CN115888821A - Composite cotton fabric, preparation method thereof and application thereof in degrading organic pollutants under offset double light sources - Google Patents
Composite cotton fabric, preparation method thereof and application thereof in degrading organic pollutants under offset double light sources Download PDFInfo
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- CN115888821A CN115888821A CN202211460201.0A CN202211460201A CN115888821A CN 115888821 A CN115888821 A CN 115888821A CN 202211460201 A CN202211460201 A CN 202211460201A CN 115888821 A CN115888821 A CN 115888821A
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- cotton fabric
- cuprous oxide
- solution
- iron oxyhydroxide
- nanoparticles
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- 229920000742 Cotton Polymers 0.000 title claims abstract description 89
- 239000004744 fabric Substances 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000000593 degrading effect Effects 0.000 title abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 78
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 66
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 66
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims abstract description 54
- 239000010949 copper Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 28
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000015556 catabolic process Effects 0.000 claims abstract description 25
- 238000006731 degradation reaction Methods 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000002791 soaking Methods 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012670 alkaline solution Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 6
- 230000009977 dual effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims description 2
- 230000031700 light absorption Effects 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 27
- 230000001699 photocatalysis Effects 0.000 abstract description 26
- 239000006260 foam Substances 0.000 abstract description 25
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract description 25
- 229940012189 methyl orange Drugs 0.000 abstract description 25
- 239000011941 photocatalyst Substances 0.000 abstract description 18
- 239000008367 deionised water Substances 0.000 abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 abstract description 14
- 229960004887 ferric hydroxide Drugs 0.000 abstract description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
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- 239000003513 alkali Substances 0.000 abstract description 3
- 229910002588 FeOOH Inorganic materials 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 21
- 239000002245 particle Substances 0.000 description 15
- 229910052724 xenon Inorganic materials 0.000 description 15
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 238000005096 rolling process Methods 0.000 description 14
- 239000006228 supernatant Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 7
- 238000004506 ultrasonic cleaning Methods 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000004005 microsphere Substances 0.000 description 6
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- 238000010521 absorption reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 239000005752 Copper oxychloride Substances 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- HKMOPYJWSFRURD-UHFFFAOYSA-N chloro hypochlorite;copper Chemical compound [Cu].ClOCl HKMOPYJWSFRURD-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 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 description 3
- -1 hydroxyl ferric oxide Chemical compound 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 230000001590 oxidative effect Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
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- 238000005303 weighing Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 239000012691 Cu precursor Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention provides a composite cotton fabric, a preparation method thereof and application thereof in degrading organic pollutants under an off-position double light source, and particularly relates to a method for degrading organic pollutants by cuprous oxide-ferric oxyhydroxide composite cotton fabric under an off-position double light source. The cuprous oxide is prepared by heating copper foam at high temperature, treating with dilute hydrochloric acid, washing with deionized water, and ultrasonically vibrating, and has a cubic structure; the iron oxyhydroxide is prepared by heating ferric chloride in sodium hydroxide solution. Soaking the cotton fabric subjected to alkali treatment in cuprous oxide-ferric hydroxide mixed solution for adsorption to prepare Cu 2 The O/FeOOH/cotton photocatalysis system can degrade organic matters under the irradiation of the offset double light sources, thereby obtaining excellent photocatalysis effect. The degradation rate of the photocatalyst to methyl orange in 1 hour can reach 97.5 percent at most. The method has the advantages of simple process, low raw material cost, recoverability, stable performance and good application prospect.
Description
Technical Field
The invention belongs to the field of semiconductor nano material photocatalysis, and particularly relates to a composite cotton fabric, a preparation method thereof and application thereof in degrading organic pollutants under an off-position double light source.
Background
Environmental pollution brings great threat to human life and health, and with the improvement of living standard of people, the requirements of people on ecological environment are higher and higher. However, the photocatalytic technology can convert environmental pollutants into substances such as carbon dioxide, water and inorganic salts, and is an environment-friendly and efficient measure for solving environmental problems. At present, semiconductor photocatalytic materials are widely used due to the advantages of simple preparation process, low cost, large-scale mass production and the like.
Cuprous oxide is a common p-type semiconductor material, has the advantage of a narrow band gap, and has a larger photoreaction range, while the narrow band gap also means that the redox capability of the cuprous oxide is weaker, and the cuprous oxide is easily subjected to photo-corrosion and has poor stability.
Patent CN113546624A discloses a copper oxide/cuprous oxide photocatalytic material grown in situ by using copper foam and a preparation method thereof, which prepares cuprous oxide/copper oxide nanoparticles with controllable morphology, but the cuprous oxide/copper oxide belongs to pp homogeneous junction photocatalysts, the band gap is small, electrons are easier to return to the ground state from an excited state, the recombination of photo-generated electrons and holes is increased rapidly, the charge separation efficiency is low, the redox capability is weak, and the photocatalytic reaction is not facilitated.
Patent CN113198469A discloses a copper-titanium heterojunction photocatalyst, and a preparation method and application thereof, wherein the photocatalyst adopts a p-type semiconductor Cu 2 O modified n-type semiconductor TiO 2 The pn heterojunction photocatalyst is obtained, but cuprous oxide prepared by the method has no composite surface protective coating, is easy to generate photo-corrosion, has poor stability and reduces the catalytic activity.
Therefore, it is urgently required to research a catalyst having excellent photocatalytic efficiency and a preparation method thereof to solve environmental problems.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses a composite cotton fabric, a preparation method thereof and application thereof in degrading organic pollutants under an off-position double light source. Firstly, alkali treatment is carried out on cotton fabric, so that the surface of the cotton fabric is rough, gaps among internal fibers are enlarged, and a large amount of nano materials can be firmly loaded; then cuprous oxide and hydroxyl ferric oxide nano particles are respectively prepared and dissolved in water to prepare a cuprous oxide-hydroxyl ferric oxide solution; and finally, soaking the cotton fabric in the solution for adsorption to obtain the cuprous oxide-iron oxyhydroxide composite cotton fabric. The sample is placed under an off-position double light source for a photocatalysis experiment, so that an excellent degradation effect can be achieved.
The invention is realized by the following scheme:
the first purpose of the invention is to provide a preparation method of a composite cotton fabric, which comprises the following steps:
(1) Dissolving cuprous oxide nanoparticles and iron oxyhydroxide nanoparticles in water to obtain a cuprous oxide-iron oxyhydroxide solution;
(2) And (3) putting the pretreated cotton fabric into the cuprous oxide-ferric hydroxide solution obtained in the step (1) for dipping to obtain the composite cotton fabric.
In one embodiment of the present invention, in step (1), the cuprous oxide nanoparticles are prepared by the following method:
and (3) putting the foamy copper into an alcohol solution, heating, then soaking in an acid solution, finally soaking in water and carrying out ultrasonic treatment, and then shaking to obtain the cuprous oxide nanoparticles. Due to the porous and high surface area characteristics of copper foam, the reaction is more complete and can provide higher Cu than other forms of copper 2 O nanocubes are the preferred copper precursor.
In one embodiment of the present invention, in step (1), the iron oxyhydroxide nanoparticles are prepared by the following method:
and mixing and heating ferric salt and an alkaline solution, and carrying out solid-liquid separation to obtain a solid phase to obtain the iron oxyhydroxide nanoparticles.
In one embodiment of the present invention, in the step (1), the mass ratio of the cuprous oxide nanoparticles to the iron oxyhydroxide nanoparticles is 1:0.25 to 1:4.
in one embodiment of the present invention, in the step (2), the step of preprocessing:
immersing the cotton fabric into an alkaline solution containing urea, and carrying out alkaline treatment at the temperature of minus 10 ℃ to minus 15 ℃ to obtain the pretreated cotton fabric.
In one embodiment of the present invention, in the step (2), the dipping time is 25min to 35min.
The second purpose of the invention is to provide the composite cotton fabric obtained by the preparation method.
The second purpose of the invention is to provide the application of the composite cotton fabric in degrading organic pollutants.
In one embodiment of the invention, the method of applying is implemented by the following steps:
s1, adding the prepared composite cotton fabric into organic pollutants, stirring in a dark condition, adding a hydrogen peroxide solution, and mixing to obtain a mixed solution;
and S2, placing the mixed solution obtained in the step S1 under an off-position double light source, stirring for reaction, detecting the light absorption intensity of the solution obtained after the reaction, and calculating the degradation rate of the organic pollutants.
In one embodiment of the present invention, in step S2, the power of the offset dual light sources is 300W, and the wavelength is 200nm to 800nm.
In one embodiment of the present invention, in step S2, the offset dual light sources are respectively disposed at positions offset by 30 ° to 60 ° on both sides of the organic pollutants.
In one embodiment of the invention, the current intensity of the offset dual light source is 10A-30A.
In one embodiment of the present invention, the present invention provides a method for preparing a composite cotton fabric, comprising the steps of:
(1) Preparing cuprous oxide nanoparticles: placing a piece of foam copper with the specification of 2.5cm multiplied by 3.5cm multiplied by 0.35cm into ethanol solution for ultrasonic cleaning for 10 min-15 min to remove organic residues on the foam copper, then heating in an oven at 370-390 ℃ for 170 min-180 min to induce the foam copper to be oxidized, then soaking the foam copper into 80 mL-100mL of 3.5mol/L dilute hydrochloric acid at room temperature for 5 min-10 min to prepare CuCl 2 Then washed with deionized water to make CuCl 2 Alkaline hydrolysis in deionized water to form Cu 2 O nanocubes, then immersing them in deionized water and sonicating for 10-20 s, and shaking the vessel for 1min 2 O is dissolved by residual Cl-in water and dissolved O 2 And further oxidizing and hydroxylating to obtain cuprous oxide nanocubes with copper oxychloride protective coatings on the surfaces, finally centrifuging the cuprous oxide nanocubes at the speed of 2700 r/min-2800 r/min, collecting the cuprous oxide nanocubes, and drying the cuprous oxide nanocubes in a vacuum drying oven at the temperature of 65 ℃ for 12 hours to prepare the cuprous oxide nanoparticles.
(2) Preparing iron oxyhydroxide nanoparticles: preparing an alkaline solution with the pH value of 12-13 by using sodium hydroxide, dissolving 0.2-1.75 g of ferric chloride into 100mL of the above solution, stirring for 3-5 min to fully dissolve the ferric chloride, heating the solution in a water bath kettle for 2.5h, centrifuging the solution at the speed of 2700-2800 r/min, collecting iron oxyhydroxide particles, washing the iron oxyhydroxide particles by using clear water, and finally drying the iron oxyhydroxide particles in a 65-DEG C vacuum drying oven for 12h to prepare the iron oxyhydroxide nanoparticles.
(3) Pretreating cotton fabric, namely putting 1g to 1.2g of the cotton fabric into a solution containing 180mL to 200mL of 12 percent urea, 7 percent sodium hydroxide and 81 percent distilled water, and placing the solution in a low-temperature constant-temperature reaction bath at the temperature of-10 ℃ to-15 ℃ for 3h to 3.5h.
(4) Dissolving 0.0375 g-1.25 g of cuprous oxide nanoparticles and 0.0375 g-1.25 g of iron oxyhydroxide particles in 250mL of deionized water to prepare a cuprous oxide-iron oxyhydroxide solution; rolling the pretreated cotton fabric for 1-2 times by using a rolling device to ensure that the cotton fabric is uniform and flat, wherein the rolling residual rate is 80-85%; and (3) soaking the rolled cotton fabric in the prepared solution for 25-35 min to enable the cotton fabric to be fully adsorbed, taking out the cotton fabric, and drying the cotton fabric in a drying oven at 60 ℃ for 2h to finally prepare the cuprous oxide-ferric hydroxide composite cotton fabric.
In one embodiment of the invention, a method of photocatalytic organic pollutants:
the prepared cuprous oxide-iron oxyhydroxide composite cotton fabric is cut into small pieces of 1cm multiplied by 1cm, the small pieces are put into 50mL of Methyl Orange (MO) solution with the concentration of 5mg/L, the mixture is stirred for 30min under the condition of keeping out of the sun, so that the adsorption-desorption balance is achieved, and then 0.2mL of hydrogen peroxide solution is dripped. Stirring the treated MO solution for 1h under an offset double light source, selecting two xenon lamps with power of 300W and wavelength of 200-800 nm from the offset double light source, respectively arranging the xenon lamps in the range of 30-60 degrees on the left side and the right side of the organic pollutant, respectively selecting 10A-30A for the xenon lamp light source intensity, taking out 3mL of MO solution after stirring for 10min, centrifuging to obtain supernatant, measuring the absorbance of the supernatant at the maximum absorption wavelength of 462nm by using an ultraviolet spectrophotometer, and calculating the degradation rate
Wherein C is t Denotes the absorbance of the methyl orange solution at t, C 0 Represents the initial absorbance of the methyl orange solution.
The technical principle of the invention is as follows:
the cuprous oxide prepared by the invention is coated with a layer of Cu on the surface 2 (OH) 3 Cl protective film which can achieve redox reversibility mainly due to Cu 2 Reduction of O to CO in water by visible light 2 ，Cu 2 O and Cu 2 (OH) 3 The redox-active surface consisting of Cl is influenced by Lewis pairs, cu 2+ As Lewis acid, OH as Lewis base, heterolysis of H 2 The water is discharged to form [ O ]]Vacancy of Cu 2 O is covered with H 2 Reduction to Cu, [ O ]]Vacancy and Cu in CO 2 Driven to produce CO and Cu 2 And O, realizing photocatalytic reaction circulation.
The n-type semiconductor and cuprous oxide are mixed to prepare the inverse heterojunction catalyst, and the surface of the cuprous oxide is modified to improve the activity and stability of the catalyst. The cubic cuprous oxide has two opposite built-in electric fields, and a strong driving force can be provided by using the offset double light sources, so that the photoproduction electron-hole pairs can be separated more effectively, and the photocatalysis efficiency is improved.
The technical scheme of the invention has the following advantages:
(1) The invention provides a cuprous oxide-iron oxyhydroxide composite cotton fabric photocatalyst, wherein cuprous oxide is a p-type semiconductor, the band gap is only 2.0eV, the larger absorption wavelength can be responded, iron oxyhydroxide is an n-type semiconductor, the band gap is 2.6eV, and the p-Cu obtained by the invention has stronger redox capability 2 The O/n-FeOOH heterojunction photocatalyst realizes effective separation of photo-generated electron-hole pairs, improves the oxidation-reduction effect, can respond to a large-range visible spectrum, and the hydrogen peroxide dropwise added in the photocatalytic test process has strong oxidizing property and can improve the photocatalytic activity, thereby obtaining excellent photocatalytic efficiency.
(2) The cuprous oxide nano-particle prepared by the invention has the surface provided with the cupric oxychloride protective coating, and the coating can make the oxidation reduction reaction of the cuprous oxide become reversible, so that the cuprous oxide has high photocatalytic activity and stability.
(3) According to the invention, cotton fabrics are used as photocatalyst substrates, the cotton fabrics are easily and firmly loaded with a large amount of nano materials due to the staggered warp and weft structures of the cotton fabrics, and the internal gaps of the fibers can be enlarged by carrying out alkali treatment on the cotton fabrics, so that the characteristic can be improved. The cotton fabric has excellent wet strength, stable property in water, difficult breakage and easy recovery.
(4) The invention provides a method for degrading organic matters of cuprous oxide-hydroxyl ferric oxide composite cotton fabric under an offset double light source, wherein the offset double light source can provide a directional driving force for charge separation, nano-cubic cuprous oxide particles have symmetrical structures and sharp edges and can reduce light scattering from other particles to the maximum extent, and the directional driving force can separate photo-generated electrons and holes from space efficiently, improve the charge separation rate of a photocatalyst and increase the photocatalytic efficiency.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is a flow chart of the preparation of cuprous oxide-iron oxyhydroxide composite cotton fabric;
FIG. 2 is a graph showing the photocatalytic degradation rate data of S1 to S5 in the present invention;
FIG. 3 is a graph showing the photocatalytic kinetics of S1 to S5 in the present invention;
description of reference numerals: the method comprises the following steps of preparing a pure cotton fabric 1, a low-temperature constant-temperature reaction bath 2, an ethanol solution 3, an alkaline solution 4, a rolling device 5, a rolling press roller 6, a waste liquid collecting tank 7, a soaking device 8, a cuprous oxide-iron oxyhydroxide solution 9, a forced air drying oven 10 and a cuprous oxide-iron oxyhydroxide composite cotton fabric 11, wherein the pure cotton fabric is prepared by the steps of washing, drying and drying.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
(1) Preparation method of cuprous oxide-iron oxyhydroxide composite cotton fabric
Preparing cuprous oxide nanoparticles: putting a piece of foam copper with the specification of 2.5cm multiplied by 3.5cm multiplied by 0.35cm into an ethanol solution, carrying out ultrasonic cleaning for 11min to remove organic residues on the foam copper, heating for 170min in an oven at 370 ℃ to induce the foam copper to be oxidized, then soaking the foam copper into 80mL of 3.5mol/L dilute hydrochloric acid at room temperature for 5min, then cleaning the foam copper with deionized water, soaking the foam copper into the deionized water and carrying out ultrasonic cleaning for 10s, shaking the container for 1min to obtain a cuprous oxide nanocube with a copper oxychloride protective coating on the surface, finally centrifuging the cuprous oxide nanocube at 2700r/min, collecting the cuprous oxide nanocube, and drying the cuprous oxide nanocube in a vacuum drying box at 65 ℃ for 12h to prepare the cuprous oxide nanoparticles.
(2) Preparation of iron oxyhydroxide nanoparticles: preparing an alkaline solution with the pH value of 12 by using sodium hydroxide, dissolving 0.2g of ferric chloride into 100mL of the solution, stirring for 3-5 min to fully dissolve the ferric chloride, heating the solution in a water bath kettle for 2.5h, centrifuging the solution at the speed of 2700r/min, collecting ferric hydroxide particles, cleaning the ferric hydroxide particles by using clear water, and finally drying the ferric hydroxide particles in a 65-DEG C vacuum drying box for 12h to prepare the ferric hydroxide nano-particles.
(3) Pretreating cotton fabrics: 1g of cotton fabric was put into 180mL of a mixed solution containing 12% urea, 7% sodium hydroxide and 81% distilled water, and the mixture was placed in a low-temperature constant-temperature reaction bath. Setting the temperature at-10 ℃ for 2h to obtain the pretreated cotton fabric.
(4) Dissolving 0.125g of cuprous oxide nanoparticles and 0.125g of iron oxyhydroxide nanoparticles in 250mL of deionized water to prepare a cuprous oxide-iron oxyhydroxide solution; rolling the pretreated cotton fabric for 1 time by a rolling device to ensure that the cotton fabric is uniform and flat, wherein the rolling residual rate is 85%; and (3) soaking the rolled cotton fabric in the prepared solution for 25min to enable the cotton fabric to be fully adsorbed, taking out the cotton fabric, and drying the cotton fabric in a drying oven at 60 ℃ for 2h to finally prepare the cuprous oxide-ferric hydroxide composite cotton fabric.
(5) Photocatalytic organic pollutants
The prepared cuprous oxide-iron oxyhydroxide composite cotton fabric is cut into small pieces of 1cm multiplied by 1cm, the small pieces are put into 50mL of Methyl Orange (MO) solution with the concentration of 5mg/L, the mixture is stirred for 30min under the condition of keeping out of the sun, so that the adsorption-desorption balance is achieved, and then 0.2mL of hydrogen peroxide solution is dripped. And (2) placing the treated MO solution under an offset double light source, stirring for 1h, selecting two xenon lamps with power of 300W and wavelength of 200-800 nm from the offset double light source, respectively arranging the xenon lamps at positions offset by 30 degrees on the left side and the right side of the organic pollutant, respectively selecting 10A and 20A for xenon lamp current, taking out 3mL of MO solution after stirring for 10min, centrifuging to obtain supernatant, measuring absorbance in the supernatant at the position with maximum absorption wavelength of 462nm by using an ultraviolet spectrophotometer, and calculating the degradation rate, wherein the degradation rate is recorded as S1.
Example 2
(1) Preparing cuprous oxide nanoparticles: putting a piece of foam copper with the specification of 2.5cm multiplied by 3.5cm multiplied by 0.35cm into an ethanol solution, carrying out ultrasonic cleaning for 15min to remove organic residues on the foam copper, heating for 180min in an oven at 390 ℃ to induce the foam copper to be oxidized, then soaking the foam copper into 100mL of 3.5mol/L dilute hydrochloric acid at room temperature for 10min, then cleaning the foam copper with deionized water, soaking the foam copper into the deionized water and carrying out ultrasonic cleaning for 20s, shaking the container for 1min to obtain a cuprous oxide nanocube with a copper oxychloride protective coating on the surface, finally centrifuging the cuprous oxide nanocube at the speed of 2800r/min, collecting the cuprous oxide nanocube, and drying for 12h in a vacuum drying box at 65 ℃ to obtain the cuprous oxide nanoparticles.
(2) Preparation of iron oxyhydroxide nanoparticles: preparing an alkaline solution with the pH value of 13 by using sodium hydroxide, dissolving 1.75g of ferric chloride into 100mL of the solution, stirring for 5min to fully dissolve the ferric chloride, heating the solution in a water bath kettle for 2.5h, centrifuging the solution at the speed of 2750r/min, collecting iron oxyhydroxide particles, cleaning the iron oxyhydroxide particles by using clear water, and finally drying the iron oxyhydroxide particles in a 65-DEG C vacuum drying oven for 12h to prepare the iron oxyhydroxide nanoparticles.
(3) Pretreating cotton fabrics: 1.2g of cotton fabric was put into a mixed solution containing 200mL of 12% urea, 7% sodium hydroxide, and 81% distilled water, and placed in a low-temperature constant-temperature reaction bath. Setting the temperature at-15 ℃ and the time at 2.5h to obtain the pretreated cotton fabric.
(4) Dissolving 0.05g of cuprous oxide nanoparticles and 0.2g of iron oxyhydroxide nanoparticles in 250mL of deionized water to prepare a cuprous oxide-iron oxyhydroxide solution; rolling the pretreated cotton fabric for 2 times by using a rolling device to ensure that the cotton fabric is uniform and flat, wherein the rolling allowance is 80%; and (3) soaking the rolled cotton fabric in the prepared solution for 30min to enable the cotton fabric to be fully adsorbed, taking out the cotton fabric, and drying the cotton fabric in a drying oven at 60 ℃ for 2h to finally prepare the cuprous oxide-ferric hydroxide composite cotton fabric.
(5) Photocatalytic organic pollutants
The prepared cuprous oxide-iron oxyhydroxide composite cotton fabric is cut into small pieces of 1cm multiplied by 1cm, the small pieces are put into 50mL of Methyl Orange (MO) solution with the concentration of 5mg/L, the mixture is stirred for 30min under the condition of keeping out of the sun, so that the adsorption-desorption balance is achieved, and then 0.2mL of hydrogen peroxide solution is dripped. And (3) placing the treated MO solution under an offset double-light source, stirring for 1h, selecting two xenon lamps with power of 300W and wavelength of 200nm-800nm from the offset double-light source, respectively arranging the xenon lamps at positions deviated from 60 degrees on the left side and the right side of the organic pollutant, respectively selecting 15A and 30A for xenon lamp current, taking out 3mL of MO solution after stirring for 10min, centrifuging to obtain supernatant, measuring absorbance of the supernatant at the position with maximum absorption wavelength of 462nm by using an ultraviolet spectrophotometer, and calculating the degradation rate, wherein the degradation rate is recorded as S2.
Example 3
This example is similar to the preparation method of example 2, except that 0.1g of cuprous oxide nanoparticles and 0.15g of iron oxyhydroxide nanoparticles were taken in step (4), and the degradation rate thereof was recorded as S3.
Example 4
(1) The preparation method of the cuprous oxide nanoparticles comprises the following steps: putting a piece of foam copper with the specification of 2.5cm multiplied by 3.5cm multiplied by 0.35cm into an ethanol solution, carrying out ultrasonic cleaning for 13min to remove organic residues on the foam copper, heating for 175min in an oven at 380 ℃ to induce the foam copper to be oxidized, then soaking the foam copper into 90mL of 3.5mol/L dilute hydrochloric acid at room temperature for 8min, then cleaning the foam copper with deionized water, soaking the foam copper into the deionized water and carrying out ultrasonic cleaning for 15s, shaking the container for 1min to obtain a cuprous oxide nanocube with a copper oxychloride protective coating on the surface, finally centrifuging the cuprous oxide nanocube at 2700r/min, collecting the cuprous oxide nanocube, and drying for 2h in a vacuum drying box at 65 ℃ to obtain the cuprous oxide nanoparticles.
(2) Preparation of iron oxyhydroxide nanoparticles: preparing an alkaline solution with the pH value of 12.5 by using sodium hydroxide, dissolving 0.75g of ferric chloride into 100mL of the solution, stirring for 3-5 min to fully dissolve the ferric chloride, heating the solution in a water bath kettle for 2.5h, centrifuging the solution at the speed of 2700r/min, collecting ferric oxyhydroxide particles, cleaning the ferric oxyhydroxide particles by using clear water, and finally drying the ferric oxyhydroxide particles in a 65-DEG C vacuum drying oven for 2h to prepare the ferric oxyhydroxide nanoparticles.
(3) Pretreating cotton fabrics: putting 1.1g of cotton fabric into a mixed solution containing 190mL of 12% urea, 7% sodium hydroxide and 81% distilled water, and placing the mixed solution in a low-temperature constant-temperature reaction bath at the temperature of-12 ℃ for 2.5 hours to obtain the pretreated cotton fabric.
(4) Dissolving 0.15g of cuprous oxide nanoparticles and 0.1g of iron oxyhydroxide nanoparticles in 250mL of deionized water to prepare a cuprous oxide-iron oxyhydroxide solution; rolling the pretreated cotton fabric for 2 times by using a rolling device to ensure that the cotton fabric is uniform and flat, wherein the rolling allowance is 80%; and (3) soaking the rolled cotton fabric in the prepared solution for 30min to enable the cotton fabric to be fully adsorbed, taking out the cotton fabric, and drying the cotton fabric in a drying oven at 60 ℃ for 2h to finally prepare the cuprous oxide-ferric hydroxide composite cotton fabric.
(5) Photocatalytic organic pollutants
The prepared cuprous oxide-iron oxyhydroxide composite cotton fabric is cut into small pieces of 1cm multiplied by 1cm, the small pieces are put into 50mL of Methyl Orange (MO) solution with the concentration of 5mg/L, the mixture is stirred for 30min under the condition of keeping out of the sun, so that the adsorption-desorption balance is achieved, and then 0.2mL of hydrogen peroxide solution is dripped. And (3) placing the treated MO solution under an offset double-light source, stirring for 1h, selecting two xenon lamps with power of 300W and wavelength of 200nm-800nm from the offset double-light source, respectively arranging the xenon lamps at positions which are offset by 45 degrees on the left side and the right side of the organic pollutant, respectively selecting 10A and 30A for xenon lamp current, taking out 3mL of MO solution after stirring for 10min, centrifuging to obtain supernatant, measuring absorbance of the supernatant at the position with maximum absorption wavelength of 462nm by using an ultraviolet spectrophotometer, and calculating the degradation rate, wherein the degradation rate is recorded as S4.
Example 5
This example is similar to the preparation method of example 4, except that 0.2g of cuprous oxide nanoparticles and 0.05g of iron oxyhydroxide nanoparticles were taken in step (4), and the degradation rate thereof was recorded as S5.
Comparative example 1
The comparative example is high-index crystal face Cu 2 O photocatalyst, firstly weighing 250mg of CuSO 4 ·5H 2 O was added to 60mL of ultrapure water, and CuSO was made by sonication 4 ·5H 2 Completely dispersing O, putting into a stirrer, fully stirring and mixing, transferring into a water bath kettle after stirring, setting the reaction temperature to 65 ℃, sequentially adding 20mL of 10mol/L potassium hydroxide aqueous solution and 10mL of 0.1mol/L ascorbic acid aqueous solution during stirring, fully reacting for 10min, immediately filtering and separating after oxidation-reduction reaction is finished, and drying in vacuum for 24h to obtain the high-index crystal face Cu efficiently utilizing visible light 2 O photocatalyst (50-Facet Cu) 2 O)。
Weighing 30mg of 50-Facet Cu 2 Placing the O photocatalyst into a 250mL jacketed bottle, adding 100mL of 15mg/L methyl orange aqueous solution, and adding a stirrer to uniformly disperse the catalyst in the liquid; using a 300W xenon lamp provided with an AM1.5 optical filter to simulate sunlight to constantly illuminate the solution in the quartz reactor, connecting the reactor with a constant temperature system, maintaining the temperature of the reaction system at 25 ℃, and carrying out photocatalytic degradation reaction for 1h; after the reaction is finished, the catalyst is separated from the filtrate by a needle filter, the content of methyl orange in the obtained filtrate is detected by an ultraviolet spectrophotometer, and the catalytic degradation effect is 67.47%.
Comparative example 2
The comparative example is a hollow microbead-supported cerium or nitrogen-doped cuprous oxide photocatalyst:
(1) 152mL and 0.3mol of 0.3mol/L copper sulfate pentahydrate solution are measured152mL of anhydrous sodium sulfite solution, 0.1485g of cerium nitrate, 0.0135g of urea, 40mL of HAc-NaA solution buffer solvent with the pH value of 6, and 5g of cenospheres taking alumina, silica and ferric oxide as main components; the diameter of the hollow micro-bead is 50-100 mu m, wherein the SiO is 2 52 to 60 percent of Al 2 O 3 16-36 percent of Fe 2 O 3 The mass percentage of the component (A) is 2.28-14.63%.
(2) Pouring 1/2 of the copper sulfate pentahydrate solution in the step one into a beaker, doping cerium nitrate into the beaker to serve as a solution a, pouring the remaining 1/2 of the copper sulfate pentahydrate solution into the beaker, doping urea into the beaker to serve as a solution b, pouring 1/2 of anhydrous sodium sulfite solution and 1/2 of buffer solvent into the beaker to serve as a solution c, and pouring the remaining 1/2 of anhydrous sodium sulfite solution and 1/2 of buffer solvent into the beaker to serve as a solution d; heating and stirring the solution a, the solution b, the solution c and the solution d in a water bath at 80 ℃ in a water bath, and heating the solution c and the solution d in a sealed state.
(3) Respectively adding 0.25g of hollow microspheres into the solution a and the solution b, then quickly pouring the solution c into the solution a, quickly pouring the solution d into the solution b, continuously carrying out sealed stirring and heating in a water bath for 20min to generate brick red precipitate, aging for 40min, then carrying out sealed heating and stirring for 20min, aging for 40min, carrying out suction filtration, and drying the solid phase in an oven at the temperature of 80 ℃ for 4h to obtain the hollow microsphere loaded cerium-doped cuprous oxide photocatalyst and the hollow microsphere loaded nitrogen-doped cuprous oxide photocatalyst. The doping amount of cerium ions in the cerium-doped cuprous oxide is 1.5%. The doping amount of nitrogen atoms in the nitrogen-doped cuprous oxide is 2%.
(4) Preparing 200mL of methyl orange solution with the concentration of 10mg/L, taking 2 parts of methyl orange solution, each of which is 100mL, pouring the methyl orange solution into beakers, placing the beakers on a magnetic stirrer, placing the beakers in a dark place, respectively adding 0.2g of hollow microsphere loaded cerium-doped cuprous oxide photocatalyst and 0.2g of hollow microsphere loaded nitrogen-doped cuprous oxide photocatalyst into the second beaker, stirring and reacting the beakers in the dark place for 30min, taking supernatant, transferring the supernatant to natural light, starting degradation, taking samples every 30min, sampling for 5 times in total, placing the obtained samples into a high-speed centrifuge for centrifugation for 5min, taking the supernatant to test the concentration of methyl orange, and degrading the degradation rate of the hollow microsphere-loaded cuprous oxide photocatalyst by 1h to be about 53.37%.
Comparative example 3
The comparative example is a sea urchin-like titanium dioxide/cuprous oxide composite material, and firstly, the sea urchin-like titanium dioxide is prepared: 5mL of ethylene glycol and 10mL of H 2 O and 5mL of 8mg/mL PVP are mixed and stirred for 1h, meanwhile, 0.5mL of isopropyl titanate (TTIP) is added into 1mL of 0.1mol/L HCl solution to be mixed, then the two are mixed and stirred to react for 2h, the mixture is transferred into a polytetrafluoroethylene reaction kettle, hydrothermal is carried out at the constant temperature of 150 ℃ for 24h, then washing is carried out for 3 times, drying is carried out in the air atmosphere of 80 ℃, and then calcining is carried out at the temperature of 400 ℃ for 1h, so that the urchin-like titanium dioxide is obtained.
Secondly, preparing the sea urchin-like titanium dioxide/cuprous oxide composite material: 70mg of Cu (Ac) 2 ·H 2 O、100mg EDTA、50mL H 2 O and 380mg echinoid-like titanium dioxide are mixed and stirred for 2h, then 20mLNaOH is added and stirred for reaction for 30min, then 0.045g CTAB is added and stirred for 20min, then 10mL 0.04g/mL ascorbic acid is added and stirred for reaction for 20min, and finally the echinoid-like titanium dioxide/cuprous oxide composite material is obtained after 3 times of washing and heating in a vacuum oven at 60 ℃ for 12 h.
The prepared sea urchin-like titanium dioxide/cuprous oxide composite material is used for catalyzing and degrading methyl orange, and the degradation rate of the methyl orange in 60min under the irradiation of visible light reaches 58.22%.
Comparative example 4
In the comparative example, when a photocatalytic experiment was performed, a xenon lamp was placed right above an organic dye, the current of the xenon lamp was selected to be 30A, and other parameters and processes were the same as those in example 3. Through detection, the degradation rate of methyl orange at 60min reaches 78.3%.
Test example 1
The degradation rate of the cuprous oxide-iron oxyhydroxide composite cotton fabric on organic pollutants, prepared in examples 1 to 5, is shown in table 1 and fig. 2.
TABLE 1 degradation rate of methyl orange by different composite cotton fabrics
As can be seen from the table 1 and the figure 2, the cuprous oxide-iron oxyhydroxide composite cotton fabric has a high photocatalytic effect, and the degradation rate of the cuprous oxide-iron oxyhydroxide composite cotton fabric to methyl orange at 60min is more than 82% and can reach 97.50% at most.
FIG. 3 is a graph of the photocatalytic kinetics of examples 1 to 5, and it can be seen from FIG. 3 that the photocatalytic process conforms to a first order kinetic formula, the slope of which can represent the photocatalytic efficiency, and the larger the slope, the higher the photocatalytic efficiency; the slopes of S1 to S5 are respectively: 0.028, 0.049, 0.064, 0.056 and 0.053. Wherein the slope of S3 is 0.064, the slope of S1 is 0.028, and it can be seen that the photocatalytic efficiency of S3 is 2.3 times that of S1.
Test example 2
The degradation rates of organic pollutants by the materials prepared in comparative examples 1 to 4 and example 3 are shown in table 2.
TABLE 2 degradation rates of different materials for organic contaminants
As can be seen from Table 2, the method for degrading organic pollutants by the cuprous oxide-iron oxyhydroxide composite cotton fabric under the off-normal double light source has higher catalytic activity, and the degradation rate reaches 97.50%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. The preparation method of the composite cotton fabric is characterized by comprising the following steps:
(1) Dissolving cuprous oxide nanoparticles and iron oxyhydroxide nanoparticles in water to obtain a cuprous oxide-iron oxyhydroxide solution;
(2) And (2) putting the pretreated cotton fabric into the cuprous oxide-iron oxyhydroxide solution obtained in the step (1) for impregnation to obtain the composite cotton fabric.
2. The preparation method according to claim 1, wherein in the step (1), the cuprous oxide nanoparticles are prepared by:
and (3) putting the foamy copper into an alcohol solution, heating, then soaking in an acid solution, and performing ultrasonic vibration to obtain the cuprous oxide nanoparticles.
3. The method according to claim 1, wherein in the step (1), the iron oxyhydroxide nanoparticles are prepared by:
and mixing and heating ferric salt and an alkaline solution, and carrying out solid-liquid separation to obtain a solid phase to obtain the iron oxyhydroxide nanoparticles.
4. The preparation method according to claim 1, wherein in the step (1), the mass ratio of the cuprous oxide nanoparticles to the iron oxyhydroxide nanoparticles is 1:0.25 to 1:4.
5. the method according to claim 1, wherein in the step (2), the step of pretreating:
immersing the cotton fabric into an alkaline solution containing urea, and carrying out alkaline treatment at the temperature of minus 10 ℃ to minus 15 ℃ to obtain the pretreated cotton fabric.
6. A composite cotton fabric obtained by the preparation method according to any one of claims 1 to 5.
7. Use of a composite cotton fabric according to claim 6 for the degradation of organic contaminants.
8. The application according to claim 7, characterized in that the method of application is implemented by the following steps:
s1, adding the prepared composite cotton fabric into organic pollutants, stirring in a dark condition, adding a hydrogen peroxide solution, and mixing to obtain a mixed solution;
and S2, placing the mixed solution obtained in the step S1 under a deviation double light source, stirring for reaction, detecting the light absorption intensity of the solution obtained after the reaction, and calculating the degradation rate of the organic pollutants.
9. The use according to claim 8, wherein in step S2, the wavelength of the offset dual light source is 200nm to 800nm.
10. The use according to claim 8, wherein in step S2, the offset dual light sources are respectively disposed at positions offset by 30 ° to 60 ° on both sides of the organic pollutants.
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