Copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material and preparation method thereof

Abstract

The present invention provides a copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material and a preparation method thereof. The composite photocatalytic material comprises indium zinc sulfide and copper hydroxyphosphate supported on the indium zinc sulfide. The indium zinc sulfide is a microsphere formed by stacking flaky indium zinc sulfide. The indium zinc sulfide comprises 90% to 99% by weight of the indium zinc sulfide in the composite photocatalytic material, and the copper hydroxyphosphate comprises 1% to 10% by weight of the indium zinc sulfide in the composite photocatalytic material. The composite photocatalytic material provided by the present invention can produce photocatalytic properties in response to sunlight with a wavelength of 300 to 2500 nm. The present invention broadens the response range of the photocatalytic material to sunlight and improves the response performance of the photocatalytic material to sunlight, effectively improving the degradation effect of the photocatalytic material on organic pollutants.

Description

Technical Field

[0001] The invention belongs to the technical field of photocatalytic materials and water treatment, and relates to a hydroxy copper phosphate / sulfur indium zinc composite photocatalytic material and a preparation method thereof. Background Art

[0002] With the continuous development of industry, the problem of water pollution caused by printing and dyeing wastewater (such as organic dyes such as methylene blue) is very serious. Therefore, the removal of organic dyes in water bodies is of great significance to the sustainable development of the ecological environment. Photocatalytic technology plays an important role in the field of water treatment. Photocatalytic technology is a technology that degrades organic pollutants in water bodies through oxidation or reduction reactions after photocatalysts absorb sunlight, separate electrons and holes. Photocatalytic technology is highly dependent on the catalytic activity of photocatalysts, so the development of efficient and economical photocatalysts is particularly important.

[0003] Photocatalytic technology is clean, efficient, low-cost, and stable, and has been an important means of removing difficult-to-degrade organic pollutants in recent years. Currently, researchers commonly use photocatalysts such as titanium dioxide and carbon nitride, but these traditional catalysts only respond to ultraviolet light and some visible light. Ultraviolet light, visible light, and infrared light account for 5%, 46%, and 49% of sunlight, respectively, so these traditional catalysts have extremely low utilization rates of sunlight. Therefore, synthesizing photocatalysts with good response to infrared light is very beneficial for improving the utilization rate of sunlight and will also be of great significance for achieving efficient purification of organic pollutants in water bodies. Summary of the Invention

[0004] In response to the problem that existing photocatalytic materials have low utilization rate of sunlight, the present invention provides a copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material and a preparation method thereof, so as to broaden the response range of the photocatalytic material to sunlight and improve the response performance of the photocatalytic material to sunlight, thereby improving the degradation effect of the photocatalytic material on organic pollutants.

[0005] In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is as follows:

[0006] A copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material comprises indium zinc sulfide and copper hydroxyphosphate supported on the indium zinc sulfide. The indium zinc sulfide is a microsphere formed by accumulation of indium zinc sulfide in a flaky structure. The indium zinc sulfide content in the composite photocatalytic material is 90wt%-99wt%, and the copper hydroxyphosphate content in the composite photocatalytic material is 1wt%-10wt%.

[0007] In the technical solution of the copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material, the composite photocatalytic material is in the form of microspheres. Furthermore, the particle size of the composite photocatalytic material is 2 to 3 μm.

[0008] In the technical solution of the above-mentioned copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material, the copper hydroxyphosphate is partially loaded on the surface of the indium zinc sulfide and partially loaded in the pore structure of the indium zinc sulfide.

[0009] In the technical solution of the copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material, the size of the copper hydroxyphosphate does not exceed 1 μm. The morphology of the copper hydroxyphosphate has no significant effect on the photocatalytic performance of the composite photocatalytic material, and the morphology of the copper hydroxyphosphate can be plate-like, block-like, or granular.

[0010] In the technical solution of the above-mentioned copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material, the morphology of the indium zinc sulfide will affect the photocatalytic performance of the composite photocatalytic material. Preferably, the indium zinc sulfide is a flower-shaped microsphere formed by the accumulation of indium zinc sulfide with a flake structure. Compared with other morphologies, the flower-shaped microspheres have a relatively larger specific surface area, which is not only beneficial to the loading of copper hydroxyphosphate, but also beneficial to increasing the degree of contact with pollutants.

[0011] In the technical solution of the above-mentioned copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material, the composite photocatalytic material can respond to sunlight with a wavelength of 300 to 2000 nm and produce photocatalytic performance. Through solid ultraviolet diffuse reflectance spectroscopy testing, it was found that the composite photocatalytic material of the present invention has a responsive performance to light with a wavelength of 300 to 2500 nm (the maximum wavelength measured by solid ultraviolet diffuse reflectance spectroscopy is 2500 nm). In other words, the composite photocatalytic material of the present invention responds to sunlight of almost the entire wavelength, which can solve the problem that existing photocatalysts, such as titanium dioxide and carbon nitride, only respond to ultraviolet light and part of visible light, and have very limited utilization of sunlight.

[0012] The present invention also provides a method for preparing the above-mentioned copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material, which comprises the following steps:

[0013] (1) fully dispersing copper hydroxyphosphate in water to form a copper hydroxyphosphate dispersion with a concentration of 0.01 to 0.5 g / L, and fully dispersing zinc indium sulfide in water to form a zinc indium sulfide dispersion with a concentration of 1 to 6 g / L, wherein the zinc indium sulfide is a flower-shaped microsphere formed by the accumulation of zinc indium sulfide in a sheet structure;

[0014] (2) According to the mass ratio of copper hydroxyphosphate to indium zinc sulfide of (1-10): (90-99), the copper hydroxyphosphate dispersion was added dropwise to the indium zinc sulfide dispersion, fully ultrasonically dispersed, and then stirred for 10-15 hours. The resulting solid phase was collected, washed with ethanol and water, and dried to obtain a copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material.

[0015] In the technical solution of the preparation method of the above-mentioned copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material, the preparation method of the indium zinc sulfide is as follows:

[0016] Zinc acetate and indium chloride are dissolved in water, and then thioacetamide is added and stirred thoroughly. The resulting mixed solution is added to an autoclave, which is sealed and reacted at 110-160° C. for 8-12 hours. The resulting solid phase product is washed with water and ethanol in sequence and dried to obtain sulfindium zinc. The mass ratio of zinc acetate, indium chloride and thioacetamide in the mixed solution is controlled to be 1:(1.8-2.2):(1.8-2.2), and the concentration of zinc acetate is 3.5-4.5 g / L.

[0017] In the technical solution of the preparation method of the above-mentioned copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material, a feasible preparation method of copper hydroxyphosphate is as follows:

[0018] Copper nitrate and disodium hydrogen phosphate are dissolved in water, and the pH value is adjusted to 6-8. The resulting mixed solution is then transferred to an autoclave, which is sealed and reacted at 110-160° C. for 8-12 hours. The resulting solid product is washed with ethanol and ultrapure water, and dried to obtain copper hydroxyphosphate. The mass ratio of copper nitrate to disodium hydrogen phosphate in the mixed solution is controlled to be (1-1.1):(1-1.1), and the concentration of copper nitrate is 18-20 g / L.

[0019] In step (2) of the technical solution of the above-mentioned method for preparing the copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material, ultrasound is preferably performed at a frequency of 20 to 40 kHz, and the ultrasonic dispersion time is preferably controlled to be 1 to 3 hours.

[0020] In step (2) of the technical solution of the above-mentioned method for preparing the copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material, the suitable stirring speed is 200-450 r / min, and the more preferred stirring speed is 250-350 r / min.

[0021] The present invention also provides the use of the aforementioned copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material for the photocatalytic degradation of organic pollutants. During use, the composite photocatalytic material is added to wastewater containing organic pollutants to be treated. Under sunlight or visible and infrared light conditions, the organic pollutants in the wastewater are agitated and degraded. When the removal rate of the organic pollutants reaches a substantially balanced state, the composite photocatalytic material is separated, thereby completing the wastewater treatment. The separated composite photocatalytic material can be reused. The organic pollutants include organic dyes.

[0022] The main reasons why the copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material provided by the present invention has excellent photocatalytic performance are as follows:

[0023] The present invention uniformly loads hydroxy copper phosphate on flower-shaped sulfur indium zinc microspheres formed by stacking sulfur indium zinc in a sheet structure through an ultrasonic combined with stirring method, thereby realizing the composite of hydroxy copper phosphate and sulfur indium zinc. The response range of pure sulfur indium zinc to sunlight is widened to the infrared light region, which enhances the utilization rate of the photocatalytic material to sunlight, promotes the separation of photogenerated electrons and holes, and is beneficial to the catalytic degradation reaction of organic pollutants (such as organic dyes). Pure sulfur indium zinc only responds to sunlight with a wavelength of 550nm or less, and electrons and holes are easily recombined after separation by excitation. The composite photocatalytic material provided by the present invention not only broadens the response wavelength of sunlight to the infrared region, but we have found through solid ultraviolet diffuse reflectance spectroscopy that the composite photocatalytic material has responsive performance to light with a wavelength of 300 to 2500nm, and after the separation of electrons and holes, electrons are transferred from sulfur indium zinc to hydroxy copper phosphate, making it more difficult for electrons and holes to recombine, thereby increasing the activity of the photocatalytic material.

[0024] Compared with the prior art, the technical solution provided by the present invention produces the following beneficial technical effects:

[0025] 1. The present invention provides a copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material. The composite photocatalytic material comprises indium zinc sulfide and copper hydroxyphosphate supported on the indium zinc sulfide. The indium zinc sulfide is formed by stacking flaky indium zinc sulfide into microspheres. The indium zinc sulfide content in the composite photocatalytic material is 90% to 99% by weight, and the copper hydroxyphosphate content in the composite photocatalytic material is 1% to 10% by weight. The composite photocatalytic material can respond to sunlight with a wavelength of 300 to 2000 nm to produce photocatalytic properties, effectively improving the utilization rate of sunlight. This solves the problem that existing photocatalysts such as titanium dioxide and carbon nitride only respond to ultraviolet light and some visible light, resulting in very limited sunlight utilization.

[0026] 2. The present invention has experimentally confirmed that the composite photocatalytic material provided by the present invention has good degradation performance for methylene blue and methyl orange under visible light and infrared light irradiation conditions, and the degradation rate is significantly higher than that of individual zinc indium sulfide and copper hydroxyphosphate. At the same time, the composite photocatalytic material provided by the present invention has excellent recycling performance. After being recycled three times, the degradation rate of methylene blue only slightly decreases, which is very beneficial for reducing the actual treatment cost of organic wastewater.

[0027] 3. The present invention also provides a method for preparing the aforementioned copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material. The copper hydroxyphosphate is loaded onto indium zinc sulfide by ultrasound combined with stirring. On the one hand, the indium zinc sulfide is a flower-shaped microsphere formed by stacking the indium zinc sulfide sheet structure, which facilitates the effective loading of the copper hydroxyphosphate and increases contact with pollutants during wastewater treatment. On the other hand, ultrasound not only promotes the uniform loading of the copper hydroxyphosphate but also increases active sites, all of which are beneficial for the photocatalytic degradation of pollutants and the engineering application of the composite photocatalytic material. Furthermore, the method of the present invention is simple to operate, can address the shortcomings of existing hydrothermal methods for synthesizing composite materials, such as high energy consumption and inconvenient operation, and can help reduce the cost of synthesizing catalytic materials.

[0028] 3. The method described in the present invention first utilizes a hydrothermal method to synthesize zinc indium sulfide and copper hydroxyphosphate. By controlling the process conditions and parameters, the morphology and structure of the materials can be accurately controlled, thereby ensuring the accuracy of the composite photocatalytic material and the consistency of the performance of the composite photocatalytic material. This provides a guarantee for the stability of the organic pollutant degradation effect of the composite photocatalytic material in engineering applications.

[0029] 4. In the method described in the present invention, copper hydroxyphosphate is evenly loaded on the surface of indium zinc sulfide by ultrasound + stirring, and a copper hydroxyphosphate / indium zinc sulfide photocatalyst can be formed after centrifugation. This solves the shortcomings of the existing hydrothermal method for synthesizing composite materials, such as high energy consumption and inconvenient operation, and reduces the cost of synthesizing catalytic materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is the SEM image of the composite photocatalytic material prepared in Example 1.

[0031] Figure 2 This is an EDS graph of the composite photocatalytic material prepared in Example 1, which shows the distribution of Zn on the surface of the composite photocatalytic material.

[0032] Figure 3 This is an EDS graph of the composite photocatalytic material prepared in Example 1, which shows the distribution of In on the surface of the composite photocatalytic material.

[0033] Figure 4 This is an EDS graph of the composite photocatalytic material prepared in Example 1, which shows the distribution of S on the surface of the composite photocatalytic material.

[0034] Figure 5 This is an EDS graph of the composite photocatalytic material prepared in Example 1, which shows the distribution of Cu on the surface of the composite photocatalytic material.

[0035] Figure 6This is an EDS graph of the composite photocatalytic material prepared in Example 1, which shows the distribution of O on the surface of the composite photocatalytic material.

[0036] Figure 7 This is an EDS graph of the composite photocatalytic material prepared in Example 1, which shows the distribution of P on the surface of the composite photocatalytic material.

[0037] Figure 8 This is a comparison chart of the rates of treating methylene blue using the composite photocatalytic material prepared in Example 1 and the sulfur indium zinc prepared in Comparative Example 1.

[0038] Figure 9 The degradation rate of methylene blue by the composite photocatalytic material changes with the number of cycles. DETAILED DESCRIPTION

[0039] The following examples further illustrate the copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material provided by the present invention, its preparation method, and its photocatalytic effect. It is important to note that the following examples are intended only to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by persons skilled in the art to the present invention based on the above-mentioned disclosure and to implement the present invention remain within the scope of protection of the present invention.

[0040] Example 1

[0041] In this example, a copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material was prepared and the treatment effect of the composite photocatalytic material on dye wastewater was tested. The steps are as follows:

[0042] (1) Preparation of carrier materials

[0043] Zinc acetate and indium chloride were weighed and added to ultrapure water, stirred for 30 minutes, and then thioacetamide (TAA) was added and stirred for another 30 minutes. The resulting mixture was added to an autoclave, which was sealed and reacted at 120°C for 10 hours. The mixture was naturally cooled to room temperature, and the resulting solid phase product was washed sequentially with ultrapure water and ethanol, centrifuged, and the solid phase was collected and dried at 60°C to obtain zinc sulfide indium. In this step, the mass ratio of zinc acetate, indium chloride, and thioacetamide in the mixture was controlled to be 1:2:2, and the concentration of zinc acetate was 4 g / L.

[0044] (2) Preparation of copper hydroxyphosphate

[0045] Copper nitrate and disodium hydrogen phosphate were added to ultrapure water and stirred until dissolved. The pH was adjusted to 7, and the resulting mixture was transferred to an autoclave. The autoclave was sealed and reacted at 120°C for 10 hours. The resulting solid phase product was washed with ethanol and ultrapure water to remove impurities, centrifuged, and the solid phase was collected and dried at 60°C to obtain copper hydroxyphosphate. In this step, the mass ratio of copper nitrate to disodium hydrogen phosphate in the mixture was controlled to be 1:1, and the concentration of copper nitrate was 18.7 g / L.

[0046] (3) Load

[0047] Copper hydroxyphosphate was fully dispersed in ultrapure water to form a 0.625 g / L copper hydroxyphosphate dispersion, and indium zinc sulfide was fully dispersed in ultrapure water to form a 5.625 g / L indium zinc sulfide dispersion. The copper hydroxyphosphate dispersion was dropwise added to the indium zinc sulfide dispersion in a mass ratio of 10:90. The mixture was ultrasonicated at a frequency of 40 kHz for 2 hours, then stirred at 350 rpm for 12 hours. The solid phase product was separated, washed three times with ethanol and ultrapure water, and centrifuged to collect the solid phase. The resulting solid phase was dried at 60°C to obtain a micron-sized copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material.

[0048] The copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material prepared in this example was measured by SEM-EDS. The results are as follows: Figures 1 to 7 As shown, Figure 1 is the SEM image of the composite photocatalytic material. Figures 2 to 7 This is the EDS diagram of the composite photocatalytic material. Figure 2 、 3 , 4, 5, 6, and 7 respectively show the distribution of Zn, In, S, Cu, O, and P on the surface of the composite photocatalytic material. Figure 1 It can be seen that the composite photocatalytic material is a flower-shaped microsphere with a particle size of 2 to 3 μm. Figures 2 to 7 It can be seen that each element of Zn, In, S, Cu, O and P can be detected on the composite photocatalytic material, which verifies that copper hydroxyphosphate is successfully loaded on zinc indium sulfide in this embodiment, and the distribution of copper hydroxyphosphate on the surface of the composite photocatalytic material is very uniform.

[0049] The composite photocatalytic material prepared in this example is used to treat simulated wastewater, where the simulated wastewater is a methylene blue solution with a concentration of 20 mg / L.

[0050] Take 50mL of simulated wastewater, add 15mg of composite photocatalytic material to the simulated wastewater, and treat the wastewater under visible light and infrared light source (the wavelength range of the infrared light source is 400-3000nm) under constant temperature and stirring conditions at 20°C. During the wastewater treatment process, samples are taken at intervals, centrifuged at a speed of 8000r / min for 5min, and the supernatant is taken to detect the concentration of methylene blue. The removal rate and degradation rate of methylene blue are calculated. The results show that the degradation rate of methylene blue by the composite photocatalytic material prepared in this embodiment is 0.02min -1 , the degradation rate diagram is as follows Figure 8 As shown, Figure 8 C0 and C in t They represent the initial concentration of methylene blue and the concentration after degradation for a certain period of time, respectively.

[0051] Comparative Example 1

[0052] In this comparative example, sulfur indium zinc was prepared and its wastewater treatment effect was tested, and the steps were as follows:

[0053] Zinc acetate and indium chloride were weighed and added to ultrapure water, stirred for 30 minutes, and then thioacetamide (TAA) was added and stirred for another 30 minutes. The resulting mixture was added to an autoclave, which was sealed and reacted at 120°C for 10 hours. The mixture was naturally cooled to room temperature, and the resulting solid phase product was washed sequentially with ultrapure water and ethanol, centrifuged, and the solid phase was collected and dried at 60°C to obtain zinc sulfide indium. In this step, the mass ratio of zinc acetate, indium chloride, and thioacetamide in the mixture was controlled to be 1:2:2, and the concentration of zinc acetate was 4 g / L.

[0054] The sulfur indium zinc prepared in this comparative example is used to treat simulated wastewater, where the simulated wastewater is a methylene blue solution with a concentration of 20 mg / L.

[0055] Take 50mL of simulated wastewater, add 15mg of sulfur indium zinc prepared in this comparative example to the simulated wastewater, and treat the wastewater under visible light and infrared light source (the wavelength range of the infrared light source is 400-3000nm) under constant temperature stirring conditions of 20°C. During the wastewater treatment process, samples are taken at intervals, centrifuged at a speed of 8000r / min for 5min, and the supernatant is taken to detect the concentration of methylene blue. The removal rate and degradation rate of methylene blue are calculated. The results show that the degradation rate of methylene blue by sulfur indium zinc prepared in this comparative example is 0.002min -1 , the degradation rate diagram is as follows Figure 8 As shown, Figure 8 C0 and C in t They represent the initial concentration of methylene blue and the concentration after degradation for a certain period of time, respectively.

[0056] Comparative Example 2

[0057] In this comparative example, copper hydroxyphosphate was prepared and its wastewater treatment effect was tested, and the steps were as follows:

[0058] Copper nitrate and disodium hydrogen phosphate were added to ultrapure water and stirred until dissolved. The pH was adjusted to 7, and the resulting mixture was transferred to an autoclave. The autoclave was sealed and reacted at 120°C for 10 hours. The resulting solid phase product was washed with ethanol and ultrapure water to remove impurities, centrifuged, and the solid phase was collected and dried at 60°C to obtain pure copper hydroxyphosphate. In this step, the mass ratio of copper nitrate to disodium hydrogen phosphate in the mixture was controlled to be 1:1, and the concentration of copper nitrate was 18.7 g / L.

[0059] The copper hydroxyphosphate prepared in this comparative example is used to treat simulated wastewater, where the simulated wastewater is a methylene blue solution with a concentration of 20 mg / L.

[0060] Take 50mL of simulated wastewater, add 15mg of hydroxy copper phosphate prepared in this comparative example to the simulated wastewater, and treat the wastewater under visible light and infrared light source (the wavelength range of the infrared light source is 400-3000nm) under constant temperature stirring conditions of 20°C. During the wastewater treatment process, samples are taken at intervals, centrifuged at a speed of 8000r / min for 5min, and the supernatant is taken to detect the concentration of methylene blue. The removal rate and degradation rate of methylene blue are calculated. The results show that the degradation rate of methylene blue by the hydroxy copper phosphate prepared in this comparative example is 0.002min -1 .

[0061] Example 2

[0062] In this example, the reusability of the copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material prepared in Example 1 was tested.

[0063] (1) A methylene blue solution with a concentration of 20 mg / L was used as simulated wastewater. 50 mL of the simulated wastewater was taken, and 15 mg of the composite photocatalytic material prepared in Example 1 was added to the simulated wastewater. The wastewater was treated under visible light and infrared light sources (the wavelength range of the infrared light source is 400-3000 nm) at a constant temperature of 20°C and stirring. During the wastewater treatment process, samples were taken at intervals, centrifuged at a speed of 8000 r / min for 5 min, and the supernatant was taken to detect the concentration of methylene blue and calculate the degradation rate of methylene blue. The result was 0.020 min -1 .

[0064] (2) The composite photocatalytic material was separated from the wastewater obtained in step (1), and was put into fresh simulated wastewater according to the process conditions of step (1) to degrade methylene blue. The wastewater was treated under a constant temperature and stirring condition of 20° C. under visible light and infrared light sources (the wavelength range of the infrared light source is 400 to 3000 nm). During the wastewater treatment process, samples were taken at intervals, centrifuged at a speed of 8000 r / min for 5 minutes, and the supernatant was taken to detect the concentration of methylene blue and calculate the degradation rate of methylene blue. The result was 0.019 min -1 .

[0065] (3) The composite photocatalytic material was separated from the wastewater obtained in step (2), and was put into fresh simulated wastewater according to the process conditions of step (1) to degrade methylene blue. The wastewater was treated under a constant temperature and stirring condition of 20° C. under visible light and infrared light sources (the wavelength range of the infrared light source is 400 to 3000 nm). During the wastewater treatment process, samples were taken at intervals, centrifuged at a speed of 8000 r / min for 5 minutes, and the supernatant was taken to detect the concentration of methylene blue and calculate the degradation rate of methylene blue. The result was 0.019 min -1 .

[0066] In this embodiment, the degradation rate of methylene blue by the composite photocatalytic material changes with the number of cycles. Figure 9 As shown by Figure 9 It can be seen that the degradation rate of methylene blue was only slightly reduced after the composite photocatalytic material prepared in Example 1 was reused three times, indicating that the composite photocatalytic material of the present invention has excellent recycling performance, which is conducive to its promotion and application in engineering practice.

[0067] Example 3

[0068] In this example, the degradation effect of the copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material prepared in Example 1 on methyl orange was tested.

[0069] (1) A methyl orange solution with a concentration of 20 mg / L was used as simulated wastewater. 50 mL of the simulated wastewater was taken, and 15 mg of the composite photocatalytic material prepared in Example 1 was added to the simulated wastewater. The wastewater was treated under visible light and infrared light sources at a constant temperature of 20° C. and stirred. During the wastewater treatment process, samples were taken at intervals, centrifuged at a speed of 8000 r / min for 5 min, and the supernatant was taken to detect the concentration of methyl orange and calculate the degradation rate of methyl orange. The result was 0.02 min -1 .

[0070] It can be seen from Examples 1 to 3 that the composite photocatalytic material provided by the present invention has good degradation performance for organic dyes including methylene blue and methyl orange.

[0071] Example 4

[0072] In this embodiment, the steps for preparing the copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material are as follows:

[0073] (1) Preparation of carrier materials

[0074] Zinc acetate and indium chloride were weighed, added to ultrapure water, and stirred for 30 minutes. Thioacetamide (TAA) was then added and stirred for another 30 minutes. The resulting mixture was added to an autoclave, which was sealed and reacted at 160°C for 8 hours. The mixture was naturally cooled to room temperature, and the resulting solid phase product was washed sequentially with ultrapure water and ethanol, centrifuged, and the solid phase was collected and dried at 60°C to obtain zinc sulfide indium. In this step, the mass ratio of zinc acetate, indium chloride, and thioacetamide in the mixture was controlled to be 1:1.8:1.8, and the concentration of zinc acetate was 3.5 g / L.

[0075] (2) Preparation of copper hydroxyphosphate

[0076] Copper nitrate and disodium hydrogen phosphate were added to ultrapure water and stirred until dissolved. The pH was adjusted to 7, and the resulting mixture was transferred to an autoclave. The autoclave was sealed and reacted at 160°C for 8 hours. The resulting solid phase product was washed with ethanol and ultrapure water to remove impurities, centrifuged, and the solid phase was collected and dried at 60°C to obtain copper hydroxyphosphate. In this step, the mass ratio of copper nitrate to disodium hydrogen phosphate in the mixture was controlled to be 1.1:1, and the concentration of copper nitrate was 18 g / L.

[0077] (3) Load

[0078] Copper hydroxyphosphate was fully dispersed in ultrapure water to form a 0.8 g / L copper hydroxyphosphate dispersion, and indium zinc sulfide was fully dispersed in ultrapure water to form a 6 g / L indium zinc sulfide dispersion. The copper hydroxyphosphate dispersion was dropwise added to the indium zinc sulfide dispersion in a mass ratio of 1:99. The mixture was ultrasonicated at a frequency of 40 kHz for 3 hours, then stirred at 350 rpm for 10 hours. The solid phase product was separated, washed three times with ethanol and ultrapure water, and centrifuged to collect the solid phase. The resulting solid phase was dried at 60°C to obtain a micron-sized copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material.

[0079] Example 5

[0080] In this embodiment, the steps for preparing the copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material are as follows:

[0081] (1) Preparation of carrier materials

[0082] Zinc acetate and indium chloride were weighed, added to ultrapure water, and stirred for 30 minutes. Thioacetamide (TAA) was then added and stirred for another 30 minutes. The resulting mixture was added to an autoclave, which was sealed and reacted at 110°C for 12 hours. The mixture was naturally cooled to room temperature, and the resulting solid phase product was washed sequentially with ultrapure water and ethanol, centrifuged, and the solid phase was collected and dried at 60°C to obtain sulfindium zinc. In this step, the mass ratio of zinc acetate, indium chloride, and thioacetamide in the mixture was controlled to be 1:2.2:2.2, and the concentration of zinc acetate was 4.5 g / L.

[0083] (2) Preparation of copper hydroxyphosphate

[0084] Copper nitrate and disodium hydrogen phosphate were added to ultrapure water and stirred until dissolved. The pH was adjusted to 7, and the resulting mixture was transferred to an autoclave. The autoclave was sealed and reacted at 160°C for 8 hours. The resulting solid phase product was washed with ethanol and ultrapure water to remove impurities, centrifuged, and the solid phase was collected and dried at 60°C to obtain copper hydroxyphosphate. In this step, the mass ratio of copper nitrate to disodium hydrogen phosphate in the mixture was controlled to be 1:1.1, and the concentration of copper nitrate was 20 g / L.

[0085] (3) Load

[0086] Copper hydroxyphosphate was fully dispersed in ultrapure water to form a 0.1 g / L copper hydroxyphosphate dispersion, and indium zinc sulfide was fully dispersed in ultrapure water to form a 1 g / L indium zinc sulfide dispersion. The copper hydroxyphosphate dispersion was added dropwise to the indium zinc sulfide dispersion in a mass ratio of 5:95. The mixture was ultrasonicated at a frequency of 40 kHz for 1 hour, then stirred at 350 rpm for 15 hours. The solid phase product was separated, washed three times with ethanol and ultrapure water, and centrifuged to collect the solid phase. The resulting solid phase was dried at 60°C to obtain a micron-sized copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material.

Claims

1. A copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material, characterized in that: The composite photocatalytic material is composed of indium zinc sulfide and copper hydroxyphosphate supported on the indium zinc sulfide. The indium zinc sulfide is a microsphere formed by the accumulation of indium zinc sulfide in a sheet structure. The content of indium zinc sulfide in the composite photocatalytic material is 90 wt% to 99 wt%, and the content of copper hydroxyphosphate in the composite photocatalytic material is 1 wt% to 10 wt%. The composite photocatalytic material has a particle size of 2 to 3 µm, the size of the copper hydroxyphosphate does not exceed 1 µm, and the indium zinc sulfide is a flower-shaped microsphere formed by the accumulation of indium zinc sulfide flakes. The composite photocatalytic material can respond to sunlight with a wavelength of 300 to 2000 nm to produce photocatalytic performance. The composite photocatalytic material is prepared by the following method: (1) fully dispersing copper hydroxyphosphate in water to form a copper hydroxyphosphate dispersion with a concentration of 0.01-0.8 g / L, and fully dispersing zinc indium sulfide in water to form a zinc indium sulfide dispersion with a concentration of 1-6 g / L, wherein the zinc indium sulfide is a flower-shaped microsphere formed by the accumulation of zinc indium sulfide in a sheet structure; (2) The copper hydroxyphosphate dispersion was added dropwise to the indium zinc sulfide dispersion in a mass ratio of (1-10) to (90-99), and the dispersion was fully ultrasonically dispersed. The mixture was then stirred for 10-15 h. The resulting solid phase was collected, washed with ethanol and water, and dried to obtain a copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material.

2. The copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material according to claim 1, characterized in that: The preparation method of the sulfur indium zinc is as follows: Zinc acetate and indium chloride are dissolved in water, and then thioacetamide is added and stirred thoroughly. The resulting mixture is added to an autoclave, which is sealed and reacted at 110-160°C for 8-12 hours. The resulting solid product is washed with water and ethanol in sequence and dried to obtain sulfindium zinc. The mass ratio of zinc acetate, indium chloride, and thioacetamide in the mixture is controlled to be 1:(1.8-2.2):(1.8-2.2), and the concentration of zinc acetate is 3.5-4.5 g / L.

3. The copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material according to claim 1, characterized in that: The preparation method of copper hydroxyphosphate is as follows: Copper nitrate and disodium hydrogen phosphate are dissolved in water, and the pH value is adjusted to 6-8. The resulting mixture is then transferred to an autoclave, which is sealed and reacted at 110-160°C for 8-12 hours. The resulting solid product is washed with ethanol and ultrapure water, and dried to obtain copper hydroxyphosphate. The mass ratio of copper nitrate to disodium hydrogen phosphate in the mixture is controlled to be (1-1.1):(1-1.1), and the concentration of copper nitrate is 18-20 g / L.

4. The copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material according to any one of claims 1 to 3, characterized in that: In step (2), ultrasound is performed at a frequency of 20 to 40 kHz.

5. The copper hydroxyphosphate / indium zinc sulfide composite photocatalytic material according to claim 4, characterized in that: In step (2), the ultrasonic dispersion time is controlled to be 1 to 3 h.

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