Preparation method and application of cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode

Abstract

The application provides a preparation method and application of a cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode. x The application solves the problems of easy aggregation and self-piling of a Ti3C2-based anode, easy leaching of metal ions of a cobalt sulfide-based anode, and easy destruction of a structure. x The application realizes derivation of typical Co-MOFs (ZIF-67) to amorphous CoS x , realizes compact growth to N-Ti3C2 interlayers and surfaces, and finally realizes common loading on carbon paper to obtain a CoS x / N-Ti3C2 / CP composite anode. The application utilizes N atom doping to regulate electronic structure and point defects to improve electronic transfer and ion diffusion dynamics, simultaneously utilizes MOFs-derived sulfides to have high specific surface area, high chemical stability and high conductivity to realize efficient degradation of organic pollutants, and has good application prospect in complex water purification and other fields.

Description

Technical Field

[0001] This invention relates to the preparation method and application of cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anodes, belonging to the field of electrocatalytic materials technology. Background Technology

[0002] Antibiotics discharged into natural water bodies not only accumulate in humans and other organisms through the food chain, but also induce the generation and horizontal transfer of antibiotic resistance genes and antibiotic-resistant bacteria. Achieving efficient antibiotic degradation is one of the key issues that needs to be addressed. Compared with other technologies, anodic electro-activated persulfate technology has significant advantages. It not only utilizes the high redox potential and long half-life of sulfate free radicals, but also uses an electric field to promote the aggregation of persulfate anions on the anode surface, accelerating electron transfer efficiency and achieving a higher yield of active substances.

[0003] Titanium carbide (Ti3C2) possesses a unique graphene-like structure, making it a promising candidate for electrocatalysis. However, due to van der Waals forces and hydrogen bonding, it exhibits aggregation and self-stacking defects, prolonging the electron transport path within multilayer electrodes and reducing the utilization rate of active sites. Doping carbon materials with nitrogen is currently an effective way to regulate electronic structure and increase electron-deficient sites. Nitrogen-doped titanium carbide (N-Ti3C2) has been shown to improve electron transfer and diffusion kinetics by adjusting the electronic and crystal structures of the matrix. However, it has not yet been applied to heterogeneous advanced oxidation systems, and the redox performance of N-Ti3C2 alone is poor. Cobalt sulfides have been proven to have excellent redox properties. Cobalt sulfides obtained using cobalt-based metal salts as precursors often suffer from morphological and structural instability. MOF-derived cobalt sulfides, while maintaining the original stable structure of MOFs, exhibit higher specific surface area, better chemical stability, and higher conductivity compared to cobalt sulfides obtained by traditional methods, resulting in higher catalytic performance and better cycle stability.

[0004] In summary, the effective combination of MOF-derived cobalt sulfide and N-Ti3C2 is feasible for the efficient electroactivation of persulfate for antibiotic degradation. However, there are currently few studies on its application in heterogeneous catalysts, and the preparation process is complex. Therefore, it is essential to provide a method for preparing cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anodes. Summary of the Invention

[0005] To address the complex preparation process of MOF-derived cobalt sulfide and N-Ti3C2 in existing technologies, this invention proposes a method for preparing and applying a cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode.

[0006] The technical solution adopted by this invention to solve the above problems is as follows: This invention proposes a method for preparing a cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode, comprising:

[0007] Step 1: After cutting the carbon paper to the preset size, soak it in concentrated nitric acid and ultrapure water in sequence, and then dry it.

[0008] Step 2: Disperse titanium carbide powder in deionized water, add dopamine hydrochloride and stir to obtain solution A. Add tris(hydroxymethyl)aminomethane hydrochloride buffer to solution A and stir thoroughly in the dark to obtain solution B.

[0009] Step 3: Centrifuge solution B, wash solution B four times with deionized water and ethanol respectively, freeze-dry the washed solution B to obtain powder, and grind the powder to obtain nitrogen-doped titanium carbide.

[0010] Step 4: Mix cobalt nitrate hexahydrate with 50 mL of methanol and stir for 30 min to obtain solution C; mix 2-methylimidazole with 50 mL of methanol and stir for 30 min to obtain solution D.

[0011] Step 5: Quickly pour solution D into solution D and stir to obtain mixed solution F. After removing the stir bar from mixed solution F, seal the mixed solution and let it stand.

[0012] Step 6: Centrifuge the mixed solution after standing, wash it with methanol 4-6 times, and freeze-dry it for 24 hours to obtain cobalt-based ZIF-67;

[0013] Step 7: Disperse nitrogen-doped titanium carbide in anhydrous ethanol, add dried carbon paper and sonicate. After sonication, add cobalt-based ZIF-67 and sonicate a second time. After the second sonication, add thioacetamide and sonicate a third time to obtain mixed solution G and sonicated carbon paper.

[0014] Step 8: Transfer the mixed solution G and the sonicated carbon paper to a 100ml reaction vessel, heat the reaction vessel to above 120℃ using an oven and keep it at that temperature, then cool it to room temperature after the holding time is complete;

[0015] Step 9: After the carbon paper has cooled to room temperature, remove it and rinse it with deionized water and anhydrous ethanol. After rinsing, dry it in a vacuum drying oven at 60°C for 8-12 hours to obtain amorphous CoS. x / N-Ti3C2 / CP composite anode material.

[0016] Optionally, the soaking time in step 1 is 6-12 hours, the temperature during the drying process is 60-80℃, and the drying time is 3-4 hours.

[0017] Optionally, in step 2, the concentration of the tris(hydroxymethyl)aminomethane hydrochloride buffer is 50 mmol / L, the pH value is 8.5, and the mass-to-volume ratio of titanium carbide powder, dopamine hydrochloride, deionized water and tris(hydroxymethyl)aminomethane hydrochloride buffer is (0.15-0.35) g:(0.25-0.45) g:20 mL:25 mL. The stirring time for preparing solution A is 1-2 h, and the stirring time for preparing solution B is 24-36 h.

[0018] Optionally, the centrifugation rate in step 3 is 8000 rpm / min, and the centrifugation time is 5-8 min.

[0019] Optionally, in step 4, the mass ratio of cobalt nitrate hexahydrate to 2-methylimidazole is (0.29-0.58) g:(0.76-2.64) g.

[0020] Optionally, the stirring time in step 5 is 5 minutes, and the standing time is 24-48 hours.

[0021] Optionally, in step 6, the centrifugation rate is 8000 rpm / min and the centrifugation time is 5-8 min.

[0022] Optionally, in step 7, the mass-to-volume ratio of nitrogen-doped titanium carbide, anhydrous ethanol, cobalt-based ZIF-67, and thioacetamide is (0.05-0.1)g:50mL:(0.05-0.1)g:(0.1-0.2)g, and the time for ultrasound, secondary ultrasound, and tertiary ultrasound is 30min.

[0023] Optionally, in step 8, the heating rate of the oven is 10-20℃ / min, the heating temperature is 120-160℃, and the holding time is 4-10h.

[0024] Applications of cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anodes include:

[0025] Amorphous CoS x / N-Ti3C2 / CP composite anode materials are used for the removal of antibiotics in aquatic environments.

[0026] The beneficial effects of this invention are:

[0027] 1. This invention uses ethanol as an organic solvent to induce cobalt-based ZIF-67 to degenerate into amorphous CoS under appropriate proportions. x This invention achieves dense growth of CoS on the surface and between layers of N-Ti3C2; simultaneously, it employs a one-step solvothermal method to achieve CoS2+ growth at 120℃ for 4 hours. x The growth of the / N-Ti3C2 composite on a carbon paper substrate is achieved under simple reaction conditions.

[0028] 2. Compared with existing Ti3C2-based anode systems and CoS x Compared to the base anode system, the MOFs-derived CoS2 series prepared in this invention have superior performance. x The / N-Ti3C2 / CP composite anode can more efficiently activate persulfate under an electric field and achieve rapid degradation of the typical antibiotic sulfamethoxazole.

[0029] 3. The CoS prepared by this invention under the optimal ratio x The / N-Ti3C2 / CP composite anode achieved 100% removal rate within 10 minutes of reaction, and its degradation kinetics conformed to pseudo-first-order kinetics with an apparent rate constant of 0.376 min. -1 With individual N-Ti3C2 / CP and CoS x Compared to the / CP anode system, the degradation effect and reaction rate are significantly improved.

[0030] 4. This invention utilizes N-Ti3C2 to improve the electronic structure and electron transport rate of the material, and utilizes MOFs to improve CoS2. x The stability of the structure and its electrochemical performance.

[0031] 5. This invention utilizes nitrogen atom doping to regulate electronic structure and point defects to improve electron transfer and ion diffusion kinetics. Simultaneously, it leverages the high specific surface area, high chemical stability, and high conductivity of MOF-derived sulfides to achieve efficient degradation of organic pollutants, resulting in the prepared CoS... x The / N-Ti3C2 / CP composite anode is used to remove antibiotics in aquatic environments and has great application prospects in the purification of complex water bodies. Attached Figure Description

[0032] Figure 1 A flowchart illustrating the preparation method of the cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode provided by the present invention;

[0033] Figure 2 CoS provided by the present invention x SEM image of the / N-Ti3C2 / CP composite anode material;

[0034] Figure 3 CoS provided by the present invention x EDS diagram of / N-Ti3C2 / CP composite anode material;

[0035] Figure 4 CoS provided by the present invention x XRD pattern of / N-Ti3C2 / CP composite anode material;

[0036] Figure 4In the figure, N-Ti3C2 is nitrogen-doped titanium carbide, Ti3C2 is titanium carbide, and CoS... x It is cobalt sulfide, CP is carbon paper, and ZIF-67 is cobalt-based ZIF-67;

[0037] Figure 5 The amorphous CoS obtained in Examples 1, 2, and 3 and Comparative Examples 1 and 2 provided by the present invention x Degradation and removal curves of sulfamethoxazole catalyzed by persulfate degradation using / N-Ti3C2 / CP composite anode material;

[0038] Figure 5 In the text, N-Ti3C2 is nitrogen-doped titanium carbide, and ZIF-67 is cobalt-based ZIF-67;

[0039] Figure 6 The amorphous CoS obtained in Examples 1, 2, and 3 and Comparative Examples 1 and 2 provided by the present invention x Pseudo-first-order kinetics of persulfate degradation of sulfamethoxazole catalyzed by / N-Ti3C2 / CP composite anode material;

[0040] Figure 6 In the middle, K obs is the apparent rate constant, N-Ti3C2 is nitrogen-doped titanium carbide, and ZIF-67 is cobalt-based ZIF-67. Example

[0041] Example 1

[0042] Combination Figure 1-6 This embodiment will be described in detail. In this embodiment, Ti3C2 is titanium carbide, CP is carbon paper, N-Ti3C2 is nitrogen-doped titanium carbide, MOFs are metal-organic framework compounds, DA is dopamine hydrochloride, Tris-HCl is tris(hydroxymethyl)aminomethane hydrochloride, Co(NO3)2·6H2O is cobalt nitrate hexahydrate, 2-MEIM is 2-methylimidazole, TAA is thioacetamide, and CoS... x It is amorphous cobalt sulfide.

[0043] like Figure 1 As shown, the preparation method of the cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode described in this embodiment includes:

[0044] S1: Cut the CP into 2cm×4cm pieces and soak them in concentrated nitric acid and ultrapure water for 6 hours in sequence, and then dry them at 60℃ for 3-4 hours;

[0045] S2: Disperse 0.2g Ti3C2 powder into 20mL deionized water, add 0.25g DA, stir for 1-2h to achieve thorough mixing to obtain solution A, then add 25mL Tris-HCl buffer to solution A, stir thoroughly in the dark for 24h to obtain solution B;

[0046] S3: Centrifuge solution B, wash it three times with deionized water and ethanol respectively, freeze-dry it for 24 hours to obtain powder, and grind the powder to obtain N-Ti3C2;

[0047] S4: Mix 0.58g Co(NO3)2·6H2O with 50mL methanol thoroughly and stir for 30min to obtain solution C; mix 1.32g 2-MEIM with 50mL methanol thoroughly and stir for 30min to obtain solution D.

[0048] S5: Quickly pour solution B into solution A, stir for 5 minutes to obtain mixed solution F, remove the stir bar, seal mixed solution F and let it stand for 24-48 hours;

[0049] S6: After standing, the mixed solution F was centrifuged, washed 6 times with methanol, and freeze-dried for 24 hours to obtain cobalt-based ZIF-67;

[0050] S7: Disperse 0.05g N-Ti3C2 in 50mL anhydrous ethanol, place the CP obtained in S1 in it, sonicate for 30min, then add 0.05g cobalt-based ZIF-67 obtained in S6, continue sonicating for 30min, then add 0.1g TAA and sonicate for another 30min to obtain mixed solution G and sonicated carbon paper;

[0051] S8: Transfer the mixed solution G obtained in S7 and the sonicated CP to a 100 mL reactor, heat it from room temperature to 120 °C at a heating rate of 10-20 °C / min in an oven, and keep it at that temperature for 4 h. Then, cool it down to room temperature in the oven.

[0052] S9: After the CP in S8 has cooled to room temperature, it is taken out, rinsed with deionized water and anhydrous ethanol, and dried in a vacuum drying oven at 60°C for 10-14 hours to obtain amorphous CoS. x The / N-Ti3C2 / CP composite anode material is named CSNTC-1.

[0053] The amorphous CoS2 prepared in this embodiment x / N-Ti3C2 / CP composite anode materials are used for the removal of antibiotics in aquatic environments.

[0054] Results of this embodiment: The mass ratio of precursor ZIF-67 to N-Ti3C2 in the material prepared in this embodiment is 1:1.

[0055] like Figure 2 As shown, Figure 2 The SEM test results for CSNTC-1 show significant defects on the N-Ti3C2 surface, while hexagonal ZIF-67 is derived into amorphous CoS. x The morphology remains unchanged and it grows densely on the surface and between layers of N-Ti3C2, and then it is co-loaded onto carbon paper.

[0056] like Figure 3 As shown, Figure 3 The EDS test results for CSNTC-1 show that five elements—C, Ti, N, S, and Co—are present on the material surface, and the spatial distribution of N, Ti, and C corresponds to... Figure 1 The multilayered structure contains defects, and the spatial distribution of the two elements, Co and S, corresponds to... Figure 1 The hexagonal shape in the diagram demonstrates successful N doping and that ZIF-67 has been fully derived into CoS. x And the two successfully reconciled.

[0057] like Figure 4 As shown, Figure 4 The XRD test results for CSNTC-1 are provided by Figure 4 (a) It can be seen that N doping disrupts the (002) crystal plane of Ti3C2, resulting in a significant decrease in the intensity of the corresponding characteristic peak around 2θ = 6°. However, the intensity of the characteristic peak at 2θ = 60.25°, which can be attributed to the (110) crystal plane, is enhanced, indicating that the structural change caused by N doping is beneficial to the exposure of the (110) crystal plane. After comparison with CoS... x A comparison of the XRD patterns of / N-Ti3C2 powders reveals that several typical sharp characteristic peaks on the XRD pattern of ZIF-67 completely disappear after solvothermal sulfidation. This indicates that ZIF-67 has degenerated into amorphous CoS. x It also indicates that the derivatization rate of ZIF-67 is close to 100%, and in CoS x The XRD curves of / N-Ti3C2 powder showed characteristic peaks at 2θ = 41.8° and 60.25°, which can be attributed to the (105) and (110) crystal planes of N-Ti3C2, proving that CoS x Successful recombination with N-Ti3C2. (By...) Figure 4 (b) It can be seen that, based on the characteristic peak of CP with relatively high intensity that can be attributed to C, it belongs to CoS. x The characteristic peak intensities of / N-Ti3C2 are relatively low, but comparison with the XRD spectrum of the CP blank reveals characteristic peaks at 2θ = 41.8° and 60.25° that can be attributed to the (105) and (110) crystal planes of N-Ti3C2, and are consistent with CoS. xThe XRD patterns of the Ti3C2 powders were completely identical, confirming the successful preparation of CSNTC-1.

[0058] The performance of CSNTC-1 prepared in this embodiment in the electro-activated persulfate degradation of sulfamethoxazole was tested. The experiment was carried out in a 300 mL electrolytic cell with a reaction solution volume of 250 mL. CSNTC-1 was used as the anode, and a constant voltage of 3 V was applied during the reaction. The amount of persulfate added was 1 mmol / L, and the initial concentration of sulfamethoxazole was 10 mg / L. The reaction temperature was controlled at 25 ± 2 °C throughout the process. The degradation performance is as follows: Figure 5 As shown, by Figure 5 It can be seen that the degradation rate of sulfamethoxazole reaches 100% within 10 minutes.

[0059] The kinetics of sulfamethoxazole degradation of CSNTC-1 obtained in this embodiment is shown in the figure below. Figure 6 As shown, the degradation process follows pseudo-first-order kinetics, and the apparent rate constant of CSNTC-1 for sulfamethoxazole is 0.376 min. -1 .

[0060] Example 2

[0061] Combination Figure 1 , Figure 5 and Figure 6 This embodiment will be described as follows: Figure 1 As shown, the only difference between this embodiment and Embodiment 1 is that the amount of N-Ti3C2 added in S7 is 0.1g.

[0062] Results: Amorphous CoS2 was prepared. x The / N-Ti3C2 / CP composite anode material, with a precursor ZIF-67 and N-Ti3C2 in a mass ratio of 1:2, is named CSNTC-2.

[0063] The CSNTC-2 prepared in this embodiment was subjected to an electro-activated persulfate degradation performance test for sulfamethoxazole, and the results are as follows: Figure 5 As shown, when a constant voltage of 3V is applied during the reaction, the amount of persulfate is 1mmol / L, the initial concentration of sulfamethoxazole is 10mg / L, and the temperature is controlled at 25±2℃ throughout the reaction, the CSNTC-2 prepared in this example showed a degradation rate of 89.6% of sulfamethoxazole in 10min.

[0064] The kinetics of sulfamethoxazole degradation of CSNTC-2 prepared in this embodiment is shown in the figure below. Figure 6 As shown, the degradation process follows pseudo-first-order kinetics, and the apparent rate constant of CSNTC-1 for sulfamethoxazole is 0.226 min. -1 .

[0065] Example 3

[0066] Combination Figure 1 , Figure 5 and Figure 6 This embodiment will be described as follows: Figure 1 As shown, the only difference between this embodiment and Embodiments 1 and 2 is that the amount of ZIF-67 added in S7 is 0.1g and the amount of TAA added is 0.2g.

[0067] Results: Amorphous CoS2 was prepared. x The / N-Ti3C2 / CP composite anode material, with a precursor ZIF-67 and N-Ti3C2 in a mass ratio of 2:1, is named CSNTC-3.

[0068] The CSNTC-3 prepared in this embodiment was subjected to an electro-activated persulfate degradation performance test for sulfamethoxazole, and the results are as follows: Figure 5 As shown, when a constant voltage of 3V is applied during the reaction, the amount of persulfate is 1mmol / L, the initial concentration of sulfamethoxazole is 10mg / L, and the temperature is controlled at 25±2℃ throughout the reaction, the CSNTC-3 prepared in this example showed a degradation rate of 92.3% of sulfamethoxazole in 10min.

[0069] The kinetics of sulfamethoxazole degradation of CSNTC-3 obtained in this embodiment is shown in the figure below. Figure 6 As shown, the degradation process follows pseudo-first-order kinetics, and the apparent rate constant of CSNTC-1 for sulfamethoxazole is 0.259 min. -1 .

[0070] Comparative Example 1

[0071] Combination Figure 5 and Figure 6 To illustrate this comparative example, the only difference between this comparative example and Example 1 is that N-Ti3C2 is not added in S7.

[0072] Results: Amorphous CoS2 was prepared. x / CP composite anode material, with a precursor ZIF-67 and N-Ti3C2 in a mass ratio of 1:0, is named CSC.

[0073] The CSC prepared in this comparative example was subjected to electro-activated persulfate degradation performance testing of sulfamethoxazole, and the results are as follows: Figure 5As shown, when a constant voltage of 3V is applied during the reaction, the amount of persulfate is 1mmol / L, the initial concentration of sulfamethoxazole is 10mg / L, and the temperature is controlled at 25±2℃ throughout the reaction, the degradation rate of sulfamethoxazole by the CSC prepared in this comparative example is 82.3% after 10min.

[0074] The degradation kinetics of sulfamethoxazole in CSC prepared in this comparative example are shown in the figure below. Figure 6 As shown, the degradation process follows pseudo-first-order kinetics, and the apparent rate constant of CSNTC-1 for sulfamethoxazole is 0.178 min. -1 .

[0075] Comparative Example 2

[0076] Combination Figure 5 and Figure 6 The only difference between this comparative example and Example 1 is that ZIF-67 and TAA are not added in S7.

[0077] Results: An N-Ti3C2 / CP composite anode was prepared with a precursor ZIF-67 and N-Ti3C2 mass ratio of 0:1, and named NTC.

[0078] The NTC prepared in this comparative example was subjected to electro-activated persulfate degradation performance testing for sulfamethoxazole, and the results are as follows: Figure 5 As shown, when a constant voltage of 3V is applied during the reaction, the amount of persulfate is 1mmol / L, the initial concentration of sulfamethoxazole is 10mg / L, and the temperature is controlled at 25±2℃ throughout the reaction, the NTC prepared in this comparative example has a degradation rate of sulfamethoxazole of 25.8% after 10min.

[0079] The degradation kinetics of sulfamethoxazole with NTC prepared in this comparative example are shown in the figure below. Figure 6 As shown, the degradation process follows pseudo-first-order kinetics, and the apparent rate constant of NTC for sulfamethoxazole is 0.028 min. -1 .

[0080] In summary, N-Ti3C2 exhibits excellent electrochemical performance, reacting at a linear rate within 10 minutes, indicating the absence of significant self-accumulation. However, the redox properties of N-Ti3C2 are limited. When reacting with highly oxidizing CoS... x After compounding, it can achieve efficient activation of persulfate and efficient degradation of sulfamethoxazole. Furthermore, compared to… Figure 5 and Figure 6 Different curves show that N-Ti3C2 and CoS xThe synergistic effect between them is not a simple additive one. Compared with the existing anolyl-activated persulfate degradation antibiotic system, the CSNTC system has excellent degradation performance. This invention provides theoretical and technical guidance for the practical application of N-Ti3C2-based electro-activated persulfate technology.

[0081] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent substitutions, and improvements made to the above embodiments without departing from the scope of the present invention, based on the technical essence of the present invention and within the spirit and principles of the present invention, shall still fall within the protection scope of the present invention.

Claims

1. A method for preparing a cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode, characterized in that, The preparation method of the cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode includes the following steps: Step 1: After cutting the carbon paper to the preset size, soak it in concentrated nitric acid and ultrapure water in sequence, and then dry it. Step 2: Disperse titanium carbide powder in deionized water, add dopamine hydrochloride and stir to obtain solution A. Add tris(hydroxymethyl)aminomethane hydrochloride buffer to solution A and stir thoroughly in the dark to obtain solution B. Step 3: Centrifuge the solution B, wash the centrifuged solution B four times with deionized water and ethanol respectively, freeze-dry the washed solution B to obtain powder, and grind the powder to obtain nitrogen-doped titanium carbide. Step 4: Mix cobalt nitrate hexahydrate with 50 mL of methanol thoroughly and stir for 30 min to obtain solution C; mix 2-methylimidazole with 50 mL of methanol thoroughly and stir for 30 min to obtain solution D. Step 5: Quickly pour the solution C into the solution D and stir to obtain a mixed solution F. After removing the stir bar from the mixed solution F, seal the mixed solution and let it stand. Step 6: Centrifuge the mixed solution after standing, wash it with methanol 4-6 times, and freeze-dry it for 24 h to obtain cobalt-based ZIF-67; Step 7: Disperse the nitrogen-doped titanium carbide in anhydrous ethanol, add dried carbon paper and sonicate, add cobalt-based ZIF-67 and sonicate a second time, add thioacetamide and sonicate a third time to obtain mixed solution G and sonicated carbon paper. Step 8: Transfer the mixed solution G and the sonicated carbon paper to a 100 mL reaction vessel, heat the reaction vessel to above 120 °C using an oven and keep it at that temperature, then cool it to room temperature after the heat preservation is complete; Step 9: After the carbon paper has cooled to room temperature, remove it and rinse it with deionized water and anhydrous ethanol. After rinsing, dry it in a vacuum drying oven at 60 °C for 8-12 h to obtain amorphous CoS. x / N-Ti3C2 / CP composite anode material.

2. The method for preparing the cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode according to claim 1, characterized in that, In step 1, the soaking time is 6-12 hours, the drying temperature is 60-80 ℃, and the drying time is 3-4 hours.

3. The method for preparing the cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode according to claim 1, characterized in that, In step 2, the concentration of the tris(hydroxymethyl)aminomethane hydrochloride buffer solution is 50 mmol / L, the pH value is 8.5, and the mass-to-volume ratio of titanium carbide powder, dopamine hydrochloride, deionized water and tris(hydroxymethyl)aminomethane hydrochloride buffer solution is (0.15-0.35) g:(0.25-0.45) g:20 mL:25 mL. The stirring time for preparing solution A is 1-2 h, and the stirring time for preparing solution B is 24-36 h.

4. The method for preparing the cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode according to claim 1, characterized in that, In step 3, the centrifugation rate is 8000 rpm and the centrifugation time is 5-8 min.

5. The method for preparing the cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode according to claim 1, characterized in that, In step 4, the mass ratio of cobalt nitrate hexahydrate to 2-methylimidazole is (0.29-0.58) g:(0.76-2.64) g.

6. The method for preparing the cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode according to claim 1, characterized in that, In step 5, the stirring time is 5 minutes and the settling time is 24-48 hours.

7. The method for preparing the cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode according to claim 1, characterized in that, In step 6, the centrifugation rate is 8000 rpm and the centrifugation time is 5-8 min.

8. The method for preparing the cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode according to claim 1, characterized in that, In step 7, the mass-to-volume ratio of nitrogen-doped titanium carbide, anhydrous ethanol, cobalt-based ZIF-67, and thioacetamide was (0.05-0.1) g: 50 mL: (0.05-0.1) g: (0.1-0.2) g, and the time for sonication, secondary sonication, and tertiary sonication was 30 min each.

9. The method for preparing the cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode according to claim 1, characterized in that, In step 8, the heating rate of the oven is 10-20 ℃ / min, the heating temperature is 120-160 ℃, and the holding time is 4-10 h.

10. The application of the cobalt sulfide / nitrogen-doped titanium carbide / carbon paper composite anode prepared by the method according to any one of claims 1-9, characterized in that, include: Amorphous CoS x / N-Ti3C2 / CP composite anode materials are used for the removal of antibiotics in aquatic environments.

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