CN110560031A - Method for improving photocatalytic activity of zinc oxide - Google Patents
Method for improving photocatalytic activity of zinc oxide Download PDFInfo
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- CN110560031A CN110560031A CN201910850192.8A CN201910850192A CN110560031A CN 110560031 A CN110560031 A CN 110560031A CN 201910850192 A CN201910850192 A CN 201910850192A CN 110560031 A CN110560031 A CN 110560031A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 67
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 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 claims abstract description 18
- 229940012189 methyl orange Drugs 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 239000011575 calcium Substances 0.000 claims abstract description 10
- 239000003208 petroleum Substances 0.000 claims abstract description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 10
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims abstract description 7
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 6
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001393 triammonium citrate Substances 0.000 claims abstract description 6
- 235000011046 triammonium citrate Nutrition 0.000 claims abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 13
- 238000006731 degradation reaction Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 10
- 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 abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000002071 nanotube Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Classifications
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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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/40—Organic compounds containing sulfur
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of zinc oxide catalysts, and particularly relates to a method for improving the photocatalytic activity of zinc oxide, which comprises the steps of preparing reaction materials by using demagnetized water, zinc nitrate hexahydrate, magnesium nitrate hexahydrate, triammonium citrate and medium-base-value calcium petroleum sulfonate; and preparing the zinc oxide composite powder by using reaction materials, bismuth nitrate pentahydrate and the like under an acidic condition. Compared with the prior art, the invention has the following advantages: the zinc oxide composite powder obtained by the invention has certain reduction in specific surface area and forbidden bandwidth compared with zinc oxide materials due to the blockage of partial pore channels of the nano tube; the light transmittance is enhanced, so that the light energy utilization rate of the zinc oxide composite powder is improved, and the degradation effect on the methyl orange solution is improved; under sunlight, the zinc oxide composite powder also has higher degradation capability on methyl orange solution, and compared with the activity of photocatalytic degradation of methyl orange of pure ZnO powder, the activity of photocatalytic degradation of methyl orange is obviously improved, so that the zinc oxide composite powder has an application prospect.
Description
Technical Field
The invention belongs to the technical field of zinc oxide catalysts, and particularly relates to a method for improving the photocatalytic activity of zinc oxide.
Background
The zinc oxide is a wide forbidden n-type semiconductor compound with excellent photocatalytic activity, is white, has good acid and alkali resistance, rich sources and no pollution to the environment, has a crystal of a hexagonal wurtzite structure, has an energy band gap of 3.3eV at room temperature, has exciton confinement energy as high as 60meV, has strong free exciton transition luminescence at an ultraviolet band, and is commonly used in the aspects of photocatalysts, luminescent secondary plates, solar cells, environmental protection, bioengineering and the like; the photocatalytic oxidation method can decompose many pollutants which are difficult to degrade into carbon dioxide, water and inorganic substances, methyl orange is the main structure of an organic compound which is difficult to degrade, the principle of degradation by utilizing the semiconductor photocatalytic technology is that when light which is equal to or more than forbidden band energy of the semiconductors irradiates the surfaces of the pollutants, an electron-hole pair can be formed between a conduction band and a valence band of the semiconductors, but the photoproduction electron-hole pair is unstable, one part of the photoproduction electron-hole pair is compounded in a mode of releasing heat energy and returns to the original state, the other part of the photoproduction electron pair is captured by an electron acceptor adsorbed on the surface of the semiconductor, the captured photoproduction electron has strong reducibility, the substances adsorbed on the surface of the semiconductor can be reduced, the hole has strong oxidizability, and organic molecules and the like adsorbed on the surface of the semiconductor can be oxidized and degraded, thus, only the trapped electron or hole reacts with the acceptor or donor to cause a photocatalytic reaction; the problems existing at present are that the utilization rate of light energy is low and the catalytic efficiency caused by the high recombination rate of photoproduction electron-hole pairs is not high; in the prior art, in order to improve the photocatalytic activity of a semiconductor, the preparation method is generally improved, the particle size or the morphology of the semiconductor is changed to improve the photocatalytic activity, noble metal, transition metal or morphology is doped to improve the photocatalytic activity, or the energy band structure of the semiconductor is changed to improve the optical activity; in various semiconductor photocatalytic materials, ZnO is nontoxic, low in cost and wide in application, a ZnO-Fe2O3 photocatalyst is prepared by adopting a sol-gel method in the prior art, a small amount of Fe2O3 is doped into hair cream to narrow a ZnO forbidden band, and the activity of degrading KCN by photocatalysis is improved; the Fe-doped ZnO nanorod prepared by a metal powder hydrolysis method can also change the band gap of ZnO, and the ZnO has the photocatalytic activity by doping elements such as La, Ag, Mn, Al, Cu, Mg or N in a proper amount, but the activity is not obviously improved, so that further research needs to be carried out on the ZnO so as to improve the photocatalytic stability of ZnO and the reaction of the ZnO to visible light.
Disclosure of Invention
The invention aims to provide a method for improving the photocatalytic activity of zinc oxide, aiming at the problem that the photocatalytic activity of the existing zinc oxide is not obviously improved.
the invention is realized by the following technical scheme: a method for improving the photocatalytic activity of zinc oxide comprises the following steps:
(1) Mixing 100 parts by weight of magnetite-removed water, 20 parts by weight of zinc nitrate hexahydrate, 2-3 parts by weight of magnesium nitrate hexahydrate, 1.2-1.8 parts by weight of triammonium citrate and 4-5 parts by weight of medium-base-value calcium petroleum sulfonate, heating to 85-95 ℃, reacting for 2-3 hours, evaporating to dryness in a water bath after the reaction is finished, and drying in an oven to obtain a reaction material;
(2) Taking 18-22 parts of reaction materials, 0.6-0.8 part of pentahydrate bismuth nitrate and 80 parts of deionized water, uniformly mixing to obtain a mixed solution, then dropwise adding 1-2 parts of triethanolamine, reacting for 40 minutes at the temperature of 160-180 ℃, adding 2.5mol/L oxalic acid solution to enable the pH value of the solution to be 4.2, stirring and reacting at the temperature of 140-160 ℃, evaporating water to dryness, and roasting for 4 hours at the temperature of 480-520 ℃ under the oxygen-enriched condition to obtain the zinc oxide composite powder with the particle size of 32-34 nm.
Particularly, the preparation method of the magnet water comprises the steps of boiling calcined magnets with the particle size not larger than 10mm in water for 3-4 hours, mixing the calcined magnets and the water according to the weight ratio of 1:8-10, filtering after the mixing is finished, and naturally cooling to obtain the magnet water;
The iron content of the calcined magnetite is 63.98-66.25%.
Wherein the base number of the medium-base-number calcium petroleum sulfonate is 140mgKOH/g, and the soap content is 25.1%; calcium petroleum sulfonate has rust resistance and thermal stability, and is commonly used for preparing various grades of internal combustion engine oil and metal working oil.
Specifically, the temperature for evaporating the water bath in the step (1) is 60 ℃, and the drying temperature in the oven is 85-95 ℃.
Specifically, the dropping speed of the triethanolamine relative to the mixed solution in the step (2) is 20-30 mL/L/min; the oxygen-enriched condition is that the oxygen concentration is 40-45%.
For a methyl orange aqueous solution with the mass concentration of 10mg/L, the adding amount of the zinc oxide composite powder is 45-55mg/100mL, the pH value is adjusted to be 7.2, ultrasonic dispersion is carried out for 30 seconds after the adding is finished, stirring is carried out for 20 minutes in a dark place, then a high-pressure mercury lamp with a light source of 250W is selected, the high-pressure mercury lamp is irradiated for 180 minutes at a position 15cm away from the liquid surface, the methyl orange degradation rate is 89.4-95.2%, and when the adding amount of the zinc oxide composite powder is 52mg/100mL, the methyl orange degradation rate is 95.2%.
compared with the prior art, the invention has the following advantages: the zinc oxide composite powder obtained by the invention has a certain reduction in specific surface area compared with a zinc oxide material due to the blockage of the partial pore channels of the nanotube, and is reduced from about 38.9 m/g to about 32.4 m/g; the forbidden bandwidth of the obtained zinc oxide composite powder is about 3.16eV, compared with the forbidden bandwidth of ZnO powder, the forbidden bandwidth is reduced to a certain extent, the light transmittance is enhanced, the light energy utilization rate of the zinc oxide composite powder can be further improved, and the degradation effect on methyl orange solution is further improved; under sunlight, the zinc oxide composite powder also has higher degradation capability on methyl orange solution, and compared with the activity of photocatalytic degradation of methyl orange of pure ZnO powder, the activity of photocatalytic degradation of methyl orange is obviously improved, so that the zinc oxide composite powder has an application prospect.
Detailed Description
FIG. 1 is a line graph showing the photocatalytic effect of the obtained photocatalysts of each group in the sun.
Wherein the addition amount of the photocatalyst in the unit of mg in the methyl orange aqueous solution with the abscissa of each 100mL and the mass concentration of 10 mg/L;
Wherein the ordinate is the degradation rate in%.
Detailed Description
the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for improving the photocatalytic activity of zinc oxide comprises the following steps:
(1) Taking 100 parts by weight of magnetite-removed water, 20 parts by weight of zinc nitrate hexahydrate, 2.5 parts by weight of magnesium nitrate hexahydrate, 1.5 parts by weight of triammonium citrate and 4.5 parts by weight of medium-base-value calcium petroleum sulfonate, mixing, heating to 90 ℃, reacting for 2-3 hours, evaporating to dryness in a water bath at the temperature of 60 ℃, and drying in an oven at the temperature of 90 ℃ to obtain a reaction material;
The preparation method of the magnet water comprises the steps of boiling calcined magnets with the particle size not larger than 10mm in water for 3.5 hours, mixing the calcined magnets and the water according to the weight ratio of 1:9, filtering after the mixture is finished, and naturally cooling to obtain the magnet water;
(2) Taking 20 parts of reaction materials, 0.7 part of pentahydrate bismuth nitrate and 80 parts of deionized water, uniformly mixing to obtain a mixed solution, then dropwise adding 1.5 parts of triethanolamine, wherein the dropwise adding speed of the triethanolamine relative to the mixed solution is 25mL/L/min, reacting for 40 minutes at the temperature of 170 ℃, adding 2.5mol/L of oxalic acid solution to enable the pH value of the solution to be 4.2, stirring and reacting at the temperature of 150 ℃, evaporating water to be dry, and roasting for 4 hours at the temperature of 500 ℃ and under the oxygen-enriched condition with the oxygen concentration of 42% to obtain the zinc oxide composite powder with the particle size of 32-34 nm.
Example 2
A method for improving the photocatalytic activity of zinc oxide comprises the following steps:
(1) Taking 100 parts by weight of magnetite-removed water, 20 parts by weight of zinc nitrate hexahydrate, 2 parts by weight of magnesium nitrate hexahydrate, 1.8 parts by weight of triammonium citrate and 4 parts by weight of medium-base-value calcium petroleum sulfonate, mixing, heating to 95 ℃, reacting for 2 hours, evaporating in a water bath at the temperature of 60 ℃ after completion, and drying in a drying oven at the temperature of 85 ℃ to obtain a reaction material;
The preparation method of the magnet water comprises the steps of boiling calcined magnets with the particle size not larger than 10mm in water for 4 hours, mixing the calcined magnets and the water according to the weight ratio of 1:10, filtering after the mixture is finished, and naturally cooling to obtain the magnet water;
(2) Taking 22 parts of reaction materials, 0.6 part of pentahydrate bismuth nitrate and 80 parts of deionized water, uniformly mixing to obtain a mixed solution, then dropwise adding 2 parts of triethanolamine, wherein the dropwise adding speed of the triethanolamine relative to the mixed solution is 30mL/L/min, reacting for 40 minutes at the temperature of 180 ℃, adding 2.5mol/L oxalic acid solution to enable the pH value of the solution to be 4.2, stirring and reacting at the temperature of 140 ℃, evaporating water to dryness, and roasting for 4 hours at the temperature of 520 ℃ under the oxygen-enriched condition with the oxygen concentration of 45% to obtain the zinc oxide composite powder with the particle size of 32-34 nm.
example 3
A method for improving the photocatalytic activity of zinc oxide comprises the following steps:
(1) Taking 100 parts by weight of magnetite-removed water, 20 parts by weight of zinc nitrate hexahydrate, 3 parts by weight of magnesium nitrate hexahydrate, 1.2 parts by weight of triammonium citrate and 5 parts by weight of medium-base-value calcium petroleum sulfonate, mixing, heating to 85 ℃, reacting for 3 hours, evaporating in a water bath at the temperature of 60 ℃ after completion, and drying in a drying oven at the temperature of 95 ℃ to obtain a reaction material;
The preparation method of the magnet water comprises the steps of boiling calcined magnets with the particle size not larger than 10mm in water for 3 hours, mixing the calcined magnets and the water in a weight ratio of 1:8, filtering after the mixture is finished, and naturally cooling to obtain the magnet water;
(2) Taking 18 parts of reaction materials, 0.8 part of pentahydrate bismuth nitrate and 80 parts of deionized water, uniformly mixing to obtain a mixed solution, then dropwise adding 1 part of triethanolamine, wherein the dropwise adding speed of the triethanolamine relative to the mixed solution is 20mL/L/min, reacting for 40 minutes at the temperature of 160 ℃, adding 2.5mol/L oxalic acid solution to enable the pH value of the solution to be 4.2, stirring and reacting at the temperature of 160 ℃, evaporating water to dryness, and roasting for 4 hours at the temperature of 480 ℃ and under the oxygen-enriched condition with the oxygen concentration of 40% to obtain the zinc oxide composite powder with the particle size of 32-34 nm.
To demonstrate the effect of the various factors in the method of increasing the photocatalytic activity of zinc oxide, multiple control groups were set on the basis of example 1, as follows:
in the control group 1, the common tap water was replaced with the demagnetized water on the premise of the example 1, and the rest contents were unchanged; setting a comparison group 2, removing magnesium nitrate hexahydrate under the premise of the embodiment 1, and keeping the rest contents unchanged; setting a comparison group 3, removing the medium-alkali petroleum calcium sulfonate on the premise of the embodiment 1, and keeping the rest contents unchanged; setting a comparison group 4, replacing the calcined magnetite with equal weight of green magnetite on the premise of the embodiment 1, wherein the iron content of the green magnetite is 46.2%, and the rest content is unchanged; setting a comparison group 5, removing the pentahydrate bismuth nitrate on the premise of the embodiment 1, and keeping the rest contents unchanged; setting a comparison group 6, removing the step of adding oxalic acid solution to adjust the pH value under the premise of the embodiment 1, and keeping the rest contents unchanged; a control group 7 was set, and the "oxygen-rich condition" was removed under the premise of example 1, and replaced with the ordinary condition, and the rest of the contents were unchanged.
The above examples and the properties of the zinc oxide composite powder prepared by the control group were tested, and meanwhile, a blank group was set to be purchased from baisheng chemical industry llc of shijiazhuan city, the particle size was 32-34nm, the specific surface area was 38.9 m/g, the forbidden bandwidth was 3.37eV, the nano zinc oxide was added in an amount of 64mg/100mL to a methyl orange aqueous solution with a mass concentration of 10mg/L, the pH value was adjusted to 6.8, ultrasonic dispersion was performed for 30 seconds after the addition was completed, stirring was performed for 20 minutes in the dark, then a high-pressure mercury lamp with a light source of 250W was selected, and the high-pressure mercury lamp was irradiated for 180 minutes at a distance of 15cm from the liquid surface, and the methyl orange degradation rate was 78.5%.
The degradation rate = (initial concentration of methyl orange-final concentration of methyl orange)/initial concentration of methyl orange, wherein the initial concentration of methyl orange and the final concentration of methyl orange are both scanned in a full-wave band of the methyl orange solution at 200-800nm by a spectrophotometer, and the final concentration of the methyl orange solution is obtained according to the corresponding relation between absorbance and concentration.
The properties of each group of zinc oxide composite powder are detected, and the obtained data are average values obtained after repeating the detection for 3 times, so that the following results are obtained:
TABLE 1
| Group of | specific surface area (m/g) | Forbidden band width (eV) | Degradation Rate (%) |
| example 1 | 32.4 | 3.16 | 95.2 |
| Example 2 | 31.9 | 3.12 | 94.7 |
| example 3 | 32.3 | 3.16 | 95.0 |
| Control group 1 | 34.8 | 3.25 | 89.3 |
| Control group 2 | 35.2 | 3.29 | 86.5 |
| Control group 3 | 33.7 | 3.21 | 92.3 |
| Control group 4 | 34.5 | 3.24 | 90.6 |
| control group 5 | 35.1 | 3.29 | 86.7 |
| control group 6 | 36.2 | 3.32 | 85.1 |
| control group 7 | 35.4 | 3.30 | 86.4 |
| Blank group | 38.9 | 33.7 | 78.5 |
as can be seen from the data in Table 1, the invention can obtain the beneficial effects of small specific surface area, reduced forbidden band width and improved degradation rate by reasonably controlling the production conditions.
In addition, the zinc oxide composite powder prepared in each example and the control group is tested on a sunny day by inquiring weather, and the weather conditions of the data source in the application are (9 am, 14 am, 7 and 14 months in 2018, the local weather is sunny, and the temperature is 26 ℃); for a methyl orange aqueous solution with the mass concentration of 10mg/L, the adding amount of the zinc oxide composite powder is 45-55mg/100mL, the pH value is adjusted to 6.8, ultrasonic dispersion is carried out for 30 seconds after the adding is finished, stirring is carried out for 20 minutes in a dark place, the zinc oxide composite powder is placed under the sunlight (without glass shielding) after the adding is finished, magnetic stirring is carried out, and the degradation effect of the methyl orange solution of each group is detected after 6 hours, so that the result shown in figure 1 is obtained, and the result shows that the photocatalytic effect is obviously increased under the sunlight in comparison with a control group and a blank group, and the photocatalytic activity is obviously improved.
Through the above groups of embodiments, it can be seen that the preparation method of the zinc oxide composite powder is simple, the particle size and performance of the zinc oxide composite powder can be controlled within a certain range by reasonably controlling various production conditions, the selection, the amount and the processing conditions of various raw materials are key for obtaining the zinc oxide composite powder with certain performance, and through reasonable preparation, the photocatalytic activity of the obtained zinc oxide composite powder can be remarkably improved, and the application range of the zinc oxide composite powder is expanded.
Claims (10)
1. A method for improving the photocatalytic activity of zinc oxide is characterized by comprising the following steps:
(1) Mixing 100 parts by weight of magnetite-removed water, 20 parts by weight of zinc nitrate hexahydrate, 2-3 parts by weight of magnesium nitrate hexahydrate, 1.2-1.8 parts by weight of triammonium citrate and 4-5 parts by weight of medium-base-value calcium petroleum sulfonate, heating to 85-95 ℃, reacting for 2-3 hours, evaporating to dryness in a water bath after the reaction is finished, and drying in an oven to obtain a reaction material;
(2) Taking 18-22 parts of reaction materials, 0.6-0.8 part of pentahydrate bismuth nitrate and 80 parts of deionized water, uniformly mixing to obtain a mixed solution, then dropwise adding 1-2 parts of triethanolamine, reacting for 40 minutes at the temperature of 160-180 ℃, adding 2.5mol/L oxalic acid solution to enable the pH value of the solution to be 4.2, stirring and reacting at the temperature of 140-160 ℃, evaporating water to dryness, and roasting for 4 hours at the temperature of 480-520 ℃ under the oxygen-enriched condition to obtain the zinc oxide composite powder.
2. The method of claim 1, wherein the magnetite water is prepared by decocting calcined magnetite with particle size of no more than 10mm in water for 3-4 hours, mixing the calcined magnetite and water at a weight ratio of 1:8-10, filtering, and naturally cooling to obtain the magnetite water.
3. The method for improving the photocatalytic activity of zinc oxide according to claim 2, wherein the calcined magnetite has an iron content of 63.98% to 66.25%.
4. the method for improving the photocatalytic activity of zinc oxide according to claim 1, wherein the medium-base-number calcium petroleum sulfonate has a base number of 140mgKOH/g and a soap content of 25.1%.
5. the method for improving the photocatalytic activity of zinc oxide according to claim 1, wherein the temperature for evaporating the water bath in the step (1) is 60 ℃ and the drying temperature in the oven is 85-95 ℃.
6. The method for improving the photocatalytic activity of zinc oxide according to claim 1, wherein the triethanolamine is added to the mixed solution at a rate of 20 to 30mL/L/min in step (2).
7. The method for improving the photocatalytic activity of zinc oxide according to claim 1, wherein the oxygen-rich condition in the step (2) is an oxygen concentration of 40 to 45%.
8. the method for improving the photocatalytic activity of zinc oxide according to claim 1, wherein the particle size of the zinc oxide composite powder is 32 to 34 nm.
9. The method for improving the photocatalytic activity of zinc oxide as recited in claim 1, wherein the zinc oxide composite powder is added in an amount of 45-55mg/100mL to a methyl orange aqueous solution with a mass concentration of 10 mg/L.
10. The method for improving the photocatalytic activity of zinc oxide as recited in claim 9, wherein the zinc oxide composite powder is added in an amount of 52mg/100mL to a methyl orange aqueous solution having a mass concentration of 10 mg/L.
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