CN113275011A - Preparation method of cuprous oxide photocatalyst with flower-ball-shaped multi-stage structure - Google Patents
Preparation method of cuprous oxide photocatalyst with flower-ball-shaped multi-stage structure Download PDFInfo
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 95
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 23
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 12
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 12
- 230000001580 bacterial effect Effects 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 239000002244 precipitate Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 230000015556 catabolic process Effects 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 9
- 238000006731 degradation reaction Methods 0.000 claims description 9
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 235000001727 glucose Nutrition 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 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 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- -1 hydroxide ions Chemical class 0.000 claims description 3
- 241000191967 Staphylococcus aureus Species 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims 1
- 229960003280 cupric chloride Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 239000003513 alkali Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 7
- 241000894006 Bacteria Species 0.000 abstract description 6
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 abstract description 3
- 239000005750 Copper hydroxide Substances 0.000 abstract description 3
- 229910001956 copper hydroxide Inorganic materials 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000002585 base Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000009630 liquid culture Methods 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000012880 LB liquid culture medium Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910000365 copper sulfate Inorganic materials 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 230000032683 aging Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000003501 co-culture Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229910018292 Cu2In Inorganic materials 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 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 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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Abstract
本发明涉及一种花球状多级结构的氧化亚铜光催化剂的制备方法。本发明首先将含铜溶液在水浴中进行高速磁力搅拌混合时加入碱液，然后向混合溶液中加入还原剂继续反应一段时间，接着经离心、洗涤、收集反应后的产物并分散于LB液体培养基中，加入菌液后移置恒温摇床内，共培养处理1～4天，最后得到了花球状多级结构的氧化亚铜。本发明方法采用不同的铜源作为前驱体，利用抗坏血酸的还原作用，将氢氧化铜沉淀还原得到氧化亚铜，通过引入细菌与氧化亚铜直接接触、蚀刻而实现对氧化亚铜沉淀形貌的调控。该材料在有机污染物光催化降解中表现出优异的催化活性。
The invention relates to a preparation method of a cuprous oxide photocatalyst with a curd-shaped multi-level structure. In the present invention, alkali solution is firstly added to the copper-containing solution during high-speed magnetic stirring and mixing in a water bath, then a reducing agent is added to the mixed solution to continue the reaction for a period of time, and then the reaction product is centrifuged, washed, collected and dispersed in LB liquid culture After adding the bacterial liquid to the base, the bacteria solution was placed in a constant temperature shaker for co-cultivation for 1 to 4 days, and finally cuprous oxide with a curd-shaped multi-level structure was obtained. The method of the invention adopts different copper sources as precursors, utilizes the reduction effect of ascorbic acid, and reduces the copper hydroxide precipitation to obtain cuprous oxide. regulation. The material exhibits excellent catalytic activity in the photocatalytic degradation of organic pollutants.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a preparation method of a cuprous oxide photocatalyst with a flower-ball-shaped multi-stage structure.
Background
Cuprous oxide is a typical p-type semiconductor, the forbidden band width is 2-2.2 eV, visible light is well absorbed, and the material source is wide, cheap and easy to obtain, so that the cuprous oxide has a wide application prospect in the fields of optical/electric devices, gas-sensitive materials, biological antibiosis, marine antifouling, photocatalysis and the like. Researches show that cuprous oxide materials with different morphologies have different physical and chemical properties, wherein cuprous oxide with a multilevel structure often shows higher catalytic activity due to the existence of high-activity crystal faces and rich grain boundaries. Therefore, the synthesis of cuprous oxide rich in a limited space is the focus of research.
At present, the methods for preparing cuprous oxide with various morphological structures are various, and generally divided into a solid-phase synthesis method, a liquid-phase synthesis method, an electrochemical method and a gas-phase synthesis method; and, using a capping agent such as SDS, CTAB or PEG, successfully preparing the monodisperse Cu with adjustable size by a liquid phase reduction method2And (3) O nanocubes. Patent document CN101041456A discloses a "preparation method of cuprous oxide hollow nanocubes", which takes a cluster formed by polyvinylpyrrolidone and sodium dodecyl sulfate as a soft template and hydrazine hydrate as a reducing agent to reduce copper ions to obtain a cuprous oxide hollow material; patent document CN 103466681a discloses "a method for preparing graded spherical cuprous oxide hollow nanoparticles", which is to use acetate as a stabilizer and hydrazine hydrate as a reducing agent to prepare graded spherical cuprous oxide hollow nanoparticles; disclosed in patent document CN 108910933A "A cuprous oxide nano material preparation method and its hydrogen evolution performance, adopt the gas phase reduction method, regard ethanediol, diethylene glycol as reducing agent, the copper-based material is the copper source, has prepared the cuprous oxide of the particular topography under the inert atmosphere of certain temperature successfully; patent document CN 105803500A discloses a method for preparing petal-shaped cuprous oxide by using TiO2the/ITO electrode is used as an anode, the conductive glass is used as a cathode, the copper acetate is used as a copper source, and the petaloid cuprous oxide is obtained by deposition under the irradiation of ultraviolet light.
The method adopts different copper sources as precursors, utilizes the reduction action of a reducing agent-ascorbic acid to reduce the copper hydroxide precipitate to obtain cuprous oxide, and realizes the regulation and control of the morphology of the cuprous oxide precipitate by introducing bacteria to be in direct contact with the cuprous oxide and etching, thereby finally obtaining the cuprous oxide with a flower-ball-shaped multilevel structure.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the preparation method for preparing the spherical cuprous oxide with the multilevel structure, which has the advantages of short process flow, simple operation and low cost. The method utilizes ascorbic acid to reduce copper hydroxide in a liquid phase to obtain cuprous oxide, and the cuprous oxide with a flower-ball-shaped multilevel structure is finally obtained by introducing bacteria to etch the cuprous oxide.
The invention has the significance of providing a novel high-efficiency and stable photocatalytic material which can be excited by visible light and has very good activity of photocatalytic degradation of organic substances, and meanwhile, the preparation process is simple and convenient and the cost is low.
In order to solve the technical problems, the technical scheme provided by the invention comprises the following steps:
step (1): adding alkali liquor into the aqueous solution containing the divalent copper salt while carrying out high-speed magnetic stirring and mixing in a water bath, wherein the molar ratio of copper ions to hydroxyl ions in the mixed copper solution is 1 (30-40);
step (2): adding a reducing agent (preferably an ascorbic acid solution) into the mixed solution in the step (1), continuously reacting for 60min, centrifuging, washing and collecting precipitates;
and (3): re-dispersing the precipitate in the step (2) in an LB liquid culture medium, adding a bacterial liquid, and placing the mixture in a constant temperature shaking table for reaction for 1-4 days; the temperature is set to 37 ℃, and the rotating speed is 200 r/min;
and (4): after completion of the culture, centrifugation and washing were carried out, and the precipitate was collected and dried.
The method firstly adopts a one-pot method to synthesize the cubic cuprous oxide, and then the cuprous oxide is dispersed in an LB liquid culture medium containing bacterial liquid and co-cultured for a period of time. And then, centrifuging, washing, collecting the precipitate and drying to obtain the cuprous oxide with the flower-ball-shaped multi-stage structure.
In the above preparation method, preferably, the copper salt includes copper chloride, copper sulfate, copper nitrate, and copper acetate.
In the preparation method, preferably, the alkali liquor comprises sodium hydroxide, ammonia water and potassium hydroxide; the reducing agent includes ascorbic acid, glucose, starch, and hydroxylamine hydrochloride.
In the preparation method, preferably, the concentration of the copper solution is 0.01-0.025 mol/L, the concentration of the alkali liquor is 0.01-0.04 mol/L, the concentration of the reducing agent is 0.06-0.6 mol/L, the reaction time is 30-60 min, and the reaction temperature is 25-50 ℃ to obtain the cubic cuprous oxide.
The copper salt is dissolved in water to form a uniform ionic solution, and Cu is added along with the alkali liquor2+With OH-Reaction to produce Cu (OH)2Adding a reducing agent to reduce and generate cubic Cu2And (4) precipitating O. Subsequently, Cu2In the process of co-culturing O and bacteria, the bacteria are adsorbed to the cubic Cu by coulomb force2Etching the (100) crystal face of O to obtain Cu with flower-ball-shaped multilevel structure2O。
In the preparation method, the particle size of the cuprous oxide with the prepared flower-ball-shaped multilevel structure is preferably 200-380 +/-10 nm.
Compared with the prior art, the invention has the advantages that:
1) the copper salt (copper sulfate, copper chloride, copper nitrate and copper acetate), the reducing agent (ascorbic acid, glucose, starch and hydroxylamine hydrochloride) and the solvent (water) adopted by the invention belong to common chemical reagents, and are cheap and easy to obtain.
2) The invention realizes the regulation and control of the shape of the cuprous oxide by bacteria without adding a surfactant, a template agent and the like.
3) The method has the advantages of simple process, mild reaction conditions, low cost and high yield of cuprous oxide, and is suitable for large-scale production.
Drawings
Fig. 1 is an X-ray powder diffraction (XRD) pattern of the cuprous oxide material of flower-ball-shaped multilevel structure prepared in example 1.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the cuprous oxide material of flower-ball-shaped multilevel structure prepared in example 1.
Fig. 3 is a Scanning Electron Microscope (SEM) image of the cuprous oxide material of flower-ball-shaped multilevel structure prepared in example 2.
Fig. 4 is a Scanning Electron Microscope (SEM) image of the cuprous oxide material of flower-ball-shaped multilevel structure prepared in example 3.
Fig. 5 is a Scanning Electron Microscope (SEM) image of the irregular flake cuprous oxide material prepared in example 4.
Fig. 6 is a graph showing the photocatalytic degradation rate of the cuprous oxide material with a flower-ball-shaped multi-stage structure prepared in example 1.
Detailed Description
For the purpose of facilitating an understanding of the objects, technical solutions and advantages of the present invention, the present invention will be described in further detail with reference to the accompanying drawings and examples, but the scope of the present invention is not limited to the specific examples below. Unless otherwise specified, the various reagents and materials used in the present invention may be commercially available products or products obtained by known methods.
A preparation method of a cuprous oxide photocatalyst with a flower-ball-shaped multi-stage structure comprises the following steps:
step (1): adding alkali liquor into the aqueous solution containing the divalent copper salt while carrying out high-speed magnetic stirring and mixing in a water bath, wherein the molar ratio of copper ions to hydroxyl ions in the mixed copper solution is 1 (30-40);
step (2): adding a reducing agent into the mixed solution obtained in the step (1), continuously stirring and reacting for 30-60 min at the reaction temperature of 25-50 ℃, and then centrifuging, washing and collecting precipitates;
and (3): re-dispersing the precipitate in the step (2) in an LB liquid culture medium, adding a bacterial liquid, and placing the mixture in a constant temperature shaking table for co-culture for 1-4 days; the temperature is set to 37 ℃, and the rotating speed is 200 r/min;
and (4): and after the culture is finished, centrifuging and washing, collecting and drying the precipitate to obtain cuprous oxide, thereby finishing the preparation of the cuprous oxide photocatalyst.
Preferably, the divalent copper salt in step (1) includes copper chloride, copper sulfate, copper nitrate and copper acetate.
Preferably, the concentration of the aqueous solution of the cupric salt in the step (1) is 0.01-0.025 mol/L.
Preferably, the temperature of the water bath in the step (1) is set to be 25-50 ℃, and the rotating speed of the magnetic stirring is 350-600 r/s.
Preferably, the alkali liquor in the step (1) comprises sodium hydroxide, ammonia water and potassium hydroxide, and the concentration of the alkali liquor is 0.01-0.04 mol/L.
Preferably, the reducing agent in the step (1) comprises ascorbic acid, glucose, starch and hydroxylamine hydrochloride, and the concentration of the reducing agent is 0.06-0.6 mol/L.
Preferably, the bacterial liquid in step (3) is gram-positive bacterium staphylococcus aureus (s.
Preferably, the prepared cuprous oxide is in a flower-ball-shaped multilevel structure.
Preferably, the particle size of the cuprous oxide prepared is 200-380 +/-10 nm.
The application of the cuprous oxide photocatalyst with the flower-ball-shaped multi-stage structure comprises the application of the cuprous oxide photocatalyst in the catalytic degradation of organic dyes, and the cuprous oxide photocatalyst has good photocatalytic degradation activity on methyl orange solution.
Example 1:
preparing 100mL of 0.01mol/L inorganic cupric salt (copper chloride, copper sulfate and copper nitrate) solution, controlling the water bath temperature to be 35 ℃, and uniformly mixing by magnetic stirring (the rotating speed is 350-600 r/s); thereafter, 20ml of 2.0M NaOH solution was added thereto, and stirring was continued for 30 min. To the above solution was added 10mL of 0.6M ascorbic acid and aging was continued for 3 h. Naturally cooling, centrifuging, washing with deionized water and ethanol for three times respectively, and drying the obtained solid sample at 60 ℃ for 12h to obtain the cubic cuprous oxide.
Step (2) the cuprous oxide prepared in the step (1) is dispersed in an LB liquid culture medium containing bacterial liquid and cultured for 4 days in a constant temperature shaking table (rotating speed: 200r/min) at 37 ℃; centrifuging, washing, collecting the precipitate, and drying at 60 ℃ for 12h to finally obtain the cuprous oxide product.
The X-ray diffraction pattern of the cubic cuprous oxide and cuprous oxide having a flower-sphere-like multilevel structure obtained in this example is shown in fig. 1, and the SEM pattern of the cuprous oxide having a flower-sphere-like multilevel structure is shown in fig. 2. X-ray diffraction analysis shows that the two products have strong diffraction peaks at 2 theta values of 29.5 degrees, 36.4 degrees, 42.2 degrees, 61.3 degrees, 73.5 degrees and 77.3 degrees, and all XRD spectrum diffraction peaks and Cu spectrum diffraction peaks2The O standard data (PDF #05-0667) were well matched and corresponded to the (110), (111), (200), (220), (311) and (222) plane crystal planes in this order. Thus, Cu was confirmed2And O crystal material. As can be seen from FIG. 2, the obtained cuprous oxide having a flower-ball-like multi-stage structure had a particle size of 380. + -.10 nm and a large specific surface area.
Example 2:
preparing 100mL of 0.01mol/L copper acetate solution, controlling the water bath temperature to be 35 ℃, and uniformly mixing by magnetic stirring (the rotating speed is 350-600 r/s); thereafter, 20ml of 2.0M NaOH solution was added thereto, and stirring was continued for 30 min. To the above solution was added 10mL of 0.6M ascorbic acid and aging was continued for 3 h. Naturally cooling, centrifuging, washing with deionized water and ethanol for three times respectively, and drying the obtained solid sample at 60 ℃ for 12h to obtain the cubic cuprous oxide.
Step (2) the cuprous oxide prepared in the step (1) is dispersed in an LB liquid culture medium containing bacterial liquid and cultured for 4 days in a constant temperature shaking table (rotating speed: 200r/min) at 37 ℃; centrifuging, washing, collecting the precipitate, and drying at 60 ℃ for 12h to finally obtain the cuprous oxide product.
The cubic cuprous oxide obtained in this example was slightly small in particle size and non-uniform in size, and the SEM image of the cuprous oxide obtained after the bacterial co-culture was as shown in fig. 3, and the cuprous oxide obtained had a porous flocculent structure.
Example 3:
preparing 100mL of 0.01mol/L inorganic divalent copper salt (copper chloride, copper sulfate and copper nitrate), controlling the temperature of a water bath to be 35 ℃, and uniformly mixing by magnetic stirring (the rotating speed is 350-600 r/s); thereafter, 20ml of 2.0M NaOH solution was added thereto, and stirring was continued for 30 min. To the above solution was added 10mL of 0.6M ascorbic acid and aging was continued for 3 h. Naturally cooling, centrifuging, washing with deionized water and ethanol for three times respectively, and drying the obtained solid sample at 60 ℃ for 12h to obtain the cubic cuprous oxide.
Step (2) the cuprous oxide prepared in the step (1) is dispersed in an LB liquid culture medium containing bacterial liquid and cultured for 2 days in a constant temperature shaking table (rotating speed: 200r/min) at 37 ℃; centrifuging, washing, collecting the precipitate, and drying at 60 ℃ for 12h to finally obtain the cuprous oxide product.
The SEM image of cuprous oxide obtained in this example is shown in fig. 4, and the obtained cuprous oxide is cubic, and the edge of the cuprous oxide is wrinkled, and the particle size is 380 ± 4 nm.
Example 4:
preparing 100mL of 0.01mol/L inorganic cupric salt (copper chloride, copper sulfate and copper nitrate) solution, controlling the water bath temperature to be 35 ℃, and uniformly mixing by magnetic stirring (the rotating speed is 350-600 r/s); thereafter, 20ml of 2.0M NaOH solution was added thereto, and stirring was continued for 30 min. To the above solution was added 10mL of 0.6M ascorbic acid and aging was continued for 3 h. Naturally cooling, centrifuging, washing with deionized water and ethanol for three times respectively, and drying the obtained solid sample at 60 ℃ for 12h to obtain the cubic cuprous oxide.
Step (2) the cuprous oxide prepared in the step (1) is dispersed in an LB liquid culture medium containing bacterial liquid and cultured for 8 days in a constant temperature shaking table (rotating speed: 200r/min) at 37 ℃; centrifuging, washing, collecting the precipitate, and drying at 60 ℃ for 12h to finally obtain the cuprous oxide product.
The SEM image of cuprous oxide obtained in this example is shown in fig. 5, and the obtained cuprous oxide is irregular and ultrathin flake.
The cuprous oxide material prepared in the above example was tested for catalytic activity. The photocatalytic activity of the sample was evaluated as the catalytic degradation efficiency of methyl orange solution (MO, 20mg/L) by a 500W xenon lamp simulating sunlight at room temperature. 10mg of the sample is weighed and dispersed in 50mL of methyl orange solution for dark reaction for 1h until equilibrium of adsorption and desorption is reached. Then, a photocatalytic experiment was performed every 30min to extract 1mL of the reaction solution. Next, the absorbance value of the solution was measured at a wavelength λ of 464nm with an ultraviolet-visible spectrophotometer, and the formula: percent (%) degradation of ═ Ct/C0×100％＝At/A0X 100% (wherein, C)tIs the concentration at a certain moment, C0At the starting concentration, AtIs the absorbance value at a certain time, A0Initial absorbance value), the degradation rate of methyl orange was calculated, and the catalytic activity results of the cuprous oxide material prepared in example 1 are shown in fig. 6.
The photocatalytic activity result shows that after 8 hours of photocatalytic reaction, the degradation efficiency of the cuprous oxide with the flower-ball-shaped multi-level structure prepared in the example 1 on MO can reach 63%; the degradation efficiency of the cuprous oxide with the porous flocculent structure prepared in the embodiment 2 on MO can reach 49.8%; the degradation efficiency of the cubic cuprous oxide with folded edges prepared in the embodiment 3 on MO can reach 47.48%; the degradation efficiency of the flaky cuprous oxide prepared in example 4 on MO can reach 15.14%. Therefore, the photocatalytic activity of the cuprous oxide can be effectively improved by changing the shape of the cuprous oxide.
Claims (10)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113441108A (en) * | 2021-08-20 | 2021-09-28 | 兰州交通大学 | Preparation method of modified attapulgite loaded nano zero-valent iron heavy metal adsorbent, product and application thereof |
| CN114471734A (en) * | 2022-01-19 | 2022-05-13 | 中国人民解放军联勤保障部队第九八九医院 | Preparation method and application of a visible light-responsive cuprous oxide/ZIF-8 heterojunction photocatalytic antibacterial material |
| CN115318290A (en) * | 2022-08-12 | 2022-11-11 | 同济大学 | A three-dimensional sea urchin-like structure Cu/Cu2O-Al2O3 nanocomposite material and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172104A (en) * | 2013-04-03 | 2013-06-26 | 浙江理工大学 | Preparation method of nano cuprous oxide |
| WO2015196866A1 (en) * | 2014-06-27 | 2015-12-30 | 江苏华东锂电技术研究院有限公司 | Method for preparing cuprous oxide |
-
2021
- 2021-05-10 CN CN202110506367.0A patent/CN113275011B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172104A (en) * | 2013-04-03 | 2013-06-26 | 浙江理工大学 | Preparation method of nano cuprous oxide |
| CN104030339A (en) * | 2013-04-03 | 2014-09-10 | 浙江理工大学 | Preparation method of cubic cuprous oxide nano material |
| WO2015196866A1 (en) * | 2014-06-27 | 2015-12-30 | 江苏华东锂电技术研究院有限公司 | Method for preparing cuprous oxide |
Non-Patent Citations (2)
| Title |
|---|
| BAO-GUANG MAO,ET AL: "Ultrasound-assisted synthesis of sea urchin-like Cu2O architectures", 《MATERIALS LETTERS》 * |
| YEHAO DENG,ET AL: "A generic in situ seed-mediated size-control method in the case of cuprous oxide nanocubes and their antibacterial activities", 《CRYSTENGCOMM》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113441108A (en) * | 2021-08-20 | 2021-09-28 | 兰州交通大学 | Preparation method of modified attapulgite loaded nano zero-valent iron heavy metal adsorbent, product and application thereof |
| CN114471734A (en) * | 2022-01-19 | 2022-05-13 | 中国人民解放军联勤保障部队第九八九医院 | Preparation method and application of a visible light-responsive cuprous oxide/ZIF-8 heterojunction photocatalytic antibacterial material |
| CN114471734B (en) * | 2022-01-19 | 2023-12-08 | 中国人民解放军联勤保障部队第九八九医院 | Preparation method and application of visible light response cuprous oxide/ZIF-8 heterojunction photocatalytic antibacterial material |
| CN115318290A (en) * | 2022-08-12 | 2022-11-11 | 同济大学 | A three-dimensional sea urchin-like structure Cu/Cu2O-Al2O3 nanocomposite material and its preparation method and application |
| CN115318290B (en) * | 2022-08-12 | 2023-11-03 | 同济大学 | A three-dimensional sea urchin-like structure Cu/Cu2O-Al2O3 nanocomposite material and its preparation method and application |
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