Preparation method of catalytic material for photocatalytic degradation of carbamazepine in sewage

Abstract

The invention provides a preparation method of a catalytic material for photocatalytic degradation of carbamazepine in sewage. The preparation method comprises the following steps: (1) preparing Cd2SnSe4 nanocrystal particles; (2) loading a praseodymium copper bromide coordination polymer [Pr4Cu2Br6 (EDOT) 4] n on the surface of the foamy copper substrate; and (3) embedding a CdPr2S4 / Cd2SnSe4 composite crystal on the surface of the praseodymium copper bromide coordination polymer [Pr4Cu2Br6 (EDOT) 4] n. The photocatalytic material prepared by the method disclosed by the invention has high-efficiency carbamazepine photocatalytic degradation rate and excellent reuse photocatalytic stability.

Description

Technical Field

[0001] The invention relates to the technical field of carbamazepine sewage treatment, in particular to a method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage. Background Art

[0002] Carbamazepine (chemical name: 5H-dibenzo[b,f]azepine-5-carboxamide) is a drug for treating epilepsy, neuropathic pain, depression and other diseases. It can block the Na - Channels can inhibit the occurrence and spread of abnormal high-frequency discharges that cause neuropathic pain; can inhibit T-type calcium channels that are closely related to epileptic seizures; can enhance the central noradrenergic nerve activity associated with depression. With the development of economy and society, carbamazepine has become a commonly used drug in the world today, and its dosage and application range are increasing. Due to the production process of carbamazepine and the large-scale therapeutic use of carbamazepine, a large amount of carbamazepine wastewater is produced. At present, carbamazepine pollutants with a concentration of milligrams have been detected in the water environment of more than 80 countries in the world. Carbamazepine wastewater has significant toxic side effects, which can cause changes in the activity of lactate dehydrogenase, oxaloacetate transaminase and glutamate transaminase in carp cells; can destroy the feeding and fertility of Daphnia pulex; inhibit the growth of tadpoles and cause malformations and disabilities; and inhibit the normal development of aquatic plants. Since carbamazepine wastewater is difficult to degrade naturally and effectively, and the removal rate of carbamazepine wastewater by traditional sewage treatment technology is low, the effective treatment of carbamazepine wastewater has reached a point where it cannot be delayed.

[0003] The photocatalytic degradation of organic pollutants can photocatalytically degrade organic pollutants through the active free radicals generated during the illumination process of the photocatalyst material, and is a potential effective treatment method for the effective treatment of carbamazepine wastewater. However, the photocatalytic degradation rate of the catalytic materials used for the photocatalytic degradation of carbamazepine wastewater is currently low, and its photocatalytic reuse performance needs to be improved urgently, which has also become a bottleneck restricting the development of photocatalytic degradation technology for carbamazepine wastewater. Summary of the invention

[0004] In order to overcome the shortcomings of the prior art, the present invention provides a method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage. The photocatalytic material prepared by the method has a high efficiency of photocatalytic degradation of carbamazepine and excellent photocatalytic stability for repeated use.

[0005] The technical solution adopted by the present invention to solve its technical problem is:

[0006] The present invention provides a method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage, comprising the following steps:

[0007] Step [1] preparing Cd2SnSe4 nanocrystalline particles;

[0008] Step [2] Loading praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the copper foam substrate n ;

[0009] Step [3] In the praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The surface is inlaid with CdPr2S4 / Cd2SnSe4 composite crystals.

[0010] Preferably, the step [1] specifically includes the following operations:

[0011] Selenious acid, stannous chloride, cadmium acetate and fluvastatin sodium are added to deionized water and mixed to form a preparation solution; the solution is heated to 70-90°C under closed conditions, reacted for 8-10 hours, cooled to room temperature and filtered to obtain a solid phase, which is placed in an oven and dried at 35-50°C for 5-8 hours to obtain the Cd2SnSe4 nanocrystalline particles.

[0012] Preferably, the amount of selenious acid added per liter of the preparation solution is 120-160 g, the amount of stannous chloride added is 190-230 g, the amount of cadmium acetate added is 180-200 g, and the amount of fluvastatin sodium added is 10-30 g.

[0013] Preferably, the step [2] specifically includes the following operations:

[0014] b1. Add 3,4-ethylenedioxythiophene and praseodymium nitrate to ethanol and mix to form an organic liquid composition; add copper sulfate, ammonium bromide and 40% by mass of hydrobromic acid to deionized water and mix to form an inorganic liquid composition;

[0015] b2. Immerse the copper foam sample in the inorganic liquid composition, then add a certain amount of organic liquid composition to the inorganic liquid composition, react at room temperature for 20-26 hours, remove the copper foam sample, wash with deionized water, and dry at room temperature to obtain a surface loaded with praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The foam copper is recorded as intermediate A.

[0016] Preferably, in step b1, the amount of 3,4-ethylenedioxythiophene added to each liter of the organic component liquid is 170-210 mL, and the amount of praseodymium nitrate added to each liter of the inorganic component liquid is 80-140 g, the amount of ammonium bromide added to each liter of the inorganic component liquid is 120-150 g, and the amount of 40% hydrobromic acid added to each liter is 350-420 mL.

[0017] Preferably, in step b2, the weight of the copper foam immersed in each liter of the inorganic component liquid is 160-220 g; and the volume ratio between the organic component liquid and the inorganic component liquid is 5-7:3-5.

[0018] Preferably, the step [3] specifically includes the following operations:

[0019] c1. Praseodymium nitrate, cadmium acetate, thioacetamide, ammonium thiosulfate, selenious acid, stannous chloride and the Cd2SnSe4 nanocrystalline particles are added to deionized water to form a composite crystal mosaic solution;

[0020] c2. Immerse the intermediate A in the composite crystal embedding solution, heat to 60-80°C, react for 6-8 hours, take out the copper foam sample, wash with deionized water, and dry at room temperature for 10-12 hours to form a praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the copper foam. n The catalytic material is obtained by embedding CdPr2S4 / Cd2SnSe4 composite crystals on the surface.

[0021] Preferably, in step c1, the amount of praseodymium nitrate added to each liter of the composite crystal embedding liquid is 60-90 g, the amount of cadmium acetate added is 90-110 g, the amount of thioacetamide added is 40-80 g, the amount of ammonium thiosulfate added is 140-170 g, the amount of selenious acid added is 30-60 g, the amount of stannous chloride added is 20-50 g, and the amount of Cd2SnSe4 nanocrystal particles added is 10-30 g.

[0022] Preferably, in step c2, the weight of the intermediate A immersed in each liter of the composite crystal embedding liquid is 130-170 g.

[0023] The positive effect of the present invention is that the photocatalytic material prepared by the method of the present invention has a praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the foam copper. n The surface is inlaid with CdPr2S4 / Cd2SnSe4 composite crystals, wherein the praseodymium of Pr4Cu2Br6 is located at the four vertices of the bottom quadrilateral that constitutes the combination of the upper and lower square pyramids of the regular octahedron, the copper of Pr4Cu2Br6 is located at the two vertices outside the bottom quadrilateral that constitutes the combination of the upper and lower square pyramids, and the bromine of Pr4Cu2Br6 is located outside the six vertices of the regular octahedron to form chemical bonds with praseodymium and copper; the sulfur atom of 3,4-ethylenedioxythiophene forms a coordination bond with the praseodymium ion of Pr4Cu2Br6, thereby forming a structural unit Pr4Cu2Br6(EDOT)4, and the structural unit Pr4Cu2Br6(EDOT)4 is polymerized to construct a three-dimensional network of praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n ; Cd2SnSe4 has an orthorhombic structure with a space group of Pbam (55); CdPr2S4 has a cubic structure with a space group of Fd-3m (227). Based on the above structural characteristics, its praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4]n The energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital is narrow, and there is a dioxyethylene bridging group, so it has good conductivity and electrochemical stability; a heterojunction can be formed at the CdPr2S4 / Cd2SnSe4 interface, and the photogenerated electrons in the conduction band of Cd2SnSe4 can combine with the photogenerated holes in the valence band of CdPr2S4, thereby effectively prolonging the lifetime of the photogenerated electrons in the conduction band of CdPr2S4 and the photogenerated holes in the valence band of Cd2SnSe4, and significantly improving the photocatalytic degradation efficiency of the prepared photocatalytic material.

[0024] In conclusion, the photocatalytic material prepared according to the present invention has a highly efficient carbamazepine photocatalytic degradation rate and excellent photocatalytic stability for repeated use. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is a schematic diagram of the preparation process of the photocatalytic material of the present invention;

[0026] Figure 2 It is the Cd2SnSe4 crystal structure of the present invention;

[0027] Figure 3 The praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] of the present invention n structure;

[0028] Figure 4 It is the CdPr2S4 / Cd2SnSe4 composite crystal structure of the present invention;

[0029] Figure 5 Schematic diagram of the microstructure of the photocatalytic material of the present invention;

[0030] Figure 6 The relative concentration of residual carbamazepine in the simulated carbamazepine-containing wastewater by photocatalytic degradation under visible light and ultraviolet light in Example 1, Comparative Example 1 and Comparative Example 2 of the present invention;

[0031] Figure 7 The relationship between the number of times Example 1, Comparative Example 1, and Comparative Example 2 are used repeatedly under visible light to treat simulated carbamazepine-containing wastewater and the relative concentration of residual carbamazepine;

[0032] Figure 8 It is the relationship between the number of uses and the relative concentration of residual carbamazepine when Example 1, Comparative Example 1 and Comparative Example 2 are repeatedly used to treat simulated carbamazepine-containing wastewater under ultraviolet light. DETAILED DESCRIPTION

[0033] Reference Figure 1 The present invention provides a method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage, comprising the following steps:

[0034] Step [1] Preparation of Cd2SnSe4 nanocrystalline particles, specifically comprising the following operations:

[0035] Selenious acid, stannous chloride, cadmium acetate and fluvastatin sodium are added to deionized water and mixed to form a preparation solution; heated to 70-90°C under closed conditions, reacted for 8-10 hours, cooled to room temperature and filtered to obtain a solid phase, and placed in an oven to dry at 35-50°C for 5-8 hours to obtain the Cd2SnSe4 nanocrystalline particles (whose molecular structure is as shown in Figure 2 As shown). In each liter of the preparation solution, the amount of selenious acid added is 120-160 g, the amount of stannous chloride added is 190-230 g, the amount of cadmium acetate added is 180-200 g, and the amount of fluvastatin sodium added is 10-30 g.

[0036] Step [2] Loading praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the copper foam substrate n , including the following operations:

[0037] b1. Add 3,4-ethylenedioxythiophene and praseodymium nitrate to ethanol and mix to form an organic composition liquid; add copper sulfate, ammonium bromide and 40% hydrobromic acid by mass to deionized water and mix to form an inorganic composition liquid; wherein, the amount of 3,4-ethylenedioxythiophene added to each liter of the organic composition liquid is 170-210 mL, the amount of praseodymium nitrate added is 140-190 g, the amount of copper sulfate added to each liter of the inorganic composition liquid is 80-140 g, the amount of ammonium bromide added is 120-150 g, and the amount of 40% hydrobromic acid added is 350-420 mL.

[0038] b2. Immerse the copper foam sample in the inorganic liquid (the weight of the copper foam immersed in each liter of the inorganic liquid is 160-220 g), then add a certain amount of organic liquid to the inorganic liquid (the volume ratio of the organic liquid to the inorganic liquid is 5-7:3-5), react at room temperature for 20-26 hours, take out the copper foam sample, wash it with deionized water, and dry it at room temperature to obtain a surface-loaded praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The copper foam is recorded as intermediate A. Wherein, the praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The structure is as Figure 3 shown.

[0039] Step [3] In the praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The surface is inlaid with CdPr2S4 / Cd2SnSe4 composite crystal, which specifically includes the following operations:

[0040] c1. The praseodymium nitrate, cadmium acetate, thioacetamide, ammonium thiosulfate, selenious acid, stannous chloride and the Cd2SnSe4 nanocrystalline particles are added to deionized water to form a composite crystal embedding solution; wherein, per liter of the composite crystal embedding solution, the amount of praseodymium nitrate added is 60 to 90 g, the amount of cadmium acetate added is 90 to 110 g, the amount of thioacetamide added is 40 to 80 g, the amount of ammonium thiosulfate added is 140 to 170 g, the amount of selenious acid added is 30 to 60 g, the amount of stannous chloride added is 20 to 50 g, and the amount of Cd2SnSe4 nanocrystalline particles added is 10 to 30 g.

[0041] c2. Immerse the intermediate A in a composite crystal embedding solution (the weight of the intermediate A immersed in each liter of the composite crystal embedding solution is 130-170 g), heat to 60-80 ° C, react for 6-8 hours, take out the foam copper sample, wash with deionized water, and dry at room temperature for 10-12 hours to form a praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the foam copper. n The surface is inlaid with CdPr2S4 / Cd2SnSe4 composite crystals to obtain the catalytic material (its microstructure is shown in FIG. Figure 5 Wherein, the CdPr2S4 / Cd2SnSe4 composite crystal structure is as shown Figure 4 shown.

[0042] The preferred embodiments of the present invention are described below by way of example.

[0043] Example 1

[0044] Preferred embodiment 1 of the present invention provides a method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage, comprising the following steps:

[0045] Step [1] Preparation of Cd2SnSe4 nanocrystalline particles, specifically comprising the following operations:

[0046] Selenous acid, stannous chloride, cadmium acetate and fluvastatin sodium are added to deionized water and mixed to form a preparation solution; the solution is heated to 85°C in a sealed condition, reacted for 9 hours, cooled to room temperature, filtered to obtain a solid phase, and dried in an oven at 40°C for 6 hours to obtain the Cd2SnSe4 nanocrystalline particles. In each liter of the preparation solution, the amount of selenous acid added is 130g, the amount of stannous chloride added is 220g, the amount of cadmium acetate added is 190g, and the amount of fluvastatin sodium added is 15g.

[0047] Step [2] Loading praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the copper foam substrate n , including the following operations:

[0048] b1. Add 3,4-ethylenedioxythiophene and praseodymium nitrate to ethanol and mix to form an organic component liquid; add copper sulfate, ammonium bromide and 40% hydrobromic acid by mass to deionized water and mix to form an inorganic component liquid; wherein, the amount of 3,4-ethylenedioxythiophene added to each liter of the organic component liquid is 190 mL, the amount of praseodymium nitrate added is 180 g, and the amount of copper sulfate added to each liter of the inorganic component liquid is 120 g, the amount of ammonium bromide added is 130 g, and the amount of 40% hydrobromic acid added is 380 mL.

[0049] b2. Immerse the copper foam sample in the inorganic liquid (the weight of the copper foam immersed in each liter of the inorganic liquid is 190 g), then add a certain amount of organic liquid to the inorganic liquid (the volume ratio of the organic liquid to the inorganic liquid is 7:5), react at room temperature for 24 hours, take out the copper foam sample, wash it with deionized water, and dry it at room temperature to obtain a surface-loaded praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The foam copper is recorded as intermediate A.

[0050] Step [3] In the praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The surface is inlaid with CdPr2S4 / Cd2SnSe4 composite crystal, which specifically includes the following operations:

[0051] c1. The praseodymium nitrate, cadmium acetate, thioacetamide, ammonium thiosulfate, selenious acid, stannous chloride and the Cd2SnSe4 nanocrystalline particles are added to deionized water to form a composite crystal embedding solution; wherein, per liter of the composite crystal embedding solution, the amount of praseodymium nitrate added is 75g, the amount of cadmium acetate added is 95g, the amount of thioacetamide added is 60g, the amount of ammonium thiosulfate added is 160g, the amount of selenious acid added is 40g, the amount of stannous chloride added is 30g, and the amount of Cd2SnSe4 nanocrystalline particles added is 25g.

[0052] c2. The intermediate A was immersed in a composite crystal embedding solution (the weight of the intermediate A immersed in each liter of the composite crystal embedding solution was 155 g), heated to 65°C, reacted for 8 hours, and the foam copper sample was taken out and washed with deionized water, and dried at room temperature for 10 hours to form a praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the foam copper. n The surface is inlaid with CdPr2S4 / Cd2SnSe4 composite crystals to obtain the catalytic material, which is recorded as Example 1.

[0053] Comparative Example 1

[0054] This comparative example 1 provides a method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage, comprising the following steps:

[0055] Step [1] Loading praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the copper foam substrate n , including the following operations:

[0056] b1. Add 3,4-ethylenedioxythiophene and praseodymium nitrate to ethanol and mix to form an organic composition liquid; add copper sulfate, ammonium bromide and 40% hydrobromic acid by mass to deionized water and mix to form an inorganic composition liquid; wherein, the amount of 3,4-ethylenedioxythiophene added to each liter of the organic composition liquid is 180 mL, the amount of praseodymium nitrate added is 150 g, the amount of copper sulfate added to each liter of the inorganic composition liquid is 90 g, the amount of ammonium bromide added is 130 g, and the amount of 40% hydrobromic acid added is 360 mL.

[0057] b2. Immerse the copper foam sample in the inorganic liquid (the weight of the copper foam immersed in each liter of the inorganic liquid is 170 g), then add a certain amount of organic liquid to the inorganic liquid (the volume ratio of the organic liquid to the inorganic liquid is 5:4), react at room temperature for 22 hours, take out the copper foam sample, wash it with deionized water, and dry it at room temperature to obtain a surface-loaded praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The foam copper is recorded as intermediate A.

[0058] Step [3] In the praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The surface is inlaid with CdPr2S4 crystal, which specifically includes the following operations:

[0059] c1. The praseodymium nitrate, cadmium acetate, thioacetamide and ammonium thiosulfate are added to deionized water to form a crystal embedding solution; wherein the amount of praseodymium nitrate added per liter of the crystal embedding solution is 80 g, the amount of cadmium acetate added is 100 g, the amount of thioacetamide added is 50 g, and the amount of ammonium thiosulfate added is 150 g.

[0060] c2. The intermediate A was immersed in a crystal embedding solution (the weight of the intermediate A immersed in each liter of the crystal embedding solution was 140 g), heated to 70°C, reacted for 7 hours, and the foam copper sample was taken out and washed with deionized water, and dried at room temperature for 10 hours to form a praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the foam copper. n CdPr2S4 crystals are embedded on the surface to obtain the catalytic material, which is recorded as Comparative Example 1.

[0061] Comparative Example 2

[0062] This comparative example 2 provides a method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage, comprising the following steps:

[0063] Step [1] Preparation of Cd2SnSe4 nanocrystalline particles, specifically comprising the following operations:

[0064] Selenous acid, stannous chloride, cadmium acetate and fluvastatin sodium are added to deionized water and mixed to form a preparation solution; heated to 80°C under a closed condition, reacted for 8 hours, cooled to room temperature and filtered to obtain a solid phase, and placed in an oven to dry at 40°C for 6 hours to obtain the Cd2SnSe4 nanocrystalline particles. In each liter of the preparation solution, the amount of selenous acid added is 140g, the amount of stannous chloride added is 210g, the amount of cadmium acetate added is 190g, and the amount of fluvastatin sodium added is 20g.

[0065] Step [2] Loading praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the copper foam substrate n , including the following operations:

[0066] b1. Add 3,4-ethylenedioxythiophene and praseodymium nitrate to ethanol and mix to form an organic composition liquid; add copper sulfate, ammonium bromide and 40% hydrobromic acid by mass to deionized water and mix to form an inorganic composition liquid; wherein, the amount of 3,4-ethylenedioxythiophene added to each liter of the organic composition liquid is 200 mL, and the amount of praseodymium nitrate added is 170 g; the amount of copper sulfate added to each liter of the inorganic composition liquid is 100 g, the amount of ammonium bromide added is 130 g, and the amount of 40% hydrobromic acid added is 400 mL.

[0067] b2. Immerse the copper foam sample in the inorganic liquid (the weight of the copper foam immersed in each liter of the inorganic liquid is 200 g), then add a certain amount of organic liquid to the inorganic liquid (the volume ratio of the organic liquid to the inorganic liquid is 5:3), react at room temperature for 22 hours, take out the copper foam sample, wash it with deionized water, and dry it at room temperature to obtain a surface-loaded praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The foam copper is recorded as intermediate A.

[0068] Step [3] In the praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The surface is inlaid with Cd2SnSe4 crystals, which specifically includes the following operations:

[0069] c1. Add cadmium acetate, selenious acid, stannous chloride and the Cd2SnSe4 nanocrystal particles to deionized water to form a crystal embedding solution; wherein, per liter of the crystal embedding solution, the amount of cadmium acetate added is 100g, the amount of selenious acid added is 40g, the amount of stannous chloride added is 30g, and the amount of Cd2SnSe4 nanocrystal particles added is 20g.

[0070] c2. The intermediate A was immersed in a composite crystal embedding solution (the weight of the intermediate A immersed in each liter of the composite crystal embedding solution was 160 g), heated to 70°C, reacted for 8 hours, and the foam copper sample was taken out and washed with deionized water, and dried at room temperature for 11 hours to form a praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the foam copper. n Cd2SnSe4 crystals are embedded on the surface to obtain the catalytic material, which is recorded as Comparative Example 2.

[0071] In order to analyze the degradation rate of carbamazepine wastewater by photocatalytic degradation of Example 1, Comparative Example 1 and Comparative Example 2 and their photocatalytic stability for repeated use, carbamazepine was added to deionized water to form simulated carbamazepine wastewater with a carbamazepine concentration of 10 mg / L. 1000 ml of simulated carbamazepine-containing wastewater was poured into beakers, and 15 g of Example 1, Comparative Example 1 and Comparative Example 2 were placed in beakers, and the simulated carbamazepine wastewater was photodegraded for 50 minutes under visible light of 550 nm and ultraviolet light of 300 nm with a 200W xenon lamp light source, respectively. At the same time, a control experimental group with only corresponding light was set up. The relative concentration of residual carbamazepine in the simulated wastewater after 50 minutes of photocatalytic degradation was as follows: Figure 6 As shown in the figure, it can be seen that the relative concentrations of residual carbamazepine in the simulated sewage by photocatalytic degradation under simulated visible light and ultraviolet light conditions in Example 1 are only 0.07 and 0.04, respectively, while under the same conditions, the relative concentrations of residual carbamazepine in Comparative Example 1 are 0.58 and 0.51, respectively, and the relative concentrations of residual carbamazepine in Comparative Example 2 reach 0.42 and 0.37, while when only illumination is used (i.e., when Example 1, Comparative Example 1 and Comparative Example 2 are not used), the relative concentrations of residual carbamazepine in the simulated sewage under simulated visible light and ultraviolet light conditions are 0.98 and 0.97, respectively.

[0072] Under the aforementioned simulated visible light and ultraviolet light conditions, Example 1, Comparative Example 1 and Comparative Example 2 were used repeatedly to treat the simulated carbamazepine wastewater (each time for photocatalytic degradation for 50 minutes), and the relationship between the number of uses and the relative concentration of residual carbamazepine was as follows: Figure 7 and Figure 8 As shown in the figure, it can be seen that the relative concentrations of residual carbamazepine in the photocatalytic degradation of simulated carbamazepine wastewater with a concentration of 10 mg / L in Example 1 when recycled for the fifth time under visible light and ultraviolet light conditions are only 0.1 and 0.09, respectively, which are much lower than the relative concentrations of residual carbamazepine in Comparative Example 1 and Comparative Example 2 when recycled for the fifth time (0.87 and 0.82, 0.78 and 0.66, respectively). Obviously, Example 1 has stable and efficient recyclable characteristics.

[0073] In summary, the photocatalytic material prepared according to the present invention has a high efficiency of carbamazepine photocatalytic degradation rate and excellent photocatalytic stability for repeated use.

[0074] To illustrate in further detail, three additional examples are provided below.

[0075] Example 2

[0076] Preferred embodiment 2 of the present invention provides a method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage, comprising the following steps:

[0077] Step [1] Preparation of Cd2SnSe4 nanocrystalline particles, specifically comprising the following operations:

[0078] Selenous acid, stannous chloride, cadmium acetate and fluvastatin sodium are added to deionized water and mixed to form a preparation solution; heated to 70°C under a closed condition, reacted for 10 hours, cooled to room temperature and filtered to obtain a solid phase, and placed in an oven to dry at 35°C for 8 hours to obtain the Cd2SnSe4 nanocrystalline particles. In each liter of the preparation solution, the amount of selenous acid added is 120g, the amount of stannous chloride added is 230g, the amount of cadmium acetate added is 180g, and the amount of fluvastatin sodium added is 10g.

[0079] Step [2] Loading praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the copper foam substrate n , including the following operations:

[0080] b1. Add 3,4-ethylenedioxythiophene and praseodymium nitrate to ethanol and mix to form an organic component liquid; add copper sulfate, ammonium bromide and 40% hydrobromic acid by mass to deionized water and mix to form an inorganic component liquid; wherein, the amount of 3,4-ethylenedioxythiophene added to each liter of the organic component liquid is 170 mL, the amount of praseodymium nitrate added is 140 g, the amount of copper sulfate added to each liter of the inorganic component liquid is 80 g, the amount of ammonium bromide added is 150 g, and the amount of 40% hydrobromic acid added is 350 mL.

[0081] b2. Immerse the copper foam sample in the inorganic liquid (the weight of the copper foam immersed in each liter of the inorganic liquid is 160 g), then add a certain amount of organic liquid to the inorganic liquid (the volume ratio of the organic liquid to the inorganic liquid is 5:3), react at room temperature for 20 hours, take out the copper foam sample, wash it with deionized water, and dry it at room temperature to obtain a surface-loaded praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The foam copper is recorded as intermediate A.

[0082] Step [3] In the praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] nThe surface is inlaid with CdPr2S4 / Cd2SnSe4 composite crystal, which specifically includes the following operations:

[0083] c1. The praseodymium nitrate, cadmium acetate, thioacetamide, ammonium thiosulfate, selenious acid, stannous chloride and the Cd2SnSe4 nanocrystalline particles are added to deionized water to form a composite crystal inlay solution; wherein, per liter of the composite crystal inlay solution, the amount of praseodymium nitrate added is 60g, the amount of cadmium acetate added is 110g, the amount of thioacetamide added is 40g, the amount of ammonium thiosulfate added is 140g, the amount of selenious acid added is 60g, the amount of stannous chloride added is 20g, and the amount of Cd2SnSe4 nanocrystalline particles added is 10g.

[0084] c2. The intermediate A was immersed in a composite crystal embedding solution (the weight of the intermediate A immersed in each liter of the composite crystal embedding solution was 130 g), heated to 60°C, reacted for 8 hours, and the foam copper sample was taken out and washed with deionized water, and dried at room temperature for 10 hours to form a praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the foam copper. n The catalytic material is obtained by embedding CdPr2S4 / Cd2SnSe4 composite crystals on the surface.

[0085] Example 3

[0086] Preferred embodiment 3 of the present invention provides a method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage, comprising the following steps:

[0087] Step [1] Preparation of Cd2SnSe4 nanocrystalline particles, specifically comprising the following operations:

[0088] Selenous acid, stannous chloride, cadmium acetate and fluvastatin sodium are added to deionized water and mixed to form a preparation solution; the solution is heated to 90°C in a sealed condition, reacted for 8 hours, cooled to room temperature, filtered to obtain a solid phase, and dried in an oven at 50°C for 5 hours to obtain the Cd2SnSe4 nanocrystalline particles. In each liter of the preparation solution, the amount of selenous acid added is 160g, the amount of stannous chloride added is 190g, the amount of cadmium acetate added is 200g, and the amount of fluvastatin sodium added is 30g.

[0089] Step [2] Loading praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the copper foam substrate n , including the following operations:

[0090] b1. Add 3,4-ethylenedioxythiophene and praseodymium nitrate to ethanol and mix to form an organic composition liquid; add copper sulfate, ammonium bromide and 40% hydrobromic acid by mass to deionized water and mix to form an inorganic composition liquid; wherein, the amount of 3,4-ethylenedioxythiophene added to each liter of the organic composition liquid is 210 mL, the amount of praseodymium nitrate added is 190 g, the amount of copper sulfate added to each liter of the inorganic composition liquid is 140 g, the amount of ammonium bromide added is 120 g, and the amount of 40% hydrobromic acid added is 420 mL.

[0091] b2. Immerse the copper foam sample in the inorganic liquid (the weight of the copper foam immersed in each liter of the inorganic liquid is 220 g), then add a certain amount of organic liquid to the inorganic liquid (the volume ratio of the organic liquid to the inorganic liquid is 7:5), react at room temperature for 26 hours, take out the copper foam sample, wash it with deionized water, and dry it at room temperature to obtain a surface-loaded praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The foam copper is recorded as intermediate A.

[0092] Step [3] In the praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The surface is inlaid with CdPr2S4 / Cd2SnSe4 composite crystal, which specifically includes the following operations:

[0093] c1. The praseodymium nitrate, cadmium acetate, thioacetamide, ammonium thiosulfate, selenious acid, stannous chloride and the Cd2SnSe4 nanocrystalline particles are added to deionized water to form a composite crystal embedding solution; wherein, per liter of the composite crystal embedding solution, the amount of praseodymium nitrate added is 90g, the amount of cadmium acetate added is 90g, the amount of thioacetamide added is 80g, the amount of ammonium thiosulfate added is 170g, the amount of selenious acid added is 30g, the amount of stannous chloride added is 50g, and the amount of Cd2SnSe4 nanocrystalline particles added is 30g.

[0094] c2. The intermediate A was immersed in a composite crystal embedding solution (the weight of the intermediate A immersed in each liter of the composite crystal embedding solution was 170 g), heated to 80°C, reacted for 6 hours, and the foam copper sample was taken out and washed with deionized water, and dried at room temperature for 12 hours to form a praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the foam copper. n The catalytic material is obtained by embedding CdPr2S4 / Cd2SnSe4 composite crystals on the surface.

[0095] Example 4

[0096] Preferred embodiment 4 of the present invention provides a method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage, comprising the following steps:

[0097] Step [1] Preparation of Cd2SnSe4 nanocrystalline particles, specifically comprising the following operations:

[0098] Selenous acid, stannous chloride, cadmium acetate and fluvastatin sodium are added to deionized water and mixed to form a preparation solution; the solution is heated to 80°C under a closed condition, reacted for 9 hours, cooled to room temperature, filtered to obtain a solid phase, and dried in an oven at 42°C for 6.5 hours to obtain the Cd2SnSe4 nanocrystalline particles. In each liter of the preparation solution, the amount of selenous acid added is 140g, the amount of stannous chloride added is 210g, the amount of cadmium acetate added is 190g, and the amount of fluvastatin sodium added is 20g.

[0099] Step [2] Loading praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the copper foam substrate n , including the following operations:

[0100] b1. Add 3,4-ethylenedioxythiophene and praseodymium nitrate to ethanol and mix to form an organic composition liquid; add copper sulfate, ammonium bromide and 40% hydrobromic acid by mass to deionized water and mix to form an inorganic composition liquid; wherein, the amount of 3,4-ethylenedioxythiophene added to each liter of the organic composition liquid is 190 mL, the amount of praseodymium nitrate added is 165 g, and the amount of copper sulfate added to each liter of the inorganic composition liquid is 110 g, the amount of ammonium bromide added is 135 g, and the amount of 40% hydrobromic acid added is 385 mL.

[0101] b2. Immerse the copper foam sample in the inorganic liquid (the weight of the copper foam immersed in each liter of the inorganic liquid is 190 g), then add a certain amount of organic liquid to the inorganic liquid (the volume ratio of the organic liquid to the inorganic liquid is 5:4), react at room temperature for 23 hours, take out the copper foam sample, wash it with deionized water, and dry it at room temperature to obtain a surface-loaded praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The foam copper is recorded as intermediate A.

[0102] Step [3] In the praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The surface is inlaid with CdPr2S4 / Cd2SnSe4 composite crystal, which specifically includes the following operations:

[0103] c1. The praseodymium nitrate, cadmium acetate, thioacetamide, ammonium thiosulfate, selenious acid, stannous chloride and the Cd2SnSe4 nanocrystalline particles are added to deionized water to form a composite crystal embedding solution; wherein, per liter of the composite crystal embedding solution, the amount of praseodymium nitrate added is 75g, the amount of cadmium acetate added is 100g, the amount of thioacetamide added is 60g, the amount of ammonium thiosulfate added is 155g, the amount of selenious acid added is 45g, the amount of stannous chloride added is 35g, and the amount of Cd2SnSe4 nanocrystalline particles added is 20g.

[0104] c2. The intermediate A was immersed in a composite crystal embedding solution (the weight of the intermediate A immersed in each liter of the composite crystal embedding solution was 150 g), heated to 70°C, reacted for 7 hours, and the foam copper sample was taken out and washed with deionized water, and dried at room temperature for 11 hours to form a praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the foam copper. n The catalytic material is obtained by embedding CdPr2S4 / Cd2SnSe4 composite crystals on the surface.

[0105] The above are only preferred embodiments of the present invention. It should be understood that the description of the above embodiments is only used to help understand the method and core ideas of the present invention, and is not used to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, etc. made within the ideas and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage, characterized in that: The following steps are included: Step [1] preparing Cd2SnSe4 nanocrystalline particles; Step [2] Loading praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the copper foam substrate n ; Step [3] In the praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The surface is inlaid with CdPr2S4 / Cd2SnSe4 composite crystals.

2. The method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage according to claim 1, characterized in that: The step [1] specifically includes the following operations: Selenious acid, stannous chloride, cadmium acetate and fluvastatin sodium are added to deionized water and mixed to form a preparation solution; the solution is heated to 70-90°C under closed conditions, reacted for 8-10 hours, cooled to room temperature and filtered to obtain a solid phase, which is placed in an oven and dried at 35-50°C for 5-8 hours to obtain the Cd2SnSe4 nanocrystalline particles.

3. The method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage according to claim 2, characterized in that: The amount of selenious acid added in each liter of the preparation solution is 120-160 g, the amount of stannous chloride added is 190-230 g, the amount of cadmium acetate added is 180-200 g, and the amount of fluvastatin sodium added is 10-30 g.

4. The method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage according to claim 1, characterized in that: The step [2] specifically includes the following operations: b1. Add 3,4-ethylenedioxythiophene and praseodymium nitrate to ethanol and mix to form an organic liquid composition; add copper sulfate, ammonium bromide and 40% by mass of hydrobromic acid to deionized water and mix to form an inorganic liquid composition; b2. Immerse the copper foam sample in the inorganic liquid composition, then add a certain amount of organic liquid composition to the inorganic liquid composition, react at room temperature for 20-26 hours, remove the copper foam sample, wash with deionized water, and dry at room temperature to obtain a surface loaded with praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] n The foam copper is recorded as intermediate A.

5. The method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage according to claim 4, characterized in that: In step b1, the amount of 3,4-ethylenedioxythiophene added to each liter of the organic component liquid is 170-210 mL, and the amount of praseodymium nitrate added to each liter of the inorganic component liquid is 80-140 g, the amount of ammonium bromide added to each liter of the inorganic component liquid is 120-150 g, and the amount of 40% hydrobromic acid added to each liter is 350-420 mL.

6. The method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage according to claim 4, characterized in that: In step b2, the weight of the copper foam immersed in each liter of the inorganic component liquid is 160-220 g; the volume ratio between the organic component liquid and the inorganic component liquid is 5-7:3-5.

7. The method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage according to claim 1, characterized in that: The step [3] specifically includes the following operations: c1. Praseodymium nitrate, cadmium acetate, thioacetamide, ammonium thiosulfate, selenious acid, stannous chloride and the Cd2SnSe4 nanocrystalline particles are added to deionized water to form a composite crystal mosaic solution; c2. Immerse the intermediate A in the composite crystal embedding solution, heat to 60-80°C, react for 6-8 hours, take out the copper foam sample, wash with deionized water, and dry at room temperature for 10-12 hours to form a praseodymium copper bromide coordination polymer [Pr4Cu2Br6(EDOT)4] on the surface of the copper foam. n The catalytic material is obtained by embedding CdPr2S4 / Cd2SnSe4 composite crystals on the surface.

8. The method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage according to claim 7, characterized in that: In step c1, the amount of praseodymium nitrate added to each liter of the composite crystal embedding liquid is 60-90 g, the amount of cadmium acetate added is 90-110 g, the amount of thioacetamide added is 40-80 g, the amount of ammonium thiosulfate added is 140-170 g, the amount of selenious acid added is 30-60 g, the amount of stannous chloride added is 20-50 g, and the amount of Cd2SnSe4 nanocrystal particles added is 10-30 g.

9. The method for preparing a catalytic material for photocatalytic degradation of carbamazepine in sewage according to claim 7, characterized in that: In step c2, the weight of the intermediate A immersed in each liter of the composite crystal embedding liquid is 130-170 g.

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