Preparation of Ce-doped BiOCOOH adsorption material
By modifying BiOCOOH with Ce doping, Ce-BiOCOOH adsorbent materials were prepared, solving the problems of low adsorption rate and difficulty in recycling of BiOCOOH, and realizing efficient and low-cost dye adsorption and recycling.
Patent Information
- Application Number
- CN202510846004.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-24
- Publication Date
- 2025-11-28
AI Technical Summary
Existing BiOCOOH adsorbent materials have low adsorption rates for dyes and are difficult to recycle, resulting in high treatment costs, low removal efficiency, and poor repeatability.
Ce-BiOCOOH adsorbent material was prepared by one-step hydrothermal method to increase its specific surface area and pore size by doping with Ce to modify BiOCOOH.
It improves the adsorption performance of dyes and the reusability of materials, with high adsorption rate, low cost, and environmental friendliness.
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Abstract
Description
TECHNICAL FIELD
[0001] The application relates to preparation of a Ce-doped BiOCOOH adsorbent material and belongs to the technical field of water treatment. BACKGROUND With the rapid development of industrial technology, synthetic dyes are applied in various industries and are environmental pollutants. Food, papermaking, leather, textile, pharmaceutical and paint industries often use these dyes as colorants. When these dyes are discharged into the water environment, they will have adverse effects on the ecological system. These dyes cause abnormal growth and development, death of aquatic organisms, and affect the balance of the water ecological system. At the same time, because of the consumption of aquatic food by humans, the biological accumulation of these toxic dyes in the water environment also indirectly affects humans and causes harm to human health. And Congo red (CR) is a common industrial dye. At present, many methods for treating dyes have been found, including membrane filtration, chemical reduction, advanced oxidation processes, etc. Adsorption is considered a viable technology that can eliminate dye pollutants from the water environment because of its high efficiency, low cost, easy operation and environmental friendliness.
[0002] Bismuth oxycarbonate (BiOCOOH) has ideal properties, including environmental friendliness, low cost and the like, and its unique layered structure is composed of interlaced [Bi2O2] 2+ layers and COOH - groups, and compared with other BiOXs with similar structures, it is more environmentally friendly. Therefore, it is a potential environmentally friendly candidate material with the least environmental risk. Although BiOCOOH has been widely used in the field of photocatalysis, there are few reports on its application as an adsorbent. Single BiOCOOH has low adsorption rate, which limits its application in dye adsorption. Moreover, from the adsorption mechanism, the adsorbent and the dye molecules mainly form chemical adsorption through chemical bonding. The process involves complex chemical changes. Compared with the weak interaction of physical adsorption, the adsorption energy formed by chemical adsorption is significantly improved, so that the dye molecules are difficult to desorb after adsorption by conventional means. Therefore, the adsorbent is difficult to realize recycling, and the cost is high in practical application. Therefore, in the application, BiOCOOH is modified to have high adsorption performance and high recycling performance.
[0003] Therefore, by doping Ce, the specific surface area and pore size of BiOCOOH are improved, and the adsorption performance is improved. SUMMARY
[0004] The purpose of this invention is to provide a method for preparing Ce-BiOCOOH adsorbent material, which aims to solve the problems of high cost, low efficiency and poor repeatability in the removal of dye pollutants from wastewater. To this end, a material with high adsorption efficiency is provided. This material is prepared by a one-step hydrothermal method and can effectively adsorb Congo red dye in wastewater.
[0005] The preparation method of a Ce-doped BiOCOOH adsorbent material includes the following steps: 1) Under magnetic stirring, a certain amount of bismuth nitrate pentahydrate was dissolved in ethylene glycol solution, and then a certain amount of sodium formate was added to the bismuth nitrate pentahydrate solution. The mixture was stirred for 1 hour to obtain a mixed solution. 2) Under magnetic stirring, a certain amount of cerium nitrate was dissolved in ethylene glycol solution and stirred for 1 hour to obtain a mixed solution; 3) Add the mixed solution from step 2) to the mixed solution from step 1), stir for 1 hour to obtain the precursor solution; 4) The precursor solution was placed in a stainless steel autoclave lined with polytetrafluoroethylene and sealed. Then it was placed in a constant temperature oven and reacted at high temperature for a certain period of time. 5) After the reaction vessel in step 4) has cooled naturally to room temperature, collect the product from the suspension by centrifugation, and then reflux it with anhydrous ethanol. The mixture was washed three times with deionized water and then placed in a constant temperature drying oven at 60℃ for 12 hours to obtain a Ce-doped BiOCOOH composite material.
[0006] According to the preparation method of claim 1, the molar ratio of bismuth nitrate pentahydrate to sodium formate is 1:1.
[0007] According to the preparation method of claim 1, the molar ratio of the doping amount of cerium nitrate to bismuth nitrate pentahydrate is (0.5-2):10.
[0008] According to the preparation method of claim 1, the temperature of the reaction vessel is 150°C. The response time is 10 hours.
[0009] The working principle of this invention is as follows: By doping BiOCOOH with a porous structure with Ce, the morphology and structure of BiOCOOH are changed, its specific surface area is increased, a new type of adsorbent material is formed, the adsorption performance of BiOCOOH is improved, and the Congo red dye is effectively treated.
[0010] The present invention has the following beneficial effects:
[0011] This invention synthesizes Ce-BiOCOOH material via a one-step hydrothermal method. The preparation process is simple, and the raw materials are readily available. This composite material exhibits excellent adsorption performance for Congo red dye and is easily recyclable. After four cycles of testing, it still maintains a high adsorption rate, demonstrating high stability and reusability. It has broad application prospects in environmental protection and remediation, materials chemistry, and other fields. Attached Figure Description
[0012] Figure 1 The image shows a scanning electron microscope (SEM) image of the BiOCOOH adsorbent material prepared in Example 1. Figure 2 The image shows a scanning electron microscope (SEM) image of the Ce-BiOCOOH adsorbent material prepared in Example 1. Figure 3 The time evolution diagram of the absorption spectrum of Ce-BiOCOOH adsorbent materials with different ratios prepared in Example 1 and the adsorption of Congo red by BiOCOOH is shown. Figure 4 The graph shows the efficiency of Ce-BiOCOOH adsorbent materials with different ratios prepared in Example 1 and the efficiency of BiOCOOH adsorption of Congo red as a function of reaction time. Figure 5 The adsorption cycle bar chart of Congo red (CR) adsorbed by the Ce-BiOCOOH adsorbent material prepared in Example 1. Detailed Implementation
[0013] The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.
[0014] Example 1 1) Under magnetic stirring, 10 mmol of bismuth nitrate pentahydrate was dissolved in ethylene glycol solution, and then 10 mmol of sodium formate was added to the bismuth nitrate pentahydrate solution. The mixture was stirred for 1 hour to obtain a mixed solution. 2) Dissolve 0.5 mmol of cerium nitrate in ethylene glycol solution under magnetic stirring and stir for 1 h to obtain a mixed solution; 3) Add the mixed solution from step 2) to the mixed solution from step 1), stir for 1 hour to obtain the precursor solution; 4) Place the precursor solution in a stainless steel autoclave lined with polytetrafluoroethylene and seal it. Then place it in a constant temperature oven and react at high temperature for a certain period of time. 5) After the reaction vessel in step 4) has cooled naturally to room temperature, the product in the suspension is collected by centrifugation, washed three times with anhydrous ethanol and deionized water respectively, and then placed in a constant temperature drying oven at 60℃ for 12h to obtain Ce-doped BiOCOOH composite material. Example 2
[0015] The difference between this embodiment and Embodiment 1 is that the amount of cerium nitrate in step 2) is 1 mmol. Everything else is the same as in Embodiment 1. Example 3
[0016] The difference between this embodiment and Embodiment 1 is that the amount of cerium nitrate in step 2) is 1.5 mmol. Everything else is the same as in Embodiment 1. Example 4
[0017] The difference between this embodiment and Embodiment 1 is that the amount of cerium nitrate in step 2) is 2 mmol. Everything else is the same as in Embodiment 1.
[0018] The performance of the Ce-BiOCOOH adsorbent materials obtained in Examples 2-4 is comparable to that of the Ce-BiOCOOH adsorbent material obtained in Example 1.
[0019] As can be seen from the above embodiments, the present invention provides a method for preparing a Ce-BiOCOOH composite material for adsorption. The method for preparing the Ce-BiOCOOH composite material of the present invention is simple, low-cost, and features no secondary pollution and low energy consumption. Compared with pure BiOCOOH material, the Ce-BiOCOOH composite material exhibits higher efficiency in adsorbing and removing Congo red from water. When the adsorption time is 5 min, the CR removal rate reaches 97.98%. After four cycles, it still has a high adsorption rate, high stability, and reusability, making it a potentially excellent wastewater treatment material.
[0020] The scanning electron microscope (SEM) image of the BiOCOOH adsorbent material prepared in Example 1 is shown below. Figure 1 As shown, pure BiOCOOH exhibits a flower-like structure, composed of numerous irregularly shaped nanosheets with a thickness of approximately 45 nm that self-assemble.
[0021] Scanning electron microscope (SEM) image of the Ce-BiOCOOH adsorbent material prepared in Example 1 is shown below. Figure 2 As shown, Ce-BiOCOOH exhibits a nanoflower structure, with a significantly smaller size compared to pure BiOCOOH. Furthermore, the interwoven and stacked nanoflowers are more tightly packed, and the pore size is significantly reduced, indicating that Ce-BiOCOOH provides a larger specific surface area.
[0022] The absorption spectra of Ce-BiOCOOH adsorbent materials with different ratios prepared in Example 1 and the adsorption of Congo red by BiOCOOH as a function of reaction time are shown below. Figure 4 As shown, the absorption peak intensity of Congo red decreased with increasing adsorption time, indicating that the concentration of Congo red decreased. The adsorption process of Congo red ended after 5 minutes.
[0023] Example 1 shows the curves of the efficiency of Ce-BiOCOOH adsorbent materials with different ratios and the adsorption efficiency of BiOCOOH on Congo red as a function of reaction time, as shown in the figure. Figure 5 As shown, Ce-BiOCOOH achieved a 98.1% removal rate of Congo red (10 mg adsorbent added to 50 mL of 100 mg / L CR solution) within 5 min.
[0024] The adsorption cycle histogram of Congo red (CR) on the Ce-BiOCOOH adsorbent material prepared in Example 1 is shown below. Figure 5 As shown, after four consecutive cyclic adsorption tests, the adsorbent maintained an adsorption rate of over 90% for Congo red, indicating its good reusability and stability.
[0025] The above description is only a preferred embodiment and a representative implementation of the present invention. The upper and lower limits and range values of each raw material and process method can achieve the present invention. Examples are not listed one by one here.
Claims
1. A method for preparing a Ce-doped BiOCOOH adsorbent material, comprising the following steps: 1) Under magnetic stirring, a certain amount of bismuth nitrate pentahydrate was dissolved in ethylene glycol solution, and then a certain amount of sodium formate was added to the bismuth nitrate pentahydrate solution. The mixture was stirred for 1 hour to obtain a mixed solution. 2) Under magnetic stirring, a certain amount of cerium nitrate was dissolved in ethylene glycol solution and stirred for 1 hour to obtain a mixed solution; 3) Add the mixed solution from step 2) to the mixed solution from step 1), stir for 1 hour to obtain the precursor solution; 4) The precursor solution was placed in a stainless steel autoclave lined with polytetrafluoroethylene and sealed. It was then placed in a constant temperature oven and reacted at high temperature for a certain period of time. 5) After the reaction vessel from step 4) has cooled naturally to room temperature, collect the product from the suspension by centrifugation and rinse with anhydrous ethanol. The mixture was washed three times with deionized water and then placed in a constant temperature drying oven at 60℃ for 12 hours to obtain a Ce-doped BiOCOOH composite material.
2. The preparation method according to claim 1, characterized in that, The molar ratio of bismuth nitrate pentahydrate to sodium formate is 1:
1.
3. The preparation method according to claim 1, characterized in that, The molar ratio of cerium nitrate doping to bismuth nitrate pentahydrate is (0.5-2):
10.
4. The preparation method according to claim 1, characterized in that, The reaction temperature in the reactor is 150℃. The response time is 10 hours.
5. The preparation method according to claim 1, characterized in that, Used to degrade the organic pollutant Congo red.