CN112604689A - Preparation of porous copper oxide skeleton catalyst for catalyzing formaldehyde decomposition - Google Patents
Preparation of porous copper oxide skeleton catalyst for catalyzing formaldehyde decomposition Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 125
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 88
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000005751 Copper oxide Substances 0.000 claims abstract description 42
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 34
- 239000010949 copper Substances 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- 238000007747 plating Methods 0.000 claims abstract description 22
- 238000009713 electroplating Methods 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 18
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 16
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 206010070834 Sensitisation Diseases 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000008313 sensitization Effects 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000009423 ventilation Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000006864 oxidative decomposition reaction Methods 0.000 abstract description 4
- 239000010970 precious metal Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000002904 solvent Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical group [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 1
- UTICYDQJEHVLJZ-UHFFFAOYSA-N copper manganese nickel Chemical group [Mn].[Ni].[Cu] UTICYDQJEHVLJZ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 1
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B01J35/56—
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- B01J35/612—
-
- B01J35/657—
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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
- B01J37/08—Heat treatment
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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
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
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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
- B01J37/16—Reducing
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
Abstract
A porous copper oxide skeleton catalyst for catalyzing formaldehyde decomposition belongs to the technical field of printed circuit boards. The catalyst is a multilayer structure formed by nickel, copper and copper oxide, wherein the innermost layer is a nickel layer, the secondary inner layer is a copper layer, and the outermost layer is a copper oxide layer. The porous copper oxide framework material for catalyzing formaldehyde decomposition is obtained by taking polyurethane foam as a basic framework and carrying out chemical nickel plating, copper electroplating and heating oxidation treatment on the basic framework. The preparation process is simple and convenient, and compared with the precious metal, the adopted raw materials are lower in price and are green and environment-friendly; the prepared porous copper oxide framework material has the advantage of large specific surface area, has high formaldehyde oxidative decomposition efficiency, and is suitable for decomposing formaldehyde generated in various ways.
Description
Technical Field
The invention belongs to the technical field of printed circuit boards, and particularly relates to preparation of a porous copper oxide framework catalyst material for catalyzing formaldehyde decomposition.
Background
Printed Circuit Boards (PCBs), also known as Printed circuit boards, are providers of electrical connections for electronic components. In the PCB industry, formaldehyde is the most widely used reducing agent in the electroless copper plating process, but since formaldehyde has carcinogenicity and teratogenicity and great harm to human health, the research on how to remove formaldehyde in copper plating waste liquid is of great significance.
How to catalytically oxidize formaldehyde at room temperature is a problem that has received much attention in recent years. At present, the research on formaldehyde catalytic oxidation mainly focuses on Ag, Au, Pt and other noble metals. Zhang et al in the article A compatible study of TiO2 supported metallic catalysts for the oxidation of formal aldehyde at room temperatureIn the rate, noble metals such as Pt, Rh, Pd and Au are loaded on TiO2On molecular sieve, the reaction path of oxidative decomposition of formaldehyde is found to be HCHO → CHOO → CO2Wherein the decomposition of formate to CO is the rate-determining step of the overall reaction. Patent application No. 201510769581.X introduces a preparation and catalysis method of a mesoporous supported copper-manganese composite oxide catalyst, which can completely catalyze the reaction of oxidizing gas formaldehyde at low temperature so as to remove formaldehyde. The patent application No. 201711418265.3 describes a preparation method and application of a catalyst for treating low concentration formaldehyde in solution, wherein the catalyst is a nickel-copper-manganese composite oxide, and can rapidly and efficiently catalyze and oxidize formaldehyde in wastewater in a short time. The existing research mainly focuses on noble metals or composite oxides of various metals, and has the disadvantages of high cost, complex preparation and difficult practical application.
Disclosure of Invention
The invention provides a preparation method of a porous copper oxide framework material for catalyzing formaldehyde decomposition, aiming at how to oxidize and decompose formaldehyde in chemical copper plating waste liquid. The porous copper oxide framework material for catalyzing formaldehyde decomposition is obtained by taking polyurethane foam as a basic framework and carrying out chemical nickel plating, copper electroplating and heating oxidation treatment on the basic framework. The preparation process is simple and convenient, and compared with the precious metal, the adopted raw materials are lower in price and are green and environment-friendly; the prepared porous copper oxide framework material has the advantage of large specific surface area, has high formaldehyde oxidative decomposition efficiency, and is suitable for decomposing formaldehyde generated in various ways.
The technical scheme adopted by the invention is as follows:
a porous copper oxide skeleton catalyst for catalyzing formaldehyde decomposition is characterized in that the catalyst is a multilayer structure formed by nickel, copper and copper oxide; wherein the innermost layer is a porous nickel skeleton with a hollow structure, and the pore diameter is 0.5-2 mm; the secondary inner layer is a copper layer which is formed on the porous nickel framework and has the thickness of 20-60 mu m; the outermost layer is a copper oxide layer with a porous structure, and the specific surface area is 0.3-2 m2/g。
A preparation method of a porous copper oxide framework catalyst for catalyzing formaldehyde decomposition is characterized by comprising the following steps:
and 3, heating and oxidizing the porous copper skeleton obtained in the step 2: pre-sintering the porous copper skeleton obtained in the step 2 at 150-250 ℃ for 10-30 minutes; and then placing the porous copper oxide framework catalyst in a muffle furnace, heating to 500-700 ℃, keeping the temperature for 10-30 minutes, naturally cooling to room temperature, and taking out to obtain the porous copper oxide framework catalyst.
Further, the preparation process of the porous nickel skeleton in the step 1 specifically comprises the following steps: polyurethane foam is used as a framework material, and is subjected to pretreatment such as oil removal, sensitization, activation and the like, and then chemical nickel plating to obtain the porous nickel framework.
Further, the copper electroplating process in the step 2 specifically comprises the following steps: preparing an electroplating solution with copper sulfate and sulfuric acid as main components, carrying out copper electroplating treatment on the porous nickel skeleton, and carrying out ventilation treatment on a cathode and an anode during electroplating to obtain the porous copper skeleton.
Further, in the process of preparing the porous nickel framework in the step 1, a nickel source adopted by chemical nickel plating is nickel sulfate, and the concentration is 15-30 g/L; the reaction temperature of the chemical nickel plating is 40-60 ℃, when the copper electroplating is carried out in the step 2, the concentration of copper sulfate pentahydrate in the electroplating solution is 60-100 g/L, the concentration of concentrated sulfuric acid is 200-300 g/L, the apparent current density is 3-5A/cm 2, and the time is 0.5-2 hours.
The invention provides a preparation method of a porous copper oxide skeleton catalyst for catalyzing formaldehyde decomposition, which comprises the following reaction processes:
the nickel ions are reduced into metallic nickel on the surface of the polyurethane foam under the action of sodium hypophosphite and a catalyst:
NiSO4+2NaH2PO2+2H2O→H2SO4+2NaH2PO3+Ni↓+H2↑
copper ions are reduced into metallic copper under the action of electrification:
Cu2++2e-→Cu↓
and (3) heating and oxidizing metal copper into copper oxide:
2Cu+O2→2CuO
compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a porous copper oxide framework catalyst for catalyzing formaldehyde decomposition, which takes polyurethane foam as a basic framework, and obtains the porous copper oxide framework material for catalyzing formaldehyde decomposition by chemical nickel plating, copper electroplating and heating oxidation treatment on the basic framework. The preparation process is simple and convenient, and compared with the precious metal, the adopted raw materials are lower in price and are green and environment-friendly; the prepared porous copper oxide framework material has the advantage of large specific surface area, has high formaldehyde oxidative decomposition efficiency, and is suitable for decomposing formaldehyde generated in various ways.
Drawings
FIG. 1 is a diagram of a finished porous copper oxide skeletal catalyst obtained in example 1;
FIG. 2 is an SEM image of the surface of the porous copper oxide framework catalyst obtained in example 1;
FIG. 3 is an SEM image of a cross section of the porous copper oxide framework catalyst obtained in example 1; wherein a is a nickel layer of an inner layer, b is a copper layer of a secondary inner layer, and c is a copper oxide layer of an outer layer;
FIG. 4 shows the results of cyclic voltammogram measurements of a nickel foam skeleton (a), a copper foam skeleton (b), and a copper foam skeleton (c) during the preparation of a porous copper oxide skeleton catalyst according to example 1;
FIG. 5 shows the results of cyclic voltammetry tests of the porous copper oxide framework catalyst obtained in example 1 in formaldehyde solutions of different concentrations.
Detailed Description
The present invention will be further described with reference to the following examples, which are not intended to limit the scope of the present invention in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
Step 1: the preparation method of the porous nickel skeleton with polyurethane foam as the skeleton material comprises the following steps:
step 1-1, deoiling: using water as solvent according to NaOH 25g/L, Na2CO3 35g/L、Na2HPO4Preparing deoiling liquid at the ratio of 50g/L, treating polyurethane foam in the deoiling liquid at the temperature of 50 ℃ for 5 minutes, taking out and washing with pure water;
step 1-2, sensitization: using water as solvent, according to SnCl2·2H2Preparing sensitizing solution by the proportion of O40 g/L and concentrated HCl 100g/L, soaking the polyurethane foam treated in the last step in the sensitizing solution for 4 minutes, taking out, hydrolyzing in pure water for 3 minutes, taking out and washing with the pure water;
step 1-3, activation: water as solvent, according to PdCl2Preparing an activating solution according to the proportion of 0.5g/L and 100g/L concentrated HCl, treating the polyurethane foam treated in the previous step in the activating solution for 3 minutes, taking out and washing with pure water;
step 1-4, chemical nickel plating: water as solvent, according to NiSO4·6H2Preparing a chemical plating solution by using the proportion of O25 g/L, anhydrous sodium acetate 20g/L, sodium citrate 20g/L, lead acetate 0.5mg/L and sodium hypophosphite 30g/L, adjusting the pH to 8-9 by using ammonia water, carrying out chemical plating on the polyurethane foam treated in the last step in the chemical plating solution at the temperature of 50 ℃ for 8 minutes until the surface is plated with a layer of nickel with silvery metallic luster, taking out, cleaning and drying to obtain the porous nickel skeleton.
Step 2: the method for electroplating copper on the porous nickel skeleton prepared in the previous step specifically comprises the following steps:
step 2-1: water as solvent, according to CuSO4·5H2O70 g/L, concentrated H2SO4 240g/L、Cl-Preparing electroplating solution according to the proportion of 0.06 g/L;
step 2-2: using 4.5A/cm2Electroplating copper on the nickel framework material prepared in the step 1 by using the apparent current density, and ventilating the cathode and the anode during electroplating for 1 hour to obtain the nickel framework materialPreparing the porous copper skeleton, taking out, cleaning and drying.
And 3, heating and oxidizing the porous copper skeleton obtained in the step 2: pre-sintering the porous copper skeleton obtained in the step 2 at 200 ℃ for 20 minutes; and then placing the porous copper oxide framework catalyst in a muffle furnace, heating to 600 ℃, keeping the temperature for 20 minutes, naturally cooling to room temperature, and taking out to obtain the porous copper oxide framework catalyst.
Fig. 2 is an SEM image of the surface morphology of the porous copper oxide framework catalyst obtained in example 1, and it can be seen that the surface has a more porous structure.
Fig. 3 is an SEM image of a cross section of the porous copper oxide skeletal catalyst obtained in example 1, and it can be seen that the cross section has a multilayer structure in which a is a nickel layer of an inner layer, b is a copper layer of a sub-inner layer, and c is a copper oxide layer of an outer layer.
In the preparation process, cyclic voltammetry testing is carried out on the porous nickel skeleton obtained in the step 1, the porous copper skeleton obtained in the step 2 and the porous copper oxide skeleton obtained in the step 3, and a three-electrode system is adopted. A working electrode: preparing a porous nickel skeleton, a porous copper skeleton and a porous copper oxide skeleton electrode; reference electrode: a mercurous sulfate electrode; counter electrode: a platinum electrode. The test results are shown in fig. 4, in which a curve is a CV curve of the porous nickel skeleton, b curve is a CV curve of the porous copper skeleton, and c curve is a CV curve of the porous copper oxide skeleton. The same oxidation current of 4mA is taken, and the observation shows that: the nickel framework has almost no catalytic effect on formaldehyde oxidation, and no oxidation or reduction current is generated; and for the copper skeleton, the oxidation potential is-0.30V, and the oxidation potential of the copper oxide foam is-0.39V, so that the copper oxide foam has lower oxidation potential and is easier to catalyze the formaldehyde to be oxidized and decomposed.
FIG. 5 shows the results of cyclic voltammetry tests of the porous copper oxide framework catalyst obtained in example 1 in formaldehyde solutions of different concentrations; wherein the curve a is the CV curve of 5mmol/L HCHO, the curve b is the CV curve of 10mmol/L HCHO, and the curve c is the CV curve of 30mmol/L HCHO. As can be seen from the figure, for the oxidation current of 6mA, the oxidation potential is in the order of 30mmol/L HCHO <10mmol/L HCHO <5mmol/L HCHO, which can obtain that the copper oxide foam catalyst is easier to catalyze the reaction for formaldehyde solution with larger concentration.
Example 2
Step 1: the preparation method of the porous nickel skeleton with polyurethane foam as the skeleton material comprises the following steps:
step 1-1, deoiling: using water as solvent according to NaOH 25g/L, Na2CO3 35g/L、Na2HPO4Preparing deoiling liquid at the ratio of 50g/L, treating polyurethane foam in the deoiling liquid at the temperature of 50 ℃ for 5 minutes, taking out and washing with pure water;
step 1-2, sensitization: using water as solvent, according to SnCl2·2H2Preparing sensitizing solution by the proportion of O40 g/L and concentrated HCl 100g/L, soaking the polyurethane foam treated in the last step in the sensitizing solution for 4 minutes, taking out, hydrolyzing in pure water for 3 minutes, taking out and washing with the pure water;
step 1-3, activation: water as solvent, according to PdCl2Preparing an activating solution according to the proportion of 0.5g/L and 100g/L concentrated HCl, treating the polyurethane foam treated in the previous step in the activating solution for 3 minutes, taking out and washing with pure water;
step 1-4, chemical nickel plating: water as solvent, according to NiSO4·6H2Preparing a chemical plating solution by using the proportion of O25 g/L, anhydrous sodium acetate 20g/L, sodium citrate 20g/L, lead acetate 0.5mg/L and sodium hypophosphite 30g/L, adjusting the pH to 8-9 by using ammonia water, carrying out chemical plating on the polyurethane foam treated in the last step in the chemical plating solution at the temperature of 50 ℃ for 8 minutes until the surface is plated with a layer of nickel with silvery metallic luster, taking out, cleaning and drying to obtain the porous nickel skeleton.
Step 2: the method for electroplating copper on the porous nickel skeleton prepared in the previous step specifically comprises the following steps:
step 2-1: according to CuSO4·5H2O75 g/L, concentrated H2SO4 240g/L、Cl-0.06g/L and SPS 1mg/L, PEG-8000500 mg/L to prepare electroplating solution;
step 2-2: using 4.5A/cm2Electroplating copper on the nickel framework material prepared in the step 1 at the apparent current density of the magnitude, and electroplatingAnd (3) ventilating the cathode and the anode during plating, wherein the plating time is 1 hour, thus obtaining the porous copper skeleton with smooth and bright surface, taking out, cleaning and drying.
And 3, heating and oxidizing the porous copper skeleton obtained in the step 2: pre-sintering the porous copper skeleton obtained in the step 2 at 200 ℃ for 20 minutes; and then placing the porous copper oxide framework catalyst in a muffle furnace, heating to 600 ℃, keeping the temperature for 20 minutes, naturally cooling to room temperature, and taking out to obtain the porous copper oxide framework catalyst.
The foregoing has described in detail the principles and features of the invention, together with the advantages thereof. The present invention relates to a method for preparing a porous copper oxide framework material for catalyzing formaldehyde decomposition, which is not limited by the above embodiments, which are described in the specification and the above embodiments only to illustrate the principle of the present invention, and various modifications can be made without departing from the spirit and scope of the present invention, and the modifications are included in the scope of the claimed invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A porous copper oxide skeleton catalyst for catalyzing formaldehyde decomposition is characterized in that the catalyst is a multilayer structure formed by nickel, copper and copper oxide; wherein the innermost layer is a porous nickel skeleton with a hollow structure, and the pore diameter is 0.5-2 mm; the secondary inner layer is a copper layer which is formed on the porous nickel framework and has the thickness of 20-60 mu m; the outermost layer is a copper oxide layer with a porous structure, and the specific surface area is 0.3-2 m2/g。
2. A preparation method of a porous copper oxide framework catalyst for catalyzing formaldehyde decomposition is characterized by comprising the following steps:
step 1, preparing a porous nickel skeleton with the aperture of 0.5-2 mm;
step 2, carrying out electro-coppering treatment on the porous nickel skeleton obtained in the step 1 to obtain a porous copper skeleton;
and 3, heating and oxidizing the porous copper skeleton obtained in the step 2: pre-sintering the porous copper skeleton obtained in the step 2 at 150-250 ℃ for 10-30 minutes; and then placing the porous copper oxide framework catalyst in a muffle furnace, heating to 500-700 ℃, keeping the temperature for 10-30 minutes, naturally cooling to room temperature, and taking out to obtain the porous copper oxide framework catalyst.
3. The method for preparing a porous copper oxide framework catalyst for catalyzing formaldehyde decomposition according to claim 2, wherein the porous nickel framework prepared in the step 1 is specifically prepared by: polyurethane foam is used as a framework material, and is subjected to oil removal, sensitization and activation treatment and then chemical nickel plating to obtain the porous nickel framework.
4. The method for preparing a porous copper oxide framework catalyst for catalyzing formaldehyde decomposition according to claim 2, wherein the step 2 copper electroplating specifically comprises the following steps: preparing an electroplating solution with copper sulfate and sulfuric acid as main components, carrying out copper electroplating treatment on the porous nickel skeleton, and carrying out ventilation treatment on a cathode and an anode during electroplating to obtain the porous copper skeleton.
5. The preparation method of the porous copper oxide framework catalyst for catalyzing formaldehyde decomposition according to claim 2, wherein in the process of preparing the porous nickel framework in the step 1, a nickel source adopted by chemical nickel plating is nickel sulfate, the concentration of the nickel source is 15-30 g/L, and the reaction temperature of the chemical nickel plating is 40-60 ℃; in the step 2, during copper electroplating, the concentration of copper sulfate pentahydrate is 60-100 g/L, the concentration of concentrated sulfuric acid is 200-300 g/L, and the apparent current density is 3-5A/cm2The time is 0.5 to 2 hours.
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