Method for preparing a porous electrode modified with protein fibers and applications thereof

Abstract

This invention discloses a method for preparing a protein fiber modified porous electrode and its application, comprising: dissolving lysozyme in deionized water to obtain a lysozyme protein solution; stirring carbon paper in the lysozyme protein denaturing solution to obtain carbon paper with attached protein fibers; immersing the carbon paper with attached protein fibers in a Na2PdCl4 solution and ultrasonically treating it to denature Pd... 2+ Dispersed on carbon paper; after standing, the reducing agent NaBH4 is added, and the fiber surface changes from bright yellow to black, Pd 2+ The Pd atoms are reduced to Pd atoms and immobilized on protein-like fibers. After standing, the fibers are washed and dried to obtain a porous electrode. This invention addresses the problem of limited reaction area and catalytic activity inherent in traditional nanoelectrodes, which makes it difficult to fundamentally solve the problem of low catalytic efficiency. By modifying the protein fibers by immobilizing Pd clusters on the protein-like fiber template, the electrode efficiency is significantly improved compared to a single Pd catalyst.

Description

Technical Field

[0001] This invention belongs to the field of wastewater treatment, specifically relating to a method for preparing a protein fiber modified porous electrode and its application. Background Technology

[0002] Ciprofloxacin has been widely used in human and veterinary medicine due to its superior properties, such as excellent tissue penetration, good bioavailability, and low toxicity and side effects. Cefixime, as a third-generation cephalosporin antibiotic, has strong antibacterial effects against Gram-negative bacteria, low allergenicity, and a long half-life. However, long-term abuse, overuse, and misapplication of antibiotics have led to their accumulation in water bodies, making antibiotics one of the emerging pollutants. Such substances released into the environment are not only difficult to biodegrade, but also cause and accelerate the growth of antibiotic resistance genes in water.

[0003] Therefore, finding a new, efficient, and environmentally friendly technology and method for treating antibiotics is of great practical significance for solving the problem of antibiotics in water bodies.

[0004] Electrochemical reduction technology is considered a sustainable and promising antibiotic removal technology due to its advantages such as environmental friendliness, high degradation efficiency, and strong oxidation capacity. However, many of these technologies suffer from various problems, including low efficiency, high cost, technical difficulty, and incomplete degradation. Summary of the Invention

[0005] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0006] In view of the problems existing in the above and / or prior art, the present invention is proposed.

[0007] Therefore, the purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing a protein fiber modified porous electrode.

[0008] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a method for preparing a protein fiber modified porous electrode, comprising,

[0009] Lysozyme was dissolved in deionized water to prepare a lysozyme protein solution;

[0010] The pH of the lysozyme protein solution was adjusted to 2, and the solution was heated and stirred to obtain a lysozyme protein denatured solution.

[0011] Carbon paper is placed in a lysozyme protein denaturation solution and stirred to obtain carbon paper with attached protein fibers.

[0012] Carbon paper with attached protein fibers was immersed in a Na₂PdCl₄ solution and ultrasonically treated to remove Pd. 2+ Disperse on carbon paper;

[0013] After standing, the reducing agent NaBH4 was added, and the fiber surface changed from bright yellow to black. Pd 2+ It is reduced to Pd atoms, which are then immobilized on protein-like fibers.

[0014] After standing, the electrode is cleaned and dried to obtain a porous electrode.

[0015] In a preferred embodiment of the preparation method described in this invention, the lysozyme is dissolved in deionized water, wherein the ratio of lysozyme protein to deionized water is 2-4 g: 180-300 mL.

[0016] As a preferred embodiment of the preparation method described in this invention, the lysozyme protein denaturation solution is prepared by heating and stirring, wherein the temperature is raised to 80-90°C, the stirring speed is 200-400 rpm, and the stirring time is 24-25 h.

[0017] In a preferred embodiment of the preparation method described in this invention, the pH of the lysozyme protein solution is adjusted to 2, wherein the solution used for adjustment includes a 1M HCl solution.

[0018] In a preferred embodiment of the preparation method described in this invention, the carbon paper is placed in a lysozyme protein denaturation solution and stirred, wherein the stirring temperature is 90°C, the stirring speed is 800-830 rpm, and the stirring time is 25-26 h.

[0019] In a preferred embodiment of the preparation method described in this invention, the carbon paper with attached protein fibers is immersed in a Na2PdCl4 solution, wherein the concentration of the Na2PdCl4 solution is 0.1M.

[0020] As a preferred embodiment of the preparation method described in this invention, the ultrasonic treatment causes Pd to... 2+ The mixture is dispersed on carbon paper, and the ultrasonic treatment is performed at a temperature of 4℃ for 30 minutes and a power of 180W.

[0021] In a preferred embodiment of the preparation method described in this invention, the reducing agent NaBH4 is added after standing, wherein the concentration of NaBH4 is 0.056M.

[0022] Another object of the present invention is to overcome the shortcomings of the prior art and provide a method for preparing a protein fiber modified porous electrode, and the application of the porous electrode prepared by the method in the degradation of cefixime and ciprofloxacin antibiotics, including,

[0023] The electrochemical reactor was divided into an anode and anode chambers by a proton exchange membrane Nafion membrane, and a protein fiber nanoelectrode was placed in the anode chamber of the electrochemical reactor.

[0024] TiSO was placed in the cathode chamber of the electrochemical reaction device;

[0025] The constant potential of the electrochemical reactor is controlled using an electrochemical workstation;

[0026] The cathode and anode electrodes have a geometric size of 3cm × 3cm.

[0027] In a preferred embodiment of the application described in this invention, the electrolyte in the electrochemical reactor comprises 500 mg / L Na₂SO₄, and the catalyst loading in the protein fiber-constructed nanoelectrode is 0.3–0.35 mg / cm³. 2 The concentration of cefixime or ciprofloxacin antibiotics in the anode chamber is 0.02 mg / L, the electrochemical working voltage is 5.0–6 V, and the electrochemical reaction time is 2–3 h.

[0028] Beneficial effects of this invention:

[0029] This invention addresses the problem of limited reaction area and low catalytic efficiency of traditional nanoelectrodes, which are also limited by the catalyst material itself. By immobilizing Pd clusters on protein-like fiber templates to modify the protein fibers, the electrode efficiency is significantly improved compared to single Pd catalysts. Attached Figure Description

[0030] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein:

[0031] Figure 1 This is an HRTEM image of the protein fiber-nanocatalyst prepared in Example 2 of the present invention.

[0032] Figure 2 This is an EDS characterization diagram of the protein fiber-nanocatalyst prepared in Example 2 of the present invention.

[0033] Figure 3This is a SEM characterization image of the protein fiber-nanocatalyst prepared in Example 2 of the present invention.

[0034] Figure 4 This is a diagram showing the electrolytic removal effect of the protein fiber-nanocatalyst prepared in Example 2 of the present invention using ciprofloxacin wastewater as a substrate.

[0035] Figure 5 This image shows the electrolytic removal effect of the Pd-protein-like fiber nanofiber electrode prepared in Comparative Example 4 of this invention on cefixime wastewater as a substrate. Detailed Implementation

[0036] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the examples in the specification.

[0037] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0038] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that excludes other embodiments. Ten embodiments and two comparative examples are provided in this specification, wherein Embodiments 1 and 2 are specific implementation schemes for preparing the electrodes, and Embodiments 3 to 10 are specific implementation schemes for energizing experiments.

[0039] The lysozyme protein used in this invention was purchased from the Sigma website; the cathode material, carbon paper, was purchased from HESEN Company in China, model HCP030N; and the TiSO film electrode was purchased from Ti-Dynamic Company. All of these are commercially available products.

[0040] Example 1

[0041] (1) Add 4g of lysozyme protein to 180mL of deionized water, adjust the pH of the solution to 2, and the final total volume of the solution is 200mL.

[0042] (2) Stir thoroughly for 24 hours on a magnetic stirrer at 90℃ and 740rpm. The acid heat causes the lysozyme protein to form protein-like fibers.

[0043] (3) The electrocatalytic anode material is carbon paper. The carbon paper is completely immersed in the solution in step (2) above and stirred for 8 hours at 90°C and 830 rpm. The carbon paper is basically attached with protein-like fibers, which can be used to immobilize metal catalysts.

[0044] (4) Pd cluster metal catalysts immobilized on carbon paper:

[0045] The carbon paper with attached protein-like fibers was completely immersed in a Na₂PdCl₄ (0.1M) solution to allow the Pd... 2+ The catalyst is uniformly dispersed on protein-like fibers to avoid metal catalyst aggregation, and Pd is promoted by ultrasonic treatment (4℃, 30 min). 2+ Dispersion on carbon paper.

[0046] (5) After standing for 24 hours, a reducing agent (0.056M NaBH4) was added to the solution. At this time, it was clearly observed that the surface of the carbon paper changed from bright yellow to black.

[0047] Prove its Pd 2+ The metal catalyst, already reduced to Pd atoms, was immobilized on protein-like fibers with a catalyst loading of 0.30 mg / cm³. 2 .

[0048] HRTEM image of the prepared protein fiber-nanocatalyst is shown below. Figure 1 As can be seen, the Afs-Pd composite material is polydisperse, and the reduced nano-Pd is uniformly distributed on the surface of AFs.

[0049] EDS characterization of the prepared protein fiber-nanocatalyst is shown in the figure. Figure 2 It can be seen that the distribution of Pd is consistent with the distribution of C and N designed in amyloid protein, which confirms the important role of AFs as a bridging template for the formation of nano Pd.

[0050] SEM characterization images of the prepared protein fiber-nanocatalysts are shown below. Figure 3 By observing the morphology of the surface material, it was proven that a three-dimensional network structure containing Pd atoms had been formed on the surface of the carbon paper.

[0051] Example 2

[0052] Removal of cefixime antibiotic using the protein fiber-nanoelectrode prepared in Example 1:

[0053] (1) The electrochemical reactor device is divided into an anode and anode chambers by a proton exchange membrane Nafion membrane, and the protein fiber nanoelectrode constructed in Example 1 is placed in the anode chamber of the electrochemical reactor device.

[0054] TiSO was placed in the cathode chamber of the electrochemical reaction device;

[0055] The initial concentration of cefixime in the anode chamber was 0.02 mg / L, and the electrolyte was 500 mg / L Na2SO4.

[0056] The electrolyte in the cathode chamber is 500 mg / L Na2SO4;

[0057] The effect of different voltages on the removal performance of cefixime antibiotics was investigated. After a continuous electrocatalytic reaction for 1 hour, a certain amount of solution was taken out with a disposable syringe to test the cefixime concentration and calculate the cefixime removal efficiency.

[0058] Cefixime removal efficiency (%) = (Antibiotic concentration before removal - Antibiotic concentration after removal) / Antibiotic concentration before removal × 100%

[0059] (2) Experimental results: The cefixime removal efficiencies of the protein fiber-constructed nanoelectrode were 78.4%, 87.6%, 88.3%, and 81.2% at working voltages of 5.0V, 5.3V, 5.6V, and 6Vs.RHE, respectively.

[0060] The above experimental results indicate that the optimal operating voltage for constructing nanoelectrodes from protein fibers is 5.6V.

[0061] Example 3

[0062] Removal of cefixime antibiotic using the protein fiber-nanoelectrode prepared in Example 1:

[0063] (1) The electrochemical reactor device is divided into an anode and anode chambers by a proton exchange membrane Nafion membrane, and the protein fiber nanoelectrode constructed in Example 2 is placed in the anode chamber of the electrochemical reactor device.

[0064] TiSO was placed in the cathode chamber of the electrochemical reaction device;

[0065] The initial concentration of cefixime in the anode chamber was 0.02 mg / L, and the electrolyte was 500 mg / L Na2SO4.

[0066] The electrolyte in the cathode chamber is 500 mg / L Na2SO4;

[0067] The applied operating voltage is 5.6V vs. RHE;

[0068] After the electrochemical reaction device has been in operation for 2 hours, the antibiotic removal performance of cefixime is measured.

[0069] (2) The test results showed that the electrocatalytic reaction device with protein fiber nanoelectrode as anode and carbon paper as cathode had a removal efficiency of 93.4% for cefixime antibiotic. The above results show that the device has a good removal effect on cefixime antibiotic.

[0070] Example 4

[0071] The working electrode anode was constructed using the protein fiber nanoelectrode from Example 1, and TiSO was used as the cathode. The removal performance of cefixime antibiotic was tested. The working voltage was 4.9V vs. RHE, and the initial concentration of pollutant was 0.04mg / L.

[0072] After the reaction device has reacted for 1 hour, a certain amount of solution is taken out with a disposable syringe to test the concentration of the remaining pollutants.

[0073] The removal efficiency of the surface electrocatalytic reaction device for cefixime antibiotic was tested experimentally using a UV-Vis spectrophotometer, and the removal rate was calculated to be 92.3%.

[0074] Example 5

[0075] The electrochemical reaction device was constructed as in Example 1, with protein fiber nanoelectrodes as the working electrode anode and TiSO as the working electrode cathode. The electrocatalytic removal performance of cefixime antibiotic was tested. The electrocatalytic working voltage was 5.6V vs. RHE, and the initial concentration of pollutants was 0.04mg / L.

[0076] After a continuous electrochemical reaction for 1 hour at its operating voltage, the solutions were taken out and their antibiotic concentrations were tested.

[0077] The experimental results showed that the surface device achieved a 97.2% removal efficiency for cefixime antibiotics.

[0078] Example 6

[0079] The protein fibers from Example 1 were used to construct a nanoelectrode, which was placed at the anode of the reactor and TiSO4 was used as the cathode. The effect of different voltages on the removal performance of ciprofloxacin antibiotic was investigated.

[0080] The initial concentration of ciprofloxacin in the anode chamber was 0.02 mg / L. After one hour of continuous electrocatalytic reaction, a certain amount of solution was taken out with a disposable syringe to test the concentration of ciprofloxacin.

[0081] Experimental results showed that the removal efficiencies of ciprofloxacin by the protein fiber-constructed nanoelectrode were 78.4%, 87.6%, 88.3%, and 81.2% at working voltages of 5.0V, 5.3V, 5.6V, and 6Vs.RHE, respectively.

[0082] The above experimental results indicate that the optimal operating voltage for constructing nanoelectrodes from protein fibers is 5.6V.

[0083] Example 7

[0084] The removal performance of ciprofloxacin antibiotic was investigated using a nanoelectrode constructed from the protein fibers in Example 1 as the working electrode anode and TiSO as the working electrode cathode.

[0085] The applied operating voltage was 5.6V vs. RHE, and the initial concentration of ciprofloxacin was 0.02 mg / L.

[0086] After the electrochemical reaction device has been reacting for 2 hours, the solution is taken out with a disposable syringe and the concentration of ciprofloxacin antibiotic is tested by ultraviolet spectrophotometry. The ciprofloxacin removal efficiency is calculated by converting the absorbance.

[0087] Tests showed that the electrocatalytic reaction device, which uses a protein fiber nanoelectrode as the anode and carbon paper as the cathode, achieved a removal efficiency of 93.4% for ciprofloxacin antibiotics. These results indicate that the device has a good removal effect on ciprofloxacin antibiotics.

[0088] Example 8

[0089] The working electrode anode was constructed using the protein fiber nanoelectrode from Example 1, and TiSO was used as the cathode to test the removal performance of ciprofloxacin antibiotic.

[0090] The applied operating voltage was 4.9V vs. RHE, and the initial pollutant concentration was 0.04mg / L;

[0091] After the reaction device has reacted for 2 hours, a certain amount of solution is taken out with a disposable syringe to test the concentration of the remaining pollutants.

[0092] The removal efficiency of the surface electrocatalytic reaction device for ciprofloxacin antibiotic was tested experimentally. The removal rate was calculated to be 92.3% using a UV-Vis spectrophotometer.

[0093] Example 9

[0094] The electrochemical reaction device was constructed as in Example 2, with protein fiber nanoelectrode as the working electrode anode and TiSO as the working electrode cathode. The electrocatalytic removal performance of ciprofloxacin antibiotic was tested, with an electrocatalytic working voltage of 5.6V vs. RHE.

[0095] After a continuous electrochemical reaction at its operating voltage for 1 hour, the solutions were taken out and the antibiotic concentration was tested. The experimental results showed that the device achieved a 97.2% removal efficiency for ciprofloxacin.

[0096] Comparative Example 1

[0097] The electrochemical reaction device was built in Example 2, and the plant protein fiber (soy protein, purchased from Taobao Gutaiwang flagship store) nanoelectrode was constructed using the method in Example 1 and used as the working electrode anode.

[0098] Specifically as follows:

[0099] (1) Add 4g of soybean protein to 180mL of deionized water, adjust the pH of the solution to 2, and the final total volume of the solution is 200mL;

[0100] (2) Stir thoroughly for 24 hours on a magnetic stirrer at 90℃ and 740rpm. The acid heat causes the protein to form protein-like fibers.

[0101] (3) The electrocatalytic anode material is carbon paper. The carbon paper is completely immersed in the solution of step (2) above and stirred for 8 hours at 90°C and 830 rpm.

[0102] The carbon paper is basically covered with protein-like fibers, which can be used to immobilize metal catalysts.

[0103] (4) Pd cluster metal catalysts immobilized on carbon paper:

[0104] The carbon paper with attached protein-like fibers was completely immersed in a Na₂PdCl₄ (0.1M) solution to allow the Pd... 2+ The catalyst is uniformly dispersed on protein-like fibers to avoid metal catalyst aggregation, and Pd is promoted by ultrasonic treatment (4℃, 30 min). 2+ Dispersion on carbon paper.

[0105] (5) After standing for 24 hours, a reducing agent (0.056M NaBH4) was added to the solution. At this time, it was clearly observed that the surface of the carbon paper changed from bright yellow to black.

[0106] Prove its Pd 2+ The metal catalyst, already reduced to Pd atoms, was immobilized on protein-like fibers with a catalyst loading of 0.30 mg / cm³. 2 .

[0107] TiSO was used as the working electrode cathode to test the electrocatalytic removal performance of ciprofloxacin antibiotic. The electrocatalytic working voltage was 5.6V vs. RHE.

[0108] After a continuous electrochemical reaction for 1 hour at its operating voltage, the solutions were taken out and their antibiotic concentrations were tested.

[0109] The experimental results showed that the surface device had a 21.6% removal efficiency for ciprofloxacin antibiotic.

[0110] Comparative Example 2

[0111] The electrochemical reaction device was constructed as in Example 2, with protein fiber nanoelectrode as the working electrode anode and TiSO as the working electrode cathode. The electrocatalytic removal performance of salbutamol was tested. The electrocatalytic working voltage was 5.6V vs. RHE, and the initial concentration of salbutamol in the anode chamber was 0.02mg / L.

[0112] After a continuous electrochemical reaction at its operating voltage for 1 hour, the solutions were taken out and their antibiotic concentrations were tested. The experimental results showed that the device achieved a 19.8% removal efficiency for salbutamol.

[0113] Comparative Example 3

[0114] Method for fabricating palladium-titanium suboxide electrodes:

[0115] Titanium suboxide was completely immersed in a Na₂PdCl₄ (0.1M) solution, and Pd was promoted by ultrasonic treatment (4℃, 30 min). 2+ After dispersion on titanium suboxide and standing for 24 hours, a reducing agent (0.056M NaBH4) was added to the solution. At this time, it was clearly observed that the surface of titanium suboxide changed from bright yellow to black.

[0116] Prove its Pd 2+ The metal catalyst was directly immobilized on the titanium suboxide after being reduced to Pd atoms, thus producing a palladium-titanium suboxide electrode.

[0117] Method for fabricating palladium-protein-fiber-titanium suboxide electrodes:

[0118] (1) Add 4g of lysozyme protein to 180mL of deionized water, adjust the pH of the solution to 2, and the final total volume of the solution is 200mL.

[0119] (2) Stir thoroughly for 24 hours on a magnetic stirrer at 90℃ and 740rpm. The acid heat causes the lysozyme protein to form protein-like fibers.

[0120] (3) Immerse the titanium suboxide completely in the solution of step (2) above, and stir for 8 hours at 90°C and 830 rpm.

[0121] Protein-like fibers are basically attached to sub-titanium oxide, which can be used to immobilize metal catalysts.

[0122] (4) Pd cluster metal catalysts immobilized on carbon paper:

[0123] The sub-titanium oxide with attached protein-like fibers was completely immersed in a Na₂PdCl₄ (0.1M) solution to allow the Pd... 2+ The catalyst was uniformly dispersed on protein-like fibers to avoid metal catalyst aggregation, and Pd was promoted by ultrasonic treatment (4℃, 30 min). 2+ Dispersion on sub-titanium oxide;

[0124] (5) After standing for 24 hours, a reducing agent (0.056M NaBH4) was added to the solution. At this time, it was clearly observed that the surface of the titanium suboxide changed from bright yellow to black; this proves that its Pd 2+ It has already been reduced to Pd atoms and the metal catalyst is immobilized on the protein-like fiber;

[0125] A constant potential of the electrochemical reactor was controlled using an electrochemical workstation, with 500 mg / L Na₂SO₄ as the electrolyte. The catalyst loading in the protein fiber-constructed nanoelectrode was 0.32 mg / cm². 2 The concentration of ciprofloxacin antibiotic in the anode chamber was 0.02 mg / L, the electrochemical working voltage was 5.6 V, and the electrochemical reaction time was 0–100 min.

[0126] See Figure 4 It can be seen that both dispersed and non-dispersed Pd composite electrodes have a degradation effect on ciprofloxacin, but the dispersed Pd nanoelectrodes show better degradation effect on ciprofloxacin wastewater.

[0127] Comparative Example 4

[0128] Method for fabricating palladium-titanium suboxide electrode: Titanium suboxide is completely immersed in a Na₂PdCl₄ (0.1M) solution, and Pd is accelerated under ultrasonic treatment (4℃, 30 min). 2+ Dispersion on sub-titanium oxide; after standing for 24 hours, a reducing agent (0.056M NaBH4) was added to the solution.

[0129] Method for fabricating palladium-protein-fiber-titanium suboxide electrode: Add 4g of lysozyme protein to 180mL of deionized water and adjust the pH of the solution to 2;

[0130] Stir thoroughly for 24 hours on a magnetic stirrer at 90°C and 740 rpm;

[0131] The electrocatalytic anode material is titanium suboxide. The titanium suboxide is completely immersed in the above solution and stirred for 8 hours at 90°C and 830 rpm.

[0132] Protein-like fibers are basically attached to sub-titanium oxide, on which metal catalysts can be immobilized. Pd cluster metal catalysts are immobilized on sub-titanium oxide. The sub-titanium oxide with attached protein-like fibers is completely immersed in a Na₂PdCl₄ (0.1M) solution to allow Pd... 2+ The catalyst is uniformly dispersed on protein-like fibers to avoid metal catalyst aggregation, and Pd is promoted by ultrasonic treatment (4℃, 30 min). 2+ Dispersion on sub-titanium oxide; after standing for 24 hours, a reducing agent (0.056M NaBH4) was added to the solution.

[0133] Determination method and steps: Place the prepared electrode in the anode chamber of the electrochemical reaction device; place TiSO in the cathode chamber of the electrochemical reaction device; the initial concentration of cefixime in the anode chamber is 0.02 mg / L, and the electrolyte is 500 mg / L Na2SO4; the electrolyte in the cathode chamber is 500 mg / L Na2SO4. During the experiment, a certain amount of solution is taken out with a disposable syringe every 20 minutes to test the concentration of cefixime.

[0134] See Figure 5 It can be seen that the palladium-protein-fiber-titanium suboxide electrode has better catalytic performance than the palladium-titanium suboxide electrode.

[0135] In summary, this electrocatalytic reaction device, using a protein fiber-modified porous electrode as the working electrode anode and TiSO as the cathode, can efficiently remove antibiotics from complex water bodies. Furthermore, the device can effectively remove multiple antibiotics coexisting in complex water bodies in a continuous flow electrolytic cell, while maintaining excellent antibiotic removal efficiency and good removal stability, demonstrating its broad application prospects in the field of water treatment technology.

[0136] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the present invention.

Claims

1. A method for preparing a protein fiber modified porous electrode, characterized in that: include, Lysozyme was dissolved in deionized water to prepare a lysozyme protein solution, wherein the ratio of lysozyme protein to deionized water was 2~4g:180~300mL; The pH of the lysozyme protein solution was adjusted to 2, and the solution was heated and stirred to obtain a denatured lysozyme protein solution. The temperature was raised to 80~90℃, the stirring speed was 200~400rpm, and the stirring time was 24~25h. Carbon paper is placed in a lysozyme protein denaturation solution and stirred to obtain carbon paper with attached protein fibers. Carbon paper with attached protein fibers was immersed in a Na₂PdCl₄ solution and ultrasonically treated to remove Pd. 2+ The solution was dispersed on carbon paper, with a concentration of 0.1 M for Na₂PdCl₄. After standing, the reducing agent NaBH4 was added, and the fiber surface changed from bright yellow to black. Pd 2+ It is reduced to Pd atoms, which are then immobilized on protein-like fibers, wherein the concentration of NaBH4 is 0.056 M. After standing, the electrode is cleaned and dried to obtain a porous electrode.

2. The preparation method according to claim 1, characterized in that: The pH of the lysozyme protein solution is adjusted to 2, wherein the solution used for adjustment includes a 1M HCl solution.

3. The preparation method according to claim 1, characterized in that: The carbon paper is placed in a lysozyme protein denaturation solution and stirred, wherein the stirring temperature is 90℃, the stirring speed is 800~830rpm, and the stirring time is 25~26h.

4. The preparation method according to claim 1, characterized in that: The ultrasonic treatment causes Pd 2+ The mixture is dispersed on carbon paper, and the ultrasonic treatment is performed at a temperature of 4°C for 30 min and a power of 180 W.

5. The application of the porous electrode prepared by any one of claims 1 to 4 in the degradation of cefixime and ciprofloxacin antibiotics, characterized in that: include, The electrochemical reactor was divided into an anode and anode chambers by a proton exchange membrane Nafion membrane, and a protein fiber nanoelectrode was placed in the anode chamber of the electrochemical reactor. TiSO was placed in the cathode chamber of the electrochemical reaction device; The constant potential of the electrochemical reactor is controlled using an electrochemical workstation; The electrode geometry of the cathode and anode is 3 cm × 3 cm.

6. The application as described in claim 5, characterized in that: The electrolyte in the electrochemical reactor includes 500 mg / L Na₂SO₄, and the catalyst loading in the protein fiber-constructed nanoelectrode is 0.3–0.35 mg / cm³. 2 The concentration of cefixime or ciprofloxacin antibiotics in the anode chamber is 0.02 mg / L, the electrochemical working voltage is 5.0~6V, and the electrochemical reaction time is 2~3h.

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