Layered double-metal hydroxide composite carbon fiber material with adjustable interlayer spacing as well as preparation method and application of layered double-metal hydroxide composite carbon fiber material

Abstract

The invention discloses a layered double-metal hydroxide composite carbon fiber material as well as a preparation method and application thereof. The material is a layered double-metal hydroxide carbon fiber compound of which the surface is loaded with anion intercalation. According to the invention, through ion exchange and induced recrystallization, layered double hydroxides with different nanoscale interlayer spacing are successfully generated on the surface of the carbon fiber, the catalytic efficiency of the composite material is obviously improved, and the reactive activity of the composite material is enhanced. The material can quickly and efficiently remove organic pollutants in a water body, has a removal rate of 90% or more on aniline in the water body, has good anti-interference ability on common anions in the water body, and has no significant degradation performance after being recycled. The raw materials involved in the material are low in cost, easy to obtain and wide in source, the energy consumption in the preparation process is low, and the material has wide application prospects in the field of wastewater advanced treatment.

Description

Technical Field

[0001] This invention relates to carbon fiber composite materials, and more particularly to a layered bimetallic hydroxide composite carbon fiber material with adjustable interlayer spacing, its preparation method, and its application. Background Technology

[0002] With the rapid development of industry and agriculture and the acceleration of urbanization, water pollution has become an increasingly serious environmental problem in many developing countries. Industrial production, agricultural non-point source pollution, and urban sewage discharge have led to a continuous increase in the concentration of pollutants such as organic matter and heavy metals in water bodies, posing a serious threat to ecosystems and human health. Among numerous pollutants, aniline, as a typical recalcitrant nitrogen-containing organic compound, has attracted much attention due to its high toxicity and chemical stability. Once aniline enters water bodies, it not only directly increases the toxicity of the water but may also cause eutrophication, induce algal blooms, and further damage water quality. More problematic is that the nitrogen element in the aniline molecule is difficult to completely oxidize and remove during degradation, easily generating nitrogen-containing organic intermediates and causing secondary pollution. Traditional advanced oxidation technologies based on persulfate (PMS) activation can generate highly oxidizing sulfate radicals, which have a certain removal effect on aniline, but they generally suffer from incomplete denitrification and the easy generation of toxic nitrogen-containing intermediates.

[0003] To overcome the limitations of the single radical pathway, researchers have designed novel catalysts to regulate reaction mechanisms and improve mineralization efficiency. Layered bimetallic hydroxides (LDHs) and their derivatives exhibit unique advantages. LDHs consist of a host layer and interlayer anions, and their tunable bimetallic sites endow the materials with excellent catalytic activity. Studies have reported a one-step method for loading LDH onto carbon fibers and achieving LDH interlayer spacing control to enhance performance. However, in such methods, LDH layer formation and anion intercalation occur simultaneously, which can affect the alignment of metal cations in the layers, leading to layer aggregation or amorphous phase formation. Especially for cobalt-containing LDH systems, the electronic effects and coordination characteristics of cobalt-based high-valence metal cations result in products with low purity and poor crystallinity prepared by the one-step method, making it difficult to form a regular layered structure. Furthermore, this method has low precision in controlling the interlayer spacing, failing to meet the precise requirements of specific catalytic reactions for the interlayer microenvironment. Summary of the Invention

[0004] Objectives of the invention: The first objective is to provide a layered bimetallic hydroxide composite carbon fiber material with adjustable interlayer spacing achieved through different anion intercalation; the second objective is to provide a method for preparing the material; and the third objective is to provide the application of the material in pollutant treatment, especially in the treatment of organic pollutants in water.

[0005] Technical solution: The layered bimetallic hydroxide composite carbon fiber material of the present invention uses carbon fiber material as a substrate and anion-intercalated layered bimetallic hydroxide is loaded on the surface.

[0006] Preferably, the anion is C4~C6. 16 Alkyl sulfonate ions.

[0007] Preferably, the metal in the layered bimetallic hydroxide is any two of cobalt, iron, nickel, zinc, aluminum, magnesium, and manganese.

[0008] The preparation method of the layered bimetallic hydroxide composite carbon fiber material of the present invention includes the following steps: (1) The carbon fiber material was cleaned and calcined under an inert atmosphere to obtain an activated carbon fiber substrate; (2) The activated carbon fiber substrate was mixed with a solution containing metal salt, and the pH was adjusted to 6.5~7.5 before hydrothermal reaction to obtain the reaction product; (3) The reaction product obtained in step 2 is soaked in water and reacts with C4~C 16 An ethanol solution of alkyl sulfonate is mixed and reacted to obtain a layered bimetallic hydroxide composite carbon fiber material.

[0009] Preferably, the cleaning step in step 1 uses a mixed solution of water, ethanol and acetone for 1.5 to 2.5 hours; the calcination step is calcination at 550 to 650 °C for 1.5 to 2.5 hours.

[0010] Preferably, step 2 includes: mixing the activated carbon fiber substrate with a solution containing metal hydrate, adding a chloride solution, adjusting the pH to 6.5-7.5 using sodium hydroxide or triethylamine under an inert atmosphere, and reacting at 110-130 °C for 5-7 h to obtain the reaction product.

[0011] Preferably, the metal salt is any two of cobalt salt hydrate, iron salt hydrate, nickel salt hydrate, zinc salt hydrate, aluminum salt hydrate, magnesium salt hydrate, and manganese salt hydrate, with a concentration of 1.2~3.0 mmol; more preferably, the metal salt hydrate is CoCl2·6H2O or FeCl3·6H2O, and the chloride salt is NaCl.

[0012] Preferably, the reaction in step 3 is carried out in a water bath at 55-65 °C for 10-14 h.

[0013] The application of the layered bimetallic hydroxide composite carbon fiber material described in this invention in pollutant treatment.

[0014] Preferably, the application is for the treatment of organic pollutants in water bodies; more preferably, the organic pollutant is aniline.

[0015] Beneficial Effects: Compared with the prior art, the present invention has the following significant advantages: 1. The present invention successfully generates layered bimetallic hydroxides with different nanoscale interlayer spacings on the surface of carbon fibers through ion exchange and induced recrystallization, which significantly improves the catalytic efficiency of the composite material and enhances its reactivity; 2. The layered bimetallic hydroxide composite carbon fiber material can quickly and efficiently remove organic pollutants from water, with a removal rate of over 90% for aniline in water, good anti-interference ability for common anions in water, and no significant attenuation in degradation performance after recycling; 3. The raw materials involved in the layered bimetallic hydroxide composite carbon fiber material are inexpensive, readily available, and widely sourced, and the preparation process has low energy consumption, showing broad application prospects in the field of advanced wastewater treatment. Attached Figure Description

[0016] Figure 1 X-ray diffraction analysis of carbon fiber composites with different layered bimetallic hydroxides; Figure 2 Linear scanning voltammetry analysis of carbon fiber composites with different layered bimetallic hydroxides; Figure 3 Fourier transform infrared spectra of carbon fiber composites with different layered bimetallic hydroxides; Figure 4 The graph shows the aniline removal performance of the layered bimetallic hydroxide composite carbon fiber materials prepared in Example 2 and Comparative Examples 2-7. Figure 5 The figures show the results of aniline removal performance and nitrogen controllable removal oxidation performance of the layered bimetallic hydroxide composite carbon fiber materials prepared in Examples 1-4 and Comparative Example 1. Figure 6 This is a graph showing the evaluation results of the anti-interference performance of the layered bimetallic hydroxide composite carbon fiber material prepared in Example 2; Figure 7 The graph shows the evaluation results of the recyclability of the layered bimetallic hydroxide composite carbon fiber material prepared in Example 2. Detailed Implementation

[0017] The technical solution of the present invention will be further described below.

[0018] All reagents used in this invention are of analytical grade. The carbon fiber CFC was purchased from Carbon Energy Technology Co., Ltd., Taiwan, China, model W0S1011.

[0019] Example 1: Preparation of layered bimetallic hydroxide composite carbon fiber material LDH / CFC-C4 (1) Immerse CFC in a water-ethanol-acetone mixed solution with a volume ratio of 1:1:1, ultrasonically clean at 200 W for 2 h, dry after washing, and cut to 2×2 cm. 2 Placed in a quartz ceramic boat, calcined in a tube furnace at 600 °C for 2 h in an argon atmosphere, and annealed to room temperature to obtain activated CFC; (2) Weigh 0.47 g CoCl2·6H2O and 0.51 g FeCl3·6H2O, dissolve them in 80 mL of deionized water, and place them in a 1×2 cm 2 CFC was ultrasonicated at 200 W for 30 min and mixed with 10 mL of 0.025 g / mL NaCl solution. Triethylamine was added dropwise under N2 protection to adjust the pH to 7. The mixture was then transferred to a polytetrafluoroethylene-lined reactor and reacted at 120 ℃ for 6 h. After the reactor cooled to room temperature, the product was removed and washed three times with ethanol and three times with water, and then dried to obtain layered bimetallic hydroxide composite carbon fiber (LDH / CFC). (3) Soak LDH / CFC in 30 mL of deionized water, weigh 1 mmol of sodium butanesulfonate and dissolve it in 70 mL of ethanol. Mix the two and heat in a water bath at 60 °C for 12 h. Wash with ethanol and water three times and then dry to obtain LDH / CFC-C4.

[0020] Example 2: Preparation of layered bimetallic hydroxide composite carbon fiber material LDH / CFC-C8 (1) Immerse CFC in a water-ethanol-acetone mixed solution with a volume ratio of 1:1:1, ultrasonically clean at 200 W for 2 h, dry after washing, and cut to 2×2 cm. 2 Placed in a quartz ceramic boat, calcined in a tube furnace at 600℃ for 2 h in an argon atmosphere, and annealed to room temperature to obtain activated CFC; (2) Weigh 0.47 g CoCl2·6H2O and 0.51 g FeCl3·6H2O, dissolve them in 80 mL of deionized water, and place them in a 1×2 cm 2 CFC was sonicated at 200 W for 30 min and mixed with 10 mL of 0.025 g / mL NaCl solution. Triethylamine was added dropwise under N2 protection to adjust the pH to 7. The mixture was then transferred to a polytetrafluoroethylene-lined reactor and reacted at 120 °C for 6 h. After the reactor cooled to room temperature, the product was removed and washed three times with ethanol and water, respectively, and then dried to obtain LDH / CFC. (3) Soak LDH / CFC in 30 mL of deionized water, weigh 1 mmol of sodium 1-octylsulfonate and dissolve it in 70 mL of ethanol. Mix the two and heat in a water bath at 60 °C for 12 h. Wash with ethanol and water three times and then dry to obtain LDH / CFC-C8.

[0021] Example 3: Preparation of layered bimetallic hydroxide composite carbon fiber material LDH / CFC-C12 (1) Immerse CFC in a water-ethanol-acetone mixed solution with a volume ratio of 1:1:1, ultrasonically clean at 200 W for 2 h, dry after washing, and cut to 2×2 cm. 2 Placed in a quartz ceramic boat, calcined in a tube furnace at 600℃ for 2 h in an argon atmosphere, and annealed to room temperature to obtain activated CFC; (2) Weigh 0.47 g CoCl2·6H2O and 0.51 g FeCl3·6H2O, dissolve them in 80 mL of deionized water, and place them in a 1×2 cm 2 CFC was sonicated at 200 W for 30 min and mixed with 10 mL of 0.025 g / mL NaCl solution. Triethylamine was added dropwise under N2 protection to adjust the pH to 7. The mixture was then transferred to a polytetrafluoroethylene-lined reactor and reacted at 120 °C for 6 h. After the reactor cooled to room temperature, the product was removed and washed three times with ethanol and water, respectively, and then dried to obtain LDH / CFC. (3) Soak LDH / CFC in 30 mL of deionized water, weigh 1 mmol of sodium dodecyl sulfonate and dissolve it in 70 mL of ethanol. Mix the two and heat in a water bath at 60 °C for 12 h. Wash with ethanol and water three times and then dry to obtain LDH / CFC-C12.

[0022] Example 4: Preparation of layered bimetallic hydroxide composite carbon fiber material LDH / CFC-C16 (1) Immerse CFC in a water-ethanol-acetone mixed solution with a volume ratio of 1:1:1, ultrasonically clean at 200 W for 2 h, dry after washing, and cut to 2×2 cm. 2 Placed in a quartz ceramic boat, calcined in a tube furnace at 600 °C for 2 h in an argon atmosphere, and annealed to room temperature to obtain activated CFC; (2) Weigh 0.47 g CoCl2·6H2O and 0.51 g FeCl3·6H2O, dissolve them in 80 mL of deionized water, and place them in a 1×2 cm 2 CFC was sonicated at 200 W for 30 min and mixed with 10 mL of 0.025 g / mL NaCl solution. Triethylamine was added dropwise under N2 protection to adjust the pH to 7. The mixture was then transferred to a polytetrafluoroethylene-lined reactor and reacted at 120 °C for 6 h. After the reactor cooled to room temperature, the product was removed and washed three times with ethanol and water, respectively, and then dried to obtain LDH / CFC. (3) Soak LDH / CFC in 30 mL of deionized water, weigh 1 mmol of sodium hexadecyl sulfonate and dissolve it in 70 mL of ethanol. After mixing the two, heat them in a water bath at 60 °C for 12 h. Wash with ethanol and water three times and then dry to obtain LDH / CFC-C16.

[0023] Comparative Example 1: Preparation of layered bimetallic hydroxide composite carbon fiber materials without anion intercalation (1) Immerse the CFC in a water-ethanol-acetone mixed solution with a volume ratio of 1:1:1, ultrasonically clean it at 200-300W for 2 hours, dry it after washing, and cut it to 2×2 cm. 2 Placed in a quartz ceramic boat, calcined in a tube furnace at 600 °C for 2 h in an argon atmosphere, and annealed to room temperature to obtain activated CFC; (2) Weigh 0.47 g CoCl2·6H2O and 0.51 g FeCl3·6H2O, dissolve them in 80 mL of deionized water, and place them in a 1×2 cm 2 The CFC was sonicated at 200 W for 30 min and mixed with 10 mL of 0.025 g / mL NaCl solution. Triethylamine was added dropwise under N2 protection to adjust the pH to 7. The mixture was then transferred to a polytetrafluoroethylene-lined reactor and reacted at 120 °C for 6 h. After the reactor cooled to room temperature, the product was removed and washed three times with ethanol and water, respectively, and then dried to obtain LDH / CFC.

[0024] Comparative Example 2: Preparation of Layered Bimetallic Hydroxide Composite Carbon Fiber Material LDH / CFC-C8 / 1 The preparation method of Example 2 is different in that: in step (2), 0.31 g CoCl2·6H2O and 0.34 g FeCl3·6H2O are weighed and dissolved in 80 mL of deionized water for preparation, and LDH / CFC-C8 / 1 is prepared.

[0025] Comparative Example 3: Preparation of Layered Bimetallic Hydroxide Composite Carbon Fiber Material LDH / CFC-C8 / 2 The preparation method of Example 2 is different in that: in step (2), 0.70 g CoCl2·6H2O and 0.77 g FeCl3·6H2O are weighed and dissolved in 80 mL of deionized water for preparation, and LDH / CFC-C8 / 2 is prepared.

[0026] Comparative Example 4: Preparation of Layered Bimetallic Hydroxide Composite Carbon Fiber Material LDH / CFC-C8 / 3 The preparation method of Example 2 is different in that NaCl solution is not added in step (2), and LDH / CFC-C8 / 3 is prepared.

[0027] Comparative Example 5: Preparation of Layered Bimetallic Hydroxide Composite Carbon Fiber Material LDH / CFC-C8 / 4 The preparation method of Example 2 is different in that: in step (2), 0.25 g NaCl is directly added to the system containing 0.47 g CoCl2·6H2O, 0.51 g FeCl3·6H2O and CFC to prepare LDH / CFC-C8 / 4.

[0028] Comparative Example 6: Preparation of Layered Bimetallic Hydroxide Composite Carbon Fiber Material LDH / CFC-C8 / 5 The preparation method of Example 2 is different in that: in step (3), LDH / CFC and 1 mmol of sodium 1-octylsulfonate are dissolved in 100 mL of deionized water and heated in a water bath at 60°C for 12 h to prepare LDH / CFC-C8 / 5.

[0029] Comparative Example 7: Preparation of Layered Bimetallic Hydroxide Composite Carbon Fiber Material LDH / CFC-C8 / 6 The preparation method of Example 2 is different in that: in step (3), LDH / CFC and 1 mmol of sodium 1-octylsulfonate are dissolved in 100 mL of ethanol and reacted to prepare LDH / CFC-C8 / 6.

[0030] Experimental Example 1: Characterization of Layered Bimetallic Hydroxide Composite Carbon Fiber Materials 1. X-ray diffraction analysis The layered bimetallic hydroxide composite carbon fiber materials prepared in Examples 1-4 or Comparative Example 1 were adhered to the sample stage and tested using an X-ray diffractometer with continuous scanning in a range of 3° to 60°.

[0031] The results are as follows Figure 1 As shown, the characteristic peaks of LDH / CFC without anion intercalation are clearly visible. The characteristic peaks at 11.7° and 34.9° correspond to the (003) and (110) crystal planes of LDH, respectively, indicating that the material has a high degree of crystallinity. The broad diffraction peak at 25.6° corresponds to the characteristic peak of CFC, indicating that LDH has been successfully crystallized and grown on the CFC surface. As butanesulfonic acid group, 1-octylsulfonic acid group, dodecylsulfonic acid group, and hexadecylsulfonic acid group are inserted as intercalating anions into the LDH interlayer, the (003) crystal plane gradually shifts to a lower angle, indicating that the intercalation of different alkyl sulfonates leads to changes in the interlayer spacing of the LDH nanoarray layer; at the same time, the material still maintains good crystallinity, indicating that LDH recrystallization on the CFC surface has been successfully induced.

[0032] 2. Linear sweep voltammetry analysis Using the layered bimetallic hydroxide composite carbon fiber materials prepared in Examples 1-4 or Comparative Example 1 as the working electrode, linear sweep voltammetry (LSV) was carried out in a three-electrode system with 1 M NaSO4 as the electrolyte. The test potential scan range was -0.6 to 0.2 V.

[0033] The results are as follows Figure 2 As shown, the cathode current densities of LDH / CFC-C4 and LDH / CFC-C8 samples were significantly higher than those of LDH / CFC without anion intercalation, demonstrating that alkyl sulfonate intercalation is an effective means to optimize the catalytic performance of the LDH / CFC / PMS system. With the increase of the alkyl chain length of the intercalated alkyl sulfonate (C4→C8→C12→C16), the PMS electrocatalytic activation activity showed a trend of first increasing and then decreasing, with 1-octyl sulfonate intercalation (i.e., Example 2) being the optimal modification scheme.

[0034] 3. Infrared spectroscopy determination The measurements were performed using a Fourier transform infrared spectrometer in transmission / attenuated total reflectance (ATR) mode, with a scanning range of 4000–400 cm⁻¹. -1 .

[0035] The results are as follows Figure 3 As shown, the LDH / CFC-C8 sample was in the range of 2800~3000 cm⁻¹ -1 The presence of characteristic peaks for alkyl chains confirms that the alkyl chain of the octyl sulfonate group has successfully inserted into the LDH interlayer; in the 1000–1200 cm⁻¹ range… -1 The appearance of the S=O stretching vibration peak at this point also confirms the presence of the sulfonate group (-SO3). - As an intercalating anion, it exists stably in the LDH interlayer, completing the exchange of anions in the LDH interlayer; at the same time, the characteristic peaks of hydroxyl and interlayer water are completely preserved and the peak shapes are not distorted, indicating that the intercalation of octyl sulfonate does not destroy the layered crystal structure of cobalt iron LDH, which is consistent with the XRD conclusion.

[0036] Experimental Example 2: Layered bimetallic hydroxide composite carbon fiber material for catalytic degradation of aniline Accurately weigh aniline and dissolve it in ultrapure water to obtain an aniline solution with a final concentration of 20 mg / L. Store the solution at 4 °C protected from light.

[0037] Measure 100 mL of the above aniline solution into a brown screw-top bottle, and add 1×2 cm of the solution prepared in Examples 1-4 or Comparative Examples 1-7 respectively. 2 Layered bimetallic hydroxide composite carbon fiber material was prepared, and then potassium persulfate with a final concentration of 0.5 mM was added. The mixture was placed in a constant temperature shaker at 25 ℃ and 160 rpm for reaction. Samples were taken at 2 min, 5 min, 10 min, 20 min and 30 min respectively.

[0038] After filtering the sample through a 0.22 μm microporous membrane, the sample was subjected to high performance liquid chromatography (HPLC) using a C18 reversed-phase column with methanol-water (60:40, v / v) as the mobile phase, a flow rate of 1.0 mL / min, a column temperature of 30 ℃, and a detection wavelength of 280 nm. The residual concentration of aniline in the sample was calculated using the aniline standard curve. The residual concentration of aniline in the samples treated in Examples 3 or Comparative Examples 2-7 was determined.

[0039] Simultaneously, NO3 was determined by ion chromatography using an anion exchange column, with 20 mmol / L NaHCO3 solution as the eluent, a flow rate of 1.0 mL / min, a column temperature of 30 ℃, and suppressed conductivity detection. - Concentration, combined with the initial total concentration of organic nitrogen, and calculated according to the law of conservation of nitrogen, showed that organic nitrogen in the samples treated in Examples 1-4 and Comparative Example 1 could be controllably removed and converted into NO3. - Conversion rate.

[0040] The results are as follows Figure 4 As shown, a) shows the aniline removal effect of LDH / CFC-C8 with different metal loadings, indicating that under the LDH loading of Example 2, it achieves the best synergistic effect with CFC and has the best aniline removal effect; b) shows the aniline removal effect of LDH / CFC-C8 obtained under different LDH crystallization conditions and ion exchange-induced recrystallization conditions. Similarly, Example 2 has the highest aniline removal rate (97.35%), indicating that the LDH / CFC-C8 synthesized under this condition has the best crystallization effect and catalytic performance.

[0041] The results are as follows Figure 5 As shown in Figure a, LDH / CFC with different interlayer spacings exhibit kinetic results for aniline. Alkyl sulfonate intercalation, by precisely controlling the CoFe-LDH interlayer spacing, optimizes the mass transfer, adsorption, and electron transport efficiency between aniline and PMS, significantly improving the catalytic degradation performance of aniline by PMS and achieving efficient and rapid degradation of aniline. Figure b shows the denitrification and directional conversion of aniline to non-toxic NO3 by LDH / CFC with different interlayer spacings. - The performance diagram shows that LDH / CFC-C8 exhibits the highest nitrogen removal and oxidation performance. In the C4→C8 stage, the interlayer spacing gradually increases with the elongation of the alkyl chain, leading to a continuous increase in degradation rate. In the C12→C16 stage, excessively large interlayer spacing weakens the confinement effect, resulting in a performance decline. C8 intercalation is the optimal interlayer spacing control scheme, achieving nitrogen removal and conversion into non-toxic and harmless inorganic NO3 through nano-confinement. - This can achieve harmless treatment, providing a clear basis for structural optimization of LDH-based catalysts in the treatment of aniline wastewater.

[0042] Experimental Example 3: Evaluation of the anti-interference performance of layered bimetallic hydroxide composite carbon fiber material LDH / CFC-C8 catalyzed aniline degradation Accurately weigh aniline and dissolve it in ultrapure water to obtain an aniline solution with a final concentration of 20 mg / L. Add 200 mg / L Cl to each solution. - SO4 2- NO3 ⁻ or HCO3 ⁻ As an interfering ion, store at 4°C away from light.

[0043] Measure 100 mL of the above solution into brown screw-top bottles, and add 1×2 cm... 2 LDH / CFC-C8 was then added, followed by the addition of 0.5 mM potassium persulfate. The mixture was then placed in a constant temperature shaker at 25 °C and 160 rpm for reaction. Samples were taken at 2 min, 5 min, 10 min, 20 min, and 30 min.

[0044] The sample was filtered through a 0.22 μm microporous membrane, and the concentration of the remaining aniline was determined.

[0045] The results are as follows Figure 6 As shown, LDH / CFC-C8 affects Cl in water. - NO3 - SO4 2- It exhibits extremely strong tolerance to common coexisting anions, and is only sensitive to HCO3-. - It exhibits slight inhibition and maintains an aniline removal rate of over 90% in all anionic systems, demonstrating excellent stability in practical water applications. This provides a reliable performance guarantee for the treatment of aniline pollution in complex industrial wastewater and natural water bodies.

[0046] Experimental Example 4: Evaluation of the recyclability of layered bimetallic hydroxide composite carbon fiber material catalyzed by LDH / CFC-C8 for aniline degradation Accurately weigh aniline and dissolve it in ultrapure water to obtain an aniline solution with a final concentration of 20 mg / L. Store the solution at 4 °C protected from light.

[0047] Measure 100 mL of the above solution into a brown screw-top bottle, and add 1×2 cm... 2 LDH / CFC-C8 was prepared, and then potassium persulfate with a final concentration of 0.5 mM was added. The mixture was placed in a constant temperature shaker at 25 ℃ and 160 rpm for reaction. Samples were taken at 2 min, 5 min, 10 min, 20 min and 30 min respectively. The experiment was repeated 5 times, and LDH / CFC-C8 was recycled.

[0048] The sample was filtered through a 0.22 μm microporous membrane, and the concentration of the remaining aniline was determined.

[0049] The results are as follows Figure 7 As shown, LDH / CFC-C8 can still maintain an aniline removal rate of over 90% after 5 cycles, indicating that the catalytic kinetics and the function of the active sites have not significantly declined, providing a reliable performance guarantee for the continuous industrial application of this catalyst in aniline wastewater treatment.

Claims

1. A layered bimetallic hydroxide composite carbon fiber material, characterized in that, The material is a layered bimetallic hydroxide with anion intercalation on its surface, based on a carbon fiber material.

2. The layered bimetallic hydroxide composite carbon fiber material according to claim 1, characterized in that, The anion is C4~C6 16 Alkyl sulfonate ions.

3. The layered bimetallic hydroxide composite carbon fiber material according to claim 1, characterized in that, The metal in the layered bimetallic hydroxide is any two of cobalt, iron, nickel, zinc, aluminum, magnesium, and manganese.

4. A method for preparing the layered bimetallic hydroxide composite carbon fiber material according to any one of claims 1 to 3, characterized in that the step include: (1) The carbon fiber material was cleaned and calcined under an inert atmosphere to obtain an activated carbon fiber substrate; (2) The activated carbon fiber substrate was mixed with a solution containing metal salt, and the pH was adjusted to 6.5~7.5 before hydrothermal reaction to obtain the reaction product; (3) The reaction product obtained in step 2 is soaked in water and reacts with C4~C 16 An ethanol solution of alkyl sulfonate is mixed and reacted to obtain a layered bimetallic hydroxide composite carbon fiber material.

5. The preparation method according to claim 4, characterized in that, The cleaning step described in step 1 involves cleaning with a mixed solution of water, ethanol, and acetone for 1.5 to 2.5 hours; the calcination step involves calcining at 550 to 650 °C for 1.5 to 2.5 hours.

6. The preparation method according to claim 4, characterized in that, Step 2 includes: mixing the activated carbon fiber substrate with a solution containing metal hydrate, then adding a chloride solution, adjusting the pH to 6.5-7.5 using sodium hydroxide or triethylamine under an inert atmosphere, and reacting at 110-130 °C for 5-7 h to obtain the reaction product.

7. The preparation method according to claim 6, characterized in that, The metal salt is any two of the following: cobalt salt hydrate, iron salt hydrate, nickel salt hydrate, zinc salt hydrate, aluminum salt hydrate, magnesium salt hydrate, and manganese salt hydrate.

8. The preparation method according to claim 4, characterized in that, The reaction described in step 3 is carried out in a water bath at 55-65 °C for 10-14 h.

9. The application of the layered bimetallic hydroxide composite carbon fiber material according to claim 1 in pollutant treatment.

10. The application according to claim 9, characterized in that, The application is for the treatment of organic pollutants in water bodies.

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