CN111013586B - Preparation method of copper-doped titanium dioxide photocatalyst - Google Patents
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 29
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 239000010936 titanium Substances 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 230000007062 hydrolysis Effects 0.000 claims abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 40
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 14
- 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 14
- 229960000583 acetic acid Drugs 0.000 claims description 11
- 239000012362 glacial acetic acid Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 22
- 238000003837 high-temperature calcination Methods 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 description 17
- 239000000843 powder Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000000227 grinding Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 238000011049 filling Methods 0.000 description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 230000029087 digestion Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 238000001782 photodegradation Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 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 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 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
- 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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- 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
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention relates to a preparation method of a copper-doped titanium dioxide photocatalyst, and belongs to the technical field of photocatalysis and environmental protection. The invention provides a preparation method of a copper-doped titanium dioxide photocatalyst, which comprises the following steps: a. and (3) mixing and dissolving: completely dissolving a copper source in an organic solvent, adding a titanium source and a pH regulator, and uniformly stirring to obtain a mixed solution; b. hydrolysis: slowly dripping water into the mixed solution obtained in the step a until gel is formed; c. hydrothermal reaction: and c, carrying out hydrothermal reaction on the gel obtained in the step b, and drying after the reaction is finished to obtain the copper-doped titanium dioxide photocatalyst. Compared with the prior art, the preparation process omits the step of high-temperature calcination, is beneficial to solving the problems of product agglomeration, reduced photocatalytic activity and the like, and can also save the production cost.
Description
Technical Field
The invention relates to a preparation method of a copper-doped titanium dioxide photocatalyst, and belongs to the technical field of photocatalysis and environmental protection.
Background
With the rapid development of global economy, environmental pollution is becoming more and more important in various countries. The most important environmental pollution is pollution of water quality, such as domestic water, industrial water and the like, and the polluted water quality contains a large amount of refractory organic matters. Thus, photocatalytic degradation materials (e.g., fe 2 O 3 、NiO、CuO、ZrO 2 、SnO 2 、WO 3 、In 2 O 3 、CdS、TiO 2 Etc.) has become a hotspot in current research. Among them, titanium dioxide is favored because of its advantages of no harm to human body, stable performance, low price, wide band gap, etc., but some drawbacks still exist: (1) The forbidden bandwidth is large, only ultraviolet rays in sunlight can be utilized, and the ultraviolet rays only account for about 4% in the sunlight spectrum, so that the application field of the titanium dioxide is greatly limited; (2) Titanium dioxide is irradiated by ultraviolet lightThe recombination probability of electron/hole pairs is high, and the photocatalytic efficiency is low. In order to improve the photocatalytic performance of titanium dioxide, the modification work of titanium dioxide currently carried out is mainly focused on doping technology, such as Fe, cr, ag, V, mn, cu, C, N, S, P and other elements. Copper is cheap and easy to obtain, and copper doping modification can effectively improve the photocatalysis performance of titanium dioxide, so that the absorption band of visible light is red shifted, and compared with doping of other elements, the titanium dioxide has obvious advantages.
The Chinese patent application of application number 201610673009.8 discloses a preparation method of a copper-doped titanium dioxide photocatalyst, which comprises the following steps: dripping 50-70mL tetrabutyl titanate into 200-250mL absolute ethanol under intense stirring, stirring for 20min to obtain uniform pale yellow transparent liquid A, dissolving 5mL deionized water with 3-5mL copper nitrate and 50-60mL absolute ethanol to obtain solution, and adding HNO 3 Regulating pH to 2-3 to obtain solution B, slowly dripping the solution B into the solution A under intense stirring to obtain light green sol, aging for 7.5-7.75h, drying at 75-78deg.C for 20-22h, grinding, and calcining at 550-600deg.C in muffle furnace for 8 h.
The technology has at least the following problems: 1. the obtained gel needs to be calcined, the calcining temperature is higher, and the generated product is easy to generate a condensation phenomenon, so that the photocatalytic activity of the product is reduced; 2. the pH value is adjusted by nitric acid, so that the corrosion is strong, the removal is difficult during calcination, and the photocatalytic activity of the product is greatly influenced.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention aims to provide a method for preparing a copper-doped titanium dioxide photocatalyst.
The invention provides a preparation method of a copper-doped titanium dioxide photocatalyst, which comprises the following steps: a. and (3) mixing and dissolving: completely dissolving a copper source in an organic solvent, adding a titanium source and a pH regulator, and uniformly stirring to obtain a mixed solution; b. hydrolysis: slowly dripping water into the mixed solution obtained in the step a until gel is formed; c. hydrothermal reaction: and c, carrying out hydrothermal reaction on the gel obtained in the step b, and drying after the reaction is finished to obtain the copper-doped titanium dioxide photocatalyst.
Further, the copper source in the step a is copper salt which is soluble in an organic solvent.
Preferably, the copper source in the step a is at least one of copper nitrate, copper sulfate and copper chloride.
Further, the organic solvent in the step a is absolute ethanol.
Further, the titanium source in the step a is at least one of tetrabutyl titanate, tetraisopropyl titanate and titanium tetrachloride.
Further, the pH adjuster in step a is glacial acetic acid.
Further, step a adjusts the pH of the solution to 2-3.
Further, copper in step a: the molar ratio of titanium is 1: (10-100).
Preferably, copper in step a: the molar ratio of titanium is 1:50.
further, the dropping speed in the step b is one drop of water every 3 seconds.
Further, the hydrothermal reaction of step c satisfies at least one of the following:
the hydrothermal reaction temperature is above 120 ℃;
preferably, the hydrothermal reaction temperature is 120-200 ℃;
the hydrothermal reaction time is more than 6 hours;
preferably, the hydrothermal reaction time is 6 to 12 hours.
Further, the drying in step c is carried out at 120 ℃ for 14 hours.
Taking the hydrolysis process of tetrabutyl titanate as an example, the hydrolysis principle is as follows:
Ti(O-CH 4 ) 4 +H 2 O→Ti(O-CH 4 ) 3 (OH)+C 4 H 9 OH
Ti(O-CH 4 ) 3 (OH)+H 2 O→Ti(O-CH 4 ) 2 (OH) 2 +C 4 H 9 OH
Ti(O-CH 4 ) 2 (OH) 2 +H 2 O→Ti(O-CH 4 )(OH) 3 +C 4 H 9 OH
Ti(O-CH 4 (OH) 3 +H 2 O→Ti(OH) 4 +C 4 H 9 OH
total reaction type Ti (O-CH) 4 ) 4 +4H 2 O→Ti(OH) 4 +4C 4 H 9 OH
Principle of hydrothermal: the hydrothermal method is a method for obtaining a high-temperature and high-pressure environment by taking water as a reaction solvent under a closed condition and taking the pressure of the water and the external temperature as conditions, so that some indissolvable or insoluble substances can be dissolved and recrystallized. The chemical reaction process for preparing the powder by the hydrothermal method is carried out in a high-pressure container in which fluid participates. At high temperature, the solute water in the sealed container becomes water vapor, filling the whole sealed container, thereby generating huge pressure. The solubility of orthotitanic acid increases with increasing temperature during heating, eventually leading to supersaturation of the solution and the gradual formation of more stable TiO 2 And (5) a crystal.
The preparation method of the copper-doped titanium dioxide photocatalyst provided by the invention mainly has the following advantages:
1. compared with the prior art, the method omits the step of high-temperature calcination, is favorable for solving the problems of product agglomeration, reduced photocatalytic activity and the like, and can also save the production cost.
2. The method for mixing, dissolving and hydrolyzing adopted by the process can shorten the gel time and avoid the aging process. The existing method generally needs to be aged for more than 7 hours after sol is formed, and some methods can be aged for 12-24 hours to completely form gel. Thus, the present invention further simplifies the production process.
Detailed Description
The invention provides a preparation method of a copper-doped titanium dioxide photocatalyst, which comprises the following steps: a. and (3) mixing and dissolving: completely dissolving a copper source in an organic solvent, adding a titanium source and a pH regulator, and uniformly stirring to obtain a mixed solution; b. hydrolysis: slowly dripping water into the mixed solution obtained in the step a until gel is formed; c. hydrothermal reaction: and c, carrying out hydrothermal reaction on the sol obtained in the step b, and drying after the reaction is finished to obtain the copper-doped titanium dioxide photocatalyst.
The present invention has been completed based on the following findings by the inventors:
when the copper-doped titanium dioxide photocatalyst is prepared by the method disclosed in Chinese patent application 201610673009.8, the solution A and the solution B are mixed to form sol/gel, and meanwhile, precipitation is carried out in the system. It was found by analysis that the reaction product formed in precipitated form could not be converted into anatase titanium dioxide in subsequent hydrothermal treatment to exert photocatalytic activity, but the conversion of the crystalline form had to be achieved by high temperature calcination. Thus, not only the operation procedure is increased, but also the problem of particle agglomeration is easy to occur in the high-temperature calcination process, and the photocatalytic activity of the product is adversely affected. In contrast, the gel formed after mixing was Ti (OH) 4 Copper can be uniformly distributed therein; through hydrothermal treatment, ti (OH) 4 The anatase titanium dioxide is generated by sol dehydration, so that the photocatalyst has photocatalytic activity, and meanwhile, the particle size of the product particles is smaller, so that the photocatalyst is beneficial to improving the photocatalytic activity. Experiments prove that the gel-form reaction product can fully realize the transformation of crystal forms after being dried, and high-temperature calcination is not needed.
Further studies have found that the amount and rate of water addition are key factors affecting the morphology of the titanium source hydrolysate. If a slow dripping mode is adopted, and the adding amount of water is strictly controlled, the generation of sediment is reduced, and the hydrolysate in gel form is mainly obtained.
Based on this, the present invention provides a new charging sequence to prepare copper doped titania photocatalyst, namely: firstly, completely dissolving a copper source in an organic solvent, adding a titanium source and a pH regulator, and uniformly stirring to obtain a mixed solution; slowly dripping water into the mixed solution until gel is formed; finally, carrying out hydrothermal reaction and drying to obtain the copper doped titanium dioxide photocatalyst. By adopting the preparation method, the gel end point is easy to control, the addition amount of water can be strictly controlled, the generation of precipitation can be effectively avoided, the high-temperature calcination step of the existing method is further omitted, the problems of product agglomeration, reduction of photocatalytic activity and the like are solved, and meanwhile, the production cost can be saved.
In addition, the method for mixing, dissolving and hydrolyzing adopted by the process can shorten the gel time and avoid the aging process. The existing method generally needs to be aged for more than 7 hours after sol is formed, and some methods can be aged for 12-24 hours to completely form gel.
The invention may also have the following additional technical features:
according to some embodiments of the invention, copper in step a: the molar ratio of titanium is 1: (10-100). Preferably, copper in step a: the molar ratio of titanium is 1:50, the photocatalyst obtained at this time has the best effect of degrading methyl orange.
According to some embodiments of the invention, the drop rate in step b is one drop of water every 3 seconds. According to the above-mentioned dropping speed, almost no precipitate formation was observed. If the dropping speed is too high, precipitation is easy to form, and the solution cannot be dissolved back and clarified.
According to some embodiments of the invention, the hydrothermal reaction temperature is 120 ℃ or higher; the hydrothermal reaction time is more than 6 hours. From the test results, both the increase of the hydrothermal temperature and the prolongation of the hydrothermal time are beneficial to the photocatalytic effect of the product. Because the hydrothermal reaction device in the laboratory generally adopts the polytetrafluoroethylene liner, the highest temperature can only bear 200 ℃, otherwise, the liner is easy to damage, and therefore, the hydrothermal reaction temperature is preferably 120-200 ℃.
The scheme of the present invention will be explained below with reference to examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the present invention and should not be construed as limiting the scope of the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
EXAMPLE 1 preparation of copper-doped Titania photocatalyst by the method of the present invention
(1) Taking 0.996g of copper nitrate and 50g of absolute ethyl alcohol, stirring to completely dissolve the copper nitrate, then dropwise adding 14g of tetrabutyl titanate, and uniformly stirring; adding glacial acetic acid until the pH value of the solution is 2-3, wherein the solution has obvious color change, and the adding amount of the glacial acetic acid is 10g;
(2) hydrolysis of tetrabutyl titanate was performed: continuously stirring the solution, slowly dripping distilled water, and dripping one drop every 3 seconds until sol is formed, wherein the adding amount of the distilled water is 26g;
(3) carrying out hydrothermal reaction: filling the formed sol into a digestion tank with a polytetrafluoroethylene lining of 100ml, and taking out the sol after the hydrothermal reaction temperature is 160 ℃ for 9 hours; drying at 120deg.C for 14h, and evaporating the solution;
(4) grinding the obtained solid powder until no granular feel exists, and detecting the photocatalytic activity, wherein the detection method comprises the following steps: a20 mg/l methyl orange solution is used as an indication solution, a 500w mercury lamp is adopted as a light source, and 0.65g sample is weighed and put into a photochemical reaction instrument for photocatalysis test. The detection result shows that the degradation rate of the photocatalytic degradation methyl orange reaches 94% in 45min and 97% in 60 min.
Comparative example 1 preparation of copper doped titanium dioxide photocatalyst by calcination
(1) Taking 0.199g of copper nitrate and 50g of absolute ethyl alcohol, stirring to completely dissolve the copper nitrate, then dropwise adding 14g of tetrabutyl titanate, and uniformly stirring; adding glacial acetic acid until the pH value of the solution is 2-3, wherein the solution has obvious color change, and the adding amount of the glacial acetic acid is 10g;
(2) hydrolysis of tetrabutyl titanate was performed: continuously stirring the solution, slowly dripping distilled water, and dripping one drop every 3 seconds until sol is formed, wherein the adding amount of the distilled water is 27.46g;
(3) carrying out hydrothermal reaction: filling the formed sol into a digestion tank with a polytetrafluoroethylene lining of 100ml, and taking out the sol after the hydrothermal reaction temperature is 200 ℃ for 9 hours; drying at 120deg.C for 14h, and evaporating the solution;
(4) calcining: grinding the obtained solid into powder, and placing the powder into a muffle furnace for calcination at 300 ℃ for 1 h;
(5) grinding the obtained solid powder until no granular feel exists, and detecting the photocatalytic activity, wherein the photodegradation rate reaches 85% within 60 min.
From the experimental results, the effect of photocatalytic degradation of methyl orange without calcining after drying the product is better than that of the calcined product.
Comparative example 2 preparation of copper doped titanium dioxide photocatalyst by calcination
(1) Taking 0.598g of copper nitrate and 50g of absolute ethyl alcohol, stirring to completely dissolve the copper nitrate, then dropwise adding 14g of tetrabutyl titanate, and uniformly stirring; adding glacial acetic acid until the pH value of the solution is 2-3, wherein the solution has obvious color change, and the adding amount of the glacial acetic acid is 10g;
(2) hydrolysis of tetrabutyl titanate was performed: continuously stirring the solution, slowly dripping distilled water, and dripping one drop every 3 seconds until sol is formed, wherein the adding amount of the distilled water is 35.81g;
(3) carrying out hydrothermal reaction: filling the formed sol into a digestion tank with a polytetrafluoroethylene lining of 100ml, and taking out the sol after the hydrothermal reaction temperature is 200 ℃ for 12 hours; drying at 120deg.C for 14h, and evaporating the solution;
(4) calcining: grinding the obtained solid into powder, and placing the powder into a muffle furnace for calcination at 120 ℃ for 1 hour;
(5) grinding the obtained solid powder until no granular feel exists, and detecting the photocatalytic activity, wherein the photodegradation rate reaches 94% within 60 min.
From the experimental results, the calcination temperature of comparative example 2 is lower than that of comparative example 1, and the photocatalytic degradation effect of methyl orange of the obtained product is better than that of comparative example 1, which is possibly related to agglomeration of catalyst particles caused by calcination under high temperature conditions.
Comparative example 3 preparation of copper doped titanium dioxide photocatalyst by calcination
(1) Taking 0.199g of copper nitrate and 50g of absolute ethyl alcohol, stirring to completely dissolve the copper nitrate, then dropwise adding 14g of tetrabutyl titanate, and uniformly stirring; adding glacial acetic acid until the pH value of the solution is 2-3, wherein the solution has obvious color change, and the adding amount of the glacial acetic acid is 10g;
(2) hydrolysis of tetrabutyl titanate was performed: continuously stirring the solution, slowly dripping distilled water, and dripping one drop every 3 seconds until sol is formed, wherein the adding amount of the distilled water is 24.16g;
(3) carrying out hydrothermal reaction: filling the formed sol into a digestion tank with a polytetrafluoroethylene lining of 100ml, and taking out the sol after the hydrothermal reaction temperature is 160 ℃ for 12 hours; drying at 120deg.C for 14h, and evaporating the solution;
(4) calcining: grinding the obtained solid into powder, and placing the powder into a muffle furnace for calcination at 200 ℃ for 1 h;
(5) grinding the obtained solid powder until no granular feel exists, and detecting the photocatalytic activity, wherein the photodegradation rate reaches 88% within 60 min.
Comparative example 4 preparation of copper doped titanium dioxide photocatalyst without calcination in the prior art
Taking 0.996g of copper nitrate, 15ml of ethanol and 5g of water, stirring to completely dissolve the copper nitrate, and preparing a solution A;
then, 14g of tetrabutyl titanate is dripped into 50g of ethanol, and is stirred uniformly, and 10g of glacial acetic acid is added to prepare a solution B;
under the condition of constant temperature stirring, gradually dripping the solution A into the solution B, vigorously stirring to enable the solution A and the solution B to be fully mutually dissolved to form transparent sol, forming precipitate at the moment, sealing the sol, and aging for 24 hours in a shade place.
Carrying out hydrothermal reaction: filling the formed sol into a digestion tank with a polytetrafluoroethylene lining of 100ml, and taking out the sol after the hydrothermal reaction temperature is 160 ℃ for 9 hours; drying at 120deg.C for 14h, and evaporating the solution;
grinding the obtained solid powder until no granular feel exists, and detecting the photocatalytic activity, wherein the photodegradation rate reaches 92% within 60 min.
Comparative example 5 preparation of copper doped titanium dioxide photocatalyst without calcination in the prior art
Slowly adding 9ml of tetrabutyl titanate into 15ml of absolute ethyl alcohol at a constant speed, and magnetically stirring uniformly to obtain a solution A;
7.5ml of absolute ethyl alcohol, 1.4ml of deionized water, 0.7ml of nitric acid and 0.996g of copper nitrate are mixed to obtain solution B;
slowly dripping the solution B into the solution A, stirring while dripping, and continuing stirring for 1h after dripping is completed to obtain a pale yellow transparent solution, namely sol; the sol obtained was placed in an incubator (25 ℃) for 48 hours to obtain a sol.
Carrying out hydrothermal reaction: filling the formed sol into a digestion tank with a polytetrafluoroethylene lining of 100ml, and taking out the sol after the hydrothermal reaction temperature is 200 ℃ for 9 hours; drying at 140 ℃ for 14 hours, and evaporating the solution;
grinding the obtained solid powder until no granular feel exists, and detecting the photocatalytic activity, wherein the photodegradation rate reaches 90% within 60 min.
It is to be noted that the particular features, structures, materials, or characteristics described in this specification may be combined in any suitable manner in any one or more embodiments. Furthermore, the various embodiments described in this specification, as well as the features of the various embodiments, can be combined and combined by one skilled in the art without contradiction.
Claims (3)
1. The preparation method of the copper-doped titanium dioxide photocatalyst is characterized by comprising the following steps of: the method comprises the following steps:
a. and (3) mixing and dissolving: completely dissolving a copper source in an organic solvent, adding a titanium source and a pH regulator, and uniformly stirring to obtain a mixed solution, wherein the copper source is at least one of copper nitrate, copper sulfate and copper chloride, the titanium source is at least one of tetrabutyl titanate, tetraisopropyl titanate and titanium tetrachloride, the pH regulator is glacial acetic acid, the pH of the solution is regulated to 2-3, and the mixed solution contains copper: the molar ratio of titanium is 1:10 to 100; the organic solvent in the step a is absolute ethyl alcohol;
b. hydrolysis: slowly dripping water into the mixed solution obtained in the step a until gel is formed, wherein the speed of dripping water is that one drop of water is dripped every 3 seconds;
c. hydrothermal reaction: and c, carrying out hydrothermal reaction on the gel obtained in the step b, and drying after the reaction is finished to obtain the copper-doped titanium dioxide photocatalyst, wherein the hydrothermal reaction temperature is 120-200 ℃, and the hydrothermal reaction time is 6-12 h.
2. The method of preparing as claimed in claim 1, wherein: copper in step a: the molar ratio of titanium is 1:50.
3. the method of preparing as claimed in claim 1, wherein: the drying described in step c was carried out at 120℃for 14h.
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