WO2024060328A1 - Silicon dioxide-rare earth composite photocatalytic material, preparation method therefor, and application thereof - Google Patents

Silicon dioxide-rare earth composite photocatalytic material, preparation method therefor, and application thereof Download PDF

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WO2024060328A1
WO2024060328A1 PCT/CN2022/124136 CN2022124136W WO2024060328A1 WO 2024060328 A1 WO2024060328 A1 WO 2024060328A1 CN 2022124136 W CN2022124136 W CN 2022124136W WO 2024060328 A1 WO2024060328 A1 WO 2024060328A1
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rare earth
photocatalytic material
silica
earth composite
composite photocatalytic
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PCT/CN2022/124136
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French (fr)
Chinese (zh)
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宁海金
黄尚明
钟松华
徐先进
马江平
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江西联锴科技有限公司
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Definitions

  • the invention belongs to the technical field of photocatalytic materials, and in particular refers to a silica-rare earth composite photocatalytic material and its preparation method and application.
  • Silica is chemically stable and non-toxic, and has important applications in electronics, rubber, plastics, coatings, food, medicines, cosmetics, textiles, construction, catalysis and other fields.
  • High specific surface area silica is suitable as a catalyst carrier material to achieve efficient adsorption and catalysis.
  • Photocatalytic materials are mainly nano-semiconductor materials such as nano-titanium dioxide, nano-zinc oxide, nano-tin dioxide, and cadmium sulfide.
  • nano-semiconductor materials such as nano-titanium dioxide, nano-zinc oxide, nano-tin dioxide, and cadmium sulfide.
  • the method of reducing the size of semiconductor materials, loading high specific surface area materials, and heteroatomic doping of semiconductor materials will be used.
  • Long afterglow materials refer to energy storage materials that can continue to emit light at night or in a dark environment after being excited. They mainly include three categories: metal sulfides, rare earth ion-doped alkaline earth metal aluminates, and rare earth ion-doped silicates. Long afterglow metal sulfide materials are chemically unstable, easy to blacken, and are gradually being eliminated. Rare earth ion-doped alkaline earth metal aluminates have the advantages of strong afterglow brightness and long luminescence time, but have disadvantages such as poor water resistance and a single luminescence spectrum.
  • Rare earth ion-doped silicates have the advantages of stable chemical properties, strong water resistance, and a rich luminescence spectrum, but the overall luminescence performance is not as good as that of rare earth ion-doped alkaline earth metal aluminates.
  • the present invention provides a silica-rare earth composite photocatalytic material and its preparation method and application.
  • the present invention adopts the sol-gel method to simultaneously load the photocatalyst and the long afterglow material on the high specific surface area silica, and utilizes the high specific surface area silica's efficient adsorption and high visible light transmittance performance to improve the photocatalyst
  • the catalytic effect while protecting the long afterglow material with poor water resistance, realizes the function of self-luminescence catalysis in low light and dark external environments, and can be promoted in fields such as sewage treatment, air filtration, and building coatings.
  • the first object of the present invention is to provide a silica-rare earth composite photocatalytic material, which includes the following components: silica, long afterglow luminescent material and photocatalytic material.
  • silica long afterglow luminescent material
  • photocatalytic material Through silica, long afterglow luminescent material, light
  • the silica-rare earth composite photocatalytic material is a composite of catalytic materials; the silica-rare earth composite photocatalytic material has a porous structure; wherein the silica-rare earth composite photocatalytic material uses silica as an overall framework, long afterglow luminescent materials and light
  • the catalytic material is uniformly fixed and supported on the silica.
  • the mass ratio of silica, long afterglow luminescent material, and photocatalytic material is 280:1-50:1-50.
  • the silica has a porous structure, is in a transparent or translucent state, and has an average pore diameter of 5 nm to 40 nm; preferably 8 nm to 20 nm.
  • the long afterglow luminescent material is a rare earth doped luminescent material;
  • the photocatalytic material is selected from one or more of metal oxides, nitrogen-doped metal oxides and carbon-doped metal oxides.
  • the rare earth doped luminescent material is selected from the group consisting of CaAl 2 O 4 :Eu 2+ , Nd 3+ , SrAl 2 O 4 :Eu 2+ ,Dy 3+ , SrAl 4 O 7 : Eu 2+ ,Dy 3+ ,SrAl 12 O 19 :Eu 2+ ,Dy 3+ ,Sr 4 Al 14 O 25 :Eu 2+ ,Dy 3+ ,BaAl 2 O 4 :Eu 2+ ,Dy 3+ ,SrAl 2 O 4 : Ce 3+ , Sr 2 Si 2 O 4 : Ce 3+ , Sr 3 SiO 5 : Eu 2+ ,Dy 3+ , Sr 2 Al 2 SiO 7 : Eu 2+ , Sr 2 ZnSi 2 O 7 : Eu 2+ ,Dy 3+ ,Sr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+
  • the average pore diameter of the silica-rare earth composite photocatalytic material is 5nm ⁇ 200nm, more preferably 8nm ⁇ 20nm; the specific surface area is 200m2 /g ⁇ 1500m2 /g, more preferably Preferably, it is 400m2 /g- 1200m2 /g.
  • the photocatalytic material is selected from one or more of metal oxides, nitrogen-doped metal oxides, and carbon-doped metal oxides.
  • the photocatalytic material is selected from the group consisting of tin dioxide, titanium dioxide, zinc oxide, nitrogen-doped tin dioxide, nitrogen-doped titanium dioxide, nitrogen-doped zinc oxide, carbon-doped tin dioxide, carbon-doped titanium dioxide and carbon One or more doped zinc oxides.
  • the photocatalytic material is in the form of nano-tin dioxide powder, nano-titanium dioxide powder, nano-zinc oxide powder, nano-nitrogen-doped tin dioxide powder, nano-nitrogen-doped titanium dioxide powder, nano-nitrogen-doped titanium dioxide powder, Mixed zinc oxide powder, nanocarbon doped tin dioxide powder, nanocarbon doped titanium dioxide powder, nanocarbon doped zinc oxide powder or nanotin dioxide dispersion, nanotitanium dioxide dispersion, nanozinc oxide dispersion, nanonitrogen doped Hybrid tin dioxide dispersion, nano nitrogen doped titanium dioxide dispersion, nano nitrogen doped zinc oxide dispersion, nano carbon doped tin dioxide dispersion, nano carbon doped titanium dioxide dispersion, nano carbon doped zinc oxide dispersion A kind of; preferably nano-tin dioxide dispersion, nano-titanium dioxide dispersion, nano-zinc oxide dispersion, nano-nitrogen-doped tin dioxide dispersion, nano-nitrogen-do
  • the mass fraction of the nanodispersion of photocatalytic material is 5% to 50%, preferably 10% to 30%, and more preferably 10% to 20%.
  • the second object of the present invention is to provide a method for preparing the silica-rare earth composite photocatalytic material, which includes the following steps:
  • step S2 add the alkali solution to the solution in step S1 and continue stirring until gel;
  • step S3 after the gel of step S2 is aged, immersing it in an organic solvent containing a surface modifier;
  • step S4 replace the solvent in the gel pores obtained in step S4 with a low surface tension solvent, and dry to obtain a hydrophobic photocatalytic material;
  • step S5 calcining the hydrophobic photocatalytic material in step S4 to obtain a hydrophilic silica-rare earth composite photocatalytic material.
  • the acid is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, citric acid, oxalic acid and acetic acid, wherein the mass fraction of the acid is 0.1 % ⁇ 5%.
  • the organic solvent is selected from methanol and/or ethanol.
  • the silicon source is selected from one of methyl orthosilicate, ethyl orthosilicate, methyltrimethoxysilane and methyltriethoxysilane, or Various.
  • step S1 the mass ratio of the silicon source, organic solvent, water, and acid is 1:1 to 6:0.2:0.01.
  • the order of adding the raw materials in step S1 is to first mix the silicon source and the organic solvent and stir evenly, then add water dropwise, stir until transparent, and finally add acid;
  • the mass ratio of the silicon source, long afterglow luminescent material and photocatalytic material is 1000:1 ⁇ 50:1 ⁇ 50.
  • the mass ratio of the silicon source, long afterglow luminescent material and photocatalytic material is 1000:10-20:10-30.
  • the base in the alkali solution is selected from one or more of NH 3 ⁇ H 2 O, triethanolamine, sodium hydroxide and potassium hydroxide.
  • the mass fraction of the alkali solution is 0.1% to 5%, and the mass of the dropped alkali solution is 1% to 10% of the silicon source.
  • the order of adding raw materials in step S1 is to first add the photocatalytic material to the mixed silicon source solution, then add the long afterglow material, and continue stirring.
  • the surface modification agent is selected from methyltrimethoxysilane, methyltriethoxysilane, octyltriethoxysilane, and hexamethyldisilazane , trimethylchlorosilane, phenyltrimethylsilane, phenyltriethylsilane, methyltriacetoxysilane, vinyltriacetoxysilane, perfluorooctyltrimethoxysilane, perfluorooctyl One or more of triethoxysilane, perfluorodecyltrimethoxysilane and perfluorodecyltriethoxysilane.
  • the mass fraction of the surface modification agent is 2% to 20%; preferably 5% to 10%.
  • the organic solvent is methanol and/or ethanol.
  • step S3 the specific aging steps are: cover the gel surface with the organic solvent in step S1 and seal it, and age it at 30°C to 80°C for 3h to 12h, preferably 40 Aging at °C ⁇ 60 °C for 5h ⁇ 8h.
  • step S3 the gel is immersed in an organic solvent containing a surface modifier, using a static immersion method or a dynamic immersion method.
  • the dynamic immersion method includes ultrasound, stirring and shaking, preferably stirring immersion, and the time is preferably 1h to 12h, preferably 3h to 8h.
  • the low surface tension solvent is selected from one or more of cyclohexane, n-octane, n-heptane, methanol, ethanol, n-propanol, n-butanol, isobutanol, acetone and hexamethyldisiloxane.
  • the drying is normal pressure drying, freeze drying, microwave drying, supercritical drying or sub-supercritical drying. Normal pressure drying, supercritical drying, and sub-supercritical drying are preferred.
  • the dried silica-rare earth composite photocatalytic material is placed in an oven at 80°C-105°C for 3 hours and the drying weight loss is measured.
  • the drying weight loss is preferably 0 to 5%. , more preferably 0 to 1%.
  • step S4 the solvent in the gel pores in step S3 is replaced with a low surface tension solvent, using a static soaking method or a dynamic soaking method.
  • the dynamic soaking method includes ultrasonic, Stirring and shaking, preferably stirring and soaking, the stirring and soaking time is 0.5h to 6h, preferably 1h to 3h.
  • the calcination temperature is 400°C to 800°C, preferably 550°C to 650°C; the constant temperature time is preferably 1h to 12h, more preferably 1h to 6h; the calcination atmosphere is Air atmosphere.
  • the third object of the present invention is to provide the application of the silica-rare earth composite photocatalytic material in catalytically degrading organic matter in wastewater and exhaust gas; wherein the organic matter is azo dyes, phenol dyes, formaldehyde, grease Or tar.
  • the present invention adopts the sol-gel method to simultaneously load the photocatalyst and the long afterglow material on the high specific surface area silica, and utilizes the high specific surface area silica's efficient adsorption and high visible light transmittance performance to simultaneously achieve It has the functions of self-luminescence, efficient adsorption, and photocatalysis in weak light and dark external environments, and can be used in fields such as sewage treatment, air filtration, and building exterior wall insulation photocatalysis.
  • the present invention realizes the possibility of photodegradation under no light conditions for a long time by incorporating rare earth long afterglow luminescent materials, storing light energy under light conditions, and radiating short-wavelength blue and green visible light under dark conditions, which greatly enhances the The afterglow time of the afterglow is long, and the photocatalytic material is used to enhance the catalytic efficiency, ultimately achieving the result of efficient catalysis; at the same time, it provides more new methods for wastewater and gas treatment.
  • Figure 1 is an electron microscope image SEM of porous silica in Example 1 of the present invention.
  • Figure 2 is a pore size distribution diagram of porous silica in Example 1 of the present invention.
  • Figure 3 shows the visible light transmittance of porous silica in Example 1 of the present invention
  • Figure 4 shows the decomposition rate of methylene blue by silica-rare earth composite photocatalytic materials in Example 2 and Comparative Example 2 of the present invention.
  • This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
  • step S2 add the ammonia solution of group B dropwise to the solution of step S1 and continue stirring until it gels;
  • step S3 after aging the gel in step S2 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane by mass fraction and stir for 8 hours;
  • step S4 Place the gel in step S3 in cyclohexane and stir for 4 hours. Place the gel in an oven at 80°C to dry for 12 hours to obtain a hydrophobic silica material with a porous structure;
  • step S5 place the porous silica material in step S4 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain a porous structure of hydrophilic silica. Silicon oxide material.
  • a scanning electron microscope (Philips-XL30) was used to obtain the microstructural picture of the porous hydrophilic silica.
  • the porous silica has a loose structure and a porous structure formed by cross-linking of nanoparticles.
  • the JW-BK200A specific surface area analyzer was used to obtain the specific surface area and pore size distribution diagram of porous silica; the specific surface area is 980m 2 /g, and the average pore size of the porous silica material is 13.2nm; as can be seen from Figure 2, this silica
  • the material has a porous structure, and the pore diameter is mainly distributed between 10nm and 20nm.
  • the transmittance of the porous silica material is measured using a UV/VIS/NIR spectrophotometer (V-570) and the accessory integrating sphere (ARN-475), as shown in the figure As shown in 3, as the wavelength increases, the transmittance increases. When the wavelength is 360nm, the transmittance reaches 60%. The average visible light transmittance of the porous silica material is about 76%.
  • This comparative example provides a method for preparing a silicon dioxide-rare earth composite photocatalytic material having similar components to those in Example 1, as follows:
  • step S2 add the ammonia solution of group B dropwise to the solution of step S1 and continue stirring until it gels;
  • step S3 after aging the gel in step S2 at 60°C for 6 hours, place the gel in an oven at 80°C to dry for 12 hours to obtain silica material;
  • the obtained silica has an average pore diameter of 3.4 nm, a specific surface area of 23 m 2 /g, and an average visible light transmittance of 85.6%. It can be seen that the material prepared in this comparative example has a low specific surface area, small pore size, and low adsorption efficiency.
  • This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
  • step S2 add the raw materials of Group B into the solution in step S1. First add the SnO 2 dispersion into the solution in step S1 and stir evenly. Then add the Ca 2 MgSi 2 O 7 :Eu 2+ and Dy 3+ powder into the solution in step S1. solution and stir;
  • step S3 add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
  • step S4 after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane with a mass fraction of 10% and stir for 8 hours;
  • step S5 place the gel in step S4 in cyclohexane and stir for 4 hours. Place the gel in an oven at 80°C to dry for 12 hours to obtain a hydrophobic silica-rare earth composite photocatalytic material;
  • step S6 place the hydrophobic silica-rare earth composite photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain Hydrophilic silica-rare earth composite photocatalytic material.
  • This comparative example provides a method for preparing a silica-rare earth composite photocatalytic material with similar components as Example 2, as follows:
  • step S2 add the raw materials of Group B into the solution of step S1 and stir evenly;
  • step S3 add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
  • step S4 after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane with a mass fraction of 10% and stir for 8 hours;
  • step S5 Place the gel in step S4 in cyclohexane and stir for 4 hours. Place the gel in an oven at 80°C for 12 hours to dry to obtain a hydrophobic silica-rare earth composite photocatalytic material;
  • step S6 placing the photocatalytic material of step S5 in a muffle furnace, raising the temperature from room temperature to 600°C at a rate of 10°C/min in an air atmosphere, and calcining at a constant temperature of 600°C for 3 hours to obtain a hydrophilic silica-rare earth composite photocatalytic material.
  • This comparative example provides a method for preparing a silica-composite photocatalytic material with similar components to Example 2, as follows:
  • step S2 adding the raw materials of group B to the solution of step S1, first adding the SnO 2 dispersion to the solution of step S1 and stirring evenly, then adding the Ca 2 MgSi 2 O 7 powder to the solution of step S1 and stirring;
  • step S3 add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
  • step S4 after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane with a mass fraction of 10% and stir for 8 hours;
  • step S5 place the gel in step S4 in cyclohexane and stir for 4 hours, then dry the gel in an oven at 80°C for 12 hours to obtain a hydrophobic silica composite photocatalytic material;
  • step S6 place the hydrophobic silica composite photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain hydrophilic Type silica composite photocatalytic material.
  • This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
  • This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
  • This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
  • This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
  • This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
  • This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
  • This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
  • step S2 add the raw materials of Group B into the solution in step S1. First add the nano-TiO 2 dispersion into the solution in step S1 and stir evenly. Then add the Ca 2 MgSi 2 O 7 : Eu 2+ , Dy 3+ powder into step S1. into the solution and stir;
  • step S3 add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
  • step S4 after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane with a mass fraction of 10% and stir for 8 hours;
  • step S5 placing the gel in step S4 in cyclohexane and stirring for 4 hours, placing the gel in an oven at 80° C. and drying for 12 hours to obtain a hydrophobic silica-rare earth composite photocatalytic material;
  • step S6 place the photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain a hydrophilic silica-rare earth composite Type photocatalytic materials.
  • This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
  • step S2 add the raw materials of Group B into the solution in step S1. First add the nano-ZnO 2 dispersion into the solution in step S1 and stir evenly. Then add the Ca 2 MgSi 2 O 7 :Eu 2+ and Dy 3+ powder into step S1. into the solution and stir;
  • step S3 add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
  • step S4 after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane with a mass fraction of 10% and stir for 8 hours;
  • step S5 place the gel in step S4 in cyclohexane and stir for 4 hours. Place the gel in an oven at 80°C to dry for 12 hours to obtain a hydrophobic silica-rare earth composite photocatalytic material;
  • step S6 place the photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain a hydrophilic silica-rare earth composite Type photocatalytic materials.
  • This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
  • step S2 add the raw materials of Group B into the solution in step S1. First add the nano-nitrogen-doped tin dioxide dispersion into the solution in step S1 and stir evenly. Then add Ca 2 MgSi 2 O 7 :Eu 2+ , Nd 3+ Add the powder to the solution in step S1 and stir;
  • step S3 add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
  • step S4 after aging the gel in step S3 at 30°C for 3 hours, soak the gel in an ethanol solution containing 20% octyltriethoxysilane with a mass fraction of 20% and stir for 8 hours;
  • step S5 Place the gel in step S4 in acetone and stir for 4 hours. Place the gel in an oven at 80°C to dry for 12 hours to obtain a hydrophobic silica-rare earth composite photocatalytic material;
  • step S6 place the photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 400°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 400°C for 6 hours to obtain a hydrophilic silica-rare earth composite Type photocatalytic materials.
  • This embodiment provides a method for preparing a silicon dioxide-rare earth composite photocatalytic material, which is as follows:
  • step S2 add the raw materials of Group B into the solution in step S1. First add the SnO 2 dispersion into the solution in step S1 and stir evenly. Then add the Ca 2 MgSi 2 O 7 :Eu 2+ and Dy 3+ powder into the solution in step S1. solution and stir;
  • step S3 add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
  • step S4 after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane with a mass fraction of 10% and stir for 8 hours;
  • step S5 place the gel in step S4 in cyclohexane and stir for 4 hours. Place the gel in an oven at 80°C to dry for 12 hours to obtain a hydrophobic silica-rare earth composite photocatalytic material;
  • step S6 place the photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain a hydrophilic silica-rare earth composite Type photocatalytic materials.
  • This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
  • step S2 add the raw materials of Group B into the solution in step S1.
  • the order is as follows: first add the SnO 2 dispersion liquid into the solution in step S1 and stir evenly, then add the Sr 4 Al 14 O 25 :Eu 2+ , Dy 3+ powder into the step S2. into the solution of S1 and stir;
  • step S3 add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
  • step S4 after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% hexamethyldisilazane by mass and stir for 8 hours;
  • step S5 place the gel in step S4 in n-propanol and stir for 4 hours. Place the gel in an oven at 80°C to dry for 12 hours to obtain a hydrophobic silica-rare earth composite photocatalytic material;
  • step S6 place the photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain a hydrophilic silica-rare earth composite Type photocatalytic materials.
  • This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
  • step S2 add the raw materials of Group B into the solution in step S1.
  • the order is as follows: first add SnO 2 powder into the solution in step S1 and stir evenly, then add SrAl 2 O 4 :Eu 2+ and Dy 3+ powder into the solution in step S1. medium and stir;
  • step S3 add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
  • step S4 after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane with a mass fraction of 10% and stir for 8 hours;
  • step S5 place the gel in step S4 in cyclohexane and stir for 4 hours. Place the gel in an oven at 80°C to dry for 12 hours to obtain a hydrophobic silica-rare earth composite photocatalytic material;
  • step S6 place the photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain a hydrophilic silica-rare earth composite Type photocatalytic materials.
  • This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
  • step S2 adding the raw materials of group B into the solution of step S1, the order is first adding the SnO 2 dispersion into the solution of step S1 and stirring evenly, then adding the BaAl 2 O 4 :Eu 2+ ,Dy 3+ powder into the solution of step S1 and stirring;
  • step S3 add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
  • step S4 after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane with a mass fraction of 10% and stir for 8 hours;
  • step S5 place the gel in step S4 in cyclohexane and stir for 4 hours, then dry the gel in an oven at 80°C for 12 hours to obtain a hydrophobic silica-rare earth composite photocatalytic material;
  • step S6 place the photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain a hydrophilic silica-rare earth composite Type photocatalytic materials.
  • This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
  • step S2 add the raw materials of Group B into the solution in step S1.
  • the sequence is as follows: first add the nanocarbon-doped tin dioxide dispersion into the solution in step S1 and stir evenly, then add (Sr,Ca) 2 MgSi 2 O 7 :Eu 2+ , Dy 3+ powder is added to the solution in step S1 and stirred;
  • step S3 add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
  • step S4 aging the gel from step S3 at 40° C. for 5 h, then immersing the gel in an ethanol solution containing 5% by mass of methyltrimethoxysilane and stirring for 8 h;
  • step S5 place the gel in step S4 in cyclohexane and stir for 4 hours, put the gel into an ethanol supercritical kettle for supercritical drying, and obtain a hydrophobic silica-rare earth composite photocatalytic material;
  • step S6 place the photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 800°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 800°C for 2 hours to obtain a hydrophilic silica-rare earth composite Type photocatalytic materials.
  • silica-composite photocatalytic materials described in Examples 2-16 and Comparative Examples 2-3 were subjected to structural characterization and methylene blue degradation testing.
  • the specific steps of the degradation test use ZQ-GHX-XE-300 light source to irradiate the composite photocatalytic material for 30 minutes, use 20mg/L methylene blue solution as the test object, take 5g of the composite photocatalytic material and put it into 1L of the above solution. , placed under dark conditions, take the solution every 30 minutes to measure the degradation rate of methylene blue, and set a blank control group.
  • the experimental results are shown in Table 20.
  • the silica-rare earth composite photocatalytic material prepared by the present invention has a larger average pore size, about 13nm-17nm, and a large specific surface area, so that the test substance can be better adsorbed in the catalyst material. Provides the possibility for efficient catalysis. Secondly, it can be seen from the degradation experiment of methylene blue that the catalytic efficiency of the materials of the embodiments of the present invention is much higher than that of the materials of Comparative Examples 2-3.
  • the present invention realizes the possibility of photodegradation under lightless conditions for a long time, greatly enhances the afterglow time of long afterglow, and cooperates with photocatalytic materials to enhance catalytic efficiency, ultimately achieving high-efficiency catalysis.
  • the result at the same time, more new methods for wastewater and gas treatment are provided.

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Abstract

A silicon dioxide-rare earth composite photocatalytic material, a preparation method therefor, and an application thereof, utilizing a sol-gel method. A photocatalyst and a long afterglow material are simultaneously loaded onto silicon dioxide having a high specific surface area. Using high-specific-surface-area silicon dioxide having efficient adsorption and high visible light transmittance performance enhances the catalytic effect of the photocatalyst while protecting the long afterglow material which has poor water resistance, achieving a self-luminous catalysis function in low-light and dark external environments.

Description

一种二氧化硅-稀土复合型光催化材料及其制备方法与应用A kind of silica-rare earth composite photocatalytic material and its preparation method and application 技术领域Technical field
本发明属于光催化材料技术领域，尤其是指一种二氧化硅-稀土复合型光催化材料及其制备方法与应用。The invention belongs to the technical field of photocatalytic materials, and in particular refers to a silica-rare earth composite photocatalytic material and its preparation method and application.
背景技术Background technique
二氧化硅具有化学稳定性，无毒性，在电子、橡胶、塑料、涂料、食品、药品、化妆品、纺织、建筑、催化等领域具有重要应用。高比表面积二氧化硅，适合作为催化剂载体材料，实现高效吸附催化的作用。Silica is chemically stable and non-toxic, and has important applications in electronics, rubber, plastics, coatings, food, medicines, cosmetics, textiles, construction, catalysis and other fields. High specific surface area silica is suitable as a catalyst carrier material to achieve efficient adsorption and catalysis.
光催化材料主要为纳米二氧化钛、纳米氧化锌、纳米二氧化锡、硫化镉等纳米半导体材料。为了提高半导体材料的催化活性以及拓宽光响应范围，将会采用减小半导体材料的尺寸，负载高比表面积材料上，对半导体材料进行异原子掺杂的方式。Photocatalytic materials are mainly nano-semiconductor materials such as nano-titanium dioxide, nano-zinc oxide, nano-tin dioxide, and cadmium sulfide. In order to improve the catalytic activity of semiconductor materials and broaden the photoresponse range, the method of reducing the size of semiconductor materials, loading high specific surface area materials, and heteroatomic doping of semiconductor materials will be used.
长余辉材料是指材料受激发后，在夜间或者黑暗的环境下能够持续发光的储能材料，主要包括金属硫化物，稀土离子掺杂碱土金属铝酸盐系，稀土离子掺杂硅酸盐系三大类。长余辉金属硫化物材料，化学不稳定，容易发黑，逐渐被淘汰。稀土离子掺杂碱土金属铝酸盐系具有余辉亮度强，发光时间长等优点，但是存在耐水性差，发光光谱单一等缺点。稀土离子掺杂硅酸盐系具有化学性能稳定、耐水性强、发光光谱丰富等优点，但是整体发光性能不如稀土离子掺杂碱土金属铝酸盐系。Long afterglow materials refer to energy storage materials that can continue to emit light at night or in a dark environment after being excited. They mainly include three categories: metal sulfides, rare earth ion-doped alkaline earth metal aluminates, and rare earth ion-doped silicates. Long afterglow metal sulfide materials are chemically unstable, easy to blacken, and are gradually being eliminated. Rare earth ion-doped alkaline earth metal aluminates have the advantages of strong afterglow brightness and long luminescence time, but have disadvantages such as poor water resistance and a single luminescence spectrum. Rare earth ion-doped silicates have the advantages of stable chemical properties, strong water resistance, and a rich luminescence spectrum, but the overall luminescence performance is not as good as that of rare earth ion-doped alkaline earth metal aluminates.
发明内容Contents of the invention
为解决上述技术问题，本发明提供了一种二氧化硅-稀土复合型光催化材料及其制备方法与应用。本发明采用溶胶凝胶的方法，将光催化剂和长余辉材料同时负载于高比表面积的二氧化硅上，利用高比表面积二氧化硅的高效吸附和高的可见光透过率性能，提高光催化剂的催化效果，同时保护耐水性差的长余辉材料，实现在弱光和黑暗的外在环境下自发光催化的功能，可推广于污水处理、空气过滤、建筑涂层等领域。In order to solve the above technical problems, the present invention provides a silica-rare earth composite photocatalytic material and its preparation method and application. The present invention adopts the sol-gel method to simultaneously load the photocatalyst and the long afterglow material on the high specific surface area silica, and utilizes the high specific surface area silica's efficient adsorption and high visible light transmittance performance to improve the photocatalyst The catalytic effect, while protecting the long afterglow material with poor water resistance, realizes the function of self-luminescence catalysis in low light and dark external environments, and can be promoted in fields such as sewage treatment, air filtration, and building coatings.
本发明的第一个目的在于提供一种二氧化硅-稀土复合型光催化材料，包括以下组分：二氧化硅、长余辉发光材料和光催化材料，通过二氧化硅、长余辉发光材料、光催化材料复合而成；所述二氧化硅-稀土复合型光催化材料为多孔结构；其中，所述二氧化硅-稀土复合型光催化材料是以二氧化硅为整体框架，长余辉发光材料和光催化材料均匀地被固定负载于二氧化硅上。The first object of the present invention is to provide a silica-rare earth composite photocatalytic material, which includes the following components: silica, long afterglow luminescent material and photocatalytic material. Through silica, long afterglow luminescent material, light The silica-rare earth composite photocatalytic material is a composite of catalytic materials; the silica-rare earth composite photocatalytic material has a porous structure; wherein the silica-rare earth composite photocatalytic material uses silica as an overall framework, long afterglow luminescent materials and light The catalytic material is uniformly fixed and supported on the silica.
在本发明的一个实施例中，所述二氧化硅、长余辉发光材料、光催化材料的质量比为 280：1～50：1～50。In one embodiment of the present invention, the mass ratio of silica, long afterglow luminescent material, and photocatalytic material is 280:1-50:1-50.
在本发明的一个实施例中，所述二氧化硅为多孔结构，呈透明或半透明状态，平均孔径为5nm～40nm；优选为8nm～20nm。In one embodiment of the present invention, the silica has a porous structure, is in a transparent or translucent state, and has an average pore diameter of 5 nm to 40 nm; preferably 8 nm to 20 nm.
其中，所述长余辉发光材料为稀土掺杂的发光材料；所述光催化材料选自金属氧化物、氮掺杂金属氧化物和碳掺杂金属氧化物中的一种或多种。Wherein, the long afterglow luminescent material is a rare earth doped luminescent material; the photocatalytic material is selected from one or more of metal oxides, nitrogen-doped metal oxides and carbon-doped metal oxides.
在本发明的一个实施例中，所述稀土掺杂的发光材料选自CaAl 2O 4:Eu 2+,Nd 3+、SrAl 2O 4:Eu 2+,Dy 3+、SrAl 4O 7:Eu 2+,Dy 3+、SrAl 12O 19:Eu 2+,Dy 3+、Sr 4Al 14O 25:Eu 2+,Dy 3+、BaAl 2O 4:Eu 2+,Dy 3+、SrAl 2O 4:Ce 3+、Sr 2Si 2O 4:Ce 3+、Sr 3SiO 5:Eu 2+,Dy 3+、Sr 2Al 2SiO 7:Eu 2+、Sr 2ZnSi 2O 7:Eu 2+,Dy 3+、Sr 2MgSi 2O 7:Eu 2+,Dy 3+、Ca 2MgSi 2O 7:Eu 2+,Dy 3+、Ba 2MgSi 2O 7:Eu 2+,Dy 3+和(Sr,Ca) 2MgSi 2O 7:Eu 2+,Dy 3+中的一种或多种；所述稀土掺杂的发光材料的发光光谱为360nm～800nm；进一步的，优选为发光光谱为400nm～550nm，余辉时间大于8h，选自CaAl 2O 4:Eu 2+,Nd 3+、SrAl 2O 4:Eu 2+,Dy 3+、SrAl 4O 7:Eu 2+,Dy 3+、Sr 4Al 14O 25:Eu 2+,Dy 3+、BaAl 2O 4:Eu 2+,Dy 3+、SrAl 2O 4:Ce 3+、Sr 2MgSi 2O 7:Eu 2+,Dy 3+、Ca 2MgSi 2O 7:Eu 2+,Dy 3+和(Sr,Ca) 2MgSi 2O 7:Eu 2+,Dy 3+的一种或多种。 In one embodiment of the invention, the rare earth doped luminescent material is selected from the group consisting of CaAl 2 O 4 :Eu 2+ , Nd 3+ , SrAl 2 O 4 :Eu 2+ ,Dy 3+ , SrAl 4 O 7 : Eu 2+ ,Dy 3+ ,SrAl 12 O 19 :Eu 2+ ,Dy 3+ ,Sr 4 Al 14 O 25 :Eu 2+ ,Dy 3+ ,BaAl 2 O 4 :Eu 2+ ,Dy 3+ ,SrAl 2 O 4 : Ce 3+ , Sr 2 Si 2 O 4 : Ce 3+ , Sr 3 SiO 5 : Eu 2+ ,Dy 3+ , Sr 2 Al 2 SiO 7 : Eu 2+ , Sr 2 ZnSi 2 O 7 : Eu 2+ ,Dy 3+ ,Sr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ ,Ca 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ ,Ba 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ and (Sr, Ca) 2 MgSi 2 O 7 :Eu 2+ , one or more of Dy 3+ ; the luminescence spectrum of the rare earth-doped luminescent material is 360nm~800nm; further, preferably The luminescence spectrum is 400nm~550nm, and the afterglow time is more than 8h. It is selected from CaAl 2 O 4 :Eu 2+ ,Nd 3+ , SrAl 2 O 4 :Eu 2+ ,Dy 3+ , SrAl 4 O 7 :Eu 2+ ,Dy 3+ , Sr 4 Al 14 O 25 :Eu 2+ ,Dy 3+ ,BaAl 2 O 4 :Eu 2+ ,Dy 3+ ,SrAl 2 O 4 :Ce 3+ ,Sr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ , Ca 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ and one or more of (Sr,Ca) 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ .
在本发明的一个实施例中，所述二氧化硅-稀土复合型光催化材料的平均孔径为5nm～200nm，更优选为8nm～20nm；比表面积为200m 2/g～1500m 2/g，更优选为400m 2/g～1200m 2/g。 In one embodiment of the present invention, the average pore diameter of the silica-rare earth composite photocatalytic material is 5nm~200nm, more preferably 8nm~20nm; the specific surface area is 200m2 /g~ 1500m2 /g, more preferably Preferably, it is 400m2 /g- 1200m2 /g.
在本发明的一个实施例中，所述光催化材料选自金属氧化物、氮掺杂金属氧化物和碳掺杂金属氧化物中一种或多种。优选地，所述光催化材料选自二氧化锡、二氧化钛、氧化锌、氮掺杂二氧化锡、氮掺杂二氧化钛、氮掺杂氧化锌、碳掺杂二氧化锡、碳掺杂二氧化钛和碳掺杂氧化锌的一种或多种。In one embodiment of the present invention, the photocatalytic material is selected from one or more of metal oxides, nitrogen-doped metal oxides, and carbon-doped metal oxides. Preferably, the photocatalytic material is selected from the group consisting of tin dioxide, titanium dioxide, zinc oxide, nitrogen-doped tin dioxide, nitrogen-doped titanium dioxide, nitrogen-doped zinc oxide, carbon-doped tin dioxide, carbon-doped titanium dioxide and carbon One or more doped zinc oxides.
在本发明的一个实施例中，所述光催化材料形态是纳米二氧化锡粉末、纳米二氧化钛粉末、纳米氧化锌粉末、纳米氮掺杂二氧化锡粉末、纳米氮掺杂二氧化钛粉末、纳米氮掺杂氧化锌粉末、纳米碳掺杂二氧化锡粉末、纳米碳掺杂二氧化钛粉末、纳米碳掺杂氧化锌粉末或者纳米二氧化锡分散液、纳米二氧化钛分散液、纳米氧化锌分散液、纳米氮掺杂二氧化锡分散液、纳米氮掺杂二氧化钛分散液、纳米氮掺杂氧化锌分散液、纳米碳掺杂二氧化锡分散液、纳米碳掺杂二氧化钛分散液、纳米碳掺杂氧化锌分散液的一种；优选为纳米二氧化锡分散液、纳米二氧化钛分散液、纳米氧化锌分散液、纳米氮掺杂二氧化锡分散液、纳米氮掺杂二氧化钛分散液、纳米氮掺杂氧化锌分散液、纳米碳掺杂二氧化锡分散液、纳米碳掺杂二氧化钛分散液、纳米碳掺杂氧化锌分散液；更优选为纳米二氧化锡水分散液、纳米二氧化钛水分散液、 纳米氧化锌水分散液、纳米氮掺杂二氧化锡水分散液、纳米氮掺杂二氧化钛水分散液、纳米氮掺杂氧化锌水分散液、纳米碳掺杂二氧化锡水分散液、纳米碳掺杂二氧化钛水分散液、纳米碳掺杂氧化锌水分散液。In one embodiment of the invention, the photocatalytic material is in the form of nano-tin dioxide powder, nano-titanium dioxide powder, nano-zinc oxide powder, nano-nitrogen-doped tin dioxide powder, nano-nitrogen-doped titanium dioxide powder, nano-nitrogen-doped titanium dioxide powder, Mixed zinc oxide powder, nanocarbon doped tin dioxide powder, nanocarbon doped titanium dioxide powder, nanocarbon doped zinc oxide powder or nanotin dioxide dispersion, nanotitanium dioxide dispersion, nanozinc oxide dispersion, nanonitrogen doped Hybrid tin dioxide dispersion, nano nitrogen doped titanium dioxide dispersion, nano nitrogen doped zinc oxide dispersion, nano carbon doped tin dioxide dispersion, nano carbon doped titanium dioxide dispersion, nano carbon doped zinc oxide dispersion A kind of; preferably nano-tin dioxide dispersion, nano-titanium dioxide dispersion, nano-zinc oxide dispersion, nano-nitrogen-doped tin dioxide dispersion, nano-nitrogen-doped titanium dioxide dispersion, nano-nitrogen-doped zinc oxide dispersion , nano-carbon doped tin dioxide dispersion, nano-carbon doped titanium dioxide dispersion, nano-carbon doped zinc oxide dispersion; more preferably, nano-tin dioxide aqueous dispersion, nano-titanium dioxide aqueous dispersion, nano-zinc oxide aqueous dispersion liquid, nanonitrogen-doped tin dioxide aqueous dispersion, nanonitrogen-doped titanium dioxide aqueous dispersion, nanonitrogen-doped zinc oxide aqueous dispersion, nanocarbon-doped tin dioxide aqueous dispersion, nanocarbon-doped titanium dioxide aqueous dispersion liquid, nanocarbon-doped zinc oxide aqueous dispersion.
在本发明的一个实施例中，所述光催化材料的纳米分散液的质量分数为5％～50％，优选为10％～30％，更优选为10％～20％。In one embodiment of the present invention, the mass fraction of the nanodispersion of photocatalytic material is 5% to 50%, preferably 10% to 30%, and more preferably 10% to 20%.
本发明的第二个目的在于提供所述的二氧化硅-稀土复合型光催化材料的制备方法，包括以下步骤：The second object of the present invention is to provide a method for preparing the silica-rare earth composite photocatalytic material, which includes the following steps:
S1，将硅源、有机溶剂、水、酸混合搅拌，之后加入长余辉发光材料、光催化材料并混匀；S1, mix and stir the silicon source, organic solvent, water, and acid, then add the long afterglow luminescent material and photocatalytic material and mix well;
S2，将碱溶液加入步骤S1的溶液中并继续搅拌至凝胶；S2, add the alkali solution to the solution in step S1 and continue stirring until gel;
S3，待步骤S2的凝胶老化后，浸泡于含有表面修饰剂的有机溶剂中；S3, after the gel of step S2 is aged, immersing it in an organic solvent containing a surface modifier;
S4，用低表面张力溶剂替换步骤S4所得凝胶孔中的溶剂，干燥获得疏水型光催化材料；S4, replace the solvent in the gel pores obtained in step S4 with a low surface tension solvent, and dry to obtain a hydrophobic photocatalytic material;
S5，将步骤S4的疏水型光催化材料进行煅烧，得到亲水型二氧化硅-稀土复合型光催化材料。S5, calcining the hydrophobic photocatalytic material in step S4 to obtain a hydrophilic silica-rare earth composite photocatalytic material.
在本发明的一个实施例中，步骤S1中，所述酸选自盐酸、硫酸、硝酸、磷酸、柠檬酸、草酸和乙酸中的一种或多种，其中，所述酸的质量分数为0.1％～5％。In one embodiment of the present invention, in step S1, the acid is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, citric acid, oxalic acid and acetic acid, wherein the mass fraction of the acid is 0.1 %~5%.
在本发明的一个实施例中，步骤S1中，所述有机溶剂选自甲醇和\或乙醇。In one embodiment of the present invention, in step S1, the organic solvent is selected from methanol and/or ethanol.
在本发明的一个实施例中，步骤S1中，所述硅源选自正硅酸甲酯、正硅酸乙酯、甲基三甲氧基硅烷和甲基三乙氧基硅烷中的一种或多种。In one embodiment of the present invention, in step S1, the silicon source is selected from one of methyl orthosilicate, ethyl orthosilicate, methyltrimethoxysilane and methyltriethoxysilane, or Various.
在本发明的一个实施例中，步骤S1中，所述硅源、有机溶剂、水、酸的质量比为1：1～6：0.2：0.01。In one embodiment of the present invention, in step S1, the mass ratio of the silicon source, organic solvent, water, and acid is 1:1 to 6:0.2:0.01.
在本发明的一个实施例中，步骤S1原料的添加顺序是先将硅源与有机溶剂混合搅拌均匀，再滴加水，搅拌至透明，最后加酸；In one embodiment of the present invention, the order of adding the raw materials in step S1 is to first mix the silicon source and the organic solvent and stir evenly, then add water dropwise, stir until transparent, and finally add acid;
在本发明的一个实施例中，步骤S1中，所述硅源、长余辉发光材料和光催化材料的质量比为1000：1～50：1～50。优选地，所述硅源、长余辉发光材料和光催化材料的质量比为1000：10～20：10～30。In one embodiment of the present invention, in step S1, the mass ratio of the silicon source, long afterglow luminescent material and photocatalytic material is 1000:1~50:1~50. Preferably, the mass ratio of the silicon source, long afterglow luminescent material and photocatalytic material is 1000:10-20:10-30.
在本发明的一个实施例中，步骤S2中，所述碱溶液中的碱选自NH 3·H 2O、三乙醇胺、氢氧化钠和氢氧化钾中的一种或多种。 In one embodiment of the present invention, in step S2, the base in the alkali solution is selected from one or more of NH 3 ·H 2 O, triethanolamine, sodium hydroxide and potassium hydroxide.
在本发明的一个实施例中，所述碱溶液的质量分数为0.1％～5％，滴加碱溶液质量为硅源的1％～10％。In one embodiment of the present invention, the mass fraction of the alkali solution is 0.1% to 5%, and the mass of the dropped alkali solution is 1% to 10% of the silicon source.
在本发明的一个实施例中，步骤S1中原料的添加顺序是先将光催化材料加入混合硅源溶液中，再添加长余辉材料，并继续搅拌。In one embodiment of the present invention, the order of adding raw materials in step S1 is to first add the photocatalytic material to the mixed silicon source solution, then add the long afterglow material, and continue stirring.
在本发明的一个实施例中，步骤S3中，所述表面修饰剂选自甲基三甲氧基硅烷、甲基三乙氧基硅烷、辛基三乙氧基硅烷、六甲基二硅氮烷、三甲基氯硅烷、苯基三甲基硅烷、苯基三乙基硅烷、甲基三乙酰氧基硅烷、乙烯基三乙酰氧基硅烷、全氟辛基三甲氧基硅烷、全氟辛基三乙氧基硅烷、全氟癸基三甲氧基硅烷和全氟癸基三乙氧基硅烷的一种或多种。所述表面修饰剂的质量分数为2％～20％；优选为5％～10％。In one embodiment of the present invention, in step S3, the surface modification agent is selected from methyltrimethoxysilane, methyltriethoxysilane, octyltriethoxysilane, and hexamethyldisilazane , trimethylchlorosilane, phenyltrimethylsilane, phenyltriethylsilane, methyltriacetoxysilane, vinyltriacetoxysilane, perfluorooctyltrimethoxysilane, perfluorooctyl One or more of triethoxysilane, perfluorodecyltrimethoxysilane and perfluorodecyltriethoxysilane. The mass fraction of the surface modification agent is 2% to 20%; preferably 5% to 10%.
在本发明的一个实施例中，步骤S3中，所述有机溶剂为甲醇和\或乙醇。In one embodiment of the present invention, in step S3, the organic solvent is methanol and/or ethanol.
在本发明的一个实施例中，步骤S3中，所述老化的具体步骤：取步骤S1中的有机溶剂覆盖于凝胶表面并密封，30℃～80℃条件下老化3h～12h，优选地40℃～60℃条件下老化5h～8h。In one embodiment of the present invention, in step S3, the specific aging steps are: cover the gel surface with the organic solvent in step S1 and seal it, and age it at 30°C to 80°C for 3h to 12h, preferably 40 Aging at ℃ ~ 60 ℃ for 5h ~ 8h.
在本发明的一个实施例中，步骤S3中，将凝胶浸泡于含有表面修饰剂的有机溶剂中，采用静态的浸泡方式或者动态的浸泡方式，动态浸泡的方式包括超声、搅拌和震荡，优选为搅拌浸泡，时间优为1h～12h，优选为3h～8h。In one embodiment of the present invention, in step S3, the gel is immersed in an organic solvent containing a surface modifier, using a static immersion method or a dynamic immersion method. The dynamic immersion method includes ultrasound, stirring and shaking, preferably stirring immersion, and the time is preferably 1h to 12h, preferably 3h to 8h.
在本发明的一个实施例中，步骤S4中，所述低表面张力溶剂选自环己烷、正辛烷、正庚烷、甲醇、乙醇、正丙醇、正丁醇、异丁醇、丙酮和六甲基二硅氧烷的一种或多种。In one embodiment of the present invention, in step S4, the low surface tension solvent is selected from one or more of cyclohexane, n-octane, n-heptane, methanol, ethanol, n-propanol, n-butanol, isobutanol, acetone and hexamethyldisiloxane.
在本发明的一个实施例中，步骤S4中，所述干燥为常压干燥、冷冻干燥、微波干燥、超临界干燥或亚超临界干燥。优选为常压干燥、超临界干燥、亚超临界干燥，干燥后的二氧化硅-稀土复合型光催化材料置于80℃-105℃烘箱3h后测量干燥失重，干燥失重优选为0～5％，更优选为0～1％。In one embodiment of the present invention, in step S4, the drying is normal pressure drying, freeze drying, microwave drying, supercritical drying or sub-supercritical drying. Normal pressure drying, supercritical drying, and sub-supercritical drying are preferred. The dried silica-rare earth composite photocatalytic material is placed in an oven at 80°C-105°C for 3 hours and the drying weight loss is measured. The drying weight loss is preferably 0 to 5%. , more preferably 0 to 1%.
在本发明的一个实施例中，步骤S4中，用低表面张力溶剂将步骤S3中的凝胶孔中的溶剂替换掉，采用静态的浸泡方式或者动态的浸泡方式，动态浸泡的方式包括超声、搅拌和震荡，优选为搅拌浸泡，搅拌浸泡时间为0.5h～6h，优选为1h～3h。In one embodiment of the present invention, in step S4, the solvent in the gel pores in step S3 is replaced with a low surface tension solvent, using a static soaking method or a dynamic soaking method. The dynamic soaking method includes ultrasonic, Stirring and shaking, preferably stirring and soaking, the stirring and soaking time is 0.5h to 6h, preferably 1h to 3h.
在本发明的一个实施例中，步骤S5中，所述煅烧温度为400℃～800℃，优选为550℃～650℃；恒温时间优选为1h～12h，更优选为1h～6h；煅烧气氛为空气气氛。In one embodiment of the present invention, in step S5, the calcination temperature is 400°C to 800°C, preferably 550°C to 650°C; the constant temperature time is preferably 1h to 12h, more preferably 1h to 6h; the calcination atmosphere is Air atmosphere.
本发明的第三个目的在于提供所述二氧化硅-稀土复合型光催化材料在催化降解废水废气中的有机物的应用；其中，所述有机物为偶氮类染料、苯酚类染料、甲醛、油脂或焦油。The third object of the present invention is to provide the application of the silica-rare earth composite photocatalytic material in catalytically degrading organic matter in wastewater and exhaust gas; wherein the organic matter is azo dyes, phenol dyes, formaldehyde, grease Or tar.
本发明的上述技术方案相比现有技术具有以下优点：The above technical solution of the present invention has the following advantages compared with the existing technology:
本发明采用溶胶凝胶的方法，将光催化剂和长余辉材料同时负载于高比表面积的二氧化硅上，利用高比表面积二氧化硅的高效吸附和高的可见光透过率性能，同时实现在弱光和黑暗外在环境下自发光、高效吸附、光催化的功能，可应用于污水处理、空气过滤、建筑外墙 隔热光催化等领域。The present invention adopts the sol-gel method to simultaneously load the photocatalyst and the long afterglow material on the high specific surface area silica, and utilizes the high specific surface area silica's efficient adsorption and high visible light transmittance performance to simultaneously achieve It has the functions of self-luminescence, efficient adsorption, and photocatalysis in weak light and dark external environments, and can be used in fields such as sewage treatment, air filtration, and building exterior wall insulation photocatalysis.
同时，本发明通过掺入稀土长余辉发光材料，光照条件下进行光能储存，黑暗条件下辐射短波长的蓝、绿可见光，实现了长时间在无光条件下进行光降解的可能，大大增强长余辉的余辉时间，且协同光催化材料增强催化效率，最终实现高效催化的结果；同时提供了更多废水废气处理的新方法。At the same time, the present invention realizes the possibility of photodegradation under no light conditions for a long time by incorporating rare earth long afterglow luminescent materials, storing light energy under light conditions, and radiating short-wavelength blue and green visible light under dark conditions, which greatly enhances the The afterglow time of the afterglow is long, and the photocatalytic material is used to enhance the catalytic efficiency, ultimately achieving the result of efficient catalysis; at the same time, it provides more new methods for wastewater and gas treatment.
附图说明Description of the drawings
为了使本发明的内容更容易被清楚的理解，下面根据本发明的具体实施例并结合附图，对本发明作进一步详细的说明，其中In order to make the content of the present invention easier to understand clearly, the present invention will be further described in detail below based on specific embodiments of the present invention and in conjunction with the accompanying drawings, wherein
图1为本发明实施例1的多孔二氧化硅电镜图SEM；Figure 1 is an electron microscope image SEM of porous silica in Example 1 of the present invention;
图2为本发明实施例1的多孔二氧化硅孔径分布图；Figure 2 is a pore size distribution diagram of porous silica in Example 1 of the present invention;
图3为本发明实施例1的多孔二氧化硅可见光透过率；Figure 3 shows the visible light transmittance of porous silica in Example 1 of the present invention;
图4为本发明实施例2和对比例2二氧化硅-稀土复合型光催化材料对亚甲基蓝的分解速率。Figure 4 shows the decomposition rate of methylene blue by silica-rare earth composite photocatalytic materials in Example 2 and Comparative Example 2 of the present invention.
具体实施方式Detailed ways
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。若未特别指明，实施例中所用技术手段为本领域技术人员所熟知的常规手段，所用原料均为市售商品。The present invention will be further described below in conjunction with the accompanying drawings and specific examples, so that those skilled in the art can better understand and implement the present invention, but the examples are not intended to limit the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art, and the raw materials used are all commercially available products.
实施例1Example 1
本实施例提供了一种二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
1、原料配比如下表1所示：1. The raw material proportions are shown in Table 1 below:
表1Table 1
Figure PCTCN2022124136-appb-000001
Figure PCTCN2022124136-appb-000001
2、按照上述质量比，工艺流程如下：2. According to the above mass ratio, the process flow is as follows:
S1，将A组原料搅拌混合，顺序先将正硅酸乙酯与乙醇混合搅拌均匀，再滴加水，搅拌至透明，最后加盐酸并搅拌；S1, stir and mix the raw materials of Group A. First, mix ethyl orthosilicate and ethanol and stir evenly, then add water dropwise, stir until transparent, and finally add hydrochloric acid and stir;
S2，将B组的氨水滴加于步骤S1的溶液并继续搅拌至凝胶；S2, add the ammonia solution of group B dropwise to the solution of step S1 and continue stirring until it gels;
S3，将步骤S2的凝胶置于60℃温度下老化6h后，将凝胶浸泡于含有质量分数为10％三甲基氯硅烷的乙醇溶液中并搅拌8h；S3, after aging the gel in step S2 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane by mass fraction and stir for 8 hours;
S4，将步骤S3中的凝胶置于环己烷中并搅拌4h，将凝胶放入80℃烘箱干燥12h，获得多孔结构的疏水型二氧化硅材料；S4. Place the gel in step S3 in cyclohexane and stir for 4 hours. Place the gel in an oven at 80°C to dry for 12 hours to obtain a hydrophobic silica material with a porous structure;
S5，将步骤S4的多孔二氧化硅材料置于马弗炉中，在空气氛围下以10℃/min从室温升至600℃，在600℃恒温煅烧3h，获得多孔结构的亲水型二氧化硅材料。S5, place the porous silica material in step S4 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain a porous structure of hydrophilic silica. Silicon oxide material.
采用扫描电子显微镜(Philips-XL30)获得多孔结构的亲水型二氧化硅的微观结构图，如图1所示，多孔二氧化硅的结构疏松，由纳米粒子交联形成的多孔结构。采用JW-BK200A比表面积分析仪获得多孔二氧化硅的比表面积和孔径分布图；比表面积为980m 2/g，多孔二氧化硅材料的平均孔径为13.2nm；由图2可知，此二氧化硅材料为多孔结构，孔径主要分布为10nm～20nm；采用UV/VIS/NIR分光光度计(V-570)，及附件积分球(ARN-475)测量多孔二氧化硅材料的透过率，如图3所示，随着波长的增大，透过率增大，当波长为360nm时，透过率达到60％，多孔二氧化硅材料的可见光平均透过率约为76％。 A scanning electron microscope (Philips-XL30) was used to obtain the microstructural picture of the porous hydrophilic silica. As shown in Figure 1, the porous silica has a loose structure and a porous structure formed by cross-linking of nanoparticles. The JW-BK200A specific surface area analyzer was used to obtain the specific surface area and pore size distribution diagram of porous silica; the specific surface area is 980m 2 /g, and the average pore size of the porous silica material is 13.2nm; as can be seen from Figure 2, this silica The material has a porous structure, and the pore diameter is mainly distributed between 10nm and 20nm. The transmittance of the porous silica material is measured using a UV/VIS/NIR spectrophotometer (V-570) and the accessory integrating sphere (ARN-475), as shown in the figure As shown in 3, as the wavelength increases, the transmittance increases. When the wavelength is 360nm, the transmittance reaches 60%. The average visible light transmittance of the porous silica material is about 76%.
对比例1Comparative example 1
本对比例提供了与实施例1类似组分的二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This comparative example provides a method for preparing a silicon dioxide-rare earth composite photocatalytic material having similar components to those in Example 1, as follows:
1、原料配比如下表2所示：1. The raw material proportions are shown in Table 2 below:
表2Table 2
Figure PCTCN2022124136-appb-000002
Figure PCTCN2022124136-appb-000002
2、按照上述质量比，工艺流程如下：2. According to the above mass ratio, the process flow is as follows:
S1，将A组原料搅拌混合，顺序先将正硅酸乙酯与乙醇混合搅拌均匀，再滴加水，搅拌至透明，最后加盐酸并搅拌；S1, stir and mix the raw materials of Group A. First, mix ethyl orthosilicate and ethanol and stir evenly, then add water dropwise, stir until transparent, and finally add hydrochloric acid and stir;
S2，将B组的氨水滴加于步骤S1的溶液并继续搅拌至凝胶；S2, add the ammonia solution of group B dropwise to the solution of step S1 and continue stirring until it gels;
S3，将步骤S2的凝胶置于60℃温度下老化6h后，将凝胶放入80℃烘箱干燥12h，获 得二氧化硅材料；S3, after aging the gel in step S2 at 60°C for 6 hours, place the gel in an oven at 80°C to dry for 12 hours to obtain silica material;
获得二氧化硅平均孔径为3.4nm，比表面积为23m 2/g，可见光平均透过率85.6％。可见，该对比例制备所得材料比表面积低、孔径小、吸附效率低。 The obtained silica has an average pore diameter of 3.4 nm, a specific surface area of 23 m 2 /g, and an average visible light transmittance of 85.6%. It can be seen that the material prepared in this comparative example has a low specific surface area, small pore size, and low adsorption efficiency.
实施例2Example 2
本实施例提供了一种二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
1、原料配比如下表3所示：1. The raw material ratio is shown in Table 3 below:
表3table 3
Figure PCTCN2022124136-appb-000003
Figure PCTCN2022124136-appb-000003
2、按照上述质量比，工艺流程如下：2. According to the above mass ratio, the process flow is as follows:
S1，将A组原料搅拌混合，先将正硅酸乙酯与乙醇混合搅拌均匀，再滴加水，搅拌至透明，最后加盐酸并搅拌；S1, stir and mix the raw materials of Group A, first mix ethyl orthosilicate and ethanol and stir evenly, then add water dropwise, stir until transparent, finally add hydrochloric acid and stir;
S2，将B组原料加入步骤S1的溶液中，先将SnO 2分散液加入步骤S1的溶液中并搅拌均匀，再将Ca 2MgSi 2O 7:Eu 2+,Dy 3+粉末加入步骤S1的溶液中并搅拌； S2, add the raw materials of Group B into the solution in step S1. First add the SnO 2 dispersion into the solution in step S1 and stir evenly. Then add the Ca 2 MgSi 2 O 7 :Eu 2+ and Dy 3+ powder into the solution in step S1. solution and stir;
S3，将氨水滴加于步骤S2的溶液并继续搅拌至凝胶；S3, add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
S4，将步骤S3的凝胶置于60℃温度下老化6h后，将凝胶浸泡于含有质量分数为10％三甲基氯硅烷的乙醇溶液中并搅拌8h；S4, after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane with a mass fraction of 10% and stir for 8 hours;
S5，将步骤S4中的凝胶置于环己烷中并搅拌4h，将凝胶放入80℃烘箱干燥12h，获得疏水型二氧化硅-稀土复合型光催化材料；S5, place the gel in step S4 in cyclohexane and stir for 4 hours. Place the gel in an oven at 80°C to dry for 12 hours to obtain a hydrophobic silica-rare earth composite photocatalytic material;
S6，将步骤S5的疏水型二氧化硅-稀土复合型光催化材料置于马弗炉中，在空气氛围下以10℃/min从室温升至600℃，在600℃恒温煅烧3h，获得亲水型二氧化硅-稀土复合型光催化材料。S6, place the hydrophobic silica-rare earth composite photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain Hydrophilic silica-rare earth composite photocatalytic material.
采用ZQ-GHX-XE-300光源照射二氧化硅-稀土复合型光催化材料30min后，以20mg/L的亚甲基蓝溶液为测试对象，取5g二氧化硅-稀土复合型光催化材料放入1L上述溶液中，置于 黑暗条件下，每隔30min取一次溶液，用于测量亚甲基蓝的降解速率。180min后亚甲基蓝的降解率达到98％。After using the ZQ-GHX-XE-300 light source to irradiate the silica-rare earth composite photocatalytic material for 30 minutes, take 20 mg/L methylene blue solution as the test object, take 5g of the silica-rare earth composite photocatalytic material and put it into 1L of the above The solution was placed in dark conditions and the solution was taken every 30 minutes to measure the degradation rate of methylene blue. The degradation rate of methylene blue reached 98% after 180 minutes.
对比例2(与实施例2进行对比，区别在于未添加长余辉发光材料)Comparative Example 2 (compared with Example 2, the difference is that no long afterglow luminescent material is added)
本对比例提供了与实施例2类似组分的二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This comparative example provides a method for preparing a silica-rare earth composite photocatalytic material with similar components as Example 2, as follows:
1、原料配比如下表4所示：1. The raw material proportions are shown in Table 4 below:
表4Table 4
Figure PCTCN2022124136-appb-000004
Figure PCTCN2022124136-appb-000004
2、按照上述质量比，工艺流程如下：2. According to the above mass ratio, the process flow is as follows:
S1，将A组原料搅拌混合，顺序先将正硅酸乙酯与乙醇混合搅拌均匀，再滴加水，搅拌至透明，最后加盐酸并搅拌；S1, stir and mix the raw materials of Group A. First, mix ethyl orthosilicate and ethanol and stir evenly, then add water dropwise, stir until transparent, and finally add hydrochloric acid and stir;
S2，将B组原料加入步骤S1的溶液中并搅拌均匀；S2, add the raw materials of Group B into the solution of step S1 and stir evenly;
S3，将氨水滴加于步骤S2的溶液并继续搅拌至凝胶；S3, add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
S4，将步骤S3的凝胶置于60℃温度下老化6h后，将凝胶浸泡于含有质量分数为10％三甲基氯硅烷的乙醇溶液中并搅拌8h；S4, after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane with a mass fraction of 10% and stir for 8 hours;
S5，将步骤S4中的凝胶置于环己烷中并搅拌4h，将凝胶放入80℃℃烘箱干燥12h，获得疏水型二氧化硅-稀土复合型光催化材料；S5. Place the gel in step S4 in cyclohexane and stir for 4 hours. Place the gel in an oven at 80°C for 12 hours to dry to obtain a hydrophobic silica-rare earth composite photocatalytic material;
S6，将步骤S5的光催化材料置于马弗炉中，在空气氛围下以10℃/min从室温升至600℃，在600℃恒温煅烧3h，获得亲水型二氧化硅-稀土复合型光催化材料。S6, placing the photocatalytic material of step S5 in a muffle furnace, raising the temperature from room temperature to 600°C at a rate of 10°C/min in an air atmosphere, and calcining at a constant temperature of 600°C for 3 hours to obtain a hydrophilic silica-rare earth composite photocatalytic material.
采用ZQ-GHX-XE-300光源照射复合型光催化材料30min后，以20mg/L的亚甲基蓝溶液为测试对象，取5g复合型光催化材料放入1L上述溶液中，置于黑暗条件下，每隔30min取一次溶液，用于测量亚甲基蓝的降解速率。60min后亚甲基蓝的降解率为20％，180min后亚甲基蓝的降解率仍为20％，溶液中的亚甲基蓝浓度不变。出现此现象的原因是：在黑暗条件下，当本对比例所得多孔材料吸附达到饱和，无法继续吸附，且在无光条件下无法继续催化降解有 机物。After using the ZQ-GHX-XE-300 light source to irradiate the composite photocatalytic material for 30 minutes, take 20 mg/L methylene blue solution as the test object, take 5g of the composite photocatalytic material and put it into 1L of the above solution, and place it under dark conditions. The solution was taken every 30 minutes to measure the degradation rate of methylene blue. The degradation rate of methylene blue is 20% after 60 minutes. The degradation rate of methylene blue is still 20% after 180 minutes. The concentration of methylene blue in the solution remains unchanged. The reason for this phenomenon is that under dark conditions, when the adsorption of the porous material obtained in this comparative example reaches saturation, it cannot continue to adsorb, and it cannot continue to catalyze the degradation of organic matter under lightless conditions.
对比例3(与实施例2进行对比，区别在于添加未掺杂稀土的Ca 2MgSi 2O 7) Comparative Example 3 (Compared with Example 2, the difference lies in the addition of Ca 2 MgSi 2 O 7 without rare earth doping)
本对比例提供了与实施例2类似组分的二氧化硅-复合型光催化材料的制备方法，具体如下：This comparative example provides a method for preparing a silica-composite photocatalytic material with similar components to Example 2, as follows:
1、原料配比如下表4所示：1. The raw material proportions are shown in Table 4 below:
表5table 5
Figure PCTCN2022124136-appb-000005
Figure PCTCN2022124136-appb-000005
2、按照上述质量比，工艺流程如下：2. According to the above mass ratio, the process flow is as follows:
S1，将A组原料搅拌混合，先将正硅酸乙酯与乙醇混合搅拌均匀，再滴加水，搅拌至透明，最后加盐酸并搅拌；S1, stir and mix the raw materials of Group A, first mix ethyl orthosilicate and ethanol and stir evenly, then add water dropwise, stir until transparent, finally add hydrochloric acid and stir;
S2，将B组原料加入步骤S1的溶液中，先将SnO 2分散液加入步骤S1的溶液中并搅拌均匀，再将Ca 2MgSi 2O 7粉末加入步骤S1的溶液中并搅拌； S2, adding the raw materials of group B to the solution of step S1, first adding the SnO 2 dispersion to the solution of step S1 and stirring evenly, then adding the Ca 2 MgSi 2 O 7 powder to the solution of step S1 and stirring;
S3，将氨水滴加于步骤S2的溶液并继续搅拌至凝胶；S3, add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
S4，将步骤S3的凝胶置于60℃温度下老化6h后，将凝胶浸泡于含有质量分数为10％三甲基氯硅烷的乙醇溶液中并搅拌8h；S4, after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane with a mass fraction of 10% and stir for 8 hours;
S5，将步骤S4中的凝胶置于环己烷中并搅拌4h，将凝胶放入80℃烘箱干燥12h，获得疏水型二氧化硅复合型光催化材料；S5, place the gel in step S4 in cyclohexane and stir for 4 hours, then dry the gel in an oven at 80°C for 12 hours to obtain a hydrophobic silica composite photocatalytic material;
S6，将步骤S5的疏水型二氧化硅复合型光催化材料置于马弗炉中，在空气氛围下以10℃/min从室温升至600℃，在600℃恒温煅烧3h，获得亲水型二氧化硅复合型光催化材料。S6, place the hydrophobic silica composite photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain hydrophilic Type silica composite photocatalytic material.
实施例3Example 3
本实施例提供了一种二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
1、原料配比如下表6所示：1. The raw material proportions are shown in Table 6 below:
表6Table 6
Figure PCTCN2022124136-appb-000006
Figure PCTCN2022124136-appb-000006
2、具体制备步骤方法同实施例2。2. The specific preparation steps are the same as those in Example 2.
实施例4Example 4
本实施例提供了一种二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
1、原料配比如下表7所示：1. The raw material proportions are shown in Table 7 below:
表7Table 7
Figure PCTCN2022124136-appb-000007
Figure PCTCN2022124136-appb-000007
2、具体制备步骤方法同实施例2。2. The specific preparation steps are the same as those in Example 2.
实施例5Example 5
本实施例提供了一种二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
1、原料配比如下表8所示：1. The raw material proportions are shown in Table 8 below:
表8Table 8
Figure PCTCN2022124136-appb-000008
Figure PCTCN2022124136-appb-000008
Figure PCTCN2022124136-appb-000009
Figure PCTCN2022124136-appb-000009
2、具体制备步骤方法同实施例2。2. The specific preparation steps are the same as those in Example 2.
实施例6Example 6
本实施例提供了一种二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
1、原料配比如下表9所示：1. The raw material proportions are shown in Table 9 below:
表9Table 9
Figure PCTCN2022124136-appb-000010
Figure PCTCN2022124136-appb-000010
2、具体制备步骤方法同实施例2。2. The specific preparation steps are the same as those in Example 2.
实施例7Example 7
本实施例提供了一种二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
1、原料配比如下表10所示：1. The raw material proportions are shown in Table 10 below:
表10Table 10
Figure PCTCN2022124136-appb-000011
Figure PCTCN2022124136-appb-000011
Figure PCTCN2022124136-appb-000012
Figure PCTCN2022124136-appb-000012
2、具体制备步骤方法同实施例2。2. The specific preparation steps are the same as those in Example 2.
实施例8Example 8
本实施例提供了一种二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
1、原料配比如下表11所示：1. The raw material proportions are shown in Table 11 below:
表11Table 11
Figure PCTCN2022124136-appb-000013
Figure PCTCN2022124136-appb-000013
2、具体制备步骤方法同实施例2。2. The specific preparation steps are the same as those in Example 2.
实施例9Example 9
本实施例提供了一种二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
1、原料配比如下表12所示：1. The raw material proportions are shown in Table 12 below:
表12Table 12
Figure PCTCN2022124136-appb-000014
Figure PCTCN2022124136-appb-000014
2、按照上述质量比，工艺流程如下：2. According to the above mass ratio, the process flow is as follows:
S1，将A组原料搅拌混合，先将正硅酸乙酯与乙醇混合搅拌均匀，再滴加水，搅拌至透明，最后加盐酸并搅拌；S1, stir and mix the raw materials of Group A, first mix ethyl orthosilicate and ethanol and stir evenly, then add water dropwise, stir until transparent, finally add hydrochloric acid and stir;
S2，将B组原料加入步骤S1的溶液中，先将纳米TiO 2分散液加入步骤S1的溶液中并搅拌均匀，再将Ca 2MgSi 2O 7:Eu 2+,Dy 3+粉末加入步骤S1的溶液中并搅拌； S2, add the raw materials of Group B into the solution in step S1. First add the nano-TiO 2 dispersion into the solution in step S1 and stir evenly. Then add the Ca 2 MgSi 2 O 7 : Eu 2+ , Dy 3+ powder into step S1. into the solution and stir;
S3，将氨水滴加于步骤S2的溶液并继续搅拌至凝胶；S3, add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
S4，将步骤S3的凝胶置于60℃温度下老化6h后，将凝胶浸泡于含有质量分数为10％三甲基氯硅烷的乙醇溶液中并搅拌8h；S4, after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane with a mass fraction of 10% and stir for 8 hours;
S5，将步骤S4中的凝胶置于环己烷中并搅拌4h，将凝胶放入80℃烘箱干燥12h，获得疏水型二氧化硅-稀土复合型光催化材料；S5, placing the gel in step S4 in cyclohexane and stirring for 4 hours, placing the gel in an oven at 80° C. and drying for 12 hours to obtain a hydrophobic silica-rare earth composite photocatalytic material;
S6，将步骤S5的光催化材料置于马弗炉中，在空气氛围下以10℃/min从室温升至600℃，在600℃恒温煅烧3h，获得亲水型二氧化硅-稀土复合型光催化材料。S6, place the photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain a hydrophilic silica-rare earth composite Type photocatalytic materials.
实施例10Example 10
本实施例提供了一种二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
1、原料配比如下表13所示：1. The raw material proportions are shown in Table 13 below:
表13Table 13
Figure PCTCN2022124136-appb-000015
Figure PCTCN2022124136-appb-000015
2、按照上述质量比，工艺流程如下：2. According to the above mass ratio, the process flow is as follows:
S1，将A组原料搅拌混合，先将正硅酸乙酯与乙醇混合搅拌均匀，再滴加水，搅拌至透明，最后加盐酸并搅拌；S1, stir and mix the raw materials of Group A, first mix ethyl orthosilicate and ethanol and stir evenly, then add water dropwise, stir until transparent, finally add hydrochloric acid and stir;
S2，将B组原料加入步骤S1的溶液中，先将纳米ZnO 2分散液加入步骤S1的溶液中并搅拌均匀，再将Ca 2MgSi 2O 7:Eu 2+,Dy 3+粉末加入步骤S1的溶液中并搅拌； S2, add the raw materials of Group B into the solution in step S1. First add the nano-ZnO 2 dispersion into the solution in step S1 and stir evenly. Then add the Ca 2 MgSi 2 O 7 :Eu 2+ and Dy 3+ powder into step S1. into the solution and stir;
S3，将氨水滴加于步骤S2的溶液并继续搅拌至凝胶；S3, add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
S4，将步骤S3的凝胶置于60℃温度下老化6h后，将凝胶浸泡于含有质量分数为10％三甲基氯硅烷的乙醇溶液中并搅拌8h；S4, after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane with a mass fraction of 10% and stir for 8 hours;
S5，将步骤S4中的凝胶置于环己烷中并搅拌4h，将凝胶放入80℃烘箱干燥12h，获得疏水型二氧化硅-稀土复合型光催化材料；S5, place the gel in step S4 in cyclohexane and stir for 4 hours. Place the gel in an oven at 80°C to dry for 12 hours to obtain a hydrophobic silica-rare earth composite photocatalytic material;
S6，将步骤S5的光催化材料置于马弗炉中，在空气氛围下以10℃/min从室温升至600℃，在600℃恒温煅烧3h，获得亲水型二氧化硅-稀土复合型光催化材料。S6, place the photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain a hydrophilic silica-rare earth composite Type photocatalytic materials.
实施例11Example 11
本实施例提供了一种二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
1、原料配比如下表14所示：1. The raw material proportions are shown in Table 14 below:
表14Table 14
Figure PCTCN2022124136-appb-000016
Figure PCTCN2022124136-appb-000016
2、按照上述质量比，工艺流程如下：2. According to the above mass ratio, the process flow is as follows:
S1，将A组原料搅拌混合，先将正硅酸乙酯与乙醇混合搅拌均匀，再滴加水，搅拌至透明，最后加盐酸并搅拌；S1, stir and mix the raw materials of Group A, first mix ethyl orthosilicate and ethanol and stir evenly, then add water dropwise, stir until transparent, finally add hydrochloric acid and stir;
S2，将B组原料加入步骤S1的溶液中，先将纳米氮掺杂二氧化锡分散液加入步骤S1的溶液中并搅拌均匀，再将Ca 2MgSi 2O 7:Eu 2+,Nd 3+粉末加入步骤S1的溶液中并搅拌； S2, add the raw materials of Group B into the solution in step S1. First add the nano-nitrogen-doped tin dioxide dispersion into the solution in step S1 and stir evenly. Then add Ca 2 MgSi 2 O 7 :Eu 2+ , Nd 3+ Add the powder to the solution in step S1 and stir;
S3，将氨水滴加于步骤S2的溶液并继续搅拌至凝胶；S3, add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
S4，将步骤S3的凝胶置于30℃温度下老化3h后，将凝胶浸泡于含有质量分数为20％辛基三乙氧基硅烷的乙醇溶液中并搅拌8h；S4, after aging the gel in step S3 at 30°C for 3 hours, soak the gel in an ethanol solution containing 20% octyltriethoxysilane with a mass fraction of 20% and stir for 8 hours;
S5，将步骤S4中的凝胶置于丙酮中并搅拌4h，将凝胶放入80℃烘箱干燥12h，获得疏水型二氧化硅-稀土复合型光催化材料；S5. Place the gel in step S4 in acetone and stir for 4 hours. Place the gel in an oven at 80°C to dry for 12 hours to obtain a hydrophobic silica-rare earth composite photocatalytic material;
S6，将步骤S5的光催化材料置于马弗炉中，在空气氛围下以10℃/min从室温升至400℃， 在400℃恒温煅烧6h，获得亲水型二氧化硅-稀土复合型光催化材料。S6, place the photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 400°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 400°C for 6 hours to obtain a hydrophilic silica-rare earth composite Type photocatalytic materials.
实施例12Example 12
本实施例提供了一种二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This embodiment provides a method for preparing a silicon dioxide-rare earth composite photocatalytic material, which is as follows:
1、原料配比如下表15所示：1. The raw material proportions are shown in Table 15 below:
表15Table 15
Figure PCTCN2022124136-appb-000017
Figure PCTCN2022124136-appb-000017
2、按照上述质量比，工艺流程如下：2. According to the above mass ratio, the process flow is as follows:
S1，将A组原料搅拌混合，先将正硅酸甲酯与甲醇混合搅拌均匀，再滴加水，搅拌至透明，最后加盐酸并搅拌；S1, stir and mix the raw materials of Group A, first mix methyl orthosilicate and methanol and stir evenly, then add water dropwise, stir until transparent, finally add hydrochloric acid and stir;
S2，将B组原料加入步骤S1的溶液中，先将SnO 2分散液加入步骤S1的溶液中并搅拌均匀，再将Ca 2MgSi 2O 7:Eu 2+,Dy 3+粉末加入步骤S1的溶液中并搅拌； S2, add the raw materials of Group B into the solution in step S1. First add the SnO 2 dispersion into the solution in step S1 and stir evenly. Then add the Ca 2 MgSi 2 O 7 :Eu 2+ and Dy 3+ powder into the solution in step S1. solution and stir;
S3，将氨水滴加于步骤S2的溶液并继续搅拌至凝胶；S3, add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
S4，将步骤S3的凝胶置于60℃温度下老化6h后，将凝胶浸泡于含有质量分数为10％三甲基氯硅烷的乙醇溶液中并搅拌8h；S4, after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane with a mass fraction of 10% and stir for 8 hours;
S5，将步骤S4中的凝胶置于环己烷中并搅拌4h，将凝胶放入80℃烘箱干燥12h，获得疏水型二氧化硅-稀土复合型光催化材料；S5, place the gel in step S4 in cyclohexane and stir for 4 hours. Place the gel in an oven at 80°C to dry for 12 hours to obtain a hydrophobic silica-rare earth composite photocatalytic material;
S6，将步骤S5的光催化材料置于马弗炉中，在空气氛围下以10℃/min从室温升至600℃，在600℃恒温煅烧3h，获得亲水型二氧化硅-稀土复合型光催化材料。S6, place the photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain a hydrophilic silica-rare earth composite Type photocatalytic materials.
实施例13Example 13
本实施例提供了一种二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
1、原料配比如下表16所示：1. The raw material proportions are shown in Table 16 below:
表16Table 16
Figure PCTCN2022124136-appb-000018
Figure PCTCN2022124136-appb-000018
2、按照上述质量比，工艺流程如下：2. According to the above mass ratio, the process flow is as follows:
S1，将A组原料搅拌混合，顺序先将正硅酸乙酯与乙醇混合搅拌均匀，再滴加水，搅拌至透明，最后加盐酸并搅拌；S1, stir and mix the raw materials of Group A. First, mix ethyl orthosilicate and ethanol and stir evenly, then add water dropwise, stir until transparent, and finally add hydrochloric acid and stir;
S2，将B组原料加入步骤S1的溶液中，顺序为先将SnO 2分散液加入步骤S1的溶液中并搅拌均匀，再将Sr 4Al 14O 25:Eu 2+,Dy 3+粉末加入步骤S1的溶液中并搅拌； S2, add the raw materials of Group B into the solution in step S1. The order is as follows: first add the SnO 2 dispersion liquid into the solution in step S1 and stir evenly, then add the Sr 4 Al 14 O 25 :Eu 2+ , Dy 3+ powder into the step S2. into the solution of S1 and stir;
S3，将氨水滴加于步骤S2的溶液并继续搅拌至凝胶；S3, add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
S4，将步骤S3的凝胶置于60℃温度下老化6h后，将凝胶浸泡于含有质量分数为10％六甲基二硅氮烷的乙醇溶液中并搅拌8h；S4, after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% hexamethyldisilazane by mass and stir for 8 hours;
S5，将步骤S4中的凝胶置于正丙醇中并搅拌4h，将凝胶放入80℃烘箱干燥12h，获得疏水型二氧化硅-稀土复合型光催化材料；S5, place the gel in step S4 in n-propanol and stir for 4 hours. Place the gel in an oven at 80°C to dry for 12 hours to obtain a hydrophobic silica-rare earth composite photocatalytic material;
S6,将步骤S5的光催化材料置于马弗炉中，在空气氛围下以10℃/min从室温升至600℃，在600℃恒温煅烧3h，获得亲水型二氧化硅-稀土复合型光催化材料。S6, place the photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain a hydrophilic silica-rare earth composite Type photocatalytic materials.
实施例14Example 14
本实施例提供了一种二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
1、原料配比如下表17所示：1. The raw material proportions are shown in Table 17 below:
表17Table 17
Figure PCTCN2022124136-appb-000019
Figure PCTCN2022124136-appb-000019
Figure PCTCN2022124136-appb-000020
Figure PCTCN2022124136-appb-000020
2、按照上述质量比，工艺流程如下：2. According to the above mass ratio, the process flow is as follows:
S1，将A组原料搅拌混合，顺序先将正硅酸乙酯与乙醇混合搅拌均匀，再滴加水，搅拌至透明，最后加盐酸并搅拌；S1, stir and mix the raw materials of Group A. First, mix ethyl orthosilicate and ethanol and stir evenly, then add water dropwise, stir until transparent, and finally add hydrochloric acid and stir;
S2，将B组原料加入步骤S1的溶液中，顺序为先将SnO 2粉末加入步骤S1的溶液中并搅拌均匀，再将SrAl 2O 4:Eu 2+,Dy 3+粉末加入步骤S1的溶液中并搅拌； S2, add the raw materials of Group B into the solution in step S1. The order is as follows: first add SnO 2 powder into the solution in step S1 and stir evenly, then add SrAl 2 O 4 :Eu 2+ and Dy 3+ powder into the solution in step S1. medium and stir;
S3，将氨水滴加于步骤S2的溶液并继续搅拌至凝胶；S3, add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
S4，将步骤S3的凝胶置于60℃温度下老化6h后，将凝胶浸泡于含有质量分数为10％三甲基氯硅烷的乙醇溶液中并搅拌8h；S4, after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane with a mass fraction of 10% and stir for 8 hours;
S5，将步骤S4中的凝胶置于环己烷中并搅拌4h，将凝胶放入80℃烘箱干燥12h，获得疏水型二氧化硅-稀土复合型光催化材料；S5, place the gel in step S4 in cyclohexane and stir for 4 hours. Place the gel in an oven at 80°C to dry for 12 hours to obtain a hydrophobic silica-rare earth composite photocatalytic material;
S6，将步骤S5的光催化材料置于马弗炉中，在空气氛围下以10℃/min从室温升至600℃，在600℃恒温煅烧3h，获得亲水型二氧化硅-稀土复合型光催化材料。S6, place the photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain a hydrophilic silica-rare earth composite Type photocatalytic materials.
实施例15Example 15
本实施例提供了一种二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
1、原料配比如下表18所示：1. The raw material ratio is shown in Table 18 below:
表18Table 18
Figure PCTCN2022124136-appb-000021
Figure PCTCN2022124136-appb-000021
2、按照上述质量比，工艺流程如下：2. According to the above mass ratio, the process flow is as follows:
S1，将A组原料搅拌混合，顺序先将正硅酸乙酯与乙醇混合搅拌均匀，再滴加水，搅拌至透明，最后加盐酸并搅拌；S1, stir and mix the raw materials of Group A. First, mix ethyl orthosilicate and ethanol and stir evenly, then add water dropwise, stir until transparent, and finally add hydrochloric acid and stir;
S2，将B组原料加入步骤S1的溶液中，顺序为先将SnO 2分散液加入步骤S1的溶液中并搅拌均匀，再将BaAl 2O 4:Eu 2+,Dy 3+粉末加入步骤S1的溶液中并搅拌； S2, adding the raw materials of group B into the solution of step S1, the order is first adding the SnO 2 dispersion into the solution of step S1 and stirring evenly, then adding the BaAl 2 O 4 :Eu 2+ ,Dy 3+ powder into the solution of step S1 and stirring;
S3，将氨水滴加于步骤S2的溶液并继续搅拌至凝胶；S3, add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
S4，将步骤S3的凝胶置于60℃温度下老化6h后，将凝胶浸泡于含有质量分数为10％三甲基氯硅烷的乙醇溶液中并搅拌8h；S4, after aging the gel in step S3 at 60°C for 6 hours, soak the gel in an ethanol solution containing 10% trimethylchlorosilane with a mass fraction of 10% and stir for 8 hours;
S5，将步骤S4中的凝胶置于环己烷中并搅拌4h，将凝胶放入80℃烘箱干燥12h，获得疏水型二氧化硅-稀土复合型光催化材料；S5, place the gel in step S4 in cyclohexane and stir for 4 hours, then dry the gel in an oven at 80°C for 12 hours to obtain a hydrophobic silica-rare earth composite photocatalytic material;
S6，将步骤S5的光催化材料置于马弗炉中，在空气氛围下以10℃/min从室温升至600℃，在600℃恒温煅烧3h，获得亲水型二氧化硅-稀土复合型光催化材料。S6, place the photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 600°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 600°C for 3 hours to obtain a hydrophilic silica-rare earth composite Type photocatalytic materials.
实施例16Example 16
本实施例提供了一种二氧化硅-稀土复合型光催化材料的制备方法，具体如下：This embodiment provides a method for preparing a silica-rare earth composite photocatalytic material, specifically as follows:
1、原料配比如下表19所示：1. The raw material proportions are shown in Table 19 below:
表19Table 19
Figure PCTCN2022124136-appb-000022
Figure PCTCN2022124136-appb-000022
2、按照上述质量比，工艺流程如下：2. According to the above mass ratio, the process flow is as follows:
S1，将A组原料搅拌混合，顺序先将甲基三甲氧基硅烷与甲醇混合搅拌均匀，再滴加水，搅拌至透明，最后加盐酸并搅拌；S1, stir and mix the raw materials of Group A. First, mix methyltrimethoxysilane and methanol and stir evenly, then add water dropwise, stir until transparent, and finally add hydrochloric acid and stir;
S2，将B组原料加入步骤S1的溶液中，顺序为先将纳米碳掺杂二氧化锡分散液加入步骤S1的溶液中并搅拌均匀，再将(Sr,Ca) 2MgSi 2O 7:Eu 2+,Dy 3+粉末加入步骤S1的溶液中并搅拌； S2, add the raw materials of Group B into the solution in step S1. The sequence is as follows: first add the nanocarbon-doped tin dioxide dispersion into the solution in step S1 and stir evenly, then add (Sr,Ca) 2 MgSi 2 O 7 :Eu 2+ , Dy 3+ powder is added to the solution in step S1 and stirred;
S3，将氨水滴加于步骤S2的溶液并继续搅拌至凝胶；S3, add ammonia water dropwise to the solution in step S2 and continue stirring until gel;
S4，将步骤S3的凝胶置于40℃温度下老化5h后，将凝胶浸泡于含有质量分数为5％甲基三甲氧基硅烷的乙醇溶液中并搅拌8h；S4, aging the gel from step S3 at 40° C. for 5 h, then immersing the gel in an ethanol solution containing 5% by mass of methyltrimethoxysilane and stirring for 8 h;
S5，将步骤S4中的凝胶置于环己烷中并搅拌4h，将凝胶放入至乙醇超临界釜进行超临界干燥，获得疏水型二氧化硅-稀土复合型光催化材料；S5, place the gel in step S4 in cyclohexane and stir for 4 hours, put the gel into an ethanol supercritical kettle for supercritical drying, and obtain a hydrophobic silica-rare earth composite photocatalytic material;
S6，将步骤S5的光催化材料置于马弗炉中，在空气氛围下以10℃/min从室温升至800℃，在800℃恒温煅烧2h，获得亲水型二氧化硅-稀土复合型光催化材料。S6, place the photocatalytic material in step S5 in a muffle furnace, raise it from room temperature to 800°C at 10°C/min in an air atmosphere, and calcine at a constant temperature of 800°C for 2 hours to obtain a hydrophilic silica-rare earth composite Type photocatalytic materials.
应用测试例Application test cases
将实施例2-16和对比例2-3中所述二氧化硅-复合型光催化材料进行结构表征，以及亚甲基蓝降解测试。其中，降解测试的具体步骤：采用ZQ-GHX-XE-300光源照射复合型光催化材料30min后，以20mg/L的亚甲基蓝溶液为测试对象，取5g复合型光催化材料放入1L上述溶液中，置于黑暗条件下，每隔30min取一次溶液，用于测量亚甲基蓝的降解速率，设置空白对照组。实验结果见表20。The silica-composite photocatalytic materials described in Examples 2-16 and Comparative Examples 2-3 were subjected to structural characterization and methylene blue degradation testing. Among them, the specific steps of the degradation test: use ZQ-GHX-XE-300 light source to irradiate the composite photocatalytic material for 30 minutes, use 20mg/L methylene blue solution as the test object, take 5g of the composite photocatalytic material and put it into 1L of the above solution. , placed under dark conditions, take the solution every 30 minutes to measure the degradation rate of methylene blue, and set a blank control group. The experimental results are shown in Table 20.
表20.二氧化硅及复合型二氧化硅的物理性质与降解情况Table 20. Physical properties and degradation of silica and composite silica
Figure PCTCN2022124136-appb-000023
Figure PCTCN2022124136-appb-000023
Figure PCTCN2022124136-appb-000024
Figure PCTCN2022124136-appb-000024
由表19可知，通过本发明制备得到的二氧化硅-稀土复合型光催化材料的平均孔径较大，约13nm-17nm，比表面积大，使得待检物可以更好的吸附在催化剂材料中，为高效催化提供可能。其次，从亚甲基蓝的降解实验可知，本发明实施例材料的催化效率远远高于对比例2-3材料的催化效率。同时，本发明通过掺入稀土长余辉发光材料，实现了长时间在无光条件下进行光降解的可能，大大增强长余辉的余辉时间，且协同光催化材料增强催化效率，最终实现高效催化的结果；同时提供了更多废水废气处理的新方法。As can be seen from Table 19, the silica-rare earth composite photocatalytic material prepared by the present invention has a larger average pore size, about 13nm-17nm, and a large specific surface area, so that the test substance can be better adsorbed in the catalyst material. Provides the possibility for efficient catalysis. Secondly, it can be seen from the degradation experiment of methylene blue that the catalytic efficiency of the materials of the embodiments of the present invention is much higher than that of the materials of Comparative Examples 2-3. At the same time, by incorporating rare earth long afterglow luminescent materials, the present invention realizes the possibility of photodegradation under lightless conditions for a long time, greatly enhances the afterglow time of long afterglow, and cooperates with photocatalytic materials to enhance catalytic efficiency, ultimately achieving high-efficiency catalysis. The result; at the same time, more new methods for wastewater and gas treatment are provided.
显然，上述实施例仅仅是为清楚地说明所作的举例，并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。Obviously, the above-mentioned embodiments are only examples for clear explanation and are not intended to limit the implementation. For those of ordinary skill in the art, other changes or modifications may be made based on the above description. An exhaustive list of all implementations is neither necessary nor possible. The obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims (10)

  1. 一种二氧化硅-稀土复合型光催化材料，其特征在于，包括以下组分：二氧化硅、长余辉发光材料和光催化材料；所述二氧化硅-稀土复合型光催化材料为多孔结构；A silica-rare earth composite photocatalytic material, characterized in that it includes the following components: silica, a long afterglow luminescent material and a photocatalytic material; the silica-rare earth composite photocatalytic material has a porous structure;
    其中，所述长余辉发光材料为稀土掺杂的发光材料；所述光催化材料选自金属氧化物、氮掺杂金属氧化物和碳掺杂金属氧化物中的一种或多种。Wherein, the long afterglow luminescent material is a rare earth-doped luminescent material; and the photocatalytic material is selected from one or more of metal oxides, nitrogen-doped metal oxides and carbon-doped metal oxides.
  2. 根据权利要求1所述的二氧化硅-稀土复合型光催化材料，其特征在于，所述稀土掺杂的发光材料选自CaAl 2O 4:Eu 2+,Nd 3+、SrAl 2O 4:Eu 2+,Dy 3+、SrAl 4O 7:Eu 2+,Dy 3+、SrAl 12O 19:Eu 2+,Dy 3+、Sr 4Al 14O 25:Eu 2+,Dy 3+、BaAl 2O 4:Eu 2+,Dy 3+、SrAl 2O 4:Ce 3+、Sr 2Si 2O 4:Ce 3+、Sr 3SiO 5:Eu 2+,Dy 3+、Sr 2Al 2SiO 7:Eu 2+、Sr 2ZnSi 2O 7:Eu 2+,Dy 3+、Sr 2MgSi 2O 7:Eu 2+,Dy 3+、Ca 2MgSi 2O 7:Eu 2+,Dy 3+、Ba 2MgSi 2O 7:Eu 2+,Dy 3+和(Sr,Ca) 2MgSi 2O 7:Eu 2+,Dy 3+中的一种或多种。 The silica-rare earth composite photocatalytic material according to claim 1, characterized in that the rare earth doped luminescent material is selected from the group consisting of CaAl 2 O 4 : Eu 2+ , Nd 3+ , and SrAl 2 O 4 : Eu 2+ ,Dy 3+ ,SrAl 4 O 7 :Eu 2+ ,Dy 3+ ,SrAl 12 O 19 :Eu 2+ ,Dy 3+ ,Sr 4 Al 14 O 25 :Eu 2+ ,Dy 3+ ,BaAl 2 O 4 :Eu 2+ ,Dy 3+ ,SrAl 2 O 4 :Ce 3+ ,Sr 2 Si 2 O 4 :Ce 3+ ,Sr 3 SiO 5 :Eu 2+ ,Dy 3+ ,Sr 2 Al 2 SiO 7 :Eu 2+ , Sr 2 ZnSi 2 O 7 : Eu 2+ , Dy 3+ , Sr 2 MgSi 2 O 7 : Eu 2+ , Dy 3+ , Ca 2 MgSi 2 O 7 : Eu 2+ , Dy 3+ , Ba 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ and one or more of (Sr,Ca) 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ .
  3. 根据权利要求1所述的二氧化硅-稀土复合型光催化材料，其特征在于，所述二氧化硅-稀土复合型光催化材料的平均孔径为5nm～200nm，比表面积为200m 2/g～1500m 2/g。 The silica-rare earth composite photocatalytic material according to claim 1, characterized in that the average pore diameter of the silica-rare earth composite photocatalytic material is 5nm~200nm, and the specific surface area is 200m2 /g~ 1500m 2 /g.
  4. 根据权利要求1所述的二氧化硅-稀土复合型光催化材料，其特征在于，所述光催化材料选自金属氧化物、氮掺杂金属氧化物和碳掺杂金属氧化物中一种或多种。The silica-rare earth composite photocatalytic material according to claim 1, characterized in that the photocatalytic material is selected from one of metal oxides, nitrogen-doped metal oxides and carbon-doped metal oxides, or Various.
  5. 权利要求1-4任一项所述的二氧化硅-稀土复合型光催化材料的制备方法，其特征在于，包括以下步骤：The preparation method of the silica-rare earth composite photocatalytic material according to any one of claims 1 to 4, characterized in that it includes the following steps:
    S1，将硅源、有机溶剂、水、酸混合搅拌，之后加入长余辉发光材料、光催化材料并混匀；S1, mix and stir the silicon source, organic solvent, water, and acid, then add the long afterglow luminescent material and photocatalytic material and mix well;
    S2，将碱溶液加入步骤S1的溶液中并继续搅拌至凝胶；S2, add the alkali solution to the solution in step S1 and continue stirring until gel;
    S3，待步骤S2的凝胶老化后，浸泡于含有表面修饰剂的有机溶剂中；S3: After the gel in step S2 is aged, it is soaked in an organic solvent containing a surface modification agent;
    S4，用低表面张力溶剂替换步骤S4所得凝胶孔中的溶剂，干燥获得疏水型光催化材料；S4, replace the solvent in the gel pores obtained in step S4 with a low surface tension solvent, and dry to obtain a hydrophobic photocatalytic material;
    S5，将步骤S4的疏水型光催化材料进行煅烧，得到亲水型二氧化硅-稀土复合型光催化材料。S5, calcining the hydrophobic photocatalytic material in step S4 to obtain a hydrophilic silica-rare earth composite photocatalytic material.
  6. 根据权利要求5所述的制备方法，其特征在于，步骤S1中，所述酸选自盐酸、硫酸、硝酸、磷酸、柠檬酸、草酸和乙酸中的一种或多种。The preparation method according to claim 5, characterized in that in step S1, the acid is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, citric acid, oxalic acid and acetic acid.
  7. 根据权利要求5所述的制备方法，其特征在于，步骤S1中，所述硅源选自正硅酸甲酯、正硅酸乙酯、甲基三甲氧基硅烷和甲基三乙氧基硅烷中的一种或多种。The preparation method according to claim 5, characterized in that in step S1, the silicon source is selected from the group consisting of methyl orthosilicate, ethyl orthosilicate, methyltrimethoxysilane and methyltriethoxysilane one or more of them.
  8. 根据权利要求5所述的制备方法，其特征在于，步骤S2中，所述碱溶液中的碱选自NH 3.H 2O、三乙醇胺、氢氧化钠和氢氧化钾中的一种或多种。 The preparation method according to claim 5, characterized in that, in step S2, the alkali in the alkali solution is selected from one or more of NH 3. H 2 O, triethanolamine, sodium hydroxide and potassium hydroxide. kind.
  9. 根据权利要求5所述的制备方法，其特征在于，步骤S3中，所述表面修饰剂选自甲基三甲氧基硅烷、甲基三乙氧基硅烷、辛基三乙氧基硅烷、六甲基二硅氮烷、三甲基氯硅烷、苯基三甲基硅烷、苯基三乙基硅烷、甲基三乙酰氧基硅烷、乙烯基三乙酰氧基硅烷、全氟辛基三甲氧基硅烷、全氟辛基三乙氧基硅烷、全氟癸基三甲氧基硅烷和全氟癸基三乙氧基硅烷的一种或多种。The preparation method according to claim 5, characterized in that, in step S3, the surface modification agent is selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, octyltriethoxysilane, hexamethylene disilazane, trimethylchlorosilane, phenyltrimethylsilane, phenyltriethylsilane, methyltriacetoxysilane, vinyltriacetoxysilane, perfluorooctyltrimethoxysilane , one or more of perfluorooctyltriethoxysilane, perfluorodecyltrimethoxysilane and perfluorodecyltriethoxysilane.
  10. 权利要求1-4中任一项所述二氧化硅-稀土复合型光催化材料在催化降解废水废气中的有机物的应用；其中，所述有机物为偶氮类染料、苯酚类染料、甲醛、油脂或焦油。Application of the silica-rare earth composite photocatalytic material in any one of claims 1 to 4 in catalytically degrading organic matter in wastewater and waste gas; wherein the organic matter is azo dyes, phenol dyes, formaldehyde, grease Or tar.
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