PEEK composite film, preparation method and application thereof
By loading a MIS/NTO composite photocatalyst onto a SO-PEEK film, the problems of difficult recovery and easy deactivation of traditional photocatalysts were solved, achieving efficient degradation of formaldehyde and rhodamine B, and improving the stability and applicability of the material.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- JILIN JUKE HIGH TECH MATERIALS CO LTD
- Filing Date
- 2026-03-11
- Publication Date
- 2026-06-23
AI Technical Summary
Traditional photocatalysts are difficult to recover in gaseous and liquid phase pollution scenarios, are prone to agglomeration and deactivation, and are likely to cause secondary pollution. In addition, the bonding force between the catalyst and the support is weak, making it difficult to balance catalytic efficiency and stability.
SO-PEEK film was used as a support to support MIS/NTO composite photocatalyst. The composite connection was modified by silane coupling agent to form an efficient heterojunction interface, thereby realizing the immobilization of the catalyst and optimizing the loading ratio of MIS and NTO.
It can efficiently degrade gaseous formaldehyde and liquid rhodamine B under visible light, effectively separating the catalyst from the reaction medium, improving the separation efficiency of photogenerated carriers, material stability and recyclability, and adapting to complex polluted environments.
Smart Images
Figure CN121797406B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of photocatalytic materials technology, specifically to a PEEK composite film, its preparation method, and its application. Background Technology
[0002] Formaldehyde (HCHO) is a typical volatile organic pollutant, widely present in materials used in interior decoration such as boards, paints, and adhesives, making it one of the main indoor air pollutants that endanger human health. Furthermore, its unregulated emissions during chemical production processes pose a persistent threat to the aquatic environment. Meanwhile, synthetic organic dyes such as Rhodamine B, widely used in industries like printing and dyeing and papermaking, have become another typical type of recalcitrant organic pollutant in aquatic environments due to their wastewater discharge. These dyes are characterized by their deep color, high toxicity, and difficulty in biodegradation, severely damaging aquatic ecosystems. Therefore, developing efficient and sustainable treatment technologies that can be adapted to both gaseous and liquid phase pollution scenarios has become an urgent practical issue.
[0003] Among numerous pollution control technologies, photocatalysis has become a research hotspot in the field of formaldehyde and organic dye degradation due to its advantages such as mild reaction conditions, thorough mineralization, and no secondary pollution. However, traditional photocatalysts are mostly in powder or particulate form, which presents technical bottlenecks in both gaseous and liquid phase pollution scenarios, including difficulties in recovery, easy agglomeration and deactivation, and the potential for secondary pollution, severely restricting their large-scale application.
[0004] To address this issue, existing research has attempted to prepare composite photocatalytic materials by loading photocatalysts onto supports such as glass and ordinary polymer films, but significant drawbacks remain. On the one hand, glass supports are fragile and have poor corrosion resistance, while ordinary polymer films (such as PET and PVDF) suffer from weak resistance to UV degradation and are prone to aging and failure after long-term use, making them unsuitable for complex and harsh gas-liquid two-phase pollution environments. On the other hand, the interfacial bonding between the catalyst and the support is weak, making it easy for the catalyst to detach during use. Furthermore, single catalysts (such as TiO2) have a narrow visible light response range, and the loading process of composite catalysts generally suffers from poor dispersibility and low interfacial charge transfer efficiency, making it difficult to simultaneously achieve catalytic efficiency and stability for formaldehyde and organic dyes. Summary of the Invention
[0005] To address the challenge of balancing catalytic efficiency and stability in existing photocatalytic technologies, this invention proposes a PEEK composite film, its preparation method, and its applications.
[0006] The specific technical solution of the present invention is as follows:
[0007] A PEEK composite film includes an SO-PEEK film substrate and a MIS / NTO composite photocatalyst supported on the SO-PEEK film substrate;
[0008] The SO-PEEK film substrate is prepared from a polyetheretherketone material whose main chain contains thioether groups;
[0009] The MIS / NTO composite photocatalyst was prepared by hydrothermal reaction of NTO nanofibers and compounds containing Mg and In elements in the presence of thioacetamide.
[0010] The NTO nanofibers were prepared by electrospinning and calcining of tetrabutyl titanate and nickel acetate tetrahydrate.
[0011] The SO-PEEK thin film substrate and the MIS / NTO composite photocatalyst are compositely linked by a silane coupling agent.
[0012] This invention also provides a method for preparing a PEEK composite film, comprising the following steps:
[0013] S1. Tetrabutyl titanate and nickel acetate tetrahydrate are dissolved in a mixed solution of N,N-dimethylformamide and anhydrous ethanol; excess polyvinylpyrrolidone is added and stirred; the solution is transferred to an electrospinning machine for electrospinning, and the obtained nanofibers are calcined to obtain NTO nanofibers.
[0014] S2. Dissolve NTO nanofibers, MgCl2·6H2O, and InCl3 in deionized water, add thioacetamide to form a homogeneous solution, and carry out a hydrothermal reaction to obtain the MIS / NTO composite photocatalyst.
[0015] S3. 4,4'-dihydroxyphenyl sulfide, 4,4'-difluorobenzophenone and anhydrous potassium carbonate were added sequentially to N,N-dimethylformamide and mixed. The reaction was carried out under inert gas protection. The product was rotary evaporated with toluene, filtered with acetone, washed with distilled water, filtered again, and dried to obtain a white powder.
[0016] S4. Add 4,4'-difluorobenzophenone and hydroquinone to diphenyl sulfone and heat to melt. Then add anhydrous potassium carbonate and anhydrous sodium carbonate, stir, and heat to react. Add the white powder to continue the reaction. After the temperature is further increased, continue the reaction. Discharge the material in cold water, crush it, wash it with acetone and distilled water, filter it, and dry it to obtain SO-PEEK powder.
[0017] S5. Mix SO-PEEK powder, antioxidant and silane coupling agent in a high-speed mixer to obtain a premix. Feed the premix into a twin-screw extruder for extrusion, cooling and pelletizing to obtain SO-PEEK pellets.
[0018] S6. SO-PEEK granules are fed into a single screw extruder, extruded and cast through a T-die, and then stretched longitudinally to obtain SO-PEEK film.
[0019] S7. The SO-PEEK film and the MIS / NTO composite photocatalyst are added to the aqueous solution of silane coupling agent, heated and stirred to carry out the hydrolysis reaction, and then washed and dried to obtain the PEEK composite film.
[0020] Preferably, in step S1, the molar ratio of tetrabutyl titanate and nickel acetate tetrahydrate is 1:1; and the volume ratio of N,N-dimethylformamide and anhydrous ethanol is 5:3.
[0021] Preferably, in step S2, the molar ratio of NTO nanofibers, MgCl2·6H2O, InCl3, and thioacetamide is 20~88:1:2:7~12; the hydrothermal reaction temperature is 160~220℃, and the time is 10~16h.
[0022] Preferably, the molar ratio of 4,4'-dihydroxyphenyl sulfide, 4,4'-difluorobenzophenone and anhydrous potassium carbonate in step S3 is 3:28:5;
[0023] The molar ratio of 4,4'-difluorobenzophenone and hydroquinone is 1:1;
[0024] The amount of the white powder used is 10-20% of the total mass of 4,4'-difluorobenzophenone and hydroquinone;
[0025] The mass ratio of anhydrous potassium carbonate to anhydrous sodium carbonate is 1~5:15~25.
[0026] Preferably, the reaction temperature in step S3 is 140~180℃, and the reaction time is 6~10h;
[0027] Preferably, the heating rate of the heating reaction in step S4 is 30℃ / h, and the reaction is carried out at 160~280℃ for 3.5h;
[0028] The reaction time after adding the white powder is 1 hour.
[0029] The temperature at which the reaction continues after further increasing is 300°C, and the reaction time is 3 hours.
[0030] Preferably, the mass ratio of the SO-PEEK powder, antioxidant, and silane coupling agent is 100:3:5.
[0031] The extrusion temperature of the twin-screw extruder is 370~390℃; the extrusion temperature of the single-screw extruder is 350~370℃.
[0032] Preferably, the mass ratio of the SO-PEEK and MIS / NTO composite photocatalyst is 50:1.5~4.5;
[0033] The mass fraction of the silane coupling agent aqueous solution is 3%;
[0034] The hydrolysis reaction is carried out at a temperature of 60-90℃ for 6-10 hours.
[0035] The present invention also provides an application of the above-mentioned PEEK composite film in the fields of gas phase pollution control or water treatment.
[0036] Compared with existing technologies, this invention constructs a photocatalytic composite system integrating an indium sulfide / nickel titanate composite photocatalyst with a polyetheretherketone (PEEK) film containing sulfide groups in its main chain, simultaneously addressing the application limitations of traditional photocatalytic materials and the application scenarios of pollutant treatment. Specific beneficial effects are as follows:
[0037] The composite film can simultaneously perform photocatalytic degradation of two typical pollutants: gaseous formaldehyde and liquid rhodamine B. Under visible light, the formaldehyde removal rate reaches 63.71% within 1 hour, and rhodamine B can be completely degraded in 10 minutes. It can address both gaseous pollution control and liquid wastewater pollution treatment, breaking through the application barrier that single photocatalytic materials are only suitable for a single scenario.
[0038] By using SO-PEEK thin films as carriers to achieve photocatalyst immobilization, the catalyst can be effectively separated from the reaction medium, completely avoiding the technical bottlenecks of traditional powder / particle photocatalysts, such as easy loss, agglomeration and deactivation, difficulty in recycling and secondary pollution, and greatly improving the safety of the material in actual use.
[0039] After optimizing the optimal loading ratio of MIS and NTO, the composite catalyst forms a highly efficient heterojunction interface, improving the separation efficiency of photogenerated carriers. The active groups for formaldehyde degradation are mainly holes and superoxide radicals, resulting in a highly efficient reaction pathway. Furthermore, the material can drive the catalytic reaction under visible light with wavelengths greater than 420 nm, eliminating the need for ultraviolet light sources, thus reducing energy consumption and broadening its applicability.
[0040] The SO-PEEK matrix retains the excellent chemical corrosion resistance and UV degradation resistance of PEEK. At the same time, the introduction of sulfide groups enhances the interfacial bonding between the matrix and the photocatalyst, preventing catalyst detachment and failure. After multiple cyclic degradation experiments, the material's formaldehyde degradation performance showed no significant attenuation, demonstrating excellent cyclic stability and adaptability to harsh and complex water pollution and multi-condition gaseous pollution environments.
[0041] By adjusting the MIS precursor feed ratio and the loading of photocatalyst in SO-PEEK films, the optimal process parameters for catalytic performance can be precisely obtained. The preparation process is highly repeatable, ensuring photocatalytic activity without compromising the formability and mechanical properties of the PEEK film, and possessing the potential for large-scale preparation and application. Attached Figure Description
[0042] Figure 1 X-ray diffraction patterns of NTO, MgIn2S4 and NTO / MIS composite photocatalysts;
[0043] Figure 2 The graph shows the degradation efficiency of formaldehyde on NTO with different MIS loading and the degradation effect of PEEK film with different NTO / MIS loading on formaldehyde.
[0044] Figure 3 The results show the degradation rates of formaldehyde and rhodamine B on the composite film.
[0045] Figure 4 Results of free radical capture experiments;
[0046] Figure 5 The results are from a formaldehyde degradation cycle test. Detailed Implementation
[0047] To make the technical solutions of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. It should be noted that the following embodiments are only used to better understand the technical solutions of the present invention and should not be construed as limiting the present invention.
[0048] Example 1.
[0049] 11.0094 g of tetrabutyl titanate and 8.0499 g of nickel acetate tetrahydrate were dissolved in 80 mL of a mixed solution of N,N-dimethylformamide and anhydrous ethanol (volume ratio 5:3). Then, 12 g of polyvinylpyrrolidone was slowly added, and the mixture was stirred for 5 h. The solution was then transferred to a 10 mL plastic syringe equipped with a 22-gauge stainless steel needle. The syringe was then transferred to an electrospinning machine and spun at 0.5 mL / h under 12 kV high voltage. -1 Electrospinning was performed at a rate of 2 °C / min. The distance between the syringe needle and the counter electrode was 15 cm. The obtained nanofibers were then electrospun at 800 °C at a rate of 2 °C / min. -1 NTO nanofibers were obtained by calcining at a heating rate of 5 h.
[0050] 20 g of NTO nanofibers, 0.3192 g of MgCl2·6H2O, and 0.6949 g of InCl3 were dissolved in 350 mL of deionized water and stirred continuously until dissolved. Then, 1.4 g of thioacetamide was added to the mixed solution to form a homogeneous solution. The resulting homogeneous solution was transferred to a 500 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner and heated at 220 °C for 16 h to obtain the MIS / NTO composite photocatalyst.
[0051] Figure 1The X-ray diffraction patterns of NTO, MgIn2S4, and NTO / MIS composite photocatalysts are shown. The characteristic diffraction peaks of NiTiO3 perfectly match the standard card, as do the characteristic diffraction peaks of MgIn2S4. The NTO / MIS composite catalyst exhibits characteristic diffraction peaks of both NTO and MgIn2S4, with no obvious impurity peaks. This indicates that the present invention successfully prepared a composite photocatalyst possessing both NTO and MIS phase structures, and that the composite process did not introduce impurities or damage the original crystal structure, providing a structural basis for its excellent photocatalytic performance.
[0052] 35 g of 4,4'-dihydroxyphenyl sulfide, 330 g of 4,4'-difluorobenzophenone, and 37 g of anhydrous potassium carbonate were sequentially added to 500 mL of N,N-dimethylformamide and mixed. The mixture was then transferred to a 1 L three-necked flask and reacted at 160 °C for 10 h under an inert gas atmosphere. The resulting reactants were rotary evaporated in toluene, filtered through acetone to remove the solvent and unreacted substances, and finally washed repeatedly with distilled water to remove inorganic salts. The mixture was then dried at 80 °C for 24 h to obtain a white powder.
[0053] 75.692 g of 4,4'-difluorobenzophenone, 38.159 g of hydroquinone, and 300 g of diphenyl sulfone were sequentially added to a 1000 mL three-necked flask and heated to melt. Then, 2.70 g of anhydrous potassium carbonate and 38.43 g of anhydrous sodium carbonate were added, and the mixture was stirred. The temperature was increased by a programmed rate of 30 °C / h, and the reaction was carried out at 160 to 280 °C for a total of 3.5 h. 20 g of the obtained white powder was mixed into the reactants, and the reaction was continued for 1 h. The temperature was then increased to 300 °C and the reaction was carried out for 3 h. The mixture was discharged in cold water, pulverized, washed with acetone and distilled water, filtered multiple times, and dried at 100 °C for 24 h to obtain a polyether ether ketone material with a thioether group in the main chain, which is the SO-PEEK powder sample.
[0054] SO-PEEK powder, 1.5g antioxidant, and 2.5g silane coupling agent are poured into a high-speed mixer and mixed evenly for 30 minutes to obtain a premix. The premix is then fed into a twin-screw extruder, extruded at 370°C, cooled, and pelletized to obtain SO-PEEK pellets.
[0055] The obtained SO-PEEK granules are fed into a single screw extruder and extruded and cast through a T-die at 370°C. After longitudinal stretching, a SO-PEEK film with a thickness of 0.2 mm is obtained.
[0056] 50g of SO-PEEK film and 1.5g of MIS / NTO were uniformly poured into 250mL of 3% (w / w) silane coupling agent aqueous solution, heated and stirred, and hydrolyzed at 80℃ for 10h. After washing and drying, a PEEK composite film with photocatalytic ability was obtained.
[0057] Example 2.
[0058] The preparation steps are the same as in Example 1, except that: "0.3192g MgCl2·6H2O, 0.6949g InCl3, 1.4g thioacetamide" is changed to "0.6384g MgCl2·6H2O, 1.3898g InCl3, 3.0g thioacetamide".
[0059] Example 3.
[0060] The preparation steps are the same as in Example 1, except that: "0.3192g MgCl2·6H2O, 0.6949g InCl3, 1.4g thioacetamide" is changed to "1.2768g MgCl2·6H2O, 2.7796g InCl3, 6.0g thioacetamide".
[0061] Comparative Example 1.
[0062] 11.0094 g of tetrabutyl titanate and 8.0499 g of nickel acetate tetrahydrate were dissolved in 80 mL of a mixed solution of N,N-dimethylformamide and anhydrous ethanol (volume ratio 5:3). Then, 12 g of polyvinylpyrrolidone was slowly added, and the mixture was stirred for 5 h. The solution was then transferred to a 10 mL plastic syringe equipped with a 22-gauge stainless steel needle. The syringe was then transferred to an electrospinning machine and spun at 0.5 mL / h under 12 kV high voltage. -1 Electrospinning was performed at a rate of 2 °C / min. The distance between the syringe needle and the counter electrode was 15 cm. The obtained nanofibers were then electrospun at 800 °C at a rate of 2 °C / min. -1 NTO nanofibers were obtained by calcining at a heating rate of 5 h.
[0063] 20 g of NTO nanofibers, 0.3192 g of MgCl2·6H2O, and 0.6949 g of InCl3 were dissolved in 350 mL of deionized water and stirred continuously until dissolved. Then, 1.4 g of thioacetamide was added to the mixed solution to form a homogeneous solution. The resulting homogeneous solution was transferred to a 500 mL stainless steel high-pressure reactor with a polytetrafluoroethylene liner and heated at 220 °C for 16 h to obtain the MIS / NTO composite photocatalyst for later use.
[0064] 35 g of 4,4'-dihydroxyphenyl sulfide, 330 g of 4,4'-difluorobenzophenone, and 37 g of anhydrous potassium carbonate were sequentially added to 500 mL of N,N-dimethylformamide and mixed. The mixture was then transferred to a 1 L three-necked flask and reacted at 160 °C for 10 h under an inert gas atmosphere. The resulting reactants were rotary evaporated in toluene, filtered through acetone to remove the solvent and unreacted substances, and finally washed repeatedly with distilled water to remove inorganic salts. The mixture was then dried at 80 °C for 24 h to obtain a white powder.
[0065] 75.692 g of 4,4'-difluorobenzophenone, 38.159 g of hydroquinone, and 300 g of diphenyl sulfone were sequentially added to a 1000 mL three-necked flask and heated to melt. Then, 2.70 g of anhydrous potassium carbonate and 38.43 g of anhydrous sodium carbonate were added, and the mixture was stirred. The temperature was increased by a programmed rate of 30 °C / h, and the reaction was carried out at 160 to 280 °C for a total of 3.5 h. Then, 20 g of white powder was mixed into the reactants, and the reaction was continued for 1 h. The temperature was then increased to 300 °C and the reaction was carried out for 3 h. The mixture was discharged in cold water, pulverized, washed with acetone and distilled water, filtered multiple times, and dried at 100 °C for 24 h to obtain a polyether ether ketone material with a thioether group in the main chain, which is the SO-PEEK powder sample.
[0066] SO-PEEK powder, 1.5g antioxidant, and 2.5g silane coupling agent are poured into a high-speed mixer and mixed evenly for 30 minutes to obtain a premix. The premix is then fed into a twin-screw extruder, extruded at 370°C, cooled, and pelletized to obtain SO-PEEK pellets.
[0067] SO-PEEK granules are fed into a single-screw extruder and extruded and cast through a T-die at 370°C. After longitudinal stretching, a SO-PEEK film with a thickness of 0.2 mm is obtained.
[0068] 50g of SO-PEEK film and 0.5g of MIS / NTO were uniformly poured into 250mL of 3% (w / w) silane coupling agent aqueous solution, heated and stirred, and hydrolyzed at 80℃ for 10h. After washing and drying, a PEEK composite film with photocatalytic ability was obtained.
[0069] Comparative Example 2.
[0070] The specific steps are the same as in Comparative Example 1, except that the amount of MIS / NTO used is changed from 0.5g to 2.5g.
[0071] Comparative Example 3.
[0072] The specific steps are the same as in Comparative Example 1, except that the amount of MIS / NTO used is changed from 0.5g to 3.5g.
[0073] Example of results.
[0074] (1) Degradation performance test of formaldehyde and rhodamine B:
[0075] A 37% formalin solution was used as the HCHO gas source. 20 mg of the composite film was placed in a sealed photocatalytic reactor. A certain volume of formalin solution was directly dripped into a glass reagent bottle inside the reactor, which was then sealed. The formalin solution was heated with infrared light to accelerate evaporation, and a gas circulation pump was used to promote the diffusion of HCHO gas. The HCHO gas was diffused in the dark for 20 min to achieve uniform distribution and ensure adsorption-desorption equilibrium between HCHO and the catalyst powder. When gas desorption equilibrium was reached, the mixture was stirred and placed under visible light (λ > 420 nm) irradiation. The change in HCHO concentration was detected using a UV spectrophotometer.
[0076] Every 10 minutes, 5 mL of gas was drawn using a syringe and quickly injected into a brown glass reagent bottle with a rubber stopper, which was pre-filled with colorimetric reagent. The brown bottle was shaken thoroughly to completely dissolve HCHO in the solution, and then placed in a 40°C water bath for 10 minutes. NH4Fe(SO4)2 was then added, shaken thoroughly, and placed in a 40°C water bath for another 10 minutes. The solution gradually turned blue-green. This blue-green solution has a characteristic absorption peak at 630 nm. By monitoring the change in absorbance at this wavelength, the formaldehyde concentration was quantitatively detected.
[0077] 20 mg of the composite membrane was added to an aqueous solution containing 20 mL of Rhodamine B. The suspension was stirred in the dark for 20 min to obtain an adsorption-desorption equilibrium between Rhodamine B and the surface of the composite membrane. The mixture was then stirred and irradiated under visible light (λ > 420 nm). Approximately 2 mL of the suspension was taken out every 10 min, centrifuged, and the pollutant concentration was measured using a UV spectrophotometer at the maximum absorption wavelength of 365 nm. The degradation rate of Rhodamine B was calculated by observing the change in absorbance.
[0078] (2) Free radical capture experiment:
[0079] To investigate the active species in the photocatalytic degradation of formaldehyde, isopropanol (·OH scavenger) and triethanolamine (h) were used. + (Scavenger) and p-benzoquinone (·O2) - A capture experiment was conducted using the aforementioned capture agent. The experimental system was consistent with the formaldehyde degradation performance test; after adding the capture agent, the change in HCHO concentration over time was monitored.
[0080] (3) Cyclic stability test:
[0081] The composite film was repeatedly used in the formaldehyde degradation experiment. After each experiment, the film was washed and dried before the next round of degradation test was conducted. A total of 5 cycles of experiments were carried out to verify the reusability of the composite film.
[0082] The above embodiments and comparative embodiments were tested, and the results are as follows:
[0083] (1) Based on the above formaldehyde degradation test method, the explanatory effects of each embodiment and comparative embodiment were tested, and the results were obtained as follows: Figure 2 The degradation comparison curves are shown. Figure 2 The main figure compares the formaldehyde absorption effect of MIS on NTO nanofibers under different loading ratios in Examples 1-3. The comparison shows that Example 1 exhibits the fastest degradation rate, indicating that at this loading ratio, MIS and NTO form a highly efficient heterojunction, resulting in the highest photogenerated carrier separation efficiency and the most complete exposure of active sites. The inset shows a comparison of the formaldehyde absorption effect of MIS / NTO on SO-PEEK films under different loading amounts in Examples 1 and Comparative Examples 1-3. The comparison shows that Example 1 exhibits the fastest degradation rate. At this loading amount, MIS / NTO is uniformly dispersed in the film, ensuring sufficient active sites without affecting the film's light transmittance.
[0084] (2) Based on the above-mentioned formaldehyde and rhodamine B degradation test methods, the thin film material in Example 1 was tested. The results were as follows: Figure 3 The degradation curves are shown. The results indicate that the composite film prepared in this invention achieves a formaldehyde removal rate of 63.71% within 1 hour of visible light irradiation; the degradation efficiency for Rhodamine B is even higher, achieving complete degradation in just 10 minutes. This result demonstrates that the composite film of this invention exhibits excellent photocatalytic degradation performance for both gaseous formaldehyde and liquid dyes.
[0085] (3) A free radical capture experiment was conducted on the thin film material in Example 1, and the results are as follows: Figure 4 As shown. Add triethanolamine (h) + (Scavenger) and p-benzoquinone (·O2) - After the addition of a scavenger, the degradation rate of HCHO was significantly inhibited; the addition of isopropanol (·OH scavenger) had no significant effect on the degradation rate. This indicates that in the photocatalytic degradation of formaldehyde by the composite film of this invention, holes (h + ) and superoxide radicals (·O2) - ) is the main active species, while hydroxyl radical (·OH) does not participate in the main reaction.
[0086] (4) Cyclic stability tests were performed on the thin film material in Example 1, and the results are as follows: Figure 5 As shown, after five reuses, the composite film maintained a formaldehyde degradation rate of over 62%, with no significant performance degradation. This result demonstrates that the composite film of this invention possesses excellent photocatalytic stability and reusability, effectively solving the technical problems of traditional powdered photocatalysts being difficult to recycle and prone to causing secondary pollution.
[0087] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.
Claims
1. A PEEK composite film, characterized in that, It includes an SO-PEEK thin film substrate and a MIS / NTO composite photocatalyst supported on the SO-PEEK thin film substrate; The SO-PEEK film substrate is prepared from a polyetheretherketone material whose main chain contains thioether groups. The preparation process of the SO-PEEK film substrate includes: 4,4'-dihydroxyphenyl sulfide, 4,4'-difluorobenzophenone and anhydrous potassium carbonate were added sequentially to N,N-dimethylformamide and mixed. The reaction was carried out under an inert gas protection. The product was rotary evaporated in toluene, filtered with acetone, washed with distilled water, filtered again, and dried to obtain a white powder. 4,4'-Difluorobenzophenone and hydroquinone were added to diphenyl sulfone and heated to melt. Then anhydrous potassium carbonate and anhydrous sodium carbonate were added, stirred, and heated to react. The white powder was added and the reaction continued. The temperature was further increased and the reaction continued. The product was discharged in cold water, crushed, washed with acetone and distilled water, filtered, and dried to obtain SO-PEEK powder. The MIS / NTO composite photocatalyst was prepared by hydrothermal reaction of NTO nanofibers and compounds containing Mg and In elements in the presence of thioacetamide. The NTO nanofibers were prepared by electrospinning and calcining of tetrabutyl titanate and nickel acetate tetrahydrate. The SO-PEEK thin film substrate and the MIS / NTO composite photocatalyst are compositely linked by a silane coupling agent.
2. A method for preparing a PEEK composite film, characterized in that, Includes the following steps: S1. Tetrabutyl titanate and nickel acetate tetrahydrate are dissolved in a mixed solution of N,N-dimethylformamide and anhydrous ethanol; excess polyvinylpyrrolidone is added and stirred; the solution is transferred to an electrospinning machine for electrospinning, and the obtained nanofibers are calcined to obtain NTO nanofibers. S2. Dissolve NTO nanofibers, MgCl2·6H2O, and InCl3 in deionized water, add thioacetamide to form a homogeneous solution, and carry out a hydrothermal reaction to obtain the MIS / NTO composite photocatalyst. S3. 4,4'-dihydroxyphenyl sulfide, 4,4'-difluorobenzophenone and anhydrous potassium carbonate were added sequentially to N,N-dimethylformamide and mixed. The reaction was carried out under inert gas protection. The product was rotary evaporated with toluene, filtered with acetone, washed with distilled water, filtered again, and dried to obtain a white powder. S4. Add 4,4'-difluorobenzophenone and hydroquinone to diphenyl sulfone and heat to melt. Then add anhydrous potassium carbonate and anhydrous sodium carbonate, stir, and heat to react. Add the white powder to continue the reaction. After the temperature is further increased, continue the reaction. Discharge the material in cold water, crush it, wash it with acetone and distilled water, filter it, and dry it to obtain SO-PEEK powder. S5. Mix SO-PEEK powder, antioxidant and silane coupling agent in a high-speed mixer to obtain a premix. Feed the premix into a twin-screw extruder for extrusion, cooling and pelletizing to obtain SO-PEEK pellets. S6. SO-PEEK granules are fed into a single screw extruder, extruded and cast through a T-die, and then stretched longitudinally to obtain SO-PEEK film. S7. The SO-PEEK film and the MIS / NTO composite photocatalyst are added to the aqueous solution of silane coupling agent, heated and stirred to carry out the hydrolysis reaction, and then washed and dried to obtain the PEEK composite film.
3. The method for preparing the PEEK composite film according to claim 2, characterized in that, In step S1, the molar ratio of tetrabutyl titanate and nickel acetate tetrahydrate is 1:1; the volume ratio of N,N-dimethylformamide and anhydrous ethanol is 5:
3.
4. The method for preparing the PEEK composite film according to claim 2, characterized in that, In step S2, the molar ratio of NTO nanofibers, MgCl2·6H2O, InCl3, and thioacetamide is 20~88:1:2:7~12; the hydrothermal reaction temperature is 160~220℃ and the time is 10~16h.
5. The method for preparing the PEEK composite film according to claim 2, characterized in that, The molar ratio of 4,4'-dihydroxyphenyl sulfide, 4,4'-difluorobenzophenone and anhydrous potassium carbonate in step S3 is 3:28:5; The molar ratio of 4,4'-difluorobenzophenone and hydroquinone in step S4 is 1:1; The amount of the white powder used is 10-20% of the total mass of 4,4'-difluorobenzophenone and hydroquinone; The mass ratio of anhydrous potassium carbonate to anhydrous sodium carbonate is 1~5:15~25.
6. The method for preparing the PEEK composite film according to claim 2, characterized in that, The reaction temperature in step S3 is 140~180℃, and the reaction time is 6~10h.
7. The method for preparing the PEEK composite film according to claim 2, characterized in that, The heating rate of the reaction described in step S4 is 30℃ / h, and the reaction is carried out at 160~280℃ for 3.5h. The reaction time after adding the white powder is 1 hour. The temperature at which the reaction continues after further increasing is 300°C, and the reaction time is 3 hours.
8. The method for preparing the PEEK composite film according to claim 2, characterized in that, The mass ratio of SO-PEEK powder, antioxidant and silane coupling agent is 100:3:5; The extrusion temperature of the twin-screw extruder is 370~390℃; the extrusion temperature of the single-screw extruder is 350~370℃.
9. The method for preparing the PEEK composite film according to claim 2, characterized in that, The mass ratio of the SO-PEEK and MIS / NTO composite photocatalyst is 50:1.5~4.5; The mass fraction of the silane coupling agent aqueous solution is 3%; The hydrolysis reaction is carried out at a temperature of 60-90℃ for 6-10 hours.
10. The application of a PEEK composite film as described in claim 1 or a PEEK composite film prepared by any one of claims 2 to 9 in the field of gas phase pollution control or water treatment.