Preparation method of metal molybdenum defect enhanced bismuth molybdate photocatalyst and application of metal molybdenum defect enhanced bismuth molybdate photocatalyst in removal of sulfamethoxazole in water
By preparing the bismuth molybdate photocatalyst VM-Bi2MoO6, which is enhanced by defects in metallic molybdenum, the problem of low visible light utilization of bismuth-based photocatalysts was solved, achieving efficient removal of sulfamethoxazole from water. Furthermore, the catalyst is reusable and adaptable to various environmental conditions.
Patent Information
- Application Number
- CN202511172436.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-21
- Publication Date
- 2025-12-02
AI Technical Summary
Existing bismuth-based photocatalysts suffer from low visible light utilization, low photogenerated carrier separation rate, and low mobility, resulting in poor removal efficiency of sulfamethoxazole from water, and traditional water treatment technologies are not ideal.
By preparing the bismuth molybdate photocatalyst VM-Bi2MoO6 with enhanced molybdenum defects, bismuth molybdate nanosheets were synthesized using hydrothermal reaction and sodium hydroxide etching, and then photocatalytically degraded sulfamethoxazole in water under xenon lamp illumination.
It achieves efficient removal of sulfamethoxazole from water, the catalyst can be reused, the removal effect is not significantly affected by pH value and inorganic anions, and the method is simple and environmentally friendly.
Smart Images
Figure CN121042014A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of wastewater treatment technology, specifically relating to a method for preparing a bismuth molybdate photocatalyst with enhanced molybdenum defect and its application in removing sulfamethoxazole from water. Background Technology
[0002] Antibiotics, as one of the most significant medical breakthroughs of the 20th century, have made substantial contributions to the prevention and treatment of infectious diseases in humans and animals. However, with the widespread use of antibiotics in human medicine and veterinary medicine, their abuse and overuse have also caused serious environmental problems.
[0003] Sulfamethoxazole is a broad-spectrum antibacterial drug widely used to eliminate inflammation and treat infections in humans and animals. However, only a small fraction of sulfamethoxazole is metabolized by humans and animals; the majority of ingested sulfamethoxazole or its metabolites ultimately enter the aquatic environment through feces, causing pollution. Due to its antibacterial activity, low bioavailability, and persistence, traditional water treatment technologies are ineffective in removing sulfamethoxazole. Therefore, it is necessary to develop innovative technologies that can effectively degrade sulfamethoxazole from wastewater.
[0004] Although existing water treatment technologies (such as adsorption, biological methods, and electrocatalysis) have been extensively studied, their effectiveness has significant limitations. Photocatalysis, due to its advantages of low energy consumption, low risk of secondary pollution, and simplicity, has been proven to be an effective method for solving environmental pollution. In the photocatalytic process, the photocatalyst absorbs photon energy to generate electrons and holes, inducing the generation of free radicals, which ultimately degrade organic pollutants.
[0005] Bismuth-based photocatalysts have become a research hotspot in the field of photocatalysis due to their unique structure-performance correlation. They possess numerous advantages, including diverse crystal structures, tunable band gaps, strong light absorption, strong oxidation capacity, good chemical stability, abundant raw material reserves, and simple preparation methods. However, in practical applications, bismuth-based photocatalysts still face challenges such as low visible light utilization, low photogenerated carrier separation rate, and low mobility, which require further improvement. Therefore, there is an urgent need for a highly efficient, economical, and environmentally friendly method for treating sulfamethoxazole. Summary of the Invention
[0006] In view of the above problems, the purpose of this invention is to propose a method for preparing a bismuth molybdate photocatalyst with enhanced molybdenum defects and its application in removing sulfamethoxazole from water. This method can achieve efficient removal of sulfamethoxazole from water and has the advantages of easy material recycling and reuse, and the removal effect is not greatly affected by factors such as pH value and various inorganic anions.
[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0008] A method for preparing a bismuth molybdate photocatalyst with enhanced molybdenum defects involves first reacting a molybdenum powder solution with a bismuth nitrate solution via hydrothermal reaction to obtain a bismuth molybdate nanosheet precursor, Bi₂MoO₆. Then, the synthesized bismuth molybdate nanosheet precursor, Bi₂MoO₆, is dispersed in a sodium hydroxide solution and stirred. After etching, a bismuth molybdate material containing molybdenum defects is obtained, namely, the bismuth molybdate photocatalyst with enhanced molybdenum defects. M -Bi2MoO6.
[0009] As a preferred embodiment of the present invention, the preparation method steps are as follows:
[0010] Step 1: Mix molybdenum powder solution and bismuth nitrate solution and stir, then perform hydrothermal reaction to obtain bismuth molybdate nanosheet precursor Bi2MoO6; wherein, the molar ratio of molybdenum powder to bismuth nitrate is 1:1~3, the hydrothermal reaction temperature is 150~170℃, and the reaction time is 8~16h.
[0011] Step 2: The bismuth molybdate nanosheet precursor Bi₂MoO₆ was dispersed in a sodium hydroxide solution and etched by ultrasonic stirring to obtain the bismuth molybdate photocatalyst V, which is enhanced by the defects of metallic molybdenum. M -Bi2MoO6.
[0012] As a further preferred technical solution of the present invention, in step 1 of the preparation method, the molybdenum powder solution is obtained by dissolving 2 mmol of molybdenum powder in 5 mL of deionized water, followed by slowly adding 5 mL of hydrogen peroxide and stirring at room temperature for 3 h. The bismuth nitrate solution is obtained by dissolving 4 mmol of bismuth nitrate in 10 mL of ethanol. In step 2, 200 mg of bismuth molybdate nanosheets are stirred and etched in 20 mL of sodium hydroxide solution with a concentration of 0.2~0.4 mol / L for 30 min to obtain the bismuth molybdate photocatalyst V with enhanced molybdenum defect enhancement. M -Bi2MoO6.
[0013] The present invention also proposes an application of the molybdenum defect-enhanced bismuth molybdate photocatalyst in the removal of sulfamethoxazole from water. The molybdenum defect-enhanced bismuth molybdate photocatalyst is added to water containing sulfamethoxazole, stirred for a period of time to reach adsorption-desorption equilibrium, and then irradiated with a xenon lamp while continuously stirring to achieve the removal of sulfamethoxazole from the water.
[0014] As a preferred embodiment of the present invention, the dosage of the molybdenum defect-enhanced bismuth molybdate photocatalyst in the system is 0.6~0.7 g / L. The xenon lamp has a power of 300W and is equipped with a 420nm cutoff filter as the light source for the photocatalytic reaction. The concentration of sulfamethoxazole in the system is 2~10 mg / L. After removal, the molybdenum defect-enhanced bismuth molybdate photocatalyst in the system is recovered and reused through centrifugation, washing, and drying.
[0015] Experiments have confirmed that the bismuth molybdate photocatalyst V prepared in this invention, which enhances the defects of metallic molybdenum, is effective. M When Bi₂MoO₆ is used in conjunction with a xenon lamp, highly efficient removal of sulfamethoxazole from water is achieved. Compared with existing technologies, the advantages of this invention are as follows:
[0016] 1. A bismuth molybdate photocatalyst with enhanced defects in metallic molybdenum can be synthesized by combining simple hydrothermal treatment with sodium hydroxide etching. M -Bi2MoO6.
[0017] 2. Synthesized bismuth molybdate photocatalyst with defect-enhanced metallic molybdenum V M -Bi2MoO6 has a high removal efficiency for sulfamethoxazole in water.
[0018] 3. Bismuth molybdate photocatalyst enhanced by defects in metallic molybdenum (V) M -Bi2MoO6 is used to remove sulfamethoxazole from water and can be reused after recycling and washing.
[0019] 4. Bismuth molybdate photocatalyst enhanced by defects in metallic molybdenum (V) M -Bi2MoO6 is used to remove sulfamethoxazole from water, and its removal effect is minimally affected by factors such as pH value and various inorganic anions. Attached Figure Description
[0020] Figure 1 The present invention provides a bismuth molybdate photocatalyst V that enhances the defects of metallic molybdenum. M A schematic diagram of the preparation of -Bi2MoO6 and its application in the removal of sulfamethoxazole from water.
[0021] Figure 2 The molybdenum defect-enhanced bismuth molybdate photocatalyst V synthesized for the example M Phase characterization results of -Bi2MoO6.
[0022] Figure 3 The molybdenum defect-enhanced bismuth molybdate photocatalyst V synthesized for the example M Scanning electron microscope image of Bi2MoO6.
[0023] Figure 4 The molybdenum defect-enhanced bismuth molybdate photocatalyst V synthesized for the example M Transmission electron microscope image of Bi2MoO6.
[0024] Figure 5 Bismuth molybdate photocatalyst V for enhancing the defects of metallic molybdenum M - Comparison of the effect of Bi₂MoO₆ addition on the removal rate of sulfamethoxazole in water; wherein the reaction system is 30 mL, the concentration of sulfamethoxazole is 5 mg / L, and the metal molybdenum defect-enhanced bismuth molybdate photocatalyst VM The dosage of -Bi2MoO6 is 20mg, and the xenon lamp power is 300W (equipped with a 420nm cutoff filter).
[0025] Figure 6 Enhanced Bismuth Molybdate Photocatalyst V for Defects in Regenerated Metallic Molybdenum M - Comparison of the effects of Bi₂MoO₆ on the removal of sulfamethoxazole from water; wherein the reaction system was 30 mL, the concentration of sulfamethoxazole was 5 mg / L, and V M The dosage of Bi2MoO6 photocatalyst is 20mg, and the xenon lamp power is 300W (equipped with a 420nm cutoff filter).
[0026] Figure 7 The effects of humic acid or different anions on the removal rate of sulfamethoxazole in water were compared; the reaction system was 30 mL, the concentration of sulfamethoxazole was 5 mg / L, the concentration of anion was 1 mmol / L, and the metal molybdenum defect-enhanced bismuth molybdate photocatalyst V was used. M The dosage of -Bi2MoO6 is 20mg, and the xenon lamp power is 300W (equipped with a 420nm cutoff filter).
[0027] Figure 8 The effect of different initial pH values of the solution on the removal rate of sulfamethoxazole in water was compared; the reaction system was 30 mL, the concentration of sulfamethoxazole was 5 mg / L, and the metal molybdenum defect-enhanced bismuth molybdate photocatalyst V was used. M The dosage of -Bi2MoO6 is 20mg, and the xenon lamp power is 300W (equipped with a 420nm cutoff filter). Detailed Implementation
[0028] The following detailed description, in conjunction with embodiments and accompanying drawings, further illustrates the preparation method of the metal molybdenum defect-enhanced bismuth molybdate photocatalyst of the present invention and its application in removing sulfamethoxazole from water.
[0029] Please see Figure 1 As shown, this invention first prepares a bismuth molybdate photocatalyst V with enhanced molybdenum defect enhancement. M -Bi2MoO6, and its use to remove sulfamethoxazole from wastewater, namely, the molybdenum defect-enhanced bismuth molybdate photocatalyst V M Bi2MoO6 was added to water containing sulfamethoxazole and stirred for a period of time to reach adsorption-desorption equilibrium. Then, a xenon lamp was turned on for illumination, and stirring was continued to remove sulfamethoxazole from the water.
[0030] Example 1
[0031] Metallic molybdenum defect-enhanced bismuth molybdate photocatalyst V M Preparation of Bi2MoO6
[0032] First, 2 mmol of molybdenum powder was dissolved in 5 mL of deionized water, followed by the slow addition of 5 mL of hydrogen peroxide. The mixture was stirred at room temperature for 3 h to form a homogeneous solution. Simultaneously, 4 mmol of bismuth nitrate was dissolved in 10 mL of ethanol to prepare another homogeneous solution. The bismuth nitrate solution was then added to the molybdenum powder solution, and the mixture was stirred for 5 min. All reactants were then transferred to a 50 mL high-pressure reactor and reacted solvatithetically at 160°C for 12 h. After the reaction was complete and cooled to room temperature, the mixture was poured into centrifuge tubes and centrifuged at 5000 rpm for 3 min. The supernatant was discarded. The product was washed three times with deionized water and once with ethanol. The product was then dried in a 60°C oven for 12 h to obtain the bismuth molybdate nanosheet precursor Bi₂MoO₆.
[0033] Next, a clean beaker was prepared, and 200 mg of bismuth molybdate nanosheets and 20 mL of sodium hydroxide solution (0.34 mol / L) were added. The mixture was ultrasonically stirred for 5 min to form a homogeneous solution, and then stirred for another 30 min at room temperature. The mixture was then poured into a centrifuge tube and centrifuged at 5000 rpm for 3 min. The supernatant was discarded. The product was washed three times with deionized water and once with ethanol. The product was then dried in a 60°C oven for 12 h to obtain the molybdenum defect-enhanced bismuth molybdate photocatalyst V. M -Bi2MoO6.
[0034] Figure 2 The bismuth molybdate photocatalyst V, which is a defect-enhanced form of metallic molybdenum synthesized by the method described in this embodiment, is... M Phase characterization results of -Bi2MoO6 Figure 3 The bismuth molybdate photocatalyst V, which is a defect-enhanced form of metallic molybdenum synthesized by the method described in this embodiment, is... M Scanning electron microscope image of Bi2MoO6 Figure 4 The bismuth molybdate photocatalyst V, which is a defect-enhanced form of metallic molybdenum synthesized by the method described in this embodiment, is... M Transmission electron microscope image of Bi₂MoO₆. The image shows that the product prepared in this invention has a plate-like structure, confirming that the prepared product is V. M -Bi2MoO6.
[0035] Example 2
[0036] Metallic molybdenum defect-enhanced bismuth molybdate photocatalyst V M Application of Bi2MoO6 in the removal of sulfamethoxazole from water
[0037] The bismuth molybdate photocatalyst V obtained in Example 1, which enhances the defect-enhanced molybdate structure, was used. M20 mg of Bi₂MoO₆ was added to 30 mL of a 5 mg / L sulfamethoxazole solution and ultrasonically dispersed. The mixture was stirred at 550 rpm for 60 min to reach adsorption-desorption equilibrium. Subsequently, a 300 W xenon lamp (equipped with a 420 nm cutoff filter) was turned on for photocatalysis. The stirring speed was maintained at 550 rpm. Results are shown below. Figure 5 . Figure 5 According to the scheme described in this embodiment, Bi2MoO6 and V M The removal rate of sulfamethoxazole in water by the Bi₂MoO₆ photocatalyst is shown in the figure. It can be seen that sulfamethoxazole does not undergo self-degradation under light irradiation alone without any photocatalyst. Under conditions of both light irradiation and the presence of a catalyst, the removal capacity of commercial titanium dioxide (P₂₅) and the Bi₂MoO₆ precursor for sulfamethoxazole is relatively limited, while the removal capacity of the molybdenum defect-enhanced bismuth molybdate photocatalyst V is significantly higher. M -Bi2MoO6 exhibits excellent sulfamethoxazole degradation performance.
[0038] Example 3
[0039] Regeneration of bismuth molybdate photocatalysts containing molybdenum defects
[0040] The system treated in Example 2 was centrifuged at 5000 rpm for 3 min, and the supernatant was discarded. It was washed three times with 35 mL of ultrapure water and three times with 15 mL of ethanol solution. During each wash, the solid was ultrasonically dispersed, and then centrifuged at 5000 rpm for 3 min, and the supernatant was discarded. Finally, the centrifuged product was dried in a 60℃ drying oven for 12 h to obtain the regenerated molybdenum defect-enhanced bismuth molybdate photocatalyst V. M -Bi2MoO6.
[0041] Example 4
[0042] Regenerated molybdenum defect-enhanced bismuth molybdate photocatalyst V M Application of Bi2MoO6 in the removal of sulfamethoxazole from water
[0043] This molybdenum defect-enhanced bismuth molybdate photocatalyst V M -Bi2MoO6 can be used and regenerated sequentially according to the schemes described in Examples 2 and 3 to achieve the purpose of recycling. The used and regenerated bismuth molybdate photocatalyst V... M After Bi2MoO6 was used again according to the schemes described in Examples 2 and 3, the removal rate of sulfamethoxazole could still reach 71.9% within 180 min. See the results below. Figure 6 . Figure 6 Enhanced Bismuth Molybdate Photocatalyst V for Defects in Regenerated Metallic Molybdenum M-Bi₂MoO₆ removes sulfamethoxazole from water. The photocatalyst V, which has been used and regenerated five times, is a defect-enhanced bismuth molybdate photocatalyst. M After Bi2MoO6 was used again according to the schemes described in Examples 2 and 3, the removal rate of sulfamethoxazole could still reach 68.6% within 180 min.
[0044] Example 5
[0045] Metallic molybdenum defect-enhanced bismuth molybdate photocatalyst V M Application of Bi₂MoO₆ in the removal of sulfamethoxazole from water under humic acid or different anionic conditions
[0046] The bismuth molybdate photocatalyst V obtained in Example 1, which enhances the defect-enhanced molybdate structure, was used. M Bi₂MoO₆ (20 mg) was added to a 30 mL solution of sulfamethoxazole (5 mg / L), along with 1 mmol / L humic acid or a common inorganic anion (corresponding to sodium ion as the cation), and then ultrasonically dispersed. The mixture was stirred at 550 rpm for 60 min to reach adsorption-desorption equilibrium. A xenon lamp (300 W, equipped with a 420 nm cutoff filter) was then used for photocatalysis. The stirring speed was maintained at 550 rpm. Results are shown below. Figure 7 . Figure 7 According to the solution described in this embodiment, and The presence of [a substance] has little impact on photocatalytic degradation; sulfamethoxazole showed a removal rate of approximately 97% within 180 minutes. However, when [a substance] is added... At that time, the photocatalytic activity decreased, and the removal rate of sulfamethoxazole reached only 57.9%. In addition, humic acid and other inorganic anions (…) , and It will inhibit the removal of sulfamethoxazole.
[0047] Example 6
[0048] Metallic molybdenum defect-enhanced bismuth molybdate photocatalyst V M Application of Bi2MoO6 in the removal of sulfamethoxazole from water under different pH conditions
[0049] The bismuth molybdate photocatalyst V obtained in Example 1, which enhances the defect-enhanced molybdate structure, was used. M Bi₂MoO₆ (20 mg) was added to 30 mL of a 5 mg / L sulfamethoxazole solution, and the solution was adjusted to different pH values (2–10) and ultrasonically dispersed. The mixture was stirred at 550 rpm for 60 min to reach adsorption-desorption equilibrium. A xenon lamp (300 W, 420 nm cutoff filter) was then used for photocatalysis. The stirring speed was maintained at 550 rpm. Results are shown below. Figure 8 . Figure 8 According to the scheme described in this embodiment, the removal of sulfamethoxazole was inhibited under pH=2 and pH=4 conditions; as the pH increased, the removal rate of sulfamethoxazole gradually increased, and when pH=10, the removal rate of sulfamethoxazole reached 76.3% within 180 min.
Claims
1. A method for preparing a bismuth molybdate photocatalyst with enhanced molybdenum defect enhancement, characterized in that, First, bismuth molybdate nanosheet precursor Bi₂MoO₆ was obtained by hydrothermal reaction of molybdenum powder solution and bismuth nitrate solution. Then, the synthesized bismuth molybdate nanosheet precursor Bi₂MoO₆ was dispersed in sodium hydroxide solution and stirred. After etching, bismuth molybdate material containing molybdenum defects was obtained, namely, bismuth molybdate photocatalyst V with enhanced molybdenum defect enhancement. M -Bi2MoO6.
2. The preparation method according to claim 1, characterized in that, The steps are as follows: Step 1: Mix molybdenum powder solution and bismuth nitrate solution and stir, then perform hydrothermal reaction to obtain bismuth molybdate nanosheet precursor Bi2MoO6; wherein, the molar ratio of molybdenum powder to bismuth nitrate is 1:1~3, the hydrothermal reaction temperature is 150~170℃, and the reaction time is 8~16h. Step 2: The bismuth molybdate nanosheet precursor Bi₂MoO₆ was dispersed in a sodium hydroxide solution and etched by ultrasonic stirring to obtain the bismuth molybdate photocatalyst V, which is enhanced by the defects of metallic molybdenum. M -Bi2MoO6.
3. The preparation method according to claim 2, characterized in that, In step 1, the molybdenum powder solution is obtained by dissolving 2 mmol of molybdenum powder in 5 mL of deionized water, then slowly adding 5 mL of hydrogen peroxide, and stirring at room temperature for 3 hours.
4. The preparation method according to claim 2, characterized in that, The bismuth nitrate solution in step 1 is obtained by dissolving 4 mmol of bismuth nitrate in 10 mL of ethanol.
5. The preparation method according to claim 2, characterized in that, In step 2, 200 mg of bismuth molybdate nanosheets were stirred and etched in 20 mL of a 0.2–0.4 mol / L sodium hydroxide solution for 30 min to obtain bismuth molybdate photocatalyst V, which is enhanced by the removal of molybdenum defects. M -Bi2MoO6.
6. The application of the molybdenum defect-enhanced bismuth molybdate photocatalyst prepared by the method according to any one of claims 1 to 5 in the removal of sulfamethoxazole from water, characterized in that, A bismuth molybdate photocatalyst with enhanced molybdenum defect was added to water containing sulfamethoxazole and stirred for a period of time to reach adsorption-desorption equilibrium. Then, a xenon lamp was turned on for illumination, and stirring was continued to remove sulfamethoxazole from the water.
7. The application as described in claim 6, characterized in that, The dosage of the metal molybdenum defect-enhanced bismuth molybdate photocatalyst in the system is 0.6~0.7 g / L.
8. The application as described in claim 6, characterized in that, The xenon lamp has a power of 300W and is equipped with a 420nm cutoff filter as the light source for the photocatalytic reaction.
9. The application as described in claim 6, characterized in that, The concentration of sulfamethoxazole in the system is 2~10 mg / L.
10. The application as described in claim 6, characterized in that, After removal, the bismuth molybdate photocatalyst with enhanced molybdenum defects in the system is recovered and reused through centrifugation, washing, and drying.