Preparation method of flexible CTs@AC carbon-carbon composite electrocatalytic anode material

Abstract

This invention discloses a method for preparing a flexible CTs@AC carbon-carbon composite electrocatalytic anode material, which relates to the interdisciplinary fields of environmental functional materials and electrochemical engineering. The invention achieves efficient modification of carbon fiber fabrics through a pyrolytic carbon deposition process, significantly enhancing their electrocatalytic activity. The process is simple, low-cost, and highly reproducible, suitable for large-scale production and industrial applications. No pollutants are generated during the preparation process. The prepared product contains a series of microcrystalline carbons with different band gaps and a wide spectral response range. The material prepared by this invention exhibits excellent performance in the degradation of organic pollutants such as Rhodamine B, possessing broad market application prospects and contributing to the practical engineering process of electrocatalytic oxidation technology.

Description

Technical Field

[0001] This invention relates to the interdisciplinary field of environmental functional materials and electrochemical engineering, and in particular to a preparation technology for electrocatalytic materials, specifically a method for preparing a flexible CTs@AC carbon-carbon composite electrocatalytic anode material. Background Technology

[0002] Electrocatalytic oxidation technology is considered one of the effective means of treating such pollutants due to its advantages such as not requiring the addition of strong oxidants, mild reaction conditions, and thorough mineralization.

[0003] Currently used titanium-based boron-doped diamond (Ti / BDD) and metal oxide coated electrodes suffer from problems such as high cost, complex preparation, poor conductivity, or insufficient stability. Carbon materials, due to their excellent conductivity, corrosion resistance, and processability, have become potential alternatives. However, the low electrocatalytic performance of raw carbon fiber fabrics limits their widespread application in the field of electrocatalysis.

[0004] Therefore, there is an urgent need to develop a simple, efficient, and low-cost method to modify carbon fiber fabrics to enhance their electrocatalytic activity and meet the needs of practical engineering applications. Summary of the Invention

[0005] To overcome the shortcomings of the prior art, this invention provides a method for preparing flexible CTs@AC carbon-carbon composite electrocatalytic anode material. This invention modifies the surface of carbon fiber fabric through a pyrolysis carbon deposition process, which significantly improves its electrocatalytic activity while maintaining its original flexibility and conductivity.

[0006] To achieve the aforementioned inventive objectives, the present invention employs the following technical solution:

[0007] A method for preparing a flexible CTs@AC carbon-carbon composite electrocatalytic anode material, the method specifically including the following steps:

[0008] Step 1: Clean the carbon fiber fabric with an ethanol / water mixture to remove surface oil and impurities, and let it air dry for later use.

[0009] The second step is to place the dried carbon fiber fabric in a heating furnace and heat it to 1000-1400℃ at a heating rate of 2-5℃ / min under an inert gas protective atmosphere.

[0010] The third step is to introduce methane gas as a carbon source at high temperature, adjust the volume ratio of inert gas to methane gas to be greater than 2:1 to 3:1, maintain the high temperature treatment for 20 to 60 minutes, so that carbon is uniformly deposited on the carbon fiber surface to form an activated carbon-like structure.

[0011] Step 4: Turn off the heating power and allow the furnace to cool naturally to room temperature to obtain the flexible CTs@AC carbon-carbon composite electrocatalytic anode material.

[0012] In the preparation method of the flexible CTs@AC carbon-carbon composite electrocatalytic anode material, the ratio of ethanol / water mixture in the first step is 1:1 to 2:1.

[0013] In the preparation method of the flexible CTs@AC carbon-carbon composite electrocatalytic anode material, the heating furnace in the second step is a tube furnace.

[0014] In the preparation method of the flexible CTs@AC carbon-carbon composite electrocatalytic anode material, the inert gas in the second step is high-purity argon, and the flow rate of high-purity argon is controlled between 50 and 200 mL / min.

[0015] In the preparation method of the flexible CTs@AC carbon-carbon composite electrocatalytic anode material, the flow rate of methane gas in the third step is 25-100 mL / min.

[0016] By employing the technical solution described above, the present invention has the following advantages:

[0017] This invention achieves efficient modification of carbon fiber fabrics through a pyrolytic carbon deposition process, significantly enhancing their electrocatalytic activity. The process is simple, low-cost, and highly reproducible, making it suitable for large-scale production and industrial applications. No pollutants are generated during the preparation process. The resulting product contains a series of microcrystalline carbons with different band gaps and a wide spectral response range. The material prepared by this invention exhibits excellent performance in the degradation of organic pollutants such as Rhodamine B, demonstrating broad market application prospects and contributing to the practical engineering of electrocatalytic oxidation technology. Attached Figure Description

[0018] Figure 1 The images shown are scanning electron microscope (SEM) images of the original CT scans in this embodiment of the invention.

[0019] Figure 2 This is a SEM image of the flexible CTs@AC carbon-carbon composite electrocatalytic anode material in an embodiment of the present invention;

[0020] Figure 3 The images show the Raman spectra of the original CTs and the CTs@AC carbon-carbon composite material in the embodiments of the present invention.

[0021] Figure 4 The above are the UV-Vis diffuse reflectance spectra fitting results of the CTs@AC carbon-carbon composite material in the embodiments of the present invention;

[0022] Figure 5The material of the flexible CTs@AC carbon-carbon composite electrocatalytic anode material in this embodiment of the invention demonstrates the degradation effect of the organic dye Rhodamine B.

[0023] Figure 6 This is the first-order kinetic equation for the degradation of the organic dye Rhodamine B by the flexible CTs@AC carbon-carbon composite electrocatalytic anode material in this embodiment of the invention. Detailed Implementation

[0024] The present invention can be explained in more detail through the following embodiments, but the present invention is not limited to the following embodiments;

[0025] The method for preparing a flexible carbon fiber fabric-supported activated carbon (CTs@AC) composite electrocatalytic anode material described in this invention, in specific implementation, is attached... Figure 1 The images are scanning electron microscope (SEM) images of the original flexible CTs. The three-dimensional (3D) structure of the original flexible CTs can provide a large specific surface area for electrocatalytic reactions.

[0026] Appendix Figure 2 SEM images of the flexible CTs@AC carbon-carbon composite electrocatalytic anode material are shown. To improve the electrocatalytic performance of the original flexible CTs, an amorphous carbon coating was introduced onto the flexible CTs to prepare the flexible CTs@AC carbon-carbon composite electrocatalytic anode material. (Attached) Figure 2 This is a SEM image of the flexible CTs@AC carbon-carbon composite electrocatalytic anode material. It can be seen that CTs@AC is not significantly different from the original CTs.

[0027] Appendix Figure 3 The images show the Raman spectra of the original CTs and the CTs@AC carbon-carbon composite material. Although the SEM images cannot show the differences between the original CTs and the CTs@AC carbon-carbon composite material, the D and G peaks of the Raman spectrum of CTs@AC are much more sensitive and stronger than those of the original CTs, indicating that amorphous carbon was successfully deposited on the surface of the original CTs, thus successfully preparing the flexible CTs@AC carbon-carbon composite electrocatalytic anode material.

[0028] Appendix Figure 4 The fitting results of the UV-Vis diffuse reflectance spectrum of CTs@AC carbon-carbon composite material show that the present invention can deposit microcrystalline carbon with different band gaps on the surface of carbon fiber fabric, such as microcrystalline carbon with a band gap of 2.10 Ev.

[0029] Appendix Figure 5 The figure shows the degradation effect of the flexible CTs@AC carbon-carbon composite electrocatalytic anode material on the organic dye Rhodamine B. As can be seen from the figure, within 120 min, the degradation of Rhodamine B by the flexible CTs@AC carbon-carbon composite electrocatalytic anode material is much greater than that of the original CTs, which further illustrates that the amorphous carbon coating has the effect of enhancing the electrocatalytic effect of the original CTs.

[0030] Appendix Figure 6 The figure shows the first-order kinetic equation for the degradation of the organic dye Rhodamine B by the flexible CTs@AC carbon-carbon composite electrocatalytic anode material. As can be seen from the figure, the rate constant of the first-order kinetic equation for the degradation of the organic dye Rhodamine B by the flexible CTs@AC carbon-carbon composite electrocatalytic anode material is 5 times that of the original CTs.

[0031] Combined with appendix Figures 1-6 The present invention discloses a method for preparing a flexible CTs@AC carbon-carbon composite electrocatalytic anode material, the preparation method specifically including the following steps:

[0032] Step 1: Clean the carbon fiber fabric with an ethanol / water mixture to remove surface oil and impurities, and let it air dry for later use; in practice, the ratio of the ethanol / water mixture is 1:1 to 2:1.

[0033] The second step is to place the dried carbon fiber fabric in a heating furnace and heat it to 1000-1400°C at a heating rate of 2-5°C / min under an inert gas protective atmosphere. In practice, the heating furnace is a tube furnace. Furthermore, the inert gas is high-purity argon, and the flow rate of high-purity argon is controlled between 50-200 mL / min.

[0034] The third step involves introducing methane gas as a carbon source at a high temperature, adjusting the volume ratio of inert gas to methane gas to 2:1 to 3:1, and maintaining the high temperature treatment for 20 to 60 minutes to allow carbon to be uniformly deposited on the carbon fiber surface to form an activated carbon-like structure. During implementation, the flow rate of the methane gas is 25 to 100 mL / min, and further, the inert gas is high-purity argon gas.

[0035] Step 4: Turn off the heating power and allow the furnace to cool naturally to room temperature to obtain the flexible CTs@AC carbon-carbon composite electrocatalytic anode material.

[0036] Specific embodiments of the present invention are as follows: Example 1:

[0037] A 10cm × 10cm carbon fiber fabric (CTs) was taken and ultrasonically cleaned for 10 minutes (150W ultrasonic power) sequentially with ethanol and deionized water (volume ratio 1:1) to remove surface impurities, and then air-dried. The sample was placed in a 100mm outer diameter quartz tube furnace and heated to 1200℃ at 3℃ / min under an argon protective atmosphere. After the temperature stabilized, methane gas was introduced, and the flow rates of argon and methane were adjusted to 150mL / min and 50mL / min, respectively. The treatment time was 30 minutes. The sample was then allowed to cool naturally to room temperature and labeled as CTs@AC.

[0038] The obtained material was used as the anode to assemble an electrolytic device, and a constant current electrocatalytic degradation experiment (0.10 A) was conducted using Rhodamine B simulated wastewater as the electrolyte, with Na₂SO₄ (1.0 g / L). The results showed that the degradation rate of Rhodamine B exceeded 74% within 120 min, and its first-order kinetic rate constant reached 0.0113 min. -1 It is 5 times that of the original carbon fiber fabric. Example 2:

[0039] The procedures of Example 1 were repeated, except that the heating rate was 2 °C / min, the maximum temperature was 1000 °C, the argon and methane flow rates were 100 mL / min and 50 mL / min, respectively, and the treatment time was 60 min. The results showed that the degradation rate of Rhodamine B was 76%, and the first-order kinetic rate constant was 0.0116 min. -1 The levels were still significantly higher than those in the control group. Example 3:

[0040] The procedures of Example 1 were repeated, except that the heating rate was 5 °C / min, the maximum temperature was 1400 °C, the argon and methane flow rates were 150 mL / min and 50 mL / min, respectively, and the treatment time was 20 min. The results showed that the degradation rate of Rhodamine B was 78%, and the first-order kinetic rate constant was 0.0126 min. -1 It exhibits superior electrocatalytic performance. Example 4:

[0041] Using a different precursor gas, such as acetylene instead of methane, while keeping other parameters the same as in Example 1, the results showed that the degradation rate of Rhodamine B was 72%, with a first-order kinetic rate constant of 0.0112 min⁻¹. -1 It is slightly lower than that of the methane system, but still better than the original material. Example 5:

[0042] The prepared CTs@AC material was used in a practical dyeing and printing wastewater treatment experiment. The results showed a COD removal rate of 56% and a color removal rate exceeding 74%, demonstrating good practical potential.

[0043] The flexible CTs@AC carbon-carbon composite electrocatalytic anode material described in this invention can be used in the degradation of organic pollutants. The organic pollutant is Rhodamine B dye, and the rate constant of the first-order kinetic equation for Rhodamine B using this material is five times that of the original carbon fiber fabric.

[0044] Compared with the prior art, the present invention has the following advantages:

[0045] Simple process: Material preparation can be completed in just one pyrolysis deposition step, without the need for complicated subsequent processing.

[0046] Low cost: It uses inexpensive carbon fiber fabric and methane gas as raw materials, making it suitable for large-scale production.

[0047] Green and environmentally friendly: No pollutants are generated during the preparation process.

[0048] Wide spectral response range: The present invention deposits a series of microcrystalline carbons with different band gaps on the surface of carbon fiber fabrics, such as microcrystalline carbons with a band gap of 2.10 Ev.

[0049] Superior performance: The obtained CTs@AC material has high electrocatalytic activity and its degradation efficiency for organic dyes such as Rhodamine B is significantly better than that of the original carbon fiber fabric. Its first-order kinetic rate constant can reach 5 times that of the original material.

[0050] Structural stability: The composite material has good mechanical flexibility and chemical stability, making it suitable for flow electrolysis cell systems.

[0051] It has broad application prospects: it can be used to treat recalcitrant organic pollutants such as dyeing and printing wastewater and pharmaceutical wastewater, and promote the industrial application of electrocatalysis technology.

[0052] in conclusion:

[0053] This invention achieves efficient modification of carbon fiber fabrics through a simple pyrolytic carbon deposition process, significantly enhancing their electrocatalytic activity. The method is simple, low-cost, and highly reproducible, making it suitable for large-scale production and industrial applications. No pollutants are generated during the preparation process. The prepared product contains a series of microcrystalline carbons with different band gaps and a wide spectral response range. The obtained material exhibits excellent performance in the degradation of organic pollutants such as Rhodamine B, possessing broad market application prospects and contributing to the practical engineering process of electrocatalytic oxidation technology.

[0054] The parts of this invention not described in detail are prior art.

[0055] The embodiments selected herein for the purpose of disclosing the inventive objectives are currently considered suitable; however, it should be understood that the invention is intended to include all variations and modifications of the embodiments that fall within the scope of this concept and invention.

Claims

1. An application of a flexible CTs@AC carbon-carbon composite electrocatalytic anode material, characterized by: The flexible CTs@AC carbon-carbon composite electrocatalytic anode material was assembled into an electrolysis device using the anode as the anode. A constant-current electrocatalytic degradation experiment was conducted using Rhodamine B simulated wastewater, with Na2SO4 as the electrolyte. The preparation method of the flexible CTs@AC carbon-carbon composite electrocatalytic anode material specifically includes the following steps: Step 1: Clean the carbon fiber fabric with an ethanol / water mixture to remove surface oil and impurities, and let it air dry for later use. The ratio of the ethanol / water mixture is 1:1 to 2:

1. The second step is to place the dried carbon fiber fabric in a heating furnace and heat it to 1000-1400℃ at a heating rate of 2-5℃ / min under an inert gas protective atmosphere. The third step involves introducing methane gas as a carbon source at a high temperature, adjusting the volume ratio of inert gas to methane gas to be greater than 2:1 to 3:1, and maintaining the high temperature treatment for 20 to 60 minutes to allow carbon to be uniformly deposited on the carbon fiber surface to form an activated carbon-like structure. The flow rate of the methane gas is 25 to 100 mL / min. Step 4: Turn off the heating power and allow the furnace to cool naturally to room temperature to obtain the flexible CTs@AC carbon-carbon composite electrocatalytic anode material.

2. The application of the flexible CTs@AC carbon-carbon composite electrocatalytic anode material according to claim 1, characterized in that: In the second step, the heating furnace is a tubular furnace.

3. The application of the flexible CTs@AC carbon-carbon composite electrocatalytic anode material according to claim 1, characterized in that: In the second step, the inert gas is high-purity argon, and the flow rate of high-purity argon is controlled at 50-200 mL / min.

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