CN116554718A - Preparation method and application of sea urchin-shaped titanium dioxide coating - Google Patents
Preparation method and application of sea urchin-shaped titanium dioxide coating Download PDFInfo
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- CN116554718A CN116554718A CN202310492507.2A CN202310492507A CN116554718A CN 116554718 A CN116554718 A CN 116554718A CN 202310492507 A CN202310492507 A CN 202310492507A CN 116554718 A CN116554718 A CN 116554718A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 63
- 239000011248 coating agent Substances 0.000 title claims abstract description 43
- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001291 vacuum drying Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000006228 supernatant Substances 0.000 claims abstract description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 13
- 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 abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 7
- 231100000719 pollutant Toxicity 0.000 claims abstract description 7
- 239000004568 cement Substances 0.000 claims abstract description 6
- 238000004321 preservation Methods 0.000 claims abstract description 6
- 230000009467 reduction Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 58
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 7
- 239000003973 paint Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 241000282414 Homo sapiens Species 0.000 description 5
- 241000257465 Echinoidea Species 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
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Abstract
The application provides a preparation method and application of sea urchin-shaped titanium dioxide paint, comprising the following steps: (1) Adding tetrabutyl titanate into a sodium hydroxide solution, stirring and ultrasonic treatment at room temperature, adding ethylene glycol into the solution, and stirring to obtain a white solution; (2) Transferring the white solution obtained in the step (1) into a reaction kettle, adjusting the heating time, the heating temperature and the heat preservation time of an oven, and pouring out the supernatant of the obtained precipitate after heating; (3) The sea urchin-shaped anatase phase titanium dioxide material is obtained by calcining the composite material prepared in the step (2) in a muffle furnace after vacuum drying, the structure is reasonable, the prepared sea urchin-shaped titanium dioxide coating has the highest specific surface area and the largest active site, the stability of chemical properties is improved, the photocatalytic effect is enhanced, and the coating can be applied to photocatalytic degradation of pollutants, reduction of NOx concentration in cement road materials and self-cleaning of photocatalysts.
Description
Technical Field
The application relates to a preparation method of a titanium dioxide coating, in particular to a preparation method and application of a sea urchin-shaped titanium dioxide coating.
Background
Along with the disordered rapid expansion of human economy and society, human substance life is greatly enriched and satisfied, but serious water and air pollution is brought at the same time, the human life and development are greatly threatened, the human society increasingly realizes that the environmental pollution is serious threat and challenge to the current generation and future survival and development of human beings, and the pollution is taken as global consensus by taking positive measures, in many pollutants, the organic pollution is the most common and serious pollution, the photocatalytic degradation technology is a green new technology for treating the organic pollution, and has the advantages of mild reaction condition, thorough purification, complete green reaction driving energy, strong oxidizing property, wide universality and the like, so the adoption of the photocatalytic technology for treating the organic pollutant by utilizing sustainable solar energy is a very promising technology for solving the ecological environment problem, the photocatalyst is a core part of the photocatalytic reaction, the higher the activity of the catalyst can be better, and the photocatalyst can be divided into different element categories according to the physical and chemical properties: compared with other semiconductor materials, tiO2 has the advantages of good stability, low price, abundant reserves, no toxicity, no harm and the like, and is one of the preferred catalyst materials widely applied in photocatalytic reactions.
In the prior art, different morphologies of TiO2 can show different catalytic performances, such as a nano tube, a nano rod, a sea urchin shape, a nano sheet and the like, wherein the sea urchin shape can obviously enhance the specific surface area, is an effective strategy for enhancing the exposure of active sites, and TiO2 has various crystal forms, the photocatalytic performance of the TiO2 can also be different, and common TiO2 crystals have rutile phase, anatase phase and brookite phase 3 crystal forms, wherein the anatase phase TiO2 has stable chemical property and the best photocatalytic effect, and the three reasons are that: 1) The higher forbidden bandwidth (3.2 eV) of the anatase phase TiO2 ensures that electron hole pairs have more positive or more negative potential and the oxidation capability is stronger; 2) The anatase phase TiO2 surface has stronger capability of adsorbing H2O, O2 and OH, and the stronger light adsorption capability is beneficial to photocatalysis, so that the photocatalytic activity is higher; 3) In the crystallization process, anatase crystal grains usually have smaller size and larger specific surface area, the main application of titanium dioxide in daily life is as pigment, titanium dioxide is the most widely used white pigment in industry, and has good dispersibility, ultraviolet shielding effect and other excellent performances, however, the existing prepared anatase phase TiO2 has lower specific surface area and fewer active sites, so that the stability of chemical properties is reduced, and the photocatalytic effect is reduced, and therefore, a preparation method of the sea urchin-shaped titanium dioxide coating is needed to solve the problems.
Disclosure of Invention
Aiming at the defects existing in the prior art, the application aims to provide a preparation method and application of sea urchin-shaped titanium dioxide paint, so as to solve the problems in the background art.
In order to achieve the above object, the present application provides a method for preparing a sea urchin-shaped titanium dioxide coating, comprising the steps of:
(1) Adding tetrabutyl titanate into a sodium hydroxide solution, stirring and ultrasonic treatment at room temperature, adding ethylene glycol into the solution, and stirring to obtain a white solution;
(2) Transferring the white solution obtained in the step (1) into a reaction kettle, adjusting the heating time, the heating temperature and the heat preservation time of an oven to perform hydrothermal reaction, pouring out supernatant of the obtained precipitate after heating, placing the supernatant in low-concentration acid solution to soak for a certain time, washing and filtering until the pH value reaches neutrality to obtain a composite material;
(3) Drying the composite material prepared in the step (2) in vacuum, and calcining in a muffle furnace to obtain a sea urchin-shaped anatase phase titanium dioxide material;
(4) Adding isopropanol into the sea urchin-shaped anatase-phase titanium dioxide material prepared in the step (3), stirring and carrying out ultrasonic treatment to prepare a suspension A;
pouring the silane coupling agent into isopropanol and stirring to obtain a solution B;
and mixing the solution A and the solution B, stirring, and transferring to a constant-temperature oil bath pot for stirring for a certain time to obtain the sea urchin-shaped titanium dioxide coating.
Preferably, the volume ratio of tetrabutyl titanate to sodium hydroxide solution in the step (1) is 1:10 to 1:80, wherein the concentration of the sodium hydroxide solution is 0.1-5 mol/L.
Preferably, the heating time of the oven in the step (2) is 5-10 ℃/min, the heating temperature is 100-200 ℃ and the heat preservation time is 6-24 hours.
Preferably, the precipitate after the hydrothermal reaction in the step (2) is washed and filtered 4 to 8 times.
Preferably, the acidic solution in the step (2) is hydrochloric acid solution, and the concentration of the acidic solution is 0.05-3 mol/L.
Preferably, the vacuum drying in step (3) is carried out at a temperature of 50 to 80 ℃ and the calcination is carried out under a pressure of less than 1kPa for 12 to 24 hours.
Preferably, the temperature of calcination in the muffle furnace after vacuum drying in the step (3) is 200-650 ℃, and the calcination is kept for 2-6 hours.
Preferably, the temperature of calcination in a muffle furnace after vacuum drying is 200 ℃, 300 ℃ or 400 ℃.
Preferably, the temperature of stirring in the constant temperature oil bath in the step (4) is 25-85 ℃, and stirring is kept for 1-6h.
Preferably, the sea urchin-shaped titanium dioxide coating prepared by the preparation method is applied to photocatalytic degradation of pollutants, reduction of NOx concentration in cement road materials and self-cleaning of photocatalysts.
According to the preparation method of the sea urchin-shaped titanium dioxide coating, the crystal phase of the sea urchin-shaped titanium dioxide coating prepared by the preparation method belongs to an anatase phase, is sea urchin-shaped in appearance, has the highest specific surface area and the most active sites, so that the chemical property of the sea urchin-shaped titanium dioxide coating is stable, and the photocatalysis effect is best;
the sea urchin-shaped titanium dioxide coating prepared by the preparation method can be applied to photocatalytic degradation of pollutants, reduction of NOx concentration in cement road materials and self-cleaning of photocatalysts.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the detailed description of non-limiting embodiments, made with reference to the accompanying drawings in which:
FIG. 1 is a chart showing XRD patterns of the sea urchin-like anatase phase titanium dioxide material of example 1 in a process for preparing a sea urchin-like titanium dioxide coating according to an embodiment of the present application;
FIG. 2 is a scanning electron microscope image of a process for preparing a sea urchin-like titanium dioxide coating according to an embodiment of the present application, prior to calcination of the composite material prepared in example 1;
FIG. 3 is a Scanning Electron Microscope (SEM) map of the calcined composite material prepared in example 1 in a method for preparing a sea urchin-like titanium dioxide coating according to an embodiment of the present application;
FIG. 4 is a Scanning Electron Microscope (SEM) map of the composite material prepared in example 2 in a method of preparing a sea urchin-like titanium dioxide coating according to an embodiment of the present application;
FIG. 5 is a Scanning Electron Microscope (SEM) map of the composite material prepared in example 3 in a method of preparing a sea urchin-like titanium dioxide coating according to an embodiment of the present application;
FIG. 6 is a graph comparing the degradation rate of rhodamine B by the sea urchin-like anatase phase titanium dioxide material prepared in each of examples 1-3 in a method for preparing a sea urchin-like titanium dioxide coating according to an embodiment of the present application.
Detailed Description
In order to make the technical means, the creation features, the achievement of the purpose and the effect achieved in the present application easy to understand, the present application is further described below in connection with the specific embodiments.
The application provides a technical scheme: a preparation method of sea urchin-shaped titanium dioxide paint comprises the following steps:
(1) Adding tetrabutyl titanate into a sodium hydroxide solution, stirring and ultrasonic treatment at room temperature, adding ethylene glycol into the solution, and stirring to obtain a white solution;
(2) Transferring the white solution obtained in the step (1) into a reaction kettle, adjusting the heating time, the heating temperature and the heat preservation time of an oven to perform hydrothermal reaction, pouring out supernatant of the obtained precipitate after heating, placing the supernatant in low-concentration acid solution to soak for a certain time, washing and filtering until the pH value reaches neutrality to obtain a composite material;
(3) Drying the composite material prepared in the step (2) in vacuum, and calcining in a muffle furnace to obtain a sea urchin-shaped anatase phase titanium dioxide material;
(4) Adding isopropanol into the sea urchin-shaped anatase-phase titanium dioxide material prepared in the step (3), stirring and carrying out ultrasonic treatment to prepare a suspension A;
pouring the silane coupling agent into isopropanol and stirring to obtain a solution B;
and mixing the solution A and the solution B, stirring, and transferring to a constant-temperature oil bath pot for stirring for a certain time to obtain the sea urchin-shaped titanium dioxide coating.
Preferably, the volume ratio of tetrabutyl titanate to sodium hydroxide solution in the step (1) is 1:10 to 1:80, wherein the concentration of the sodium hydroxide solution is 0.1-5 mol/L.
Preferably, the heating time of the oven in the step (2) is 5-10 ℃/min, the heating temperature is 100-200 ℃ and the heat preservation time is 6-24 hours.
Preferably, the precipitate after the hydrothermal reaction in the step (2) is washed and filtered 4 to 8 times.
Preferably, the acidic solution in the step (2) is hydrochloric acid solution, and the concentration of the acidic solution is 0.05-3 mol/L.
Preferably, the vacuum drying in step (3) is carried out at a temperature of 50 to 80 ℃ and the calcination is carried out under a pressure of less than 1kPa for 12 to 24 hours.
Preferably, the temperature of calcination in the muffle furnace after vacuum drying in the step (3) is 200-650 ℃, and the calcination is kept for 2-6 hours.
Preferably, the temperature of calcination in a muffle furnace after vacuum drying is 200 ℃, 300 ℃ or 400 ℃.
Preferably, the temperature of stirring in the constant temperature oil bath in the step (4) is 25-85 ℃, and stirring is kept for 1-6h.
Preferably, the sea urchin-shaped titanium dioxide coating prepared by the preparation method is applied to photocatalytic degradation of pollutants, reduction of NOx concentration in cement road materials and self-cleaning of photocatalysts.
In the following, according to a method for preparing a sea urchin-like titanium dioxide coating according to the present application, specific examples, example 1,
(11) 1mL of tetrabutyl titanate is added into 52mL of sodium hydroxide solution (1.5 mol/L), after stirring for 20 minutes and ultrasonic treatment for 5 minutes, 106mL of ethylene glycol is added into the solution, and stirring is carried out for 10 minutes, so as to obtain a white solution;
(12) Transferring the white solution into a reaction kettle, heating an oven for 5 ℃ per minute, preserving heat for 12 hours at 150 ℃, pouring out supernatant liquid of the obtained precipitate, placing the supernatant liquid into a hydrochloric acid solution with the concentration of 0.1mol/L for soaking for 12 hours, washing and filtering until the pH value reaches neutrality to obtain a composite material;
(13) Vacuum drying the composite material for 12 hours at 60 ℃, and calcining the composite material for 4 hours at 200 ℃ in a muffle furnace to obtain a sea urchin-shaped anatase phase titanium dioxide material;
(14) Adding 20ml of isopropanol into 0.5g of sea urchin-like anatase-phase titanium dioxide material, stirring for 30min, and performing ultrasonic treatment for 30min to prepare a suspension A;
pouring 2ml of silane coupling agent into 20ml of isopropanol and stirring to obtain a solution B;
mixing the solution A and the solution B, stirring for 30min, transferring to a constant temperature (35 ℃) oil bath pot, and stirring for 2h to obtain the sea urchin-shaped titanium dioxide coating.
In the case of example 2,
(21) 1mL of tetrabutyl titanate is added into 52mL of sodium hydroxide solution (1.5 mol/L), after stirring for 20 minutes and ultrasonic treatment for 5 minutes, 106mL of ethylene glycol is added into the solution, and stirring is carried out for 10 minutes, so as to obtain a white solution;
(22) Transferring the white solution into a reaction kettle, heating an oven for 5 ℃ per minute, preserving heat for 12 hours at 150 ℃, pouring out supernatant liquid of the obtained precipitate, placing the supernatant liquid into a hydrochloric acid solution with the concentration of 0.1mol/L for soaking for 12 hours, washing and filtering until the pH value reaches neutrality to obtain a composite material;
(23) Vacuum drying the composite material for 12 hours at 60 ℃, and calcining the composite material for 4 hours at 300 ℃ in a muffle furnace to obtain a sea urchin-shaped anatase phase titanium dioxide material;
(24) Adding 20ml of isopropanol into 0.5g of sea urchin-like anatase-phase titanium dioxide material, stirring for 30min, and performing ultrasonic treatment for 30min to prepare a suspension A;
pouring 2ml of silane coupling agent into 20ml of isopropanol and stirring to obtain a solution B;
mixing the solution A and the solution B, stirring for 30min, transferring to a constant temperature (35 ℃) oil bath pot, and stirring for 2h to obtain the sea urchin-shaped titanium dioxide coating.
In the case of example 3,
(31) 1mL of tetrabutyl titanate is added into 52mL of sodium hydroxide solution (1.5 mol/L), after stirring for 20 minutes and ultrasonic treatment for 5 minutes, 106mL of ethylene glycol is added into the solution, and stirring is carried out for 10 minutes, so as to obtain a white solution;
(32) Transferring the white solution into a reaction kettle, heating an oven for 5 ℃ per minute, preserving heat for 12 hours at 150 ℃, pouring out supernatant liquid of the obtained precipitate, placing the supernatant liquid into a hydrochloric acid solution with the concentration of 0.1mol/L for soaking for 12 hours, washing and filtering until the pH value reaches neutrality to obtain a composite material;
(33) Vacuum drying the composite material for 12 hours at 60 ℃, and calcining the composite material for 4 hours at 400 ℃ in a muffle furnace to obtain a sea urchin-shaped anatase phase titanium dioxide material;
(34) Adding 20ml of isopropanol into 0.5g of sea urchin-like anatase-phase titanium dioxide material, stirring for 30min, and performing ultrasonic treatment for 30min to prepare a suspension A;
pouring 2ml of silane coupling agent into 20ml of isopropanol and stirring to obtain a solution B;
mixing the solution A and the solution B, stirring for 30min, transferring to a constant temperature (35 ℃) oil bath pot, and stirring for 2h to obtain the sea urchin-shaped titanium dioxide coating.
In summary, the preparation method and application of the sea urchin-shaped titanium dioxide coating according to the present application, according to the sea urchin-shaped titanium dioxide coating prepared by the preparation method of examples 1-3, and referring to the graph of the degradation rate of rhodamine B in fig. 6, it can be known that the degradation performance of the composite material obtained in examples 1-3 is compared, and certain degradation capability is shown, so that the sea urchin-shaped titanium dioxide coating prepared by the preparation method of the present application can be applied in photocatalytic degradation of pollutants, in addition, the conventional sea urchin-shaped titanium dioxide coating which has been doped in highways has the effect of reducing nitrogen oxides, has the effect of self-cleaning when being smeared on glass or on roofs, and in the same way, the sea urchin-shaped titanium dioxide coating prepared per se can be applied in reduction of NOx concentration in cement road materials and self-cleaning of photocatalysts;
XRD, SEM and other tests were carried out on the materials obtained in examples 1-3, and the results are shown in FIGS. 1-6, wherein the XRD results in FIG. 1 show that the sea urchin-like anatase phase titanium dioxide material was prepared in example 1;
the SEM morphology results referring to fig. 2 and 3 show that the composite material prepared in example 1 in fig. 2 is a Scanning Electron Microscope (SEM) morphology before calcination, and the composite material prepared in example 1 in fig. 3 is a SEM morphology after calcination, so that the prepared material is sea urchin-shaped, and the calcined composite material shows better morphology than the composite material before calcination;
referring to fig. 4 and 5, in which fig. 4 is a scanning electron microscope spectrum of the composite material prepared in example 2, and fig. 5 is a scanning electron microscope spectrum of the composite material prepared in example 3, it is known that the morphology of the composite material is still in a sea urchin shape, and therefore, it is known that the crystal phase of the sea urchin-shaped titanium dioxide coating prepared by the preparation method of the present application belongs to an anatase phase, and the morphology is a sea urchin shape, and has the highest specific surface area and the most active sites, so that the chemical property is stable, and the photocatalytic effect is the best.
Wherein in fig. 6, the hydrothermal values 150-12: placing the reaction kettle in an oven during hydrothermal reaction, heating to 150 ℃ and preserving heat for 12 hours;
150-12-200-4: placing the reaction kettle in an oven, heating to 150 ℃ and preserving heat for 12 hours, and calcining in a muffle furnace at 200 ℃ for 4 hours;
150-12-300-4: placing the reaction kettle in an oven, heating to 150 ℃ and preserving heat for 12 hours, and then calcining in a muffle furnace at 300 ℃ for 4 hours;
150-12-400-4: the reaction vessel representing the hydrothermal reaction was placed in an oven, heated to 150℃and incubated for 12 hours, and then calcined in a muffle furnace at 400℃for 4 hours.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The preparation method of the sea urchin-shaped titanium dioxide coating is characterized by comprising the following steps of:
(1) Adding tetrabutyl titanate into a sodium hydroxide solution, stirring and ultrasonic treatment at room temperature, adding ethylene glycol into the solution, and stirring to obtain a white solution;
(2) Transferring the white solution obtained in the step (1) into a reaction kettle, adjusting the heating time, the heating temperature and the heat preservation time of an oven to perform hydrothermal reaction, pouring out supernatant of the obtained precipitate after heating, placing the supernatant in low-concentration acid solution to soak for a certain time, washing and filtering until the pH value reaches neutrality to obtain a composite material;
(3) Drying the composite material prepared in the step (2) in vacuum, and calcining in a muffle furnace to obtain a sea urchin-shaped anatase phase titanium dioxide material;
(4) Adding isopropanol into the sea urchin-shaped anatase-phase titanium dioxide material prepared in the step (3), stirring and carrying out ultrasonic treatment to prepare a suspension A;
pouring the silane coupling agent into isopropanol and stirring to obtain a solution B;
and mixing the solution A and the solution B, stirring, and transferring to a constant-temperature oil bath pot for stirring for a certain time to obtain the sea urchin-shaped titanium dioxide coating.
2. The method for preparing the sea urchin-shaped titanium dioxide coating according to claim 1, wherein the volume ratio of tetrabutyl titanate to sodium hydroxide solution in the step (1) is 1:10 to 1:80, wherein the concentration of the sodium hydroxide solution is 0.1-5 mol/L.
3. The method for preparing a sea urchin-like titanium dioxide coating according to claim 1, wherein the oven in step (2) has a heating time of 5-10 ℃/min, a heating temperature of 100-200 ℃ and a holding time of 6-24 hours.
4. The method for preparing a sea urchin-shaped titanium dioxide coating according to claim 1, wherein the precipitate after the hydrothermal reaction in step (2) is washed and filtered 4-8 times.
5. The method for preparing a sea urchin-like titanium dioxide coating according to claim 1, wherein the acidic solution in the step (2) is a hydrochloric acid solution with a concentration of 0.05-3 mol/L.
6. The method for producing a sea urchin-like titanium dioxide coating according to claim 1, wherein the vacuum drying in step (3) is performed under a vacuum drying condition of 50 to 80 ℃, and the vacuum drying is performed under a calcination pressure of less than 1kPa for 12 to 24 hours.
7. The method for preparing a sea urchin-like titanium dioxide coating according to claim 1, wherein the temperature of calcination in a muffle furnace after vacuum drying in step (3) is 200-650 ℃ and maintained for 2-6 hours.
8. The method for preparing a sea urchin-like titanium dioxide coating according to claim 7, wherein the temperature of calcination in a muffle furnace after vacuum drying is 200 ℃, 300 ℃ or 400 ℃.
9. The method for producing a sea urchin-like titanium dioxide coating according to claim 1, wherein the temperature of stirring in the constant temperature oil bath in step (4) is 25-85 ℃ and maintained for 1-6 hours.
10. Use of the sea urchin-shaped titanium dioxide coating prepared by the preparation method according to any one of claims 1-9 in photocatalytic degradation of pollutants, reduction of NOx concentration in cement road materials and self-cleaning of photocatalysts.
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