A non-rare metal doped copper-based upconversion photocatalytic material and a preparation method thereof

Abstract

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

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of material preparation, in particular to a non-rare earth metal doped copper-based upconversion photocatalytic material and a preparation method thereof. BACKGROUND

[0002] After being taken by human and livestock, most of the antibiotics cannot be fully absorbed and enter the water environment with excrement. The residual antibiotics migrate to animals and plants and human bodies through water bodies, thereby causing various serious consequences. There are many methods for treating water body pollution of organic matters, such as physical adsorption, chemical oxidation, biological degradation, etc. In recent years, the semiconductor-based photocatalytic technology has attracted great attention in the field of wastewater treatment due to its simple operation, high treatment efficiency, good stability, and high product mineralization degree.

[0003] At present, various traditional photocatalytic materials need to be activated under ultraviolet light, and the light conversion efficiency is limited. Moreover, ultraviolet light accounts for a very low proportion in sunlight. Upconversion materials can convert low-energy light into high-energy light, which can greatly improve the light conversion and pollutant degradation efficiency of the material. However, the preparation of upconversion materials still has many challenges. At present, the synthesis of upconversion materials mostly needs rare earth metals, such as CaF2:yb 3+ / Er 3+ , NaYF4:yb 3+ / Er 3+ , and BaGdF5:yb 3+ / Er 3+ . Taking CaF2:yb 3+ / Er 3+ as an example, the rare earth material is doped into the CaF2 matrix. The rare earth ion has a unique electronic 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 realizing the promotion of photon energy. However, the rare earth metal is expensive, which is not conducive to the mass production and application of upconversion materials.

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

[0005] The present application relates to the technical field of material preparation, in particular to a non-rare earth metal doped copper-based upconversion photocatalytic material and a preparation method thereof.

[0006] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions:

[0007] The application provides a preparation method of a non-rare metal doped copper-based up-conversion photocatalytic material.

[0008] (1) mixing Cu(NO3)2.3H2O, (NH4)2HPO4 and water, and then placing the mixture in a homogeneous reactor to perform a 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 to (NH4)2HPO4 in the step (1) is 1:2-3:1.

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

[0012] Preferably, the molar volume ratio of Cu(NO3)2.3H2O to water in the step (1) is 3-21 mol:50-80 mL.

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

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

[0015] Preferably, the temperature of the drying in the step (2) is 50-70 DEG C.

[0016] The time of the drying in the step (2) is 6-12 h.

[0017] The application further provides a Cu2(OH)PO4 photocatalytic material prepared by the preparation method of the non-rare metal doped copper-based up-conversion photocatalytic material.

[0018] The application further provides an application of the non-rare metal doped copper-based up-conversion photocatalytic material in treating sewage.

[0019] The application has the following beneficial effects:

[0020] (1) the application mixes Cu(NO3)2.3H2O, (NH4)2HPO4 and water, and then adopts a hydrothermal method to prepare Cu2(OH)PO4, the condition is mild, the operation is simple, the photocatalytic degradation effect of pollutants is remarkable, the stability is good, the cost is low, and the rare metal does not need to be introduced, so that the application is suitable for industrialized production and application;

[0021] (2) The prepared sample has a greater absorbable wavelength, improves the light conversion efficiency of the photocatalytic material and the performance of photocatalytic degradation of pollutants, so that the photocatalytic activity is improved. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 XRD diffraction pattern of the Cu2(OH)PO4 photocatalytic material of Examples 1-4;

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

[0024] Figure 3 Upconversion pattern of the Cu2(OH)PO4 photocatalytic material of Example 2;

[0025] Figure 4 Degradation effect pattern of the Cu2(OH)PO4 photocatalytic material of Example 2 on doxycycline hydrochloride in wastewater. DETAILED DESCRIPTION

[0026] The present application provides a preparation method of a non-rare metal doped copper-based upconversion photocatalytic material, comprising the following steps:

[0027] (1) mixing Cu(NO3)2·3H2O, (NH4)2HPO4 and water, and then placing them in a homogeneous reactor to perform a hydrothermal reaction, to obtain a mixture;

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

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

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

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

[0032] In the present application, Cu(NO3)2*3H2O, (NH4)2HPO4 and water are mixed, and then the mixture is put into a homogeneous reactor to perform hydrothermal reaction after the solution becomes homogenate.

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

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

[0035] In the present application, the temperature of the hydrothermal reaction in step (1) is preferably 150-220℃, further preferably 160-210℃, and more preferably 170-200℃.

[0036] In the present application, the time of the hydrothermal reaction in step (1) is preferably 8-16 h, further preferably 9-15 h, and more preferably 10-14 h.

[0037] In the present application, the mixture in step (1) is first filtered, then washed with distilled water after filtration, and then dried in a vacuum environment.

[0038] In the present application, the washing times are preferably 1-6 times, further preferably 2-5 times, and more preferably 3-4 times.

[0039] In the present application, the drying temperature in step (2) is preferably 50-70℃, further preferably 52-68℃, and more preferably 55-65℃.

[0040] In the present application, the drying time in step (2) is preferably 6-12 h, further preferably 7-11 h, and more preferably 8-10 h.

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

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

[0043] The present application also provides the 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 application further provides application of the non-rare metal doped copper-based up-conversion photocatalytic material in treating sewage.

[0045] The technical solutions provided by the application are described in detail below in combination with examples, but they should not be understood as limiting the protection scope of the application.

[0046] Example 1

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

[0048] Example 2

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

[0050] Example 3

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

[0052] Example 4

[0053] Mix 10 mol Cu(NO3)2·3H2O and 10 mol (NH4)2HPO4 solution in a proportion of 1:1 by molar ratio with 70 mL of water, stir at a rate of 800 rpm for 30 min until the solution is homogenate, then place in a homogeneous reactor for hydrothermal reaction at 180℃ for 12 h, obtain a mixture, filter the mixture first, then wash the filtered product with distilled water 3 times to remove impurities, then place in a vacuum drying oven, dry at 60℃ for 8 h, then grind the dried product through a 200 mesh sieve to obtain Cu2(OH)PO4 photocatalytic material.

[0054] Effect test:

[0055] The Cu2(OH)PO4 photocatalytic material prepared in Examples 1-4 is detected by an X-ray diffractometer, as shown in Figure 1 .

[0056] As can be seen from Figure 1 , the diffraction peak of the Cu2(OH)PO4 photocatalytic material prepared in the application has a good corresponding relationship with the typical Cu2(OH)PO4 material.

[0057] The Cu2(OH)PO4 photocatalytic material prepared in Example 2 is observed by a scanning electron microscope, as shown in Figure 2 .

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

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

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

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

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

[0063] From the above examples, the application provides a non-rare earth metal doped copper-based up-conversion photocatalytic material and a preparation method thereof, which comprises the following steps: mixing Cu(NO3)2.3H2O, (NH4)2HPO4 and water, and then placing the mixture in a homogeneous reactor to perform a hydrothermal reaction to obtain a mixture; and drying the mixture to obtain the Cu2(OH)PO4 photocatalytic material. The application mixes Cu(NO3)2.3H2O, (NH4)2HPO4 and water, and then uses a hydrothermal method to prepare Cu2(OH)PO4, which has the advantages of mild conditions, simple operation, remarkable effect of photocatalytic degradation of pollutants, good stability, low cost, no need to introduce rare earth metals, and suitability for industrialized production and application. The prepared sample has a larger absorbable wavelength, improves the light conversion efficiency of the photocatalytic material and the performance of photocatalytic degradation of pollutants, and thus improves the photocatalytic activity.

[0064] The above only describes the preferred embodiments of the application, and it should be noted that, for those skilled in the art, some improvements and refinements can be made without departing from the principles of the application, and these improvements and refinements should also be considered as the protection scope of the application.

Claims

1. A method for preparing a non-rare earth metal-doped copper-based upconversion photocatalyst, characterized in that, Includes the following steps: (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) The mixture is dried to obtain Cu2(OH)PO4 photocatalytic material; In step (1), the molar ratio of Cu(NO3)2·3H2O and (NH4)2HPO4 is 1:2~3:1; The temperature of the hydrothermal reaction in step (1) is 150~220℃; The hydrothermal reaction time in step (1) is 8~16 h.

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

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

4. The method for preparing a non-rare earth metal-doped copper-based upconversion photocatalyst material according to claim 1, characterized in that, The drying temperature in step (2) is 50~70℃; The drying time in step (2) is 6~12 h.

5. The Cu2(OH)PO4 photocatalyst material obtained by the preparation method of a non-rare earth metal-doped copper-based upconversion photocatalyst material according to any one of claims 1 to 4.

6. The application of the non-rare earth metal-doped copper-based upconversion photocatalyst material as described in claim 5 in wastewater treatment.

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