CN114042444A - Preparation method of titanium dioxide-based nano photocatalytic film - Google Patents

Preparation method of titanium dioxide-based nano photocatalytic film Download PDF

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Publication number
CN114042444A
CN114042444A CN202111392588.6A CN202111392588A CN114042444A CN 114042444 A CN114042444 A CN 114042444A CN 202111392588 A CN202111392588 A CN 202111392588A CN 114042444 A CN114042444 A CN 114042444A
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titanium dioxide
substrate
steps
based nano
suspension
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CN202111392588.6A
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Chinese (zh)
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徐婕
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Jiangsu Zhongke Ruina Environmental Technology Co ltd
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Jiangsu Zhongke Ruina Environmental Technology Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063Titanium; Oxides or hydroxides thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/40Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0215Coating
    • B01J37/0217Pretreatment of the substrate before coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0236Drying, e.g. preparing a suspension, adding a soluble salt and drying

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of a titanium dioxide-based nano photocatalytic film, which comprises the following steps: s1, cleaning the substrate; s2, pretreating the substrate through a calcium hydroxide solution; s3, preparing titanium dioxide suspension; s4, spraying the titanium dioxide suspension on the surface of the substrate through an ink-jet printer; and S5, drying and calcining to obtain the titanium dioxide film. The titanium dioxide suspension coating is realized in an ink-jet printing mode, so that the coating uniformity is improved, and the shape and thickness of the film can be adjusted; through calcium hydroxide pretreatment, silicate with a fluffy structure is generated on the surface of the substrate, so that the stress of titanium dioxide film shrinkage is reduced, and the generation of cracks is reduced.

Description

Preparation method of titanium dioxide-based nano photocatalytic film
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a preparation method of a titanium dioxide-based nano photocatalyst film.
Background
With the improvement of living standard and the enhancement of environmental awareness, people have higher and higher requirements on air quality. VOCs are one of the main pollutants of air, and seriously threaten the physical health of people. As a high-efficiency, nontoxic and stable photocatalytic material, the nano titanium dioxide has good photocatalytic activity in liquid phase and gas phase reactions, and is gradually valued by people.
Under the irradiation of light, the titanium dioxide surface is excited to generate electrons and holes. The electrons and the holes have extremely strong reducing power, rapidly migrate to the surface of the organic compound and activate the adsorbed oxygen and moisture to generate hydroxyl radicals and super anionic oxygen ions with extremely strong oxidizing power, rapidly oxidize and decompose various organic compounds and partial inorganic substances into water and carbon dioxide, and have extremely strong functions of sterilization, deodorization, mildew prevention, pollution prevention, self cleaning and air purification. Meanwhile, the nano titanium dioxide has the characteristics that oxygen molecules and water molecules in the air are utilized to convert contacted organic matters into carbon dioxide and water, the carbon dioxide and the water do not change, the theoretical effective period is very long, the maintenance cost is low, and the nano titanium dioxide is widely applied to various fields of food, medicines, cosmetics and the like.
The existing method for preparing the nano catalyst film mainly comprises a sol-gel method, an evaporation method and the like, and has the defects of complex process and high cost; and because the expansion rates of the substrate and the titanium dioxide film are different, cracks are easily generated on the surface of the titanium dioxide film, and the firmness of the titanium dioxide film is influenced.
Disclosure of Invention
The invention aims to provide a preparation method of a titanium dioxide-based nano photocatalyst film, which aims to solve the technical problems mentioned in the background technology and is realized by the following technical scheme:
a preparation method of a titanium dioxide-based nano photocatalytic film comprises the following steps:
s1, cleaning the substrate;
s2, pretreating the substrate through a calcium hydroxide solution;
s3, preparing titanium dioxide suspension;
s4, spraying the titanium dioxide suspension on the surface of the substrate through an ink-jet printer;
and S5, drying and calcining to obtain the titanium dioxide film.
Further, the cleaning the substrate in step S1 includes the following steps:
s11, placing the substrate into deionized water containing a cleaning agent, and continuously carrying out ultrasonic cleaning for 20 min;
s12, placing the substrate processed in the step S11 into a hydrofluoric acid solution with the mass fraction of 5%, and continuously carrying out ultrasonic cleaning for 15 min;
and S13, sequentially placing the substrate processed in the S12 into absolute ethyl alcohol and deionized water, and continuously carrying out ultrasonic cleaning for 20 min.
Further, the preprocessing in step S2 includes the following steps:
s21, placing the substrate in a saturated calcium hydroxide solution at 90 ℃ for treatment for 8-24 h;
s22, placing the substrate processed by the S21 into deionized water, continuously carrying out ultrasonic cleaning for 5min, and then washing with the deionized water for 5min
Further, the step S3 of preparing the titanium dioxide suspension includes the following steps:
s31, mixing the nano titanium dioxide powder, the dispersing agent and terpineol according to the molar ratio of 1:2:6 to prepare titanium dioxide suspension;
s32, ultrasonically shaking the titanium dioxide suspension prepared in the S31 for 30 min.
Further, the drying and calcining in step S5 includes the following steps:
s51, drying the substrate sprayed with the titanium dioxide suspension at the temperature of 80-130 ℃ for 5-10 min;
s52, calcining the substrate treated by the S51 at the temperature of 600-800 ℃ for 1.5-2 h.
Further, the substrate is quartz glass.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
1. the titanium dioxide suspension coating is realized in an ink-jet printing mode, so that the coating uniformity is improved, and the shape and thickness of the film can be adjusted;
2. through calcium hydroxide pretreatment, silicate with a fluffy structure is generated on the surface of the substrate, so that the stress of titanium dioxide film shrinkage is reduced, and the generation of cracks is reduced.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention.
Fig. 1 is a flowchart of an embodiment of the present application.
Detailed Description
For better understanding of the above technical solutions, the following detailed descriptions will be made in conjunction with the drawings and the detailed description of the present specification, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a titanium dioxide-based nano photocatalytic film comprises the following steps:
s1, cleaning the substrate; the cleanliness of the substrate directly influences the film forming quality of the titanium dioxide-based nano photocatalytic film, the surface of the substrate is not clean in place, the titanium dioxide film is easily distributed unevenly, the adhesive force is poor, and preferably, the substrate is quartz glass, namely pure silica glass.
The specific cleaning steps are as follows: s11, putting the substrate into deionized water containing a cleaning agent, and continuously ultrasonically cleaning for 20min, wherein the cleaning agent is a glass cleaning agent; s12, placing the substrate cleaned by the cleaning agent into a hydrofluoric acid solution with the mass fraction of 5% for continuous ultrasonic cleaning for 15min, wherein hydrofluoric acid has strong corrosivity to glass substances, can effectively react with glass surface substances, and improves the cleaning effect; s13, placing the substrate subjected to hydrofluoric acid pickling treatment into absolute ethyl alcohol and deionized water in sequence, and continuously carrying out ultrasonic cleaning for 20 min.
S2, pretreating the substrate through a calcium hydroxide solution; the method comprises the following steps of (1) reacting calcium hydroxide solution with silicon dioxide on the surface of a substrate to generate insoluble calcium silicate and water, and further forming a fluffy calcium silicate layer on the surface of the substrate, wherein the method comprises the following specific steps: s21, placing the substrate in a saturated calcium hydroxide solution at 90 ℃ for treatment for 8h to form a fluffy calcium silicate layer on the surface of the substrate; and S22, placing the substrate processed by the S21 into deionized water, continuously carrying out ultrasonic cleaning for 5min, then washing for 5min by using the deionized water, and washing away residual calcium hydroxide.
S3, preparing a titanium dioxide suspension, which comprises the following steps: s31, mixing the nano titanium dioxide powder and the dispersing agent according to the molar ratio of 1:2 to prepare titanium dioxide dispersion liquid, uniformly dispersing the titanium dioxide, and mixing the dispersion liquid and terpineol according to the molar ratio of 1:2 to prepare titanium dioxide suspension; and S32, ultrasonically vibrating the titanium dioxide suspension prepared in the S31 for 30min, so that the uniformity of the titanium dioxide is improved, and the agglomeration of the titanium dioxide powder is avoided.
S4, spraying the titanium dioxide suspension on the surface of the substrate through an ink-jet printer;
specifically, the ink jet printer includes ink horn, linear module, shower nozzle and heating gun, and heating gun and shower nozzle are fixed on linear module in step, and the heating gun is used for preheating the base plate. When the device is used, the titanium dioxide suspension is poured into the ink box, the heating gun and the spray head move synchronously, the heating gun preheats the substrate in advance, and then the spray head sprays the titanium dioxide suspension on the surface of the substrate. The substrate is preheated by the heating gun, so that floating dust on the surface of the substrate can be blown out, volatilization of a solvent in the titanium dioxide suspension can be increased, and the drying speed is increased. The spraying amount of the ink-jet printer and the moving speed of the spray head can be adjusted, so that the thickness of the titanium dioxide film can be adjusted.
S5, drying and calcining to obtain the titanium dioxide film, which comprises the following steps:
s51, drying the substrate sprayed with the titanium dioxide suspension for 10min at the temperature of 80 ℃ to obtain a uniform titanium dioxide film; and S52, calcining the dried titanium dioxide film at the temperature of 600 ℃ for 2h to obtain the stable and porous titanium dioxide film.
Example 2
The technical scheme of the embodiment 2 is basically the same as that of the embodiment 1, and the difference is that the drying temperature of the titanium dioxide suspension in the step S51 is 130 ℃, and the drying time is 5 min; in the step S52, the calcining temperature of the titanium dioxide film is 800 ℃, and the calcining time is 1.5 h.
In the calcining process, the thermal expansion coefficient of the glass substrate is different from that of the titanium dioxide film, the linear expansion coefficient of the titanium dioxide film is 25/DEG C, the variation range of the linear expansion coefficient of the glass substrate is (5.8-150) multiplied by 107/DEG C, and a large difference exists between the two. By forming the calcium silicate layer with a fluffy structure on the surface of the glass substrate, the titanium dioxide film on the surface of the glass substrate is buffered in shrinkage, the stress concentration of the film is avoided, and the cracking is reduced or avoided.
The technical scheme in the embodiment of the application at least has the following technical effects or advantages:
1. the titanium dioxide suspension coating is realized in an ink-jet printing mode, so that the coating uniformity is improved, and the shape and thickness of the film can be adjusted;
2. through calcium hydroxide pretreatment, silicate with a fluffy structure is generated on the surface of the substrate, so that the stress of titanium dioxide film shrinkage is reduced, and the generation of cracks is reduced.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Unless specifically stated otherwise, the relative arrangement of the steps, numerical expressions and numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. A preparation method of a titanium dioxide-based nano photocatalytic film is characterized by comprising the following steps:
s1, cleaning the substrate;
s2, pretreating the substrate through a calcium hydroxide solution;
s3, preparing titanium dioxide suspension;
s4, spraying the titanium dioxide suspension on the surface of the substrate through an ink-jet printer;
and S5, drying and calcining to obtain the titanium dioxide film.
2. The method for preparing a titanium dioxide based nano photocatalytic film as claimed in claim 1, wherein the step of cleaning the substrate in step S1 comprises the steps of:
s11, placing the substrate into deionized water containing a cleaning agent, and continuously carrying out ultrasonic cleaning for 20 min;
s12, placing the substrate processed in the step S11 into a hydrofluoric acid solution with the mass fraction of 5%, and continuously carrying out ultrasonic cleaning for 15 min;
and S13, sequentially placing the substrate processed in the S12 into absolute ethyl alcohol and deionized water, and continuously carrying out ultrasonic cleaning for 20 min.
3. The method for preparing titanium dioxide based nano photocatalytic film according to claim 1, wherein the pretreatment in step S2 comprises the following steps:
s21, placing the substrate in a saturated calcium hydroxide solution at 90 ℃ for treatment for 8-24 h;
and S22, placing the substrate processed by the S21 into deionized water, continuously carrying out ultrasonic cleaning for 5min, and then washing for 5min by using the deionized water.
4. The method for preparing titanium dioxide based nano photocatalytic film according to claim 1, wherein the step of preparing titanium dioxide suspension in step S3 comprises the following steps:
s31, mixing the nano titanium dioxide powder, the dispersing agent and terpineol according to the molar ratio of 1:2:6 to prepare titanium dioxide suspension;
s32, ultrasonically shaking the titanium dioxide suspension prepared in the S31 for 30 min.
5. The method for preparing titanium dioxide based nano photocatalytic film according to claim 1, wherein the drying and calcining in step S5 comprises the following steps:
s51, drying the substrate sprayed with the titanium dioxide suspension at the temperature of 80-130 ℃ for 5-10 min;
s52, calcining the substrate treated by the S51 at the temperature of 600-800 ℃ for 1.5-2 h.
6. The method of claim 1, wherein the substrate is quartz glass.
CN202111392588.6A 2021-11-23 2021-11-23 Preparation method of titanium dioxide-based nano photocatalytic film Withdrawn CN114042444A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111392588.6A CN114042444A (en) 2021-11-23 2021-11-23 Preparation method of titanium dioxide-based nano photocatalytic film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111392588.6A CN114042444A (en) 2021-11-23 2021-11-23 Preparation method of titanium dioxide-based nano photocatalytic film

Publications (1)

Publication Number Publication Date
CN114042444A true CN114042444A (en) 2022-02-15

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