CN110813348A - Full-spectrum response fluorine-doped ammonium tungsten bronze photocatalyst and preparation method thereof - Google Patents
Full-spectrum response fluorine-doped ammonium tungsten bronze photocatalyst and preparation method thereof Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/39—
Abstract
The invention discloses a fluorine-doped ammonium tungsten bronze photocatalyst with full-spectrum response and a preparation method thereof. Adding tungsten chloride and ammonium acetate into an n-propanol solution, and dissolving by ultrasonic to obtain a solution A; adding a hydrofluoric acid solution into the solution A to obtain a solution B, and reacting for 12-72 hours at the temperature of 180-220 ℃; and naturally cooling the reaction product, washing and drying to obtain the fluorine-doped ammonium tungsten bronze photocatalyst with full-spectrum response. The catalyst has the degradation rate of more than 35 percent of rhodamine B in 180min of ultraviolet irradiation, the degradation rate of more than 90 percent of rhodamine B in 120min of visible light irradiation, the degradation rate of more than 80 percent of rhodamine B in 180min of near-infrared irradiation, still has high degradation rate and stable activity after five photocatalytic experiments, and can be stably used for a long time. The method has the advantages of simple operation, wide raw material source, low cost and high pollutant degradation rate.
Description
Technical Field
The invention belongs to the field of environmental purification and green energy utilization, and relates to a full-spectrum corresponding fluorine-doped ammonium tungsten bronze photocatalyst and a preparation method thereof.
Background
The rapid development of the human society in the 21 st century has made great progress in science and technology and humanity, but the problems of resource exhaustion and ecological environment deterioration in the current generation are increasingly highlighted, and a serious challenge is brought to human beings. The sustainable development becomes a necessary road for the contemporary society to realize the sustainabilityTwo major challenges facing development are energy and environmental issues. The photocatalyst is a chemical substance which can change the chemical reaction rate under the irradiation of light and does not participate in the reaction per se. The photocatalyst not only can fully utilize green renewable energy sunlight, but also can be repeatedly utilized without changing the properties of the photocatalyst, and can be used for preparing hydrogen by photolysis to degrade organic and inorganic pollutants in water. The application of the photocatalysis technology in the aspects of environmental purification, microbial sterilization, surface self-cleaning, energy catalysis and the like provides a solution for people. With TiO2The traditional photocatalyst represented by the general formula has the characteristics of chemical and light corrosion resistance, stable property, no toxicity, high catalytic activity, low price and the like, and is widely applied to the fields of pollutant degradation, water decomposition for hydrogen production, solar cells, pigments and the like. However, the traditional photocatalyst has a large forbidden band width, and can only utilize ultraviolet light and visible light, which only account for 5% and 43% of sunlight respectively. Since 52% of near-infrared light is rarely used, there is a trend toward the development of near-infrared photocatalysts from the viewpoint of the full use of sunlight and the degradation of environmental pollution.
Ammonium Tungsten Bronze (ATB), a non-stoichiometric compound. Blue oxide containing a certain amount of ammonium. With ATB as the main phase and WO2.90The blue tungsten oxide as the main phase is a high-quality raw material for producing tungsten materials, and because Ammonium Tungsten Bronze (ATB) has high activity and large specific surface area, and is easy to generate physical adsorption and chemical reaction when being mixed with a salt solution, people like to use ATB as a tungsten source when producing doped tungsten powder. Ammonium tungsten bronze is mainly used for heat insulation of architectural glass surfaces because of its excellent absorption properties in the near infrared region.
Tungsten bronze materials are a class of substances that have a strong absorption in the near infrared region. At present, research on tungsten bronze materials focuses on near-infrared shielding performance, and reports on photocatalytic performance of tungsten bronze materials are rare. Chinese patent application 201810200279.6(CN 108558230 a, published 2018.09.21) discloses a method for preparing a high visible light photocatalytic composite material loaded with silver oxide on a tungsten bronze substrate. The degradation rate of the composite material prepared by the application can reach more than 95% within 30 min. However, silver oxide has poor stability, and is reduced into silver by photo-generated electrons in the photocatalysis process, so that the performance of the composite photocatalyst is attenuated.
Chinese patent 201610014726.X (CN 105668632A, published 2016.06.15) discloses a variable-valence metal-catalyzed and doped tungsten bronze Ax-MyWO3Firstly, preparing solid colloidal tungstic acid as tungsten source, mixing it with M source, proper solvent and inducer, adding proper quantity of variable valence metal A salt, synthesizing variable valence catalytic and doped tungsten bronze A by thermal reactionx-MyWO3A multifunctional nanoparticle; although the patent synthesizes nanoparticles with excellent near-infrared light shielding performance, the photocatalytic performance of the nanoparticles under ultraviolet light irradiation is poor.
Chinese patent application 201410614449.7 discloses a preparation method of a full-spectrum solar photocatalyst, which uses titanium dioxide as a substrate and loads rare earth oxide, although a composite material with good dispersibility and stable chemical properties can be obtained, the visible light photocatalysis performance of the composite material is poor, and the degradation rate of 20mg/L methyl orange in 120min is only 59% under 500W visible light; the full spectrum of the application refers to ultraviolet light and visible light, does not contain near infrared light photocatalysis performance, and utilizes rare earth metal, so that the raw material is expensive and the cost is high.
The Chinese invention patent 2016104783512 discloses a full-spectrum response type ammonium tungsten bronze-titanium dioxide composite photocatalyst, which is prepared by the following steps: adding 0.1-1.0 g of ammonium tungstate into 20-80 mL of ethylene glycol, and magnetically stirring and dissolving at the temperature of 80-200 ℃; cooling to room temperature, adding 0.1-1.0 g of titanium dioxide serving as a raw material, performing ultrasonic dispersion, and stirring to obtain a suspension; adding 10-80 mL of acetic acid into the suspension and stirring to obtain a mixed liquid, transferring the mixed liquid into a hydrothermal kettle, and carrying out hydrothermal reaction for 10-72 hours at the temperature of 160-240 ℃; and sequentially using deionized water and ethanol to respectively centrifugally wash the precipitate, and drying to obtain the ammonium tungsten bronze-titanium dioxide composite photocatalyst. The photocatalyst has photocatalytic activity under ultraviolet light, visible light and even infrared spectrum, realizes the absorption and utilization of the full spectrum of sunlight, and has wide application prospect in the fields of environmental pollution treatment and purification, environmental protection functional materials and the like. However, the method has complex preparation process and long reaction time, and the prepared sample has poor visible light and near infrared light photocatalytic activity.
The photocatalyst in the prior art can only utilize ultraviolet light and visible light or can only utilize near infrared light with a certain range or a single wavelength mostly, and cannot realize the full utilization of sunlight. Although the composite material widens the spectrum utilization range, the near infrared light has low photocatalytic efficiency.
Disclosure of Invention
The invention aims to provide a full-spectral-response fluorine-doped ammonium tungsten bronze photocatalyst with a simple synthesis process and a preparation method thereof, and solves the problems of narrow spectrum utilization range and low near-infrared light photocatalysis efficiency of the photocatalyst.
The ammonium tungsten bronze is a plasma resonance material with strong absorption in near infrared light, and the near infrared light photocatalysis performance of the ammonium tungsten bronze is limited due to the large forbidden band width. By carrying out certain doping modification on the ammonium tungsten bronze, the material changes the composition structure, improves the photocatalytic performance, realizes the full spectrum utilization of sunlight, and has great significance for the full utilization of renewable energy sources and the practical application of a photocatalyst.
The method takes normal propyl alcohol as a solvent, tungsten chloride and ammonium acetate as a tungsten source and an ammonium source, and hydrofluoric acid is added for fluorine ion doping. Substitution of doped fluorine atoms for WO6The position of the octahedral lattice oxygen, due to the non-equivalent substitution, generates free electrons. The doped ammonium tungsten bronze not only has strong near infrared light absorption, but also has excellent ultraviolet-visible-near infrared light photocatalysis performance, and the photocatalysis performance is efficient and stable, and can be stably used for a long time. The method has the advantages of simple and easy synthesis steps, wide raw material source and higher practical application value.
The invention can greatly improve the ultraviolet-visible-near infrared photocatalysis performance of the tungsten bronze material, and the promotion mechanism of the photocatalysis for realizing full-spectrum response is as follows: doped fluoride ion is not substituted with equivalenceWO in ammonium tungsten bronze6The position of lattice oxygen in the octahedron generates a large number of free electrons. On the one hand, these free electrons will be W in ammonium tungsten bronzes6+Reduction to W5+High concentration of W5+Formation of defect energy level (W) below the conduction band of ammonium tungsten bronze5+) The energy required by electronic transition is reduced, the spectrum utilization range is widened, and the ultraviolet-visible-near infrared photocatalysis performance of the tungsten bronze material is improved; on the other hand, a large amount of free electrons generated by fluorine doping exist near the Fermi level, and due to the existence of the surface electrons, the local plasma resonance effect of the fluorine-doped ammonium tungsten bronze can be excited by near infrared light to form free hot electrons, so that the free hot electrons participate in the photocatalytic degradation process, and the near infrared light photocatalytic performance of the ammonium tungsten bronze material is improved. The ultraviolet-visible-near infrared photocatalysis performance of the tungsten bronze material is greatly improved under the combined action of the two aspects.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for synthesizing fluorine-doped ammonium tungsten bronze photocatalyst comprises the following steps:
(1) measuring a certain volume of n-propanol in a beaker, weighing a certain mass of tungsten chloride and ammonium acetate, adding the tungsten chloride and the ammonium acetate into the n-propanol solution, and performing ultrasonic dissolution to obtain a solution A.
(2) Pouring the solution A in the step (1) into a 100mL p-polyphenyl reaction kettle, measuring a certain volume of hydrofluoric acid solution, and adding the hydrofluoric acid solution into the solution A to obtain a solution B. Reacting for 12-72 h at 180-220 ℃.
(3) And (3) naturally cooling, washing the reaction product with deionized water and absolute ethyl alcohol for 3-5 times respectively, and drying to obtain the fluorine-doped ammonium tungsten bronze photocatalyst with full spectral response.
In order to further achieve the purpose of the invention, the volume of the n-propanol solution is preferably 50-80 mL.
Preferably, the molar ratio of ammonium to tungsten in the solution A in the step (1) is 0.33-2: 1.
preferably, the molar ratio of fluorine to tungsten in the solution B in the step (2) is 3.73-14.9: 1.
preferably, the drying temperature in the step (3) is 40-60 ℃.
Compared with the prior art, the invention has the following advantages:
(1) compared with the single application of the existing patent to the tungsten bronze in the near infrared shielding performance, the invention expands the application of the tungsten bronze from the single heat insulation shielding field to the near infrared photocatalysis field by utilizing the characteristic of strong near infrared absorption of the tungsten bronze, and realizes the multifunctional application of the tungsten bronze material.
(2) According to the invention, the tungsten bronze material is doped and modified, the photocatalytic activity of the tungsten bronze material is improved by changing the composition and the structure of the tungsten bronze, and the photocatalytic activity of the tungsten bronze material is improved by using secondary synthesis means such as compounding, noble metal loading and the like instead of improving the photocatalytic activity of the tungsten bronze material by using secondary synthesis means, so that the problem of poor photocatalytic activity of the tungsten bronze material in a near-infrared region is fundamentally solved.
(3) Fluorine-doped ammonium tungsten bronzes still have a plasmon resonance effect and have strong absorption in the near infrared region. The defect that the traditional photocatalyst can only utilize ultraviolet light to catalyze light or can only utilize single near infrared light or near infrared light to catalyze low efficiency is overcome, and the light energy utilization rate and the near infrared light photocatalysis efficiency are improved.
(4) The fluorine-doped ammonium tungsten bronze synthesized by the method still has high degradation rate and stable activity after five times of circulating photocatalytic experiments, and can be stably used for a long time. The invention has simple experimental method, easy repetition of synthesis process and low requirement on experimental equipment. The fluorine-doped ammonium tungsten bronze can fully utilize ultraviolet-visible-near infrared light, has high-efficiency photocatalytic efficiency, and has wide application prospects in the aspects of environmental management and energy utilization.
Drawings
Fig. 1 is XRD patterns of fluorine-doped ammonium tungsten bronze and non-doped fluorine-doped ammonium tungsten bronze photocatalysts prepared in example 1 and comparative example 1.
FIG. 2 is an X-ray photoelectron spectroscopy (XPS) chart of the product obtained in example 1.
Fig. 3 shows near-infrared absorption spectra of fluorine-doped ammonium tungsten bronze and fluorine-free ammonium tungsten bronze prepared in example 1 and comparative example 1.
FIG. 4 is a graph showing the effect of ultraviolet photocatalytic degradation of rhodamine B on fluorine-doped ammonium tungsten bronze and fluorine-free ammonium tungsten bronze prepared in example 1 and comparative example 1.
FIG. 5 is a graph showing the effect of photocatalytic degradation of rhodamine B by visible light of fluorine-doped ammonium tungsten bronze and fluorine-free ammonium tungsten bronze prepared in example 1 and comparative example 1.
FIG. 6 is a graph showing the effect of near-infrared photocatalytic degradation of rhodamine B on fluorine-doped ammonium tungsten bronze and fluorine-free ammonium tungsten bronze prepared in example 1 and comparative example 1.
FIG. 7 is a graph showing the effect of the cycle test on fluorine-doped ammonium tungsten bronze prepared in example 1.
FIG. 8 is a mechanism diagram of the enhancement of near-infrared photocatalytic performance of fluorine-doped ammonium tungsten bronze prepared by the present invention.
Detailed Description
For a better understanding of the present invention, the present invention is further described below with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
Example 1
A preparation method of a full-spectrum response fluorine-doped ammonium tungsten bronze photocatalyst comprises the following steps:
1) weighing 60mL of n-propanol solution, putting the n-propanol solution into a 100mL beaker, weighing 0.1166g of ammonium acetate and 0.6g of tungsten chloride, adding the ammonium acetate and the tungsten chloride into the n-propanol solution, and performing ultrasonic treatment until the ammonium acetate and the tungsten chloride are dissolved to obtain a yellow solution;
2) the yellow solution was then transferred to a 100mL internal lining of a p-polyphenyl reaction vessel and 0.75mL of hydrofluoric acid solution was added dropwise to the solution.
3) And sealing the reaction kettle, putting the reaction kettle into an oven, reacting for 24 hours at 190 ℃, naturally cooling, respectively washing the sample for three times by using deionized water and ethanol, centrifuging, and drying at 60 ℃ to prepare the fluorine-doped ammonium tungsten bronze photocatalyst with full-spectrum response. The product obtained is (NH)4)0.33WO2.26F0.74。
Comparative example 1
1) Weighing 60mL of n-propanol solution, putting the n-propanol solution into a 100mL beaker, weighing 0.1166g of ammonium acetate and 0.6g of tungsten chloride, adding the ammonium acetate and the tungsten chloride into the n-propanol solution, and performing ultrasonic treatment until the ammonium acetate and the tungsten chloride are dissolved to obtain a yellow solution;
2) and transferring the yellow solution into a 100mL lining of a p-polyphenyl reaction kettle, sealing the reaction kettle, putting the reaction kettle into an oven, reacting for 24h at 190 ℃, naturally cooling, respectively washing the sample for three times by using deionized water and ethanol, centrifuging, and drying at 60 ℃ to prepare the pure ammonium tungsten bronze material.
Example 2
A preparation method of a full-spectrum response fluorine-doped ammonium tungsten bronze photocatalyst comprises the following steps:
(1) 60mL of n-propanol solution was weighed into a 100mL beaker, 0.1166g of ammonium acetate and 0.6g of tungsten chloride were weighed into the n-propanol solution, sonicated until dissolved to give a yellow solution, which was then transferred to a 100mL liner of a p-polyphenyl reaction vessel and 0.25mL of hydrofluoric acid solution was added dropwise to the solution. And sealing the reaction kettle, putting the reaction kettle into an oven, reacting for 24h at 190 ℃, naturally cooling, respectively washing the sample for three times by using deionized water and ethanol, centrifuging, and drying at 60 ℃ to obtain the fluorine-doped ammonium tungsten bronze photocatalyst with full-spectrum response. The product obtained is (NH)4)0.33WO2.46F0.54。
Example 3
A preparation method of a full-spectrum response fluorine-doped ammonium tungsten bronze photocatalyst comprises the following steps:
(1) 60mL of n-propanol solution was weighed into a 100mL beaker, 0.1166g of ammonium acetate and 0.6g of tungsten chloride were weighed into the n-propanol solution, sonicated until dissolved to give a yellow solution, which was then transferred to a 100mL inner liner of a p-polyphenyl reaction vessel and 1mL of hydrofluoric acid solution was added dropwise to the solution. And sealing the reaction kettle, putting the reaction kettle into an oven, reacting for 24h at 190 ℃, naturally cooling, respectively washing the sample for three times by using deionized water and ethanol, centrifuging, and drying at 60 ℃ to obtain the fluorine-doped ammonium tungsten bronze photocatalyst with full-spectrum response. The product obtained is (NH)4)0.33WO2.2F0.8。
Example 4
A preparation method of a full-spectrum response fluorine-doped ammonium tungsten bronze photocatalyst comprises the following steps:
(1) 50mL of n-propanol solution was weighed into a 100mL beaker, 0.0389g of ammonium acetate and 0.6g of tungsten chloride were weighed into the n-propanol solution, sonicated until dissolved to give a yellow solution, which was then transferred to a 100mL liner of a p-polyphenyl reaction vessel and 0.75mL of hydrofluoric acid solution was added dropwise to the solution. And sealing the reaction kettle, putting the reaction kettle into an oven, reacting for 24h at 190 ℃, naturally cooling, respectively washing the sample for three times by using deionized water and ethanol, centrifuging, and drying at 60 ℃ to obtain the fluorine-doped ammonium tungsten bronze photocatalyst with full-spectrum response. The product obtained is (NH)4)0.25WO2.26F0.74。
Example 5
A preparation method of a full-spectrum response fluorine-doped ammonium tungsten bronze photocatalyst comprises the following steps:
(1) 50mL of n-propanol solution was weighed into a 100mL beaker, 0.1166g of ammonium acetate and 0.6g of tungsten chloride were weighed into the n-propanol solution, sonicated until dissolved to give a yellow solution, which was then transferred to a 100mL liner of a p-polyphenyl reaction vessel and 0.5mL of hydrofluoric acid solution was added dropwise to the solution. And sealing the reaction kettle, putting the reaction kettle into an oven, reacting for 24h at 190 ℃, naturally cooling, respectively washing the sample for three times by using deionized water and ethanol, centrifuging, and drying at 60 ℃ to obtain the fluorine-doped ammonium tungsten bronze photocatalyst with full-spectrum response. The product obtained is (NH)4)0.33WO2.37F0.63。
Example 6
A preparation method of a full-spectrum response fluorine-doped ammonium tungsten bronze photocatalyst comprises the following steps:
(1) 80mL of n-propanol solution was weighed into a 100mL beaker, 0.2332g of ammonium acetate and 0.6g of tungsten chloride were weighed into the n-propanol solution, sonicated until dissolved to give a yellow solution, which was then transferred to a 100mL liner of a p-polyphenyl reaction vessel and 0.75mL of hydrofluoric acid solution was added dropwise to the solution. Sealing the reaction kettle, placing the reaction kettle in an oven to react for 24h at 190 ℃, naturally cooling, and usingAnd respectively washing the sample for three times by using ionized water and ethanol, centrifuging, and drying at 60 ℃ to obtain the fluorine-doped ammonium tungsten bronze photocatalyst with full-spectrum response. The product obtained is (NH)4)0.25WO2.26F0.74。
Example 7
A preparation method of a full-spectrum response fluorine-doped ammonium tungsten bronze photocatalyst comprises the following steps:
(1) 60mL of n-propanol solution was weighed into a 100mL beaker, 0.1166g of ammonium acetate and 0.6g of tungsten chloride were weighed into the n-propanol solution, sonicated until dissolved to give a yellow solution, which was then transferred to a 100mL liner of a p-polyphenyl reaction vessel and 0.75mL of hydrofluoric acid solution was added dropwise to the solution. And sealing the reaction kettle, putting the reaction kettle into an oven, reacting for 24h at 180 ℃, naturally cooling, washing the sample for three times by using deionized water and ethanol respectively, centrifuging, and drying at 60 ℃ to obtain the fluorine-doped ammonium tungsten bronze photocatalyst with full-spectrum response. The product obtained is (NH)4)0.33WO2.26F0.74。
Example 8
A preparation method of a full-spectrum response fluorine-doped ammonium tungsten bronze photocatalyst comprises the following steps:
(1) 60mL of n-propanol solution was weighed into a 100mL beaker, 0.1166g of ammonium acetate and 0.6g of tungsten chloride were weighed into the n-propanol solution, sonicated until dissolved to give a yellow solution, which was then transferred to a 100mL liner of a p-polyphenyl reaction vessel and 0.75mL of hydrofluoric acid solution was added dropwise to the solution. And sealing the reaction kettle, putting the reaction kettle into an oven, reacting for 24h at 220 ℃, naturally cooling, respectively washing the sample for three times by using deionized water and ethanol, centrifuging, and drying at 60 ℃ to obtain the fluorine-doped ammonium tungsten bronze photocatalyst with full-spectrum response. The product obtained is (NH)4)0.33WO2.26F0.74。
The ultraviolet-visible-near infrared photocatalysis experiment and cycle experiment test method of the full-spectrum response fluorine-doped ammonium tungsten bronze photocatalyst obtained in the embodiment is as follows:
ultraviolet light photocatalytic effect test of sample (photocatalytic degradation of rhodamine B for example)
Preparing 50mg/L and 20mg/L rhodamine B solution. (1) 0.05g of the sample of example 1 and the sample of comparative example 1 are respectively weighed and dispersed in 50mL of 50mg/L rhodamine B solution, and the sample is adsorbed for 5 hours under the dark condition, so that the sample reaches saturated adsorption.
(2) After adsorption was complete, the sample was centrifuged and the saturated adsorption was transferred to 50mL of 20mg/L rhodamine solution B and magnetically stirred in the dark for 30min to reach adsorption equilibrium. (3) A high-pressure mercury lamp of 500W is used as an ultraviolet light source, the illumination is carried out for 3h, and samples are taken every 30 min. (4) Centrifuging the obtained solution, taking supernatant, testing the absorbance of the rhodamine B solution in different illumination time by using a cary-60 type ultraviolet-visible spectrophotometer produced by Agilent, and calculating according to Lambert beer's law to obtain the concentration of the rhodamine B solution in different illumination time. (5) And drawing a degradation rate graph of the sample by taking the illumination time as an abscissa and the concentration as an ordinate.
Visible light photocatalytic effect test of sample (photocatalytic degradation of rhodamine B for example)
50mg/L and 20mg/L rhodamine B solutions are respectively prepared. (1) 0.05g of the sample of example 1 and the sample of comparative example 1 are respectively weighed and dispersed in 50mL of 50mg/L rhodamine B solution, and the sample is adsorbed for 5 hours under the dark condition, so that the sample reaches saturated adsorption. (2) After adsorption was complete, the sample was centrifuged and the saturated adsorption was transferred to 50mL of 20mg/L rhodamine solution B and magnetically stirred in the dark for 30min to reach adsorption equilibrium. (3) A300W xenon lamp is used as a visible light source, the light is irradiated for 2h, and samples are taken every 30 min. (4) Centrifuging the obtained solution, taking supernatant, testing the absorbance of the rhodamine B solution in different illumination time by using a cary-60 type ultraviolet-visible spectrophotometer produced by Agilent, and calculating according to Lambert beer's law to obtain the concentration of the rhodamine B solution in different illumination time. (5) And drawing a degradation rate graph of the sample by taking the illumination time as an abscissa and the concentration as an ordinate.
Near infrared light photocatalytic effect test of sample (photocatalytic degradation of rhodamine B for example)
50mg/L and 20mg/L rhodamine B solutions are respectively prepared. (1) 0.05g of the sample of example 1 and the sample of comparative example 1 are respectively weighed and dispersed in 50mL of 50mg/L rhodamine B solution, and the sample is adsorbed for 5 hours under the dark condition, so that the sample reaches saturated adsorption. (2) After adsorption was complete, the sample was centrifuged and the saturated adsorption was transferred to 50mL of 20mg/L rhodamine solution B and magnetically stirred in the dark for 30min to reach adsorption equilibrium. (3) A375W infrared lamp is used as a near infrared light source, light with the wavelength less than 760nm is filtered by a filter, the light is irradiated for 3 hours, and samples are taken every 30 min. (4) Centrifuging the obtained solution, taking supernatant, testing the absorbance of the rhodamine B solution in different illumination time by using a cary-60 type ultraviolet-visible spectrophotometer produced by Agilent, and calculating according to Lambert beer's law to obtain the concentration of the rhodamine B solution in different illumination time. (5) And drawing a degradation rate graph of the sample by taking the illumination time as an abscissa and the concentration as an ordinate.
Cyclic experimental test method (example of photocatalytic degradation of rhodamine B)
(1) 0.05g of example 1 is weighed and dispersed in 50mL of 50mg/L rhodamine B solution, and the sample is adsorbed for 5 hours under the dark condition, so that the sample is saturated and adsorbed. (2) After adsorption was complete, the sample was centrifuged and the saturated adsorption was transferred to 50mL of 20mg/L rhodamine solution B and magnetically stirred in the dark for 30min to reach adsorption equilibrium. (3) A375W infrared lamp is used as a near infrared light source, light with the wavelength less than 760nm is filtered by a filter, the light is irradiated for 3 hours, and samples are taken every 30 min. (4) Centrifuging the obtained solution, taking supernatant, testing the absorbance of the rhodamine B solution at different illumination times by using a cary-60 type ultraviolet-visible spectrophotometer produced by Agilent, calculating the concentration of the rhodamine B solution at different illumination times according to Lambert beer law (5), centrifuging the solution after illumination, and repeating the steps (2), (3) and (4); this was repeated four times.
FIG. 1 is an XRD pattern of the photocatalyst prepared in example 1 and comparative example 1 using an X-ray diffractometer of X' Pert PRO type by Pasacaceae, the Netherlands, using a Cu target KαAnd (4) rays. The analysis shows that the diffraction peak and hexagonal (NH) of comparative example 14)0.33WO3(JCPDS No.42-0452) demonstrates that the product of comparative example 1 is (NH)4)0.33WO3. Diffraction peaks of example 1 compared to diffraction pattern of comparative example 1Slightly offset to a small angle. From bragg equation 2dsin θ ═ n λ (where d is the interplanar spacing, θ is the diffraction angle, and λ is the incident wavelength), it is known that the interplanar spacing increases. This is due to substitution of fluorine atoms [ WO6]Lattice oxygen atoms in octahedra, so cause diffraction peaks to shift to small angles. The shift in the diffraction peak thus demonstrates the successful incorporation of the F ion (NH)4)0.33WO3. The F doping amount can be obtained by X-ray photoelectron spectroscopy (XPS) analysis. The F/W ratio of example 1 was 0.74 according to XPS test, and thus the product obtained in example 1 was (NH)4)0.33WO2.26F0.74。
FIG. 2 is X-ray photoelectron spectroscopy (XPS) of example 1. As can be seen from fig. 2, the main element of comparative example 1 is O, W, N, while the main element of example 1 is F, O, W, N. Further demonstrating the successful incorporation of F ions into the ammonium tungsten bronze crystals.
Fig. 3 is a near infrared light absorption spectrum of the photocatalyst prepared in example 1 and comparative example 1. The instrument used was Lambda950, platinum Elmer instruments Inc. USA. It can be seen that the fluorine-doped ammonium tungsten bronze prepared in example 1 has significantly higher absorption in the near infrared region than the ammonium tungsten bronze prepared in comparative example 1. It is found by calculation that the absorbance of comparative example 1 in the near infrared region is 52.8%, and the absorbance of example 1 in the near infrared region is increased to 70.0%. Therefore, after doping F, the absorption capacity of example 1 in the near infrared region is greatly enhanced, which means that the F-doped ammonium tungsten bronze can absorb more sunlight, so that more photogenerated carriers can be excited, and the photocatalytic activity can be improved.
Fig. 4 is a graph showing the ultraviolet photocatalytic effect of fluorine-doped ammonium tungsten bronze and ammonium tungsten bronze prepared in example 1 and comparative example 1. As can be seen, the concentration of the rhodamine B solution of the ammonium tungsten bronze prepared in the comparative example 1 is reduced by 19 percent through illumination of ultraviolet light for 180 min; the rhodamine B solution concentration of the fluorine-doped ammonium tungsten bronze prepared in example 1 decreased by 36%.
Fig. 5 is a graph showing the visible light photocatalytic effect of fluorine-doped ammonium tungsten bronze and ammonium tungsten bronze prepared in example 1 and comparative example 1. As can be seen, the concentration of the rhodamine B solution of the ammonium tungsten bronze prepared in the comparative example 1 is reduced by 51 percent through the illumination of 120min ultraviolet light; the rhodamine B solution concentration of the fluorine-doped ammonium tungsten bronze prepared in example 1 decreased by 93%.
Fig. 6 is a graph showing the near-infrared photocatalytic effect of fluorine-doped ammonium tungsten bronze and ammonium tungsten bronze prepared in example 1 and comparative example 1. As can be seen, the concentration of the rhodamine B solution of the ammonium tungsten bronze prepared in the comparative example 1 is reduced by 20% through the illumination of 120min ultraviolet light; the rhodamine B solution concentration of the fluorine-doped ammonium tungsten bronze prepared in example 1 decreased by 83%.
The ultraviolet-visible-near infrared light photocatalysis performance of the fluorine-doped ammonium tungsten bronze is superior to that of the non-fluorine-doped ammonium tungsten bronze, particularly the near infrared light photocatalysis effect, and the near infrared light photocatalysis performance of the fluorine-doped ammonium tungsten bronze is four times that of the non-fluorine-doped ammonium tungsten bronze.
FIG. 7 is a cycle experiment for fluorine doped ammonium tungsten bronze prepared in example 1. It can be seen from the figure that, after five times of near-infrared light photocatalysis, the fluorine-doped ammonium tungsten bronze prepared in example 1 still has stable photocatalytic performance, and provides possibility for long-term stable practical application of the bronze.
FIG. 8 is a mechanism diagram of the enhancement of near-infrared photocatalytic performance of fluorine-doped ammonium tungsten bronze prepared by the invention. The enhancement mechanism is divided into two parts: on the one hand, the doped fluoride ion does not equivalently replace WO6The position of lattice oxygen in the octahedron, free electrons are generated. And W in ammonium tungsten bronze6+Is reduced into W by electrons5+Result in W5+The concentration is increased. High concentration of W5+Formation of defect energy level (W) below the conduction band of ammonium tungsten bronze5+). Under near infrared light irradiation, electrons in the valence band are excited by the excited band defect level (W)5+) The excited electrons react with oxygen to form O2 -Leaving a hole in the valence band, which reacts with water to form OH; on the other hand, a large number of free electrons generated by fluorine doping exist in the vicinity of the fermi level, and the local plasmon resonance effect of fluorine-doped ammonium tungsten bronze can be excited by near-infrared light due to the existence of these surface electrons. Therefore, under the excitation of near infrared light, free electrons near the Fermi level are excited to the conduction band to form plasmaHot electrons. These plasma thermoelectrons can generate O with oxygen2 -(ii) a The separation of electrons and holes can be promoted by a strong electric field caused by the local plasma resonance of fluorine-doped ammonium tungsten bronze. O produced in this process2 -、·OH、h+Can degrade the rhodamine B. Due to local plasma resonance, the near-infrared absorption of the fluorine-doped ammonium tungsten bronze is enhanced, and electron holes are generated and separated, and the near-infrared photocatalysis performance of the fluorine-doped ammonium tungsten bronze is enhanced under the combined action of the two.
The above effects are mainly illustrated by selecting the product of the example 1 and comparing the product with the product of the comparative example 1, and the effects of other examples are basically consistent with the effects of the example 1 and are not repeated meaningfully.
From the test results of the above embodiments and the accompanying drawings, it can be seen that the photocatalyst of the present invention realizes the ultraviolet-visible-near infrared light response, the degradation rate of the photocatalyst is 36% -65% in 180min under ultraviolet light, the degradation rate of the photocatalyst is 87% -96% in 120min under visible light, and the degradation rate of the photocatalyst is 47% -83% in 180min under near infrared light. And the photocatalyst still has high degradation rate and stable activity after five times of photocatalytic experiments, and can be stably used for a long time. The invention solves the problems of insufficient sunlight utilization and low photocatalytic efficiency of the traditional photocatalyst and solves the problem of low near infrared photocatalytic efficiency of tungsten bronze materials. According to the invention, the electron distribution and the energy band structure of the ammonium tungsten bronze are improved in a fluorine doping mode, so that the ammonium tungsten bronze shows higher photocatalytic activity in all bands while the absorption characteristic of the ammonium tungsten bronze on near infrared light is kept, and the application field of the tungsten bronze is expanded. Compared with the existing full-spectrum photocatalyst, the preparation method has the advantages of simple preparation process, wide raw material source, low cost and high photocatalytic activity, and has wide application prospect in the environmental protection fields of sewage treatment, self-cleaning and the like.
It should be noted that the above embodiments do not limit the technical solution of the present invention in any way. Any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention still fall within the scope of the technical solution of the present invention.
Claims (9)
1. A preparation method of a fluorine-doped ammonium tungsten bronze photocatalyst with full-spectrum response is characterized by comprising the following steps:
1) adding tungsten chloride and ammonium acetate into an n-propanol solution, and dissolving by ultrasonic to obtain a solution A;
2) adding a hydrofluoric acid solution into the solution A to obtain a solution B, and reacting for 12-72 hours at the temperature of 180-220 ℃;
3) and (3) naturally cooling the reaction product obtained in the step (2), washing and drying to obtain the fluorine-doped ammonium tungsten bronze photocatalyst with full-spectrum response.
2. The method of claim 1, wherein the method comprises the steps of: the molar ratio of ammonium to tungsten atoms in the solution A is 0.33-2: 1.
3. the method of claim 1, wherein the method comprises the steps of: the molar ratio of fluorine atoms to tungsten atoms in the solution B is 3.73-14.9: 1.
4. the method of claim 1, wherein the method comprises the steps of: the step of adding the hydrofluoric acid solution into the solution A is to add the solution A obtained in the step 1) into a reaction kettle with the p-polyphenyl as a lining, and then add the hydrofluoric acid solution.
5. The method of claim 1, wherein the method comprises the steps of: the drying temperature in the step (3) is 40-60 ℃.
6. The method of claim 1, wherein the method comprises the steps of: the washing is respectively washing 3-5 times by deionized water and absolute ethyl alcohol.
7. The method of claim 1, wherein the method comprises the steps of: the concentration of the hydrofluoric acid added in the step (2) is 40 percent by weight.
8. A fluorine-doped ammonium tungsten bronze photocatalyst with full-spectrum response is characterized in that: which is obtained by the production method according to any one of claims 1 to 8; the chemical formula of the fluorine-doped ammonium tungsten bronze photocatalyst is (NH)4)xWO3-yFy(ii) a Wherein x is more than or equal to 0.25 and less than or equal to 0.33, and y is more than or equal to 0.54 and less than or equal to 0.8.
9. The fluorine doped ammonium tungsten bronze photocatalyst having a full spectrum response of claim 8, wherein: the fluorine-doped ammonium tungsten bronze photocatalyst has a degradation rate of 36-65% in 180min under ultraviolet light, a degradation rate of 87-96% in 120min under visible light, and a degradation rate of 47-83% in 180min under near infrared light.
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