CN113209973A - ZnO-Cu2Preparation method and application of O-AC photocatalyst - Google Patents
ZnO-Cu2Preparation method and application of O-AC photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 94
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 36
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 36
- 239000004246 zinc acetate Substances 0.000 claims abstract description 36
- 229910003399 ZnO-Cu Inorganic materials 0.000 claims abstract description 33
- 239000010949 copper Substances 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000000987 azo dye Substances 0.000 claims abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 235000006408 oxalic acid Nutrition 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 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
- 230000001699 photocatalysis Effects 0.000 abstract description 22
- 238000007146 photocatalysis Methods 0.000 abstract description 20
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000011701 zinc Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 20
- 230000015556 catabolic process Effects 0.000 description 20
- 238000006731 degradation reaction Methods 0.000 description 20
- 238000001179 sorption measurement Methods 0.000 description 19
- 239000000975 dye Substances 0.000 description 12
- 239000011787 zinc oxide Substances 0.000 description 10
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000004480 active ingredient Substances 0.000 description 6
- 239000001048 orange dye Substances 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229960005489 paracetamol Drugs 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- VCSZKSHWUBFOOE-UHFFFAOYSA-N dioxidanium;sulfate Chemical compound O.O.OS(O)(=O)=O VCSZKSHWUBFOOE-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
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- B01J35/39—
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention relates to ZnO-Cu2A preparation method and application of an O-AC photocatalyst belong to the technical field of photocatalysis. Activated carbon and zinc acetate [ (CH)3COO)2Zn·2H2O]Copper acetate (C)4H6CuO4·H2O) is taken as a raw material to prepare a catalyst, and the weight ratio of active carbon: zinc acetate: copper acetate is 1-10: 1-2: 1-2, roasting the obtained material in an inert atmosphere at the roasting temperature of 400-800 ℃ for 60-150 min according to the ratio of the mass of the dried material to the microwave power of 1: 30-60 g/W to obtain ZnO-Cu2An O-AC photocatalyst. ZnO-Cu prepared by the invention2The O-AC photocatalyst can effectively degrade azo dyes such as methyl orange and the like, and has good environmental protection benefit.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to ZnO-Cu2A preparation method of an O-AC photocatalyst and application thereof.
Background
The water-soluble azo dye represented by methyl orange has the characteristics of complex structure, stable chemical property, high toxicity and poor biodegradability, and is difficult to degrade by the traditional method, thereby causing serious environmental problems.
At present, the treatment method of azo dye wastewater such as methyl orange mainly comprises a physical adsorption method, a biological method and a chemical method. The single physical adsorption method is adopted, and the adsorbent is easily saturated and difficult to regenerate; the biological method utilizes screened microorganisms for degradation, but the microorganisms have certain requirements on conditions such as nutrient substances, pH, temperature and the like, are difficult to use in a large scale and often need to be used in combination with other methods; the chemical method has high cost and is easy to bring secondary pollution.
TiO2The photocatalysis technology shows good photocatalysis degradation effect in sewage treatment, has the advantages of low price, strong oxidation capability, no secondary pollution and the like, but has low quantum yield, easy recombination of photoproduction hole-electron, low solar energy utilization rate and TiO2The photocatalyst mainly absorbs the ultraviolet part with the wavelength of 300-400 nm in sunlight. In practical applications, the photocatalytic light source is generally an ultraviolet lamp. Published under the number CN 103041795AThe invention also discloses a preparation method of the titanium dioxide photocatalyst suitable for photocatalytic degradation of methyl orange, and raw materials for preparing the catalyst comprise titanyl sulfate dihydrate and sodium oxalate. The method has the advantages of simple equipment, simple and convenient operation, cheap raw materials and the like, but the roasting time is overlong, the reaction must be carried out under the condition of strong acid, and the degradation amount is low. Therefore, finding an inexpensive and practical treatment method for treating industrial wastewater is an urgent task in the future. In addition, although methyl orange is studied by using other catalysts, an organic solvent is often used as an auxiliary agent, the preparation process is complicated, and the degradation effect is poor.
The Activated Carbon (AC) has a developed pore structure and a large specific surface area, so that the activated carbon has super-strong adsorption capacity. Meanwhile, the activated carbon is a non-polar adsorbent, has stable chemical property and wide application. But as the application of activated carbon becomes more widespread, more waste activated carbon is produced. If the waste activated carbon is not treated or is not treated properly, secondary pollution and other environmental problems can be caused. The conventional methods for regenerating activated carbon include thermal regeneration and chemical regeneration, which mostly only recover part of the adsorption performance, and most of the regenerated activated carbon is treated as hazardous waste.
Disclosure of Invention
The band gap of ZnO is 3.37ev, the band gap is wider, and the wider band gap can only absorb the ultraviolet light part in sunlight. Easily causes light corrosion, and Zn (OH) is formed in the photocatalysis process under the alkaline condition2Etc., which limit the application of ZnO. Cu2The O band gap is 2.0-2.2Ev, the visible light band (390-780 nm) can be excited, and Cu2The O crystal lattice has a semiconductor energy band formed by a full-filled valence band and an empty conduction band, so that the O crystal lattice has good photocatalytic activity, adsorbability and other catalytic activities. The inventor finds that ZnO and Cu can be calcined under microwave conditions by taking active carbon as a carrier through a large amount of experimental research2Good coupling effect is generated between O, and the ZnO-Cu with the adsorption-photocatalysis function is obtained2An O-AC catalyst.
Based on the followingThe invention provides a ZnO-Cu2The preparation method and the application of the O-AC photocatalyst are simple and have good methyl orange degradation effect.
In order to realize the purpose, the invention is realized by the following technical scheme:
the ZnO-Cu2The preparation method of the O-AC photocatalyst comprises the following steps:
(1) dissolving zinc acetate and copper acetate in absolute ethyl alcohol, and stirring in a water bath until the zinc acetate and the copper acetate are completely dissolved to obtain a solution A;
(2) adding activated carbon, and continuously stirring for 1-5 h;
(3) dissolving oxalic acid in absolute ethyl alcohol, heating in a water bath at 60 ℃, and stirring until the oxalic acid is completely dissolved to obtain a solution B;
(4) adding the solution B into the solution A at a speed of 20d/min, and continuously stirring for 1-3 h; filtration and drying of the resulting solid in a drying cabinet for 6 h.
(5) Roasting the material obtained in the step (4) in an inert atmosphere by microwave at 400-800 ℃ for 60-150 min according to the dry basis mass and microwave power ratio of 1: 30-60 g/W to obtain ZnO-Cu2An O-AC photocatalyst.
Furthermore, the concentration of zinc acetate in the solution A is 0.167-0.5 mol/L, and the concentration of copper acetate is 0.167-1.0 mol/L.
Furthermore, the molar ratio of the dissolved zinc acetate to the dissolved copper acetate in the solution A is 2: 1-4.
Further, in the step (2), the molar concentration of oxalic acid in absolute ethyl alcohol is 0.334-4 mol/L.
Furthermore, in the step (4), the molar ratio of the sum of the molar masses of zinc acetate and copper acetate dissolved in the solution A to the molar mass of oxalic acid dissolved in the solution B is 1: 1-4.
Further, the inert atmosphere in the step (5) is an atmosphere with an inert gas pressure of 2-4 MPa, and the used inert gas is nitrogen or argon.
Further, the activated carbon in the step (2) is obtained by ultrasonic cleaning in distilled water and drying.
Further, the ZnO-Cu2O-AC lightThe catalyst is applied to the degradation of azo dyes under visible light or ultraviolet light.
The invention has the beneficial effects that:
the invention provides a novel azo dye photocatalyst, which takes zinc acetate and copper acetate as raw materials to provide active components of zinc oxide and cuprous oxide. Through reaction with acetic acid and control of various technological indexes in the reaction process, active ingredients of zinc oxide and cuprous oxide which are effectively coupled are obtained, the active ingredients are effectively adsorbed and dispersed in the active carbon, and finally ZnO-Cu with efficient degradation and adsorption-photocatalysis functions is obtained2The degradation rate of the O-AC catalyst on methyl orange can reach over 75 percent, and the highest degradation rate can reach 98 percent.
The invention adopts microwave heating, not only utilizes the selective heating of microwave, low energy consumption and high heating speed, but also utilizes the characteristics of microwave heating from inside to outside and different wave absorbing effects of different substances, quickly decomposes the carrier formed on the surface of the active carbon and is beneficial to improving the industrialized production efficiency.
The invention not only can use new active carbon, but also can use inactive active carbon as raw material, thereby reducing the discharge of chemical waste and the pollution to the environment, and realizing the resource utilization of the waste.
The method has the advantages of simple operation, short reaction time, low cost and no pollution.
The photocatalyst prepared by the method can not only adsorb the dye, but also degrade the dye by photocatalysis.
Drawings
FIG. 1 is a scanning electron micrograph of a deactivated activated carbon according to example 2 of the present invention;
FIG. 2 shows ZnO-Cu obtained in example 2 of the present invention2Scanning electron micrographs of O-AC;
FIG. 3 shows ZnO-Cu prepared in example 2 of the present invention2XRD pattern of O-AC;
FIG. 4 ZnO-Cu prepared in example 2 of the present invention2And (3) a physical diagram of the methyl orange dye in different time of O-AC photocatalysis.
Detailed Description
The ZnO-Cu2The preparation method of the O-AC photocatalyst comprises the following stepsThe method comprises the following steps:
(1) dissolving zinc acetate and copper acetate in absolute ethyl alcohol, and stirring in a water bath until the zinc acetate and the copper acetate are completely dissolved to obtain a solution A;
(2) adding activated carbon, continuing stirring for 1-5 h, and fully soaking to enable zinc acetate and copper acetate to be attached to the activated carbon.
(3) Dissolving oxalic acid in absolute ethyl alcohol, heating in a water bath at 60 ℃, and stirring until the oxalic acid is completely dissolved to obtain a solution B;
(4) adding the solution B into the solution A at a speed of 20d/min, and continuously stirring for 1-3 h; weak acid is prepared by strong acid, so that zinc acetate and copper acetate loaded on activated carbon are replaced by insoluble zinc oxalate and copper oxalate of ethanol, the filtration is carried out, and the obtained solid is dried in a drying oven.
(5) Roasting the material obtained in the step (4) in an inert atmosphere by microwave at 400-800 ℃ for 60-150 min according to the dry basis mass-to-microwave power ratio of 1: 30-60 g/W, controlling roasting temperature and time, heating from inside to outside by utilizing selective heating of microwave, having high heating speed and low energy consumption, rapidly decomposing zinc oxalate and copper oxalate loaded on the surface of active carbon, confirming by a scanning electron microscope picture, and performing microwave treatment to obtain the active carbon containing ZnO and Cu2O as the main active component and finally obtaining ZnO-Cu2An O-AC photocatalyst.
Wherein:
in the solution A, the concentration of zinc acetate is 0.167-0.5 mol/L, and the concentration of copper acetate is 0.167-1.0 mol/L. The molar ratio of zinc acetate to copper acetate is 2: 1-4.
In the step (2), activated carbon: the mass ratio of the sum of zinc acetate and copper acetate is 1-10: 1 to 4. The molar mass ratio of the activated carbon to the zinc acetate and the copper acetate is not too small or too large, the zinc acetate and the copper acetate are too high in concentration due to too small molar mass ratio, and active ingredients generated after subsequent steps are too much to be effectively dispersed in a pore structure of the activated carbon or even block pores of the activated carbon, so that the effective contact area with methyl orange in the photocatalytic degradation process is reduced, and the degradation or adsorption capacity is reduced; too high leads to too low concentration of the load, and too few active ingredients are generated after subsequent steps, which is not beneficial to photocatalytic degradation or adsorption of methyl orange azo dyes.
In the step (3), the concentration of oxalic acid in the absolute ethyl alcohol is 0.334-4 mol/L. Oxalic acid must be completely dissolved in absolute ethanol.
C2O4H2:(CH3COO)2Zn is at least 1:1 (molar ratio) to completely convert zinc acetate into zinc oxalate, and copper acetate is similar to the above. Therefore, it is necessary to ensure C2O4H2:[(CH3COO)2Zn+CH3COO)2Cu)]At least not less than 1:1 (molar ratio).
The inert atmosphere in the step (5) is an atmosphere with the inert gas pressure of 2-4 MPa, and the used inert gas is nitrogen or argon.
The activated carbon in the step (2) can be new activated carbon or regenerated activated carbon obtained by ultrasonic cleaning in distilled water and drying, and the inventor finds that the treated regenerated activated carbon is used as an adsorption carrier and the obtained ZnO-Cu is used as an adsorption carrier through a large amount of experimental researches2The O-AC photocatalyst still has better degradation effect, wherein the effect is closer to that of new active carbon when the regenerated active carbon of waste water generated in the process of producing medicines such as paracetamol medicines and the like is used as a carrier.
ZnO-Cu prepared by the invention2The O-AC photocatalyst is applied to the degradation of azo dyes under visible light or ultraviolet light, and the degradation rate can reach 98 percent.
ZnO-Cu prepared by the invention2O-AC photocatalysts can also be used for adsorbing azo dyes.
In order to make the objects, technical solutions and advantages of the present invention more apparent, preferred embodiments of the present invention will be described in detail below to facilitate understanding of the skilled person.
Example 1
ZnO-Cu2The preparation method of O-AC photocatalysis comprises the following specific steps:
And 2, dissolving 0.01mol of zinc acetate and 0.02mol of copper acetate in 60mL of absolute ethyl alcohol, stirring in a water bath at 60 ℃ until the zinc acetate and the copper acetate are completely dissolved to obtain a solution A, then adding the treated activated carbon, and continuously stirring for 1, 2, 3 and 4 hours respectively. Dissolving 0.08mol of oxalic acid in 40mL of absolute ethyl alcohol, heating in a water bath at 60 ℃, stirring and dissolving to obtain a solution B. Adding B into A at 20d/min, and stirring for 1, 2, and 3 h.
Step 3, roasting the material obtained in the step 2 for 120min at the roasting temperature of 500 ℃ according to the ratio of the dried material mass to the microwave power of 1:55g/W, and preparing the ZnO-Cu at the inert gas pressure of 3.0MPa2An O-AC photocatalyst.
The above ZnO-Cu2The O-AC can be used for adsorbing dye wastewater and degrading dye through photocatalysis.
ZnO-Cu prepared by the above steps2Carrying out methylene blue adsorption by using an O-AC photocatalyst, and carrying out photocatalytic degradation on methyl orange, wherein the methylene blue adsorption value of the solution A after adding the inactivated activated carbon is continuously stirred for 3 hours, the methylene blue adsorption value of the solution B after adding the solution B after continuously stirring for 2 hours is optimal with the effect of photocatalytic methyl orange, the stirring time is not too long or too short, the activated carbon is not completely soaked due to too short stirring time, the loading capacity is too low, active ingredients generated after subsequent steps are too low, and the subsequent photocatalytic degradation of methyl orange dye is not facilitated; too high load concentration is caused by overlong, active ingredients which are not beneficial to subsequent step treatment are effectively dispersed in an active carbon pore structure, even active carbon pores are blocked, so that the effective contact area with methyl orange in the photocatalytic degradation process is reduced, and the degradation or adsorption capacity is reduced. The best group of methylene blue has an adsorption value of 150mg/g and has a degradation rate of 96% for methyl orange with an initial concentration of 200 mg/L.
Example 2
ZnO-Cu2The preparation method of O-AC photocatalysis comprises the following specific steps:
And 2, dissolving 0.02mol of zinc acetate and 0.04mol of copper acetate in 60mL of absolute ethyl alcohol, stirring in a water bath at 60 ℃ until the zinc acetate and the copper acetate are completely dissolved to obtain a solution A, adding the treated activated carbon, and continuously stirring for 3 hours. Dissolving 0.16mol of oxalic acid in 40mL of absolute ethyl alcohol, heating in a water bath at 60 ℃, stirring and dissolving to obtain a solution B. Adding B into A at 20d/min, and stirring for 2 h.
Step 3, roasting the material obtained in the step 2 for 120min at the roasting temperature of 500 ℃ according to the ratio of the dried material mass to the microwave power of 1:55g/W, and preparing the ZnO-Cu under the inert gas pressure of 3MPa2An O-AC photocatalyst.
ZnO-Cu prepared in this example2As shown in the scanning electron micrograph (attached figure 2) of O-AC, the modified activated carbon has less collapse phenomenon on the surface of the activated carbon due to the supporting effect of the formed metal microcrystals, and the ZnO particles on the surface of the activated carbon partially agglomerate, so that Cu is formed2The O particles are relatively dispersed. The obtained ZnO-Cu2XRD pattern of O-AC (fig. 3), from which diffraction peaks of ZnO at angles of 2 θ =31.67, 34.32, 36.15, 47.43, 56.49 and 62.74 ° are seen, indicating that ZnO was successfully loaded into activated carbon, and Cu at angles of 2 θ =29.46, 36.3, 42.18 and 61.24 ° is seen2Diffraction peak of O, indicating Cu2O was successfully loaded into activated carbon.
The ZnO-Cu prepared in this example2The O-AC photocatalyst photocatalysts degradation of methyl orange dye at different times, and the obtained real object diagram is shown in fig. 4, wherein T =0min, 20min, 40min, 60min, 80min, 100min, 120min, 140min, and methyl orange with residual concentration at 160min are respectively from left to right in fig. 4. It can be seen from the graph that the residual concentration of methyl orange dye is almost unchanged at T =40min and 60min under no light source condition, indicating ZnO — Cu2The O-AC adsorption reaches saturation; when T =100min, the residual concentration of the methyl orange dye is obviously reduced under the irradiation of ultraviolet-visible light; after T =140min, the methyl orange dye was almost degraded to colorless; the solution was almost transparent at T =160min, indicating ZnO-Cu2The O-AC has better function of degrading methyl orange by photocatalysis. In summary, ZnO-Cu2The O-AC catalyst not only has an adsorption function, but also has better photocatalytic performance.
Example 3
ZnO-Cu2The preparation method of O-AC photocatalysis comprises the following specific steps:
And 2, dissolving 0.01mol of zinc acetate and 0.01mol of copper acetate in 60mL of absolute ethyl alcohol, stirring in a water bath at 60 ℃ until the zinc acetate and the copper acetate are completely dissolved to obtain a solution A, adding the treated activated carbon, and continuously stirring for 3 hours. Dissolving 0.08mol of oxalic acid in 40mL of absolute ethyl alcohol, heating in a water bath at 60 ℃, stirring and dissolving to obtain a solution B. Adding B into A at 20d/min, and stirring for 2 h.
Step 3, roasting the material obtained in the step 2 for 120min at the roasting temperature of 500 ℃ according to the ratio of the dried material mass to the microwave power of 1:55g/W, and preparing the ZnO-Cu under the inert gas pressure of 3MPa2An O-AC photocatalyst.
The above ZnO-Cu2The O-AC can be used for adsorbing dye wastewater and degrading dye through photocatalysis.
ZnO-Cu prepared by the steps2The methylene blue adsorption value of the O-AC photocatalyst is 122mg/g, and the degradation rate of methyl orange with the initial concentration of 200mg/L is 82%.
Example 4
ZnO-Cu2The preparation method of O-AC photocatalysis comprises the following specific steps:
Step 2, roasting the material obtained in the step 2 for 120min at the roasting temperature of 500 ℃ according to the ratio of the dried material mass to the microwave power of 1:55g/W, and preparing the ZnO-Cu under the inert gas pressure of 3MPa2An O-AC photocatalyst.
The above ZnO-Cu2The O-AC can be used for adsorbing dye wasteWater may in turn be used to photocatalytically degrade dyes.
ZnO-Cu prepared by the steps2The methylene blue adsorption value of the O-AC photocatalyst is 115mg/g, and the degradation rate of methyl orange with the initial concentration of 200mg/L reaches 79%.
Example 5
ZnO-Cu2The preparation method of O-AC photocatalysis comprises the following specific steps:
And 2, dissolving 0.01mol of zinc acetate and 0.02mol of copper acetate in 60mL of absolute ethyl alcohol, stirring in a water bath at 60 ℃ until the zinc acetate and the copper acetate are completely dissolved to obtain a solution A, adding the treated activated carbon, and continuously stirring for 3 hours. Dissolving 0.08mol of oxalic acid in 40mL of absolute ethyl alcohol, heating in a water bath at 60 ℃, stirring and dissolving to obtain a solution B. Adding B into A at 20d/min, and stirring for 2 h.
Step 3, roasting the material obtained in the step 2 for 120min at the roasting temperature of 400 ℃ according to the ratio of the dried material mass to the microwave power of 1:45g/W, and preparing the ZnO-Cu at the inert gas pressure of 3MPa2An O-AC photocatalyst.
The above ZnO-Cu2The O-AC can be used for adsorbing dye wastewater and degrading dye through photocatalysis.
ZnO-Cu prepared by the steps2The methylene blue adsorption value of the O-AC photocatalyst is 125mg/g, and the degradation rate of methyl orange with the initial concentration of 200mg/L reaches 87%.
Example 6
ZnO-Cu2The preparation method of O-AC photocatalysis comprises the following specific steps:
and 2, dissolving 0.01mol of zinc acetate and 0.02mol of copper acetate in 60mL of absolute ethyl alcohol, stirring in a water bath at 60 ℃ until the zinc acetate and the copper acetate are completely dissolved to obtain a solution A, adding the treated activated carbon, and continuously stirring for 3 hours. Dissolving 0.08mol of oxalic acid in 40mL of absolute ethyl alcohol, heating in a water bath at 60 ℃, stirring and dissolving to obtain a solution B. Adding B into A at 20d/min, and stirring for 2 h.
Step 3, roasting the material obtained in the step 2 for 120min at the roasting temperature of 600 ℃ according to the ratio of the dried material mass to the microwave power of 1:60g/W, and preparing the ZnO-Cu under the inert gas pressure of 3MPa2An O-AC photocatalyst.
The above ZnO-Cu2The O-AC can be used for adsorbing dye wastewater and degrading dye through photocatalysis.
ZnO-Cu prepared by the steps2The methylene blue adsorption value of the O-AC photocatalyst is 129mg/g, and the degradation rate of methyl orange with the initial concentration of 200mg/L reaches 90%.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. ZnO-Cu2The preparation method of the O-AC photocatalyst is characterized by comprising the following steps: the ZnO-Cu2The preparation method of the O-AC photocatalyst comprises the following steps:
(1) dissolving zinc acetate and copper acetate in absolute ethyl alcohol, and stirring in a water bath until the zinc acetate and the copper acetate are completely dissolved to obtain a solution A;
(2) adding activated carbon, and continuously stirring for 1-5 h;
(3) dissolving oxalic acid in absolute ethyl alcohol, heating in a water bath at 60 ℃, and stirring until the oxalic acid is completely dissolved to obtain a solution B;
(4) dropwise adding the solution B into the solution A, and continuously stirring for 1-3 h; filtering, and drying the obtained solid in a drying oven;
(5) roasting the dried material obtained in the step (4) in an inert atmosphere by microwave for 60-150 min at 400-800 ℃ according to the dry basis mass to microwave power ratio of 1: 30-60 g/W to obtain ZnO-Cu2An O-AC photocatalyst.
2. ZnO-Cu according to claim 12The preparation method of the O-AC photocatalyst is characterized by comprising the following steps: in the solution A, the concentration of zinc acetate is 0.167-0.5 mol/L, and the concentration of copper acetate is 0.167-1.0 mol/L.
3. ZnO-Cu according to claim 1 or 22The preparation method of the O-AC photocatalyst is characterized by comprising the following steps: in the solution A, the molar ratio of the dissolved zinc acetate to the dissolved copper acetate is 2: 1-4.
4. ZnO-Cu according to claim 12The preparation method of the O-AC photocatalyst is characterized by comprising the following steps: in the step (2), the molar concentration of oxalic acid in the absolute ethyl alcohol is 0.334-4 mol/L.
5. ZnO-Cu according to claim 12The preparation method of the O-AC photocatalyst is characterized by comprising the following steps: in the step (4), the molar ratio of the sum of the moles of zinc acetate and copper acetate dissolved in the solution A to the moles of oxalic acid dissolved in the solution B is 1: 1-4.
6. ZnO-Cu according to claim 32The preparation method of the O-AC photocatalyst is characterized by comprising the following steps: in the step (4), the molar ratio of the sum of the moles of zinc acetate and copper acetate dissolved in the solution A to the moles of oxalic acid dissolved in the solution B is 1: 1-4.
7. ZnO-Cu according to claim 12The preparation method of the O-AC photocatalyst is characterized by comprising the following steps: the inert atmosphere in the step (5) is an atmosphere with the inert gas pressure of 2-4 MPa, and the used inert gas is nitrogen or argon.
8. ZnO-Cu according to claim 12The preparation method of the O-AC photocatalyst is characterized by comprising the following steps: and (3) ultrasonically cleaning the activated carbon in the step (2) in distilled water, and drying to obtain regenerated activated carbon.
9. ZnO-Cu according to any of claims 1 to 82The O-AC photocatalyst is characterized in that the ZnO-Cu photocatalyst2The application of the O-AC photocatalyst in degrading azo dye materials under visible light or ultraviolet light.
10. ZnO-Cu according to any of claims 1 to 82The O-AC photocatalyst is characterized in that the ZnO-Cu photocatalyst2The application of O-AC photocatalyst in adsorbing azo dye.
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