Porous titanium-based tin antimony electrode and preparation method and preparation system device thereof

Abstract

The invention provides a porous titanium-based tin antimony electrode and a preparation method and a preparation system device.The preparation method comprises the steps that 1, an alcohol solvent, acid, tin tetrachloride and antimony trichloride are mixed, then a surfactant is added, mixing is conducted, and a precursor solution is obtained; wherein the surface active agent comprises an ether group surface active agent; and (2) loading a porous titanium substrate with the precursor solution obtained in the step (1), and calcining to obtain the porous titanium-based tin antimony electrode. By adding the ether-based surfactant, the viscosity of the precursor solution can be effectively reduced, and the precursor solution can enter the pore channels of the porous electrode, so that the precursor solution is uniformly distributed on the pore channels and the surface of the porous titanium substrate, and the internal reaction area of the porous titanium substrate is fully and effectively utilized; the porous titanium substrate can be prevented from being exposed, and the service life of the electrode is prolonged.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrodes, and relates to a porous titanium-based tin-antimony electrode, a preparation method thereof, and a preparation system device. Background Art

[0002] Anode materials can be mainly divided into inert anodes (such as Pt or boron-doped diamond, etc.) and active electrodes (such as SnO2 or RuO2, etc.). Although inert anodes have the advantages of high stability, high electrode efficiency, and long service life, their high cost and shortage of electrode materials also restrict their further development.

[0003] Among many active electrodes, tin-antimony electrodes have the advantages of high catalytic activity, wide potential window, low cost, and high stability compared with other active electrodes, and are widely used in various fields, including batteries, electrolysis, electrocatalytic, etc. In addition, the preparation of tin-antimony electrodes is relatively simple and easy to mass-produce, which is also one of the reasons for their popularity.

[0004] At present, the preparation methods of tin-antimony electrodes mainly include: sol-gel method, chemical vapor deposition method, electrodeposition method, and thermal decomposition method. Among them, the sol-gel method is a widely used preparation method. Its advantages are mild reaction conditions, high purity and high homogeneity of the prepared electrode materials. In addition, the sol-gel method has good scalability and can realize the preparation of large-area electrode materials. The sol-gel method is mostly used to prepare flat tin-antimony electrodes. However, flat electrodes do not have a pore structure and have a small effective reaction area. In order to further optimize the performance of tin-antimony electrodes, researchers have improved the electrodes.

[0005] The patent with the publication number CN114249395A provides a preparation method of a tin-antimony embedded lead dioxide electrocatalytic membrane electrode. This method uses anodic oxidation to prepare titanium dioxide nanotubes, and on this basis, a tin-antimony coating and a lead dioxide coating are loaded by thermal decomposition and electrodeposition respectively. However, this patent has the problem of cumbersome preparation process. At the same time, the high viscosity of the precursor solution will make it difficult for the solution to enter the pores of the substrate and the titanium dioxide tubes, resulting in waste of the reaction area, and the exposed titanium substrate will reduce the service life of the electrode. The introduction of lead dioxide also brings the risk of lead dissolution to the electrode, endangering the safety of the human body and the environment.

[0006] Therefore, there is an urgent need to provide a preparation method of a tin-antimony electrode with simple steps, which can reduce the viscosity of the precursor solution, enable the precursor solution to enter the pores of the substrate, avoid the exposure of the substrate, and avoid the risk of lead dissolution. Summary of the Invention

[0007] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide a porous titanium-based tin-antimony electrode, a preparation method thereof, and a preparation system device. By adding an ether-based surfactant, the present invention can effectively reduce the viscosity of the precursor solution, enabling the precursor solution to enter the pores of the porous electrode, so that the pores and surface of the porous titanium substrate are evenly distributed with the precursor solution, making full and effective use of the internal reaction area of the porous titanium substrate, avoiding the exposure of the porous titanium substrate, prolonging the service life of the electrode, and improving the electrode stability. In addition, the preparation method of the present invention has simple steps and does not introduce lead, thus avoiding the risk of lead dissolution.

[0008] To achieve this purpose, the present invention adopts the following technical solutions:

[0009] In the first aspect, the present invention provides a preparation method of a porous titanium-based tin-antimony electrode, and the preparation method includes:

[0010] (1) Mix an alcohol solvent, an acid, tin tetrachloride, and antimony trichloride, and then add a surfactant for mixing to obtain a precursor solution; wherein, the surfactant includes an ether-based surfactant;

[0011] (2) Load the porous titanium substrate with the precursor solution obtained in step (1), and after calcination, obtain the porous titanium-based tin-antimony electrode.

[0012] The present invention provides a preparation method of a porous titanium-based tin-antimony electrode. By adding an ether-based surfactant, the viscosity of the precursor solution can be effectively reduced, making it easier to load the precursor solution. There are a large number of tiny pores inside the porous titanium substrate, and the effective reaction area is large. The precursor solution can enter the pores of the porous electrode, so that the pores and surface of the porous titanium substrate are evenly distributed with the precursor solution, making full and effective use of the internal reaction area of the porous titanium substrate, and avoiding the exposure of the porous titanium substrate, prolonging the service life of the electrode. In addition, the preparation method of the present invention has simple steps and does not introduce lead, thus avoiding the risk of lead dissolution. Therefore, by using the preparation method of the present invention to prepare a porous titanium-based tin-antimony electrode, the electrode reaction efficiency can be improved, the energy consumption can be reduced, the use effect can be enhanced, and the service life can be prolonged.

[0013] Preferably, the alcohol solvent includes any one or a combination of at least two of ethylene glycol, propylene glycol, or butanol.

[0014] Preferably, the acid includes any one or a combination of at least two of citric acid, tartaric acid, or acetic acid.

[0015] In the present invention, the purpose of selecting specific alcohol solvents and acids is to produce an esterification reaction during heating to generate ester substances, which can better adhere to the electrode.

[0016] Preferably, the molar ratio of the alcohol solvent, acid, tin tetrachloride, and antimony trichloride is (100 - 150):(10 - 30):(1 - 5):(0.5 - 1). Among them, the selection range of the alcohol solvent "100 - 150" can be, for example, 100, 110, 120, 130, 140, or 150, etc.; the selection range of the acid "10 - 30" can be, for example, 10, 15, 20, 25, or 30, etc.; the selection range of tin tetrachloride "1 - 5" can be, for example, 1, 2, 3, 4, or 5, etc.; the selection range of antimony trichloride "0.5 - 1" can be, for example, 0.5, 0.6, 0.7, 0.8, 0.9, or 1, etc.

[0017] In the present invention, by adjusting the proportions of the alcohol solvent, acid, tin tetrachloride, and antimony trichloride, that is, increasing the proportions of the alcohol solvent and acid, the viscosity of the precursor solution can be effectively reduced. Within the above proportion range, although the proportions of antimony trichloride and tin tetrachloride are reduced, the sewage degradation ability of the prepared electrode is not reduced.

[0018] In the present invention, when the molar proportions of the alcohol solvent and acid are too high, it will cause the viscosity of the active solution to decrease, making it difficult to adhere to the titanium substrate. The proportions of tin and antimony in it decrease, making it difficult to achieve a large load on the titanium substrate, resulting in waste of alcohol and acid, and ultimately the sewage treatment efficiency of the prepared electrode is poor; when the molar proportions of the alcohol solvent and acid are too low, the viscosity of the active solution increases, and it cannot be evenly dispersed on the titanium substrate, resulting in waste of tin and antimony, and the viscous active solution will enter the pores of the titanium substrate, causing pore blockage, reducing the specific surface area of the electrode, and resulting in poor sewage treatment effect.

[0019] Preferably, the ether-based surfactant includes any one or a combination of at least two of alkylphenol polyoxyethylene ether, Tween, or polyether polyol.

[0020] In the present invention, under the combined action of adjusting the proportions of the alcohol solvent, acid, tin tetrachloride, and antimony trichloride and adding a surfactant, the viscosity of the precursor solution can be significantly reduced.

[0021] Preferably, the molar ratio of the surfactant to the alcohol solvent is (1 - 5):100, for example, it can be 1:100, 2:100, 3:100, 4:100, or 5:100, etc.

[0022] In the present invention, when the molar ratio of the surfactant to the alcohol solvent is too large, it will cause the service life of the porous titanium-based tin-antimony electrode to be significantly reduced, and the water treatment efficiency and energy consumption will increase significantly; when the molar ratio of the surfactant to the alcohol solvent is too small, the viscosity of the precursor solution will be too high, making it difficult to enter the pores of the titanium substrate, and it will accumulate on the surface of the pores, causing blockage, affecting the water treatment efficiency and energy consumption.

[0023] Preferably, the pore size of the porous titanium substrate is 1 - 200 μm, for example, it can be 1 μm, 3 μm, 10 μm, 50 μm, 100 μm, 200 μm, etc.

[0024] As a preferred technical solution of the present invention, the preparation method specifically includes:

[0025] (Ⅰ) At 50 - 90 °C (for example, it can be 50 °C, 60 °C, 70 °C, 80 °C, or 90 °C, etc.), soak the porous titanium substrate with an acid solution to obtain a pretreated porous titanium substrate; wherein, the acid solution includes any one or a combination of at least two of oxalic acid with a concentration of 5 - 10 wt% (for example, it can be 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, etc.), hydrofluoric acid with a concentration of 30 - 50 wt% (for example, it can be 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt%, etc.), or nitric acid with a concentration of 70 - 90 wt% (for example, it can be 70 wt%, 75 wt%, 80 wt%, 85 wt%, or 90 wt%, etc.) (when using a combination of hydrofluoric acid and nitric acid, the soaking temperature is 50 °C, and the soaking time is 0.5 - 1 h, such as 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h, or 1 h, etc.).

[0026] (Ⅱ) Mix an alcohol solvent and an acid, and continuously stir at a speed of 200 - 300 rpm (for example, it can be 200 rpm, 250 rpm, or 300 rpm, etc.) at a temperature of 60 - 80 °C (for example, it can be 60 °C, 70 °C, or 80 °C, etc.) for 0.5 - 1 h (for example, 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h, or 1 h, etc.), then raise the temperature to 85 - 95 °C (for example, it can be 85 °C, 90 °C, or 95 °C, etc.), add stannic chloride and antimony trichloride, and stir and mix for 1.5 - 2 h (for example, 1.5 h, 1.6 h, 1.7 h, 1.8 h, 1.9 h, or 2 h, etc.), and then add an ether-based surfactant and continue to stir and mix for 0.5 - 1 h (for example, 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h, or 1 h, etc.) to obtain a precursor solution.

[0027] Among them, the alcohol solvent includes any one or a combination of at least two of ethylene glycol, propylene glycol, or butanol; the acid includes any one or a combination of at least two of citric acid, tartaric acid, or acetic acid; the ether-based surfactant includes any one or a combination of at least two of alkylphenol polyoxyethylene ether, Tween, or polyether polyol; the molar ratio of the alcohol solvent, acid, stannic chloride, and antimony trichloride is (100 - 150):(10 - 30):(1 - 5):(0.5 - 1); the molar ratio of the surfactant and the alcohol solvent is (1 - 5):100.

[0028] (III) The pretreated porous titanium substrate is loaded with the precursor solution, and then the loaded product is heated at 120 - 140 °C (such as 120 °C, 130 °C or 140 °C, etc.) for 10 - 20 min (such as 10 min, 15 min or 20 min, etc.), and then calcined at 400 - 550 °C (such as 400 °C, 450 °C, 500 °C or 550 °C, etc.) for 1 - 2 h (such as 1 h, 1.5 h or 2 h, etc.) to obtain the porous titanium-based tin-antimony electrode.

[0029] In a second aspect, the present invention provides a preparation system device for a porous titanium-based tin-antimony electrode, and the preparation method described in the first aspect is carried out using the preparation system device for the porous titanium-based tin-antimony electrode.

[0030] The preparation system device for the porous titanium-based tin-antimony electrode includes:

[0031] A mixing device for mixing the raw materials of the precursor solution.

[0032] A loading device for loading the porous titanium substrate.

[0033] A calcining device for calcining the loaded product.

[0034] Among them, the loading device includes a loading main body, the loading main body includes a loading cavity for accommodating the porous titanium substrate, and a first conical cavity and a second conical cavity respectively located on both sides of the loading cavity. The flared ends of the first conical cavity and the second conical cavity are communicated with the loading cavity.

[0035] A precursor solution storage device and a circulation pump are sequentially arranged on the connecting pipeline at the constricted ends of the first conical cavity and the second conical cavity.

[0036] In the preparation system device for the porous titanium-based tin-antimony electrode provided by the present invention, the loading device adopted can improve the loading effect. The porous titanium substrate is placed in the loading cavity, and with the circulation pump as the power source, the precursor solution can be forced to flow into the internal pores of the substrate, thereby preparing an electrode with a more uniform tin-antimony coating. Through this forced over-current method, the precursor solution can only flow through the internal pores of the substrate, so as to achieve uniform loading of the internal pores of the substrate. Due to this characteristic, the porous titanium-based tin-antimony electrode prepared by the present invention has the advantages of ultra-high service life, extremely high reaction efficiency and low energy consumption.

[0037] Preferably, the circulation pump includes a peristaltic pump.

[0038] Preferably, the loading cavity is cylindrical, and the two circular ends of the loading cavity are respectively communicated with the flared ends of the first conical cavity and the second conical cavity.

[0039] Preferably, the circular end area of the load cavity is larger than the flared end area of the first conical cavity and also larger than the flared end area of the second conical cavity.

[0040] Preferably, a first spiral hollow tube is connected to the constricted end of the first conical cavity, and a second spiral hollow tube is connected to the constricted end of the second conical cavity. The output ends of the first spiral hollow tube and the second spiral hollow tube are connected.

[0041] Preferably, the load body is divided into a first body and a second body. Grooves are provided at the centers of the top surfaces of the first body and the second body. After the top surfaces of the first body and the second body are butted, the load cavity is formed; the bottom surfaces of the grooves of the first body and the second body are respectively communicated with the first conical cavity and the second conical cavity.

[0042] Preferably, a silica gel pad A, a silica gel pad B and a silica gel pad A are sequentially stacked between the first body and the second body. Both the silica gel pad A and the silica gel pad B are provided with openings.

[0043] Preferably, the opening size of the silica gel pad A is the same as the bottom surface size of the porous titanium substrate.

[0044] Preferably, the opening size of the silica gel pad B is smaller than the bottom surface size of the porous titanium substrate.

[0045] In the present invention, the opening size of the silica gel pad B is smaller than the bottom surface size of the porous titanium substrate, which can stably press the substrate inside the groove, prevent the substrate from shaking, and avoid the risk of the solution flowing out from the periphery of the substrate.

[0046] Preferably, the top surfaces of the first body and the second body are provided with grooves having the same size. Silica gel pads C are provided on the bottom surfaces of the grooves. The silica gel pads C are provided with openings, and the outer periphery of the silica gel pads C is attached to the inner side wall of the grooves.

[0047] In the present invention, the annular silica gel pads C are placed between the bottom surface of the circular groove and the porous titanium substrate, which can prevent the solution from flowing away along the gap between the groove and the substrate.

[0048] In a third aspect, the present invention provides a porous titanium-based tin-antimony electrode, which is prepared by the preparation method described in the first aspect.

[0049] The system refers to an equipment system, a device system or a production device.

[0050] The numerical ranges described in the present invention not only include the above-listed point values, but also include any point values between the above numerical ranges that are not listed. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the ranges.

[0051] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0052] (1) The present invention provides a method for preparing a porous titanium-based tin-antimony electrode. By adding a surfactant, polyvinyl ether, the viscosity of the precursor solution can be effectively reduced, making it easier to load the precursor solution. There are a large number of tiny pores inside the porous titanium substrate, and the effective reaction area is relatively large. The precursor solution can enter the pores inside the porous electrode, so that the pores and the surface of the porous titanium substrate are evenly distributed with the precursor solution, making full and effective use of the internal reaction area of the porous titanium substrate and avoiding the exposure of the porous titanium substrate, thereby prolonging the service life of the electrode. In addition, the preparation method of the present invention has simple steps and does not introduce lead, avoiding the risk of lead dissolution.

[0053] (2) In the porous titanium-based tin-antimony electrode preparation system device provided by the present invention, the adopted loading device can improve the loading effect. By placing the porous titanium substrate in the loading chamber and using the circulating pump as the power source, the precursor solution can be forced to flow into the pores inside the substrate, and then an electrode with a more uniform tin-antimony coating can be prepared. Through this forced over-current method, the precursor solution can only flow through the pores inside the substrate, thereby achieving uniform loading inside the pores of the substrate.

[0054] (3) The porous titanium-based tin-antimony electrode prepared by the present invention has the advantages of ultra-high service life, extremely high reaction efficiency, and low energy consumption. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 It is a schematic flow chart of the method for preparing a porous titanium-based tin-antimony electrode provided by an embodiment of the present invention;

[0056] Figure 2 It is a schematic diagram of the mixing device provided by an embodiment of the present invention;

[0057] Figure 3 It is a schematic diagram of the loading device provided by an embodiment of the present invention;

[0058] Figure 4 It is a schematic diagram of the second main body, silicone pad A, silicone pad B, and silicone pad C provided by an embodiment of the present invention;

[0059] Figure 5 It is an assembled perspective view of the first main body and the second main body provided by an embodiment of the present invention;

[0060] Figure 6 It is an assembled schematic diagram of the first main body and the second main body provided by an embodiment of the present invention;

[0061] Figure 7 It is a schematic diagram of electrolyzing sewage using the loading device provided by an embodiment of the present invention;

[0062] Wherein, 1 - the first main body; 2 - the second main body; 3 - the precursor solution storage device; 4 - the circulation pump; 5 - the groove; 6 - the second conical cavity; 7 - the second spiral hollow tube; 8 - the silica gel pad A; 9 - the silica gel pad B; 10 - the silica gel pad C; 11 - the first spiral hollow tube; 12 - the screw hole. Specific embodiments

[0063] It should be understood that in the description of the present invention, the orientation or positional relationship indicated by the terms "center", "longitudinal", "transverse", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. is based on the orientation or positional relationship shown in the drawings. It is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of the present invention. In addition, the terms "first", "second", etc. are only used for descriptive purposes and cannot be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, the features defined with "first", "second", etc. may explicitly or implicitly include one or more of such features.

[0064] It should be noted that in the description of the present invention, unless otherwise clearly defined and limited, the terms "set", "connected", "connected to" should be understood in a broad sense. For example, it may be a fixed connection, a detachable connection, or an integral connection; it may be a mechanical connection or an electrical connection; it may be directly connected or indirectly connected through an intermediate medium, and it may be the communication inside two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood through specific circumstances.

[0065] The technical solution of the present invention will be further described below through specific embodiments.

[0066] In one embodiment, the present invention provides a method for preparing a porous titanium-based tin-antimony electrode, and its process is as Figure 1 shown, and the preparation method includes:

[0067] (1) Pretreat the porous titanium substrate to obtain a pretreated porous titanium substrate;

[0068] (2) Mix an alcohol solvent and an acid, then add tin tetrachloride and antimony trichloride for mixing, and then add a surfactant to continue mixing to obtain a precursor solution; use the precursor solution to load the pretreated porous titanium substrate;

[0069] (3) Calcinate the loaded product to obtain the porous titanium-based tin-antimony electrode.

[0070] In another embodiment, the present invention provides a preparation system device for a porous titanium-based tin-antimony electrode, and the preparation system device for the porous titanium-based tin-antimony electrode includes:

[0071] A mixing device for mixing the raw materials of the precursor solution; a loading device for loading the porous titanium substrate; a calcination device for calcining the product after loading;

[0072] Among them, the mixing device includes a mixer and a mixing container placed on the mixer, as Figure 2 shown;

[0073] The loading device includes a loading main body, and the loading main body is divided into a first main body 1 and a second main body 2, as Figure 3 shown. The structures of the two are exactly the same. Circular grooves 5 with a depth of 3 mm are provided at the centers of the top surfaces of the first main body 1 and the second main body 2. Screw holes 12 are provided on the first main body 1 and the second main body 2, and the two can be fixedly connected by screws. A cylindrical loading cavity is formed after the top surfaces of the first main body 1 and the second main body 2 are butted. The loading cavity is used to accommodate the porous titanium substrate, as Figure 5 and Figure 6 shown; The two circular ends of the loading cavity are respectively communicated with a first conical cavity and a second conical cavity 6. The flared ends of the first conical cavity and the second conical cavity 6 are communicated with the loading cavity; the area of the circular end of the loading cavity is larger than the area of the flared end of the first conical cavity and at the same time larger than the area of the flared end of the second conical cavity 6;

[0074] Silicone pad A8, silicone pad B9 and silicone pad A8 are sequentially stacked between the first main body 1 and the second main body 2. The inner diameter of the opening of silicone pad A8 is 35 mm and the thickness is 1 mm; the inner diameter of the opening of silicone pad B9 is 27 mm and the thickness is 2 mm. Annular silicone pads C10 are provided in the circular grooves 5 of the first main body 1 and the second main body 2. The outer diameter of the annular silicone pad C10 is equal to the bottom diameter of the circular groove 5, so that the outer periphery of the annular silicone pad C10 fits with the inner side wall of the circular groove 5; the inner diameter of the annular silicone pad C10 is the same as the diameter of the flared ends of the first conical cavity and the second conical cavity 6, and the thickness of the annular silicone pad C10 is 1 mm, as Figure 4 shown;

[0075] The constricted end of the first conical cavity is connected to a first spiral hollow tube 11, and the constricted end of the second conical cavity 6 is connected to a second spiral hollow tube 7; A precursor solution storage device 3 and a circulation pump 4 are sequentially arranged on the connecting pipeline of the output ends of the first spiral hollow tube 11 and the second spiral hollow tube 7. The circulation pump 4 is a peristaltic pump;

[0076] The calcination device is a muffle furnace.

[0077] Example 1

[0078] This example provides a preparation method of a porous titanium-based tin-antimony electrode, and the preparation method is carried out by using the porous titanium-based tin-antimony electrode preparation system device of the above embodiment; the preparation method includes:

[0079] (1) At 90 °C, the porous titanium substrate is soaked in oxalic acid with a concentration of 10 wt% for 1 h to obtain a pretreated porous titanium substrate; wherein, the diameter of the porous titanium substrate is 35 mm, the thickness is 3 mm, and the pore diameter is 3 μm.

[0080] (2) Ethylene glycol is placed in a stirring container, citric acid is mixed into the ethylene glycol at 80 °C, and the mixture is stirred at a speed of 200 r / min for 0.5 h, then the temperature is raised to 90 °C, tin tetrachloride and antimony trichloride are added and stirred and mixed for 1.5 h, and then Tween is added and stirred and mixed for another 0.5 h to obtain a precursor solution; wherein, the molar ratio of the four substances is ethylene glycol:citric acid:tin tetrachloride:antimony trichloride = 140:30:5:1, and the molar ratio of Tween to ethylene glycol is 5:100;

[0081] (3) The precursor solution is placed in the precursor solution storage device 3, two pretreated porous titanium substrates are respectively placed in the grooves 5 of the first main body 1 and the second main body 2, and the silica gel pad B9 is located between the two substrates. Using a peristaltic pump as the power source, the precursor solution is allowed to flow through the internal pore channels of the substrate to load the substrate for 0.5 h; then the loaded product is heated at 140 °C for 10 min and then calcined at 500 °C for 2 h to obtain a porous titanium-based tin-antimony electrode.

[0082] Example 2

[0083] This example provides a preparation method of a porous titanium-based tin-antimony electrode, and the preparation method is carried out by using the porous titanium-based tin-antimony electrode preparation system device of the above embodiment; the preparation method includes:

[0084] (1) At 50 °C, the porous titanium substrate is soaked in hydrofluoric acid with a concentration of 50% for 0.5 h to obtain a pretreated porous titanium substrate; wherein, the diameter of the porous titanium substrate is 35 mm, the thickness is 3 mm, and the pore diameter is 10 μm.

[0085] (2) Put ethylene glycol into a stirring container, mix citric acid into the ethylene glycol at 70 °C, continuously stir at a speed of 250 r / min for 1 h, then heat up to 90 °C, add tin tetrachloride and antimony trichloride and stir and mix for 2 h, and then add polyether polyol and continue to stir and mix for 1 h to obtain a precursor solution; among them, the molar ratio of the four substances is ethylene glycol:citric acid:tin tetrachloride:antimony trichloride = 120:20:5:0.5, and the molar ratio of polyether polyol to ethylene glycol is 3:100;

[0086] (3) Put the precursor solution into the precursor solution storage device 3, place 2 pretreated porous titanium substrates in the grooves 5 of the first main body 1 and the second main body 2 respectively, with the silica gel pad B9 located between the 2 substrates, use a peristaltic pump as the power source, make the precursor solution flow through the inner pore channels of the substrates, load the substrates for 15 min; then heat the loaded product at 120 °C for 20 min, and then calcine at 550 °C for 1 h to obtain a porous titanium-based tin-antimony electrode.

[0087] Example 3

[0088] This example provides a preparation method of a porous titanium-based tin-antimony electrode, and the preparation method is carried out by using the porous titanium-based tin-antimony electrode preparation system device of the above-mentioned embodiment; the preparation method includes:

[0089] (1) Immerse the porous titanium substrate in 80% nitric acid at 70 °C for 0.5 h to obtain a pretreated porous titanium substrate; among them, the diameter of the porous titanium substrate is 35 mm, the thickness is 3 mm, and the pore diameter is 100 μm.

[0090] (2) Put ethylene glycol into a stirring container, mix citric acid into the ethylene glycol at 60 °C, continuously stir at a speed of 300 r / min for 0.5 h, then heat up to 95 °C, add tin tetrachloride and antimony trichloride and stir and mix for 1.5 h, and then add alkylphenol polyoxyethylene ether and continue to stir and mix for 0.5 h to obtain a precursor solution; among them, the molar ratio of the four substances is ethylene glycol:citric acid:tin tetrachloride:antimony trichloride = 100:10:1:1, and the molar ratio of alkylphenol polyoxyethylene ether to ethylene glycol is 1:100;

[0091] [[ID=1⑧]](3) Put the precursor solution into the precursor solution storage device 3, place 2 pretreated porous titanium substrates in the grooves 5 of the first main body 1 and the second main body 2 respectively, with the silica gel pad B9 located between the 2 substrates, use a peristaltic pump as the power source, make the precursor solution flow through the inner pore channels of the substrates, load the substrates for 1 h; then heat the loaded product at 130 °C for 15 min, and then calcine at 400 °C for 2 h to obtain a porous titanium-based tin-antimony electrode.

[0092] Example 4

[0093] The difference between this example and Example 1 is that the molar ratio of ethylene glycol:citric acid:tin tetrachloride:antimony trichloride is adjusted to 160:30:1:0.5, so that the ratio of the total molar amount of ethylene glycol and citric acid to the total molar amount of tin tetrachloride and antimony trichloride is adjusted to 190:1.5.

[0094] The remaining preparation methods and parameters are exactly the same as those in Example 1.

[0095] Example 5

[0096] The difference between this example and Example 1 is that the molar ratio of ethylene glycol:citric acid:tin tetrachloride:antimony trichloride is adjusted to 90:10:5:1, so that the ratio of the total molar amount of ethylene glycol and citric acid to the total molar amount of tin tetrachloride and antimony trichloride is adjusted to 100:6.

[0097] The remaining preparation methods and parameters are exactly the same as those in Example 1.

[0098] Example 6

[0099] The difference between this example and Example 1 is that the molar ratio of Tween and ethylene glycol is adjusted to 6:100.

[0100] The remaining preparation methods and parameters are exactly the same as those in Example 1.

[0101] Example 7

[0102] The difference between this example and Example 1 is that the molar ratio of Tween and ethylene glycol is adjusted to 0.5:100.

[0103] The remaining preparation methods and parameters are exactly the same as those in Example 1.

[0104] Comparative Example 1

[0105] The difference between this comparative example and Example 1 is that Tween is not added when preparing the precursor solution.

[0106] The remaining preparation methods and parameters are exactly the same as those in Example 1.

[0107] Comparative Example 2

[0108] The difference between this comparative example and Example 1 is that Tween is replaced with sodium dodecyl sulfonate.

[0109] The remaining preparation methods and parameters are exactly the same as those in Example 1.

[0110] Comparative Example 3

[0111] The difference between this comparative example and Example 1 lies in that in step (3), instead of using a loading device for loading, the precursor solution is directly brush-coated on the surface of the titanium substrate, and after drying, the porous titanium-based tin-antimony electrode is obtained.

[0112] The remaining preparation methods and parameters are exactly the same as those in Example 1.

[0113] Performance test

[0114] Using the porous titanium-based tin-antimony electrodes provided in the above examples and comparative examples as the anode, and a cathode with a diameter of 3.5 cm (titanium mesh) to electrolyze the thermal power plant sewage. Using the loading device in the above implementation manner as the reaction device for the electrolysis reaction. Specifically, as Figure 7 shown, 1 porous titanium-based tin-antimony anode is placed in the groove 5 of the second main body 2, a silica gel pad A8 is sleeved on its outer periphery, a silica gel pad B9 is placed on its surface, and then a cathode, 1 silica gel pad A8 and the first main body 1 are sequentially arranged, and they are assembled in the above order; at the same time, the precursor solution storage device 3 is replaced with a sewage storage device; after connecting the anode and the cathode to the power supply, the sewage is electrolyzed.

[0115] Adopting the accelerated life experiment process to test the electrode life, so that the electrode life measured in the experiment can be used to predict the life of the electrode operating under actual working conditions. The empirical formula for electrode life prediction is as follows:

[0116] Among them, τ1 and τ2 respectively represent the accelerated experiment life and the life of the electrode operating under actual working conditions (min), i1 and i2 respectively represent the current of the electrode in the accelerated life experiment and the current magnitude of the electrode under actual working conditions (mA), and n is an empirical value, and the common value ranges from 1.4 to 2.0, and the value in this experiment is 1.7.

[0117] In the above electrode accelerated life experiment, the electrode is carried out under the conditions that the electrolyte is 0.5 M H2SO4 and the current density is 500 mA·cm -2 . When the electrode voltage rises by 5 V compared with the initial voltage, it is considered that the electrode fails, and the experimental duration at this time is recorded as the accelerated life of the electrode.

[0118] Test methods for efficiency and energy consumption: The energy consumption values (EEO) required for the electrode to remove pollutants of a unit order of magnitude and the energy consumption (ECTOC) required to remove a unit mass of TOC are used to characterize the energy consumption required in the process of the electrode degrading 4-CP. The calculation formulas of EEO and ECTOC are as follows:

[0119] Among them, U represents the cell voltage (V), I represents the magnitude of the applied current (A), t represents the reaction time (h), V represents the volume of the reaction solution (50 mL), C0 and Ct represent the organic matter concentrations at the initial moment and at the reaction time t respectively, and ΔTOC represents the change value of TOC at time t during the reaction (mg·L -1 ). (The reaction efficiency is calculated based on the time required to remove 90% of the total TOC. The shorter the time, the higher the efficiency, and the energy consumption is also calculated based on this standard)

[0120] The results are shown in Table 1

[0121] Table 1

[0122]

[0123]

[0124] (The service life in the table is the actual life after conversion using the formula)

[0125] Analysis:

[0126] From the results of Examples 1-3, it can be seen that by using the preparation method of the present invention, by regulating the raw material ratio of the precursor solution and introducing an ether-based surfactant, the viscosity of the precursor solution can be significantly reduced, and through the loading device of the present invention, the precursor solution can enter the pores inside the porous electrode, so that the pores and surface of the porous titanium substrate are uniformly loaded with the precursor solution. The prepared porous titanium-based tin-antimony electrode has the advantages of ultra-high service life, extremely high reaction efficiency, and low energy consumption.

[0127] From Examples 1 and 4-5, it can be seen that when the molar ratio of ethylene glycol to citric acid is too large, the viscosity of the active solution will decrease, making it difficult to adhere to the titanium substrate, and the proportion of tin and antimony in it will decrease, making it difficult to achieve a large amount of loading on the titanium substrate, resulting in waste of alcohol and acid, and the efficiency of the finally prepared electrode for treating sewage is poor; when the molar ratio of ethylene glycol to citric acid is too small, the viscosity of the active solution will increase, and it cannot be evenly dispersed on the titanium substrate, resulting in waste of tin and antimony, and the viscous active solution will enter the pores of the titanium substrate, resulting in pore blockage, reducing the specific surface area of the electrode, and causing poor sewage treatment effect.

[0128] From Examples 1 and 6-7, it can be seen that when the molar ratio of Tween to ethylene glycol is too large, the service life of the porous titanium-based tin-antimony electrode will be significantly reduced, and the water treatment efficiency and energy consumption will increase significantly; when the molar ratio of Tween to ethylene glycol is too small, the viscosity of the precursor solution will be too large, making it difficult to enter the pores of the titanium substrate, and it will accumulate on the surface of the pores, causing blockage and affecting the water treatment efficiency and energy consumption.

[0129] It can be seen from Example 1 and Comparative Examples 1-2 that if no surfactant is added when preparing the precursor solution, the viscosity of the precursor solution will be too high, making it difficult to enter the pores of the titanium substrate and causing accumulation on the surface of the pores, resulting in blockage and affecting the water treatment efficiency and energy consumption. If other types of surfactants, such as sodium dodecyl sulfate, are added when preparing the precursor solution, it is difficult to improve the viscosity of the precursor, leading to a reduction in service life and affecting the water treatment efficiency and energy consumption.

[0130] It can be seen from Example 1 and Comparative Examples 1-3 that if the loading is not carried out using the loading device of the present invention but the precursor solution is directly brushed onto the surface of the titanium substrate, it is difficult to penetrate the precursor solution into the pores of the titanium substrate, and only surface loading can be achieved, without being able to utilize the rich pore structure of the titanium substrate.

[0131] The above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived within the technical scope disclosed by the present invention fall within the protection scope and disclosure scope of the present invention.

Claims

1. A preparation method of a porous titanium-based tin-antimony electrode, characterized in that, The preparation method includes: (1) Mix an alcohol solvent, an acid, tin tetrachloride, and antimony trichloride, and then add a surfactant for mixing to obtain a precursor solution; wherein, the surfactant includes an ether-based surfactant; (2) Use the precursor solution described in step (1) to load a porous titanium substrate, and after calcination, obtain the porous titanium-based tin-antimony electrode.

2. The preparation method according to claim 1, characterized in that, The alcohol solvent includes any one or a combination of at least two of ethylene glycol, propylene glycol, or butanol; Preferably, the acid includes any one or a combination of at least two of citric acid, tartaric acid, or acetic acid.

3. The preparation method according to claim 1 or 2, characterized in that, The molar ratio of the alcohol solvent, the acid, tin tetrachloride, and antimony trichloride is (100 - 150):(10 - 30):(1 - 5):(0.5 - 1); Preferably, the ether-based surfactant includes any one or a combination of at least two of alkylphenol polyoxyethylene ether, Tween, or polyether polyol; Preferably, the molar ratio of the surfactant to the alcohol solvent is (1 - 5):

100.

4. The preparation method according to any one of claims 1-3, characterized in that, The pore size of the porous titanium substrate is 1 - 200 μm.

5. The preparation method according to any one of claims 1-4, characterized in that, The specific preparation method includes: (Ⅰ) Immerse the porous titanium substrate in an acid solution at 50 - 90 °C to obtain a pretreated porous titanium substrate; wherein, the acid solution includes any one or a combination of at least two of oxalic acid with a concentration of 5 - 10 wt%, hydrofluoric acid with a concentration of 30 - 50 wt%, or nitric acid with a concentration of 70 - 90 wt%; (Ⅱ) Mix the alcohol solvent and the acid, continuously stir at a speed of 200 - 300 rpm at a temperature of 60 - 80 °C for 0.5 - 1 h, then raise the temperature to 85 - 95 °C, add tin tetrachloride and antimony trichloride for stirring and mixing for 1.5 - 2 h, and then add the ether-based surfactant and continue stirring and mixing for 0.5 - 1 h to obtain a precursor solution; wherein, the alcohol solvent includes any one or a combination of at least two of ethylene glycol, propylene glycol, or butanol; the acid includes any one or a combination of at least two of citric acid, tartaric acid, or acetic acid; the ether-based surfactant includes any one or a combination of at least two of alkylphenol polyoxyethylene ether, Tween, or polyether polyol; the molar ratio of the alcohol solvent, the acid, tin tetrachloride, and antimony trichloride is (100 - 150):(10 - 30):(1 - 5):(0.5 - 1); the molar ratio of the surfactant to the alcohol solvent is (1 - 5):100; (Ⅲ) Use the precursor solution to load the pretreated porous titanium substrate, then heat the loaded product at 120 - 140 °C for 10 - 20 min, and then calcine at 400 - 550 °C for 1 - 2 h to obtain the porous titanium-based tin-antimony electrode.

6. A preparation system device for a porous titanium-based tin-antimony electrode, characterized in that, The preparation method according to any one of claims 1 - 5 is carried out using the porous titanium-based tin-antimony electrode preparation system device; The porous titanium-based tin-antimony electrode preparation system device includes: A mixing device for mixing the raw materials of the precursor solution; A loading device for loading the porous titanium substrate; A calcination device for calcining the loaded product; Among them, the loading device includes a loading body, the loading body includes a loading cavity for accommodating a porous titanium substrate, and a first conical cavity and a second conical cavity respectively located on both sides of the loading cavity. The flared ends of the first conical cavity and the second conical cavity communicate with the loading cavity; A precursor solution storage device and a circulation pump are sequentially arranged on the connecting pipeline at the constricted ends of the first conical cavity and the second conical cavity.

7. The porous titanium-based tin-antimony electrode preparation system device according to claim 6, characterized in that, The loading cavity is cylindrical, and the two circular ends of the loading cavity communicate with the flared ends of the first conical cavity and the second conical cavity respectively; Preferably, the area of the circular end of the loading cavity is larger than the area of the flared end of the first conical cavity and also larger than the area of the flared end of the second conical cavity.

8. The porous titanium-based tin-antimony electrode preparation system device according to claim 6 or 7, characterized in that, The constricted end of the first conical cavity is connected to a first spiral hollow tube, the constricted end of the second conical cavity is connected to a second spiral hollow tube, and the output ends of the first spiral hollow tube and the second spiral hollow tube are connected.

9. The porous titanium-based tin-antimony electrode preparation system device according to any one of claims 6-8, characterized in that, The loading body is divided into a first body and a second body. Grooves are provided at the centers of the top surfaces of the first body and the second body. After the top surfaces of the first body and the second body are butted, the loading cavity is formed; the bottom surfaces of the grooves of the first body and the second body communicate with the first conical cavity and the second conical cavity respectively.

10. A porous titanium-based tin-antimony electrode, characterized in that, The porous titanium-based tin-antimony electrode is prepared by the preparation method according to any one of claims 1-5.

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