CN115212897A - Self-standing nano porous copper-loaded nonacopper pentasulfide nanosheet composite material and preparation method and application thereof - Google Patents
Self-standing nano porous copper-loaded nonacopper pentasulfide nanosheet composite material and preparation method and application thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 131
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 118
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000002135 nanosheet Substances 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 239000003344 environmental pollutant Substances 0.000 claims description 15
- 231100000719 pollutant Toxicity 0.000 claims description 15
- 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 13
- 229940043267 rhodamine b Drugs 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 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 10
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 9
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 claims description 9
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 8
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 238000002074 melt spinning Methods 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000012792 core layer Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- -1 zirconium metals Chemical class 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 18
- 229910045601 alloy Inorganic materials 0.000 abstract description 14
- 239000000956 alloy Substances 0.000 abstract description 14
- 239000000843 powder Substances 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 25
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 238000002835 absorbance Methods 0.000 description 9
- 239000000975 dye Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 210000003041 ligament Anatomy 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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Abstract
The invention relates to a self-supporting nano porous copper loaded nona-copper pentasulfide nanosheet composite material and a preparation method and application thereof. The composite material is a thin strip sample with the width of 1-2 mm and the thickness of 20-40 mu m, and comprises an amorphous matrix, nano porous copper covered on the surface of the matrix, and a nonalcoholic pentasulfide nanosheet loaded on the surface of the nano porous copper; the preparation method adopts an in-situ growth process, adopts a mixed solution of sodium hydroxide and sodium sulfide as an anodic oxidation electrolyte, and carries out anodic oxidation on the nano-porous copper after the alloy of the amorphous precursor is removed, so as to obtain the self-standing nano-porous copper loaded nonacopper pentasulfide nanosheet composite material. The self-supporting nano porous copper-loaded nonacopper pentasulfide nanosheet composite material prepared by the invention is easy to recover after photocatalytic application, and overcomes the defects that the traditional powder is not easy to collect and is easy to cause secondary pollution.
Description
The technical field is as follows:
the invention relates to the technical field of preparation of a nine-copper pentasulfide material, and mainly relates to application of a self-supporting nano porous copper-loaded nine-copper pentasulfide nanosheet composite material in the field of photocatalysis.
The background art comprises the following steps:
the nonacopper pentasulfide is a p-type narrow band gap (1.2-2.1 eV) semiconductor material and has excellent visible light response. Due to the good photocatalytic activity, the photocatalyst shows good application prospect in the aspects of photocatalytic degradation of organic pollutants and the like. It is well known that the degradation performance of a catalyst depends mainly on the size and specific surface area of the material. Therefore, the nanometer grade nonacopper pentasulfide catalyst with a porous structure is prepared, so that a large number of reaction active sites can be provided, the permeability of the material can be improved, the transmission of light is facilitated, and the aim of improving the photocatalytic degradation performance of the material is fulfilled.
In the prior art, publication No. CN 111589457B 'A photocatalytic material for in-situ growth of three-dimensional copper sulfide by a copper mesh, a preparation method and an application thereof', a copper mesh is taken as a working electrode and is soaked in Na 2 And applying voltage to the S solution to perform anodic oxidation reaction. The sample prepared by the technology needs to be added with a strong oxidant H 2 O 2 As a cocatalystThe degradation can be carried out, the degradation rate is slow, and 50mL of 10mg/L Methylene Blue (MB) can be degraded in 240 min;
prior art, publication No. CN 107399717B' Cu for battery negative electrode 9 S 5 The preparation method of the @ C nano composite material' needs to use a mixed solution of sulfur powder, ammonia water, absolute ethyl alcohol and monohydrate copper acetate, react for 8 hours at 150 ℃ by using a hydrothermal reaction kettle, obtain a precipitate after cooling, and perform annealing treatment at 400 ℃ to obtain Cu 9 S 5 A material. The experiment process is complex and time-consuming, powder is easy to shield each other, agglomeration is easy to cause, the powder is not easy to recover after application, and the possibility of secondary pollution is increased.
The invention content is as follows:
the invention aims to provide an effective, rapid, safe and environment-friendly preparation method of a self-supporting nano porous copper-loaded nonacopper pentasulfide nanosheet composite material, aiming at the defects that a powder catalyst in the prior art is unrecoverable and easily causes secondary pollution. The material comprises an amorphous matrix, nano porous copper covered on the surface of the matrix, and a nonacopper pentasulfide nanosheet growing on the surface of the nano porous copper in situ. The preparation method adopts an in-situ growth process, adopts a mixed solution of sodium hydroxide and sodium sulfide as an anodic oxidation electrolyte, and carries out anodic oxidation on the nano-porous copper after the alloy of the amorphous precursor is removed, so as to obtain the self-standing nano-porous copper loaded nonacopper pentasulfide nanosheet composite material. The self-standing nano porous copper-loaded nonacopper pentasulfide nanosheet composite material prepared by the invention is easy to recover after photocatalytic application, and overcomes the defects that the traditional powder is not easy to collect and is easy to cause secondary pollution.
The technical scheme of the invention is as follows:
a self-supporting nano porous copper loaded nonacopper pentasulfide nanosheet composite material is a thin strip sample with the width of 1-2 mm and the thickness of 20-40 mu m, and comprises an amorphous matrix, nano porous copper covered on the surface of the matrix, and a nonacopper pentasulfide nanosheet loaded on the surface of the nano porous copper;
the amorphous matrix component is Cu x Zr y Wherein x and y are atomic percent, x is more than or equal to 35 and less than or equal to 65, y is more than or equal to 35 and less than or equal to 65, and x + y =100; the thickness of the amorphous substrate core layer is 20-40 mu m, the thickness of the single-side nano-porous copper is 4-8 mu m, the thickness of the single-side loaded nine-copper pentasulfide layer is 2-5 mu m, the thickness of the first-stage nine-copper pentasulfide nanosheet is 15-25 nm, the thickness of the second-stage nine-copper pentasulfide layer is 3-10 nm, and nanopores with the pore size and the width of 2-3 nm are distributed on the nine-copper pentasulfide nanosheet.
The preparation method of the self-supporting nano porous copper-loaded nona-copper pentasulfide nanosheet composite material comprises the following steps:
firstly, preparing an amorphous alloy thin strip sample
Weighing pure copper and pure zirconium metal according to the proportion of the target components. And cleaning with deionized water to obtain pure metal components. Cleaning, putting the cleaned copper-zirconium alloy ingot into a vacuum arc melting furnace to prepare a copper-zirconium alloy ingot, polishing, cleaning, putting the polished copper-zirconium alloy ingot into a quartz tube of a vacuum strip throwing machine, and blowing and casting the polished copper-zirconium alloy ingot in a high-purity argon environment to obtain an amorphous precursor with the width of about 1-2 mm and the thickness of about 20-40 mu m; wherein the vacuum degree of the smelting furnace and the melt-spinning machine is 3 multiplied by 10 -4 ～3×10 -3 Pa, the blowing and casting pressure is 0.5-2.0 MPa;
secondly, preparing the nano porous copper matrix by dealloying
A natural dealloying process is adopted, the sample obtained in the first step is taken as a precursor, the precursor is soaked in 0.01-0.2M HF acid for 0.5-6.5 h, the sample is washed by deionized water after being taken out, a nano porous copper sample is obtained, and the corrosion temperature is 25-35 ℃;
step three, preparing the self-supporting nano porous copper loaded nona-copper pentasulfide nanosheet composite material through anodic oxidation
And (3) adopting a three-electrode system, taking a platinum net as a counter electrode, taking Ag/AgCl as a reference electrode, taking the porous copper prepared in the third step as a working electrode for anodic oxidation, and cleaning the prepared composite material by using deionized water to obtain the self-supporting nano porous copper loaded nonalcoholic pentasulfide nanosheet composite material.
Wherein in the anodic oxidation reaction, the electrolyte is Na 2 Mixed solution of S and NaOH, na 2 The concentration of S is 0.25-1M, the molar ratio isNa 2 S is NaOH (1-4) and (1-4); the current density is 5-30 mA/cm 2 The reaction time is 30-600 s, and the reaction temperature is 25-35 ℃.
The purities of the copper and the zirconium are both 99.99%.
According to the preparation method of the self-standing nano porous copper-loaded nonacopper pentasulfide nanosheet composite material, the size of the prepared amorphous thin strip is 1cm multiplied by 1mm multiplied by 20 micrometers to 10cm multiplied by 2mm multiplied by 40 micrometers.
The self-standing nano porous copper-loaded nona-copper pentasulfide nanosheet composite material is applied to photocatalytic degradation of pollutants.
The pollutant is preferably one or two of rhodamine B and methylene blue.
The method specifically comprises the following steps: 4-5 mg of the prepared self-supporting nano-porous copper-loaded nonacopper pentasulfide nanosheet composite material is soaked in 5-20 mL of pollutant solution with the concentration of 5-15 mg/L. Using a 300W xenon lamp as a light source, wherein the illumination intensity is 30-50 mW/cm 2 After being irradiated by a light source for 10-100 min, pollutants are degraded.
The self-standing nano porous copper-loaded nonacopper pentasulfide nanosheet composite material and the equipment and raw materials used in the preparation method thereof are all obtained through known approaches, and related technologies can be mastered by those skilled in the art.
The invention has the substantive characteristics that:
in the prior art of the subject group (publication number "CN 108295854B"), the adopted anodic oxidation electrolyte is a mixed solution of sodium hydroxide and sodium sulfate, and because no sulfur source is added, cuprous oxide is obtained, and a cluster-shaped nanowire structure is microscopically shown; in the invention, the component of the anodic oxidation electrolyte adopts a mixed solution of sodium hydroxide and sodium sulfide, and a new component with a load of nonacuprum pentasulfide is obtained by utilizing the principle of anodic oxidation. The material microscopically shows a structure of the intricate interweaving of the nano sheets. The catalyst does not need to use H 2 O 2 The cocatalyst can degrade organic pollutant by visible light, and the invention prepares a new material based on the prior art, and widens the range of materialsThe light response range improves the photocatalytic performance.
(1) The invention develops a novel method for preparing nona-copper pentasulfide, in the prior art, copper sulfide is always used as an active substance in the field of photocatalytic degradation, and a mixed solution of sodium sulfide and sodium hydroxide is used as an anodic oxidation electrolyte to obtain a nona-copper pentasulfide nanosheet with a higher crystal face index, and the nona-copper pentasulfide nanosheet is applied to the field of photocatalysis, so that the nona-copper pentasulfide nanosheet has a higher photocatalytic performance.
(2) In terms of the preparation method, the invention has the essential characteristic that the flexible thin strip with excellent mechanical property and mechanical property is selected as a precursor, thereby overcoming the defect that the traditional thin strip material is fragile. And a series of electrochemical parameters suitable for the anodic oxidation of the thin strip and the component proportion of the electrolyte are explored.
(3) The invention uses the flexible amorphous thin strip as a precursor, prepares the self-supporting nano porous copper load base material by the dealloying technology, the inner core of the material is an amorphous matrix, and the amorphous matrix has excellent mechanical property and mechanical property, so the matrix has certain flexibility and support property. Then, an anodic oxidation process is used, a layer of nona-copper pentasulfide nanosheet is loaded on the nano-porous copper substrate, the self-supporting nona-copper pentasulfide photocatalytic material is prepared for the first time, and the material is applied to the field of photocatalysis.
Compared with the prior art, the invention has the following beneficial effects
(1) The invention takes a copper-zirconium alloy amorphous ribbon as a precursor, and prepares a self-supporting nano porous copper loaded nonacopper pentasulfide nanosheet composite material with multi-level holes for the first time, wherein the self-supporting nano porous copper loaded nonacopper pentasulfide nanosheet composite material comprises a copper-zirconium amorphous matrix used as an inner core, a nano porous copper layer and a nonacopper pentasulfide nanosheet loaded on the nano porous copper layer. The amorphous precursor can be used for preparing nano porous copper metal with ligament width of 20-40 nm and pore size of 50-70 nm through dealloying. Then, carrying out anodic oxidation to grow the quintrosulfide nonacopper nanosheet with the thickness of 3-25 nm and the pore size of 2-3 nm in situ.
(2) According to the invention, a blow-casting process, a dealloying process and an anodic oxidation process are combined together to prepare the self-standing nano porous copper-loaded nonacopper pentasulfide nanosheet composite material, in the anodic oxidation process, the nonacopper pentasulfide first grows a first-stage nanosheet with a larger sheet-shaped structure on the nano porous copper, then a second-stage nanosheet with a smaller sheet-shaped structure continues to grow on the first-stage nanosheet, and the nonacopper pentasulfide nanosheets are interlaced, so that porous structures with different sizes are formed, the specific surface area of the material is improved, more reactive sites are provided, and the self-standing nano porous copper-loaded nonacopper pentasulfide nanosheet composite material has unique nanosheet structure and performance advantages in the field of photocatalysis.
(3) The self-supporting nano porous copper-loaded nonacopper pentasulfide nanosheet composite material prepared by the invention has higher photocatalytic performance, and can be prepared without using H 2 O 2 Under the condition of the cocatalyst, the organic pollutants are degraded by visible light irradiation, the illumination response range is widened, and the photocatalytic activity is improved.
(4) Compared with the traditional powder material, the self-supporting nano porous copper loaded nonacopper pentasulfide nanosheet composite material prepared by the invention has the advantages that secondary pollution caused by difficult collection can be avoided, the agglomeration phenomenon of powder is avoided, and the ion transmission efficiency is increased.
Drawings
FIG. 1: SEM image of nona-copper pentasulfide nanosheets prepared in example 1
FIG. 2: high power SEM images of nona-copper pentasulfide nanosheets prepared in example 1
FIG. 3: TEM image of nonalcoholic pentasulfide nanosheets prepared in example 1
FIG. 4: XRD pattern of nona-copper pentasulfide nanosheets prepared in example 1
Detailed Description
Example 1
Selection of alloy composition Cu 40 Zr 60 According to the components of the target alloy, pure metals with the mass fraction of 99.99 percent are selected and divided intoThe total amount of the metal raw materials was 10g, each of 3.171g (40 at.%) copper and 6.829g (60 at.%) zirconium. The alloy raw materials are put into a vacuum melting furnace and repeatedly melted for four times under the environment of high-purity argon to ensure the uniformity of the alloy components, and each time lasts for one minute. Cooling to room temperature along with the furnace, taking out Cu 40 Zr 60 A metal ingot.
For Cu 40 Zr 60 The ingot was polished using 120 mesh sandpaper to remove surface oxides. Then using hydraulic pliers to cut the ingot into small ingots of 2-3 g for standby.
2-3 g of cast ingot is placed in a quartz test tube, and a vacuum strip throwing machine is used for blowing and casting metal in a molten state under the environment of high-purity argon under a certain pressure difference to obtain an amorphous alloy thin strip precursor. Wherein the pressure difference of blowing and casting is 1.0MPa, and the vacuum degree is 9 multiplied by 10 -4 Pa, the width of the amorphous alloy thin strip precursor is 2mm, and the thickness is 25 mu m.
And (3) immersing the amorphous precursor obtained in the last step into 0.05M HF solution for dealloying for 3h, taking out the amorphous precursor, and cleaning the sample by using deionized water to obtain a uniform nanoporous copper sample with a ligament hole bicontinuous structure. The thickness of the unilateral nano-porous copper is about 4 μm, the ligament width is about 40nm, and the pore size is about 60nm.
A three-electrode system is adopted, a platinum net is taken as a counter electrode, ag/AgCl is taken as a reference electrode, porous copper prepared by dealloying is taken as a working electrode for anodic oxidation, and the constant current density is 10mA/cm 2 The reaction time is 300s, and the reaction temperature is 25 ℃. The electrolyte is Na 2 Mixed solution of S and NaOH, wherein Na 2 The S concentration was 0.5M and the NaOH concentration was 0.5M.
And cleaning the prepared composite material with deionized water to obtain the self-supporting nano porous copper-loaded nonacopper pentasulfide nanosheet composite material.
The test scheme for photocatalytic degradation of pollutants by the self-supporting nano porous copper-loaded nonacopper pentasulfide nanosheet composite material prepared through the steps is as follows:
selecting rhodamine B as a simulated pollutant to carry out a photocatalysis experiment, selecting 10mL of rhodamine B solution with the concentration of 10mg/L as the simulated pollutant, using a 300W xenon lamp as a light source,the illumination intensity is 50mW/cm 2 . In the experiment, 5mg of the prepared self-supporting nano-porous copper-loaded nonacopper pentasulfide nanosheet composite material is soaked in a rhodamine B solution, and the absorbance change of the solution after degradation for different time is researched. The change in absorbance can be measured by an ultraviolet-visible spectrophotometer (UV 1920). The self-supporting nano porous copper-loaded nona-copper pentasulfide nanosheet composite material prepared by the method is degraded for 10min, 30min and 50min, and the absorbance obtained by testing through an ultraviolet-visible spectrophotometer is known, and after the dye is degraded for 50min, the dye is successfully degraded and decomposed into CO 2 And H 2 And O. And then, a cycle stability test is carried out, and the degradation efficiency is still more than 95% after five cycles of degradation of the same type of dye, which indicates that the material has good cycle stability.
Fig. 1 is an SEM image of the nonacopper pentasulfide nanosheet prepared in this example, demonstrating that the nonacopper pentasulfide nanosheet having a multilevel pore structure was successfully prepared in this example.
Fig. 2 is a high power SEM image of the nonacopper pentasulfide nanosheets prepared in this example, demonstrating that a uniform nanosheet structure is generated on the surface of the material.
Fig. 3 is a TEM image of the nona-copper pentasulfide nanosheets prepared in this example, demonstrating that the material is nanoporous.
Fig. 4 is an XRD spectrum of the nonacopper pentasulfide nanosheet prepared in this example, and the diffraction peaks in the XRD spectrum correspond to XRD card JCPDS #47-1748, which proves that the nonacopper pentasulfide is successfully prepared in this example.
Example 2
Selection of alloy composition Cu 40 Zr 60 According to the target alloy components, pure metals with the mass fraction of 99.99 percent are selected, and the metal raw materials are respectively copper 3.171g (40 at.%), zirconium 6.829g (60 at.%), and the total amount is 10 g. The alloy raw materials are put into a vacuum melting furnace and repeatedly melted for four times under the environment of high-purity argon to ensure the uniformity of the alloy components, and each time lasts for one minute. Cooling to room temperature along with the furnace, taking out Cu 40 Zr 60 A metal ingot.
For Cu 40 Zr 60 The metal ingot is 120 meshesAnd (5) polishing by using sand paper to remove oxides on the surface. Then using hydraulic pliers to cut the ingot into small ingots of 2-3 g for standby.
2-3 g of cast ingot is placed in a quartz test tube, and a vacuum strip throwing machine is used for blowing and casting metal in a molten state under the environment of high-purity argon under a certain pressure difference to obtain an amorphous alloy thin strip precursor. Wherein the pressure difference of blowing and casting is 1.0MPa, and the vacuum degree is 9 multiplied by 10 -4 Pa, the width of the amorphous alloy thin strip precursor is 2mm, and the thickness is 25 μm.
And (3) immersing the amorphous precursor obtained in the last step into 0.01M HF solution for dealloying for 6.5h, taking out the amorphous precursor, and cleaning the sample by using deionized water to obtain a uniform nano porous copper sample with a ligament hole bicontinuous structure. The thickness of the unilateral nanoporous copper is about 5 μm, the ligament width is about 60nm, and the pore size is about 75nm.
A three-electrode system is adopted, a platinum net is taken as a counter electrode, ag/AgCl is taken as a reference electrode, porous copper prepared by dealloying is taken as a working electrode for anodic oxidation, and the constant current density is 5mA/cm 2 The reaction time is 600s, and the reaction temperature is 25 ℃. The electrolyte is Na 2 Mixed solution of S and NaOH, wherein Na 2 The S concentration was 0.8M, and the NaOH concentration was 0.35M.
And cleaning the prepared composite material with deionized water to obtain the self-supporting nano porous copper-loaded nonacopper pentasulfide nanosheet composite material.
The test scheme for photocatalytic degradation of pollutants by the self-supporting nano porous copper-loaded nonacopper pentasulfide nanosheet composite material prepared through the steps is as follows:
selecting rhodamine B and methylene blue as simulated pollutants to respectively carry out a photocatalytic experiment, wherein the simulated pollutants are 10mL of rhodamine B solution with the concentration of 10mg/L and 10mL of methylene blue solution with the concentration of 10mg/L, a 300W xenon lamp is used as a light source, and the illumination intensity is 50mW/cm 2 . In the experiment, 5mg of the prepared self-standing nano-porous copper-loaded nonacopper pentasulfide nanosheet composite is soaked in a mixed solution, and the absorbance change of the solution after degradation for different time is researched. The change in absorbance can be measured by a uv-vis spectrophotometer. The self-supporting nano-poly prepared by the inventionThe porous copper-loaded nona-copper pentasulfide nanosheet composite material is degraded for 20min, 40min and 60min, the absorbance obtained by testing with an ultraviolet-visible spectrophotometer is known, and after the porous copper-loaded nona-copper pentasulfide nanosheet composite material is degraded for 40min, the methylene blue dye is successfully degraded and decomposed into CO 2 And H 2 O, rhodamine B dye also remains. After 60min, the rhodamine B dye is successfully degraded and decomposed into CO 2 And H 2 And (O). And then, carrying out a cycling stability test, and finding that the degradation efficiency is still more than 97% after five cycles of degradation of the same type of dye, which indicates that the material has good cycling stability.
Example 3
Selection of alloy composition Cu 40 Zr 60 According to the target alloy components, pure metals with the mass fraction of 99.99% are selected, and the pure metals are respectively copper 3.171g (40 at.%), zirconium 6.829g (60 at.%), and 10g in total. The alloy raw materials are put into a vacuum melting furnace and repeatedly melted for four times under the environment of high-purity argon to ensure the uniformity of the alloy components, and each time lasts for one minute. Cooling to room temperature along with the furnace, taking out Cu 40 Zr 60 A metal ingot.
For Cu 40 Zr 60 The ingot was polished using 120 mesh sandpaper to remove surface oxides. Then using hydraulic pliers to cut the ingot into small ingots of 2-3 g for standby.
Placing 2-3 g of cast ingot into a quartz test tube, and carrying out blow casting on the metal in a molten state under a certain pressure difference by using a vacuum melt-spinning machine under the environment of high-purity argon to obtain an amorphous alloy thin strip precursor. Wherein the pressure difference of blowing and casting is 1.0MPa, and the vacuum degree is 9 multiplied by 10 -4 Pa, the width of the amorphous alloy thin strip precursor is 2mm, and the thickness is 25 μm.
And (3) immersing the amorphous precursor obtained in the last step into 0.2M HF solution for dealloying for 0.5h, taking out the amorphous precursor, and cleaning the sample by using deionized water to obtain a uniform nano porous copper sample with a ligament hole bicontinuous structure. The thickness of the unilateral nano-porous copper is about 4 μm, the ligament width is about 80nm, and the pore size is about 60nm.
Adopts a three-electrode system, takes a platinum net as a counter electrode, ag/AgCl as a reference electrode and porous copper prepared by dealloying as a working electrode to carry out anodic oxidationConstant current density of 30mA/cm 2 The reaction time is 30s, and the reaction temperature is 25 ℃. The electrolyte is Na 2 Mixed solution of S and NaOH, wherein Na 2 The S concentration was 0.3M and the NaOH concentration was 0.6M.
And cleaning the prepared composite material with deionized water to obtain the self-supporting nano porous copper-loaded nonacopper pentasulfide nanosheet composite material.
The test scheme for photocatalytic degradation of pollutants by the self-supporting nano porous copper-loaded nonacopper pentasulfide nanosheet composite material prepared through the steps is as follows:
selecting rhodamine B and methylene blue as simulated pollutants to respectively perform a photocatalytic experiment, wherein the simulated pollutants are 5mL of rhodamine B solution with the concentration of 5mg/L and 5mL of methylene blue solution with the concentration of 5mg/L, a 300W xenon lamp is used as a light source, and the illumination intensity is 30mW/cm 2 . In the experiment, 4mg of the prepared self-standing nano-porous copper-loaded nonacopper pentasulfide nanosheet composite is soaked in a mixed solution, and the absorbance change of the solution after degradation for different time is researched. The change in absorbance can be measured by an ultraviolet-visible spectrophotometer. The self-supporting nano porous copper-loaded nonacopper pentasulfide nanosheet composite material prepared by the method is degraded for 20min, 40min and 60min, and the absorbance obtained by testing through an ultraviolet-visible spectrophotometer is known, and after the self-supporting nano porous copper-loaded nonacopper pentasulfide nanosheet composite material is degraded for 20min, methylene blue dye is successfully degraded and decomposed into CO 2 And H 2 O, rhodamine B dye also remains. After 60min, rhodamine B dye is successfully degraded and decomposed into CO 2 And H 2 And O. And then, carrying out a cycling stability test, and finding that the degradation efficiency is still more than 94% after five cycles of degradation of the same type of dye, which indicates that the material has good cycling stability.
Comparative example 1:
during anodic oxidation treatment, the selected current density is 50mA/cm 2 The reaction time is 20min. Other conditions are as in example 1, and the nanoporous copper-supported nonacopper pentasulfide nanosheet composite material obtained after anodic oxidation is fragile, poor in mechanical properties and loses flexibility.
Comparative example 2:
anodeDuring the oxidation treatment, the selected electrolyte is 1M Na with single component 2 And (5) preparing an S solution. Under other conditions as in example 1, the supported nona-copper pentasulfide nanosheet on the surface of the nanoporous copper is enlarged after anodic oxidation, so that the specific surface area of the material is reduced, and the photocatalytic performance of the material is inhibited.
The above comparisons are failed cases, and the qualified self-supporting nano-porous copper loaded nona-copper pentasulfide nanosheet composite material cannot be obtained due to the fact that parameters prepared by the method are changed randomly.
The invention determines relevant process parameters after adjusting experiment parameters for many times, strictly controlling process links and implementing the process without limitation. The amorphous precursor needs to be smelted in a high-purity argon environment, parameters are not changed randomly, and otherwise, metal impurities are generated. In the anodic oxidation treatment process, electrolyte and electricity utilization parameters are not required to be regulated and controlled at will, otherwise, the self-standing nano porous copper loaded nonacopper pentasulfide nanosheet composite material cannot be prepared, and the photocatalytic performance is seriously affected.
The invention includes not only the steps listed in the examples, but also any equivalent changes of the technical solution of the invention by those skilled in the art through reading the description of the invention, which are covered by the claims of the invention.
The invention is not the best known technology.
Claims (7)
1. A self-supporting nano porous copper loaded nonacopper pentasulfide nanosheet composite material is characterized in that the composite material is a thin strip sample with the width of 1-2 mm and the thickness of 20-40 mu m, and comprises an amorphous matrix, nano porous copper covered on the surface of the matrix, and a nonacopper pentasulfide nanosheet loaded on the surface of the nano porous copper;
the amorphous matrix component is Cu x Zr y Wherein x and y are atomic percent, x is more than or equal to 35 and less than or equal to 65, y is more than or equal to 35 and less than or equal to 65, and x + y =100; wherein the thickness of the amorphous matrix core layer is 20-40 μm, the thickness of the unilateral nano-porous copper is 4-8 μm, the thickness of the unilateral loaded nonacopper pentasulfide layer is 2-5 μm, the thickness of the first-level nonacopper pentasulfide nanosheet is 15-25 nm, the thickness of the second-level nonacopper pentasulfide layer is 3-10 nm,nanopores with the pore size of 2-3 nm are distributed on the nonalcoholic pentasulfide nanosheet.
2. The method of preparing a free-standing nanoporous copper supported nonalcoholic pentasulfide nanosheet composite as recited in claim 1, wherein the method comprises the steps of:
firstly, preparing an amorphous alloy thin strip sample
Weighing pure copper and pure zirconium metal according to the proportion of target components, putting the pure copper and the pure zirconium metal into a vacuum arc melting furnace to be melted to prepare a copper-zirconium alloy ingot, then polishing and cleaning the copper-zirconium alloy ingot, putting the cleaned copper-zirconium alloy ingot into a quartz tube of a vacuum strip throwing machine, and obtaining an amorphous precursor with the width of about 1-2 mm and the thickness of about 20-40 mu m in a blowing casting process in the environment of high-purity argon; wherein the vacuum degree of the smelting furnace and the melt-spinning machine is 3 multiplied by 10 -4 ～3×10 -3 Pa, the blowing and casting pressure is 0.5-2.0 MPa;
second, the nano-porous copper matrix is prepared by dealloying
A natural dealloying process is adopted, the sample obtained in the first step is taken as a precursor, the precursor is soaked in 0.01-0.2M HF acid for 0.5-6.5 h at the temperature of 25-35 ℃, and the sample is washed by deionized water after being taken out, so that the nano-porous copper is obtained;
step three, preparing the self-supporting nano porous copper loaded nona-copper pentasulfide nanosheet composite material through anodic oxidation
Adopting a three-electrode system, taking a platinum mesh as a counter electrode, taking Ag/AgCl as a reference electrode, taking the porous copper prepared in the third step as a working electrode for anodic oxidation, and cleaning the prepared composite material by using deionized water to obtain the self-supporting nano porous copper loaded nona-copper pentasulfide nanosheet composite material;
wherein in the anodic oxidation reaction, the electrolyte is Na 2 Mixed solution of S and NaOH, na 2 The concentration of S is 0.25-1M, the mol ratio is Na 2 S is NaOH (1-4) and (1-4); the current density is 5-30 mA/cm 2 The reaction time is 30-600 s, and the reaction temperature is 25-35 ℃.
3. The method of preparing a free-standing nanoporous copper-supported nonalcoholic pentasulfide nanosheet composite as recited in claim 2, wherein the pure copper and pure zirconium metals are each 99.99% pure.
4. The method of making a free-standing nanoporous copper-supported nonalcoholic pentasulfide nanosheet composite as recited in claim 2, wherein the amorphous ribbon produced has dimensions of 1cm x 1mm x 20 μm to 10cm x 2mm x 40 μm.
5. Use of the free-standing nanoporous copper supported nonalcopper sulfide nanosheet composite of claim 1, characterized as being for photocatalytic degradation of contaminants.
6. Use of the free-standing nanoporous copper supported nonalcoholic pentasulfide nanosheet composite as recited in claim 5, comprising the steps of: soaking 4-5 mg of the prepared self-supporting nano porous copper-loaded nonacopper pentasulfide nanosheet composite material in 5-20 mL of pollutant solution with the concentration of 5-15 mg/L; using a 300W xenon lamp as a light source, wherein the illumination intensity is 30-50 mW/cm 2 After being irradiated by a light source for 10-100 min, pollutants are degraded.
7. The use of the free-standing nanoporous copper-supported nona-copper pentasulfide nanosheet composite of claim 5, wherein the contaminant is one or both of rhodamine B and methylene blue.
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| CN112206664A (en) * | 2020-10-22 | 2021-01-12 | 西北师范大学 | One-step anodic oxidation preparation process of inorganic flexible super-hydrophobic super-oleophylic copper mesh |
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| WO2002027072A1 (en) * | 2000-09-28 | 2002-04-04 | Stewart Lloyd Shipard | Hydrometallurgical processes utilising solutions containing dissolved ferric and/or ferrous salts |
| CN106830049A (en) * | 2017-03-14 | 2017-06-13 | 吉林大学 | A kind of Cu of nanometer sheet composition9 S5The preparation method of hollow 26 face body |
| CN111589457A (en) * | 2020-03-25 | 2020-08-28 | 陕西科技大学 | Photocatalytic material for in-situ growth of three-dimensional copper sulfide on copper mesh, preparation method and application |
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