CN114797833A - Preparation method of photocatalyst material and photocatalyst glass - Google Patents

Preparation method of photocatalyst material and photocatalyst glass Download PDF

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CN114797833A
CN114797833A CN202210371542.4A CN202210371542A CN114797833A CN 114797833 A CN114797833 A CN 114797833A CN 202210371542 A CN202210371542 A CN 202210371542A CN 114797833 A CN114797833 A CN 114797833A
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photocatalyst
glass
sol
preparing
aqueous solution
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CN114797833B (en
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蒋沛辰
杨啸天
虞倩
胡经国
许小勇
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Yangzhou University
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Yangzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J37/0215—Coating
    • B01J37/0228—Coating in several steps
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/71—Photocatalytic coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment

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  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
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Abstract

The invention discloses a preparation method of a photocatalyst material and photocatalyst glass, which comprises the following steps: preparing KI aqueous solution, adding an acidic additive into the KI aqueous solution to adjust the pH value, and then adding Bi (NO) into the KI aqueous solution 3 ) 3 5H2O, stirring until the solution is transparent, finally adding p-benzoquinone alcohol solution, uniformly mixing to obtain raw material sol, and coating the raw material sol on the surface of a substrate material; drying the once coated substrate material, calcining at high temperature for 1 hour, and after the calcining is finished and the substrate material is cooled to room temperature, forming a BiOI seed layer on the surface of the substrate material; preparing dimethyl sulfoxide sol of vanadyl acetylacetonate, and coating the dimethyl sulfoxide sol of vanadyl acetylacetonate on the surface of the BiOI seed layer(ii) a Annealing the substrate material after the secondary coating at the temperature of 350-550 ℃ for 2 hours, and forming a finished product of the composite nano-porous BiVO on the surface of the substrate material after natural cooling 4 And (3) a layer. In the invention, a narrow-bandgap semiconductor BiVO is selected 4 The photocatalyst can respond to visible light to stimulate the catalytic oxidation of the photocatalyst, and has excellent degradation effect.

Description

Preparation method of photocatalyst material and photocatalyst glass
Technical Field
The invention relates to the field of photocatalysts, in particular to a preparation method of a photocatalyst material and photocatalyst glass.
Background
The photocatalyst technology means that the semiconductor material generates electron-hole thermal charge under light irradiation to react with water and oxygen in the environment to continuously generate active hydroxyl free radicals and superoxide ion free radicals, shows the oxidation-reduction catalytic capability induced by light, can attack bacterial cell membranes and virus proteins, can decompose most organic pollutants into water and carbon dioxide, and has application values of sterilization, disinfection, mildew prevention, pollution resistance, air purification, sewage degradation and the like.
However, the current application development of the photocatalyst technology has some bottleneck defects, most of the photocatalyst active materials are nano titanium dioxide, although the photocatalyst active materials are relatively stable and transparent and do not influence the color of the body, the intrinsic wide band gap of the photocatalyst active materials enables the photocatalyst active materials to only respond to near ultraviolet light accounting for about 4% of energy in the solar spectrum, the photocatalytic effect is extremely limited, and if an ultraviolet irradiation light source is additionally arranged, the application cost is increased, and the application range is limited.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of the embodiments of the application and to briefly introduce some preferred embodiments, and in this section as well as in the abstract and the application title of the application may be simplified or omitted to avoid obscuring the purpose of this section, the abstract and the application title, and such simplifications or omissions are not intended to limit the scope of the application.
The present application has been made in view of the above and/or other problems occurring in the prior art.
Therefore, the technical problem to be solved by the application is: the existing nano titanium dioxide photocatalyst material needs to be additionally provided with an ultraviolet irradiation light source in the application process, and the cost is higher.
In order to solve the technical problem, the application provides the following technical scheme: a preparation method of a photocatalyst material comprises the following steps:
primary coating: preparing KI aqueous solution, adding an acidic additive into the KI aqueous solution until the pH value of the KI aqueous solution is 1.6-1.8, and then adding Bi (NO) into the KI aqueous solution 3 ) 3 .5H 2 O, stirring until the solution is transparent, finally adding p-benzoquinone alcohol solution into the transparent solution, uniformly mixing to obtain raw material sol, and coating the raw material sol on the surface of a clean and dry substrate material;
seed layer formation: drying the once coated substrate material, calcining at high temperature for 1 hour, and after the calcining is finished and the substrate material is cooled to room temperature, forming a BiOI seed layer on the surface of the substrate material;
secondary coating: preparing dimethyl sulfoxide sol of vanadyl acetylacetonate, and coating the dimethyl sulfoxide sol of vanadyl acetylacetonate on the surface of the BiOI seed layer;
forming a composite nano layer: annealing the substrate material after the secondary coating at the temperature of 350-550 ℃ for 2 hours, and forming a finished product of composite nano-porous BiVO on the surface of the substrate material after the calcination 4 And (3) a layer.
As a preferable embodiment of the preparation method of the photocatalyst material described in the present application, wherein: in the primary coating: the pH value of the KI aqueous solution is preferably 1.7.
As a preferable embodiment of the preparation method of the photocatalyst material described in the present application, wherein: in the primary coating: the concentration of the KI aqueous solution is 0.4mol/L, and the Bi (NO) is 3 ) 3 .5H 2 The concentration of O is 0.04mol/L, and the alcohol solution of p-benzoquinone is 0.23 mol/L.
As a preferable embodiment of the preparation method of the photocatalyst material described in the present application, wherein: in the primary coating: the coating amount was 1000ml/m 2 。
As a preferable embodiment of the preparation method of the photocatalyst material described in the present application, wherein: in the formation of the seed layer: the calcination temperature was 300 ℃.
As a preferable embodiment of the preparation method of the photocatalyst material described in the present application, wherein: in the secondary coating: the concentration of the dimethyl sulfoxide sol of vanadyl acetylacetonate was 0.2 mol/L.
As a preferable embodiment of the preparation method of the photocatalyst material described in the present application, wherein: in the secondary coating: the coating amount was 2000ml/m 2 。
As a preferable embodiment of the preparation method of the photocatalyst material described in the present application, wherein: in the formation of the composite nano-layer: the annealing temperature is preferably 450 ℃.
A photocatalyst glass is characterized in that: the photocatalyst glass comprises a glass substrate and a composite nanoporous BiVO on the surface of the glass substrate 4 Layer of said composite nanoporous BiVO 4 A layer formed on a surface of a glass substrate by the method of any of claims 1-9.
The beneficial effect of this application: in the invention, a narrow-band-gap semiconductor BiVO is selected 4 The photocatalyst can respond to visible light to stimulate the catalytic oxidation, decompose organic molecules, induce the degradation of pollutants, sterilize, prevent mildew and resist pollution and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a top SEM photograph of a photocatalyst active material provided in example 1 of the present application;
FIG. 2 is an SEM photograph of a cross section of a photocatalyst-active material heard in example 1 of the present application;
FIG. 3 is a top SEM photograph of a photocatalyst active material provided in example 2 of the present application;
FIG. 4 is a top SEM photograph of a photocatalyst active material provided in example 3 of the present application;
FIG. 5 is a top SEM photograph of a photocatalytically active material provided in comparative example 2 of the present application;
FIG. 6 is a top SEM photograph of a photocatalytically active material provided in comparative example 3 of the present application;
FIG. 7 is a top SEM photograph of the photocatalyst active material provided in example 4 of the present application;
FIG. 8 is a top SEM photograph of a photocatalytically active material provided in example 5 of the present application;
FIG. 9 shows the results of the degradation of rhodamine RhB by the photocatalytic glasses provided in example 1 and comparative example 1 of the present application;
FIG. 10 shows the result of 4 consecutive rhodamine RhB degradations performed on the photocatalyst glass provided in example 1 of the present application.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present application more comprehensible, embodiments accompanying the present application are described in detail below with reference to the accompanying drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, but the present application may be practiced in other ways than those described herein, and it will be apparent to those of ordinary skill in the art that the present application is not limited to the specific embodiments disclosed below.
Next, the present application will be described in detail with reference to the drawings, and in the detailed description of the embodiments of the present application, the cross-sectional views illustrating the structure of the device are not enlarged partially according to the general scale for convenience of illustration, and the drawings are only examples, which should not limit the scope of the protection of the present application. In addition, the three-dimensional dimensions of length, width and depth should be included in the actual fabrication.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the present application. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
The embodiment provides a photocatalyst glass, which is prepared by the following steps:
S 1 -1. preparing 0.4mol/L KI aqueous solution, adding HNO 3 The pH was adjusted to 1.7, and then 0.04mol/L Bi (NO) was added thereto 3 ) 3 .5H 2 And stirring the solution until the solution is transparent. And then adding 0.23mol/L p-benzoquinone alcoholic solution into the transparent solution, and uniformly stirring to obtain the raw material sol.
S 1 -2. taking glass with clean and dry surface as a substrate material, and adding 1000ml/m of raw material sol 2 Spraying the glass surface.
S 1 And-3, drying the coated glass sprayed with the raw material sol in a constant-temperature drying box at 50 ℃, putting the dried coated glass into a muffle furnace, heating to 300 ℃ at the speed of 5 ℃/min, and calcining at the constant temperature for 1 hour. After the calcination is finished, naturally cooling the film-coated glass to room temperature, and forming a BiOI seed layer on the surface of the glass.
S 1 -4. preparation of 0.2M vanadyl acetylacetonate (C10H) 14 O 5 V) dimethyl sulfoxide (DMSO) sol, and dissolving the sol at 2000ml/m 2 Spraying the mixture on the surface of the BiOI modified glass.
S 1 -5, putting the glass sprayed twice into a muffle furnace again, raising the temperature to 450 ℃ at the speed of 2 ℃/min, annealing for 2 hours, putting the glass into 1mol/L NaOH aqueous solution for soaking for 30 minutes after natural cooling to remove residual V on the surface of the material 2 O 5 Finally, taking out the glass and drying to obtain the BiVO with the composite nano-porous formed on the surface 4 The photocatalyst glass of the layer.
Example 2
The embodiment provides a photocatalyst glass, which is prepared by the following steps:
S 2 -1. preparing 0.4mol/L KI aqueous solution, adding HNO 3 The pH was adjusted to 1.6, and then 0.04mol/L Bi (NO) was added thereto 3 ) 3 .5H 2 And stirring the solution until the solution is transparent. And then adding 0.23mol/L p-benzoquinone alcoholic solution into the transparent solution, and uniformly stirring to obtain the raw material sol.
S 2 -2. get tableGlass with clean and dry surface is used as a substrate material, and the raw material sol is added at the concentration of 1000ml/m 2 Spraying the glass surface.
S 2 And-3, drying the coated glass sprayed with the raw material sol in a constant-temperature drying box at 50 ℃, putting the dried coated glass into a muffle furnace, heating to 300 ℃ at the speed of 5 ℃/min, and calcining at the constant temperature for 1 hour. After the calcination is finished, naturally cooling the film-coated glass to room temperature, and forming a BiOI seed layer on the surface of the glass.
S 2 -4. preparation of 0.2M vanadyl acetylacetonate (C10H) 14 O 5 V) dimethyl sulfoxide (DMSO) sol, and dissolving the sol at 2000ml/m 2 Spraying the mixture on the surface of the BiOI modified glass.
S 2 -5, putting the glass sprayed twice into a muffle furnace again, raising the temperature to 450 ℃ at the speed of 2 ℃/min, annealing for 2 hours, putting the glass into 1mol/L NaOH aqueous solution for soaking for 30 minutes after natural cooling to remove residual V on the surface of the material 2 O 5 Finally, taking out the glass and drying to obtain the BiVO with the composite nano-porous formed on the surface 4 The photocatalyst glass of the layer.
Example 3
The embodiment provides a photocatalyst glass, which is prepared by the following steps:
S 3 -1, preparing 0.4mol/L KI aqueous solution, adding HNO 3 The pH was adjusted to 1.8, and then 0.04mol/L Bi (NO) was added thereto 3 ) 3 .5H 2 And stirring the solution until the solution is transparent. And then adding 0.23mol/L p-benzoquinone alcoholic solution into the transparent solution, and uniformly stirring to obtain the raw material sol.
S 3 -2. taking glass with clean and dry surface as a substrate material, and adding 1000ml/m of raw material sol 2 Spraying the glass surface.
S 3 And-3, drying the coated glass sprayed with the raw material sol in a constant-temperature drying box at 50 ℃, putting the dried coated glass into a muffle furnace, heating to 300 ℃ at the speed of 5 ℃/min, and calcining at the constant temperature for 1 hour. After the calcination is finished, naturally cooling the film-coated glass to room temperature, and forming a BiOI seed layer on the surface of the glass.
S 3 Preparation of 0.2M vanadyl acetylacetonate (C10H) 14 O 5 V) dimethyl sulfoxide (DMSO) sol, and dissolving the sol at 2000ml/m 2 Spraying the mixture on the surface of the BiOI modified glass.
S 3 -5, putting the glass sprayed twice into a muffle furnace again, raising the temperature to 450 ℃ at the speed of 2 ℃/min, annealing for 2 hours, putting the glass into 1mol/L NaOH aqueous solution for soaking for 30 minutes after natural cooling to remove residual V on the surface of the material 2 O 5 Finally, taking out the glass and drying to obtain the BiVO with the composite nano-porous formed on the surface 4 The photocatalyst glass of the layer.
Example 4
The embodiment provides a photocatalyst glass, which is prepared by the following steps:
S 4 -1. preparing 0.4mol/L KI aqueous solution, adding HNO 3 The pH was adjusted to 1.7, and then 0.04mol/L Bi (NO) was added thereto 3 ) 3 .5H 2 And stirring the solution until the solution is transparent. And then adding 0.23mol/L p-benzoquinone alcoholic solution into the transparent solution, and uniformly stirring to obtain the raw material sol.
S 4 -2. taking the glass with clean and dry surface as a substrate material, and dissolving the raw material sol at 1000ml/m 2 Spraying the glass surface.
S 4 And-3, drying the coated glass sprayed with the raw material sol in a constant-temperature drying box at 50 ℃, putting the dried coated glass into a muffle furnace, heating to 300 ℃ at the speed of 5 ℃/min, and calcining at the constant temperature for 1 hour. After the calcination is finished, naturally cooling the film-coated glass to room temperature, and forming a BiOI seed layer on the surface of the glass.
S 4 -4. preparation of 0.2M vanadyl acetylacetonate (C10H) 14 O 5 V) dimethyl sulfoxide (DMSO) sol, and dissolving the sol at 2000ml/m 2 Spraying the mixture on the surface of the BiOI modified glass.
S 4 -5, putting the glass sprayed twice into a muffle furnace again, raising the temperature to 350 ℃ at the speed of 2 ℃/min, annealing for 2 hours, and putting the glass into 1mol/L NaOH aqueous solution after natural coolingSoaking for 30min to remove residual V on the surface of the material 2 O 5 Finally, taking out the glass and drying to obtain the BiVO with the composite nano-porous formed on the surface 4 The photocatalyst glass of the layer.
Example 5
The embodiment provides a photocatalyst glass, which is prepared by the following steps:
S 5 -1. preparing 0.4mol/L KI aqueous solution, adding HNO 3 The pH was adjusted to 1.7, and then 0.04mol/L Bi (NO) was added thereto 3 ) 3 .5H 2 And stirring the solution until the solution is transparent. And then adding 0.23mol/L p-benzoquinone alcoholic solution into the transparent solution, and uniformly stirring to obtain the raw material sol.
S 5 -2. taking glass with clean and dry surface as a substrate material, and adding 1000ml/m of raw material sol 2 Spraying the glass surface.
S 5 And-3, drying the coated glass sprayed with the raw material sol in a constant-temperature drying box at 50 ℃, putting the dried coated glass into a muffle furnace, heating to 300 ℃ at the speed of 5 ℃/min, and calcining at the constant temperature for 1 hour. After the calcination is finished, naturally cooling the film-coated glass to room temperature, and forming a BiOI seed layer on the surface of the glass.
S 5 -4. preparation of 0.2M vanadyl acetylacetonate (C10H) 14 O 5 V) dimethyl sulfoxide (DMSO) sol, and dissolving the sol at 2000ml/m 2 Spraying the mixture on the surface of the BiOI modified glass.
S 5 -5, putting the glass sprayed twice into a muffle furnace again, raising the temperature to 550 ℃ at the speed of 2 ℃/min, annealing for 2 hours, and after natural cooling, putting the glass into 1mol/L NaOH aqueous solution to soak for 30 minutes so as to remove residual V on the surface of the material 2 O 5 Finally, taking out the glass and drying to obtain the BiVO with the composite nano-porous formed on the surface 4 The photocatalyst glass of the layer.
Comparative example 1
This comparative example provides a conventional nano-titania photocatalyst glass.
Comparative example 2
The comparative example provides a photocatalyst glass prepared by the following steps:
S 6 -1. preparing 0.4mol/L KI aqueous solution, adding HNO 3 The pH was adjusted to 0.5, and then 0.04mol/L Bi (NO) was added thereto 3 ) 3 5H2O solution and stirring until the solution is clear. And then adding 0.23mol/L p-benzoquinone alcoholic solution into the transparent solution, and uniformly stirring to obtain the raw material sol.
S 6 -2. taking glass with clean and dry surface as a substrate material, and adding 1000ml/m of raw material sol 2 Spraying the glass surface.
S 6 And-3, drying the coated glass sprayed with the raw material sol in a constant-temperature drying box at 50 ℃, putting the dried coated glass into a muffle furnace, heating to 300 ℃ at the speed of 5 ℃/min, and calcining at the constant temperature for 1 hour. After the calcination is finished, naturally cooling the film-coated glass to room temperature, and forming a BiOI seed layer on the surface of the glass.
S 6 -4. preparation of 0.2M vanadyl acetylacetonate (C10H) 14 O 5 V) dimethyl sulfoxide (DMSO) sol, and dissolving the sol at 2000ml/m 2 Spraying the mixture on the surface of the BiOI modified glass.
S 6 -5, putting the glass sprayed twice into a muffle furnace again, raising the temperature to 450 ℃ at the speed of 2 ℃/min, annealing for 2 hours, putting the glass into 1mol/L NaOH aqueous solution for soaking for 30 minutes after natural cooling to remove residual V on the surface of the material 2 O 5 Finally, taking out the glass and drying to obtain the BiVO with the composite nano-porous formed on the surface 4 The photocatalyst glass of the layer.
Comparative example 3
The comparative example provides a photocatalyst glass prepared by the following steps:
S 7 -1. preparing 0.4mol/L KI aqueous solution, adding HNO 3 The pH was adjusted to 3, and then 0.04mol/L Bi (NO) was added thereto 3 ) 3 .5H 2 And stirring the solution until the solution is transparent. And then adding 0.23mol/L p-benzoquinone alcoholic solution into the transparent solution, and uniformly stirring to obtain the raw material sol.
S 7 -2. taking glass with clean and dry surface as a substrate material, and adding 1000ml/m of raw material sol 2 Spraying the glass surface.
S 7 And-3, drying the coated glass sprayed with the raw material sol in a constant-temperature drying box at 50 ℃, putting the dried coated glass into a muffle furnace, heating to 300 ℃ at the speed of 5 ℃/min, and calcining at the constant temperature for 1 hour. After the calcination is finished, naturally cooling the film-coated glass to room temperature, and forming a BiOI seed layer on the surface of the glass.
S 7 -4. preparation of 0.2M vanadyl acetylacetonate (C10H) 14 O 5 V) dimethyl sulfoxide (DMSO) sol, and dissolving the sol at 2000ml/m 2 Spraying the mixture on the surface of the BiOI modified glass.
S 7 -5, putting the glass sprayed twice into a muffle furnace again, raising the temperature to 450 ℃ at the speed of 2 ℃/min, annealing for 2 hours, putting the glass into 1mol/L NaOH aqueous solution for soaking for 30 minutes after natural cooling to remove residual V on the surface of the material 2 O 5 Finally, taking out the glass and drying to obtain the BiVO with the composite nano-porous formed on the surface 4 The photocatalyst glass of the layer.
Testing of photocatalyst glass Properties
(1) The cross-sectional structures of the photocatalyst glasses obtained in examples 1 to 3 and comparative examples 2 to 3 were observed by a scanning electron microscope, and the results of the observation are shown in FIGS. 1 to 6.
With reference to fig. 1-4, it can be clearly seen that when the PH is 1.6-1.8, a nanoporous structure can be formed, the morphology difference of the nanostructure is small, wherein the morphology is optimal when the PH is 1.7, when the PH is 1.6, the size of part of particles is insufficient, and uniform porous morphology cannot be formed, when the PH is 1.8, most of the particles are formed without problems, and a certain amount of particle accumulation occurs in part of the regions.
And with reference to fig. 5-6, it is clear that the formation effect of the nano-array is not ideal when the pH is too high or too low. Thus, it can be concluded that: the better nano array structure can be obtained when the pH value is 1.6-1.7, and the pH value is 1.7 is most preferable.
(2) The cross-sectional structure of the photocatalyst glass obtained in example 4 to 5 was observed by a scanning electron microscope, and the results of the observation are shown in FIGS. 7 to 8.
With reference to fig. 1 and 7-8, it can be seen that the nanoparticles have better forming effect when the annealing temperature is selected to be 350-550 ℃. The difference is that the crystallization of the particles is not good enough and the particle size becomes small when the temperature is 350 c, and the worm particles and the porous structure cannot be uniformly formed. The morphology at 550 ℃ and 450 ℃ do not differ much, but the particles are more dense and the pores are relatively smaller, relatively unfavourable for reaction with the solution. Therefore, it can be concluded that better nano-array structures can be obtained when annealing is performed at 350 ℃ to 550 ℃, and that annealing temperature of 450 ℃ is most preferable.
(3) The photocatalyst glasses of example 1 and comparative example 1 were taken and cut into 2X 5cm 2 The test specimens of (1) were placed in 30mL of an aqueous solution (4X 10) containing rhodamine RhB, respectively -6 mol/L), the photocatalytic degradation performance under irradiation of visible light (not less than 400nm) is detected, and the test result is shown in FIG. 9:
it can be clearly seen that in the absence of the photocatalyst glass, RhB itself cannot be self-degraded under the background of illumination and temperature rise; under the action of photocatalyst glass, the concentration of the RhB solution is obviously reduced along with the increase of illumination time, and almost all the solution is degraded when the solution is irradiated for 100min (the temperature of the solution is controlled at room temperature of 25 ℃); because the solution temperature is also increased by illumination, when the temperature is kept at 60 ℃, the degradation rate is faster, and the solution can be completely degraded only in 60 min.
Meanwhile, compared with the traditional titanium dioxide photocatalyst glass, the photocatalyst glass provided by the invention has the advantage that the degradation performance is obviously improved. On the one hand, the traditional titanium dioxide photocatalyst material can only respond to near ultraviolet light with energy accounting for about 4% of the solar spectrum due to the intrinsic wide band gap, and the photocatalytic effect is extremely limited. The invention selects the narrow band gap semiconductor BiVO 4 The photocatalyst material can respond to visible light to stimulate the photocatalyst catalytic oxidation, so that the photocatalyst material provided by the invention has a better degradation effect under the same illumination condition.
On the other hand, when the microstructure of the photocatalyst active material of the present invention is analyzed by combining the electron microscope photographs of fig. 1 and fig. 2, it can be seen that the photocatalyst active material on the surface of the photocatalyst glass provided by the present invention is formed by orderly stacking nanoparticles having a height of about 1 μm. The ultrafine nanoparticles are communicated to form a large number of holes, obviously have large specific surfaces, can preferentially expose surface active sites, and are beneficial to sewage or polluted gas permeation and organic molecule surface adsorption when being applied to degrading organic pollutants in water or gas, and meanwhile, photon capture can be improved through optical scattering in a porous local area, so that the photocatalyst glass RhB aqueous solution has a better degradation effect compared with the traditional photocatalyst material in a degradation test.
With further reference to the experimental data of fig. 10, the degradation test of the photocatalyst glass provided in example 1 was repeatedly verified, the photocatalyst performance was stable, and no significant attenuation occurred in 4 times of repeated tests. The photocatalyst glass provided by the invention has excellent durability and stability.
In addition, the preparation method of the photocatalyst material provided by the invention is to directly grow the nano material on the surface of the substrate material through the catalytic carrier. Compared with the mode of compounding the photocatalyst material and the substrate material by the adhesive in the traditional process, the preparation process provided by the invention has the advantages that the substrate material and the photocatalyst material are stronger in stability and closer in contact, and the problem of falling-off of the photocatalyst material caused by aging of the adhesive in later use is avoided.
In summary, the photocatalyst glass provided by the invention has the following beneficial effects:
1. in the invention, a narrow-band-gap semiconductor BiVO is selected 4 The photocatalyst can respond to visible light to stimulate the photocatalyst catalytic oxidation, and the defect that the traditional photocatalyst material has high requirement on a light source is overcome.
2. The photocatalyst glass surface active layer of the invention has a porous network structure formed by the mutually communicated superfine nano particles, has ultrahigh specific surface area, is beneficial to the permeation and adsorption of harmful molecules of liquid phase and gas phase flow, simultaneously enhances optical scattering and absorption, and jointly promotes the photocatalyst effect.
3. When the photocatalyst glass is applied to degrading organic sewage, rapid and efficient pollutant degradation can be realized under the irradiation of visible light, and the degradation effect is stably attenuated in multiple tests, namely, the photocatalyst glass has better photocatalyst activity and durability. In addition, the photocatalyst active material grows on the surface layer of the substrate material, so that the problem of falling off of the photocatalyst material caused by aging of the adhesive is avoided, and the durability of the photocatalyst glass is further improved.
It is important to note that the construction and arrangement of the present application as shown in the various exemplary embodiments is illustrative only. Although only a few embodiments have been described in detail in this disclosure, those skilled in the art who review this disclosure will readily appreciate that many modifications are possible (e.g., variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters (e.g., temperatures, pressures, etc.), mounting arrangements, use of materials, colors, orientations, etc.) without materially departing from the novel teachings and advantages of the subject matter recited in this application. For example, elements shown as integrally formed may be constructed of multiple parts or elements, the position of elements may be reversed or otherwise varied, and the nature or number of discrete elements or positions may be altered or varied. Accordingly, all such modifications are intended to be included within the scope of this application. The order or sequence of any process or method steps may be varied or re-sequenced according to alternative embodiments. In the claims, any means-plus-function clause is intended to cover the structures described herein as performing the recited function and not only structural equivalents but also equivalent structures. Other substitutions, modifications, changes and omissions may be made in the design, operating conditions and arrangement of the exemplary embodiments without departing from the scope of the present application. Therefore, the present application is not limited to a particular embodiment, but extends to various modifications that nevertheless fall within the scope of the appended claims.
Moreover, in an effort to provide a concise description of the exemplary embodiments, all features of an actual implementation may not be described (i.e., those unrelated to the presently contemplated best mode of carrying out the application, or those unrelated to enabling the application).
It should be appreciated that in the development of any such actual implementation, as in any engineering or design project, numerous implementation-specific decisions may be made. Such a development effort might be complex and time consuming, but would nevertheless be a routine undertaking of design, fabrication, and manufacture for those of ordinary skill having the benefit of this disclosure, without undue experimentation.
It should be noted that the above-mentioned embodiments are only used for illustrating the technical solutions of the present application and not for limiting, and although the present application is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present application without departing from the spirit and scope of the technical solutions of the present application, which should be covered by the claims of the present application.

Claims (10)

1. A preparation method of a photocatalyst material is characterized in that: the method comprises the following steps:
primary coating: preparing KI aqueous solution, adding an acidic additive into the KI aqueous solution until the pH value of the KI aqueous solution is 1.6-1.8, and then adding Bi (NO) into the KI aqueous solution 3 ) 3 .5H 2 O, stirring until the solution is transparent, finally adding p-benzoquinone alcohol solution into the transparent solution, uniformly mixing to obtain raw material sol, and coating the raw material sol on the surface of a clean and dry substrate material;
seed layer formation: drying the once coated substrate material, calcining at high temperature for 1 hour, and after the calcining is finished and the substrate material is cooled to room temperature, forming a BiOI seed layer on the surface of the substrate material;
secondary coating: preparing dimethyl sulfoxide sol of vanadyl acetylacetonate, and coating the dimethyl sulfoxide sol of vanadyl acetylacetonate on the surface of the BiOI seed layer;
forming a composite nano layer: annealing the substrate material after the secondary coating at the temperature of 350-550 ℃ for 2 hours, and forming a finished product of the composite nano-porous BiVO on the surface of the substrate material after natural cooling 4 And (3) a layer.
2. The method for preparing a photocatalytic material according to claim 1, characterized in that: in the primary coating: the pH value of the KI aqueous solution is preferably 1.7.
3. The method for preparing a photocatalytic material according to claim 1 or 2, characterized in that: in the primary coating: the concentration of the KI aqueous solution is 0.4mol/L, and the Bi (NO) is 3 ) 3 .5H 2 The concentration of O is 0.04mol/L, and the alcohol solution of p-benzoquinone is 0.23 mol/L.
4. The method for preparing a photocatalytic material according to claim 3, characterized in that: in the primary coating: the coating amount was 1000ml/m 2 。
5. The method for preparing a photocatalytic material according to any one of claims 1, 2, and 4, wherein: in the formation of the seed layer: the calcination temperature was 300 ℃.
6. The method for preparing a photocatalytic material according to claim 5, wherein: in the secondary coating: the concentration of the dimethyl sulfoxide sol of vanadyl acetylacetonate was 0.2 mol/L.
7. The method for preparing a photocatalytic material according to claim 5, wherein: in the secondary coating: the coating amount was 2000ml/m 2 。
8. The method for preparing a photocatalytic material according to claim 6 or 7, characterized in that: in the formation of the composite nano-layer: the annealing temperature is preferably 450 ℃.
9. The method for preparing a photocatalytic material according to claim 8, wherein: in the formation of the composite nano-layer: and (3) soaking the calcined substrate material in a sodium hydroxide aqueous solution for 30 minutes, and drying after soaking.
10. A photocatalyst glass is characterized in that: the photocatalyst glass comprises a glass substrate and a composite nanoporous BiVO on the surface of the glass substrate 4 Layer of said composite nanoporous BiVO 4 A layer formed on a surface of a glass substrate by the method of any of claims 1-9.
CN202210371542.4A 2022-04-11 2022-04-11 Preparation method of photocatalyst material and photocatalyst glass Active CN114797833B (en)

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CN113235124A (en) * 2021-05-18 2021-08-10 西北师范大学 S-FeOOH/bismuth vanadate composite photo-anode and preparation method thereof
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