Optical fiber material for removing chlorophenols from water

Abstract

The application discloses a kind of optical fiber materials for removing chlorophenol in water body, the optical fiber material is sequentially composed of optical fiber core, optical fiber cladding, photocatalytic layer and chloride ion adsorption material from inside to outside;Wherein, the optical fiber core is air, the optical fiber cladding is quartz, the photocatalytic layer is Ti3C2Tx / BiOBr- OV and is coated on the outside surface of optical fiber cladding;The chloride ion adsorption material is MOF-808-EDTA fiber, is helical, and is located outside photocatalytic layer;The optical fiber core one end is light beam incident end;Light beam can be transmitted into optical fiber core by light beam incident end, then refract into optical fiber cladding, and finally refract transmission to photocatalytic layer.The optical fiber material can degrade chlorophenol in water body, carbon dioxide, water and chloride ion are generated after chlorophenol is degraded, helical chloride ion adsorption material adsorbs chloride ion, finally realizes the complete removal of chlorophenol in water body, can be widely used in the degradation of toxic organic pollutants in wastewater and chloride ion adsorption.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, and more specifically to an optical fiber material for removing chlorophenol from water. Background Technology

[0002] With the rapid development of industry and agriculture, chlorophenol compounds are widely used as chemical raw materials in pesticides, herbicides, flame retardants, wood preservatives, dyes, and personal care products. Chlorophenol compounds are structurally stable but possess high toxicity, lipid solubility, and are difficult to biodegrade naturally, easily accumulating in the environment and transferring to organisms, posing a serious threat to human life. In response to these circumstances, relevant departments have listed chlorophenol compounds as priority pollutants for water pollution control. Therefore, developing methods and efficient, environmentally friendly materials for the removal of chlorophenols from water bodies is of great significance.

[0003] Currently, the main methods for removing chlorophenol from water include adsorption, membrane separation, biological methods, electrochemical oxidation, and photocatalysis. Adsorption and membrane separation methods cannot completely remove chlorophenol, only transferring it, which can easily cause secondary pollution. Biological methods decompose pollutants through the metabolism of microorganisms; however, this method is difficult to degrade high concentrations of toxic organic matter and has a slow dechlorination rate. While electrochemical oxidation has high degradation efficiency for chlorophenol, it is energy-intensive and costly, and cannot remove chloride ions from the decomposition products of chlorophenol. Photocatalysis, on the other hand, is a novel pollutant treatment technology developed in recent years. Due to its advantages of low cost, low pollution, and high reaction efficiency, it is widely used in pollutant degradation. Immobilized photocatalysis technology, in particular, overcomes the disadvantages of suspended photocatalysis systems, such as easy aggregation of photocatalysts, difficulty in recovery, and light-limited reaction systems. Therefore, immobilized photocatalysis technology has attracted widespread attention from researchers in the field of wastewater treatment.

[0004] Currently, the supports used to immobilize photocatalysts mainly include inorganic materials, organic materials, and magnetically separable supports. Among these materials, optical fibers are one of the most effective supports due to their excellent light transmission performance, high light energy utilization efficiency, strong corrosion resistance, and ease of photocatalyst adhesion to the fiber surface. Although photocatalytic materials constructed using optical fiber supports can achieve continuous and stable removal of toxic organic pollutants, the degradation efficiency of organic pollutants is significantly affected by the performance of the photocatalyst film coated on the optical fiber surface. This results in the current low efficiency of photocatalyst-coated optical fibers in degrading phenolic toxic organic pollutants. More importantly, in the photocatalytic degradation of chlorophenol wastewater, chlorophenol is converted into H2O, CO2, and chloride ions, which existing immobilized photocatalyst materials cannot remove. Due to the strong corrosiveness of chloride ions, direct discharge without treatment can harm crops, metals, building materials, and human health. Summary of the Invention

[0005] In view of the above-mentioned shortcomings of the existing technology, the purpose of the present invention is to provide an optical fiber material for removing chlorophenol from water, so as to solve the problems of low efficiency in degrading chlorophenol toxic organic pollutants by optical fibers coated with photocatalysts and the inability to remove chloride ions formed by degradation at the same time.

[0006] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0007] An optical fiber material for removing chlorophenol from water, comprising, from the inside out, an optical fiber core, an optical fiber cladding, a photocatalytic layer, and a chloride ion adsorbent; wherein the optical fiber core is air, the optical fiber cladding is quartz, the photocatalytic layer is Ti3C2Tx / BiOBr-OV and is coated on the outer surface of the optical fiber cladding; and the chloride ion adsorbent is MOF-808-EDTA fiber, which is helical and located outside the photocatalytic layer.

[0008] One end of the fiber core is the beam incident end; the beam can be transmitted into the fiber core through the beam incident end, then refracted into the fiber cladding, and finally refracted to the photocatalytic layer.

[0009] Preferably, the Ti3C2Tx / BiOBr-OV is prepared by the following method:

[0010] BiOBr-OV powder was dissolved in water, and then Ti3C2Tx powder was added. The mixture was stirred for 2-3 hours. The precipitate was separated by centrifugation and collected. After drying, the Ti3C2Tx / BiOBr-OV was obtained. The mass ratio of BiOBr-OV to Ti3C2Tx was (0.1-0.3):(0.01-0.03).

[0011] Preferably, the BiOBr-OV is prepared by the following method:

[0012] Bismuth nitrate pentahydrate and potassium bromide were dissolved in water and stirred to obtain mixture A; the concentration of bismuth nitrate pentahydrate in mixture A was 9-17 mg / mL and the concentration of potassium bromide was 3.5-7 mg / mL; mixture A was placed in a reaction vessel and sealed, and reacted at 160-180℃ for 3-5 h; the product after reaction was centrifuged and the precipitate was collected, dried to obtain BiOBr;

[0013] BiOBr was dissolved in water, and mannitol and polyvinylpyrrolidone were added. The mixture was stirred continuously to obtain mixture B. In mixture B, the concentration of BiOBr was 2-10 mg / mL, the concentration of mannitol was 12-20 mg / mL, and the concentration of polyvinylpyrrolidone was 2-7 mg / mL. Then, mixture B was placed in a reaction vessel and sealed, and reacted at 160-180°C for 3-5 hours. The obtained product was centrifuged and the precipitate was collected and dried to obtain BiOBr-OV.

[0014] Preferably, the Ti3C2Tx is prepared by the following method:

[0015] Ti3AlC2 was slowly added to hydrofluoric acid, with a concentration of 0.05–0.1 g / mL. The aluminum layer was extracted by magnetic stirring at room temperature for 20–24 h. The precipitate was then obtained by centrifugation, and the precipitate was washed by centrifugation multiple times and dried to obtain the Ti3C2Tx.

[0016] Preferably, the chloride ion adsorbent material is prepared by the following method:

[0017] Step 1: Trimethylbenzene and zirconium oxychloride octahydrate are added to a mixed solution of N,N-dimethylformamide and formic acid and allowed to dissolve completely; wherein the mass ratio of trimethylbenzene and zirconium oxychloride octahydrate is (1-1.5):(4-5); then, the dissolved mixture is placed in an autoclave and reacted at 130-150°C for 36-48 h; subsequently, the reaction product is washed multiple times with N,N-dimethylformamide and anhydrous acetone, and dried to obtain MOF-808 material;

[0018] Step 2: Activate the MOF-808 material obtained in Step 1 at 120-150℃, add the activated MOF-808 and disodium ethylenediaminetetraacetate to water and mix, heat to 60-80℃ and react for 24-36 h, centrifuge, wash and dry to obtain MOF-808-EDTA; wherein, the mass ratio of activated MOF-808 to disodium ethylenediaminetetraacetate is (0.05-0.1):(0.8-1);

[0019] Step 3: Dissolve MOF-808-EDTA in N-methylpyrrolidone, add polyvinylpyrrolidone and polyethersulfone, and continuously stir at 60-70°C to obtain MOF-808-EDTA spinning solution; wherein, the mass ratio of MOF-808-EDTA, polyvinylpyrrolidone and polyethersulfone is (0.1-0.3):1.5-2):(4.5-5);

[0020] Step 4: The MOF-808-EDTA spinning solution is used to form filaments through a spinning device, and then passed through a mold to form a spiral chloride ion adsorbent material.

[0021] Preferably, the optical fiber cladding and the photocatalytic layer are combined by the following method:

[0022] (1) The hollow quartz optical fiber was ultrasonically cleaned multiple times using acetone, ethanol and sodium hydroxide solutions in sequence.

[0023] (2) Water and acetylacetone were added to Ti3C2Tx / BiOBr-OV powder in sequence and continuously mixed and ground. After ultrasonic treatment, the powder was added to anhydrous ethanol, Triton X-100, polyethylene glycol and ethylene glycol were added, and the mixture was continuously stirred to obtain a stable Ti3C2Tx / BiOBr-OV sol. The mass ratio of Ti3C2Tx / BiOBr-OV, deionized water, acetylacetone, anhydrous ethanol, Triton X-100, polyethylene glycol and ethylene glycol was (1~2):(2~4):(0.5~2):(5~15):(0.3~1.5):(0.15~0.3):(1~3).

[0024] (3) First, seal one end of the hollow quartz fiber with paraffin, and then coat the outer surface of the hollow quartz fiber with Ti3C2Tx / BiOBr-OV sol by dip-coating method; then, sinter at 180-200℃ for 12-20h to obtain photocatalytic fiber.

[0025] Preferably, the chloride ion adsorbent material is combined with the photocatalytic fiber by the following method:

[0026] The photocatalytic fiber is inserted into a spiral MOF-808-EDTA fiber and sintered at 170-200℃ for 4-8 hours to achieve coupling between the photocatalytic fiber and the chloride ion adsorption material, thereby obtaining the optical fiber material.

[0027] Preferably, the optical fiber material is capable of degrading chlorophenol in water and simultaneously adsorbing chloride ions formed after degradation.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] In the optical fiber material of this invention, the photocatalyst Ti3C2Tx / BiOBr-OV in the photocatalytic layer generates electron-hole pairs upon photoexcitation. The holes and electrons migrate to the surface of the photocatalytic layer and undergo a redox reaction with adsorbed water molecules, generating highly oxidizing oxygen-containing free radicals. These free radicals then decompose chlorophenol, a toxic organic pollutant, converting it into carbon dioxide, water, and chloride ions. The formed chloride ions are adsorbed by a spiral-shaped chloride ion adsorbent material surrounding the photocatalytic layer, ultimately achieving complete removal of chlorophenol from the water. Attached Figure Description

[0030] Figure 1 The diagram shows the photocatalytic optical fiber structures prepared in Examples 10-12.

[0031] Figure 2 The diagram shows the structure of the spiral chloride ion adsorbent materials prepared in Examples 13-15.

[0032] Figure 3 The diagram shows the structure of the optical fiber materials prepared in Examples 16-18.

[0033] Figure 4 The graph shows the changes in the concentration of 2,4,6-trichlorophenol within 10 hours during the photocatalytic degradation of 2,4,6-trichlorophenol using different catalytic materials.

[0034] Figure 5 The graph shows the changes in chloride ion concentration over 12 hours during the photocatalytic degradation of 2,4,6-trichlorophenol using different catalytic materials.

[0035] In the figure: 1 is the fiber core, 2 is the cladding, 3 is the photocatalytic layer, 4 is the spiral chloride ion adsorbent material, and 5 is the incident beam. Detailed Implementation

[0036] The technical solutions of the present invention will be clearly and completely described in conjunction with the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the present invention are within the scope of protection of the present invention.

[0037] Unless otherwise specified in the specific circumstances, the numerical ranges listed herein include upper and lower limits, as well as all integers and fractions within that range, but are not limited to the specific values ​​listed when the range is defined.

[0038] I. An optical fiber material for removing chlorophenol from water

[0039] The optical fiber material of this invention is composed, from the inside out, of an optical fiber core 1, an optical fiber cladding 2, a photocatalytic layer 3, and a chloride ion adsorption material 4; for example... Figures 1-3 As shown, the fiber core is air, the fiber cladding is quartz, and the photocatalytic layer is Ti3C2Tx / BiOBr-OV, covering the outer surface of the fiber cladding. The chloride ion adsorption material is MOF-808-EDTA fiber, spiral-shaped, and located outside the photocatalytic layer. One end of the fiber core is the beam incident end; the incident beam 5 can be transmitted into the fiber core through the beam incident end, then refracted into the fiber cladding, and finally refracted to the photocatalytic layer.

[0040] To achieve complete removal of chlorophenol from water, this invention conducted in-depth research and found that while existing catalytic materials can degrade chlorophenol, they cannot handle the chloride ions formed during chlorophenol degradation. Furthermore, simply combining chloride-adsorbing materials with chlorophenol-degrading materials might negatively impact their individual performance, leading to a situation where the benefits outweigh the benefits. Therefore, this invention designs optical fiber materials that can efficiently degrade chlorophenol while simultaneously handling chloride ions. The combination of the photocatalyst and the chloride-adsorbing material does not affect their individual performance, ensuring that the photocatalyst efficiently degrades chlorophenol and the chloride-adsorbing material efficiently adsorbs chloride ions.

[0041] In some embodiments, the Ti3C2Tx / BiOBr-OV is prepared by the following method:

[0042] BiOBr-OV powder was dissolved in water, and then Ti3C2Tx powder was added. The mixture was stirred continuously for 2–3 hours. The precipitate was separated by centrifugation and collected, then dried to obtain the Ti3C2Tx / BiOBr-OV. The mass ratio of BiOBr-OV to Ti3C2Tx was (0.1–0.3):(0.01–0.03). Controlling the amounts of BiOBr-OV and Ti3C2Tx within this range ensures the optimal combination and avoids affecting the catalytic effect. Therefore, the mass ratio of BiOBr-OV to Ti3C2Tx can be 0.1:0.01, 0.2:0.02, 0.3:0.03, etc., as well as all ranges and sub-ranges between these values. It should be understood that, in the embodiments, any of the above ranges can be combined with any other range.

[0043] In some embodiments, the BiOBr-OV is prepared by the following method:

[0044] Bismuth nitrate pentahydrate and potassium bromide were dissolved in water and stirred to obtain mixture A; the concentration of bismuth nitrate pentahydrate in mixture A was 9–17 mg / mL, and the concentration of potassium bromide was 3.5–7 mg / mL. Mixture A was placed in a reaction vessel and sealed, and reacted at 160–180°C for 3–5 h; the product after reaction was centrifuged and the precipitate was collected and dried to obtain BiOBr; BiOBr was dissolved in water, and mannitol and polyvinylpyrrolidone were added, and the mixture was stirred continuously to obtain mixture B; the concentration of BiOBr in mixture B was 2–10 mg / mL, the concentration of mannitol was 12–20 mg / mL, and the concentration of polyvinylpyrrolidone was 2–7 mg / mL; mixture B was then placed in a reaction vessel and sealed, and reacted at 160–180°C for 3–5 h; the obtained product was centrifuged and the precipitate was collected and dried to obtain BiOBr-OV.

[0045] In some embodiments, the Ti3C2Tx is prepared by the following method:

[0046] Ti3AlC2 was slowly added to hydrofluoric acid, with a concentration of 0.05–0.1 g / mL. The aluminum layer was extracted by magnetic stirring at room temperature for 20–24 h. The precipitate was then obtained by centrifugation, and the precipitate was washed by centrifugation multiple times and dried to obtain the Ti3C2Tx.

[0047] In some embodiments, the chloride ion adsorbent material is prepared by the following method:

[0048] Step 1: Trimethylbenzene and zirconium oxychloride octahydrate are added to a mixed solution of N,N-dimethylformamide and formic acid and allowed to dissolve completely; wherein the mass ratio of trimethylbenzene and zirconium oxychloride octahydrate is (1-1.5):(4-5); then, the dissolved mixture is placed in an autoclave and reacted at 130-150°C for 36-48 h; subsequently, the reaction product is washed multiple times with N,N-dimethylformamide and anhydrous acetone, and dried to obtain MOF-808 material;

[0049] Step 2: Activate the MOF-808 material obtained in Step 1 at 120-150℃, add the activated MOF-808 and disodium ethylenediaminetetraacetate to water and mix, heat to 60-80℃ and react for 24-36 h, centrifuge, wash and dry to obtain MOF-808-EDTA; wherein, the mass ratio of activated MOF-808 to disodium ethylenediaminetetraacetate is (0.05-0.1):(0.8-1);

[0050] Step 3: Dissolve MOF-808-EDTA in N-methylpyrrolidone, add polyvinylpyrrolidone and polyethersulfone, and continuously stir at 60-70°C to obtain MOF-808-EDTA spinning solution; wherein, the mass ratio of MOF-808-EDTA, polyvinylpyrrolidone and polyethersulfone is (0.1-0.3):(1.5-2):(4.5-5);

[0051] Step 4: The MOF-808-EDTA spinning solution is used to form filaments through a spinning device, and then passed through a mold to form a spiral chloride ion adsorbent material.

[0052] In some embodiments, the optical fiber cladding and the photocatalytic layer are combined by the following method:

[0053] (1) The hollow quartz optical fiber was ultrasonically cleaned multiple times using acetone, ethanol and sodium hydroxide solutions in sequence.

[0054] (2) Water and acetylacetone were added to Ti3C2Tx / BiOBr-OV powder in sequence and continuously mixed and ground. After ultrasonic treatment, the powder was added to anhydrous ethanol, Triton X-100, polyethylene glycol and ethylene glycol were added, and the mixture was continuously stirred to obtain a stable Ti3C2Tx / BiOBr-OV sol. The mass ratio of Ti3C2Tx / BiOBr-OV, deionized water, acetylacetone, anhydrous ethanol, Triton X-100, polyethylene glycol and ethylene glycol was (1~2):(2~4):(0.5~2):(5~15):(0.3~1.5):(0.15~0.3):(1~3).

[0055] (3) First, seal one end of the hollow quartz fiber with paraffin, and then coat the outer surface of the hollow quartz fiber with Ti3C2Tx / BiOBr-OV sol by dip-coating method; then, sinter at 180-200℃ for 12-20h to obtain photocatalytic fiber.

[0056] In some embodiments, the chloride ion adsorption material is combined with photocatalytic fibers by the following method:

[0057] The photocatalytic fiber is inserted into a spiral MOF-808-EDTA fiber and sintered at 170-200℃ for 4-8 hours to achieve coupling between the photocatalytic fiber and the chloride ion adsorption material, thereby obtaining the optical fiber material.

[0058] In some embodiments, the optical fiber material can degrade chlorophenol in water and simultaneously adsorb chloride ions formed after degradation.

[0059] II. Implementation Examples

[0060] Example 1: Preparation of BiOBr-OV

[0061] First, 486 mg of bismuth nitrate pentahydrate and 178.5 mg of potassium bromide were added to 30 mL of deionized water and stirred vigorously for 20 min. The resulting mixture was then transferred to a Teflon-lined autoclave and sealed, and reacted at 160 °C for 3 h. Finally, the precipitate was collected by centrifugation at 3500 rpm and dried in a vacuum oven at 80 °C for 10 h to obtain BiOBr powder. 150 mg of the obtained BiOBr powder was dissolved in 30 mL of deionized water, and 600 mg of mannitol and 200 mg of polyvinylpyrrolidone were added, and the mixture was stirred vigorously for 20 min. The resulting mixture was then transferred to a Teflon-lined autoclave and sealed, and reacted at 160 °C for 3 h. Finally, the precipitate was collected by centrifugation at 3500 rpm and dried in a vacuum oven at 80 °C for 10 h to obtain BiOBr-OV.

[0062] Example 2: Preparation of BiOBr-OV

[0063] This example is an adjustment based on Example 1, differing only in the amounts of raw materials used: bismuth nitrate pentahydrate is used at 480 mg, potassium bromide at 175 mg, BiOBr at 60 mg, mannitol at 400 mg, and polyvinylpyrrolidone at 100 mg. All other steps remain identical.

[0064] Example 3: Preparation of BiOBr-OV

[0065] This example is an adjustment based on Example 1, differing only in the following amounts: Bismuth nitrate pentahydrate is used at 500 mg, potassium bromide at 200 mg, and the reaction temperature of bismuth nitrate pentahydrate and potassium bromide is 180°C for 5 hours. BiOBr is used at 300 mg, mannitol at 600 mg, and polyvinylpyrrolidone at 200 mg, and the reaction temperature of BiOBr with mannitol and polyvinylpyrrolidone is 180°C for 5 hours. All other steps are identical.

[0066] Example 4: Preparation of Ti3C2Tx

[0067] First, 1.2g of Ti3AlC2 was slowly added to a Teflon container containing 20mL of hydrofluoric acid, and the aluminum layer was extracted for 24h under magnetic stirring at 25℃. Then, the precipitate was obtained by centrifugation at 3500 rpm, followed by washing with 5mL of deionized water by centrifugation at 3500 rpm. This process was repeated 2-4 times. Finally, the Ti3C2Tx powder was obtained by drying at 70℃ overnight.

[0068] Example 5: Preparation of Ti3C2Tx

[0069] This is an adjustment based on Example 4, the difference being that the amount of raw materials is different: the amount of Ti3AlC2 is 1g and the amount of hydrofluoric acid is 15mL. The rest of the steps are exactly the same.

[0070] Example 6: Preparation of Ti3C2Tx

[0071] This is an adjustment based on Example 4, the difference being that the amount of raw materials is different: the amount of Ti3AlC2 is 1.4g and the amount of hydrofluoric acid is 17mL. The remaining steps are exactly the same.

[0072] Example 7: Preparation of Ti3C2Tx / BiOBr-OV

[0073] The BiOBr-OV powder obtained in Example 1 was dissolved in 30–50 mL of deionized water; then the Ti3C2Tx powder obtained in Example 4 was added, and the mixture was stirred for 2 h; finally, the precipitate was collected by centrifugation at 3000 rpm and dried at 60 °C for 10 h to obtain the Ti3C2Tx / BiOBr-OV photocatalyst. The mass ratio of BiOBr-OV to Ti3C2Tx was 0.1:0.01.

[0074] Example 8: Preparation of Ti3C2Tx / BiOBr-OV

[0075] The BiOBr-OV powder obtained in Example 2 was dissolved in 30–50 mL of deionized water; then the Ti3C2Tx powder obtained in Example 5 was added, and the mixture was stirred for 2.5 h; finally, the precipitate was collected by centrifugation at 3500 rpm and dried at 70 °C for 14 h to obtain the Ti3C2Tx / BiOBr-OV photocatalyst. The mass ratio of BiOBr-OV to Ti3C2Tx was 0.3:0.03.

[0076] Example 9: Preparation of Ti3C2Tx / BiOBr-OV

[0077] The BiOBr-OV powder obtained in Example 3 was dissolved in 30–50 mL of deionized water; then the Ti3C2Tx powder obtained in Example 6 was added, and the mixture was stirred for 3 h; finally, the precipitate was collected by centrifugation at 4000 rpm and dried at 80 °C for 24 h to obtain the Ti3C2Tx / BiOBr-OV photocatalyst. The mass ratio of BiOBr-OV to Ti3C2Tx was 0.2:0.02.

[0078] Example 10: Fabrication of photocatalytic optical fiber

[0079] 1) The hollow quartz optical fiber was ultrasonically cleaned for 10 minutes in sequence with acetone, ethanol and sodium hydroxide solution.

[0080] 2) Add 1g of the photocatalyst powder obtained in Example 7 to a grinding mortar, add 4ml of deionized water and 1ml of acetylacetone in sequence and mix and grind; after ultrasonic treatment for 10min, transfer to 10mL of anhydrous ethanol, add 1mL of Triton X-100 and 0.15g of polyethylene glycol and 2ml of ethylene glycol, stir for 10min to obtain photocatalyst sol.

[0081] 3) First, seal one end of the hollow optical fiber with paraffin wax, and then coat the photocatalyst sol obtained in step 2) onto the surface of the hollow quartz optical fiber using the dip-coating method. Finally, sinter the sol at 200°C in a muffle furnace for 12 hours.

[0082] Example 11: Fabrication of photocatalytic optical fiber

[0083] An improvement was made based on Example 10, the difference being that the photocatalyst prepared in Example 8 was used to fabricate the photocatalytic fiber, and the sintering temperature was 180℃ for 19 hours. The mass ratio of Ti3C2Tx / BiOBr-OV, deionized water, acetylacetone, anhydrous ethanol, Triton X-100, polyethylene glycol, and ethylene glycol was 1:2:0.5:5:0.3:1.

[0084] Example 12: Fabrication of photocatalytic optical fiber

[0085] An improvement was made based on Example 10, the difference being that the photocatalyst prepared in Example 9 was used to make photocatalytic fibers, and the sintering temperature was 190℃ for 20 hours. The mass ratio of Ti3C2Tx / BiOBr-OV, deionized water, acetylacetone, anhydrous ethanol, Triton X-100, polyethylene glycol, and ethylene glycol was 2:4:2:15:1.5:3.

[0086] Example 13: Preparation of Helical Chloride Ion Adsorbent Material

[0087] 1) First, 1.05 g of trimesic acid and 4.83 g of zirconium oxychloride octahydrate were added to a mixed solution of 225 mL of N,N-dimethylformamide and 225 mL of formic acid and completely dissolved at room temperature. Then, the mixture was placed in a Teflon-lined autoclave and heated at 130 °C for 48 hours. The synthesized white powder was then washed three times with N,N-dimethylformamide and twice with anhydrous acetone. The acetone-exchanged sample was then dried at room temperature for 24 hours. Finally, it was dried at 80 °C for 12 hours to obtain MOF-808 material.

[0088] 2) First, MOF-808 was activated overnight at 150℃. Then, 0.05g of activated MOF-808 and 0.93g of disodium ethylenediaminetetraacetate (EDTA-2Na) were added to 25mL of water. The mixture was then placed in a screw-cap glass jar and heated to 60℃ for 24h. The solid was collected by centrifugation and washed with plenty of water to remove unreacted EDTA. Next, the solid powder was immersed in anhydrous acetone several times to remove the moisture from MOF-808-EDTA. Finally, the obtained sample was vacuum dried overnight at 80℃ to obtain MOF-808-EDTA powder.

[0089] 3) First, dissolve the MOF-808-EDTA powder obtained in step 2) in 23.7g of N-methylpyrrolidone and stir evenly; then add 1.5g of polyvinylpyrrolidone and 4.8g of polyethersulfone, and stir at 60℃ for 10h to obtain MOF-808-EDTA spinning solution;

[0090] 4) Let the MOF-808-EDTA spinning solution stand and cool for 12 hours to eliminate air bubbles; then inject the spinning solution into the deionized water coagulation bath at a flow rate of 10 ml / min and maintain an air gap of 3 cm using an injection pump. Soak the spun filaments in the deionized water coagulation bath for 24 hours to obtain filaments with chloride ion adsorption properties; finally, wind the above filaments evenly onto a quartz tube with an outer diameter of 1 mm and dry at 60°C for 2 hours to obtain a spiral chloride ion adsorption material.

[0091] Example 14: Preparation of Helical Chloride Ion Adsorbent Material

[0092] This is an improvement on Example 13, differing only in the amounts of raw materials used: 1g of trimesic acid, 4g of zirconium oxychloride octahydrate, 0.07g of activated MOF-808, 0.8g of disodium ethylenediaminetetraacetate, 23g of N-methylpyrrolidone, 1.7g of polyvinylpyrrolidone, and 4.5g of polyethersulfone. All other steps remain identical.

[0093] Example 15: Preparation of Helical Chloride Ion Adsorbent Material

[0094] This is an improvement on Example 13, differing only in the amounts of raw materials used: 1.5g of trimesic acid, 5g of zirconium oxychloride octahydrate, 0.1g of activated MOF-808, 1g of disodium ethylenediaminetetraacetate, 25g of N-methylpyrrolidone, 2g of polyvinylpyrrolidone, and 5g of polyethersulfone. All other steps remain identical.

[0095] Example 16: Assembly of photocatalytic optical fiber and helical chloride ion adsorption coupling material

[0096] The photocatalytic optical fiber obtained in Example 10 is inserted into the spiral chloride ion adsorption material obtained in Example 13, and both are sintered in a muffle furnace at 200°C for 4 hours to achieve coupling between the photocatalytic optical fiber and the spiral chloride ion adsorption material, thereby obtaining the optical fiber material described in this invention.

[0097] Example 17: Assembly of photocatalytic optical fiber and helical chloride ion adsorption coupling material

[0098] The photocatalytic optical fiber obtained in Example 11 is inserted into the spiral chloride ion adsorption material obtained in Example 14, and both are sintered in a muffle furnace at 180°C for 6 hours to achieve coupling between the photocatalytic optical fiber and the spiral chloride ion adsorption material, thereby obtaining the optical fiber material described in this invention.

[0099] Example 18: Assembly of photocatalytic optical fiber and helical chloride ion adsorption coupling material

[0100] The photocatalytic optical fiber obtained in Example 12 is inserted into the spiral chloride ion adsorption material obtained in Example 15, and both are sintered in a muffle furnace at 170°C for 8 hours to achieve coupling between the photocatalytic optical fiber and the spiral chloride ion adsorption material, thereby obtaining the optical fiber material described in this invention.

[0101] III. Performance Comparison

[0102] To characterize the degradation performance of p-chlorophenol, removal experiments were conducted on 2,4,6-trichlorophenol wastewater with a concentration of 100 mg / L under the conditions of 35℃ and pH 7. The catalysts used are as follows:

[0103] (1) The photocatalytic optical fibers prepared in Examples 10-12 were used alone for removal experiments;

[0104] (2) The chloride ion adsorbent materials prepared in Examples 13-15 were used alone for removal experiments;

[0105] (3) The photocatalytic optical fibers obtained in Examples 10-12 and the chloride ion adsorption materials obtained in Examples 13-15 were not coupled and assembled, and the two were placed independently in chlorophenol water for removal experiments;

[0106] (4) The optical fiber materials prepared in Examples 16-18 were used to conduct removal experiments.

[0107] The change in 2,4,6-trichlorophenol concentration during photocatalytic degradation was detected, such as... Figure 4As shown, at 10 hours, the removal rate of 2,4,6-trichlorophenol wastewater using only the chloride ion adsorbent material was 6.75%, indicating that the chloride ion adsorbent materials prepared in Examples 13-15 could only adsorb a small amount of 2,4,6-trichlorophenol and could not degrade it. The removal rate of 2,4,6-trichlorophenol wastewater using only the photocatalytic optical fiber prepared in Examples 10-12 was 65.6%. Although this degradation effect was better than that of using the chloride ion adsorbent material alone, the overall degradation effect was still relatively low. However, this also proves that the photocatalytic optical fiber prepared in Examples 10-12 can degrade some chlorophenols. The photocatalytic optical fibers obtained in Examples 10-12 and the chloride ion adsorption materials obtained in Examples 13-15 were not coupled and were placed independently in chlorophenol-containing water. The removal rate of 2,4,6-trichlorophenol wastewater was 79.05%. This indicates that the combined use of these two materials can indeed improve the removal efficiency of chlorophenol to a certain extent. It is speculated that this is because the photocatalytic optical fiber generates chloride ions during the degradation of chlorophenol, and the chloride ion adsorption material can adsorb these generated chloride ions, thereby promoting the catalytic degradation of chlorophenol by the photocatalytic optical fiber. The optical fiber materials prepared in Examples 16-18 achieved a removal rate of 96.7% for 2,4,6-trichlorophenol wastewater. This demonstrates that whether or not the photocatalytic optical fiber and the chloride ion adsorption material are coupled has a significant impact on the removal efficiency of chlorophenol. Figure 4 The data shows that the degradation effect after coupling is significantly better than that without coupling, which proves that the optical fiber material described in this invention has a higher degradation efficiency for 2,4,6-trichlorophenol wastewater. Furthermore, the coupling between the photocatalytic optical fiber and the chloride ion adsorption material does not reduce its degradation effect on chlorophenol, but rather improves it.

[0108] The changes in chloride ion concentration during photocatalytic degradation are as follows: Figure 5As shown in the figures, during the degradation of 2,4,6-trichlorophenol by the photocatalytic optical fibers prepared in Examples 10-12, the chloride ion concentration continuously increased, reaching 1005.5 μmol / L after 12 hours. This indicates that the photocatalytic optical fibers prepared in Examples 10-12 can only degrade chlorophenol and cannot handle the chloride ions formed during chlorophenol degradation. This also proves that the photocatalytic optical fibers prepared in Examples 10-12 do not have an adsorption effect on chloride ions. During the degradation of 2,4,6-trichlorophenol by the chloride ion adsorbent materials prepared in Examples 13-15, the chloride ion concentration remained unchanged at 0 μmol / L, indicating that the chloride ion adsorbent materials prepared in Examples 13-15 cannot degrade 2,4,6-trichlorophenol. The photocatalytic optical fibers obtained in Examples 10-12 and the chloride ion adsorbent materials obtained in Examples 13-15 were placed independently in chlorophenol water without coupling. During the degradation of 2,4,6-trichlorophenol, the chloride ion concentration first increased and then decreased, dropping to 380.5 μmol / L at 12 hours. This indicates that although the two materials can adsorb chloride ions to a certain extent when they are not coupled, this adsorption effect is relatively limited. The chloride ion concentration decreased at 4 hours, but the decrease was not large and was relatively gradual, which also indicates that the chloride ion adsorbent material was not effective at this time, and the adsorption capacity of the chloride ion adsorbent material was gradually approaching saturation. In the degradation of 2,4,6-trichlorophenol by the optical fiber materials prepared in Examples 16-18, the chloride ion concentration initially increased, indicating that a large number of chloride ions were formed during the degradation process. However, the chloride ion concentration then rapidly decreased after reaching a low peak, indicating that the optical fiber material was simultaneously degrading 2,4,6-trichlorophenol and adsorbing a large number of chloride ions. This resulted in the chloride ion concentration dropping to 34.5 μmol / L after 12 hours. This demonstrates that the optical fiber material can effectively remove chloride ions formed during the degradation process while simultaneously degrading chlorophenol, and that the degradation and adsorption processes are simultaneous and unaffected. This allows the optical fiber material to completely remove chlorophenol from the water. Furthermore, after 4 hours, the chloride ion concentration decreased significantly and gradually approached zero, indicating that the adsorption of chloride ions by the optical fiber material continued throughout the 12 hours and did not reach saturation. Compared to the uncoupled experiment, this further proves that coupling the process enables the optical fiber material to have a higher chloride ion adsorption capacity.

[0109] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the technical solutions. Those skilled in the art should understand that any modifications or equivalent substitutions to the technical solutions of the present invention without departing from the spirit and scope of the present invention should be covered within the scope of the claims of the present invention.

Claims

1. An optical fiber material for removing chlorophenol from water, characterized in that, The optical fiber material is composed of an optical fiber core, an optical fiber cladding, a photocatalytic layer, and a chloride ion adsorption material from inside to outside; wherein the optical fiber core is air, the optical fiber cladding is quartz, the photocatalytic layer is Ti3C2Tx / BiOBr-OV and is coated on the outer surface of the optical fiber cladding; and the chloride ion adsorption material is MOF-808-EDTA fiber, is in a spiral shape, and is located outside the photocatalytic layer. One end of the optical fiber core is a light beam incident end; a light beam can be transmitted into the optical fiber core through the light beam incident end, then refracted into the optical fiber cladding, and finally refracted and transmitted to the photocatalytic layer. The chloride ion adsorption material is combined with the photocatalytic fiber by the following method: The photocatalytic optical fiber is inserted into the spiral MOF-808-EDTA fiber, and sintering is performed at 170-200°C for 4-8h to realize coupling of the photocatalytic fiber and the chloride ion adsorption material, thereby obtaining the optical fiber material; The chloride ion adsorption material is prepared by the following method: Step 1: Resorcinal and zirconium oxychloride octahydrate are added to a mixed solution of N,N-dimethylformamide and formic acid to completely dissolve them; wherein the mass ratio of resorcinal to zirconium oxychloride octahydrate is (1-1.5):(4-5); then, the dissolved mixture solution is placed in an autoclave and reacted at 130-150°C for 36-48h; subsequently, the reaction product is washed with N,N-dimethylformamide and anhydrous acetone multiple times, and dried to obtain MOF-808 material; Step 2: The MOF-808 material obtained in step 1 is activated at 120-150°C, and the activated MOF-808 and disodium ethylenediaminetetraacetate are added to water and mixed, heated to 60-80°C, and reacted for 24-36h; after centrifugal washing and drying, MOF-808-EDTA is obtained; wherein the mass ratio of the activated MOF-808 to disodium ethylenediaminetetraacetate is (0.05-0.1):(0.8-1); Step 3: MOF-808-EDTA is dissolved with N-methylpyrrolidone, polyvinylpyrrolidone and polyether sulfone are added, and continuous stirring is performed at 60-70°C to obtain MOF-808-EDTA spinning solution; wherein the mass ratio of MOF-808-EDTA, polyvinylpyrrolidone and polyether sulfone is (0.1-0.3):(1.5-2):(4.5-5); Step 4: The MOF-808-EDTA spinning solution forms a filamentous fiber through a spinning device, and then forms a spiral chloride ion adsorption material through a mold.

2. The optical fiber material for removing chlorophenols from water according to claim 1, wherein The Ti3C2Tx / BiOBr-OV is prepared by the following method: BiOBr-OV powder is dissolved with water, then Ti3C2Tx powder is added, and continuous stirring is performed for 2-3h; the precipitate is collected after centrifugal separation and drying to obtain the Ti3C2Tx / BiOBr-OV; Wherein, the mass ratio of BiOBr-OV to Ti3C2Tx is (0.1-0.3):(0.01-0.03).

3. The optical fiber material for removing chlorophenols from water bodies as claimed in claim 2 wherein, The BiOBr-OV is prepared by the following method: Dissolve bismuth nitrate pentahydrate and potassium bromide in water and stir to obtain mixture A; in the mixture A, the concentration of bismuth nitrate pentahydrate is 9-17 mg / mL, and the concentration of potassium bromide is 3.5-7 mg / mL; place the mixture A in a reaction kettle and seal, and allow it to react at 160-180℃ for 3-5 h; centrifuge the product after reaction and collect the precipitate, and dry to obtain BiOBr; Dissolve BiOBr in water, and add mannitol and polyvinylpyrrolidone, and continuously stir to obtain mixture B; in the mixture B, the concentration of BiOBr is 2-10 mg / mL, the concentration of mannitol is 12-20 mg / mL, and the concentration of polyvinylpyrrolidone is 2-7 mg / mL; then place the mixture B in a reaction kettle and seal, and allow it to react at 160-180℃ for 3-5 h; centrifuge the obtained product and collect the precipitate, and dry to obtain the BiOBr-OV.

4. The optical fiber material for removing chlorophenols from water according to claim 2, wherein The Ti3C2Tx is prepared by the following method: Slowly add Ti3AlC2 into hydrofluoric acid, and the concentration of Ti3AlC2 in the hydrofluoric acid is 0.05-0.1 g / mL; magnetically stir at room temperature for 20-24 h to extract the aluminum layer; then centrifugally separate to obtain the precipitate, and perform multiple centrifugal washing on the precipitate, and dry to obtain the Ti3C2Tx.

5. The optical fiber material for removing chlorophenols from water according to claim 1, wherein The optical fiber cladding and the photocatalytic layer are combined by the following method: (1) sequentially use acetone, ethanol, and sodium hydroxide solution to ultrasonically clean the hollow quartz optical fiber multiple times; (2) sequentially add deionized water, acetylacetone to the Ti3C2Tx / BiOBr-OV powder and continuously mix and grind, then ultrasonically treat and add anhydrous ethanol, add Triton X-100, polyethylene glycol, and ethylene glycol, and continuously stir to obtain a stable Ti3C2Tx / BiOBr-OV sol; wherein the mass ratio of Ti3C2Tx / BiOBr-OV, deionized water, acetylacetone, anhydrous ethanol, Triton X-100, polyethylene glycol, and ethylene glycol is (1-2):(2-4):(0.5-2):(5-15):(0.3-1.5):(0.15-0.3):(1-3); (3) first seal one end of the hollow quartz optical fiber with paraffin, and then use the pull-coating film method to coat the Ti3C2Tx / BiOBr-OV sol on the outer surface of the hollow quartz optical fiber; then sinter at 180-200℃ for 12-20 h to obtain the photocatalytic fiber.

6. The optical fiber material for removing chlorophenols from water according to claim 1, wherein The optical fiber material can degrade chlorophenol in water and simultaneously adsorb the chloride ions formed after degradation.

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