CN117380172A - Photocatalytic self-cleaning metal hydroxide/TiO with amphiphilic structure 2 Hydrosol and preparation method and application thereof - Google Patents

Photocatalytic self-cleaning metal hydroxide/TiO with amphiphilic structure 2 Hydrosol and preparation method and application thereof Download PDF

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CN117380172A
CN117380172A CN202311311463.5A CN202311311463A CN117380172A CN 117380172 A CN117380172 A CN 117380172A CN 202311311463 A CN202311311463 A CN 202311311463A CN 117380172 A CN117380172 A CN 117380172A
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tio
hydrosol
metal hydroxide
colloid
polyvinylpyrrolidone
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CN117380172B (en
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卢启芳
韩若婷
刘梦雨
张兴雨
郭恩言
魏明志
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Qilu University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • 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
    • B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
    • 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
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • 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
    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • B01D53/8675—Ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Abstract

The invention relates to a photocatalysis self-cleaning metal hydroxide/TiO with an amphiphilic structure 2 Hydrosol and its preparation method and application are provided. The invention firstly prepares metal hydroxide/TiO 2 Colloid, then polyvinylpyrrolidone is introduced and stirred for h to obtain metal hydroxide/TiO 2 The invention prepares the photocatalysis self-cleaning metal hydroxide/TiO with good dispersivity and excellent photocatalysis performance by adopting a precipitation method 2 The hydrosol realizes the efficient removal of harmful pollutants in water or atmosphere under sunlight, and the method is simple and feasible, can be used for large-scale production, and greatly improves the application efficiency. The invention creatively introduces polyvinylpyrrolidone into heterojunction metal hydroxide/TiO 2 In the colloid, the heterojunction metal hydroxide/TiO is obviously improved 2 Photocatalytic properties.

Description

Photocatalytic self-cleaning metal hydroxide/TiO with amphiphilic structure 2 Hydrosol and preparation method and application thereof
Technical Field
The invention relates to a photocatalysis self-cleaning metal hydroxide/TiO with an amphiphilic structure 2 Hydrosol and a preparation method and application thereof belong to the technical field of photocatalysis self-cleaning materials.
Background
With the progress of society and science and technology, people experience the problem of continuously deteriorating ecological environment when enjoying convenience brought by scientific and technological achievements, wherein the environmental problem of organic matter pollution in water bodies is highly valued all over the world. In particular, strict environmental protection laws are issued in China, strict standards are regulated on pollutants in water environment, particularly persistent organic pollutants in wastewater have high environmental toxicity and nondegradability, and the pollutants are difficult to effectively eliminate by the traditional biological or physicochemical method. Therefore, the development of advanced technologies for effectively eliminating such contaminants is not only an important scientific challenge, but also has great practical application significance.
The semiconductor photocatalysis technology is an advanced water treatment technology which appears in recent years, can deeply mineralize organic pollutants, has low energy consumption and raw material consumption, simple process, does not damage the background environment and has no secondary pollution, and is a very promising environment-friendly water treatment method. Nanometer titanium dioxide (TiO) 2 ) Has the advantages of no toxicity, no harm and no corrosiveness, and plays an important role in treating environmental pollution; and TiO 2 The nano particles are easy to obtain, reasonable in price and high in chemical stability, and have wide application prospects in photocatalytic degradation of pollutants. However, a single TiO 2 The high recombination rate of the photocatalyst carriers leads to low quantum efficiency of the photocatalytic reaction, and the low photocatalytic reaction rate is a main factor which prevents the industrialization of the photocatalytic wastewater treatment technology. In the semiconductor photocatalytic reaction process, how to increase the transfer rate of the photo-generated electrons or reduce the recombination of photo-generated electron-hole pairs is controlled by the transfer rate of the photo-generated electrons to the surface of the photocatalyst for absorbing oxygen, and has become a target for research by researchers. An effective method is to mix TiO 2 The nano material is compounded with other semiconductors, and the rapid transfer of photo-generated electron-hole pairs under the illumination condition is promoted by constructing a heterostructure material, so that the photocatalysis efficiency is improved.
Zinc hydroxide (Zn (OH) 2 ) The method is mainly used for producing precursors of zinc compounds, such as zinc oxide, zinc sulfate, zinc nitrate and the like, and has limited photocatalytic performance due to larger forbidden bandwidth (5.1-5.6 eV), so that the method has few researches in the field of photocatalytic degradation. In (OH) 3 Is also a wide bandgap semiconductor (eg=5.15 eV), and is typically an intermediate for hydrothermally synthesizing indium oxide materials, and has been omitted from past material studies. Zn (OH) 2 And In (OH) 3 Has good stability and durability, and can be used for a long time under severe environmental conditions, which leads to Zn (OH) 2 And In (OH) 3 As a photocatalyst, is more reliable and economical in practical applications.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a photocatalysis self-cleaning structure with an amphiphilic structureMetal hydroxide/TiO 2 Hydrosol and its preparation method and application are provided.
The metal hydroxide/TiO of the present invention 2 The hydrosol has a microscopic morphology of nano particles with a particle size of 5-10nm, is in a sol shape in water, is a colorless transparent film after being sprayed on the surface of a substrate to form a film, has a light transmittance of more than 99%, and has a hydrophilic and lipophilic amphiphilic function.
The invention adopts a precipitation method to prepare the photocatalysis self-cleaning metal hydroxide/TiO with good dispersivity and excellent photocatalysis performance 2 The hydrosol realizes the efficient removal of harmful pollutants in water or atmosphere under sunlight, and the method is simple and feasible, can be used for large-scale production, and greatly improves the application efficiency.
Description of the terminology:
room temperature: the room temperature according to the invention has the meaning known in the art and generally refers to 20-25 ℃.
The technical scheme of the invention is as follows:
photocatalytic self-cleaning metal hydroxide/TiO with amphiphilic structure 2 The hydrosol has microscopic morphology of nano particles with the size of 5-10nm, is in a sol shape in water, is a colorless transparent film after being sprayed on the surface of a substrate to form a film, has light permeability of more than 99%, and has hydrophilic and oleophilic amphiphilicity functions.
The photocatalysis self-cleaning metal hydroxide/TiO with the amphiphilic structure 2 The preparation method of the hydrosol comprises the following steps:
(1) TiO is mixed with 2 Uniformly mixing the nano powder with deionized water, and stirring for 5-30min to obtain TiO 2 A colloid;
(2) Adding aqueous solution of acetic acid metal salt into TiO 2 Stirring in colloid for 5-30min to obtain mixture;
(3) Adding alkaline aqueous solution into the mixture, stirring for 5-30min to obtain metal hydroxide/TiO 2 A colloid;
(4) To metal hydroxide/TiO 2 Adding polyvinylpyrrolidone into the colloid, stirring for 8-14h to obtain metal hydroxide/TiO with viscosity of 5-50Pa.S 2 And (3) hydrosol.
According toIn the preferred embodiment of the present invention, in the step (1), tiO 2 The mass volume ratio of the deionized water to the deionized water is (0.1-120): (0.1-15), units g/L.
Further preferably, in the step (1), tiO 2 The mass volume ratio of the deionized water to the deionized water is (50-100): (5-10), units of g/L.
According to a preferred embodiment of the present invention, in step (2), the metal acetate is zinc acetate or indium acetate.
According to a preferred embodiment of the present invention, in the step (2), the concentration of the aqueous metal acetate solution is 0.1 to 5mol/L.
According to a preferred embodiment of the invention, in step (2), tiO 2 The mass volume ratio of the powder to the aqueous solution of the metal acetate is (0.1-120): (0.01-0.5), unit g/mL.
Further preferred, tiO 2 The mass volume ratio of the powder to the aqueous solution of the metal acetate is (50-100): (0.1-0.5), units g/mL.
According to the invention, in step (3), the alkaline aqueous solution is preferably sodium hydroxide solution having a concentration of 0.1 to 5mol/L.
According to a preferred embodiment of the present invention, in step (3), tiO 2 The mass volume ratio of the powder to the alkaline aqueous solution is (0.1-120): (0.04-0.6), units g/mL.
Further preferably, in the step (3), tiO 2 The mass volume ratio of the powder to the alkaline aqueous solution is (50-100): (0.1-0.6), units g/mL.
According to a preferred embodiment of the invention, in step (4), the polyvinylpyrrolidone is K88-K90 polyvinylpyrrolidone.
According to a preferred embodiment of the invention, in step (4), the polyvinylpyrrolidone has a weight average molecular weight of 100 to 150 ten thousand.
According to the present invention, it is preferable that in the step (4), the addition amount of polyvinylpyrrolidone is equal to the metal hydroxide/TiO 2 The mass ratio of the colloid is (0.5-50): (1.2-120).
According to the present invention, zn (OH) is preferably produced when the metal acetate is zinc acetate 2 /TiO 2 When the nanometer hydrosol and the acetic acid metal salt are indium acetate, in (OH) is prepared 3 /TiO 2 Nanometer scaleAnd (3) hydrosol.
Photocatalytic self-cleaning metal hydroxide/TiO with amphiphilic structure 2 The hydrosol is used for photocatalytic degradation of organic pollutants under sunlight irradiation, is sprayed on the outer wall of a building, is uniformly formed into a film within 5-30min, and is used for efficiently removing harmful pollutants such as ozone, formaldehyde, nitrogen sulfide and the like in the air.
Zn (OH) according to the invention 2 /TiO 2 And In (OH) 3 /TiO 2 The nano hydrosol has photocatalysis performance under the irradiation of sunlight, and can effectively degrade organic pollutants in wastewater. In addition, zn (OH) with viscosity of 5-50 Pa.S is prepared 2 /TiO 2 And In (OH) 3 /TiO 2 The nanometer hydrosol can be sprayed on the outer wall of a building with various colors, and is uniformly formed into a film within 5-30min, so as to efficiently remove harmful pollutants such as ozone, formaldehyde, nitrogen oxides, sulfur oxides and the like in the air.
The invention adopts a precipitation method to prepare the metal hydroxide/TiO 2 The hydrosol has the advantages of large specific surface area, more reactive sites, low photo-generated electron-hole pair recombination rate, high light energy utilization rate and the like, and can effectively inhibit the recombination of photo-generated carriers and improve the quantum efficiency, thereby efficiently carrying out photocatalytic degradation reaction.
The invention creatively introduces polyvinylpyrrolidone into heterojunction metal hydroxide/TiO 2 In the colloid, on one hand, polyvinylpyrrolidone is used as a shaping film forming agent, and after forming a uniform solution with a colloid photocatalyst, the uniform solution is sprayed to form a film for degrading harmful pollutants such as ozone, formaldehyde, nitrogen oxides, sulfur oxides and the like in the air; on the other hand, more importantly, the introduction of polyvinylpyrrolidone significantly improves the heterojunction metal hydroxide/TiO 2 The photocatalytic performance is also affected by the model and weight average molecular weight of polyvinylpyrrolidone, the transmittance is obviously improved, and the reason is analyzed that PVP provides lone pair electrons and metal hydroxide/TiO through N atoms and O atoms in the molecular structure 2 The surface atoms of the nano particles coordinate to form coordination bonds which are adsorbed on the surfaces of the nano particles, so that the formed steric hindrance effect can obviously reduce the attraction between particles and prevent the particles from being blockedPreventing the mutual contact between particles, thereby effectively preventing the continuous growth of crystal grains, ensuring the stability of sol and improving the photocatalysis performance.
The invention has the technical characteristics and advantages that:
1. the invention creatively introduces polyvinylpyrrolidone into heterojunction metal hydroxide/TiO 2 In the colloid, on one hand, polyvinylpyrrolidone is used as a shaping film forming agent, and after forming a uniform solution with a colloid photocatalyst, the uniform solution is sprayed to form a film for degrading harmful pollutants such as ozone, nitrogen sulfide and the like in the air; on the other hand, more importantly, the introduction of polyvinylpyrrolidone significantly improves the heterojunction metal hydroxide/TiO 2 The photocatalytic performance is also affected by the model and weight average molecular weight of polyvinylpyrrolidone, and the transmittance is obviously improved.
2. Zn (OH) prepared by the invention 2 /TiO 2 And In (OH) 3 /TiO 2 The hydrosol consists of nano particles with the wavelength of 5-10nm, is colloidal in water, and has the light transmittance of 99% so as to greatly improve the utilization rate of sunlight; and Zn (OH) 2 /TiO 2 And In (OH) 3 /TiO 2 The heterostructure formed by the hydrosol photocatalyst is more beneficial to the transmission and separation of photo-generated electrons and photo-generated holes, so that the hydrosol photocatalyst can better perform oxidation-reduction reaction, and higher photocatalytic efficiency is achieved.
3. Zn (OH) prepared by the invention 2 /TiO 2 And In (OH) 3 /TiO 2 Polyvinylpyrrolidone (K88-K90) used in the hydrocolloid is dissolved in Zn (OH) 2 /TiO 2 And In (OH) 3 /TiO 2 The hydrosol colloid is transparent, has viscosity of 5-50 Pa.S, and can be sprayed on building outer wall with various colors to form a film for 5-30min, and after forming the film, the film is colorless and odorless.
4. When exposed to urban environment in automobile exhaust, a large amount of particles can be deposited on the outer wall of a building to influence the appearance, and Zn (OH) prepared by the method is used for preparing the composite material 2 /TiO 2 And In (OH) 3 /TiO 2 The hydrosol has the characteristics of hydrophilicity and oleophylic property, can enable a water film oil film to rapidly spread on the whole coating surface, and after rain washing,the dirt is automatically separated from the hydrophilic membrane layer.
5. The metal hydroxide/TiO of the present invention 2 The hydrosol is stable and does not contain auxiliary components, so that the harmful pollutants in water or atmosphere can be efficiently removed under the sunlight, and Zn (OH) 2 /TiO 2 And In (OH) 3 /TiO 2 The hydrosol can be produced in a large scale, and the application efficiency is greatly improved.
6. The invention obtains the metal hydroxide/TiO with excellent hydrophilic-lipophilic amphiphilicity and photocatalysis performance by the simplest method 2 And (3) hydrosol.
Drawings
FIG. 1 shows 0.2% Zn (OH) of example 1 2 /TiO 2 Hydrosol material, 0.2% in (OH) prepared in example 8 3 /TiO 2 Hydrosol material and TiO prepared in comparative example 1 2 X-ray diffraction (XRD) patterns of the hydrosol material;
FIG. 2 shows 0.2% Zn (OH) of example 1 2 /TiO 2 Hydrosol material and TiO prepared in comparative example 1 2 SEM of hydrosol material, a, b being TiO 2 Hydrosol material, c is 0.2% Zn (OH) 2 /TiO 2 Hydrosol material with d of 0.2% Zn (OH) 2 /TiO 2 An elemental distribution image of the hydrosol material;
FIG. 3 shows 0.2% Zn (OH) of example 1 2 /TiO 2 Hydrosol material and TiO prepared in comparative example 1 2 N of hydrosol material 2 Adsorption-desorption isotherms; a is 0.2% Zn (OH) 2 /TiO 2 Hydrosol material, b is TiO 2 A hydrosol material;
FIG. 4 shows Zn (OH) s prepared in examples 1-7 2 /TiO 2 Hydrosol material, 0.2% in (OH) prepared in example 8 3 /TiO 2 Hydrosol material and TiO prepared in comparative example 1 2 An ultraviolet-visible diffuse reflectance spectrum of the hydrosol material;
FIG. 5 shows Zn (OH) s prepared in examples 1-7 2 /TiO 2 Hydrosol material and TiO prepared in comparative example 1 2 Photo current image of hydrosol material;
FIG. 6 shows Zn (OH) s prepared in examples 1-7 2 /TiO 2 Hydrosol material and TiO prepared in comparative example 1 2 Impedance image of the hydrosol material;
FIG. 7 shows Zn (OH) s prepared in examples 1-7 2 /TiO 2 Hydrosol material and TiO prepared in comparative example 1 2 A photocatalytic degradation profile of the hydrosol material;
FIG. 8 shows 0.2% Zn (OH) of example 1 2 /TiO 2 Hydrosol material, tiO from comparative example 1 2 Hydrosol material, tiO from comparative example 2 2 Colloidal material and 0.2% Zn (OH) prepared in comparative example 3 2 /TiO 2 A photocatalytic degradation curve of the colloidal material;
FIG. 9 shows 0.2% Zn (OH) of example 1 2 /TiO 2 Hydrosol material, tiO from comparative example 1 2 Hydrosol material, 0.2% Zn (OH) prepared in comparative example 3 2 /TiO 2 Ultraviolet-visible light transmittance of the gel material;
FIG. 10 is a sample of 0.2% Zn (OH) 2 /TiO 2 Hydrosol material, tiO from comparative example 1 2 Wetting property test chart of hydrosol material.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description, it is to be understood that the terms used in this specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description set forth herein is merely a preferred example for the purpose of illustration and is not intended to limit the scope of the invention, so that it should be understood that other equivalents or modifications may be made thereto without departing from the spirit and scope of the invention.
The following examples are merely illustrative of embodiments of the present invention and are not intended to limit the invention in any way, and those skilled in the art will appreciate that modifications may be made without departing from the spirit and scope of the invention. Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available; the equipment used is conventional equipment. Wherein: the polyvinylpyrrolidone is polyvinylpyrrolidone K90, and the weight average molecular weight is 130 ten thousand.
Example 1
0.2％Zn(OH) 2 /TiO 2 The preparation method of the hydrosol comprises the following steps:
(1) Zinc acetate was dissolved in deionized water at a concentration of 1M;
(2) Sodium hydroxide is dissolved in deionized water, and the concentration is 1M;
(3) 100g of TiO 2 Dissolving in 10L deionized water, stirring for 20min to obtain TiO 2 A colloid;
(4) 0.2mL of 1M zinc acetate solution was taken in TiO 2 Stirring the mixture in the colloid for 20min.
(5) 0.4mL of 1M sodium hydroxide solution was weighed into (4), and stirred for 20min to obtain 0.2% Zn (OH) 2 /TiO 2 And (5) colloid.
(6) 50g of polyvinylpyrrolidone having a weight average molecular weight of 130 ten thousand and K90 are weighed out in 0.2% Zn (OH) 2 /TiO 2 Stirring for 10h to obtain Zn (OH) with viscosity of 30 Pa.S and 0.2% in the colloid 2 /TiO 2 And (3) hydrosol.
Example 2
0.1％Zn(OH) 2 /TiO 2 The hydrosol preparation method comprises the following steps:
(1) Zinc acetate was dissolved in deionized water at a concentration of 1M;
(2) Sodium hydroxide is dissolved in deionized water, and the concentration is 1M;
(3) 100g of TiO 2 Dissolving in 10L deionized water, stirring for 15min to obtain TiO 2 A colloid;
(4) 0.1mL of 1M zinc acetate solution was taken in TiO 2 In the colloid, stirring for 15min.
(5) 0.2mL of 1M sodium hydroxide solution was weighed into (4), and stirred for 15min to obtain 0.1% Zn (OH) 2 /TiO 2 And (5) colloid.
(6) 50g of polyvinylpyrrolidone having a weight average molecular weight of 130 ten thousand and K90 are weighed out in 0.1% Zn (OH) 2 /TiO 2 Stirring for 10h to obtain Zn (OH) with viscosity of 30 Pa.S and 0.1% in the colloid 2 /TiO 2 And (3) hydrosol.
Example 3
0.3％ Zn(OH) 2 /TiO 2 The hydrosol preparation method comprises the following steps:
(1) Zinc acetate was dissolved in deionized water at a concentration of 1M;
(2) Sodium hydroxide is dissolved in deionized water, and the concentration is 1M;
(3) 100g of TiO 2 Dissolving in 10L deionized water, stirring for 20min to obtain TiO 2 A colloid;
(4) 0.3mL of 1M zinc acetate solution was taken in TiO 2 Stirring the mixture in the colloid for 20min.
(5) 0.6mL of 1M sodium hydroxide solution was weighed into (4), and stirred for 20min to obtain 0.3% Zn (OH) 2 /TiO 2 And (5) colloid.
(6) 50g of polyvinylpyrrolidone having a weight average molecular weight of 130 ten thousand and K90 are weighed out in 0.3% Zn (OH) 2 /TiO 2 Stirring for 10h in colloid to obtain Zn (OH) with viscosity of 30 Pa.S 0.3% 2 /TiO 2 And (3) hydrosol.
Example 4
0.4％Zn(OH) 2 /TiO 2 The hydrosol preparation method comprises the following steps:
(1) Zinc acetate was dissolved in deionized water at a concentration of 1M;
(2) Sodium hydroxide is dissolved in deionized water, and the concentration is 1M;
(3) 100g of TiO 2 Dissolving in 10L deionized water, stirring for 15min to obtain TiO 2 A colloid;
(4) 0.4mL of 1M zinc acetate solution was taken in TiO 2 In the colloid, stirring for 15min.
(5) 0.8mL of 1M sodium hydroxide solution was weighed into (4), and stirred for 15min to obtain 0.4% Zn (OH) 2 /TiO 2 And (5) colloid.
(6) 50g of polyvinylpyrrolidone having a weight average molecular weight of 130 ten thousand and K90 are weighed out in 0.4% Zn (OH) 2 /TiO 2 Stirring for 9h in the colloid to obtain Zn (OH) with viscosity of 30 Pa.S and 0.4 percent 2 /TiO 2 And (3) hydrosol.
Example 5
0.5％Zn(OH) 2 /TiO 2 The hydrosol preparation method comprises the following steps:
(1) Zinc acetate was dissolved in deionized water at a concentration of 1M;
(2) Sodium hydroxide is dissolved in deionized water, and the concentration is 1M;
(3) 100g of TiO 2 Dissolving in 10L deionized water, stirring for 20min to obtain TiO 2 A colloid;
(4) 0.5mL of 1M zinc acetate solution was taken in TiO 2 In the colloid, stirring for 18min.
(5) 1.0mL of 1M sodium hydroxide solution was weighed into (4), and stirred for 18min to obtain 0.5% Zn (OH) 2 /TiO 2 And (5) colloid.
(6) 50g of polyvinylpyrrolidone having a weight average molecular weight of 130 ten thousand and K90 are weighed out in 0.5% Zn (OH) 2 /TiO 2 Stirring for 10h in colloid to obtain Zn (OH) with viscosity of 30 Pa.S 0.5% 2 /TiO 2 And (3) hydrosol.
Example 6
1％Zn(OH) 2 /TiO 2 The hydrosol preparation method comprises the following steps:
(1) Zinc acetate was dissolved in deionized water at a concentration of 1M;
(2) Sodium hydroxide is dissolved in deionized water, and the concentration is 1M;
(3) 100g of TiO 2 Dissolving in 10L deionized water, stirring for 12min to obtain TiO 2 A colloid;
(4) 1.0mL of 1M zinc acetate solution was taken in TiO 2 In the colloid, stirring for 12min.
(5) 2.0mL of 1M sodium hydroxide solution is taken in the step (4), and the mixture is stirred for 12min to obtain 1% Zn (OH) 2 /TiO 2 And (5) colloid.
(6) 50g of a polyethylene K90 having a weight average molecular weight of 130 ten thousand was weighed outPyrrolidone in 1% Zn (OH) 2 /TiO 2 Stirring for 11h in the colloid to obtain 1% Zn (OH) with viscosity of 30 Pa.S 2 /TiO 2 And (3) hydrosol.
Example 7
5％Zn(OH) 2 /TiO 2 The hydrosol preparation method comprises the following steps:
(1) Zinc acetate was dissolved in deionized water at a concentration of 1M;
(2) Sodium hydroxide is dissolved in deionized water, and the concentration is 1M;
(3) 100g of TiO 2 Dissolving in 10L deionized water, stirring for 25min to obtain TiO 2 A colloid;
(4) 5.0mL of 1M zinc acetate solution was taken in TiO 2 In the colloid, stirring for 25min.
(5) 10.0mL of 1M sodium hydroxide solution was weighed into (4), and stirred for 25min to obtain 5% Zn (OH) 2 /TiO 2 And (5) colloid.
(6) 50g of polyvinylpyrrolidone having a weight average molecular weight of 130 ten thousand and K90 are weighed out in 5% Zn (OH) 2 /TiO 2 Stirring for 12h to obtain 5% Zn (OH) with viscosity of 30 Pa.S 2 /TiO 2 And (3) hydrosol.
Example 8
0.2％In(OH) 3 /TiO 2 The hydrosol preparation method comprises the following steps:
(1) Dissolving indium acetate in deionized water at a concentration of 1M;
(2) Sodium hydroxide is dissolved in deionized water, and the concentration is 1M;
(3) 100g of TiO 2 Dissolving in 10L deionized water, stirring for 5-30min to obtain TiO 2 A colloid;
(4) 0.2mL of 1M zinc acetate solution was taken in TiO 2 Stirring the mixture in the colloid for 10min.
(5) 0.4mL of 1M sodium hydroxide solution was weighed into (4), and stirred for 10min to obtain 0.2% in (OH) 3 /TiO 2 And (5) colloid.
(6) 50g of polyvinylpyrrolidone having a weight average molecular weight of 130 ten thousand and K90 are weighed out in 0.2% of in (OH) 3 /TiO 2 ColloidStirring for 13h to obtain 0.2% in (OH) with viscosity of 30 Pa.S 3 /TiO 2 And (3) hydrosol.
Comparative example 1
TiO 2 The hydrosol preparation method comprises the following steps:
(1) 100g of TiO 2 Dissolving in 10L deionized water, stirring for 20min to obtain TiO 2 A colloid;
(2) 50g of polyvinylpyrrolidone having a weight average molecular weight of 130 ten thousand and K90 are weighed into TiO 2 Stirring for 8-14h in colloid to obtain TiO with viscosity of 20Pa.S 2 And (3) hydrosol.
Comparative example 2
TiO 2 The colloid preparation method comprises the following steps:
100g of TiO 2 Dissolving in 10L deionized water, stirring for 5-30min to obtain TiO 2 And (5) colloid.
Comparative example 3
0.2％ Zn(OH) 2 /TiO 2 The colloid preparation method is the same as in example 1, except that step (6) is not performed, i.e., polyvinylpyrrolidone is not introduced.
Experimental example 1
The photocatalytic materials prepared in examples 1 to 8 and comparative example 1 were subjected to performance test, and specific test results are as follows:
0.2% Zn (OH) produced in example 1 2 /TiO 2 Hydrosol material, 0.2% in (OH) prepared in example 8 3 /TiO 2 Hydrosol material and TiO prepared in comparative example 1 2 The X-ray diffraction (XRD) spectrum of the hydrosol material is shown in FIG. 1, and FIG. 1 shows 0.2% Zn (OH) 2 /TiO 2 、0.2％In(OH) 3 /TiO 2 TiO (titanium dioxide) 2 The crystal structure and phase purity of the hydrosol material. The corresponding sharp diffraction peak indicates that the sample has excellent crystallinity.
0.2% Zn (OH) produced in example 1 2 /TiO 2 Hydrosol material and TiO prepared in comparative example 1 2 SEM of hydrosol material is shown in FIG. 2, a, b is TiO 2 The material has a particle size of about 5-10nm and c is 0.2% Zn (OH) 2 /TiO 2 Hydrosol material, zn (OH) can be seen 2 Uniform loading, no generation of large particles and still maintaining TiO 2 Particle size of 5-10nm, d is 0.2% Zn (OH) 2 /TiO 2 The element distribution image of the hydrosol material proves the existence of Zn element;
0.2% Zn (OH) produced in example 1 2 /TiO 2 Hydrosol material and TiO prepared in comparative example 1 2 The specific surface image of the hydrosol material is shown in FIG. 3, and as can be seen from FIG. 3, 0.2% Zn (OH) 2 /TiO 2 The specific surface of the hydrosol material is 183.999m 2 /g，TiO 2 The specific surface of the hydrosol material is 145.664m 2 Load Zn (OH) 2 The specific surface area of the rear sample is increased, and the active site is increased, so that the generation of reactive species can be promoted, and the smooth proceeding of the photocatalytic oxidation-reduction reaction is ensured.
0.2% Zn (OH) produced in examples 1-7 2 /TiO 2 Material, 0.2% in (OH) obtained in example 8 3 /TiO 2 Material and TiO prepared in comparative example 1 2 The UV-visible diffuse reflectance image of the hydrosol material is shown in FIG. 4, from which 0.2% Zn (OH) can be seen in FIG. 4 2 /TiO 2 The absorption edge of the hydrosol material is 380-450nm, and is compounded with Zn (OH) 2 After which a red shift, a blue shift, in particular 0.2% Zn (OH), occurs to varying degrees 2 /TiO 2 The absorption edge of (C) corresponds to the longest wavelength, indicating 0.2% Zn (OH) 2 /TiO 2 Under the irradiation of simulated sunlight, the required excitation energy is minimum, the absorption spectrum range is wider, and the photocatalysis performance is better.
0.2% Zn (OH) produced in examples 1-7 2 /TiO 2 Hydrosol material and TiO prepared in comparative example 1 2 The photocurrent image of the material is shown in FIG. 5, in which the steps of different heights reflect the separation capability of the photo-generated carriers of the photocatalyst, and it is seen from the graph that 0.2% Zn (OH) is prepared in example 1 2 /TiO 2 Hydrosol materials have the greatest photocurrent and highest quantum efficiency.
0.2% Zn (OH) produced in examples 1-7 2 /TiO 2 Hydrosol material and TiO prepared in comparative example 1 2 Hydrosol materialAs shown in FIG. 6, the arc size reflects the electron transport ability of the photocatalyst, and the smaller the radius, the more easily the electrons are transported, and it is seen from the graph that 0.2% Zn (OH) is produced in example 1 2 /TiO 2 Hydrosol materials have minimal resistance and maximal electron transport capacity.
Application experiment example 1
Photocatalytic degradation of rhodamine B (RhB)
0.2% Zn (OH) produced in examples 1-7 2 /TiO 2 Material, 0.2% in (OH) obtained in example 8 3 /TiO 2 Material and TiO prepared in comparative example 1 2 The material is applied to the photocatalytic degradation of rhodamine B (RhB) solution, the concentration of the rhodamine B (RhB) solution is 10mg/L, and the specific steps are as follows:
firstly, 10mL of the sol is added into 30mL of rhodamine B (RhB) solution at room temperature, and then the mixture is placed in a dark box and magnetically stirred for 30min to reach adsorption-desorption equilibrium; then, a simulated light source is turned on, and 3mL of solution is taken every 5 min; the absorbance of the sol at the highest peak (530-570 nm) was measured with a UV-2550 spectrophotometer.
FIG. 7 shows Zn (OH) s prepared in examples 1-7 2 /TiO 2 Material, 0.2% in (OH) obtained in example 8 3 /TiO 2 Material and TiO prepared in comparative example 1 2 The degradation curve of the material for photocatalytic degradation of rhodamine B (RhB) under simulated sunlight is shown by the graph, and the degradation rate of the material for the examples 1-7 can reach 83.1-95.7% in 30min, wherein the performance of the material for the example 1 is optimal, the degradation rate is 95.7%, and meanwhile, the degradation rate is 0.2% in (OH) 3 /TiO 2 Degradation rate at 30min was 87.1%, indicating that Zn (OH) was prepared 2 /TiO 2 Materials and In (OH) 3 /TiO 2 The carrier separation is promoted under the irradiation of simulated sunlight, and the photocatalysis efficiency is improved.
FIG. 8 shows 0.2% Zn (OH) of example 1 2 /TiO 2 Hydrosol material, tiO from comparative example 1 2 Hydrosol material, tiO from comparative example 2 2 Colloidal material and 0.2% Zn (OH) prepared in comparative example 3 2 /TiO 2 Degradation of colloid material under simulated sunlight irradiation for photocatalytic degradation of rhodamine B (RhB)The curve, compared with comparative example 3, in example 1, the PVP is introduced, and the degradation effect of the colloidal solution is higher than that of comparative example 3, which shows that PVP adsorbs RhB macromolecules on the catalyst particles through surface adsorption, so that the surface properties of the RhB macromolecules are changed, the number of active sites is increased, and the reaction rate and selectivity are improved. Meanwhile, PVP can also protect the catalyst from being damaged by light irradiation, so that the service life of the catalyst is prolonged.
FIG. 9 shows 0.2% Zn (OH) of example 1 2 /TiO 2 Hydrosol material, tiO from comparative example 1 2 Hydrosol material, 0.2% Zn (OH) prepared in comparative example 3 2 /TiO 2 Ultraviolet-visible light transmittance of the gel material. The larger the transmittance value is, the better the light transmittance is, and the TiO is added in comparative example 1 2 After that, the transmittance was reduced, and Zn (OH) was compounded 2 After that, the transmittance was increased, and the transmittance was significantly improved after the PVP was introduced in example 1, as compared with comparative example 3, probably due to the fact that the PVP had the ability to absorb light, particularly in the uv region, which helped to enhance the efficiency of the photocatalytic reaction, and the catalyst absorbed uv light better.
Application experiment example 2
Contact angle test
0.2% Zn (OH) produced in example 1 2 /TiO 2 Material and TiO prepared in comparative example 1 2 Uniformly coating the material on 2X 2cm glass by a rotary film coater, and drying for 5-30min; water and oil droplets were used on the surface of the film layers of example 1 and comparative example 1, respectively.
FIGS. 10a, b are the surface of water droplets on the film layers of example 1 and comparative example 1; FIGS. 10c and d show oil droplets on the surfaces of the films of example 1 and comparative example 1. As can be seen from FIG. 10, the contact angle of example 1 is significantly smaller than that of comparative example 1, illustrating the composite Zn (OH) of the present invention 2 Post hydrophilicity increased, 0.2% Zn (OH) 2 /TiO 2 The material has hydrophilicity and super lipophilicity.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be apparent to one skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.

Claims (10)

1. Photocatalytic self-cleaning metal hydroxide/TiO with amphiphilic structure 2 The hydrosol has microscopic morphology of nano particles with the size of 5-10nm, is in a sol shape in water, is sprayed on the surface of a substrate to form a film, is a colorless transparent film, has light permeability of more than 99%, and has hydrophilic and oleophilic amphiphilicity functions.
2. The photocatalytic self-cleaning metal hydroxide/TiO with amphiphilic structure according to claim 1 2 The preparation method of the hydrosol comprises the following steps:
(1) TiO is mixed with 2 Uniformly mixing the nano powder with deionized water, and stirring for 5-30min to obtain TiO 2 A colloid;
(2) Adding aqueous solution of acetic acid metal salt into TiO 2 Stirring in colloid for 5-30min to obtain mixture;
(3) Adding alkaline aqueous solution into the mixture, stirring for 5-30min to obtain metal hydroxide/TiO 2 A colloid;
(4) To metal hydroxide/TiO 2 Adding polyvinylpyrrolidone into the colloid, stirring for 8-14h to obtain metal hydroxide/TiO with viscosity of 5-50Pa.S 2 And (3) hydrosol.
3. The method according to claim 2, wherein in the step (1), tiO 2 The mass volume ratio of the deionized water to the deionized water is (0.1-120): (0.1-15), units g/L.
4. The method according to claim 2, wherein in the step (2), the metal acetate is zinc acetate or indium acetate.
5. The method according to claim 2, wherein in the step (2), the concentration of the aqueous metal acetate solution is 0.1 to 5mol/L.
6. The method according to claim 2, wherein in the step (2), tiO 2 The mass volume ratio of the powder to the aqueous solution of the metal acetate is (0.1-120): (0.01-0.5), unit g/mL.
7. The process according to claim 2, wherein in the step (3), the aqueous alkaline solution is a sodium hydroxide solution having a concentration of 0.1 to 5mol/L, tiO 2 The mass volume ratio of the powder to the alkaline aqueous solution is (0.1-120): (0.04-0.6), units g/mL.
8. The process according to claim 2, wherein in the step (4), the polyvinylpyrrolidone is K88-K90 polyvinylpyrrolidone, and the polyvinylpyrrolidone has a weight average molecular weight of 100 to 150 ten thousand.
9. The process according to claim 2, wherein in the step (4), polyvinylpyrrolidone is added in an amount corresponding to the metal hydroxide/TiO ratio 2 The mass ratio of the colloid is (0.5-50): (1.2-120).
10. The photocatalytic self-cleaning metal hydroxide/TiO with amphiphilic structure according to claim 1 2 The hydrosol is used for photocatalytic degradation of organic pollutants under sunlight irradiation, is sprayed on the outer wall of a building, is uniformly formed into a film within 5-30min, and is used for efficiently removing harmful pollutants such as ozone, formaldehyde, nitrogen sulfide and the like in the air.
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