Titanium-platinum-ruthenium-tantalum metal oxide composite material and preparation method and application thereof

Abstract

The invention relates to a titanium-platinum-ruthenium-tantalum metal oxide composite material and a preparation method and application thereof.The titanium-platinum-ruthenium-tantalum metal oxide composite material comprises a titanium substrate and a metal oxide coating attached to the surface of the titanium substrate, and the metal oxide coating comprises a titanium oxide, a platinum oxide, a ruthenium oxide and a tantalum oxide; the titanium-platinum-ruthenium-tantalum metal oxide composite material is abbreviated as a TiPtRuTaOx composite material, and the value range of x is 2-3. The TiPtRuTaOx high-catalytic-activity electrode is prepared by regulating and controlling the proportion of Ti, Pt, Ru and Ta in the alloy, adjusting the charge structure on the surface of a matrix and improving the electrochemical active surface, the catalytic activity of an anode material in the water electrolysis process can be improved, the electrolysis energy consumption can be reduced, the degradation energy consumption of an electrochemical oxidation technology in high-chlorine-content organic wastewater can be reduced, and the application prospect is wide. Meanwhile, the production cost of the anode electrode is reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of electrolysis of water, in particular to a titanium platinum ruthenium tantalum metal oxide composite material and a preparation method and application thereof. BACKGROUND

[0002] With the continuous exploitation of oil and natural gas, the amount of produced water is increasing. This produced water is usually high-chlorine organic wastewater with high toxicity and high salt content. Compared with traditional wastewater treatment technology, electrochemical oxidation technology has become an effective and feasible method for treating oil and gas field produced water due to its small footprint, no need to add chemicals and other advantages. In the electrochemical oxidation technology, the selection of anode material is crucial, which needs to have good catalytic activity and durability.

[0003] In chlorine-containing organic wastewater, the main reaction is Cl - Active substances with oxidation function (such as Cl2, ClO - , etc.) formed under the action of electrocatalysis oxidize and degrade organic matter. Therefore, it is necessary to prepare anode materials with high electrocatalytic chlorine evolution reaction (CER) activity and high oxygen evolution potential. Therefore, it is necessary to prepare anode materials with high ClOR (chloride oxidation reaction) activity and high oxygen evolution potential.

[0004] At present, the most advanced electrocatalytic chlorine evolution reaction (CER) catalyst is the so-called dimensionally stable anode (DSA), which is composed of a titanium (Ti) substrate (i.e., base) covered with an electroactive layer of a mixture of ruthenium dioxide (RuO2) and titanium dioxide (TiO2), i.e., a RuO2-TiO2 coated electrode. Subsequently, several metals (Ir, Ta, etc.) were introduced into the RuO2-TiO2 coated electrode to improve the inherent activity of DSA for CER.

[0005] However, due to the scarcity and high price of the noble metal Ir, the cost of the modified DSA is significantly increased. SUMMARY

[0006] Therefore, the present application provides a titanium platinum ruthenium tantalum metal oxide composite material and a preparation method and application thereof. By using platinum instead of the expensive noble metal iridium in the existing DSA, the cost of material manufacturing is reduced, and since the dispersed Pt nanoparticles have activity for ClOR (chloride oxidation reaction), the ClOR (chloride oxidation reaction) selectivity of the composite material is improved, thereby effectively improving the anode reaction catalytic performance of the composite material as a catalyst in oil and gas field produced water and reducing the reaction energy consumption.

[0007] In order to achieve the above object, the present application adopts the following technical solutions.

[0008] According to a first aspect of the present application, there is provided a titanium platinum ruthenium tantalum metal oxide composite material, comprising a titanium substrate and a metal oxide coating layer attached to the surface of the titanium substrate, the metal oxide coating layer comprising titanium oxide, platinum oxide, ruthenium oxide and tantalum oxide, the titanium platinum ruthenium tantalum metal oxide composite material being abbreviated as TiPtRuTaO x The composite material, wherein the value of x ranges from 2 to 3.

[0009] The titanium platinum ruthenium tantalum metal oxide composite material, in the metal oxide coating layer, the molar ratio of titanium oxide, platinum oxide, ruthenium oxide and tantalum oxide in terms of the atomic moles of Ti, Pt, Ru and Ta is (0.35-0.5):(0-0.10):(0.20-0.30):(0.20-0.30), wherein the platinum oxide is not 0.

[0010] The titanium platinum ruthenium tantalum metal oxide composite material, in the titanium platinum ruthenium tantalum metal oxide composite material, the thickness of the metal oxide coating layer is 5-30 μm.

[0011] The titanium platinum ruthenium tantalum metal oxide composite material, the loading amount of the metal metal oxide on the surface of the titanium substrate is 1.5 mg / cm 2 -4 mg / cm 2 .

[0012] In the present application, Pt has good chlorine evolution selectivity, and the use of Pt instead of Ir can reduce the manufacturing cost of the existing electrode material.

[0013] According to a second aspect of the present application, there is provided a preparation method of the titanium platinum ruthenium tantalum oxide composite material, comprising the following steps:

[0014] (1) pretreating a titanium substrate to obtain a pretreated titanium substrate;

[0015] (2) dissolving a platinum compound, a ruthenium compound and a tantalum compound in an inorganic acid solution to obtain a platinum-ruthenium-tantalum mixed metal solution, then mixing the platinum-ruthenium-tantalum mixed metal solution with an organic titanium compound and a mixed solution of citric acid-polyol to obtain a titanium-platinum-ruthenium-tantalum mixed metal solution;

[0016] (3) coating the titanium-platinum-ruthenium-tantalum mixed metal solution obtained in step (2) on the surface of the pretreated titanium substrate, and drying to obtain a titanium substrate containing a titanium-platinum-ruthenium-tantalum metal coating layer;

[0017] (4) Anneal the titanium substrate containing the titanium-platinum-ruthenium-tantalum metal coating obtained in step (3) to obtain a titanium-platinum-ruthenium-tantalum metal oxide composite material; that is, TiPtRuTaO x Composite materials.

[0018] In the above method for preparing titanium-platinum-ruthenium-tantalum oxide composite materials, repeating steps (3) and (4) allows for the preparation of titanium-platinum-ruthenium-tantalum metal oxides (TiPtRuTaO) with different metal oxide loading amounts. x Composite materials.

[0019] In the above preparation method of titanium-platinum-ruthenium-tantalum oxide composite material, in step (1), the pretreatment of the titanium substrate includes: washing the polished titanium substrate in acetone and NaOH solution to remove surface grease, and then washing it with water (e.g., deionized water); and then etching the washed titanium substrate in oxalic acid solution.

[0020] In the above preparation method of titanium-platinum-ruthenium-tantalum oxide composite material, in step (1), the mass concentration of the NaOH solution is 10% to 15%.

[0021] In the above preparation method of titanium-platinum-ruthenium-tantalum oxide composite material, in step (1), the mass concentration of the oxalic acid solution is 10% to 30%.

[0022] In the above-mentioned method for preparing titanium-platinum-ruthenium-tantalum oxide composite materials, in step (2), the platinum compound includes at least one of ammonium chloroplatinate (NH4PtCl6), sodium chloroplatinate (Na2PtCl6), platinum nitrate (e.g., H2[Pt(NO2)6]) and ammonium fluoroplatinate (NH4[PtF6]).

[0023] In the above preparation method of titanium-platinum-ruthenium-tantalum oxide composite material, in step (2), the ruthenium compound includes at least one of sodium ruthenate (Na2H2RuO6) and sodium chlororuthenate (Na3[HRuCl6]).

[0024] In the above preparation method of titanium-platinum-ruthenium-tantalum oxide composite material, in step (2), the tantalum compound includes at least one of tantalum pentachloride (TaCl5), sodium tantalate (Na2TaO3) and tantalum nitrate (H2[Ta(NO3)6]).

[0025] In the above preparation method of titanium-platinum-ruthenium-tantalum oxide composite material, in step (2), the organic titanium compound includes at least one of tetrabutyl titanate (Ti(C4H9O)4) and titanium isopropoxide.

[0026] In the method for preparing the titanium-platinum-ruthenium-tantalum oxide composite material, the organic titanium compound, the platinum compound, the ruthenium compound and the tantalum compound in step (2) are in the molar ratio of Ti:Pt:Ru:Ta = 5-10:0-2:3-5:3-5, and the molar amount of the platinum compound is not 0.

[0027] In the method for preparing the titanium-platinum-ruthenium-tantalum oxide composite material, the organic titanium compound, the platinum compound, the ruthenium compound and the tantalum compound in step (2) are in the molar ratio of Ti:Pt:Ru:Ta = 10:1:5:4.

[0028] In the method for preparing the titanium-platinum-ruthenium-tantalum oxide composite material, the polyol in step (2) includes at least one of diols and triols.

[0029] In the method for preparing the titanium-platinum-ruthenium-tantalum oxide composite material, the diol in step (2) includes at least one of ethylene glycol (C2H6O2), propylene glycol and butylene glycol.

[0030] In the method for preparing the titanium-platinum-ruthenium-tantalum oxide composite material, the triol in step (2) includes glycerol.

[0031] In the method for preparing the titanium-platinum-ruthenium-tantalum oxide composite material, the citric acid and the polyol can form a metal complex with the metal ions, and the polyol is used to promote the dissolution of the organic titanium compound.

[0032] In the method for preparing the titanium-platinum-ruthenium-tantalum oxide composite material, the volume ratio of citric acid (C6H8O7) to polyol in the mixed solution of citric acid-polyol in step (2) is 1:5-1:3.

[0033] In the method for preparing the titanium-platinum-ruthenium-tantalum oxide composite material, the inorganic acid solution in step (2) includes a hydrochloric acid solution.

[0034] In the method for preparing the titanium-platinum-ruthenium-tantalum oxide composite material, the concentration of the hydrochloric acid solution in step (2) is 18.5%-27.75%.

[0035] In the method for preparing the titanium-platinum-ruthenium-tantalum oxide composite material, the coating in step (3) includes any one of electrostatic spraying, coating and pneumatic spraying.

[0036] In the method for preparing the titanium-platinum-ruthenium-tantalum oxide composite material, the mixed slurry (i.e., the iridium-ruthenium mixed solution containing the organic catalyst) in step (3) is coated on the titanium-based substrate, and a constant-temperature drying treatment is performed in a vacuum environment.

[0037] In the method for preparing the titanium-platinum-ruthenium-tantalum oxide composite material, the drying treatment in step (3) includes vacuum drying.

[0038] In the method for preparing the titanium platinum ruthenium tantalum oxide composite material, the drying treatment in step (3) is performed at a temperature of 70-90℃.

[0039] In the method for preparing the titanium platinum ruthenium tantalum oxide composite material, the drying treatment in step (3) is performed for 20-40 minutes.

[0040] In the method for preparing the titanium platinum ruthenium tantalum oxide composite material, the annealing in step (4) is performed at a temperature of 200-400℃.

[0041] In the present application, by controlling the annealing temperature, the adhesion between the titanium substrate and the metal oxide coating can be improved. In addition, a reasonable annealing temperature can also avoid the damage of the annealing treatment to the TiPtRuTaO x The active components in the composite material can have adverse effects, thereby reducing the activity of the catalyst. For example, too high annealing treatment temperature can cause the loss of active components due to the generation of volatile or sublimable substances, thereby reducing the activity of the TiPtRuTaO x The catalytic activity of the composite material.

[0042] In the method for preparing the titanium platinum ruthenium tantalum oxide composite material, the annealing in step (4) is performed for 0.5-3 hours.

[0043] In the method for preparing the titanium platinum ruthenium tantalum oxide composite material, the annealing in step (4) is performed at a temperature of 200-400℃.

[0044] In the present application, a reasonable heating rate is beneficial to the uniform heating of the surface of the material to be treated, and is not prone to cracks and pores, thereby avoiding the exposure of the substrate during the use of the obtained composite material as an electrode, causing the passivation of the Ti substrate, and further causing the deactivation of the electrode.

[0045] In the method for preparing the titanium platinum ruthenium tantalum oxide composite material, the annealing in step (4) is performed in an air or oxygen atmosphere.

[0046] In the present application, the annealing treatment of the titanium platinum ruthenium tantalum metal coating coated on the surface of the titanium substrate can reduce the hardness, improve the machinability, reduce the residual stress, stabilize the size, reduce the deformation and crack tendency, refine the grains, adjust the structure, and eliminate the structural defects.

[0047] In the method for preparing the titanium platinum ruthenium tantalum oxide composite material, the loading amount of the titanium platinum ruthenium tantalum metal oxide on the surface of the titanium substrate in step (5) is 1.5-4 mg / cm 2 .

[0048] In the method for preparing the titanium platinum ruthenium tantalum oxide composite material, the coating thickness of the titanium platinum ruthenium tantalum metal oxide on the surface of the titanium substrate in step (5) is 5-30 microns.

[0049] According to a third aspect of the present application, the titanium platinum ruthenium tantalum metal oxide composite material is applied as a catalyst or electrode for anodic chlorine evolution reaction in electrolysis of seawater or organic wastewater or produced water of oil and gas fields.

[0050] The titanium platinum ruthenium tantalum metal oxide (TiPtRuTaO x ) composite material according to the present application is applied as an electrode for anodic oxygen evolution reaction in electrolysis of water, especially organic wastewater, and has a high oxygen evolution potential, can avoid generation of oxygen evolution side reactions, and the hydroxyl and free chlorine generated on the surface of the electrode can synergistically degrade organic matter in the wastewater, thereby obtaining a high anodic degradation effect.

[0051] In addition, the TiPtRuTaO x composite material according to the present application contains Pt, and has a high degradation performance in a neutral pH and a high Cl environment when used as an electrode. The specific principle is as follows:

[0052] R+·OH ads → intermediates → CO2+H2O

[0053] R+ClO - → intermediates → CO2+H2O+Cl -

[0054] MO X (·OH)+Cl - → MO X (HOCl)+e -

[0055] R+MO X (HClO) → intermediates → MO X +CO2+H2O+Cl - +H +

[0056] The TiPtRuTaO x composite material according to the present application contains Ta, which can reduce the addition amount of Pt, Ru and other metals and enhance the durability of the electrode material. The TiPtRuTaO x composite material according to the present application can be used as a catalyst for degradation of pollutants in high-chlorine organic wastewater.

[0057] In the application, the titanium platinum ruthenium tantalum metal oxide composite material can catalyze degradation of organic matters in oil and gas field produced water when used as an anode reaction catalyst or an anode, and improve the degradation performance of the organic matters.

[0058] In the application, the titanium platinum ruthenium tantalum metal oxide (TiPtRuTaO x ) composite material can degrade more than 90% of organic matters in 2 hours in simulated water of 0.4 mol / L NaCl+0.10 mol / L Na2SO4+100 mg / L phenol.

[0059] The TiPtRuTaO x composite material according to the application can effectively improve the anode reaction catalytic performance of the catalyst in oil and gas field produced water by improving the ClOR (chloride oxidation reaction) selectivity of the electrode material, and reduce the reaction energy consumption.

[0060] In the application, the above technical features can be freely combined to form new technical solutions without conflict.

[0061] The above technical solution provided by the embodiments of the application has the following advantages compared with the prior art.

[0062] (1) The application adjusts the ratio of Ti, Pt, Ru and Ta in the alloy, adjusts the charge structure of the substrate surface, improves the electrochemical active surface, and prepares the TiPtRuTaO x high-catalytic-activity electrode;

[0063] (2) The titanium-based metal oxide electrode of the TiPtRuTaO x composite material prepared by the application replaces the existing titanium-based ruthenium iridium anode, and reduces the production cost of the anode electrode;

[0064] (3) When the TiPtRuTaO x composite material prepared according to the technical solution of the application is used as an anode material or a catalyst, the catalytic activity of the anode material in the water electrolysis process can be improved, and the electrolysis energy consumption can be reduced; in addition, the degradation energy consumption of the electrochemical oxidation technology in high-chlorine-containing organic wastewater can also be reduced;

[0065] (4) When the TiPtRuTaO x composite material according to the application is used for electrolysis of high-chlorine-containing organic wastewater, the COD degradation efficiency can reach 90-100% in 2 hours. BRIEF DESCRIPTION OF DRAWINGS

[0066] The accompanying drawings, which are incorporated into and form part of the specification, illustrate embodiments consistent with the application and, together with the specification, serve to explain the principles of the application.

[0067] Figure 1 TiPtRuTaO prepared for Example 1 in the present application x TiRuTaO in Comparative Example 1 x The chlorine evolution potential diagram of the composite material and commercial Ti / RuO2-IrO2, wherein the electrolyte solution is saturated sodium chloride solution.

[0068] Figure 2 TiPtRuTaO prepared for Example 1 in the present application x TiRuTaO in Comparative Example 1 x The oxygen evolution potential diagram of the composite material and commercial Ti / RuO2-IrO2, wherein the electrolyte solution is 1 mol / L NaOH.

[0069] Figure 3 TiPtRuTaO prepared for Example 1 in the present application x TiRuTaO in Comparative Example 1 x The phenol degradation efficiency diagram of the composite material and commercial Ti / RuO2-IrO2.

[0070] Figure 4 TiPtRuTaO prepared for Example 1 in the present application x TiRuTaO in Comparative Example 1 x The energy consumption diagram of the composite material and commercial Ti / RuO2-IrO2. DETAILED DESCRIPTION

[0071] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are some but not all of the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0072] According to some embodiments of the first aspect of the present application, a titanium platinum ruthenium tantalum metal oxide composite material is provided, comprising a titanium substrate and a metal oxide coating layer attached to the surface of the titanium substrate, the metal oxide coating layer comprising titanium oxide, platinum oxide, ruthenium oxide and tantalum oxide, and the titanium platinum ruthenium tantalum metal oxide composite material is abbreviated as TiPtRuTaO x The composite material, wherein the value range of x is 2-3 (for example, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8 or 2.9).

[0073] According to some embodiments of the first aspect of the present application, in the metal oxide coating, the molar ratio of titanium oxide, platinum oxide, ruthenium oxide and tantalum oxide is (0.35-0.5):(0-0.10):(0.20-0.30):(0.20-0.30) in terms of atomic moles, wherein the platinum oxide is not 0.

[0074] According to some embodiments of the first aspect of the present application, in the metal oxide coating, the molar ratio of titanium oxide, platinum oxide, ruthenium oxide and tantalum oxide is (0.35-0.5):(0.02-0.10):(0.20-0.30):(0.20-0.30) in terms of atomic moles, wherein the platinum oxide is not 0.

[0075] According to some embodiments of the first aspect of the present application, in the metal oxide coating, the molar ratio of titanium oxide, platinum oxide, ruthenium oxide and tantalum oxide is (0.3-0.5):(0.02-0.10):(0.24-0.30):(0.20-0.30) in terms of atomic moles.

[0076] According to some embodiments of the first aspect of the present application, in the titanium platinum ruthenium tantalum metal oxide composite material, the thickness of the metal oxide coating is 5-30 μm (for example, 10 μm, 15 μm, 20 μm, 25 μm or 28 μm).

[0077] According to some embodiments of the first aspect of the present application, the loading amount of the metal metal oxide on the surface of the titanium substrate is 1.5 mg / cm 2 -4 mg / cm 2 (for example, 2 mg / cm 2 , 2.5 mg / cm 2 , 3 mg / cm 2 , 3.5 mg / cm 2 or 3.8 mg / cm 2 ).

[0078] In the present application, Pt has good chlorine evolution selectivity, and the use of Pt instead of Ir can reduce the manufacturing cost of the existing electrode material.

[0079] According to some embodiments of the second aspect of the present application, a preparation method of the above titanium platinum ruthenium tantalum oxide composite material is provided, comprising the following steps:

[0080] (1) pretreating a titanium substrate to obtain a pretreated titanium substrate;

[0081] (2) dissolving a platinum compound, a ruthenium compound and a tantalum compound in an inorganic acid solution to obtain a platinum-ruthenium-tantalum mixed metal solution, and then mixing the platinum-ruthenium-tantalum mixed metal solution with a mixed solution of an organic titanium compound and a citric acid-polyol to obtain a titanium-platinum-ruthenium-tantalum mixed metal solution;

[0082] (3) coating the titanium-platinum-ruthenium-tantalum mixed metal solution obtained in step (2) on a surface of a pretreated titanium substrate, and drying to obtain a titanium-platinum-ruthenium-tantalum metal-containing coated titanium substrate;

[0083] (4) annealing the titanium-platinum-ruthenium-tantalum metal-containing coated titanium substrate obtained in step (3) to obtain a titanium-platinum-ruthenium-tantalum metal oxide composite material; namely, TiPtRuTaO x .

[0084] According to some embodiments of the second aspect of the present application, in the preparation method, steps (3) and (4) are repeated to prepare titanium-platinum-ruthenium-tantalum metal oxide (TiPtRuTaO x ) composite materials with different metal oxide loadings.

[0085] According to some embodiments of the second aspect of the present application, in step (1), the pretreatment of the titanium substrate includes: washing the polished titanium substrate in acetone and a NaOH solution to remove surface grease, and then washing with water (e.g., deionized water); and then etching the washed titanium substrate in an oxalic acid solution.

[0086] According to some embodiments of the second aspect of the present application, in step (1), the mass concentration of the NaOH solution is 10% to 15% (e.g., 11%, 12%, 13% or 14%).

[0087] According to some embodiments of the second aspect of the present application, in step (1), the mass concentration of the oxalic acid solution is 10% to 30% (e.g., 12%, 15%, 20%, 25% or 28%).

[0088] According to some embodiments of the second aspect of the present application, in step (2), the platinum compound includes at least one of ammonium chloroplatinate (NH4PtCl6), sodium chloroplatinate (Na2PtCl6), platinum nitrate (e.g., H2[Pt(NO2)6]) and ammonium fluoroplatinate (NH4[PtF6]).

[0089] According to some embodiments of the second aspect of the present application, in step (2), the ruthenium compound includes at least one of sodium ruthenate (Na2H2RuO6) and sodium chlororuthenate (Na3[HRuCl6]).

[0090] According to some embodiments of the second aspect of the present application, in the step (2), the tantalum compound comprises at least one of tantalum pentachloride (TaCl5), sodium tantalate (Na2TaO3), and tantalum nitrate (H2[Ta(NO3)6]).

[0091] According to some embodiments of the second aspect of the present application, in the step (2), the organic titanium compound comprises at least one of titanium tetrabutoxide (Ti(C4H9O)4) and titanium isopropoxide.

[0092] According to some embodiments of the second aspect of the present application, in the step (2), the organic titanium compound, the platinum compound, the ruthenium compound, and the tantalum compound are in a molar ratio of Ti:Pt:Ru:Ta of 5-10:0-2:3-5:3-5, and the molar amount of the platinum compound is not 0.

[0093] According to some embodiments of the second aspect of the present application, in the step (2), the organic titanium compound, the platinum compound, the ruthenium compound, and the tantalum compound are in a molar ratio of Ti:Pt:Ru:Ta of 10:1:5:4.

[0094] According to some embodiments of the second aspect of the present application, in the step (2), the polyol comprises at least one of diol and triol.

[0095] According to some embodiments of the second aspect of the present application, in the step (2), the diol comprises at least one of ethylene glycol (C2H6O2), propylene glycol, and butylene glycol.

[0096] According to some embodiments of the second aspect of the present application, in the step (2), the triol comprises glycerol.

[0097] In the present application, the citric acid and the polyol can form a metal complex with the metal ions, and in addition, the use of the polyol is advantageous for promoting the dissolution of the organic titanium compound.

[0098] According to some embodiments of the second aspect of the present application, in the step (2), the volume ratio of citric acid (C6H8O7) to polyol in the mixed solution of citric acid-polyol is 1:5-1:3 (for example, 1:4.5, 1:4, or 1:1.35).

[0099] According to some embodiments of the second aspect of the present application, in the step (2), the inorganic acid solution comprises a hydrochloric acid solution.

[0100] According to some embodiments of the second aspect of the present application, in the step (2), the concentration of the hydrochloric acid solution is 18.5%-27.75% (for example, 19%, 20%, 22%, 25%, or 27%).

[0101] According to some embodiments of the second aspect of the present application, in step (3), the coating includes any one of electrostatic spraying, painting, and airbrushing.

[0102] According to some embodiments of the second aspect of the present application, in step (3), the mixed slurry (i.e., the iridium-ruthenium mixed solution containing the organic catalyst) is coated on the titanium-based substrate and dried at a constant temperature in a vacuum environment.

[0103] According to some embodiments of the second aspect of the present application, in step (3), the drying process includes vacuum drying.

[0104] According to some embodiments of the second aspect of the present application, in step (3), the drying process is performed at a temperature of 70-90°C (e.g., 75°C, 80°C, or 85°C).

[0105] According to some embodiments of the second aspect of the present application, in step (3), the drying process is performed for a time period of 5-40 minutes.

[0106] According to some embodiments of the second aspect of the present application, in step (4), the annealing temperature is 200-400°C (e.g., 220°C, 250°C, 280°C, 300°C, 320°C, 350°C, or 380°C).

[0107] In the present application, by controlling the annealing temperature, the adhesion between the titanium substrate and the metal oxide coating is improved. In addition, a reasonable annealing temperature can also avoid the loss of active components due to the generation of volatile or sublimable substances during the annealing process, thereby reducing the activity of the TiPtRuTaO x The active components in the composite material have an adverse effect, thereby reducing the activity of the catalyst. For example, too high an annealing temperature can cause the loss of active components due to the generation of volatile or sublimable substances, thereby reducing the activity of the TiPtRuTaO x catalytic activity of the composite material.

[0108] According to some embodiments of the second aspect of the present application, in step (4), the annealing is performed for a time period of 0.5-3 hours (e.g., 0.8 hours, 1 hour, 1.5 hours, 2 hours, or 2.5 hours).

[0109] According to some embodiments of the second aspect of the present application, in step (4), the annealing is performed by increasing the temperature to the annealing temperature at a rate of 2-5°C / min (e.g., 2.5°C / min, 3°C / min, 3.5°C / min, 4°C / min, or 4.5°C / min).

[0110] In the present application, the reasonable heating rate is beneficial to make the surface of the material to be treated evenly heated, and is not easy to produce cracks and form pores, thereby avoiding the problems that the obtained composite material as an electrode appears substrate exposure in the use process, causes Ti substrate passivation, and further causes electrode deactivation.

[0111] According to some embodiments of the second aspect of the present application, in the step (4), the annealing treatment is performed in an air or oxygen atmosphere.

[0112] In the present application, the annealing treatment of the titanium platinum ruthenium tantalum metal coating coated on the surface of the titanium substrate can reduce hardness, improve machinability; reduce residual stress, stabilize size, reduce deformation and crack tendency; refine grains, adjust structure, and eliminate structure defects.

[0113] According to some embodiments of the second aspect of the present application, in the step (5), the loading amount of the titanium platinum ruthenium tantalum metal oxide on the surface of the titanium substrate is 1.5-4 mg / cm 2 (For example, 2 mg / cm 2 , 2.5 mg / cm 2 , 3 mg / cm 2 , 3.5 mg / cm 2 , or 3.8 mg / cm 2 ).

[0114] According to some embodiments of the second aspect of the present application, in the step (5), the coating thickness of the titanium platinum ruthenium tantalum metal oxide on the surface of the titanium substrate is 5-30 μm (for example, 10 μm, 15 μm, 20 μm, 25 μm, or 28 μm).

[0115] According to the third aspect of the present application, a use of the above-mentioned titanium platinum ruthenium tantalum metal oxide composite material as a catalyst or electrode for anodic chlorine evolution reaction in electrolysis of seawater or organic wastewater or produced water of oil and gas field is provided.

[0116] In the above-mentioned use, when the titanium platinum ruthenium tantalum metal oxide composite material is used as an anode reaction catalyst or an anode in the produced water of oil and gas field, it can catalyze the degradation of organic matter in the produced water of oil and gas field, and improve the degradation performance of organic matter.

[0117] In the above-mentioned use, the titanium platinum ruthenium tantalum metal oxide (TiPtRuTaO x ) composite material can degrade more than 90% of organic matter in 0.4 mol / L NaCl+0.10 mol / L Na2SO4+100 mg / L phenol simulated water within 2 h.

[0118] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present application can be purchased from the market or can be prepared by existing methods.

[0119] In the present application, the products obtained by each of the embodiments and the comparative examples are subjected to performance tests by the following method.

[0120] Electrochemical performance test

[0121] In order to obtain the electrochemical performance of the products obtained by each of the embodiments and the comparative examples in the present application, the products are tested by LSV test using a three-electrode system, in which a Pt electrode is used as the counter electrode, a saturated calomel electrode is used as the reference electrode, and the products obtained by each of the embodiments and the comparative examples are used as the working electrode; the voltage range of the LSV test is 0-2.5 V vs RHE, and the scanning rate is 10 mV / s. In addition, the electrochemical performance of a commercial Ti / RuO2-IrO2 (as a comparative sample) is tested by the same method as described above.

[0122] Degradation test

[0123] In a two-electrode system, a graphite plate (or a titanium plate or stainless steel can also be used) is used as the cathode, and the products obtained by each of the embodiments and Comparative Example 1 are used as the anode, and the products are subjected to degradation test in a saturated sodium chloride solution electrolyte at 10 mA / cm 2 Under constant current, the degradation test is performed in a saturated sodium chloride solution electrolyte. The cathode and the anode have the same geometric area (5*5*2 cm 2 , wherein 2 represents the double sides of the cathode and the anode), and the distance between the plates is 10 mm. In addition, the commercial Ti / RuO2-IrO2 (as a comparative sample) is subjected to degradation test by the same method as described above.

[0124] Example 1

[0125] A titanium platinum ruthenium tantalum metal oxide composite material, which is abbreviated as TiPtRuTaO x The composite material is prepared by the following steps:

[0126] S1, pretreatment of the Ti substrate: the polished Ti plate is washed in acetone and 10% NaOH solution for 30 min to remove surface grease, and then washed thoroughly with deionized water; then the washed Ti plate is etched in a 10 wt% oxalic acid solution for 2 h, and then washed thoroughly with deionized water, and dried to obtain a roughened Ti substrate, i.e., a pretreated Ti substrate;

[0127] S2, preparation of mixed metal solution: 0.05 mmol H2PtCl6·H2O, 0.25 mmol RuCl3·3H2O and 0.20 mmol TaCl5 were weighed and dissolved in 5 mL hydrochloric acid to obtain mixed solution A, 0.50 mmol Ti(C4H9O)4 was weighed and added to a mixed solution (5 mL) of citric acid (C6H8O7) and ethylene glycol (C2H6O2) in a volume ratio of 1:4, and stirred rapidly to form mixed solution B; mixed solution B was quickly poured into mixed solution A and stirred vigorously for 5 min to obtain mixed solution C;

[0128] S3, the mixed solution C obtained in step S2 was uniformly brushed on the surface of the pretreated Ti substrate, and placed in a vacuum drying box at 60°C for drying for 10 min to obtain a Ti plate containing a TiPtRuTa metal coating;

[0129] S4, the coated Ti plate obtained in step S3 was placed in an air atmosphere high-temperature tube furnace, and heated at a rate of 5°C / min to 400°C and calcined for 1 h to obtain TiPtRuTaO -1 , i.e. a titanium-based PtRuTa composite material; x

[0130] S5, steps S3 and S4 were repeated to obtain a TiPtRuTaO x catalyst with a coating thickness of 6-15 μm of metal oxide on the surface of the Ti substrate, wherein the loading of the metal oxide is 2.536 mg / cm 2 .

[0131] The TiPtRuTaO x composite material obtained in this example has an overpotential of 2.0 V when used as an anode for electrolysis of water at a current density of 10 mA / cm 2 .

[0132] The TiPtRuTaO x composite material obtained in this example can degrade more than 90% of organic matter in 2 h at a current density of 10 mA / cm 2 in simulated water of 0.4 mol / L NaCl + 0.10 mol / L Na2SO4 + 100 mg / L phenol.

[0133] Example 2

[0134] A titanium platinum ruthenium tantalum metal oxide composite material, abbreviated as TiPtRuTaO x composite material, a preparation method thereof comprising the following steps:

[0135] ​S1. Pretreatment of Ti substrate: The polished Ti plate was washed in acetone and 10% NaOH solution for 30 min to remove surface grease, and then thoroughly washed with deionized water; the washed Ti plate was then etched in 10wt% oxalic acid solution for 2 h, and then thoroughly washed with deionized water. After drying, a roughened Ti substrate was obtained, that is, the pretreated Ti substrate.

[0136] S2. Preparation of mixed metal solutions: Weigh 0.05 mmol H2PtCl6·H2O, 0.25 mmol RuCl3·3H2O, and 0.20 mmol TaCl5 and dissolve them in 5 mL of hydrochloric acid to obtain mixed solution A. Weigh 0.50 mmol Ti(C4H9O)4 and add it to a mixed solution (5 mL) of citric acid (C6H8O7) and ethylene glycol (C2H6O2) with a volume ratio of 1:4. Stir rapidly to form mixed solution B. Quickly pour mixed solution B into mixed solution A and stir vigorously for 5 min to obtain mixed solution C.

[0137] S3. The mixed solution C obtained in step S2 is uniformly coated on the surface of the pretreated Ti substrate and dried in a vacuum drying oven at 60°C for 10 minutes to obtain a Ti plate containing a TiPtRuTa metal coating.

[0138] S4. Place the Ti plate with the TiPtRuTa metal coating obtained in step S3 into a high-temperature tube furnace with an air atmosphere, and heat it at 2°C for 2 minutes. -1 The temperature was increased to 200℃ and calcined for 1 hour to obtain TiPtRuTaO. x Composite materials;

[0139] S5. Repeat steps S3 and S4 to obtain a TiPtRuTaO coating with a thickness of 6-15 μm on the Ti substrate surface. x catalyst.

[0140] The TiPtRuTaO obtained in this embodiment x When composite materials are used as the anode for water electrolysis, at 10 mA / cm 2 The overpotential at the current density is 1.75V.

[0141] The TiPtRuTaO obtained in this embodiment x The composite material was tested in simulated water containing 0.4 mol / L NaCl + 0.10 mol / L Na₂SO₄ + 100 mg / L phenol at 10 mA / cm². 2 At the given current density, more than 90% of organic matter can be degraded within 2 hours.

[0142] Example 3

[0143] The embodiment provides a preparation method of a titanium platinum ruthenium tantalum metal oxide composite material, which is different from that in the embodiment 1 in that the titanium platinum ruthenium tantalum metal oxide coating thickness of the titanium platinum ruthenium tantalum metal oxide composite material (abbreviated as TiPtRuTaO x composite) prepared is 15-25 microns. Other technical solutions are the same as those in the embodiment 1.

[0144] The TiPtRuTaO x composite obtained in the embodiment is used as an anode for electrolysis of water, and has an overpotential of 1.75 V under a current density of 10 mA / cm 2 .

[0145] The TiPtRuTaO x composite obtained in the embodiment can degrade more than 90% of organic matters within 2 h under a current density of 10 mA / cm 2 in simulated water of 0.4 mol / L NaCl+0.10 mol / L Na2SO4+100 mg / L phenol.

[0146] Comparative example 1

[0147] A titanium ruthenium tantalum metal oxide composite material, abbreviated as TiRuTaO x composite, and the preparation method is different from that in the embodiment 1 in that Ti(C4H9O)4 is not added in the step S2, and other steps and process parameters are the same as those in the embodiment 1. The specific preparation method is as follows:

[0148] S1, pretreatment of the Ti substrate: the polished Ti plate is washed in acetone and a 10% NaOH solution for 30 min to remove surface grease, and then washed with deionized water; then the washed Ti plate is etched in a 10 wt% oxalic acid solution for 2 h, and then washed with deionized water, and dried to obtain a roughened Ti substrate, that is, a pretreated Ti substrate;

[0149] S2, preparation of a mixed metal solution: 0.05 mmol of H2PtCl6·H2O, 0.25 mmol of RuCl3·3H2O and 0.20 mmol of TaCl5 are weighed and dissolved in 5 mL of hydrochloric acid to obtain a mixed solution A, a solution (5 mL) formed by citric acid (C6H8O7) and ethylene glycol (C2H6O2) in a volume ratio of 1:4 is denoted as mixed solution B, and the mixed solution B is quickly poured into the mixed solution A and continuously stirred for 5 min to obtain a mixed solution C;

[0150] S3, the mixed solution C obtained in the step S2 is uniformly brushed on the surface of the pretreated Ti substrate, and then placed in a vacuum drying box at 60 DEG C for drying for 10 minutes to obtain a Ti plate containing a TiRuTa metal coating.

[0151] S4. Place the coated Ti plate obtained in step S3 into a high-temperature tube furnace with an air atmosphere and heat it at 5°C for 5 minutes. -1 The temperature was increased to 400℃ and calcined for 1 hour to obtain TiRuTaO. x Composite materials;

[0152] S5. Repeat steps S3 and S4 to obtain a TiRuTaO coating with a thickness of 6-15 μm on the Ti substrate surface. x catalyst.

[0153] The TiRuTaO obtained in this comparative example x When composite materials are used as the anode for water electrolysis, at 10 mA / cm 2 The overpotential at the current density is 1.75V.

[0154] The TiRuTaO obtained in this comparative example x The composite material was tested in simulated water containing 0.4 mol / L NaCl + 0.10 mol / L Na₂SO₄ + 100 mg / L phenol at 10 mA / cm². 2 At the current density, about 50% of organic matter can be degraded within 2 hours.

[0155] Electrochemical performance and degradation performance

[0156] Figure 1 The TiPtRuTaO prepared in Example 1 of this invention is shown. x Composite material and TiRuTaO in Comparative Example 1 x Chlorine evolution potential curves of composite materials and commercial Ti / RuO2-IrO2 in saturated sodium chloride solution.

[0157] Figure 2 The TiPtRuTaO prepared in Example 1 of this invention is shown. x Composite material and TiRuTaO in Comparative Example 1 x Oxygen evolution potential curves of composite materials and commercial Ti / RuO2-IrO2 in 1 mol / L NaOH solution.

[0158] Figure 3 The TiPtRuTaO prepared in Example 1 of this invention is shown. x Composite material and TiRuTaO in Comparative Example 1 x Phenol degradation efficiency of composite materials and commercial Ti / RuO2-IrO2.

[0159] Figure 4TiPtRuTaO prepared in Example 1 of the present application x The TiPtRuTaO prepared in Example 1 of the present application x The energy consumption of the composite material and the commercial Ti / RuO2-IrO2.

[0160] The energy consumption of the composite material and the commercial Ti / RuO2-IrO2. Figure 1 The energy consumption of the composite material and the commercial Ti / RuO2-IrO2. Figure 2 It can be seen that, Figure 1 The energy consumption of the composite material and the commercial Ti / RuO2-IrO2. Figure 2 The chlorine evolution potential and the oxygen evolution potential of the electrode are explained. Compared with the traditional titanium-based ruthenium-iridium anode (commercial product Ti / RuO2-IrO2), the TiPtRuTaO prepared according to the technical solution of the present application has x The chlorine evolution potential difference of the composite material is small, but the oxygen evolution potential is obviously improved.

[0161] The energy consumption of the composite material and the commercial Ti / RuO2-IrO2. Figure 2 It can be seen that, when the current density is 10mA / cm 2 The oxygen evolution potential of the commercial titanium-based ruthenium-iridium anode (Ti / RuO2-IrO2) is 1.7V, and the oxygen evolution potential of the TiPtRuTaO prepared in Example 1 of the present application x The composite material anode is improved to 2.0V. It can be seen that, Figure 3 The TiPtRuTaO prepared according to the technical solution of the present application has x The TOC (Total Organic Carbon) removal rate of the composite material anode at 120min can reach 95%, which is much higher than that of the commercial Ti / RuO2-IrO2. This is because the TiPtRuTaO x The composite material catalyst has a higher oxygen evolution potential, which can effectively inhibit the generation of the oxygen evolution side reaction. In addition, the TiPtRuTaO x The catalyst has better CIOR selectivity, and the generated Cl2, ClO - and other active substances with oxidation effect can oxidize and degrade the organic matter, so that it has better degradation performance, and thus the reaction energy consumption is also obviously reduced (as shown in Figure 4 ).

Claims

1. A titanium platinum ruthenium tantalum metal oxide composite material, characterized by, The titanium platinum ruthenium tantalum metal oxide composite includes a titanium substrate and a metal oxide coating attached to a surface of the titanium substrate, the metal oxide coating including titanium oxide, platinum oxide, ruthenium oxide, and tantalum oxide, and the titanium platinum ruthenium tantalum metal oxide composite is abbreviated as TiPtRuTaO x The composite material, wherein x is in a range of 2 to 3.

2. The titanium platinum ruthenium tantalum metal oxide composite of claim 1, wherein, The molar ratio of titanium oxide, platinum oxide, ruthenium oxide and tantalum oxide in the metal oxide coating is (0.35-0.5):(0-0.10):(0.20-0.30):(0.20-0.30) in terms of atomic moles, wherein the platinum oxide is not 0. 3.The titanium platinum ruthenium tantalum metal oxide composite material according to claim 1, characterized in that, The thickness of the metal oxide coating in the titanium platinum ruthenium tantalum metal oxide composite material is 5-30 μm.

4. The method of claim 1, wherein the titanium platinum ruthenium tantalum oxide composite is prepared by a process comprising: The loading of metal metal oxide on the surface of the titanium substrate is 1.5 mg / cm 2 ~ 4 mg / cm 2 .

5. A method for producing the titanium platinum ruthenium tantalum oxide composite material according to any one of claims 1 to 4, characterized by, The preparation method comprises the following steps: (1) pretreating a titanium substrate to obtain a pretreated titanium substrate; (2) dissolving platinum compounds, ruthenium compounds and tantalum compounds in an inorganic acid solution to obtain a platinum-ruthenium-tantalum mixed metal solution, and then mixing the platinum-ruthenium-tantalum mixed metal solution with a mixed solution of organic titanium compounds and citric acid-polyol to obtain a titanium-platinum-ruthenium-tantalum mixed metal solution; (3) coating the titanium-platinum-ruthenium-tantalum mixed metal solution obtained in step (2) on the surface of the pretreated titanium substrate, and drying to obtain a titanium substrate containing a titanium-platinum-ruthenium-tantalum metal coating; (4) annealing the titanium substrate with titanium platinum ruthenium tantalum metal coating obtained in step (3) to obtain a titanium platinum ruthenium tantalum metal oxide composite, i.e. TiPtRuTaO x composites. 6.The preparation method of the titanium platinum ruthenium tantalum oxide composite material according to claim 5, characterized in that, In the preparation method, steps (3) and (4) are repeated to prepare titanium platinum ruthenium tantalum metal oxide composite materials with different metal oxide loadings. 7.The preparation method of the titanium platinum ruthenium tantalum oxide composite material according to claim 5, characterized in that, In step (1), the pretreatment of the titanium substrate comprises washing the polished titanium substrate in acetone and NaOH solution to remove surface grease, and then washing with water; and then etching the washed titanium substrate in an oxalic acid solution.

8. The method of claim 7, wherein the titanium platinum ruthenium tantalum oxide composite is prepared by a method comprising: depositing a first layer of titanium platinum ruthenium tantalum oxide on a substrate; and depositing a second layer of titanium platinum ruthenium tantalum oxide on the first layer of titanium platinum ruthenium tantalum oxide. In step (1), the mass concentration of the NaOH solution is 10%-15%, and the mass concentration of the oxalic acid solution is 10%-30%. 9.The preparation method of the titanium platinum ruthenium tantalum oxide composite material according to claim 5, characterized in that, In step (2), the platinum compounds include at least one of ammonium chloroplatinate (NH4PtCl6), sodium chloroplatinate (Na2PtCl6), platinum nitrate (for example, H2[Pt(NO2)6]) and ammonium fluoroplatinate (NH4[PtF6]); The ruthenium compounds include at least one of sodium ruthenate and sodium chlororuthenate; The tantalum compounds include at least one of tantalum pentachloride, sodium tantalate and tantalum nitrate; The organic titanium compounds include at least one of tetrabutyl titanate and titanium isopropoxide.

10. The method of claim 5, wherein the titanium platinum ruthenium tantalum oxide composite is prepared by a process comprising: In step (2), the organic titanium compounds, platinum compounds, ruthenium compounds and tantalum compounds are in a molar ratio of Ti:Pt:Ru:Ta of 5-10:0-2:3-5:3-5, and the amount of substance of the platinum compounds is not 0. ​ 11. The method of claim 10, wherein the titanium platinum ruthenium tantalum oxide composite is prepared by a method comprising: In step (2), the organic titanium compounds, platinum compounds, ruthenium compounds and tantalum compounds are in a molar ratio of Ti:Pt:Ru:Ta of 10:1:5:

4.

12. The method of claim 5, wherein the titanium platinum ruthenium tantalum oxide composite is prepared by a method comprising: The polyol in the step (2) comprises at least one of diol and triol; the diol comprises at least one of ethylene glycol (C2H6O2), propylene glycol and butanediol; the triol comprises glycerol; ​ The inorganic acid solution comprises a hydrochloric acid solution.

13. The method of claim 5, wherein the titanium platinum ruthenium tantalum oxide composite is prepared by a method comprising: depositing a first layer of titanium platinum ruthenium tantalum oxide on a substrate; and depositing a second layer of titanium platinum ruthenium tantalum oxide on the first layer of titanium platinum ruthenium tantalum oxide. In the step (2), the volume ratio of citric acid to polyol in the mixed solution of citric acid and polyol is 1:5 to 1:

3.

14. The method of claim 5, wherein the titanium platinum ruthenium tantalum oxide composite is prepared by a method comprising: depositing a first layer of titanium platinum ruthenium tantalum oxide on a substrate; and depositing a second layer of titanium platinum ruthenium tantalum oxide on the first layer of titanium platinum ruthenium tantalum oxide. In the step (3), the coating comprises any one of electrostatic spraying, coating and pneumatic spraying.

15. The method of claim 5, wherein the titanium platinum ruthenium tantalum oxide composite is prepared by a method comprising: depositing a first layer of titanium platinum ruthenium tantalum oxide on a substrate; and depositing a second layer of titanium platinum ruthenium tantalum oxide on the first layer of titanium platinum ruthenium tantalum oxide. In the step (3), the mixed slurry is coated on a titanium-based substrate and dried at a constant temperature in a vacuum environment.

16. The method of claim 15, wherein the titanium platinum ruthenium tantalum oxide composite is prepared by a method comprising: In the step (3), the drying process comprises vacuum drying.

17. The method of claim 5, wherein the titanium platinum ruthenium tantalum oxide composite is prepared by a method comprising: In the step (4), the annealing process is performed at an annealing temperature of 200-400℃ at a temperature rising rate of 2-5℃ / min for 0.5-3 hours. ​ 18. The method of claim 5, wherein the titanium platinum ruthenium tantalum oxide composite is prepared by a method comprising: In the step (4), the annealing process is performed in an air or oxygen atmosphere. ​ 19. Use of the titanium platinum ruthenium tantalum oxide composite material according to any one of claims 1-5 as a catalyst or electrode for anodic chlorine evolution reaction in electrolysis of seawater or organic wastewater or produced water of oil and gas fields.

20. Use of the titanium platinum ruthenium tantalum oxide composite material according to claim 19 as a catalyst or electrode for anodic chlorine evolution reaction in electrolysis of seawater or organic waste water or produced water from oil and gas fields, characterized in that, The titanium platinum ruthenium tantalum oxide composite material can degrade more than 90% of organic matter in a simulated water of 0.4 mol / L NaCl+0.10 mol / L Na2SO4+100 mg / L phenol within 2 hours.

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