Electrode material loaded with schafferite and preparation method and application thereof

Abstract

The application discloses an electrode material loaded with schottky minerals and a preparation method and application thereof, and belongs to the technical field of water pollution treatment. The electrode comprises a substrate and schottky minerals loaded on the substrate, wherein the loading amount of the schottky minerals on the substrate is 1-18.8 mg / cm 2 The schottky minerals are directly grown in situ on the substrate to form the loading.

Description

Technical Field

[0001] This invention belongs to the field of water pollution treatment technology, and in particular relates to an electrode material loaded with Schiele minerals, its preparation method and application. Background Technology

[0002] In today's society, water resources are severely scarce, and water pollution further exacerbates this shortage. With the rapid development of industrial technology, large amounts of industrial wastewater are generated, accompanied by the emergence of many high-concentration, highly toxic, and novel pollutants. Therefore, the purification of industrial wastewater has gradually become a crucial issue urgently needing to be addressed in environmental protection. Electrochemical water treatment technology generally does not require the introduction of other substances; the reactants are electrons. Through the directional transfer and precise control of electrons, the rate and efficiency of the environmental interface are enhanced. This characteristic fundamentally reflects the low pollution and environmentally friendly nature of electrochemical treatment processes. Reactants directly enter the reaction system to participate in the reaction, allowing for a wider variety of organic compounds to participate, lower requirements, and improved energy utilization efficiency. Based on different working principles and methods, electrochemical water treatment technologies can be divided into: electrocoagulation, electroadsorption, electrooxidation, electro-Fenton, electroreduction, and electrodeposition, etc., and can be coupled with other processes through the combined action of multiple electrochemical reactions to achieve the purpose of wastewater purification and treatment. In these electrochemical treatment processes, mass transfer is the core factor directly affecting treatment efficiency.

[0003] During the electro-Fenton process, under the influence of direct current, a two-electron reduction reaction occurs at the cathode, continuously producing H₂O₂. Subsequently, the resulting H₂O₂ can further react with added Fe. 2+ The Fenton reaction occurs, generating highly oxidizing ·OH. This ·OH can react with organic pollutants (R) to degrade them, eventually mineralizing them into water and carbon dioxide. However, the H2O2 generated at the cathode participates in the Fenton reaction, but it is accompanied by side reactions. Furthermore, the ·OH generated by the Fenton reaction has a very short lifespan, preventing it from fully combining with pollutants and significantly reducing the efficiency of electro-oxidation.

[0004] Therefore, from an overall perspective, providing an electro-Fenton oxidation electrode with high mass transfer efficiency can effectively improve the degradation efficiency of pollutants. Summary of the Invention

[0005] 1. The problem to be solved

[0006] In view of the problem of low efficiency of existing electrodes in electrochemically degrading pollutants in wastewater, the present invention provides an electrode material loaded with Schiele minerals and its preparation method, which can be used to electrochemically degrade pollutants in wastewater.

[0007] 2. Technical Solution

[0008] To solve the above problems, the technical solution adopted by the present invention is as follows:

[0009] The first aspect of the present invention provides an electrode material loaded with Schiele mineral, the electrode comprising a substrate and Schiele mineral loaded on the substrate;

[0010] The loading of the Scherdmannite on the substrate was 1 mg / cm³. 2 -18.8mg / cm 2 .

[0011] According to any embodiment of the first aspect of the present invention, the substrate is any one of graphite felt, carbon paper, or carbon fiber cloth.

[0012] According to any embodiment of the first aspect of the invention, the Schiele mineral is grown directly in situ on the substrate to form the load.

[0013] A second aspect of the present invention provides a method for preparing an electrode material loaded with Schiele minerals, comprising the steps of:

[0014] 1) Prepare a substrate, the surface of which is a hydrophilic surface;

[0015] Prepare a solution containing ferrous ions, wherein the concentration of ferrous ions in the solution is 0.02-0.1 mol / L; and the pH value of the solution is 2-4.

[0016] 2) Keep the substrate in contact with the solution, during which H2O2 is added to the solution and the solution is adjusted with alkali to maintain its pH at 2-4;

[0017] The total amount of H2O2 added is 1.2 to 2 times that of ferrous ions;

[0018] The H2O2 is added in N stages, where N is 4 to 8.

[0019] The contact time is 6-24 hours, and the temperature is 20-40℃;

[0020] 3) After contact is completed, the substrate is dried to obtain the electrode material loaded with Schiele mineral.

[0021] It should be noted that the "hydrophobicity of the substrate surface" will affect the loading of Scheringer minerals on the substrate. In fact, excessive hydrophobicity of the substrate surface is not conducive to the loading of Scheringer minerals. Therefore, the substrate surface is generally required to be hydrophilic.

[0022] Furthermore, the main function of the "substrate" is to support, conduct electricity, and fix Scheringer minerals. Based on this, theoretically, any material that meets the following conditions can be used as the "substrate" of this invention: it is conductive; it can serve as a seed crystal for the growth of Scheringer minerals and can fix the Scheringer minerals; it has certain pores that allow water to pass through.

[0023] Furthermore, the “substrate” can be any of the following: graphite felt, carbon paper, carbon fiber cloth.

[0024] In any embodiment of the second aspect of the present invention, 1), the substrate has a thickness of 1 to 8 mm.

[0025] It should be noted that the thickness of the “substrate” as described herein will also affect the loading of Schiele mineral and the conductivity of the electrode. If the thickness is too small, the loading will be too low, especially the loading inside the graphite felt will be very small and it will be easy to peel off after loading. If the thickness is too large, the resistance will be too high and the conductivity will be poor. Therefore, the thickness of the “substrate” is preferably 1 to 5 mm.

[0026] In any embodiment of the second aspect of the present invention, in step 1), the substrate surface is pretreated.

[0027] As described herein, the purpose of treating the substrate with nitric acid solution or Triton is primarily to ensure that the substrate has a hydrophilic surface, which is beneficial for the subsequent growth of Schiele minerals and to ensure the corresponding loading capacity; based on this, examples can be given as follows:

[0028] The substrate is treated with a nitric acid solution; or,

[0029] The substrate is treated using a Triton process; or...

[0030] The substrate was treated with nitric acid solution and Triton.

[0031] Furthermore, it is preferable to soak the substrate in a nitric acid solution. This is because, in practice, it has been found that although Triton has a good effect on improving hydrophilicity, and treating the substrate with Triton can meet the requirements for surface hydrophilicity, Triton is prone to leaving residues on the substrate. To a certain extent, these residual Tritons can affect the growth of Schiele minerals on the substrate, limiting the final loading of Schiele minerals on the substrate.

[0032] More preferably, the substrate is soaked in a nitric acid solution with a concentration of 2-8 mol / L for a period of not less than 3 hours.

[0033] The "immersion treatment" described herein helps to create Fe in the internal voids of the substrate during subsequent steps.2+ Therefore, during the process of synthesizing Schiele mineral loading, it can be ensured that the substrate can be fully loaded with the required Schiele mineral.

[0034] According to any embodiment of the first aspect of the present invention, in step 2), a material having a diameter of 1 cm is used. 2 The base area is calculated, and at this point, the volume of the solution containing ferrous ions is 80–400 mL.

[0035] For example, with a diameter of 1cm 2 The base area calculation uses a solution with a ferrous ion concentration of 0.04 mol / L and a volume of 200 mL.

[0036] In any embodiment of the second aspect of the present invention, in step 2), the solution is adjusted N times with sodium hydroxide during the contact to maintain its pH at 2-4;

[0037] The value of N is between 4 and 8.

[0038] In any embodiment of the second aspect of the present invention, in step 2), H2O2 and alkali are added alternately to the solution.

[0039] In any embodiment of the second aspect of the present invention, in step 3), after contact is completed, the substrate is first cleaned and then dried.

[0040] The present invention provides an electrode material loaded with Schiele minerals according to any embodiment of the first aspect of the present invention, or an electrode material loaded with Schiele minerals prepared by a method provided according to any embodiment of the second aspect of the present invention. The third aspect of the present invention provides an application of the electrode material loaded with Schiele minerals to treat organic pollutants in wastewater by electrochemical means.

[0041] According to any embodiment of the third aspect of the present invention, the application of electro-Fenton oxidation for treating organic pollutants in wastewater.

[0042] According to any embodiment of the third aspect of the present invention, organic pollutants in wastewater are treated by electro-Fenton under conditions of pH 2-7.

[0043] According to any embodiment of the third aspect of the present invention, the organic pollutant includes, but is not limited to, ciprofloxacin hydrochloride and tetracycline.

[0044] Beneficial effects

[0045] (1) The electrode material loaded with Schiele minerals provided by this invention develops a new application for Schiele minerals. When the electrode material is applied to the electro-Fenton oxidation to reduce pollutants in wastewater, the iron ions in the Schiele minerals can be directly used as the iron source for the Fenton reaction without the need for external Fe addition. 2+ ;

[0046] Meanwhile, the electrode material loaded with Schiele minerals can also generate hydrogen peroxide itself during the electro-Fenton oxidation degradation of pollutants in wastewater, without the need for additional external hydrogen peroxide.

[0047] (2) The electrode material supported on Schiele minerals provided by this invention, when applied to electro-Fenton oxidation to reduce pollutants in wastewater, allows the iron ions in the Schiele minerals to act as an iron source for the Fenton reaction, fully reacting with the oxidant to generate highly oxidizing ·OH to oxidize and degrade organic pollutants. This greatly solves the problem that in traditional electro-Fenton oxidation processes, the electrode needs to simultaneously adsorb the oxidant and the added Fe. 2+ Only then can the two react on their surface to produce ·OH, which has strong oxidizing properties, to oxidize and degrade organic pollutants, thus solving the problem of low mass transfer efficiency.

[0048] Furthermore, the electrode material loaded with Schiele minerals provided by this invention contains SO4 in the Schiele minerals. 2- By applying electricity, SO4 is formed, which can work in conjunction with OH radicals to oxidize and degrade organic pollutants, thereby achieving more efficient degradation of pollutants in water.

[0049] (3) In traditional Scheringer mineral preparation, hydrogen peroxide is typically added to a solution containing ferrous ions all at once. However, our research has found that this method of adding hydrogen peroxide causes the pH of the solution to drop rapidly below 2, leading to rapid hydrolysis and mineralization, which affects the crystal form, morphology, mineralization rate, and loading amount of Scheringer mineral onto the substrate. Based on this finding, the electrode material for loading Scheringer mineral provided by this invention adds hydrogen peroxide in 4 to 8 stages. This slow oxidation helps maintain a relatively stable pH throughout the contact process, effectively controlling the mineralization rate of Scheringer mineral and its loading amount onto the substrate.

[0050] (4) The electrode material loaded with Schiele minerals provided by the present invention, with H2O2 and alkali added to the solution in multiple and alternating steps, can further maintain the relative stability of the solution pH value through the alkali, so that the Schiele minerals generated on the substrate have the best adsorption performance.

[0051] (5) The electrode material loaded with Schiele minerals provided by the present invention is applied to the electro-Fenton oxidation to reduce pollutants in wastewater. It has a stable effect and the treated electrode can be reused. It has a significant effect in the electro-Fenton process of pollutants such as ciprofloxacin hydrochloride (CIP) and tetracycline (TC). It has good application prospects in the field of water treatment. Attached Figure Description

[0052] Figure 1 This is a scanning electron microscope image of the graphite felt-based electrode material loaded with Schiele minerals prepared in Example 1 of the present invention;

[0053] Figure 2 This is a photograph of the graphite felt-based electrode material loaded with Schiele minerals prepared in Example 1 of the present invention.

[0054] Figure 3 The graph shows the degradation effect of the electrode prepared in Example 1 of this invention on the pollutant ciprofloxacin hydrochloride (CIP) in wastewater under different voltages.

[0055] Figure 4 The free radical spectrum generated during the degradation of ciprofloxacin hydrochloride (CIP) pollutant in wastewater using the electrode prepared in Example 1 of this invention;

[0056] Figure 5 The graph shows the degradation effect of the electrode prepared in Example 1 of this invention on the pollutant ciprofloxacin hydrochloride (CIP) in wastewater at different pH values.

[0057] Figure 6 The image shows the XRD pattern of the graphite felt-based electrode material loaded with Schiele minerals prepared in Example 1 of this invention.

[0058] Figure 7 Electro-Fenton degradation performance for other pollutants (tetracycline TC, ciprofloxacin hydrochloride CIP, sulfonamide SMX, tilmicosin TIL). Detailed Implementation

[0059] This disclosure will be more readily understood by referring to the following description, taken in conjunction with the accompanying drawings and examples, all of which form part of this disclosure. It should be understood that this disclosure is not limited to the specific products, methods, conditions, or parameters described and / or illustrated herein. Furthermore, the terminology used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting, unless otherwise stated.

[0060] It should also be understood that, for clarity, certain features of this disclosure may be described herein in the context of individual embodiments, but may also be provided in combination with each other in individual embodiments. That is, unless obviously incompatible or specifically excluded, each individual embodiment is considered to be combinable with any other embodiment, and such combination is considered to represent another different embodiment. Conversely, for brevity, various features of this disclosure described in the context of individual embodiments may also be provided individually or in any sub-combination. Finally, while a particular embodiment may be described as part of a series of steps or part of a more general structure, each step or substructure may also be considered an independent embodiment in itself.

[0061] Unless otherwise stated, it should be understood that each individual element in the list and each combination of individual elements in the list will be interpreted as a different embodiment. For example, a list of embodiments denoted as "A, B, or C" should be interpreted as including embodiments "A", "B", "C", "A or B", "A or C", "B or C", or "A, B, or C".

[0062] In this disclosure, the singular forms of the articles “a,” “one,” and “the” also include the corresponding plural references, and references to a particular value include at least that particular value, unless the context clearly indicates otherwise. Thus, for example, a reference to “substance” is a reference to at least one of such substance and its equivalents.

[0063] Ordinal terms such as “first” and “second” may be used to describe various components or fluids, but these components and fluids are not limited by these terms. Therefore, without departing from the teachings of this disclosure, these terms are used only to distinguish one component / fluid from another.

[0064] When an item is described using the combined terms “...and / or ...", the description should be understood to include any one of the listed items and all combinations thereof.

[0065] Generally, the use of the term "about" indicates an approximation that can vary depending on the desired characteristics obtained from the disclosed subject matter and will be interpreted in a context-dependent manner based on function. Therefore, those skilled in the art will be able to interpret a degree of difference on a case-by-case basis. In some cases, the number of significant figures used when expressing a particular value can be a representative technique for determining the difference allowed by the term "about." In other cases, a gradient within a range of values ​​can be used to determine the range of differences allowed by the term "about." Furthermore, all ranges in this disclosure are inclusive and composable, and references to values ​​described within a range include every value within that range.

[0066] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains; the terms used herein and / or include any and all combinations of one or more of the associated listed items.

[0067] The present invention provides an electrode material loaded with Schiele mineral, comprising a substrate and Schiele mineral loaded on the substrate; wherein,

[0068] The substrate is any one of graphite felt, carbon cloth, and carbon fiber cloth;

[0069] The loading of the Scherdmannite on the substrate was 1 mg / cm³. 2 -18.8mg / cm 2 .

[0070] The Schiele minerals grow directly in situ on the substrate.

[0071] The present invention also provides a method for preparing the electrode material supported on Schiff mineral, the method comprising the following steps:

[0072] 1) Prepare the substrate and a solution containing ferrous ions;

[0073] 2) Keep the substrate in contact with the solution;

[0074] 3) After contact is completed, the substrate is dried to obtain the electrode material loaded with Schiele mineral.

[0075] More specifically, regarding "Step 1) preparing the substrate and a solution containing ferrous ions;",

[0076] This includes preparing a substrate, which can be any of the following: graphite felt, carbon paper, or carbon fiber cloth; the size of the substrate can be cut to size as needed. Generally, the thickness of the substrate is required to be 1–8 mm; and further, the surface of the substrate is required to be hydrophilic. Therefore, the substrate can be treated with nitric acid solution or Triton to make it hydrophilic, thus meeting the aforementioned hydrophilicity requirement.

[0077] It also includes preparing a solution with a ferrous ion concentration of 0.02-0.1 mol / L and a pH value of 2-4; a possible operating method is to prepare a FeSO4·7H2O solution and adjust the pH value with an alkali (such as sodium hydroxide) solution and a dilute acid (such as sulfuric acid) solution.

[0078] More specifically, regarding "step 2) keeping the substrate in contact with the solution;"

[0079] Keep the substrate in contact with the solution;

[0080] The temperature during contact is 25-35℃.

[0081] The contact time is 6-24 hours;

[0082] During the contact period, H2O2 is added to the solution N times, and the solution is adjusted with alkali N times during the contact period to keep its pH at 2-4. H2O2 and alkali are added to the solution alternately, wherein the value of N is 4-8.

[0083] Based on this, a possible operating procedure is as follows: Immerse the substrate in the solution containing ferrous ions, and add 2-4 mL of 30% H2O2 in portions, adding 0.5 mL every 15 minutes, and adjusting the pH to 2-4 with sodium hydroxide every 30 minutes; in addition, the reaction can be carried out in a shaker to meet the requirement of a contact temperature of 28°C, and the shaker can be shaken at an amplitude of 180 rpm to enhance the contact effect between the substrate and ferrous ions and hydrogen peroxide.

[0084] It should be further explained that the contact process involves oxidizing ferrous oxide with hydrogen peroxide, a process of hydrolysis and mineralization. Shaking is to ensure thorough mixing and reaction. Especially when the chosen substrate is a graphite felt with long fibers, we expect the graphite felt to have the highest possible loading of Schöndorfite, while simultaneously minimizing and avoiding uneven growth of Schöndorfite on the graphite felt or large differences in loading at different locations; shaking also helps to prevent the precipitation of reactants.

[0085] More specifically, regarding "step 3) after contact is completed, the substrate is subjected to freeze-drying treatment":

[0086] After the substrate has come into contact with the solution in step 2) above, the substrate is removed. To remove excess ions and impurities from the surface, it is generally recommended to first clean the substrate and then freeze-dry it. Therefore, a possible procedure is to first wash it with dilute sulfuric acid, followed by washing with water.

[0087] The electrode material supported on Schiele minerals provided above, or the electrode material supported on Schiele minerals prepared by the above method, can be used as an electrode for the electrochemical degradation of organic pollutants in wastewater; it is particularly suitable as an electrode for electro-Fenton oxidation to treat organic pollutants in wastewater under pH conditions of 2-7, wherein the organic pollutants include, but are not limited to, ciprofloxacin hydrochloride and tetracycline.

[0088] The present invention will be further illustrated below with reference to specific embodiments, but these embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in this technical field. The essential features and significant effects of the present invention can be seen from the following embodiments. The described embodiments are some, but not all, embodiments of the present invention, and therefore do not limit the present invention in any way. Any non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are within the protection scope of the present invention.

[0089] Example 1

[0090] This embodiment 1 provides an electrode material loaded with Schiele mineral. The electrode material uses a graphite felt substrate with dimensions of 2.0cm*10.0cm and a thickness of 3mm as the base, on which Schiele mineral is loaded at a loading amount of 3.13mg / cm³. 2 .

[0091] The structure of the graphite felt-based electrode material loaded with Schönstein minerals (also abbreviated as GF / Sch electrode-1) was characterized using scanning electron microscopy. Figure 1 As shown in the figure, it can be seen that the bristle-like Schiele mineral was successfully and uniformly grown on the carbon fiber. Figure 6 The image shows the XRD pattern of the graphite felt-based electrode material loaded with Schiele minerals prepared in Example 1 of this invention.

[0092] like Figure 2 The image shown is a physical diagram of the electrode material.

[0093] Regarding the GF / Sch electrode described above, this Example 1 also provides a specific preparation method, including the following steps:

[0094] (1) Cut the graphite felt (GF) into 2.0cm*10.0cm pieces, prepare 500mL of 3M dilute nitric acid, soak the cut graphite felt in it for 12h, take it out and wash it to remove the surface acid, then soak it in DI (deionized water) for 12h, take it out, wash it and put it in an oven at 50℃ to dry.

[0095] (2) Prepare a solution of 5.56g FeSO4·7H2O + 250mL water; adjust the pH of the solution to 2-4 with sodium hydroxide and dilute sulfuric acid, and immerse the graphite felt in the solution;

[0096] (3) Take 3 mL of 30% H2O2 and add it to the above solution in portions, adding 0.5 mL every 15 minutes. After every 30 minutes, adjust the pH with sodium hydroxide to stabilize it at 2-4. Place the reaction in a shaker (28℃, 180 rpm, 24 h).

[0097] (4) The loaded graphite felt was removed, washed with dilute sulfuric acid and water, and then freeze-dried in a freeze dryer for 48 hours. It was weighed to obtain the GF / Sch electrode-1 as described above.

[0098] Example 2

[0099] In this Example 2, the GF / Sch electrode-1 provided in Example 1 is used to conduct an experiment on the removal of pollutants from water, as detailed below:

[0100] The GF / Sch electrode-1 was cut to 1.5cm*2.0cm and fixed on the working electrode. The control electrode was a blank graphite felt (1.5cm*2.0cm). The distance between the two electrodes was 1.5cm. An immersion reactor was used. In order to enhance the mass transfer efficiency between the two electrodes, the reaction was continuously stirred. During the loading process, the electrodes were fully immersed in the reaction solution.

[0101] The following uses solutions containing the contaminant ciprofloxacin hydrochloride (CIP) and tetracycline (TC) as examples to conduct specific electro-Fenton oxidation tests. The solution information is shown in Table 1.

[0102] Table 1 Information on solutions containing ciprofloxacin hydrochloride (CIP) and solutions containing tetracycline (TC).

[0103] pollutant concentration pH value <![CDATA[Concentration of electrolyte (Na2SO4)]]> solution volume Solution containing ciprofloxacin hydrochloride (CIP) 20ppm 6.0±0.1 50mM 50mL Solution containing tetracycline (TC) 20ppm 6.0±0.1 50mM 50mL Solution containing sulfonamide (SMX) 20ppm 6.0±0.1 50mM 50mL Solutions containing tilmicosin (TIL) 20ppm 6.0±0.1 50mM 50mL

[0104] During the electro-Fenton reaction, oxygen is continuously bubbled into the reaction solution;

[0105] The concentration of pollutants was sampled at intervals, and the pollutants in the reaction solution were degraded by electro-Fenton degradation under different voltage conditions.

[0106] Depend on Figure 3 It can be seen that the degradation effect of electro-Fenton action on ciprofloxacin hydrochloride (CIP) varies under different voltage conditions. When the appropriate voltage conditions are met, the mass transfer efficiency between the two plates is higher, thus resulting in a better degradation effect on ciprofloxacin hydrochloride (CIP). Within the optimal voltage range (2.0–3.0 V), the degradation rate of ciprofloxacin hydrochloride (CIP) by the GF / Sch electrode-1 can reach over 90%.

[0107] During the experiment, the detection of free radicals revealed the generation of hydroxyl radicals and sulfate radicals, as shown in the attached diagram. Figure 4 As shown, the presence of hydroxyl radicals and sulfate radicals is a key factor in promoting the improvement of electro-Fenton efficiency.

[0108] like Figure 5As shown, under a voltage of 2.0V, the pH values ​​of the solutions listed in Table 1 were adjusted during the experiment. It was found that the solutions in the pH range of 3-7 had a good degradation effect on ciprofloxacin hydrochloride (CIP), indicating that it has a relatively broad range of applications in water treatment.

[0109] Within a voltage range of 2.0–3.0 V, the electro-Fenton effect achieved a degradation rate of over 88% for tetracycline (TC). This indicates that the GF / Sch electrode-1 is widely used in practical water treatment processes.

[0110] like Figure 7 As shown, at a voltage of 2.0V, the electro-Fenton effect also achieved a degradation effect of over 50% on sulfonamide SMX and tilmicosin TIL, indicating that the GF / Sch electrode-1 has a wide range of practical applications in water treatment.

[0111] Example 3

[0112] This embodiment 3 also provides another GF / Sch electrode and its specific preparation method. The method is basically the same as that in embodiment 1, except that in (1), the graphite felt is soaked in a 1 wt% concentration Triton (X-100) solution for 12 h.

[0113] The rest is the same as in Example 1.

[0114] Overall, the GF / Sch electrode-2, when applied to the electro-Fenton oxidation degradation of tetracycline in wastewater, also showed good degradation effect. However, compared with the GF / Sch electrode-1, the electro-Fenton oxidation degradation effect of tetracycline in wastewater was better than that of the GF / Sch electrode-2.

[0115] The reason is that, compared with GF / Sch electrode-1, the GF / Sch electrode-2 prepared in this embodiment has weaker hydrophilicity than that treated with nitric acid, lower Schersch mineral loading, and fewer defects on the graphite felt substrate.

[0116] Example 4

[0117] This embodiment 4 also provides several other GF / Sch electrodes, the preparation methods of which are the same as in embodiment 1, and the basic information of the GF / Sch electrodes is shown in Table 2.

[0118] Table 2 shows the GF / Sch electrode also provided in Example 4.

[0119] base thickness GF / Sch electrode-3 Graphite felt <![CDATA[1mm,3.13mg / cm 2 Load GF / Sch electrode-4 Graphite felt <![CDATA[5mm,3.13mg / cm 2 Load GF / Sch electrode-5 Graphite felt <![CDATA[3mm,0.94mg / cm 2 Load GF / Sch electrode-6 Graphite felt <![CDATA[3mm,18.8mg / cm 2 Load

[0120] Comparative Example 1

[0121] Comparative Example 1 also provides a GF / Sch electrode-D1 for comparison, which is prepared in the same way as in Example 1, except that:

[0122] GF / Sch electrode-D1, in (1), the graphite felt is soaked in pure water for 12 hours, and the rest is the same as in Example 1;

[0123] In addition, pure graphite felt (GF electrode-D2) is provided in this embodiment for comparison.

[0124] Example 5

[0125] Using the same method as in Example 2, the solution containing ciprofloxacin hydrochloride (CIP) was subjected to electro-Fenton oxidation treatment at a voltage of 2V, and the results are shown in Table 3.

[0126] Table 3 shows the results of electro-Fenton oxidation treatment of solutions containing ciprofloxacin hydrochloride (CIP) (C / C0).

[0127]

[0128]

[0129] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for producing a Schottky mineral-loaded electrode material, characterized by, The method comprises the steps of: 1) preparing a substrate, the surface of which is a hydrophilic surface; treating the substrate with a nitric acid solution and / or triton; preparing a solution containing divalent iron ions, the concentration of the divalent iron ions in the solution being 0.02-0.1 mol / L, and the pH value of the solution being 2-4; the substrate is any one of a graphite felt, a carbon paper and a carbon fiber cloth; 2) keeping the substrate in contact with the solution, adding H2O2 into the solution during the contact, and adjusting the solution with a base to keep the pH value at 2-4; the total amount of the added H2O2 is 1.2-2 times the amount of the divalent iron ions; the H2O2 is added in N times, and the value of N is 4-8; the contact time is 6-24 h, and the temperature is 20-40℃; 3) after the contact, drying the substrate to obtain the electrode material loaded with the schottky mineral.

2. The method of producing a load shkiverite electrode material according to claim 1, characterized in that, in the step 2), the solution is adjusted with a base for N times during the contact to keep the pH value at 2-4; the value of N is 4-8.

3. The method of producing a load schermanite electrode material according to claim 2, characterized by, in the step 2), H2O2 and a base are alternately added into the solution.

4. The method of producing a load shkiverite electrode material according to claim 2, characterized by, in the step 3), after the contact, the substrate is washed first, and then dried.

5. The method of producing a shieierite-loaded electrode material according to any one of claims 1 to 4, characterized by, the organic pollutants in wastewater are treated by electro-Fenton under the condition that the pH value is 2-7.

6. The method of producing a shiehtite-loaded electrode material according to any one of claims 1 to 4, characterized by, the electrode comprises a substrate and a schottky mineral loaded on the substrate; The loading of the schermanite on the substrate is 1 to 18.8 mg / cm 2 ; the schottky mineral is directly grown in situ on the substrate to form the loading; the substrate is any one of a graphite felt, a carbon paper and a carbon fiber cloth.

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