-porous copper strip into a container (NH)4)2S2O8The treatment time is 5s in the mixed solution of the deionized water and 10mol/L NaOH; and after the alkaline oxidation method, repeatedly cleaning the sample by using deionized water and absolute ethyl alcohol until the solution is completely cleaned, airing at room temperature and storing to obtain the copper hydroxide nanobelt/nano porous copper composite material.
8. The application of the copper hydroxide nanobelt/nano-porous copper composite material is characterized in that the copper hydroxide nanobelt/nano-porous copper composite material is ultrasonically shaken and crushed into powder, the powder is placed into a methyl orange solution bottle, the bottle is placed into a shaking table with the shaking speed of 280rpm, and the bottle is reacted for 60min under a 40W fluorescent lamp to complete degradation.
9. The use of the copper hydroxide nanoribbon/nanoporous copper composite according to claim 8, wherein the copper hydroxide nanoribbon/nanoporous copper composite is in the shape of a nanoribbon.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102943187A (en) * | 2012-11-19 | 2013-02-27 | 河北工业大学 | Preparation method of nano porous copper |
| CN106226382A (en) * | 2016-08-08 | 2016-12-14 | 北京科技大学 | Nano porous copper/Cu (OH)2nano-wire array sensor electrode material and preparation method thereof |
| CN107366011A (en) * | 2017-07-18 | 2017-11-21 | 河北工业大学 | A kind of nano porous copper load ultrafine copper oxide nanowire composite and its preparation method and application |
| CN108046402A (en) * | 2017-12-04 | 2018-05-18 | 沈阳大学 | A kind of method using cu-based amorphous alloys degradation pigment wastewater |
| CN108193255A (en) * | 2018-01-30 | 2018-06-22 | 河北工业大学 | A kind of supported porous cuprous nano piece composite material of nano porous copper and preparation method thereof |
| CN108265192A (en) * | 2018-01-30 | 2018-07-10 | 河北工业大学 | A kind of respirable laminar nano Porous Cu silver composite material and preparation method thereof |
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- 2018-07-12 CN CN201810763016.6A patent/CN110714196A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102943187A (en) * | 2012-11-19 | 2013-02-27 | 河北工业大学 | Preparation method of nano porous copper |
| CN106226382A (en) * | 2016-08-08 | 2016-12-14 | 北京科技大学 | Nano porous copper/Cu (OH)2nano-wire array sensor electrode material and preparation method thereof |
| CN107366011A (en) * | 2017-07-18 | 2017-11-21 | 河北工业大学 | A kind of nano porous copper load ultrafine copper oxide nanowire composite and its preparation method and application |
| CN108046402A (en) * | 2017-12-04 | 2018-05-18 | 沈阳大学 | A kind of method using cu-based amorphous alloys degradation pigment wastewater |
| CN108193255A (en) * | 2018-01-30 | 2018-06-22 | 河北工业大学 | A kind of supported porous cuprous nano piece composite material of nano porous copper and preparation method thereof |
| CN108265192A (en) * | 2018-01-30 | 2018-07-10 | 河北工业大学 | A kind of respirable laminar nano Porous Cu silver composite material and preparation method thereof |
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Application publication date: 20200121 |