CN114797833B - Preparation method of photocatalyst material and photocatalyst glass - Google Patents

Preparation method of photocatalyst material and photocatalyst glass Download PDF

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CN114797833B
CN114797833B CN202210371542.4A CN202210371542A CN114797833B CN 114797833 B CN114797833 B CN 114797833B CN 202210371542 A CN202210371542 A CN 202210371542A CN 114797833 B CN114797833 B CN 114797833B
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glass
solution
photocatalyst
sol
coating
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CN114797833A (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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Catalysts (AREA)

Abstract

The application discloses a preparation method of a photocatalyst material and photocatalyst glass, which comprises the following steps: preparing aqueous KI solution, adding acidic additive to adjust pH, and adding Bi (NO) 3 ) 3 5H2O is stirred until the solution is transparent, and finally p-benzoquinone alcohol solution is added, and raw material sol is obtained after uniform mixing, and is coated on the surface of a substrate material; drying the primary coated substrate material, calcining at high temperature for 1 hour, and cooling to room temperature after calcining, wherein a BiOI seed layer is formed 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; annealing the substrate material subjected to the secondary coating at 350-550 ℃ for 2 hours, and forming a finished product of composite nano-porous BiVO on the surface of the substrate material after natural cooling 4 A layer. The method selects the narrow bandgap semiconductor BiVO 4 Can respond to the catalytic oxidation of the visible light excitation light catalyst and has excellent degradation effect.

Description

Preparation method of photocatalyst material and photocatalyst glass
Technical Field
The application relates to the field of photocatalysts, in particular to a preparation method of a photocatalyst material and photocatalyst glass.
Background
The photocatalyst technology refers to that the semiconductor material generates electron-hole thermal charge under the irradiation of light, and reacts with water and oxygen in the environment to continuously generate active hydroxyl free radicals and superoxide ion free radicals, so that the photocatalyst material shows photoinduction oxidation-reduction catalytic capability, can attack bacterial cell membranes and virus proteins, and can decompose most organic pollutants into water and carbon dioxide, thereby having application values of sterilization, mildew resistance, pollution resistance, air purification, sewage degradation and the like.
However, the application development of the current photocatalyst technology encounters some bottleneck defects, most of photocatalyst active materials are nano titanium dioxide, and although the nano titanium dioxide is relatively stable and transparent, the bulk color is not affected, but the intrinsic wide band gap of the photocatalyst active materials can only respond to near ultraviolet light accounting for about 4% of energy in 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 intended to summarize some aspects of embodiments of the application and to briefly introduce some preferred embodiments, which may be simplified or omitted in this section and in the description abstract and application names of the application so as not to obscure the objects of this section, description abstract and application names, which are not intended to limit the scope of the application.
The present application has been made in view of the above and/or problems occurring in the prior art.
Therefore, the technical problems to be solved by the application are as follows: the existing nano titanium dioxide photocatalyst material needs to be additionally provided with an ultraviolet irradiation light source in the application process, and has high cost.
In order to solve the technical problems, the application provides the following technical scheme: a preparation method of a photocatalyst material comprises the following steps:
primary coating: preparing aqueous KI solution, adding acidic additive to the aqueous KI solution until the pH of the aqueous KI solution is 1.6-1.8, and adding Bi (NO) 3 ) 3 .5H 2 O, stirring until the solution is transparent, 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 primary coated substrate material, calcining at high temperature for 1 hour, and cooling to room temperature after calcining, wherein a BiOI seed layer is formed on the surface of the substrate material;
and (3) 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;
composite nanolayer formation: annealing the substrate material subjected to the secondary coating at 350-550 ℃ for 2 hours, and forming a finished product of composite nano-porous BiVO on the surface of the substrate material after calcining 4 A layer.
As a preferable scheme of the preparation method of the photocatalyst material, the application comprises the following steps: in the primary coating: the pH of the aqueous KI solution is preferably 1.7.
As a preferable scheme of the preparation method of the photocatalyst material, the application comprises the following steps: in the primary coating: the concentration of the KI aqueous solution was 0.4mol/L, and the concentration of Bi (NO 3 ) 3 .5H 2 The concentration of O is 0.04mol/L, and the concentration of the p-benzoquinone alcohol solution is 0.23mol/L.
As a preferable scheme of the preparation method of the photocatalyst material, the application comprises the following steps: in the primary coating: coating amount is 1000ml/m 2 。
As a preferable scheme of the preparation method of the photocatalyst material, the application comprises the following steps: in the seed layer formation: the calcination temperature was 300 ℃.
As a preferable scheme of the preparation method of the photocatalyst material, the application comprises the following steps: in the secondary coating: the concentration of the dimethyl sulfoxide sol of vanadyl acetylacetonate is 0.2mol/L.
As a preferable scheme of the preparation method of the photocatalyst material, the application comprises the following steps: in the secondary coating: the coating amount was 2000ml/m 2 。
As a preferable scheme of the preparation method of the photocatalyst material, the application comprises the following steps: in the formation of the composite nanolayer: the annealing temperature is preferably 450 ℃.
The photocatalyst glass is characterized in that: the photocatalyst glass comprises a glass substrate and a composite nano porous BiVO on the surface of the glass substrate 4 Layer of the composite nanoporous BiVO 4 A layer formed on a surface of a glass substrate by the method of any one of claims 1-9.
The application has the beneficial effects that: the method selects the narrow bandgap semiconductor BiVO 4 Can respond to visible light excitation light catalyst catalytic oxygenDecomposing organic molecules, inducing pollutant degradation, sterilizing, disinfecting, mildew-proof, and anti-fouling functions.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a top SEM photograph of a photo-catalytic active material according to example 1 of the present application;
FIG. 2 is a cross-sectional SEM photograph of a photo-catalytic active material of example 1;
FIG. 3 is a top SEM photograph of the photo-catalytic active material according to example 2 of the present application;
FIG. 4 is a top SEM photograph of the photo-catalytic active material according to example 3 of the present application;
FIG. 5 is a top SEM photograph of the photo-catalytic active material according to comparative example 2;
FIG. 6 is a top SEM photograph of the photo-catalytic active material according to comparative example 3 of the present application;
FIG. 7 is a top SEM photograph of the photo-catalytic active material according to example 4 of the present application;
FIG. 8 is a top SEM photograph of the photo-catalytic active material according to example 5 of the present application;
FIG. 9 is a graph showing the results of rhodamine RhB degradation tests performed on the photocatalytic glass provided in example 1 and comparative example 1 of the present application;
FIG. 10 shows the results of a series of 4 rhodamine RhB degradation tests performed on the photocatalytic glass according to example 1 of the present application.
Detailed Description
In order that the above-recited objects, features and advantages of the present application will become more readily apparent, a more particular description of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended 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 other than those described herein, and persons skilled in the art will readily appreciate that the present application is not limited to the specific embodiments disclosed below.
In the following detailed description of the embodiments of the present application, reference is made to the accompanying drawings, which form a part hereof, and in which are shown by way of illustration only, and in which is shown by way of illustration only, and in which the scope of the application is not limited for ease of illustration. In addition, the three-dimensional dimensions of length, width and depth should be included in actual fabrication.
Further still, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the 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 preparation of 0.4mol/L KI aqueous solution by addition of HNO 3 The pH was adjusted to 1.7, and then Bi (NO) was added thereto in an amount of 0.04mol/L 3 ) 3 .5H 2 O solution and stirring until the solution is transparent. And then adding 0.23mol/L p-benzoquinone alcohol solution into the transparent solution, and uniformly stirring to obtain raw material sol.
S 1 Taking glass with clean and dry surface as a base material, and dissolving the raw material sol at 1000ml/m 2 Spraying the glass onto the surface of the glass.
S 1 And 3, placing the coated glass sprayed with the raw material sol into a constant temperature drying box at 50 ℃ for drying, and placing the coated glass into a horse boiling furnace for constant temperature calcination for 1 hour after the drying is finished, and heating to 300 ℃ at 5 ℃/min. After the calcination is completed, the coated glass is naturally cooled to room temperature, and a BiOI seed layer is formed on the surface of the glass.
S 1 Preparation of 0.2M vanadyl acetylacetonate (C10H) 14 O 5 V) dimethyl sulfoxide (DMSO) sol and mixing the sol at 2000ml/m 2 Spraying the glass onto the surface of the BiOI modified glass.
S 1 5, putting the glass sprayed twice into a horse boiling furnace again, heating to 450 ℃ at 2 ℃/min for annealing treatment for 2 hours, and soaking the glass in 1mol/L NaOH aqueous solution for 30 minutes after natural cooling to remove V remained on the surface of the material 2 O 5 Finally, the glass is taken out and dried to obtain the composite nano porous BiVO with the surface formed 4 The photocatalyst glass of the layer.
Example 2
The embodiment provides a photocatalyst glass, which is prepared by the following steps:
S 2 preparation of 0.4mol/L KI aqueous solution by addition of HNO 3 The pH was adjusted to 1.6, and then Bi (NO) was added thereto in an amount of 0.04mol/L 3 ) 3 .5H 2 O solution and stirring until the solution is transparent. And then adding 0.23mol/L p-benzoquinone alcohol solution into the transparent solution, and uniformly stirring to obtain raw material sol.
S 2 Taking glass with clean and dry surface as a base material, and dissolving the raw material sol at 1000ml/m 2 Spraying the glass onto the surface of the glass.
S 2 And 3, placing the coated glass sprayed with the raw material sol into a constant temperature drying box at 50 ℃ for drying, and placing the coated glass into a horse boiling furnace for constant temperature calcination for 1 hour after the drying is finished, and heating to 300 ℃ at 5 ℃/min. After the calcination is completed, the coated glass is naturally cooled to room temperature, and a BiOI seed layer is formed on the surface of the glass.
S 2 Preparation of 0.2M vanadyl acetylacetonate (C10H) 14 O 5 V) dimethyl sulfoxide (DMSO) sol and mixing the sol at 2000ml/m 2 Spraying the glass onto the surface of the BiOI modified glass.
S 2 5, putting the glass sprayed twice into a horse boiling furnace again, heating to 450 ℃ at 2 ℃/min for annealing treatment for 2 hours, and soaking the glass in 1mol/L NaOH aqueous solution for 30 minutes after natural cooling to obtain the final productRemoving residual V on the surface of the material 2 O 5 Finally, the glass is taken out and dried to obtain the composite nano porous BiVO with the surface formed 4 The photocatalyst glass of the layer.
Example 3
The embodiment provides a photocatalyst glass, which is prepared by the following steps:
S 3 preparation of 0.4mol/L KI aqueous solution by addition of HNO 3 The pH was adjusted to 1.8, and then Bi (NO) was added thereto in an amount of 0.04mol/L 3 ) 3 .5H 2 O solution and stirring until the solution is transparent. And then adding 0.23mol/L p-benzoquinone alcohol solution into the transparent solution, and uniformly stirring to obtain raw material sol.
S 3 Taking glass with clean and dry surface as a base material, and dissolving the raw material sol at 1000ml/m 2 Spraying the glass onto the surface of the glass.
S 3 And 3, placing the coated glass sprayed with the raw material sol into a constant temperature drying box at 50 ℃ for drying, and placing the coated glass into a horse boiling furnace for constant temperature calcination for 1 hour after the drying is finished, and heating to 300 ℃ at 5 ℃/min. After the calcination is completed, the coated glass is naturally cooled to room temperature, and a BiOI seed layer is formed on the surface of the glass.
S 3 Preparation of 0.2M vanadyl acetylacetonate (C10H) 14 O 5 V) dimethyl sulfoxide (DMSO) sol and mixing the sol at 2000ml/m 2 Spraying the glass onto the surface of the BiOI modified glass.
S 3 5, putting the glass sprayed twice into a horse boiling furnace again, heating to 450 ℃ at 2 ℃/min for annealing treatment for 2 hours, and soaking the glass in 1mol/L NaOH aqueous solution for 30 minutes after natural cooling to remove V remained on the surface of the material 2 O 5 Finally, the glass is taken out and dried to obtain the composite nano porous BiVO with the surface formed 4 The photocatalyst glass of the layer.
Example 4
The embodiment provides a photocatalyst glass, which is prepared by the following steps:
S 4 preparation of 0.4mol/L KI aqueous solution by addition of HNO 3 The pH was adjusted to 1.7, and then Bi (NO) was added thereto in an amount of 0.04mol/L 3 ) 3 .5H 2 O solution and stirring until the solution is transparent. And then adding 0.23mol/L p-benzoquinone alcohol solution into the transparent solution, and uniformly stirring to obtain raw material sol.
S 4 Taking glass with clean and dry surface as a base material, and dissolving the raw material sol at 1000ml/m 2 Spraying the glass onto the surface of the glass.
S 4 And 3, placing the coated glass sprayed with the raw material sol into a constant temperature drying box at 50 ℃ for drying, and placing the coated glass into a horse boiling furnace for constant temperature calcination for 1 hour after the drying is finished, and heating to 300 ℃ at 5 ℃/min. After the calcination is completed, the coated glass is naturally cooled to room temperature, and a BiOI seed layer is formed on the surface of the glass.
S 4 Preparation of 0.2M vanadyl acetylacetonate (C10H) 14 O 5 V) dimethyl sulfoxide (DMSO) sol and mixing the sol at 2000ml/m 2 Spraying the glass onto the surface of the BiOI modified glass.
S 4 5, putting the glass sprayed twice into a horse boiling furnace again, heating to 350 ℃ at 2 ℃/min for annealing treatment for 2 hours, and soaking the glass in 1mol/L NaOH aqueous solution for 30 minutes after natural cooling to remove V remained on the surface of the material 2 O 5 Finally, the glass is taken out and dried to obtain the composite nano porous BiVO with the surface formed 4 The photocatalyst glass of the layer.
Example 5
The embodiment provides a photocatalyst glass, which is prepared by the following steps:
S 5 preparation of 0.4mol/L KI aqueous solution by addition of HNO 3 The pH was adjusted to 1.7, and then Bi (NO) was added thereto in an amount of 0.04mol/L 3 ) 3 .5H 2 O solution and stirring until the solution is transparent. And then adding 0.23mol/L p-benzoquinone alcohol solution into the transparent solution, and uniformly stirring to obtain raw material sol.
S 5 Taking glass with clean and dry surface as a base material, and dissolving the raw material sol at 1000ml/m 2 Spraying the glass onto the surface of the glass.
S 5 And 3, placing the coated glass sprayed with the raw material sol into a constant temperature drying box at 50 ℃ for drying, and placing the coated glass into a horse boiling furnace for constant temperature calcination for 1 hour after the drying is finished, and heating to 300 ℃ at 5 ℃/min. After the calcination is completed, the coated glass is naturally cooled to room temperature, and a BiOI seed layer is formed on the surface of the glass.
S 5 Preparation of 0.2M vanadyl acetylacetonate (C10H) 14 O 5 V) dimethyl sulfoxide (DMSO) sol and mixing the sol at 2000ml/m 2 Spraying the glass onto the surface of the BiOI modified glass.
S 5 5, putting the glass sprayed twice into a horse boiling furnace again, heating to 550 ℃ at 2 ℃/min for annealing treatment for 2 hours, and soaking the glass in 1mol/L NaOH aqueous solution for 30 minutes after natural cooling to remove V remained on the surface of the material 2 O 5 Finally, the glass is taken out and dried to obtain the composite nano porous BiVO with the surface formed 4 The photocatalyst glass of the layer.
Comparative example 1
The comparative example provides a traditional nano titanium dioxide photocatalyst glass.
Comparative example 2
The comparative example provides a photocatalyst glass, which is prepared by the following steps:
S 6 preparation of 0.4mol/L KI aqueous solution by addition of HNO 3 The pH was adjusted to 0.5, followed by adding Bi (NO) at 0.04mol/L 3 ) 3 5H2O solution and stirring until the solution is transparent. And then adding 0.23mol/L p-benzoquinone alcohol solution into the transparent solution, and uniformly stirring to obtain raw material sol.
S 6 Taking glass with clean and dry surface as a base material, and dissolving the raw material sol at 1000ml/m 2 Spraying the glass onto the surface of the glass.
S 6 And 3, placing the coated glass sprayed with the raw material sol into a constant temperature drying box at 50 ℃ for drying, and placing the coated glass into a horse boiling furnace for constant temperature calcination for 1 hour after the drying is finished, and heating to 300 ℃ at 5 ℃/min. After the calcination is completed, the coated glass is naturally cooled to room temperature, and a BiOI seed layer is formed on the surface of the glass.
S 6 Preparation of 0.2M vanadyl acetylacetonate (C10H) 14 O 5 V) dimethyl sulfoxide (DMSO) sol and mixing the sol at 2000ml/m 2 Spraying the glass onto the surface of the BiOI modified glass.
S 6 5, putting the glass sprayed twice into a horse boiling furnace again, heating to 450 ℃ at 2 ℃/min for annealing treatment for 2 hours, and soaking the glass in 1mol/L NaOH aqueous solution for 30 minutes after natural cooling to remove V remained on the surface of the material 2 O 5 Finally, the glass is taken out and dried to obtain the composite nano porous BiVO with the surface formed 4 The photocatalyst glass of the layer.
Comparative example 3
The comparative example provides a photocatalyst glass, which is prepared by the following steps:
S 7 preparation of 0.4mol/L KI aqueous solution by addition of HNO 3 The pH was adjusted to 3, and then Bi (NO) was added thereto in an amount of 0.04mol/L 3 ) 3 .5H 2 O solution and stirring until the solution is transparent. And then adding 0.23mol/L p-benzoquinone alcohol solution into the transparent solution, and uniformly stirring to obtain raw material sol.
S 7 Taking glass with clean and dry surface as a base material, and dissolving the raw material sol at 1000ml/m 2 Spraying the glass onto the surface of the glass.
S 7 And 3, placing the coated glass sprayed with the raw material sol into a constant temperature drying box at 50 ℃ for drying, and placing the coated glass into a horse boiling furnace for constant temperature calcination for 1 hour after the drying is finished, and heating to 300 ℃ at 5 ℃/min. After the calcination is completed, the coated glass is naturally cooled to room temperature, and a BiOI seed layer is formed on the surface of the glass.
S 7 Preparation of 0.2M vanadyl acetylacetonate (C10H) 14 O 5 V) dimethyl sulfoxide (DMSO) sol and mixing the sol at 2000ml/m 2 Spraying the glass onto the surface of the BiOI modified glass.
S 7 5, putting the glass sprayed twice into a horse boiling furnace again, heating to 450 ℃ at 2 ℃/min for annealing treatment for 2 hours, and putting the glass into a NaOH aqueous solution with the concentration of 1mol/L after natural coolingSoaking for 30min to remove residual V on the surface of the material 2 O 5 Finally, the glass is taken out and dried to obtain the composite nano porous BiVO with the surface formed 4 The photocatalyst glass of the layer.
Photocatalyst glass performance test
(1) The photocatalytic glasses prepared in examples 1 to 3 and comparative examples 2 to 3 were observed for their cross-sectional structures by a scanning electron microscope, and the observation results are shown in FIGS. 1 to 6.
It is obvious from the accompanying figures 1-4 that nano porous structures can be formed when the pH is between 1.6 and 1.8, the morphology difference of the nano structures is small, wherein the morphology is optimal when the pH is 1.7, the particle size is insufficient at part of the particles at the pH of 1.6, uniform porous morphology cannot be formed, most of the particles are formed without problems when the pH is 1.8, and a certain particle accumulation can be generated in part of the regions.
While, in combination with FIGS. 5-6, it is evident that the formation of the nanoarrays is not ideal when the pH is too high or too low. Thus, it can be concluded that: a good nanoarray structure can be obtained at a pH of 1.6-1.7, and most preferably at a pH of 1.7.
(2) The photocatalytic glass obtained in examples 4 to 5 was observed by a scanning electron microscope for its cross-sectional structure, and the observation results are shown in FIGS. 7 to 8.
With reference to fig. 1 and 7-8, it can be seen that the nanoparticles have a good 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 when the temperature is 350 ℃, the particle size becomes small, and worm particles and porous structures are not uniformly formed. The morphology at 550 ℃ and the difference at 450 ℃ are not large, but the particles are denser, the pores are relatively smaller, and the reaction with the solution is relatively unfavorable. Thus, it can be concluded that better nanoarray structures can be obtained when annealing is at 350 ℃ to 550 ℃, with annealing temperatures of 450 ℃ being most preferred.
(3) The photocatalytic glass of example 1 and comparative example 1 was taken and cut to 2X 5cm 2 Respectively, 30mL of an aqueous solution (4X 10) containing rhodamine RhB was added thereto -6 mol/L), the photocatalytic degradation performance under the irradiation of visible light (more than or equal to 400 nm) is detected, and the test result is shown in figure 9:
it is obvious that when the photocatalyst glass is not present, rhB itself will not self-degrade under the illumination and heating background; under the action of photocatalyst glass, the concentration of the RhB solution is obviously reduced along with the increase of illumination time, and the RhB solution is almost completely degraded when irradiated for 100min (the temperature of the solution is controlled at room temperature of 25 ℃); because the temperature of the solution is also increased by illumination, the degradation rate is faster when the temperature is kept at 60 ℃, and the solution can be degraded completely only in 60 minutes.
Meanwhile, compared with the traditional titanium dioxide photocatalyst glass, the photocatalyst glass has very obvious improvement of degradation performance. This is because the intrinsic wide band gap of the conventional titanium dioxide photocatalyst material makes it only able to respond to near ultraviolet light accounting for about 4% of the energy in the solar spectrum, and the photocatalytic effect is extremely limited. The application selects the narrow bandgap semiconductor BiVO 4 The photocatalyst material provided by the application has better degradation effect under the same illumination condition.
On the other hand, by analyzing the microstructure of the photocatalyst active material according to the present application in combination with the electron microscope photographs of fig. 1 and 2, it can be seen that the photocatalyst glass provided by the present application has a surface in which the photocatalyst active material is orderly stacked with nanoparticles having a height of about 1 μm. The superfine nano particles are communicated to form a large number of holes, obviously have a large specific surface, can preferentially expose surface active sites, and are beneficial to sewage or sewage gas permeation and organic molecule surface adsorption when applied to degrading organic pollutants in water or gas, and photon capture can be improved by porous local optical scattering, so that the photocatalyst glass RhB aqueous solution degradation test of the application shows better degradation effect compared with the traditional photocatalyst material.
Further referring to the experimental data of fig. 10, the degradation test of the photocatalytic glass provided in example 1 was repeatedly verified, the photocatalytic performance was stable, and no significant attenuation occurred in 4 repeated tests. The photocatalyst glass provided by the application has excellent durability and stability.
In addition, the preparation method of the photocatalyst material provided by the application is that the nano material is directly grown on the surface of the substrate material through the catalytic carrier. Compared with the traditional process in which the photocatalyst material and the substrate material are compounded by the adhesive, the preparation process provided by the application has the advantages that the substrate material and the photocatalyst material are stronger in stability and better and tighter in contact, and the problem that the photocatalyst material falls off due to aging of the adhesive in later use is avoided.
In summary, the photocatalyst glass provided by the application has the following beneficial effects:
1. the method selects the narrow bandgap semiconductor BiVO 4 Can respond to the catalytic oxidation of the visible light excitation light catalyst, and solves the defect that the traditional photocatalyst material has high requirements on light sources.
2. The photocatalyst glass surface active layer of the application is a porous network structure formed by mutually communicated ultrafine nano particles, has ultrahigh specific surface area, is favorable for permeation and adsorption of harmful molecules flowing in liquid phase and gas phase, enhances optical scattering and absorption, and promotes the photocatalyst effect together.
3. When the photocatalyst glass is applied to degrading organic sewage, the photocatalyst glass can realize rapid and efficient pollutant degradation under the irradiation of visible light, and the degradation effect is stable in multiple tests, namely the photocatalyst glass has good photocatalyst activity and durability. In addition, the photocatalyst active material is automatically grown on the surface layer of the substrate material, so that the problem that the photocatalyst material falls off due to ageing 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 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., temperature, pressure, etc.), mounting arrangements, use of materials, colors, orientations, etc.) without materially departing from the novel teachings and advantages of the subject matter described 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 present 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 applications. Therefore, the application is not limited to the specific embodiments, but extends to various modifications that nevertheless fall within the scope of the appended claims.
Furthermore, 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 not associated with the best mode presently contemplated for carrying out the application, or those not associated with practicing 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.
It should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted without departing from the spirit and scope of the technical solution of the present application, which is intended to be covered in the scope of the claims of the present application.

Claims (5)

1. The photocatalyst glass is characterized in that: the photocatalyst glass comprises a glass substrate and a composite nano porous BiVO on the surface of the glass substrate 4 A layer;
the composite nano porous BiVO 4 A method of making a layer comprising:
primary coating: preparing an aqueous KI solution, adding an acidic additive into the aqueous KI solution until the pH value of the aqueous KI solution is 1.6-1.8, and then adding Bi (NO) 3 ) 3 ·5H 2 O, stirring until the solution is transparent, 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 primary coated substrate material, calcining at high temperature for 1 hour, and cooling to room temperature after calcining, wherein a BiOI seed layer is formed on the surface of the substrate material;
and (3) 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;
composite nanolayer formation: annealing the substrate material subjected to the secondary coating at 350-550 ℃ for 2 hours, and naturally cooling to form a finished product of the composite nano porous BiVO on the surface of the substrate material 4 A layer;
in the primary coating: the coating mode is spray coating, and the coating amount is 1000ml/m 2 ；
In the seed layer formation: the calcination temperature is 300 ℃;
in the secondary coating: the concentration of dimethyl sulfoxide sol of vanadyl acetylacetonate is 0.2mol/L, and the coating amount is 2000ml/m 2 。
2. The photocatalyst glass as defined in claim 1, wherein: in the primary coating, the pH of the aqueous KI solution was 1.7.
3. The photocatalyst glass as defined in claim 1, wherein: by a means ofIn the primary coating: the concentration of the KI aqueous solution was 0.4mol/L, and the concentration of Bi (NO 3 ) 3 ·5H 2 The concentration of O is 0.04mol/L, and the concentration of the p-benzoquinone alcohol solution is 0.23mol/L.
4. The photocatalyst glass as defined in claim 1, wherein: in the formation of the composite nanolayer: the annealing temperature was 450 ℃.
5. The photocatalyst material according to claim 1, wherein: in the formation of the composite nanolayer: and (3) soaking the calcined substrate material in a sodium hydroxide aqueous solution for 30 minutes, and drying after the soaking is finished.
CN202210371542.4A 2022-04-11 2022-04-11 Preparation method of photocatalyst material and photocatalyst glass Active CN114797833B (en)

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