Ti / IrTaOX (at) R catalyst as well as preparation method and application thereof

Abstract

The invention relates to a Ti / IrTaOX-coated R catalyst and a preparation method and application thereof.The preparation method comprises the following steps that 1, iridium salt and tantalum salt are dissolved in hydrochloric acid to obtain a mixed solution A, and then the mixed solution A is mixed with a citric acid-diol mixed solution to obtain a mixed solution B; (2) drying and annealing the mixed solution B to obtain mixed metal oxide powder; (3) mixing the mixed metal oxide powder with an organic catalyst, isopropanol, a Nafion suspension and water in an organic solvent to obtain mixed slurry; and (4) coating the mixed slurry on a titanium-based substrate, and drying to obtain the Ti / IrTaOX (at) R catalyst. Specific functional groups are added into an existing iridium-tantalum metal coating material, so that the prepared titanium-based iridium-tantalum anode material has relatively high CER selectivity, and meanwhile, due to the addition of organic matters, the oxygen evolution potential of an electrode can be improved, side reactions are inhibited, and the reaction energy consumption is reduced.

Description

Technical Field

[0001] This invention relates to the field of water electrolysis, and more particularly to a Ti / IrTaO X @R catalysts, their preparation methods, and applications. Background Technology

[0002] With the continuous extraction of oil and natural gas, the amount of produced water is constantly increasing. This produced water is typically high-chlorinated organic wastewater, characterized by high toxicity and high salinity. Compared with traditional wastewater treatment technologies, electrochemical oxidation technology has become an effective and feasible method for treating oil and gas field produced water due to its advantages such as small footprint and no need for reagent addition. In electrochemical oxidation technology, the selection of the anode material is crucial, requiring good catalytic activity and durability. While traditional titanium-based iridium-tantalum coated electrodes possess efficient redox capabilities to decompose recalcitrant pollutants and strong corrosion resistance in wastewater treatment, their low oxygen evolution potential (OEP) leads to reduced treatment efficiency due to the generation of OEP side reactions during wastewater degradation. Therefore, increasing the OEP of the electrode is an effective way to improve its catalytic efficiency. Summary of the Invention

[0003] In view of this, the present invention provides a Ti / IrTaO X @R catalysts, their preparation methods, and applications: By improving the oxygen evolution potential and CER selectivity of electrode materials, the catalytic performance of catalysts in the anodic reaction of oil and gas field produced water can be effectively enhanced, while reducing reaction energy consumption. Simultaneously, this preparation method enables the large-scale production of titanium-based iridium-tantalum anode materials containing organic catalysts.

[0004] According to the Ti / IrTaO of the present invention X @R catalysts, through the innovative addition of organic functional groups (e.g., amide groups) to the traditional iridium-tantalum metal electrode coating, result in anode materials exhibiting high selectivity for the chlorine evolution reaction (CER). Simultaneously, the addition of organic matter increases the oxygen evolution potential of the electrode, thereby suppressing side reactions and reducing reaction energy consumption. CER activity and selectivity comparable to DSA indicate that organic catalysts are more promising than commonly believed in demanding electrochemical applications. Clearly, there are many opportunities for exploration in the interdisciplinary fields of organic chemistry, inorganic chemistry, and electrochemistry.

[0005] To achieve the above objectives, the present invention adopts the following technical solution.

[0006] According to a first aspect of the present invention, a Ti / IrTaO is provided. X @R catalyst, the Ti / IrTaO XThe @R catalyst comprises a titanium-based substrate and TiO and IrTaO adhering to the surface of the titanium-based substrate. X And amide organic compounds; wherein X is 2 to 3.

[0007] The above Ti / IrTaO X @R catalyst, wherein the amide organic compound includes at least one of N-(4-hydroxyphenyl)acetamide and N-acetyl-o-aminobenzoic acid.

[0008] The above Ti / IrTaO X @R catalyst, wherein the titanium-based substrate is made of titanium-based material.

[0009] The above Ti / IrTaO X @R catalyst, wherein the titanium-based substrate includes any one of titanium plate, titanium mesh, titanium foam and TiO2-NTs.

[0010] TiO2-NTs refers to TiO2 nanotube arrays, which are a form of nano-TiO2. They have a higher specific surface area, can provide dispersion of noble metal particles on their surface, and can bind more stably with metals.

[0011] The above Ti / IrTaO X @R catalyst, the Ti / IrTaO X In the @R catalyst, the molar ratio of iridium to tantalum is 1:1 to 1:9.

[0012] The above Ti / IrTaO X @R catalyst, the organic catalyst is in the Ti / IrTaO X The mass percentage of the @R catalyst is 1–10 wt%.

[0013] According to a second aspect of the present invention, a Ti / IrTaO3 described above is provided. X The preparation method of @R catalyst includes the following steps:

[0014] (1) Dissolve iridium salt and tantalum salt in hydrochloric acid to obtain mixture A, and then mix mixture A with a citric acid-diol mixture to obtain mixture B;

[0015] (2) The mixture B is dried and then annealed to obtain mixed metal oxide powder;

[0016] (3) The mixed metal oxide powder obtained in step (2) is mixed with an organic catalyst, isopropanol, Nafion suspension and water (e.g., ultrapure water or pure water) in an organic solvent to obtain a mixed slurry, i.e., an iridium-tantalum mixture containing an organic catalyst.

[0017] (4) The mixed slurry is coated onto a titanium-based substrate and then dried to obtain Ti / IrTaO. X @R catalyst.

[0018] In the above preparation method, in step (1), the iridium salt includes at least one of iridium chloride (IrCl3), iridium oxide (IrO2), and iridium pentacarbonyl (Ir(CO)5).

[0019] In the above preparation method, in step (1), the tantalum salt includes at least one of tantalum oxide (Ta2O5), tantalum chloride (TaCl5), sodium tantalate (Na2TaO3), and tantalum nitrate (H2[Ta(NO3)6]).

[0020] In the above preparation method, in step (1), the volume ratio of citric acid (C6H8O7) to diol in the citric acid-diol mixed solution is 1:5 to 1:3.

[0021] In the above preparation method, in step (1), the diol includes at least one of ethylene glycol (C2H6O2), propylene glycol, and butanediol.

[0022] In this invention, citric acid and glycol form complexes with metal ions, which is beneficial for coating preparation.

[0023] In the above preparation method, in step (1), the concentration of hydrochloric acid is 18.5% to 27.75%.

[0024] In the above preparation method, the drying process in step (2) includes vacuum drying.

[0025] In the above preparation method, in step (2), the drying temperature is 85-95℃.

[0026] In the above preparation method, the drying time in step (2) is 20 to 40 minutes.

[0027] In the above preparation method, the annealing temperature in step (2) is 200-600℃.

[0028] In the above preparation method, the annealing time in step (2) is 1.5 to 3 hours.

[0029] In the above preparation method, in step (2), the annealing treatment is carried out in an air or oxygen atmosphere.

[0030] In this invention, an oxidation reaction of the metal occurs during the annealing process, resulting in a metal oxide powder with stable dimensions and refined grains.

[0031] In the above preparation method, in step (3), the mass concentration of the Nafion suspension is 0-10%, and the concentration of the Nafion suspension is not 0.

[0032] In this invention, the Nafion suspension acts as a binder.

[0033] In the above preparation method, in step (3), the mixed metal oxide powder, organic catalyst, isopropanol, Nafion suspension and water are mixed in an organic solvent at a mass ratio of (0.9-1.1):(0.9-1.1):(5.8-6.2):(5.8-6.2):(3.8-4.2).

[0034] In the above preparation method, in step (3), the mixed metal oxide powder is mixed with organic catalyst, isopropanol, Nafion suspension and water in an organic solvent at a mass ratio of 1:1:(5.8~6.2):(5.8~6.2):(3.8~4.2).

[0035] In the above preparation method, in step (3), the mixed metal oxide powder is mixed with organic catalyst, isopropanol, Nafion suspension and water in an organic solvent at a mass ratio of 1:1:6:6:4.

[0036] In the above preparation method, in step (3), the organic catalyst includes at least one of N-(4-hydroxyphenyl)acetamide and N-acetyl-o-aminobenzoic acid.

[0037] In this invention, an organic catalyst is introduced onto the iridium-tantalum metal electrode coating. The organic functional groups (e.g., amide groups) present in the organic catalyst can enhance the chlorine evolution selectivity.

[0038] In the above preparation method, in step (3), the organic solvent includes at least one of ethanol and propanol.

[0039] In the above preparation method, the mixing time in step (3) is 3 to 5 hours.

[0040] In the above preparation method, in step (4), the loading amount of the mixed slurry coated on the titanium substrate is 4-6 mg / cm³. 2 .

[0041] In the above preparation method, in step (4), the coating includes any one of electrostatic spraying, coating and pneumatic spraying.

[0042] In the above preparation method, in step (4), the mixed slurry (i.e., the iridium-ruthenium mixture containing an organic catalyst) is coated on a titanium-based substrate and dried at a constant temperature in a vacuum environment.

[0043] In the above preparation method, the constant temperature in step (4) is 15-25℃.

[0044] In the above preparation method, step (4) involves coating the mixed slurry onto the electrode, drying it at a constant temperature in a vacuum environment, and then performing heat treatment in an argon atmosphere.

[0045] The above preparation method further includes the pretreatment of the titanium-based substrate.

[0046] In the above preparation method, the pretreatment of the titanium-based substrate includes: washing the polished titanium-based substrate material in acetone and NaOH solution to remove surface grease, and then washing it with deionized water; then etching the washed titanium-based substrate in oxalic acid solution.

[0047] In the above preparation method, the mass concentration of NaOH solution in the pretreatment of the titanium-based substrate is 10% to 15%.

[0048] In the above preparation method, the oxalic acid solution has a mass concentration of 10% to 30% in the pretreatment of the titanium-based substrate.

[0049] According to a third aspect of the present invention, a Ti / IrTaO3 described above is provided. X @R catalysts are used as catalysts or electrodes for the chlorine evolution reaction at the anode in the electrolysis of seawater, organic wastewater, or produced water from oil and gas fields.

[0050] The Ti / IrTaO according to the present invention X When @R catalysts are used as electrodes for the oxygen evolution reaction at the anode in water electrolysis, especially in organic wastewater, they have a high oxygen evolution potential, which can avoid the generation of oxygen evolution side reactions. The hydroxyl groups and free chlorine generated on the electrode surface can work synergistically to degrade organic matter in wastewater, thereby achieving a high anode degradation effect.

[0051] In the above applications, the Ti / IrTaO X When @R catalysts are used in the anodic reaction of produced water in oil and gas fields, they can catalyze the degradation of organic matter in the produced water and improve the degradation performance of organic matter.

[0052] In the above applications, the Ti / IrTaO X The organic catalyst in the @R catalyst is N-(4-hydroxyphenyl)acetamide, and its loading on the Ti-based electrode surface is 4 mg / cm³. 2 At that time, the Ti / IrTaO XThe @R catalyst can degrade more than 90% of organic matter within 2 hours in simulated water containing 0.25 mol / L NaCl, 0.10 mol / L Na2SO4, and 100 mg / L phenol.

[0053] In this invention, the above-mentioned technical features can be freely combined to form new technical solutions, provided they do not conflict with each other.

[0054] The technical solutions provided in the embodiments of the present invention have the following advantages compared with the prior art:

[0055] (1) This invention prepares Ti / IrTaO X @R catalyst introduces amide-based organic functional groups into the traditional iridium-tantalum metal coating, giving it high CER selectivity. At the same time, the addition of organic matter increases the oxygen evolution potential of the electrode, thereby suppressing the occurrence of side reactions and reducing reaction energy consumption.

[0056] (2) By introducing organic functional groups into the titanium-based iridium-tantalum anode material, the present invention can also improve the performance and stability of the coating by improving the adhesion of the coating, increasing the oxygen evolution potential and suppressing side reactions. Attached Figure Description

[0057] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.

[0058] Figure 1 The Ti / IrTaO prepared in Example 1 of this invention X @R catalyst and titanium-based iridium-tantalum anode material in Comparative Example 1 and chlorine evolution electrode potential diagram of commercial Ti / IrO2-Ta2O5 (saturated sodium chloride solution as electrolyte).

[0059] Figure 2 The Ti / IrTaO prepared in Example 1 of this invention X @R catalyst and titanium-based iridium-tantalum anode material in Comparative Example 1 and commercial Ti / IrO2-Ta2O5 oxygen evolution potential diagram (1 mol / L NaOH as electrolyte).

[0060] Figure 3 The Ti / IrTaO prepared in Example 1 of this invention X Phenol degradation efficiency of @R catalyst compared to titanium-based iridium-tantalum anode material in Comparative Example 1 and commercial Ti / IrO2-Ta2O5.

[0061] Figure 4 The Ti / IrTaO prepared in Example 1 of this invention XEnergy consumption graph of @R catalyst compared to titanium-based iridium-tantalum anode material in Comparative Example 1 and commercial Ti / IrO2-Ta2O5. Detailed Implementation

[0062] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Unless otherwise specified, all raw materials, reagents, instruments, and equipment used in the present invention can be purchased on the market or prepared by existing methods.

[0063] According to some embodiments of the first aspect of the present invention, a Ti / IrTaO is provided. X @R catalyst, the Ti / IrTaO X The @R catalyst comprises a titanium-based substrate, the surface of which contains oxides of titanium, iridium, and tantalum, and an organic catalyst; the Ti / IrTaO X @R catalyst can be represented as Ti / IrTaO X @R catalyst, where X ranges from 2 to 3 (e.g., 2.2, 2.3, 2.4, 2.5, 2.7, 2.8 or 2.9), and R represents an organic catalyst.

[0064] According to some embodiments of the first aspect of the invention, the organic catalyst comprises a compound containing an amide functional group or an amide organic compound.

[0065] That is, this application provides a Ti / IrTaO X @R catalyst, the Ti / IrTaO X The @R catalyst comprises a titanium-based substrate and TiO and IrTaO adhering to the surface of the titanium-based substrate. X And amide organic compounds; wherein X is 2 to 3.

[0066] According to some embodiments of the first aspect of the invention, the organic catalyst comprises at least one of N-(4-hydroxyphenyl)acetamide and N-acetyl-o-aminobenzoic acid.

[0067] According to some embodiments of the first aspect of the present invention, the titanium-based substrate is made of titanium-based material, including any one of titanium plate, titanium mesh, titanium foam and Ti / TiO2-NTs.

[0068] According to some embodiments of the first aspect of the invention, the molar ratio of iridium to tantalum is 1:1 to 1:9 (e.g., 1:2, 1:3, 1:4, 1:5, 1:6, 1:7 or 1:8).

[0069] According to some embodiments of the first aspect of the invention, the organic catalyst is in the Ti / IrTaO X The mass percentage of the @R catalyst is 1 to 10 wt% (e.g., 2 wt%, 3 wt%, 4 wt%, 5 wt%, 7 wt%, 8 wt% or 9 wt%).

[0070] According to a second aspect of the present invention, a Ti / IrTaO3 described above is provided. X The preparation method of @R catalyst includes the following steps:

[0071] (1) Dissolve iridium salt and tantalum salt in hydrochloric acid to obtain mixture A, and then mix mixture A with a citric acid-diol mixture to obtain mixture B;

[0072] (2) The mixture B is dried and then annealed to obtain mixed metal oxide powder;

[0073] (3) The mixed metal oxide powder obtained in step (2) is mixed with an organic catalyst, isopropanol, Nafion suspension and water (e.g., ultrapure water or pure water) in an organic solvent to obtain a mixed slurry, i.e., an iridium-ruthenium mixture containing an organic catalyst.

[0074] (4) The mixed slurry is coated onto a titanium-based substrate and then dried to obtain Ti / IrTaO. X @R catalyst.

[0075] In the above preparation method, in step (1), the iridium salt includes at least one of iridium chloride (IrCl3), iridium oxide (IrO2), and iridium pentacarbonyl (Ir(CO)5).

[0076] In the above preparation method, in step (1), the tantalum salt includes at least one of tantalum oxide (Ta2O5), tantalum chloride (TaCl5), sodium tantalate (Na2TaO3), and tantalum nitrate (H2[Ta(NO3)6]).

[0077] According to some embodiments of the second aspect of the present invention, in step (1), the volume ratio of citric acid (C6H8O7) to diol in the citric acid-diol mixed solution is 1:5 to 1:3 (e.g., 1:4.5, 1:4 or 1:1.35).

[0078] According to some embodiments of the second aspect of the present invention, in step (1), the diol includes at least one of ethylene glycol (C2H6O2), propylene glycol and butanediol.

[0079] In this invention, citric acid and glycol form complexes with metal ions, which is beneficial for coating preparation.

[0080] According to some embodiments of the second aspect of the present invention, in step (1), the concentration of hydrochloric acid is 18.5% to 27.75% (e.g., 19%, 20%, 22%, 25% or 27%).

[0081] According to some embodiments of the second aspect of the present invention, in step (2), the drying process includes vacuum drying, the temperature of the drying process is 85-95°C (e.g., 86°C, 88°C, 90°C or 93°C), and the drying time is 20-40 minutes (e.g., 22 minutes, 25 minutes, 30 minutes, 32 minutes, 35 minutes or 38 minutes).

[0082] According to some embodiments of the second aspect of the present invention, in step (2), the annealing temperature is 200 to 600°C (e.g., 250°C, 300°C, 400°C, 450°C, 500°C or 550°C).

[0083] According to some embodiments of the second aspect of the present invention, in step (2), the annealing time is 1.5 to 3 hours (e.g., 1.8 hours, 2 hours or 2.5 hours).

[0084] According to some embodiments of the second aspect of the present invention, in step (2), the annealing process is carried out in an air or oxygen atmosphere.

[0085] In this invention, an oxidation reaction of the metal occurs during the annealing process, resulting in a metal oxide powder with stable dimensions and refined grains.

[0086] According to some embodiments of the second aspect of the present invention, in step (3), the mixed metal oxide powder is mixed with the organic catalyst, isopropanol, Nafion suspension and water in an organic solvent at a mass ratio of (0.9-1.1):(0.9-1.1):(5.8-6.2):(5.8-6.2):(3.8-4.2), preferably 1:1:(5.8-6.2):(5.8-6.2):(3.8-4.2), and even more preferably 1:1:6:6:4.

[0087] According to some embodiments of the second aspect of the present invention, in step (3), the organic solvent includes at least one of ethanol and propanol.

[0088] According to some embodiments of the second aspect of the present invention, in step (3), the concentration of the Nafion suspension is 0 to 10% (e.g., 1%, 2%, 3%, 5%, 7% or 9%), and the concentration of the Nafion suspension is not 0.

[0089] According to some embodiments of the second aspect of the present invention, in step (3), the organic catalyst comprises at least one of N-(4-hydroxyphenyl)acetamide and N-acetyl-o-aminobenzoic acid.

[0090] In this invention, an organic catalyst is introduced onto the iridium-tantalum metal electrode coating. The organic functional groups (e.g., amide groups) present in the organic catalyst can enhance the chlorine evolution selectivity.

[0091] According to some embodiments of the second aspect of the present invention, in step (3), the organic solvent includes at least one of ethanol and propanol.

[0092] According to some embodiments of the second aspect of the present invention, in step (3), the mixing time is 3 to 5 hours (e.g., 3.2 hours, 3.5 hours, 4 hours, 4.5 hours or 4.8 hours).

[0093] According to some embodiments of the second aspect of the present invention, in step (4), the loading amount of the mixed slurry coated on the titanium substrate is 4-6 mg / cm³. 2 (For example, 4.2 mg / cm) 2 4.5 mg / cm 2 5mg / cm 2 5.2 mg / cm 2 5.5 mg / cm 2 Or 5.8 mg / cm 2 ).

[0094] According to some embodiments of the second aspect of the present invention, in step (4), the coating includes any one of electrostatic spraying, coating and pneumatic spraying.

[0095] According to some embodiments of the second aspect of the present invention, in step (4), the mixed slurry (i.e., the iridium-ruthenium mixture containing an organic catalyst) is coated onto a titanium-based substrate and dried at a constant temperature in a vacuum environment.

[0096] According to some embodiments of the second aspect of the present invention, in step (4), the constant temperature is 15 to 25°C (e.g., 18°C, 20°C, 22°C or 24°C).

[0097] According to some embodiments of the second aspect of the present invention, in step (4), after coating the mixed slurry onto a titanium-based substrate and drying it at a constant temperature in a vacuum environment, the mixture is further subjected to heat treatment in an argon atmosphere.

[0098] According to some embodiments of the second aspect of the present invention, in step (4), the heat treatment in an argon atmosphere is performed at a temperature of 190 to 200°C (e.g., 192°C, 195°C, 197°C or 199°C) for a time of 10 to 20 seconds (e.g., 12 seconds, 15 seconds or 18 seconds).

[0099] According to some embodiments of the second aspect of the present invention, the preparation method further includes pretreatment of the titanium-based substrate.

[0100] According to some embodiments of the second aspect of the present invention, the pretreatment of the titanium-based substrate includes: washing the polished titanium-based substrate in acetone and NaOH solution to remove surface grease, and then washing it with deionized water; and then etching the washed titanium-based substrate in oxalic acid solution.

[0101] In this invention, after the titanium plate undergoes a two-step surface treatment with NaOH solution and oxalic acid, channels or vacancies that allow precious metals to settle can be formed on the surface of the titanium plate.

[0102] According to some embodiments of the second aspect of the present invention, in the pretreatment of the titanium-based substrate, the mass concentration of the NaOH solution is 10% to 15% (e.g., 11%, 12%, 13% or 14%).

[0103] According to some embodiments of the second aspect of the present invention, in the pretreatment of the titanium-based substrate, the mass concentration of the oxalic acid solution is 10% to 30% (e.g., 12%, 15%, 20%, 25% or 28%).

[0104] According to some embodiments of the third aspect of the present invention, a Ti / IrTaO3 described above is provided. X @R catalysts are used as catalysts or electrodes for the chlorine evolution reaction at the anode in the electrolysis of seawater, organic wastewater, or produced water from oil and gas fields.

[0105] In this invention, the Ti / IrTaO X When @R catalysts are used in the anodic reaction of produced water in oil and gas fields, they can catalyze the degradation of organic matter in the produced water and improve the degradation performance of organic matter.

[0106] According to some embodiments of the third aspect of the present invention, the Ti / IrTaO X The organic catalyst in the @R catalyst is N-(4-hydroxyphenyl)acetamide, and its loading on the Ti-based electrode surface is 4 mg / cm³. 2 At that time, the Ti / IrTaOX The @R catalyst can degrade more than 90% of organic matter within 2 hours in simulated water containing 0.25 mol / L NaCl, 0.10 mol / L Na2SO4, and 100 mg / L phenol.

[0107] This invention innovatively adds organic functional groups to the titanium-based iridium-tantalum electrode coating, which not only increases the oxygen evolution potential of the electrode and inhibits the occurrence of oxygen evolution side reactions, but also improves the chlorine evolution selectivity (CER) of the electrode, thereby generating more free chlorine; at the same time, the generation of more free chlorine can synergistically improve the catalytic degradation efficiency of the electrode.

[0108] By increasing organic functional groups, the adhesion, corrosion resistance, and other properties of the coating can be improved. The introduction of organic functional groups can increase the branches and cross-linking points of the molecular chains, enhance the interaction forces between molecules, thereby strengthening the adhesion and density of the coating, making the coating more uniform and stable, and reducing the possibility of solvent penetration.

[0109] In the prior art, the oxygen evolution potential of conventional iridium-tantalum electrodes is 1.5–1.8 V. The Ti / IrTaO prepared according to the technical solution of this invention… X The oxygen evolution potential of the @R catalyst is 1.8–2.0 V (e.g., 1.81 V, 1.85 V, 1.90 V or 1.95 V).

[0110] In this invention, the increase in oxygen evolution potential may be due to the following: Increasing the number of organic functional groups increases the chemical complexity of the coating, leading to an increase in the electron cloud density within the coating. This enhances the electron transfer capability of the oxygen evolution reaction, resulting in an increased oxygen evolution potential. This means that at a given voltage, the energy required for the oxygen evolution reaction to occur on the coating increases, making the coating more stable in an electrochemical environment.

[0111] Furthermore, by introducing organic functional groups into the titanium-based iridium-tantalum electrode coating material, this invention can alter the chemical reactivity of the coating surface, making it less prone to side reactions. For example, by introducing active groups, harmful substances in the surrounding environment can be adsorbed or catalyzed, reducing the likelihood of adverse reactions with the coating. Additionally, increasing the number of organic functional groups can also increase the coating's density and impermeability, reducing the penetration of electrolytes or solvents, thereby lowering the possibility of side reactions.

[0112] Example 1

[0113] A Ti / IrTaO X The preparation method of @R catalyst includes the following steps:

[0114] S1. Wash the polished Ti mesh in acetone and 10% NaOH solution for 30 min to remove surface grease, and then wash it thoroughly with deionized water; then etch the washed Ti mesh in 10wt% oxalic acid solution for 2 h, and then wash it thoroughly with deionized water, and dry it for later use to obtain the pretreated Ti-based electrode.

[0115] S2. Weigh 0.02 mmol IrCl3·H2O and 0.12 mmol TaCl5 and dissolve them in 1 mL of hydrochloric acid to obtain mixture A. Then add mixture A to a mixed solution (2 mL) of citric acid (C6H8O7) and ethylene glycol (C2H6O2) in a volume ratio of 1:4 and stir rapidly to form mixture B.

[0116] S3. Dry the mixture B obtained in step S2 in a vacuum drying oven at 90°C for 30 minutes, and then place it in a high-temperature tube furnace under air atmosphere at 5°C for 1 minute. -1 The temperature was increased to 400℃ and calcined for 1 hour to obtain iridium-tantalum mixed metal oxide powder.

[0117] S4. The iridium-tantalum mixed metal oxide powder obtained in step S3 is mixed with N-(4-hydroxyphenyl)acetamide (organic catalyst), isopropanol, 5% Nafion suspension and ultrapure water in anhydrous ethanol at a mass ratio of 1:1:6:6:4 for 4 hours to form a mixed slurry, namely, an iridium-ruthenium mixed slurry containing an organic catalyst.

[0118] S5. The mixed slurry obtained in step S4 is coated onto the pretreated Ti-based electrode surface using electrostatic spraying to obtain a coated Ti-based electrode. The coating loading on the Ti-based electrode surface is 5 mg / cm³. 2 The coated Ti-based electrode was then dried in a vacuum oven at a constant temperature of 20°C to obtain a titanium-based iridium-tantalum anode material Ti / IrTaO containing an organic catalyst. X @R catalyst, where X = 2.2 to 2.4, and R represents an organic catalyst.

[0119] Example 2

[0120] A Ti / IrTaO X The preparation method of @R catalyst includes the following steps:

[0121] S1. The polished Ti mesh is washed in acetone and 10% NaOH solution for 30 min to remove surface grease, and then thoroughly washed with deionized water; the washed Ti mesh is then etched in 10wt% oxalic acid solution for 2 h, and then thoroughly washed with deionized water, and dried for later use to obtain the pretreated Ti-based electrode.

[0122] S2. Weigh 0.02 mmol IrCl3H2O and 0.08 mmol TaCl5 and dissolve them in 1 mL of hydrochloric acid to obtain mixture A. Then add mixture A to a mixed solution (2 mL) of citric acid (C6H8O7) and ethylene glycol (C2H6O2) with a volume ratio of 1:4 and stir rapidly to form mixture B.

[0123] S3. Dry the mixture B obtained in step S2 in a vacuum drying oven at 90°C for 30 minutes, and then place it in a high-temperature tube furnace under air atmosphere at 5°C for 1 minute. -1 The temperature was increased to 600℃ and calcined for 1 hour to anneal the powder, resulting in iridium-tantalum mixed metal oxide powder.

[0124] S4. The iridium-tantalum mixed metal oxide powder obtained in step S3 is mixed with N-acetyl-o-aminobenzoic acid, isopropanol, 5% Nafion suspension and ultrapure water in anhydrous ethanol at a mass ratio of 1:1:6:6:4 for 4 hours to form a mixed slurry, namely, an iridium-ruthenium mixed slurry containing an organic catalyst.

[0125] S5. The mixed slurry obtained in step S4 is coated onto the pretreated Ti-based electrode using electrostatic spraying, with a loading amount of 4 mg / cm³. 2 A Ti-based electrode with a coating was obtained; then, the Ti-based electrode with the coating was dried in a vacuum oven at a constant temperature of 20°C to obtain a titanium-based iridium-tantalum anode material Ti / IrTaO containing an organic catalyst. X @R catalyst, where X = 2.2 to 2.4, and R represents an organic catalyst.

[0126] Comparative Example 1

[0127] A method for preparing a titanium-based iridium-tantalum anode material includes the following steps:

[0128] S1. Wash the polished Ti mesh in acetone and 10% NaOH solution for 30 min to remove surface grease, and then wash it thoroughly with deionized water; then etch the washed Ti mesh in 10wt% oxalic acid solution for 2 h, and then wash it thoroughly with deionized water, and dry it for later use to obtain the pretreated Ti-based electrode.

[0129] S2. Weigh 0.02 mmol IrCl3·H2O and 0.12 mmol TaCl5 and dissolve them in 1 mL of hydrochloric acid to obtain mixture A. Then add mixture A to a mixed solution (2 mL) of citric acid (C6H8O7) and ethylene glycol (C2H6O2) in a volume ratio of 1:4 and stir rapidly to form mixture B.

[0130] S3. Dry the mixture B obtained in step S2 in a vacuum drying oven at 90°C for 30 minutes, and then place it in a high-temperature tube furnace under air atmosphere at 5°C for 1 minute. -1 The temperature was increased to 400℃ and calcined for 1 hour to obtain iridium-tantalum mixed metal oxide powder.

[0131] S4. The iridium-tantalum mixed metal oxide powder obtained in step S3 is mixed with isopropanol, 5% Nafion suspension and ultrapure water in anhydrous ethanol at a mass ratio of 1:6:6:4 for 4 hours to form a mixed slurry, namely, an iridium-ruthenium mixed slurry containing an organic catalyst.

[0132] S5. The mixed slurry obtained in step S4 is coated onto the pretreated Ti-based electrode surface using electrostatic spraying to obtain a coated Ti-based electrode. The coating loading on the Ti-based electrode surface is 5 mg / cm³. 2 The coated Ti-based electrode was dried in a vacuum oven at a constant temperature of 20°C to obtain the titanium-based iridium-tantalum anode material Ti / IrTaO. X Catalyst, x = 2.2–2.4.

[0133] Electrochemical performance testing

[0134] The Ti / IrTaO prepared in Example 1 of this invention X @R catalyst and titanium-based iridium-tantalum anode material (Ti / IrTaO) obtained in Comparative Example 1 X LSV testing was performed on catalysts and commercial Ti / IrO2-Ta2O5 using a three-electrode system, with a Pt electrode as the counter electrode and a saturated calomel electrode as the reference electrode. The LSV testing voltage range was 0–2.5 V vs RHE, and the scan rate was 10 mV / s.

[0135] Figure 1 The Ti / IrTaO prepared in Example 1 of this invention is shown. X @R catalyst and the titanium-based iridium-tantalum anode material Ti / IrTaO prepared in Comparative Example 1 X Catalyst, and the potential curve of chlorine evolution of commercial Ti / RuO2-IrO2 in saturated sodium chloride solution.

[0136] Figure 2 The Ti / IrTaO prepared in Example 1 of this invention is shown. X @R catalyst and the titanium-based iridium-tantalum anode material Ti / IrTaO obtained in Comparative Example 1 X Catalyst, and the potential curve of commercial Ti / RuO2-IrO2 in 1 mol / L NaOH solution.

[0137] Degradation test

[0138] A two-electrode system is used, with a graphite plate as the cathode (or a titanium plate or stainless steel plate), and the anode using the titanium-based iridium-tantalum anode material Ti / IrTaO containing the organic catalyst prepared in Example 1. X @R catalyst and the titanium-based iridium-tantalum anode material Ti / IrTaO prepared in Comparative Example 1 X Catalysts, and commercial Ti / RuO2-IrO2, at 10 mA / cm 2 Degradation tests were conducted in a saturated sodium chloride solution electrolyte under constant current density. The anode and cathode had equal geometric areas (5*5*2cm²). 2 (where 2 represents the two sides of the anode and cathode), and the distance between the plates is 10mm.

[0139] Figure 3 The Ti / IrTaO titanium-based iridium-tantalum anode material containing an organic catalyst prepared in Example 1 of this invention is shown. X @R catalyst and the titanium-based iridium-tantalum anode material Ti / IrTaO obtained in Comparative Example 1 X Catalysts, and the phenol degradation efficiency of commercial Ti / RuO2-IrO2.

[0140] Figure 4 The Ti / IrTaO titanium-based iridium-tantalum anode material containing an organic catalyst prepared in Example 1 of this invention is shown. X @R catalyst and the titanium-based iridium-tantalum anode material Ti / IrTaO obtained in Comparative Example 1 X Catalysts, and energy consumption of commercial Ti / IrO2-Ta2O5.

[0141] Depend on Figure 1 and Figure 2 It can be seen that, Figure 1 and Figure 2 The oxygen evolution potential and chlorine evolution potential of the electrodes are explained. Compared with the traditional titanium-based iridium-tantalum anode (commercial product Ti / IrO2-Ta2O5), the titanium-based iridium-tantalum anode material Ti / IrTaO2 containing an organic catalyst prepared according to the technical solution of this invention is superior. X The chlorine evolution potential of the @R catalysts showed little difference, but the oxygen evolution potential was significantly increased.

[0142] Depend on Figure 2 It can be seen that at a current density of 10 mA / cm² 2 At that time, the oxygen evolution potential of commercial iridium-tantalum anodes (Ti / IrO2-Ta2O5) was 1.7V. The Ti / IrTaO2 prepared in Example 1 of this invention... X The oxygen evolution potential of the @R catalyst as an anode material is increased to 2.0V. Figure 3It can be seen that, according to the present invention, Ti / IrTaO X The @R catalyst, used as an anode material, achieved a TOC removal rate of up to 95% after 120 min, significantly higher than the Ti / IrTaO anode material obtained in Comparative Example 1. X Catalysts and commercially available Ti / IrO2-Ta2O5. This is due to Ti / IrTaO X @R catalysts have higher oxygen evolution potentials, which can effectively suppress the formation of oxygen evolution side reactions, thereby significantly reducing reaction energy consumption (e.g., Figure 4 (As shown).

[0143] In summary, the Ti / IrTaO prepared according to the technical solution of this invention... X The @R catalyst achieves a higher oxygen evolution potential, and the generated free chlorine and ·OH and other active substances with oxidizing effects oxidize and degrade organic matter, thereby giving it better degradation performance.

Claims

1. A Ti / IrTaO X @R catalyst, characterized in that, The Ti / IrTaO X The @R catalyst comprises a titanium-based substrate and TiO and IrTaO adhering to the surface of the titanium-based substrate. X And amide organic compounds, wherein X is 2 to 3.

2. The Ti / IrTaO according to claim 1 X @R catalyst, characterized in that, The titanium-based substrate uses titanium-based materials, including any one of titanium plates, titanium mesh, titanium foam, and TiO2-NTs.

3. The Ti / IrTaO according to claim 2 X @R catalyst, characterized in that, The amide organic compound includes at least one of N-(4-hydroxyphenyl)acetamide and N-acetyl-o-aminobenzoic acid.

4. The Ti / IrTaO according to claim 1 X @R catalyst, characterized in that, The Ti / IrTaO X In the @R catalyst, the molar ratio of iridium to tantalum is 1:1 to 1:9; The amide organic compound in the Ti / IrTaO X The mass percentage of the @R catalyst is 1 wt% to 10 wt%.

5. A Ti / IrTaO according to any one of claims 1-4 X The preparation method of @R catalyst is characterized in that, The preparation method includes the following steps: (1) Dissolve iridium salt and tantalum salt in an inorganic acid to obtain a mixture A, and then mix the mixture A with a citric acid-diol mixture to obtain a mixture B; (2) The mixture B obtained in step (1) is dried to obtain an organic-loaded iridium-tantalum coating, and then annealed to obtain a mixed metal oxide powder. (3) The mixed metal oxide powder obtained in step (2) is mixed with an organic catalyst, isopropanol, Nafion suspension and water in an organic solvent to obtain a mixed slurry; (4) The mixed slurry is coated onto a titanium-based substrate and then dried to obtain Ti / IrTaO. X @R catalyst.

6. The Ti / IrTaO according to claim 5 X The preparation method of @R catalyst is characterized in that, In step (1), the iridium salt includes at least one of iridium chloride, iridium oxide, and iridium pentacarbonyl; the tantalum salt includes at least one of tantalum oxide, tantalum chloride, sodium tantalate, and tantalum nitrate.

7. The Ti / IrTaO according to claim 5 X The preparation method of @R catalyst is characterized in that, In step (1), the volume ratio of citric acid to diol in the citric acid-diol mixed solution is 1:5 to 1:

3.

8. The Ti / IrTaO according to claim 5 X The preparation method of @R catalyst is characterized in that, In step (2), the drying process includes vacuum drying; the drying temperature is 85-95°C, and the drying time is 20-40 minutes.

9. The Ti / IrTaO according to claim 5 X The preparation method of @R catalyst is characterized in that, In step (2), the annealing temperature is 200-600℃ and the annealing time is 1.5-3 hours.

10. The Ti / IrTaO according to claim 5 X The preparation method of @R catalyst is characterized in that, In step (2), the annealing process is carried out in an air or oxygen atmosphere.

11. The Ti / IrTaO according to claim 5 X The preparation method of @R catalyst is characterized in that, In step (3), the mixed metal oxide powder is mixed with the organic catalyst, isopropanol, Nafion suspension and water in an organic solvent at a mass ratio of (0.9-1.1):(0.9-1.1):(5.8-6.2):(5.8-6.2):(3.8-4.2).

12. The Ti / IrTaO according to claim 5 X The preparation method of @R catalyst is characterized in that, In step (3), the organic solvent includes at least one of ethanol and propanol; The organic catalyst includes at least one amide organic compound selected from N-(4-hydroxyphenyl)acetamide and N-acetyl-o-aminobenzoic acid.

13. The Ti / IrTaO according to claim 5 X The preparation method of @R catalyst is characterized in that, In step (4), the loading amount of the mixed slurry coated on the titanium substrate is 4-6 mg / cm³. 2 .

14. The Ti / IrTaO according to claim 5 X The preparation method of @R catalyst is characterized in that, In step (4), the coating is performed using either electrostatic spraying or ultrasonic spraying.

15. The Ti / IrTaO according to claim 5 X The preparation method of @R catalyst is characterized in that, In step (4), the mixed slurry is coated onto a titanium-based substrate and dried in a vacuum environment at a constant temperature of 15-25°C.

16. The Ti / IrTaO according to claim 5 X The preparation method of @R catalyst is characterized in that, The preparation method further includes a pretreatment of the titanium substrate, which includes: washing the polished titanium substrate in acetone and NaOH solution, and then washing it with deionized water; and then etching the washed titanium substrate in oxalic acid solution.

17. The Ti / IrTaO according to claim 16 X The preparation method of @R catalyst is characterized in that, In the pretreatment of the titanium-based electrode, the mass concentration of the NaOH solution is 8% to 12%.

18. The Ti / IrTaO according to claim 16 X The preparation method of @R catalyst is characterized in that, The oxalic acid solution has a mass concentration of 15wt% to 30wt%.

19. The application of a Ti / IrTaOX@R catalyst according to any one of claims 1-4 as a catalyst or electrode for the anodic chlorine evolution reaction in the electrolysis of seawater, organic wastewater, or produced water from oil and gas fields.

20. The Ti / IrTaO according to claim 19 X The application of @R catalyst as a catalyst or electrode for the anodic chlorine evolution reaction in the electrolysis of seawater, organic wastewater, or produced water from oil and gas fields is characterized by the following: In the electrolysis of water using produced water from oil and gas fields as feedstock, the Ti / IrTaO... X @R catalyst is used as the anode, wherein the organic catalyst is N-(4-hydroxyphenyl)acetamide, and the loading on the Ti-based substrate surface is 4 mg / cm³. 2 At that time, the Ti / IrTaO X @R catalyst in simulated water containing 0.25 mol / L NaCl, 0.10 mol / L Na₂SO₄, and 100 mg / L phenol, under a constant current of 10 mA / cm². 2 Under these conditions, it can degrade more than 90% of organic matter within 2 hours.

Images