CN113546624A - Copper oxide/cuprous oxide photocatalytic material for in-situ growth of foamy copper and preparation method and application thereof - Google Patents
Copper oxide/cuprous oxide photocatalytic material for in-situ growth of foamy copper and preparation method and application thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 96
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 89
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 48
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 43
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 43
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 39
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 39
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 75
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 54
- 239000006260 foam Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 40
- 239000008367 deionised water Substances 0.000 claims abstract description 39
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 39
- 230000003647 oxidation Effects 0.000 claims abstract description 39
- 239000003792 electrolyte Substances 0.000 claims abstract description 27
- 239000011780 sodium chloride Substances 0.000 claims abstract description 27
- 238000000137 annealing Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 239000013543 active substance Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 11
- 239000002073 nanorod Substances 0.000 abstract description 8
- 230000031700 light absorption Effects 0.000 abstract description 4
- 229960004643 cupric oxide Drugs 0.000 description 38
- 230000001276 controlling effect Effects 0.000 description 9
- 238000001962 electrophoresis Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- 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
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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
- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a copper oxide/cuprous oxide photocatalytic material for foam copper in-situ growth, a preparation method and application thereof, wherein NaOH is dissolved in deionized water to obtain a solution A; adding NaCl into the solution A to obtain a solution B, and adding a dispersing agent into the solution B to obtain a solution C; taking a foam copper sheet as an anode, an inert electrode as a cathode and a solution C as an electrolyte, carrying out oxidation treatment on the anode, and then repeatedly washing the foam copper sheet subjected to anodic oxidation by deionized water to obtain a product D attached with a black active substance; and annealing the product D to obtain the copper oxide/cuprous oxide photocatalytic material with in-situ growth of the foamy copper. The phase-controllable copper oxide/cuprous oxide photocatalytic film material is obtained, the regulation and control of the microscopic morphology of the material from the coexistence of nanorod nanoparticles to nanoparticles are realized, and the regulation and control of the light absorption and the photocatalytic activity of the photocatalytic film through controlling the phase and the morphology are realized.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to copper oxide/cuprous oxide (Cu) growth in situ for foamy copper2O/CuO) photocatalytic material, and a preparation method and application thereof.
Background
In recent ten years, with the rapid development of the industry in China. As the total amount of dye production is in the world, the pollution problem caused by waste water generated by industries such as dye waste water, organic chemical industry and the like is becoming more and more serious. Dye wastewater has become one of the main factors threatening the ecological environment and human life health. The treatment of dye wastewater is imminent, and therefore, the development of environmentally friendly dye wastewater treatment is a very important subject. In recent years, copper oxide is widely applied to the fields of lithium ion batteries, sensors, supercapacitors, photocatalytic hydrogen production and the like. The copper oxide has the advantages of being in a narrow band gap (1.2-2.1 eV) band gap range, rich in storage capacity, low in cost, non-toxic, safe and the like. In addition, as a typical transition group semiconductor metal oxide, copper oxide is favored in photocatalysis due to its wide photoresponse range, good photocatalytic activity, adsorptivity, nontoxicity, environmental friendliness and other characteristics.
Although copper oxide has great potential in the aspect of photocatalytic application, the problems that a common photo-generated carrier of a narrow-bandgap photocatalyst is easy to compound, the phenomenon of photo-corrosion in the photocatalytic process is large, powder photocatalysis is difficult to recover and the like are still faced. Therefore, the activity of the copper oxide photocatalyst in practical application is greatly lower than the theoretical activity, and the problem of low commercial popularization and application value is faced.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a copper oxide/cuprous oxide photocatalytic material for foam copper in-situ growth, a preparation method and application thereof aiming at the defects in the prior art, and solve the problem that a powder photocatalyst is difficult to recover by in-situ synthesis of a copper oxide photocatalytic film on a metal substrate with high electron transfer rate. The purpose of dimming the performance of the catalyst is achieved by optimizing the ratio of copper oxide to cuprous oxide and the micro-geometry structure and reducing the recombination of photon-generated carriers.
The invention adopts the following technical scheme:
a preparation method of a copper oxide/cuprous oxide photocatalytic material with in-situ growth of foamy copper comprises the following steps:
dissolving NaOH in deionized water to obtain a solution A; adding NaCl into the solution A to obtain a solution B, and adding a dispersing agent into the solution B to obtain a solution C; taking a foam copper sheet as an anode, an inert electrode as a cathode and a solution C as an electrolyte, carrying out oxidation treatment on the anode, and then repeatedly washing the foam copper sheet subjected to anodic oxidation by deionized water to obtain a product D attached with a black active substance; and annealing the product D to obtain the copper oxide/cuprous oxide photocatalytic material with in-situ growth of the foamy copper.
Specifically, deionized water is used as a solvent, and the molar mass ratio of NaOH to NaCl is 1 (1-5).
Specifically, NaCl is added into the solution A and stirred for 20-30 min to obtain a solution B, and a dispersing agent is added into the solution B and stirred for 30-40 min to obtain a solution C.
Specifically, the dispersing agent is polyethylene glycol with the concentration of 0.1-2 g/L and the relative molecular mass of 400.
Specifically, the oxidation treatment of the anode specifically comprises:
controlling the current to be 5-30 mA, controlling the voltage to be 5-50V, carrying out oxidation treatment on the anode for 5-180 min, and keeping the temperature of the electrolyte at room temperature-70 ℃ in the oxidation process of the anode and stirring at constant temperature.
Specifically, the inert electrode includes C or Pt.
Specifically, the annealing treatment temperature is 200-550 ℃, the temperature rising speed is 5 ℃/min, and the time is 2-4 h.
Specifically, the preparation of the foam copper sheet comprises the following steps:
cutting the foam copper, sequentially putting the cut foam copper into absolute ethyl alcohol, acetone and deionized water for ultrasonic treatment for 5-8 min, and then soaking the cut foam copper in hydrochloric acid with the concentration of 0.1-1M for 5-20 min to obtain the foam copper sheet.
The invention also provides a copper oxide/cuprous oxide photocatalytic material prepared by the method, wherein the copper oxide/cuprous oxide photocatalytic material is formed by in-situ growth of copper foam.
The invention also provides the application of the copper oxide/cuprous oxide photocatalytic material prepared by the method and growing in situ or the application of the copper oxide/cuprous oxide photocatalytic material prepared by the method in photocatalytic degradation of organic matters.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention relates to a preparation method of a copper oxide/cuprous oxide photocatalytic material for in-situ growth of copper foam, which comprises the steps of dissolving NaOH in deionized water to obtain a solution A; adding NaCl into the solution A to obtain a solution B, and adding a dispersing agent into the solution B to obtain a solution C; taking a foam copper sheet as an anode, an inert electrode as a cathode and a solution C as an electrolyte, carrying out oxidation treatment on the anode, and then repeatedly washing the foam copper sheet subjected to anodic oxidation by deionized water to obtain a product D attached with a black active substance; and annealing the product D to obtain the copper oxide/cuprous oxide photocatalytic material grown in situ by the foamy copper, so as to obtain the copper oxide/cuprous oxide photocatalytic film material with controllable phase, synthesizing a recyclable photocatalyst film on the foamy copper in situ in a large area, regulating and controlling the micro morphology of the material from the coexistence of nanorod nanoparticles to the nanoparticles, and regulating and controlling the light absorption and photocatalytic activity of the photocatalytic film by controlling the phase and the morphology.
Furthermore, the molar mass ratio of NaOH to NaCl is adjusted to realize that the ion concentration of the electrolyte is not changed and OH in the electrolyte is adjusted-The concentration of (c).
Furthermore, the crystal grains of the in-situ grown seed crystal layer can be effectively changed by adjusting the concentration of the dispersant polyethylene glycol.
Furthermore, the oxidation time can effectively adjust the concentration of copper ions by adjusting the external current in the anodic oxidation process, thereby effectively adjusting the density of the seed crystal layer and realizing controllable morphology.
Furthermore, the proportion of the copper oxide and cuprous oxide phases which grow in situ can be effectively adjusted by adjusting the annealing temperature, and the adjustment of the visible light absorption range and the oxidation-reduction potential of the synthesized catalytic film is realized.
Furthermore, by adjusting the soaking time of the copper foam in hydrochloric acid and the concentration of the hydrochloric acid, the removal and surface activation of the oxide film on the surface of the base copper foam are realized, and the uniform growth of the seed crystal layer is ensured.
Furthermore, the inert electrodes C and Pt ensure that the cathode electrode does not react with the electrolyte, and ensure that the anodic oxidation reaction can be stably carried out.
In conclusion, the preparation equipment has low requirement, is slightly influenced by the outside, has simple method, low cost and high controllability, and is suitable for large-scale industrial production.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a graph comparing X-ray diffraction patterns obtained from different anodizing times in examples 1 and 2;
FIG. 2 is a scanning electron microscope image of different magnifications of the surface of the cleaned foam copper, wherein (a) is a scanning electron microscope image with a 500 μm scale, and (b) is a scanning electron microscope image with a 50 μm scale;
FIG. 3 is a scanning electron micrograph of a sample prepared in example 1 at different magnifications, wherein (a) is a scanning electron micrograph on a 50 μm scale, (b) is a scanning electron micrograph on a 10 μm scale, and (c) is a scanning electron micrograph on a 1 μm scale;
FIG. 4 is a scanning electron micrograph of a sample prepared in example 2 at different magnifications, wherein (a) is a scanning electron micrograph on a 50 μm scale, (b) is a scanning electron micrograph on a 10 μm scale, and (c) is a scanning electron micrograph on a 1 μm scale;
FIG. 5 is a scanning electron micrograph of a sample prepared in example 3 at different magnifications, wherein (a) is 1 μm and (b) is 500 nm.
Detailed Description
It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the specification of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be further understood that the term "and/or" as used in this specification and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items.
The invention provides a preparation method of a copper oxide/cuprous oxide photocatalytic material for in-situ growth of foamy copper, which comprises the following steps:
s1, cutting the foamy copper into a sheet-shaped result, sequentially putting the sheet-shaped result into absolute ethyl alcohol, acetone and deionized water for ultrasonic treatment, and soaking the sheet-shaped result in 0.1-1M hydrochloric acid for 5-20 min; obtaining a cleaned foam copper sheet;
s2, dissolving NaOH in deionized water to obtain a solution A; adding NaCl into the solution A to obtain a solution B, wherein the molar mass ratio of the NaOH to the NaCl is 1-5;
s3, adding 0.1-2 g/L of dispersant polyethylene glycol (PEG) with the relative molecular mass of 400 into the solution B to obtain a solution C;
s4, adjusting output parameters of a triple-constant electrophoresis apparatus, controlling the current to be 5-30 mA, controlling the voltage to be 5-50V, taking an inert electrode as a cathode, taking the foamy copper prepared in the step S1 as an anode, taking the solution C prepared in the step S3 as an electrolyte, carrying out oxidation treatment on the anode for 5-180 min, keeping the temperature of the electrolyte at room temperature-70 ℃ during the oxidation process of the anode and stirring at constant temperature, and then repeatedly washing the foamy copper subjected to the oxidation of the anode with deionized water to obtain a product D with a black active substance attached to a copper mesh;
the inert electrode comprises C, Pt or Pd.
S5, placing the product D in a muffle furnace, and annealing at 200-550 ℃ for 2-4 h at a heating rate of 5 ℃/min to obtain the copper oxide/cuprous oxide photocatalytic material for in-situ growth of the copper foam.
The copper oxide/cuprous oxide photocatalytic material for in-situ growth of the foamy copper is prepared by the method, the catalyst film simplifies the catalyst recycling process, and avoids the defects that a powder catalyst is not easy to recycle in the water degradation process, and the residue produces secondary pollution and the like.
The foam copper film provided by the invention is in a nano scale, and Cu grows in situ on a foam copper substrate2O/CuO; copper sulfide material grown in situ on copper mesh is in micron scale, and Cu grown on foam copper2The O/CuO is formed by nano-rods and nano-particles, the surfaces of the nano-rods are smooth, the nano-rods vertically and uniformly grow on a foam copper substrate, the geometrical morphology structure formed by the nano-rods and the nano-particles is obviously changed along with the change of synthesis conditions, and the Cu/CuO is formed by the Cu2The ratio of O to CuO is changed accordingly. Thereby changing the specific surface area and phase composition of the catalyst.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Cutting the foamy copper into a sheet structure, sequentially adding absolute ethyl alcohol, acetone and deionized water, respectively performing ultrasonic treatment for 5min, and soaking in 1.0M hydrochloric acid for 5min to obtain a plurality of clean foamy copper;
(2) dissolving 1M NaOH in 300ml deionized water to obtain a solution A;
(3) dissolving 2.5M NaCl in the solution A, stirring for 20min to obtain a solution B containing NaOH and NaCl, adding 0.1g/L PEG with the relative molecular mass of 400 into the solution B, and continuously stirring for 30min to obtain a solution C.
(4) Adjusting output parameters of a triple constant electrophoresis apparatus, outputting the parameters at a constant current of 10mA, oxidizing the anode for 10min by using graphite as a cathode, foamed copper as an anode and solution C as electrolyte, keeping the electrolyte at a constant temperature of 70 ℃ during the anodic oxidation process, stirring, and repeatedly washing the anode with deionized water to obtain a product D;
(5) and placing the product D in a muffle furnace, annealing at 200 ℃, heating to 400 ℃ at the speed of 5 ℃/min, preserving the temperature for 120min, and naturally cooling to room temperature to obtain the copper oxide/cuprous oxide photocatalytic material with copper-attached foamy copper in-situ growth.
Example 2
(1) Cutting the foamy copper into a sheet structure, sequentially adding absolute ethyl alcohol, acetone and deionized water, respectively performing ultrasonic treatment for 5min, and soaking in 1M hydrochloric acid for 5min to obtain a plurality of clean foamy copper;
(2) dissolving 1M NaOH in 300ml deionized water to obtain a solution A;
(3) dissolving 2.5M NaCl in the solution A, stirring for 20min to obtain a solution B containing NaOH and NaCl, adding 0.5g/L PEG with the relative molecular mass of 400 into the solution B, and continuously stirring for 30min to obtain a solution C.
(4) Adjusting output parameters of a triple constant electrophoresis apparatus, carrying out constant output by using a current of 10mA, carrying out anodic oxidation for 30min by using graphite as a cathode, using foam copper as an anode and using the solution C as an electrolyte, keeping the electrolyte at a constant temperature of 70 ℃ during anodic oxidation, stirring, and repeatedly washing the anode with deionized water to obtain a product D;
(5) and placing the product D in a muffle furnace, annealing at 250 ℃, heating to 400 ℃ at the speed of 5 ℃/min, preserving the temperature for 120min, and naturally cooling to room temperature to obtain the copper oxide/cuprous oxide photocatalytic material with copper-attached foamy copper in-situ growth.
Example 3
(1) Cutting the foamy copper into a sheet structure, sequentially adding absolute ethyl alcohol, acetone and deionized water, respectively performing ultrasonic treatment for 6min, and soaking in 0.6M hydrochloric acid for 6min to obtain a plurality of clean foamy copper;
(2) dissolving 1M NaOH in 300ml deionized water to obtain a solution A;
(3) dissolving 2.5M NaCl in the solution A, stirring for 24min to obtain a solution B containing NaOH and NaCl, adding 1g/L PEG with the relative molecular mass of 400 into the solution B, and continuously stirring for 34min to obtain a solution C.
(4) Adjusting output parameters of a triple constant electrophoresis apparatus, carrying out constant output by using a current of 20mA, carrying out anodic oxidation for 30min by using graphite as a cathode, foamed copper as an anode and a solution C as an electrolyte, keeping the electrolyte at a constant temperature of 70 ℃ during anodic oxidation, stirring, and repeatedly washing the anode with deionized water to obtain a product D;
(5) and placing the product D in a muffle furnace, annealing at 400 ℃, heating to 400 ℃ at the speed of 5 ℃/min, preserving the temperature for 120min, and naturally cooling to room temperature to obtain the copper oxide/cuprous oxide photocatalytic material with copper-attached foamy copper in-situ growth.
Example 4
(1) Cutting the foamy copper into a sheet structure, sequentially adding absolute ethyl alcohol, acetone and deionized water, respectively performing ultrasonic treatment for 7min, and soaking in 0.4M hydrochloric acid for 7min to obtain a plurality of clean foamy copper;
(2) dissolving 1M NaOH in 300ml deionized water to obtain a solution A;
(3) dissolving 2.5M NaCl in the solution A, stirring for 26min to obtain a solution B containing NaOH and NaCl, adding 1.2g/L PEG with the relative molecular mass of 400 into the solution B, and continuously stirring for 36min to obtain a solution C.
(4) Adjusting output parameters of a triple-constant electrophoresis apparatus, carrying out constant output by using a current of 15mA, using graphite as a cathode, using foam copper as an anode and using the solution C as an electrolyte, carrying out anodic oxidation for 80min, keeping the electrolyte at a constant temperature of 40 ℃ during the anodic oxidation process, stirring, and repeatedly washing the anode with deionized water to obtain a product D;
(5) and placing the product D in a muffle furnace, annealing at 550 ℃, heating to 550 ℃ at the speed of 5 ℃/min, and preserving heat for 120min to obtain the copper oxide/cuprous oxide photocatalytic material with copper-attached foamy copper in-situ growth.
Example 5
(1) Cutting the foamy copper into a sheet structure, sequentially adding absolute ethyl alcohol, acetone and deionized water, respectively performing ultrasonic treatment for 8min, and soaking in 0.2M hydrochloric acid for 7min to obtain a plurality of clean foamy copper;
(2) dissolving 1M NaOH in 300ml deionized water to obtain a solution A;
(3) dissolving 1M NaCl in the solution A, stirring for 28min to obtain a solution B containing NaOH and NaCl, adding 1.6g/L PEG with the relative molecular mass of 400 into the solution B, and continuing to stir for 38min to obtain a solution C.
(4) Adjusting output parameters of a triple constant electrophoresis apparatus, carrying out constant output by using a current of 20mA, carrying out anodic oxidation for 120min by using graphite as a cathode, foamed copper as an anode and a solution C as an electrolyte, keeping the electrolyte at room temperature during anodic oxidation, stirring at constant temperature, and repeatedly washing the anode with deionized water to obtain a product D;
(5) and placing the product D in a muffle furnace, annealing at 500 ℃, heating to 450 ℃ at the speed of 5 ℃/min, and preserving heat for 120min to obtain the copper oxide/cuprous oxide photocatalytic material with copper-attached foamy copper in-situ growth.
Example 6
(1) Cutting the foamy copper into a sheet structure, sequentially adding absolute ethyl alcohol, acetone and deionized water, respectively performing ultrasonic treatment for 5min, and soaking in 0.1M hydrochloric acid for 10min to obtain a plurality of clean foamy copper;
(2) dissolving 1M NaOH in 300ml deionized water to obtain a solution A;
(3) dissolving 1.5M NaCl in the solution A, stirring for 30min to obtain a solution B containing NaOH and NaCl, adding 2g/L PEG with the relative molecular mass of 400 into the solution B, and continuously stirring for 40min to obtain a solution C.
(4) Adjusting output parameters of a triple constant electrophoresis apparatus, carrying out constant output by using a current of 30mA, carrying out anodic oxidation for 180min by using graphite as a cathode, foamed copper as an anode and a solution C as an electrolyte, keeping the electrolyte at a constant temperature of 30 ℃ during anodic oxidation, stirring, and repeatedly washing the anode with deionized water to obtain a product D;
(5) and placing the product D in a muffle furnace, annealing at 550 ℃, heating to 550 ℃ at the speed of 5 ℃/min, and preserving heat for 240min to obtain the copper oxide/cuprous oxide photocatalytic material with copper-attached foamy copper in-situ growth.
Example 7
(1) Cutting the foamy copper into a sheet structure, sequentially adding absolute ethyl alcohol, acetone and deionized water, respectively performing ultrasonic treatment for 5min, and soaking in 1M hydrochloric acid for 20min to obtain a plurality of clean foamy copper;
(2) dissolving 1M NaOH in 300ml deionized water to obtain a solution A;
(3) dissolving 1.5M NaCl in the solution A, stirring for 30min to obtain a solution B containing NaOH and NaCl, adding 2g/L PEG with the relative molecular mass of 400 into the solution B, and continuously stirring for 40min to obtain a solution C.
(4) Adjusting output parameters of a triple constant electrophoresis apparatus, carrying out constant output by using a current of 30mA, carrying out anodic oxidation for 180min by using graphite as a cathode, foamed copper as an anode and a solution C as an electrolyte, keeping the electrolyte at a constant temperature of 70 ℃ during anodic oxidation, stirring, and repeatedly washing the anode with deionized water to obtain a product D;
(5) and placing the product D in a muffle furnace, annealing at 550 ℃, heating to 550 ℃ at the speed of 5 ℃/min, and preserving heat for 240min to obtain the copper oxide/cuprous oxide photocatalytic material with copper-attached foamy copper in-situ growth.
Example 8
(1) Cutting the foamy copper into a sheet structure, sequentially adding absolute ethyl alcohol, acetone and deionized water, respectively performing ultrasonic treatment for 8min, and soaking in 0.8M hydrochloric acid for 15min to obtain a plurality of clean foamy copper;
(2) dissolving 1M NaOH in 300ml deionized water to obtain a solution A;
(3) dissolving 5M NaCl in the solution A, stirring for 28min to obtain a solution B containing NaOH and NaCl, adding 1.8g/L PEG with the relative molecular mass of 400 into the solution B, and continuing to stir for 38min to obtain a solution C.
(4) Adjusting output parameters of a triple-constant electrophoresis apparatus, carrying out constant output by using a current of 5mA, carrying out anodic oxidation for 120min by using graphite as a cathode, foamed copper as an anode and a solution C as an electrolyte, keeping the electrolyte at room temperature during anodic oxidation, stirring at constant temperature, and repeatedly washing the anode with deionized water to obtain a product D;
(5) and placing the product D in a muffle furnace, annealing at 500 ℃, heating to 250 ℃ at the speed of 5 ℃/min, and preserving heat for 120min to obtain the copper oxide/cuprous oxide photocatalytic material with copper-attached foamy copper in-situ growth.
Referring to fig. 1, combining the results of the reactions in fig. 1, the relative ratio of cupric oxide to cuprous oxide in the samples obtained in examples 1 and 2 was changed at different anodic oxidation growth times, wherein the sample produced in example 1 with a shorter oxidation time had a relatively higher content of cupric oxide than the sample produced in example 2, because more elemental copper was converted into copper ions and the formed cupric oxide and cuprous oxide were converted with the increase of anodic oxidation time, so the relative content of cupric oxide in the sample increased with the increase of oxidation time.
Referring to FIG. 2, the copper foam treated with organic substances and dilute hydrochloric acid has no damage to the copper foam itself and has surface impurity particles.
Referring to fig. 3, the copper oxide/cuprous oxide obtained in example 1 grows in situ on the surface of the copper foam and is tightly combined with the substrate, and a nano-film material containing nano-particles and nano-rods is generated on the framework of the copper foam.
Referring to fig. 5, on the basis of example 2, a nano-film containing only nano-particles is obtained by controlling the oxidation current, and a larger and denser seed layer is formed on the surface of the copper foam due to a larger output current in the anodization process, so that only nano-particles are on the surface of the copper foam.
In conclusion, the copper oxide/cuprous oxide photocatalytic material for in-situ growth of copper foam and the preparation method and application thereof can obtain the phase-controllable copper oxide/cuprous oxide photocatalytic film material, realize the regulation and control of the micro morphology of the material from the coexistence of nanorod nanoparticles to the nanoparticles, and realize the regulation and control of the light absorption and photocatalytic activity of the photocatalytic film by controlling the phase and the morphology.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a copper oxide/cuprous oxide photocatalytic material with in-situ growth of copper foam is characterized by comprising the following steps:
dissolving NaOH in deionized water to obtain a solution A; adding NaCl into the solution A to obtain a solution B, and adding a dispersing agent into the solution B to obtain a solution C; taking a foam copper sheet as an anode, an inert electrode as a cathode and a solution C as an electrolyte, carrying out oxidation treatment on the anode, and then repeatedly washing the foam copper sheet subjected to anodic oxidation by deionized water to obtain a product D attached with a black active substance; and annealing the product D to obtain the copper oxide/cuprous oxide photocatalytic material with in-situ growth of the foamy copper.
2. The method according to claim 1, wherein deionized water is used as a solvent, and the molar mass ratio of NaOH to NaCl is 1 (1-5).
3. The method according to claim 1, wherein NaCl is added to the solution A and stirred for 20-30 min to obtain a solution B, and a dispersing agent is added to the solution B and stirred for 30-40 min to obtain a solution C.
4. The method according to claim 1, wherein the dispersant is polyethylene glycol having a concentration of 0.1 to 2g/L relative to a molecular mass of 400.
5. The method according to claim 1, wherein the oxidation treatment of the anode is in particular:
controlling the current to be 5-30 mA, controlling the voltage to be 5-50V, carrying out oxidation treatment on the anode for 5-180 min, and keeping the temperature of the electrolyte at room temperature-70 ℃ in the oxidation process of the anode and stirring at constant temperature.
6. The method of claim 1, wherein the inert electrode comprises C or Pt.
7. The method according to claim 1, wherein the annealing treatment is carried out at a temperature of 200 to 550 ℃, a temperature rise rate of 5 ℃/min, and a time of 2 to 4 hours.
8. The method according to claim 1, characterized in that the preparation of the foam copper sheet is in particular:
cutting the foam copper, sequentially putting the cut foam copper into absolute ethyl alcohol, acetone and deionized water for ultrasonic treatment for 5-8 min, and then soaking the cut foam copper in hydrochloric acid with the concentration of 0.1-1M for 5-20 min to obtain the foam copper sheet.
9. A copper oxide/cuprous oxide photocatalytic material grown in situ from copper foam, prepared by the method of claim 1.
10. The use of the copper foam in-situ growth copper oxide/cuprous oxide photocatalytic material prepared according to the method of claim 1 or the copper foam in-situ growth copper oxide/cuprous oxide photocatalytic material according to claim 9 in photocatalytic degradation of organic matter.
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