Non-rare earth metal doped copper-based up-conversion photocatalytic material and preparation method thereof

Abstract

The invention belongs to the technical field of material preparation, and provides a non-rare earth metal doped copper-based up-conversion photocatalytic material and a preparation method thereof.The preparation method comprises the following steps that Cu (NO3) 2.3 H2O, (NH4) 2HPO4 and water are mixed and then placed in a homogeneous reactor to be subjected to a hydrothermal reaction, and a mixture is obtained; and drying the mixture to obtain the Cu2 (OH) PO4 photocatalytic material. Cu (NO3) 2.3 H2O, (NH4) 2HPO4 and water are mixed and then Cu2 (OH) PO4 is prepared by adopting a hydrothermal method, the conditions are mild, the operation is simple, the effect of photocatalytic degradation of pollutants is obvious, the stability is good, the cost is relatively low, rare earth metal does not need to be introduced, and the method is suitable for industrial production and application; the prepared sample has larger absorbable wavelength, and the light conversion efficiency of the photocatalytic material and the performance of photocatalytic degradation of pollutants are improved, so that the photocatalytic activity is improved.

Description

Technical Field

[0001] The invention relates to the technical field of material preparation, and in particular to a non-rare earth metal-doped copper-based up-conversion photocatalytic material and a preparation method thereof. Background Art

[0002] After being taken by humans and animals, most antibiotics cannot be fully absorbed and enter the water environment with excrement. The residual antibiotics then migrate to animals, plants and humans through the water, causing various serious consequences. There are many ways to treat organic water pollution: physical adsorption, chemical oxidation, biodegradation, etc. Semiconductor-based photocatalytic technology has received great attention in the field of wastewater treatment in recent years due to its simple operation, high treatment efficiency, good stability, and high product mineralization.

[0003] Currently, various traditional photocatalytic materials need to be activated under ultraviolet light, and the light conversion efficiency is limited. In addition, ultraviolet light accounts for a very low proportion of sunlight. Upconversion materials can convert low-energy light into high-energy light, which can greatly improve the light conversion and pollutant degradation efficiency of materials. However, there are still many challenges in the preparation of upconversion materials. Currently, most synthetic upconversion materials require rare earth metals, such as CaF2:yb 3+ / Er 3+ 、NaYF4:yb 3+ / Er 3+ Upconversion materials and BaGdF5:Yb 3+ / Er 3+ . With CaF2:yb 3+ / Er 3+ For example, rare earth materials are doped into the CaF2 matrix. Rare earth ions have a unique electron layer structure and energy level arrangement, which can convert low-energy light (such as near-infrared light) into high-energy light (such as visible light or ultraviolet light), thereby achieving an increase in photon energy. However, rare earth metals are expensive, which is not conducive to the large-scale preparation and application of upconversion materials.

[0004] In general, the current preparation of upconversion materials has the following problems: complex process, high price, high cost, unstable performance, etc. Therefore, it is of great significance to develop a new type of high-efficiency, low-cost upconversion material and its preparation method. Summary of the invention

[0005] The purpose of the present invention is to provide a non-rare earth metal doped copper-based upconversion photocatalytic material and a preparation method thereof, which converts low-energy photons into high-energy photons through upconversion technology, improves the utilization rate of the light source, expands the spectral response range of the material, enhances the photocatalytic activity, and better improves the photocatalytic material's ability to degrade pollutants.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a method for preparing a non-rare earth metal-doped copper-based upconversion photocatalytic material, comprising the following steps:

[0008] (1) Cu(NO3)2·3H2O, (NH4)2HPO4 and water are mixed and placed in a homogeneous reactor for hydrothermal reaction to obtain a mixture;

[0009] (2) Drying the mixture to obtain the Cu2(OH)PO4 photocatalytic material.

[0010] Preferably, the molar ratio of Cu(NO3)2·3H2O and (NH4)2HPO4 in step (1) is 1:2 to 3:1.

[0011] Preferably, the molar volume ratio of (NH4)2HPO4 and water in step (1) is 0.5-20 mol:50-80 mL.

[0012] Preferably, in step (1), the molar volume ratio of Cu(NO3)2·3H2O to water is 3-21 mol:50-80 mL.

[0013] Preferably, the temperature of the hydrothermal reaction in step (1) is 150-220°C;

[0014] The time of the hydrothermal reaction in step (1) is 8 to 16 hours.

[0015] Preferably, the drying temperature in step (2) is 50-70°C;

[0016] The drying time in step (2) is 6 to 12 hours.

[0017] The invention also provides a Cu2(OH)PO4 photocatalytic material obtained by a preparation method of a non-rare earth metal-doped copper-based up-conversion photocatalytic material.

[0018] The present invention also provides an application of a non-rare earth metal-doped copper-based up-conversion photocatalytic material in treating sewage.

[0019] The present invention has the following beneficial effects:

[0020] (1) The present invention mixes Cu(NO3)2·3H2O, (NH4)2HPO4 and water and then uses a hydrothermal method to prepare Cu2(OH)PO4. The conditions are mild, the operation is simple, the photocatalytic degradation effect of pollutants is significant, the stability is good and the cost is low. No rare earth metals need to be introduced and it is suitable for industrial production and application.

[0021] (2) The samples prepared by the present invention have a larger absorbable wavelength, which improves the light conversion efficiency of the photocatalytic material and the performance of photocatalytic degradation of pollutants, thereby improving the photocatalytic activity. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 XRD diffraction patterns of Cu2(OH)PO4 photocatalytic materials of Examples 1 to 4;

[0023] Figure 2 This is the SEM image of the Cu2(OH)PO4 photocatalytic material of Example 2;

[0024] Figure 3 This is the upconversion diagram of the Cu2(OH)PO4 photocatalytic material of Example 2;

[0025] Figure 4 This is a diagram showing the degradation effect of the Cu2(OH)PO4 photocatalytic material of Example 2 on doxycycline hydrochloride in wastewater. DETAILED DESCRIPTION

[0026] The present invention provides a method for preparing a non-rare earth metal-doped copper-based upconversion photocatalytic material, comprising the following steps:

[0027] (1) Cu(NO3)2·3H2O, (NH4)2HPO4 and water are mixed and placed in a homogeneous reactor for hydrothermal reaction to obtain a mixture;

[0028] (2) Drying the mixture to obtain the Cu2(OH)PO4 photocatalytic material.

[0029] In the present invention, the molar ratio of Cu(NO3)2·3H2O and (NH4)2HPO4 solution in step (1) is preferably 1:2 to 3:1, more preferably 1:1 to 2.5:1, and more preferably 1.5:1 to 2:1.

[0030] In the present invention, the molar volume ratio of (NH4)2HPO4 and water in step (1) is preferably 0.5-20 mol:50-80 mL, more preferably 2-18 mol:55-75 mL, and more preferably 5-15 mol:60-70 mL.

[0031] In the present invention, the molar volume ratio of Cu(NO3)2·3H2O to water in step (1) is preferably 3-21 mol:50-80 mL, more preferably 5-18 mol:55-75 mL, and more preferably 10-15 mol:60-70 mL.

[0032] In the present invention, Cu(NO3)2·3H2O, (NH4)2HPO4 and water are mixed until the solution is in a homogenous slurry state and then placed in a homogeneous reactor for hydrothermal reaction.

[0033] In the present invention, the stirring rate of the mixing in step (1) is preferably 600 to 1000 rpm, more preferably 700 to 900 rpm, and even more preferably 750 to 850 rpm.

[0034] In the present invention, the mixing time in step (1) is preferably 20 to 40 min, more preferably 22 to 38 min, and even more preferably 25 to 35 min.

[0035] In the present invention, the temperature of the hydrothermal reaction in step (1) is preferably 150 to 220°C, more preferably 160 to 210°C, and even more preferably 170 to 200°C.

[0036] In the present invention, the time of the hydrothermal reaction in step (1) is preferably 8 to 16 hours, more preferably 9 to 15 hours, and even more preferably 10 to 14 hours.

[0037] In the present invention, the mixture in step (1) is first filtered, then washed with distilled water, and then dried under vacuum.

[0038] In the present invention, the number of washing is preferably 1 to 6 times, more preferably 2 to 5 times, and even more preferably 3 to 4 times.

[0039] In the present invention, the drying temperature in step (2) is preferably 50 to 70°C, more preferably 52 to 68°C, and even more preferably 55 to 65°C.

[0040] In the present invention, the drying time in step (2) is preferably 6 to 12 hours, more preferably 7 to 11 hours, and even more preferably 8 to 10 hours.

[0041] In the present invention, the dried product is ground to obtain the Cu2(OH)PO4 photocatalytic material.

[0042] In the present invention, the particle size of the Cu2(OH)PO4 photocatalytic material is preferably 150-250 mesh, more preferably 170-230 mesh, and even more preferably 190-210 mesh.

[0043] The present invention also provides a Cu2(OH)PO4 photocatalytic material obtained by the preparation method of the non-rare earth metal-doped copper-based up-conversion photocatalytic material.

[0044] The present invention also provides application of the non-rare earth metal-doped copper-based up-conversion photocatalytic material in treating sewage.

[0045] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0046] Example 1

[0047] 10 mol of Cu(NO3)2·3H2O and (NH4)2HPO4 were mixed with 70 mL of water in any proportion within the molar ratio range of 1:2 to 3:1, stirred at a rate of 800 rpm for 30 min until the solution was in a homogenous state, and then placed in a homogeneous reactor for hydrothermal reaction at 180°C for 12 h to obtain a mixture, the mixture was first filtered, and then the filtered product was washed 3 times with distilled water to remove impurities, and then placed in a vacuum drying oven and dried at 60°C for 8 h, and then the dried product was ground through a 200-mesh sieve to obtain a Cu2(OH)PO4 photocatalytic material.

[0048] Example 2

[0049] 10 mol Cu(NO3)2·3H2O and 5 mol (NH4)2HPO4 were mixed with 70 ml water in a molar ratio of 2:1, stirred at a rate of 800 rpm for 30 min until the solution was in a homogenous state, and then placed in a homogeneous reactor for hydrothermal reaction at 180°C for 12 h to obtain a mixture, the mixture was first filtered, and then the filtered product was washed 3 times with distilled water to remove impurities, and then placed in a vacuum drying oven and dried at 60°C for 8 h, and then the dried product was ground through a 200-mesh sieve to obtain a Cu2(OH)PO4 photocatalytic material.

[0050] Example 3

[0051] 5 mol Cu(NO3)2·3H2O and 10 mol (NH4)2HPO4 were mixed with 70 mL of water in a molar ratio of 1:2, stirred at 800 rpm for 30 min until the solution was in a homogenous state, and then placed in a homogeneous reactor for hydrothermal reaction at 180°C for 12 h to obtain a mixture, the mixture was first filtered, and then the filtered product was washed 3 times with distilled water to remove impurities, and then placed in a vacuum drying oven and dried at 60°C for 8 h, and then the dried product was ground through a 200-mesh sieve to obtain a Cu2(OH)PO4 photocatalytic material.

[0052] Example 4

[0053] 10 mol Cu(NO3)2·3H2O and 10 mol (NH4)2HPO4 solution were mixed with 70 mL water in a molar ratio of 1:1, stirred at 800 rpm for 30 min until the solution was in a homogenous state, and then placed in a homogeneous reactor for hydrothermal reaction at 180°C for 12 h to obtain a mixture, the mixture was first filtered, and then the filtered product was washed 3 times with distilled water to remove impurities, and then placed in a vacuum drying oven and dried at 60°C for 8 h, and then the dried product was ground through a 200-mesh sieve to obtain a Cu2(OH)PO4 photocatalytic material.

[0054] Effect test:

[0055] The Cu2(OH)PO4 photocatalytic materials prepared in Examples 1 to 4 were tested by X-ray diffractometer. Figure 1 shown.

[0056] from Figure 1 It can be seen that the diffraction peaks of the Cu2(OH)PO4 photocatalytic material prepared in the present application have a good correspondence with the typical Cu2(OH)PO4 material.

[0057] The Cu2(OH)PO4 photocatalytic material prepared in Example 2 was observed by scanning electron microscopy. Figure 2 shown.

[0058] from Figure 2 It can be seen that the Cu2(OH)PO4 photocatalytic material prepared in Example 2 of the present application is in block form, has a larger specific surface area, and can provide more active sites.

[0059] The Cu2(OH)PO4 photocatalytic material prepared in Example 2 was irradiated with a 980nm laser, and the upconversion of the material was as follows: Figure 3 shown.

[0060] from Figure 3 It can be seen that at an excitation wavelength of 980 nm, the Cu2(OH)PO4 photocatalytic material prepared in Example 2 of the present application has an absorption peak at 400-600 nm, indicating that the material has up-conversion performance.

[0061] The Cu2(OH)PO4 photocatalytic material prepared in Example 2 was prepared into different solution concentrations (10 mg / L, 25 mg / L, 50 mg / L, 100 mg / L, 200 mg / L), and then put into wastewater to observe the degradation effect of Cu2(OH)PO4 at different concentrations on doxycycline hydrochloride in wastewater at different times. Figure 4 shown.

[0062] from Figure 4It can be seen that when the degradation is 120min, the degradation efficiency of doxycycline hydrochloride in wastewater with a concentration of 10mg / L Cu2(OH)PO4 is 54%, the degradation efficiency of doxycycline hydrochloride in wastewater with a concentration of 25mg / L Cu2(OH)PO4 is 76%, the degradation efficiency of doxycycline hydrochloride in wastewater with a concentration of 50mg / L Cu2(OH)PO4 is 83%, the degradation efficiency of doxycycline hydrochloride in wastewater with a concentration of 100mg / L Cu2(OH)PO4 is 83.4%, and the degradation efficiency of doxycycline hydrochloride in wastewater with a concentration of 200mg / L Cu2(OH)PO4 is 84%. It can be seen that the Cu2(OH)PO4 prepared in the present application has good photocatalytic degradation performance

[0063] As can be seen from the above embodiments, the present invention provides a non-rare earth metal doped copper-based upconversion photocatalytic material and a preparation method thereof, comprising the following steps: mixing Cu(NO3)2·3H2O, (NH4)2HPO4 and water and placing in a homogeneous reactor for hydrothermal reaction to obtain a mixture; drying the mixture to obtain a Cu2(OH)PO4 photocatalytic material. The present invention prepares Cu2(OH)PO4 by a hydrothermal method after mixing Cu(NO3)2·3H2O, (NH4)2HPO4 and water. The conditions are mild, the operation is simple, the photocatalytic degradation of pollutants is significant, the stability is good and the cost is low, and it is suitable for industrial production and application without the introduction of rare earth metals. The sample prepared by the present invention has a larger absorbable wavelength, which improves the light conversion efficiency of the photocatalytic material and the performance of photocatalytic degradation of pollutants, thereby improving the photocatalytic activity.

[0064] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a non-rare earth metal-doped copper-based upconversion photocatalytic material, characterized in that: The following steps are involved: (1) Cu(NO3)2·3H2O, (NH4)2HPO4 and water are mixed and placed in a homogeneous reactor for hydrothermal reaction to obtain a mixture; (2) Drying the mixture to obtain the Cu2(OH)PO4 photocatalytic material.

2. The method for preparing a non-rare earth metal-doped copper-based upconversion photocatalytic material according to claim 1, characterized in that: The molar ratio of Cu(NO3)2·3H2O to (NH4)2HPO4 in step (1) is 1:2 to 3:

1.

3. The method for preparing a non-rare earth metal-doped copper-based upconversion photocatalytic material according to claim 1, characterized in that: The molar volume ratio of (NH4)2HPO4 and water in step (1) is 0.5-20 mol:50-80 mL.

4. The method for preparing a non-rare earth metal-doped copper-based upconversion photocatalytic material according to claim 1, characterized in that: In the step (1), the molar volume ratio of Cu(NO3)2·3H2O to water is 3-21 mol:50-80 mL.

5. The method for preparing a non-rare earth metal-doped copper-based upconversion photocatalytic material according to claim 1, characterized in that: The temperature of the hydrothermal reaction in step (1) is 150-220° C.; The time of the hydrothermal reaction in step (1) is 8 to 16 hours.

6. The method for preparing a non-rare earth metal-doped copper-based upconversion photocatalytic material according to claim 1, characterized in that: The drying temperature in step (2) is 50-70°C; The drying time in step (2) is 6 to 12 hours.

7. The Cu2(OH)PO4 photocatalytic material obtained by the preparation method of a non-rare earth metal-doped copper-based up-conversion photocatalytic material as described in any one of claims 1 to 6.

8. Use of the non-rare earth metal-doped copper-based up-conversion photocatalytic material according to claim 7 in treating sewage.

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