An MXene-functionalized cotton fabric, its preparation method and application

Abstract

The present invention provides an MXene-functionalized cotton fabric, a preparation method thereof, and an application thereof, belonging to the technical field of functional textile materials. The present invention prepares a multi-layer MXene cotton fabric functional material by an impregnation method, and attaches multi-layer MXene to the surface of the cotton fabric by means of hydrogen bond binding. The MXene is attached to the surface and between the fibers of the cotton fabric to obtain an MXene-functionalized cotton fabric with good catalytic activity and chemical stability. The MXene-functionalized cotton fabric of the present invention can be applied to the treatment of dye sewage, and the photocatalytic degradation rate of methylene blue is as high as 97.7%. After multiple cycles of degradation, the degradation rate of methylene blue does not decrease significantly, and the MXene-functionalized cotton fabric has good photo-stability. Through performance testing, it is shown that the MXene-functionalized cotton fabric also has good ultraviolet resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of functional textile materials, and in particular to an MXene-functionalized cotton fabric, a preparation method thereof, and an application thereof. Background Art

[0002] As a major country in the textile printing and dyeing industry, due to the wide variety and complex composition of dyes, printing and dyeing wastewater has become a relatively prominent problem in China's environmental governance. Currently, the methods for removing dyes from water mainly include three types: physical methods, chemical methods, and biological methods. Among them, physical methods have a high cost and difficult regeneration of treatment agents; chemical methods are prone to cause secondary pollution of pollutants generated; while biological methods are specific to dyes and have low efficiency. Photocatalytic treatment of printing and dyeing wastewater is one of the most effective and inexpensive methods, which allows the complete mineralization of these environmentally harmful dyes. Moreover, photocatalytic degradation has the advantages of being non-toxic, low energy consumption, simple operation, mild reaction conditions, and being able to effectively remove organic pollutants in wastewater, and thus occupies a great advantage in dye sewage treatment. To achieve the best performance, one of the most important process parameters that need to be optimized is the selection of the catalyst. Some current photocatalytic materials have problems such as slow degradation efficiency, poor recyclability, and difficult recovery. Therefore, it is crucial to study a photocatalyst material with excellent photocatalytic degradation and stable cycling performance and easy recovery. Summary of the Invention

[0003] The purpose of the present invention is to provide an MXene-functionalized cotton fabric, a preparation method thereof, and an application thereof, so as to solve the technical problems existing in the above-mentioned prior art.

[0004] To achieve the above-mentioned invention purpose, the present invention provides the following technical solutions:

[0005] The present invention provides a preparation method of an MXene-functionalized cotton fabric, comprising the following steps:

[0006] 1) Aluminum titanium carbide is successively mixed and reacted with lithium fluoride and hydrochloric acid solution, and the obtained reaction solution is successively subjected to pickling, centrifugation, and freeze-drying to obtain multi-layer MXene powder;

[0007] 2) The multi-layer MXene powder and water are mixed to obtain an MXene suspension;

[0008] 3) The cotton fabric is impregnated in the MXene suspension and dried, and the process is repeated 5 to 10 times to obtain the MXene-functionalized cotton fabric.

[0009] Further, the mass-volume ratio of the aluminum titanium carbide, lithium fluoride, and hydrochloric acid solution is 1.0 - 2.0 g: 1.0 - 2.0 g: 20 - 40 mL;

[0010] The concentration of the hydrochloric acid solution is 5 - 15 mol / L.

[0011] Further, in the step 1), the temperature of the mixing reaction is 30 - 50 °C, and the time of the mixing reaction is 30 - 48 h.

[0012] Further, the reagent used for pickling is hydrochloric acid solution, the concentration of the hydrochloric acid solution is 1 - 2 mol / L, and the number of pickling times is 2 - 5 times.

[0013] Further, the concentration of the MXene suspension is 2 - 8 mg / mL.

[0014] Further, in the step 3), the time for single impregnation is 4 - 10 min.

[0015] Further, in the step 3), the drying temperature is 70 - 90 °C, and the drying time is 15 - 40 min.

[0016] The present invention provides a kind of MXene-functionalized cotton fabric.

[0017] The present invention also provides an application of the MXene-functionalized cotton fabric in dye sewage treatment.

[0018] The beneficial effects of the present invention:

[0019] MXenes, as a new type of green material, are composed of transition metal carbides, carbonitrides and nitrides. Due to their porous structure, hydrophilicity, conductivity, excellent structural stability, adjustable interlayer spacing and sufficient bandgap energy, they are one of the attractive photocatalyst materials for the removal of many pollutants. MXene can promote the generation of photoinduced carriers and the transport of electron-hole pairs in a short time, and has good application prospects in the field of photocatalysis.

[0020] The present invention prepares a multi-layer MXene cotton fabric functional material by an impregnation method, and attaches the multi-layer MXene to the surface of the cotton fabric by means of hydrogen bond binding. MXene is attached to the surface and between the fibers of the cotton fabric to obtain an MXene-functionalized cotton fabric with good catalytic activity and chemical stability.

[0021] In the present invention, the fabric substrate and the catalyst are tightly combined by intermolecular hydrogen bonds, which can solve the problem of secondary pollution of water body caused by the catalyst in the water purification system.

[0022] The MXene cotton fabric functional material of the present invention is also verified to have ultraviolet resistance. Description of the Drawings

[0023] Figure 1 It is the SEM diagram of the MXene-functionalized cotton fabric of Example 1 of the present invention;

[0024] Figure 2Absorbance curve of MXene-functionalized cotton fabric for degrading methylene blue dye in Example 1 of the present invention;

[0025] Figure 3 Efficiency diagram of MXene-functionalized cotton fabric for degrading methylene blue dye in Example 1 of the present invention;

[0026] Figure 4 Efficiency curve of MXene-functionalized cotton fabric for degrading methylene blue dye after being reused three times in Example 1 of the present invention. Detailed implementation manners

[0027] The present invention provides a method for preparing MXene-functionalized cotton fabric, comprising the following steps:

[0028] 1) Aluminum titanium carbide is successively mixed and reacted with lithium fluoride and hydrochloric acid solution, and the obtained reaction solution is successively pickled, centrifuged, and freeze-dried to obtain multi-layer MXene powder;

[0029] 2) The multi-layer MXene powder and water are mixed to obtain an MXene suspension;

[0030] 3) The cotton fabric is impregnated in the MXene suspension and dried, and the process is repeated 5 to 10 times to obtain the MXene-functionalized cotton fabric.

[0031] In the present invention, in step 3), the number of repetitions is preferably 6 to 9 times, and more preferably 8 times.

[0032] In the present invention, the mass-volume ratio of the aluminum titanium carbide, lithium fluoride, and hydrochloric acid solution is 1.0 - 2.0 g: 1.0 - 2.0 g: 20 - 40 mL, preferably 1.2 - 1.8 g: 1.2 - 1.8 g: 25 - 35 mL, and more preferably 1.5 g: 1.5 g: 30 mL.

[0033] In the present invention, the concentration of the hydrochloric acid solution is 5 - 15 mol / L, preferably 8 - 12 mol / L, and more preferably 10 mol / L.

[0034] In the present invention, in step 1), the temperature of the mixed reaction is 30 - 50 °C, preferably 35 - 45 °C, and more preferably 40 °C; the time of the mixed reaction is 30 - 48 h, preferably 35 - 42 h, and more preferably 36 h.

[0035] In the present invention, the reagent used for pickling is hydrochloric acid solution, and the concentration of the hydrochloric acid solution is 1 - 2 mol / L, preferably 1 mol / L; the number of pickling times is 2 - 5 times, preferably 3 - 4 times.

[0036] In the present invention, the concentration of the MXene suspension is 2 to 8 mg / mL, preferably 3 to 6 mg / mL, and more preferably 4 to 5 mg / mL.

[0037] In the present invention, the cotton fabric is pretreated before impregnation. The pretreatment is to soak the cotton fabric in an ethanol solution, wash it three times by shaking, and then dry it at 60°C to remove the impurities remaining on the surface of the cotton fabric.

[0038] In the present invention, in step 3), the single impregnation time is 4 to 10 min, preferably 5 to 8 min, and more preferably 6 to 7 min.

[0039] In the present invention, in step 3), the drying temperature is 70 to 90°C, preferably 75 to 85°C, and more preferably 80°C; the drying time is 15 to 40 min, preferably 20 to 30 min.

[0040] The present invention provides a kind of MXene-functionalized cotton fabric.

[0041] The present invention also provides an application of the MXene-functionalized cotton fabric in dye sewage treatment.

[0042] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0043] Example 1

[0044] Preparation of MXene-functionalized cotton fabric:

[0045] Pretreatment of cotton fabric: Soak the cotton fabric in an ethanol solution, wash it three times by shaking to remove the impurities remaining on the fabric surface, and dry it at 60°C for standby.

[0046] Preparation of multi-layer MXene: Slowly add 1.5 g of titanium aluminum carbide powder in small amounts to a mixed solution of 1.5 g of lithium fluoride and 30 mL of 10 M hydrochloric acid. After fully stirring and reacting at 40°C in a constant temperature water bath environment for 36 h, wash the obtained reaction solution with 1 M hydrochloric acid three times, and then centrifuge and wash this solution multiple times until the pH of the supernatant after centrifugation is greater than 6. After freeze-drying for 12 h, the multi-layer MXene powder required for the experiment is prepared.

[0047] Preparation of MXene suspension: Take 0.2 g of the obtained multi-layer MXene powder and place it in 40 mL of deionized water, stir evenly to obtain the required MXene suspension.

[0048] Preparation of MXene-functionalized cotton fabric: The cotton fabric was placed in the obtained MXene suspension, impregnated at room temperature for 5 min, dried at 80 °C, impregnated repeatedly 8 times, and finally the MXene-functionalized cotton fabric was obtained.

[0049] Example 2

[0050] Preparation of MXene-functionalized cotton fabric:

[0051] Pretreatment of cotton fabric: The cotton fabric was soaked in an ethanol solution, washed by shaking three times to remove the impurities remaining on the fabric surface, and dried at 60 °C for standby.

[0052] Preparation of multi-layer MXene: 1.8 g of titanium aluminum carbide powder was slowly added in small amounts to a mixed solution of 1.8 g of lithium fluoride and 35 mL of 10 M hydrochloric acid. After fully stirring and reacting in a 45 °C constant temperature water bath environment for 30 h, the obtained reaction solution was pickled 3 times with 1 M hydrochloric acid, and then the solution was centrifuged and washed with water multiple times until the pH of the supernatant after centrifugation was greater than 6. After freeze-drying for 12 h, the multi-layer MXene powder required for the experiment was prepared.

[0053] Preparation of MXene suspension: 0.32 g of the obtained multi-layer MXene powder was placed in 40 mL of deionized water and stirred evenly to obtain the required MXene suspension.

[0054] Preparation of MXene-functionalized cotton fabric: The cotton fabric was placed in the obtained MXene suspension, impregnated at room temperature for 5 min, dried at 80 °C, impregnated repeatedly 8 times, and finally the MXene-functionalized cotton fabric was obtained.

[0055] Example 3

[0056] Preparation of MXene-functionalized cotton fabric:

[0057] Pretreatment of cotton fabric: The cotton fabric was soaked in an ethanol solution, washed by shaking three times to remove the impurities remaining on the fabric surface, and dried at 60 °C for standby.

[0058] Preparation of multi-layer MXene: 2 g of titanium aluminum carbide powder was slowly added in small amounts to a mixed solution of 2 g of lithium fluoride and 35 mL of 10 M hydrochloric acid. After fully stirring and reacting in a 45 °C constant temperature water bath environment for 35 h, the obtained reaction solution was pickled 3 times with 1 M hydrochloric acid, and then the solution was centrifuged and washed with water multiple times until the pH of the supernatant after centrifugation was greater than 6. After freeze-drying for 12 h, the multi-layer MXene powder required for the experiment was prepared.

[0059] Preparation of MXene suspension: Take 0.1 g of the obtained multi-layer MXene powder and place it in 40 mL of deionized water, stir evenly to obtain the required MXene suspension.

[0060] Preparation of MXene-functionalized cotton fabric: Place the cotton fabric in the obtained MXene suspension, immerse it at room temperature for 5 min, dry it at 80 °C, repeat the immersion 10 times, and finally obtain the MXene-functionalized cotton fabric.

[0061] Application Example 1

[0062] Characterize the photocatalytic performance of the MXene-functionalized cotton fabric obtained in Example 1:

[0063] Add 100 mL of methylene blue (MB) solution to a glass reaction vessel, then immerse a 2 cm × 2 cm MXene-functionalized cotton fabric in the methylene blue (MB) solution. The initial concentration of the methylene blue solution is 10 mg / mL. First, stir for 30 min under dark conditions before illumination. After the catalyst and the dye reach the adsorption-desorption equilibrium, turn on the GEL-HXUV300 xenon light source for photocatalytic reaction. Take samples every 20 min after illumination, measure the absorbance of the residual dye in the solution with a SPECORD@210PLUS ultraviolet-visible spectrophotometer, and then calculate the degradation rate of the dye according to the change in the absorbance of the solution.

[0064] Degradation rate (%) = (C0 - C t ) / C t = (A0 - A t ) / A t

[0065] C0: Initial concentration of the dye solution; C t is the concentration of the fuel solution at time t of illumination; A0 is the initial absorbance of the dye solution, and A t is the absorbance of the fuel solution at time t after illumination.

[0066] Characterize the microscopic morphology of the MXene-functionalized cotton fabric obtained in Example 1. It can be seen from Figure 1 that the surface of the cotton fiber is rough and there is a large amount of substance attached. After analysis, it is found that MXene powder is attached to the surface of the cotton fabric. At the same time, it can be clearly seen that relatively complete multi-layer MXene is attached to the surface of the cotton fabric, indicating that MXene has been successfully attached to the surface of the cotton fabric.

[0067] Evaluate the photocatalytic activity of the MXene-functionalized cotton fabric by degrading methylene blue (MB) under full light irradiation. The results are as Figure 2 shown. As the irradiation time prolongs, the absorbance of the MB solution at 664 nm decreases significantly and almost disappears after 150 min of illumination. Figure 3The change of methylene blue concentration (C / C0) with reaction time during the photocatalytic reduction process is described, where C and C0 represent the concentration and initial concentration of methylene blue respectively. The results show that 97.7% of MB is degraded by the MXene-functionalized cotton fabric after 150 min of visible light irradiation, indicating that the prepared photocatalyst has high photocatalytic activity in the decomposition of MB.

[0068] The MXene-functionalized cotton fabric for photocatalytic degradation of methylene blue was taken out of the dye solution and dried in an oven at 60 °C, and then added to 100 mL of the dye solution with an initial concentration of 10 mg / L of the dye methylene blue. First, it was stirred in the dark for 30 min before illumination. After the catalyst and the dye reached the adsorption-desorption equilibrium, the GEL-HXUV300 xenon lamp light source was turned on for photocatalytic reaction. Samples were taken every 20 min after illumination, and the absorbance of the residual dye in the solution was measured with a SPECORD@210PLUS ultraviolet-visible spectrophotometer, and then the degradation rate of the dye was calculated based on the change in the absorbance of the solution. Figure 4 It shows that after three repeated cycles, the photocatalytic degradation rate of MB does not decrease significantly, indicating that the MXene-functionalized cotton fabric has good photo-stability.

[0069] Application Example 2

[0070] The ultraviolet protection coefficient (UPF) was used to analyze the ultraviolet protection ability of the fabric. The anti-ultraviolet properties of the non-functionalized cotton fabric in Example 1 and the MXene-functionalized cotton fabric obtained in Example 1 were tested, and the results are shown in Table 1 below. It can be seen from the table that the UPF value of the original cotton fabric is 16 and it has no anti-ultraviolet property, while the UPF value of the functional fabric after MXene attachment is much greater than 50 (GB / T 18830-2009), and T(UVA)=0.05%, indicating that the functional fabric has good anti-ultraviolet properties.

[0071] Table 1 Comparison of anti-ultraviolet properties of original cotton fabric and MXene-functionalized fabric

[0072] Item T(UVA) T(UVB) UPF Raw cotton fabric 18.74％ 18.71％ 16 MXene-functionalized cotton fabric 0.05％ 0.05％ ＞50

[0073] It can be seen from the above examples that the present invention provides a MXene-functionalized cotton fabric and its preparation method and application. The present invention prepares a multi-layer MXene cotton fabric functional material by an impregnation method, and attaches multi-layer MXene to the surface of the cotton fabric by means of hydrogen bond binding. MXene is attached to the surface and between the fibers of the cotton fabric to obtain a MXene-functionalized cotton fabric with good catalytic activity and chemical stability. The UPF value of the functional fabric after MXene attachment is much greater than 50 (GB / T 18830-2009), and T(UVA)=0.05%, indicating that the functional fabric has good anti-ultraviolet properties.

[0074] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A preparation method of MXene-functionalized cotton fabric, characterized in that It includes the following steps: 1) Mix aluminum titanium carbide with lithium fluoride and hydrochloric acid solution successively for reaction. The resulting reaction solution is successively pickled, centrifuged, and freeze-dried to obtain multi-layer MXene powder; 2) Mix the multi-layer MXene powder with water to obtain an MXene suspension; 3) Immerse the cotton fabric in the MXene suspension and dry it, repeating 5 to 10 times to obtain the MXene-functionalized cotton fabric; The concentration of the MXene suspension is 2 to 8 mg / mL; The time for single immersion is 4 to 10 min.

2. The preparation method according to claim 1, wherein The mass-volume ratio of the aluminum titanium carbide, lithium fluoride, and hydrochloric acid solution is 1.0 to 2.0 g: 1.0 to 2.0 g: 20 to 40 mL; The concentration of the hydrochloric acid solution is 5 to 15 mol / L.

3. The preparation method according to claim 1 or 2, characterized in that, In step 1), the temperature of the mixing reaction is 30 to 50 °C, and the time of the mixing reaction is 30 to 48 h.

4. The preparation method according to claim 3, characterized in that, The reagent used for pickling is hydrochloric acid solution, the concentration of the hydrochloric acid solution is 1 to 2 mol / L, and the number of pickling times is 2 to 5 times.

5. The preparation method according to claim 4, wherein, In step 3), the drying temperature is 70 to 90 °C, and the drying time is 15 to 40 min.

6. The MXene-functionalized cotton fabric obtained by the preparation method according to any one of claims 1 to 5.

7. The application of the MXene-functionalized cotton fabric according to claim 6 in dye sewage treatment.

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