Piezoelectric fuel cell and use thereof

Abstract

The application discloses a piezoelectric fuel cell and application thereof. The electrode of the application comprises a conductive substrate and a catalytic film fixed on the conductive substrate material, and the catalytic film comprises granular tetragonal phase BaTiO3, has good piezoelectric performance, strong active material loading firmness, simple preparation, low cost and other advantages, and can fully utilize mechanical energy and organic wastewater in the environment when used in the fuel cell, so that stable power generation and degradation of organic pollutants are simultaneously realized. Meanwhile, the tetragonal phase BaTiO3 of the catalytic film on the electrode of the application can improve the conductive performance and piezoelectric performance of the electrode by loading SnO2 or doped SnO2, and the electrode loaded with SnO2 or doped with SnO2 also has good piezoelectric performance, strong active material loading firmness, and simultaneously realizes stable power generation and effective degradation of organic pollutants, and is suitable for the fields of environmental protection and energy.

Description

Technical Field

[0001] This invention relates to the field of electrode and battery technology, and more specifically to a piezoelectric fuel cell and its applications. Background Technology

[0002] Rapid industrialization and population growth have generated a significant amount of organic wastewater, which, if discharged directly, could cause serious environmental pollution. However, organic wastewater also contains chemical energy. It is estimated that the chemical energy stored in wastewater worldwide could meet almost one-third of the world's energy needs. Therefore, developing a green and efficient new technology for recovering chemical energy from wastewater is imperative.

[0003] A fuel cell is a power generation device that converts the chemical energy stored in organic matter into electrical energy. It is considered the fourth generation of high-efficiency power generation technology after hydropower, thermal power, and nuclear power. Commonly used fuel cells in current technologies include microbial fuel cells and photocatalytic fuel cells. These utilize the biochemical reactions of microorganisms and light energy to drive the fuel cell's operation, respectively. However, microorganisms have strict requirements regarding the pH value and pollutant concentration of their living environment, while photocatalysis typically requires ultraviolet light, making it unsuitable for large-scale applications.

[0004] Piezoelectric materials are semiconductor materials that can mediate the interconversion of mechanical energy and electrical energy. Piezoelectric catalysis is an emerging, green, and efficient advanced oxidation technology that uses nano- and micro-piezoelectric materials as catalysts. It is commonly used for the treatment of organic wastewater. However, as pollutant concentrations decrease during treatment, it becomes difficult to recover chemical energy and achieve stable power generation during piezoelectric catalysis. Therefore, there is an urgent need to develop a fuel cell that can effectively utilize both the mechanical energy in the environment and the chemical energy of organic pollutants, providing stable power generation and having a wide range of applications. Summary of the Invention

[0005] In order to overcome the problems existing in the prior art, one objective of the present invention is to provide an electrode and a method for preparing the same; another objective of the present invention is to provide a fuel cell and its application.

[0006] The inventive concept of this invention:

[0007] This invention designs a piezoelectric fuel cell. Firstly, the anode of the piezoelectric fuel cell is prepared by repeatedly drop-coating and drying a tetragonal nanophase t-BaTiO3 or a composite material containing tetragonal nanophase t-BaTiO3 (e.g., Sb-SnO2 / t-BaTiO3 composite catalyst) onto a conductive material (e.g., ITO conductive glass). A graphite or metal electrode (e.g., platinum electrode) is used as the cathode, and a membrane separates the anode and cathode chambers, controlling the anode chamber to be in an oxygen-free environment and the cathode chamber to be in an oxygen-rich environment. Simultaneously, wastewater is used as the electrolyte, and organic pollutants in the wastewater are used as "fuel," thereby constructing a complete green fuel cell (e.g., ...). Figure 8 (As shown).

[0008] The working mechanism of this fuel cell is as follows: First, mechanical energy such as ultrasound or stirring is used to excite the anode of the piezoelectric fuel cell to generate a piezoelectric effect. Under anaerobic conditions, this drives the oxidative degradation of organic pollutants while releasing electrons. These released electrons, driven by the piezoelectric field, flow to the cathode through an external circuit, forming a current. This achieves both stable electricity generation through the piezoelectric effect and the degradation of organic pollutants (e.g., ...). Figure 8 (As shown). Currently, microbial fuel cells are driven by bioenergy, and photocatalytic fuel cells are driven by light energy. The fundamental difference between this piezoelectric fuel cell and other fuel cells lies in its driving force: mechanical energy. Mechanical energy excites the nano-piezoelectric catalyst to generate a piezoelectric potential, driving the separation of charge carriers in the piezoelectric catalytic material and producing the following series of redox reactions:

[0009] The anode reaction (Vibration, where e represents electrons and h represents holes) in a piezoelectric fuel cell:

[0010]

[0011] h + +H₂O→·OH+H + +e (2)

[0012] 2·OH + organic matter → CO2 + 2H2O + 2e (3)

[0013] 2h + +Organic matter→CO2+2H+ + (4)

[0014] Cathode reaction:

[0015] O2 + e → O2 - (5)

[0016] ·O2 - +H + +H2O→1.5 H2O2 (6)

[0017] 2H + +2e→H2 (7)

[0018] Based on the above reactions, the piezoelectric fuel cell of the present invention can simultaneously achieve the degradation of organic pollutants and the recovery of chemical energy.

[0019] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0020] In a first aspect, the present invention provides an electrode comprising: a conductive substrate and a catalytic film immobilized on the conductive substrate material;

[0021] The catalytic membrane comprises particulate tetragonal BaTiO3.

[0022] Preferably, the conductive substrate is made of one or more of ITO conductive glass, FTO conductive glass, carbon, and metal.

[0023] More preferably, the conductive substrate is one or more of ITO conductive glass, FTO conductive glass, carbon cloth, titanium plate, copper plate, and nickel plate.

[0024] Preferably, the thickness of the catalytic film is 0.05 μm to 0.60 μm.

[0025] More preferably, the thickness of the catalytic film is 0.10 μm to 0.45 μm.

[0026] Preferably, the impedance of the electrode is 90Ω to 3000Ω.

[0027] More preferably, the impedance of the electrode is 100Ω to 400Ω.

[0028] Preferably, the X-ray diffraction pattern of the tetragonal BaTiO3 has two characteristic peaks at a 2θ position of 44.5° to 45.5°.

[0029] Specifically, the tetragonal BaTiO3 is t-BaTiO3, and the X-ray diffraction pattern is measured under copper target conditions.

[0030] Preferably, the particle size of the granular tetragonal BaTiO3 is 30 nm to 160 nm.

[0031] More preferably, the particle size of the granular tetragonal BaTiO3 is 40 nm to 120 nm.

[0032] Preferably, the catalytic film further includes SnO2 and / or Sb-doped SnO2, and the SnO2 and / or Sb-doped SnO2 is loaded on the surface of the particulate tetragonal BaTiO3.

[0033] More preferably, the catalytic film further includes Sb-doped SnO2, and the Sb-doped SnO2 is loaded on the surface of the particulate tetragonal BaTiO3.

[0034] Preferably, the interplanar spacing of the (200) crystal plane of the Sb-doped SnO2 is 0.24 nm to 0.26 nm.

[0035] Preferably, the Sb-doped SnO2 is granular, and the particle size of the Sb-doped SnO2 is 1 nm to 10 nm.

[0036] Preferably, the mass ratio of Sb to SnO2 in the Sb-doped SnO2 is 0.1:100 to 1.0:100.

[0037] More preferably, the mass ratio of Sb to SnO2 in the Sb-doped SnO2 is 0.2:100 to 0.5:100.

[0038] Preferably, the mass fraction of Sb-doped SnO2 in the catalytic membrane is 0.1% to 1.0%.

[0039] More preferably, the mass fraction of Sb-doped SnO2 in the catalytic membrane is 0.3% to 0.6%.

[0040] Preferably, the catalytic membrane loading in the electrode is 0.01 mg / cm³. 2 ~10mg / cm 2 .

[0041] Preferably, the catalytic membrane loading in the electrode is 0.05 mg / cm³. 2 ~4mg / cm 2 .

[0042] Specifically, at 0.01 mg / cm 2 To illustrate the meaning of the loading amount here, the area of ​​the conductive substrate surface on which the catalytic film is loaded is 1 cm². 2 At that time, the mass of the catalyst film supported on it was 0.01 mg.

[0043] Secondly, the present invention provides a method for preparing an electrode, comprising the following steps:

[0044] 1) The cubic phase barium titanate was calcined to obtain the tetragonal phase BaTiO3;

[0045] 2) The tetragonal BaTiO3 and the binder are mixed and drop-coated onto a conductive substrate to obtain an electrode containing a catalytic film.

[0046] Preferably, the X-ray diffraction pattern of the cubic barium titanate described in step 1) has only one characteristic peak at a position of 2θ of 44.5° to 45.5°.

[0047] Specifically, the cubic BaTiO3 phase is c-BaTiO3, and the X-ray diffraction pattern is measured under copper target conditions. Preferably, the cubic barium titanate phase is purchased from Aladdin Reagents, Inc., with the following product parameters: 99.9% metals basis, particle size <100 nm, CAS number: 12047-27-7.

[0048] Preferably, the calcination temperature in step 1) is 400℃~600℃.

[0049] Preferably, the calcination treatment in step 1) is carried out in an air atmosphere.

[0050] Preferably, the heating rate during calcination in step 1) is 5°C / min to 12°C / min.

[0051] Preferably, the calcination treatment in step 1) takes 1 to 5 hours.

[0052] More preferably, the calcination treatment in step 1) takes 2 to 4 hours.

[0053] Preferably, the mass ratio of the tetragonal BaTiO3 to the binder in step 2) is 0.01 g / mL to 0.8 g / mL.

[0054] More preferably, the mass ratio of the tetragonal BaTiO3 to the binder in step 2) is 0.1 g / mL to 0.5 g / mL.

[0055] Preferably, the adhesive in step 2) is one or more of polyvinyl alcohol (PVA), polyacrylate, and Nafion solution with a mass fraction of 0.05% to 5%.

[0056] Preferably, the solvent in the Nafion solution is water and ethanol, wherein the volume fraction of ethanol is 40% to 60%.

[0057] Preferably, step 2) further includes a drying step, and the drop-coating and drying steps need to be repeated 2 to 6 times.

[0058] More preferably, the drop-coating and drying steps in step 2) need to be repeated 3 to 5 times.

[0059] Preferably, the drying temperature is 80℃~110℃.

[0060] It should be noted that the slurry is prepared by mixing the tetragonal BaTiO3 and the binder described in step 2).

[0061] Preferably, in step 2), the ratio of the mass of the slurry used for drop coating to the area of ​​the conductive substrate to be drop-coated is 0.05 mL / cm². 2 ~5mL / cm 2 .

[0062] More preferably, in step 2), the ratio of the mass of the slurry used for drop coating to the area of ​​the conductive substrate to be drop-coated is 0.08 mL / cm². 2 ~3mL / cm 2 .

[0063] Thirdly, the present invention provides a method for preparing an electrode, comprising the following steps:

[0064] 1) The cubic phase barium titanate was calcined to obtain the tetragonal phase BaTiO3;

[0065] 2) The tetragonal BaTiO3 was dispersed in an organic reagent to obtain a suspension of tetragonal BaTiO3;

[0066] 3) After mixing the tetragonal BaTiO3 suspension with SnCl4 solution and SbCl3 solution, alkali was added and the mixture was calcined to obtain a composite material with Sb-doped SnO2 supported on the surface of tetragonal BaTiO3.

[0067] 4) The composite material and the adhesive are mixed and drop-coated onto a conductive substrate to obtain an electrode containing a catalytic film.

[0068] Preferably, the X-ray diffraction pattern of the cubic barium titanate described in step 1) has only one characteristic peak at a position of 2θ of 44.5° to 45.5°.

[0069] Specifically, the cubic phase BaTiO3 is c-BaTiO3, and the X-ray diffraction pattern is measured under copper target conditions.

[0070] Preferably, step 4) further includes drying and calcination.

[0071] Specifically, the calcination treatment in step 4) is to strengthen the immobilization strength of the catalyst film on the conductive substrate, and at the same time, it can also promote the further transformation of barium titanate into tetragonal BaTiO3 in the composite material. Preferably, the cubic barium titanate is purchased from Aladdin Reagents, Inc., with the following product parameters: 99.9% metals basis, particle size <100nm, CAS number: 12047-27-7.

[0072] Preferably, the heating rate during calcination in steps 1), 3), and 4) is 5–12 °C / min.

[0073] Preferably, the calcination temperature in steps 1), 3), and 4) is 400℃ to 600℃.

[0074] Preferably, the calcination treatments described in steps 1), 3), and 4) are carried out in an air atmosphere.

[0075] Preferably, the calcination treatment time in steps 1) and 4) is 1h to 5h, and the calcination treatment time in step 3) is 0.5h to 2h.

[0076] More preferably, the calcination time in steps 1) and 4) is 2h to 4h, and the calcination time in step 3) is 0.8h to 1.5h.

[0077] Preferably, step 1) further includes a grinding step, and the grinding time is 20 min to 30 min.

[0078] Preferably, the mass ratio of the tetragonal BaTiO3 to the volume ratio of the organic reagent in step 2) is 0.01 g / L to 0.5 g / mL.

[0079] More preferably, the mass ratio of the tetragonal BaTiO3 to the volume ratio of the organic reagent in step 2) is 0.05 g / L to 0.2 g / L.

[0080] Preferably, the organic reagent in the tetragonal BaTiO3 suspension, the solvent in the SnCl4 solution, and the solvent in the SbCl3 solution in step 3) are each individually selected from one or more of methanol, ethanol, ethylene glycol, glycerol, acetone, dimethyl sulfoxide, and N,N-dimethylformamide.

[0081] Preferably, the concentration of the SnCl4 solution in step 3) is 0.1 g / L to 1.0 g / L.

[0082] More preferably, the concentration of the SnCl4 solution in step 3) is 0.2 g / L to 0.6 g / L.

[0083] Preferably, the concentration of the SnCl4 solution in step 3) is 0.5 g / L to 3.0 g / L.

[0084] More preferably, the concentration of the SnCl4 solution in step 3) is 0.8 g / L to 1.5 g / L.

[0085] Preferably, the volume ratio of the tetragonal BaTiO3 suspension, SnCl4 solution, and SbCl3 solution in step 3) is 10:(0.5-5):(0.005-0.05).

[0086] More preferably, the volume ratio of the tetragonal BaTiO3 suspension, SnCl4 solution, and SbCl3 solution in step 3) is 10:(0.8-3):(0.008-0.03).

[0087] Preferably, the mixing operation in step 3) is stirring, and the stirring time is 0.5h to 1.5h.

[0088] Preferably, the alkali in step 3) is one or more of ammonia, sodium hydroxide, and potassium hydroxide.

[0089] More preferably, the alkali in step 3) is ammonia water with a concentration of 0.5 mol / L to 3 mol / L.

[0090] Preferably, step 3) further includes a precipitation step.

[0091] Specifically, the precipitation step involves adding alkali and stirring to fully hydrolyze and precipitate the alkali and salt in the system to form a mixed precursor. This precursor is then calcined to obtain a composite material in which Sb-doped SnO2 is loaded onto the tetragonal BaTiO3 surface.

[0092] Preferably, the precipitation step is maintained by stirring, and the stirring time in the precipitation step is 4h to 10h.

[0093] Preferably, the mass ratio of the composite material to the volume ratio of the adhesive in step 4) is 0.01 g / mL to 0.8 g / mL.

[0094] More preferably, the mass ratio of the composite material to the volume ratio of the adhesive in step 4) is 0.06 g / mL to 0.2 g / mL.

[0095] Preferably, the adhesive in step 4) is one or more of polyvinyl alcohol (PVA), polyacrylate, and Nafion solution with a mass fraction of 0.05% to 5%.

[0096] Preferably, the solvent in the Nafion solution is water and ethanol, and the volume fraction of ethanol is 40% to 60%.

[0097] Preferably, step 4) further includes a drying step, and the drop-coating and drying steps need to be repeated 2 to 6 times.

[0098] More preferably, the drop-coating and drying steps in step 4) need to be repeated 3 to 5 times.

[0099] Preferably, the drying temperature is 80℃~110℃.

[0100] It should be noted that the slurry is prepared by mixing the composite material and the adhesive described in step 4).

[0101] Preferably, in step 2), the ratio of the volume of the slurry used for drop coating to the area of ​​the conductive substrate to be drop-coated is 0.05 mL / cm². 2 ~5mL / cm 2 .

[0102] More preferably, in step 2), the ratio of the volume of the slurry used for drop coating to the area of ​​the conductive substrate to be drop-coated is 0.08 mL / cm². 2 ~3mL / cm 2 .

[0103] Fourthly, the present invention provides a fuel cell comprising: a container, a device for providing mechanical energy, a cathode, an anode, and wastewater containing organic pollutants;

[0104] The cathode and anode are both placed in the container; the anode is the electrode described in the first aspect or the electrode prepared by the preparation method described in the second aspect; and the anode is placed in an electrolyte containing organic wastewater.

[0105] Specifically, the fuel cell may be a single-chamber battery.

[0106] Preferably, the fuel cell further includes a membrane and a separator, wherein the membrane separates the container into a cathode chamber and an anode chamber.

[0107] Specifically, the fuel cell may be a dual-chamber or multi-chamber battery.

[0108] Preferably, the volume of the container is 100mL to 500mL.

[0109] Preferably, the volume of the container is 60mL to 480mL.

[0110] Preferably, the volume ratio of the anode to the wastewater containing organic pollutants is 1:100 to 1:300.

[0111] Preferably, the device providing mechanical energy is at least one of a mixer, an ultrasonic machine, a vibrator, and a pump.

[0112] More preferably, the device providing mechanical energy is an ultrasonic machine, and the container is placed inside the ultrasonic machine.

[0113] Preferably, the cathode is one or more of platinum sheet, graphite, activated carbon fiber, and stainless steel plate.

[0114] More preferably, the cathode material is one or more of platinum sheet, graphite, and activated carbon fiber.

[0115] Preferably, the cathode and anode are identical in shape and size.

[0116] Preferably, the partition is installed directly above the cathode chamber and the anode chamber and is connected to the side walls of the cathode chamber and the anode chamber.

[0117] Specifically, the partition creates conditions for providing an oxygen-free or aerobic environment in the cathode chamber and the anode chamber.

[0118] Preferably, the cathode chamber and the anode chamber have the same volume.

[0119] Preferably, the membrane is one or more of the following: a Nafion 117 perfluorinated membrane, a cellulose acetate ultrafiltration membrane, and a polyvinylidene fluoride microfiltration membrane.

[0120] Preferably, the membrane pore size is 40 nm to 0.50 μm.

[0121] More preferably, the membrane pore size of the diaphragm is 0.20 μm to 0.45 μm.

[0122] Preferably, the wastewater containing organic pollutants further includes a strong electrolyte, which is one or more of potassium sulfate and sodium sulfate.

[0123] Preferably, the concentration of the strong electrolyte in the electrolyte is 0.1 mol / L to 1.0 mol / L.

[0124] Specifically, potassium sulfate and sodium sulfate can improve the conductivity of the electrolyte.

[0125] Preferably, the organic pollutant is one or more of metronidazole, phenol, methylene blue, and formic acid.

[0126] Preferably, the concentration of organic pollutants in the wastewater containing organic pollutants is 50 mg / L to 5000 mg / L.

[0127] More preferably, the concentration of organic pollutants in the wastewater containing organic pollutants is 100 mg / L to 1000 mg / L.

[0128] Fifthly, the present invention provides an application of a fuel cell as described in the fourth aspect in wastewater treatment.

[0129] Sixthly, the present invention provides a method capable of simultaneously treating organic wastewater and generating electricity, comprising the following steps:

[0130] Wastewater containing organic pollutants is added to the container, and the anode of the fuel cell described in the fourth aspect is placed in the wastewater containing organic pollutants.

[0131] By connecting the anode and cathode of the fuel cell described in the fourth aspect and turning on the device that provides mechanical energy, it is possible to simultaneously treat organic wastewater and generate electricity.

[0132] Preferably, the method for simultaneously treating organic wastewater and generating electricity includes the following steps:

[0133] Wastewater containing organic pollutants is added to the anode chamber, and the anode of the fuel cell described in the fourth aspect is placed in the wastewater containing organic pollutants.

[0134] Air or oxygen is introduced into the cathode chamber, and a protective gas is introduced into the anode chamber; the cathode and anode of the fuel cell in the fourth aspect are connected, and the device that provides mechanical energy is turned on, thus realizing the simultaneous treatment of organic wastewater and power generation.

[0135] Specifically, in the initial state, both the anode chamber and the cathode chamber contain wastewater containing organic pollutants; moreover, the wastewater containing organic pollutants contains strong electrolytes and organic wastewater, and the concentrations are the same.

[0136] Preferably, the device for providing mechanical energy is an ultrasonic machine, which is disposed outside the container of the fuel cell in the fourth aspect, and is used to provide mechanical energy to the anode of the fuel cell.

[0137] Preferably, the ultrasonic machine is configured with a power of 60W to 150W and a frequency of 30kHz to 50kHz.

[0138] Preferably, the protective gas is one or more of nitrogen, argon, helium, and neon.

[0139] Preferably, the flow rate of the air or oxygen is 80 mL / min to 120 mL / min.

[0140] Preferably, the flow rate of the protective gas is 80 mL / min to 120 mL / min.

[0141] Preferably, the simultaneous treatment of organic wastewater and power generation is carried out at a temperature of 15°C to 25°C.

[0142] Preferably, the wastewater containing organic pollutants also includes a strong electrolyte, which is one or more of potassium sulfate and sodium sulfate.

[0143] Preferably, the organic pollutant is one or more of metronidazole, phenol, methylene blue, and formic acid.

[0144] Preferably, the concentration of organic pollutants in the wastewater containing organic pollutants is 50 mg / L to 5000 mg / L.

[0145] More preferably, the concentration of organic pollutants in the wastewater containing organic pollutants is 100 mg / L to 1000 mg / L.

[0146] Preferably, the stable current for power generation is 0.8μA to 5μA.

[0147] The beneficial effects of this invention are as follows: The electrode of this invention comprises a conductive substrate and a catalytic membrane immobilized on the conductive substrate material. The catalytic membrane comprises particulate tetragonal BaTiO3, which possesses advantages such as good piezoelectric properties, strong loading of active materials, simple preparation, and low cost. Its application in fuel cells can fully utilize mechanical energy and organic wastewater in the environment, thereby simultaneously achieving stable power generation and degradation of organic pollutants. Specifically:

[0148] (1) The catalytic film on the electrode of the present invention also includes Sb-doped SnO2, thereby further improving the piezoelectric properties of the film and reducing the resistance of the electrode.

[0149] (2) The electrode provided by the present invention has good piezoelectric properties and strong catalytic membrane loading. When used as an anode in a fuel cell, it can achieve stable power generation for at least 2 hours.

[0150] (3) This invention provides a fuel cell (i.e., a piezoelectric catalytic reactor) that uses mechanical energy as the driving force, nano-piezoelectric materials as catalysts and energy converters, and utilizes the piezoelectric effect to convert mechanical energy into piezoelectric potential and catalytically degrade pollutants while recovering electrochemical energy from the pollutants. It can be applied to the field of generating electricity while treating wastewater, so as to solve the problem that the current piezoelectric catalytic process cannot recover chemical energy from pollutants.

[0151] (4) The fuel cell provided by the present invention can be a single-chamber or multi-chamber battery;

[0152] (5) The fuel cell of the present invention can effectively achieve stable power generation and degradation of different types of organic pollutants at normal temperature and pressure. Attached Figure Description

[0153] Figure 1 X-ray powder diffraction patterns of commercial c-BaTiO3 and calcined barium titanate powder.

[0154] Figure 2 The images show X-ray diffraction patterns of the electrode containing the piezoelectric catalytic membrane in Example 2 and the electrode containing the piezoelectric composite catalytic membrane in Example 6.

[0155] Figure 3 The X-ray photoelectron spectrum of the electrode containing the piezoelectric composite catalytic membrane in Example 6 is shown.

[0156] Figure 4 This is a scanning electron microscope image of the electrode containing the t-BaTiO3 catalytic film in Example 2.

[0157] Figure 5This is a transmission electron microscope (TEM) image of the Sb-SnO2 / t-BaTiO3 solid powder from Example 6.

[0158] Figure 6 The piezoelectric microscopy-piezoelectric response diagram and butterfly diagram are of the electrode containing the t-BaTiO3 catalytic film in Example 2 and the electrode containing the Sb-SnO2 / t-BaTiO3 catalytic film layer in Example 6.

[0159] Figure 7 The EIS-Nyquist spectra and equivalent circuit diagrams are shown for the electrode containing the t-BaTiO3 catalytic film in Example 2 and the electrode containing the Sb-SnO2 / t-BaTiO3 catalytic film layer in Example 6.

[0160] Figure 8 This is a schematic diagram illustrating the working principle of the dual-chamber piezoelectric fuel cell in this invention.

[0161] The anode is an electrode with ITO conductive glass as the substrate and Sb-SnO2 / t-BaTiO3 piezoelectric catalytic membrane as the electrode; the cathode is a Pt sheet electrode; the diaphragm is a PVDF thin film; the electrolyte is an aqueous sodium sulfate solution; the "fuel" is organic pollutants; the anode chamber is an oxygen-free environment; and the cathode chamber is an oxygen-rich environment. Detailed Implementation

[0162] The present invention will be further described in detail below with reference to specific embodiments. These embodiments are only used to explain the present invention and are not intended to limit the scope of the present invention. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods; the materials and reagents used are commercially available unless otherwise specified.

[0163] The 0.45 g / L SnCl4 ethanol solution used in this invention is prepared by dissolving SnCl4 in ethanol. The solution uses ethanol as solvent and SnCl4 as solute, and the SnCl4 content in the solution is 0.45 g / L.

[0164] The 0.98 g / L SbCl3 ethanol solution is prepared by dissolving SbCl3 in ethanol. The solution uses ethanol as solvent and SbCl3 as solute, and the content of SbCl3 in the solution is 0.98 g / L.

[0165] The cubic barium titanate used in this embodiment of the invention was purchased from Aladdin Reagent Company. Product parameters: 99.9% metals basis, particle size <100nm, average particle size approximately 50nm, CAS number: 12047-27-7.

[0166] Example 1

[0167] This embodiment provides a method for preparing an electrode, including the following steps:

[0168] 1) Take 0.2g of c-BaTiO3 (i.e., cubic phase barium titanate, c in c-BaTiO3 is an abbreviation for cubic, indicating cubic phase, trade name: nano barium titanate, CAS number: 12047-27-7, average particle size: about 50nm, purchased from Aladdin Company) and place it in 1.5mL of ethanol aqueous solution containing 0.05% (weight fraction) Nafion (ethanol volume fraction 50%, purchased from Aladdin Reagent Company, CAS number: 31175-20-9, catalog number: P400491), and after sonication for 10min and uniform dispersion, obtain a suspension containing c-BaTiO3;

[0169] 2) Drop-coat 0.375 mL of the c-BaTiO3 suspension from step 1) onto a 3 cm × 5 cm ITO conductive glass (thickness: 1.5 mm), and then dry it at 105 °C for 1 h. Repeat the drop-coating and drying operation 4 times to obtain ITO conductive glass with a c-BaTiO3 coating.

[0170] 3) Place the ITO conductive glass with c-BaTiO3 coating from step 2) in a muffle furnace and calcine it at 500°C for 2 hours. After natural cooling, an electrode with piezoelectric catalytic film (i.e. an electrode with t-BaTiO3 catalytic film layer) is obtained.

[0171] In step 3), the calcination is carried out in an air atmosphere, and the heating rate used in the calcination is 10℃ / min.

[0172] The impedance of the ITO conductive glass in this embodiment was 10 Ω / cm, as measured by scanning electron microscopy and an electrochemical workstation (Gamry 600+). 2 In this embodiment, the thickness of the piezoelectric catalytic membrane of the electrode containing the piezoelectric catalytic membrane is 0.44 μm; the catalytic membrane is assembled from particulate materials with an average particle size of 90 nm; the electrochemical impedance of the electrode containing the piezoelectric catalytic membrane in this embodiment is 2465 Ω.

[0173] Example 2

[0174] This embodiment provides a method for preparing an electrode. The only difference between this embodiment and Embodiment 1 is that the amount of c-BaTiO3 is replaced with 0.15g, and the method includes the following steps:

[0175] 1) Take 0.15g of c-BaTiO3 (i.e., cubic phase barium titanate, trade name: nano barium titanate, CAS No.: 12047-27-7, average particle size: about 50nm, purchased from Aladdin Company) and place it in 1.5mL of ethanol aqueous solution containing 0.05% (w / w) Nafion (ethanol volume fraction 50%, purchased from Aladdin Reagent Company, catalog number: P400491). After sonication for 10min, the mixture is uniformly dispersed to obtain a suspension containing c-BaTiO3.

[0176] 2) Drop-coat 0.375 mL of the c-BaTiO3 suspension from step 1) onto a 3 cm × 5 cm ITO conductive glass (thickness: 1.5 mm), and then dry it at 105 °C for 1 h. Repeat the drop-coating and drying operation 4 times to obtain ITO conductive glass with a c-BaTiO3 coating.

[0177] 3) Place the ITO conductive glass with c-BaTiO3 coating from step 2) in a muffle furnace and calcine it at 500°C for 2 hours. After natural cooling, an electrode with piezoelectric catalytic film (i.e. an electrode with t-BaTiO3 catalytic film layer) is obtained.

[0178] In step 3), the calcination is carried out in an air atmosphere, and the heating rate used in the calcination is 10℃ / min.

[0179] The electrode containing the piezoelectric catalytic membrane in Example 2 was tested using a scanning electron microscope (JEOL, JSM-6330F). The test results are as follows: Figure 4 As shown, where, Figure 4 In the image, 'a' represents a 34× electron microscope image. Figure 4 In Figure a, b is a magnified electron microscope image (magnification: 5.05K×) of the piezoelectric catalytic membrane. Figure 4 In Figure b, c is the electron microscope image of the region measured at a magnification of 30.00 K×.

[0180] According to scanning electron microscopy and electrochemical workstation (Gamry 600+), the thickness of the piezoelectric catalytic film in the electrode containing the piezoelectric catalytic film in this embodiment is 0.33 μm (e.g., ...). Figure 4 (As shown in a and b in the figure); the catalyst membrane is assembled from particulate materials with a particle size distribution of 40nm to 150nm and an average particle size of 90nm (as shown in the figure). Figure 4 (as shown in c); the electrochemical impedance of the electrode containing the piezoelectric catalytic membrane in this embodiment is 2580Ω.

[0181] Example 3

[0182] This embodiment provides a method for preparing an electrode. The only difference between this embodiment and Embodiment 1 is that the amount of c-BaTiO3 is replaced with 0.1g, and the method includes the following steps:

[0183] 1) Take 0.1g of c-BaTiO3 (i.e., cubic phase barium titanate, trade name: nano barium titanate, CAS No.: 12047-27-7, average particle size: about 50nm, purchased from Aladdin Company) and place it in 1.5mL of ethanol aqueous solution containing 0.05% (w / w) Nafion (ethanol volume fraction 50%, purchased from Aladdin Reagent Company, catalog number: P400491). After sonication for 10min, the mixture is uniformly dispersed to obtain a suspension containing c-BaTiO3.

[0184] 2) Drop-coat 0.375 mL of the c-BaTiO3 suspension from step 1) onto a 3 cm × 5 cm ITO conductive glass (thickness: 1.5 mm), and then dry it at 105 °C for 1 h. Repeat the drop-coating and drying operation 4 times to obtain ITO conductive glass with a c-BaTiO3 coating.

[0185] 3) Place the ITO conductive glass with c-BaTiO3 coating from step 2) in a muffle furnace and calcine it at 500°C for 2 hours. After natural cooling, an electrode with piezoelectric catalytic film (i.e. an electrode with t-BaTiO3 catalytic film layer) is obtained.

[0186] In step 3), the calcination is carried out in an air atmosphere, and the heating rate used in the calcination is 10℃ / min.

[0187] According to the scanning electron microscope and electrochemical workstation (Gamry 600+), the thickness of the piezoelectric catalytic membrane of the electrode in this embodiment is 0.21 μm; the catalytic membrane is assembled from particulate materials with an average particle size of 90 nm; the electrochemical impedance of the electrode containing the piezoelectric catalytic membrane in this embodiment is 1726 Ω.

[0188] Example 4

[0189] This embodiment provides a method for preparing an electrode. The only difference between this embodiment and Embodiment 1 is that the amount of c-BaTiO3 is replaced with 0.05g, and the method includes the following steps:

[0190] 1) Take 0.05g of c-BaTiO3 (i.e., cubic phase barium titanate, trade name: nano barium titanate, CAS No.: 12047-27-7, average particle size: about 50nm, purchased from Aladdin Company, catalog number: P400491) and place it in 1.5mL of ethanol aqueous solution containing 0.05% (weight fraction) Nafion (ethanol volume fraction 50%, purchased from Aladdin Reagent Company). After sonication for 10min, the mixture is uniformly dispersed to obtain a suspension containing c-BaTiO3.

[0191] 2) Drop-coat 0.375 mL of the c-BaTiO3 suspension from step 1) onto a 3 cm × 5 cm ITO conductive glass (thickness: 1.5 mm), and then dry it at 105 °C for 1 h. Repeat the drop-coating and drying operation 4 times to obtain ITO conductive glass with a c-BaTiO3 coating.

[0192] 3) Place the ITO conductive glass with c-BaTiO3 coating from step 2) in a muffle furnace and calcine it at 500°C for 2 hours. After natural cooling, an electrode with piezoelectric catalytic film (i.e. an electrode with t-BaTiO3 catalytic film layer) is obtained.

[0193] In step 3), the calcination is carried out in an air atmosphere, and the heating rate used in the calcination is 10℃ / min.

[0194] According to the scanning electron microscope and electrochemical workstation (Gamry 600+), the thickness of the piezoelectric catalytic membrane of the electrode containing the piezoelectric catalytic membrane in this embodiment is 0.10 μm; the catalytic membrane is assembled from particulate materials with an average particle size of 90 nm; the electrochemical impedance of the electrode containing the piezoelectric catalytic membrane in this embodiment is 788 Ω.

[0195] Example 5

[0196] This embodiment provides a method for preparing an electrode, including the following steps:

[0197] 1) Take 1g of c-BaTiO3 (i.e., cubic phase barium titanate, trade name: nano barium titanate, CAS number: 12047-27-7, average particle size: about 50nm, purchased from Aladdin Company) and place it in a ceramic boat. Then place it in a muffle furnace and calcine it at 500℃ in an air atmosphere for 2 hours. After natural cooling to a temperature below 40℃, take it out and grind it for 20-30 minutes to obtain calcined barium titanate (i.e., t-BaTiO3).

[0198] 2) Disperse the t-BaTiO3 from step 1) in 100 mL of anhydrous ethanol by ultrasonication to obtain an ethanol solution of 0.1 g / L t-BaTiO3;

[0199] Add 10 mL of 0.45 g / L SnCl4 ethanol solution and 0.1 mL of 0.98 g / L SbCl3 ethanol solution dropwise to 100 mL of 0.1 g / L t-BaTiO3 ethanol solution, and stir for 1 h; then add 10 mL of 1 M ammonia water, maintain stirring for 8 h, centrifuge, wash, dry at 80 °C, and calcine at 500 °C in air for 1 h to obtain composite piezoelectric catalyst material (i.e., Sb-SnO2 / t-BaTiO3 solid powder);

[0200] 3) Take 0.2g of Sb-SnO2 / t-BaTiO3 and place it in 1.5mL of ethanol aqueous solution containing 0.05% (w / w) Nafion (ethanol volume fraction 50%, purchased from Aladdin Reagent Company, catalog number: P400491). After ultrasonic dispersion for 10min, a suspension containing composite piezoelectric catalyst material (i.e., a suspension containing Sb-SnO2 / t-BaTiO3) is obtained.

[0201] 4) Drop-coat 0.375 mL of the Sb-SnO2 / t-BaTiO3 suspension from step 3) onto a 3 cm × 5 cm ITO conductive glass (thickness: 1.5 mm), and then dry it at 105 °C for 1 h. Repeat the drop-coating and drying operation 4 times to obtain an ITO conductive glass with an Sb-SnO2 / t-BaTiO3 coating.

[0202] 5) Place the ITO conductive glass with Sb-SnO2 / t-BaTiO3 coating from step 4) in a muffle furnace and calcine it for 2 hours under an air atmosphere and a temperature of 500℃. After natural cooling, an electrode with a piezoelectric composite catalytic film (i.e. an electrode with an Sb-SnO2 / t-BaTiO3 catalytic film layer) is obtained.

[0203] In step 1) and step 2), the heating rate is 10℃ / min.

[0204] According to the scanning electron microscope and electrochemical workstation (Gamry 600+), the thickness of the piezoelectric composite catalytic membrane in this embodiment was measured to be 0.43 μm; the piezoelectric composite catalytic membrane was assembled from particulate materials; the electrochemical impedance of the electrode containing the piezoelectric composite catalytic membrane in this embodiment was 398 Ω.

[0205] Example 6

[0206] This embodiment provides a method for preparing an electrode, which differs from Embodiment 5 in that the amount of Sb-SnO2 / t-BaTiO3 in step 3) is replaced with 0.15g, and includes the following steps:

[0207] 1) Take 1g of c-BaTiO3 (i.e., cubic phase barium titanate, trade name: nano barium titanate, CAS number: 12047-27-7, average particle size: about 50nm, purchased from Aladdin Company) and place it in a ceramic boat. Then place it in a muffle furnace and calcine it at 500℃ in an air atmosphere for 2 hours. After natural cooling to a temperature below 40℃, take it out and grind it for 20-30 minutes to obtain calcined barium titanate (i.e., t-BaTiO3).

[0208] 2) Disperse the t-BaTiO3 from step 1) in 100 mL of anhydrous ethanol by ultrasonication to obtain an ethanol solution of 0.1 g / L t-BaTiO3;

[0209] Add 10 mL of 0.45 g / L SnCl4 ethanol solution and 0.1 mL of 0.98 g / L SbCl3 ethanol solution dropwise to 100 mL of 0.1 g / L t-BaTiO3 ethanol solution, and stir for 1 h; then add 10 mL of 1 M ammonia water, maintain stirring for 8 h, centrifuge, wash, dry at 80 °C, and calcine at 500 °C in air for 1 h to obtain composite piezoelectric catalyst material (i.e., Sb-SnO2 / t-BaTiO3 solid powder);

[0210] 3) Take 0.15g of Sb-SnO2 / t-BaTiO3 and place it in 1.5mL of ethanol aqueous solution containing 0.05% (w / w) Nafion (ethanol volume fraction 50%, purchased from Aladdin Reagent Company, catalog number: P400491). After ultrasonic dispersion for 10min, a suspension containing composite piezoelectric catalyst material (i.e., a suspension containing Sb-SnO2 / t-BaTiO3) is obtained.

[0211] 4) Drop-coat 0.375 mL of the Sb-SnO2 / t-BaTiO3 suspension from step 3) onto a 3 cm × 5 cm ITO conductive glass (thickness: 1.5 mm), and then dry it at 105 °C for 1 h. Repeat the drop-coating and drying operation 4 times to obtain an ITO conductive glass with an Sb-SnO2 / t-BaTiO3 coating.

[0212] 5) Place the ITO conductive glass with Sb-SnO2 / t-BaTiO3 coating from step 2) in a muffle furnace and calcine it for 2 hours in an air atmosphere at a temperature of 500℃. After natural cooling, an electrode with a piezoelectric composite catalytic film (i.e. an electrode with an Sb-SnO2 / t-BaTiO3 catalytic film layer) is obtained.

[0213] In step 1) and step 2), the heating rate is 10℃ / min.

[0214] According to the scanning electron microscope and electrochemical workstation (Gamry 600+), the thickness of the piezoelectric composite catalytic membrane in this embodiment was measured to be 0.33 μm; the piezoelectric composite catalytic membrane was assembled from particulate materials; the electrochemical impedance of the electrode containing the piezoelectric catalytic membrane in this embodiment was 317 Ω.

[0215] Example 7

[0216] This embodiment provides a method for preparing an electrode, which differs from Embodiment 5 in that the amount of Sb-SnO2 / t-BaTiO3 in step 3) is replaced with 0.10g, and includes the following steps:

[0217] 1) Take 1g of c-BaTiO3 (i.e., cubic phase barium titanate, trade name: nano barium titanate, CAS number: 12047-27-7, average particle size: about 50nm, purchased from Aladdin Company) and place it in a ceramic boat. Then place it in a muffle furnace and calcine it at 500℃ in an air atmosphere for 2 hours. After natural cooling to a temperature below 40℃, take it out and grind it for 20-30 minutes to obtain calcined barium titanate (i.e., t-BaTiO3).

[0218] 2) Disperse the t-BaTiO3 from step 1) in 100 mL of anhydrous ethanol by ultrasonication to obtain an ethanol solution of 0.1 g / L t-BaTiO3;

[0219] Add 10 mL of 0.45 g / L SnCl4 ethanol solution and 0.1 mL of 0.98 g / L SbCl3 ethanol solution dropwise to 100 mL of 0.1 g / L t-BaTiO3 ethanol solution, and stir for 1 h; then add 10 mL of 1 M ammonia water, maintain stirring for 8 h, centrifuge, wash, dry at 80 °C, and calcine at 500 °C in air for 1 h to obtain composite piezoelectric catalyst material (i.e., Sb-SnO2 / t-BaTiO3 solid powder);

[0220] 3) Take 0.1g of Sb-SnO2 / t-BaTiO3 and place it in 1.5mL of ethanol aqueous solution containing 0.05% (w / w) Nafion (ethanol volume fraction 50%, purchased from Aladdin Reagent Company, catalog number: P400491). After ultrasonic dispersion for 10min, a suspension containing composite piezoelectric catalyst material is obtained.

[0221] 4) Drop-coat 0.375 mL of the suspension from step 3) onto a 3 cm × 5 cm ITO conductive glass (thickness: 1.5 mm), and then dry it at 105 °C for 1 h. Repeat the drop-coating and drying operation 4 times to obtain ITO conductive glass with Sb-SnO2 / t-BaTiO3 coating.

[0222] 5) Place the ITO conductive glass with Sb-SnO2 / t-BaTiO3 coating from step 4) in a muffle furnace and calcine it for 2 hours under an air atmosphere and a temperature of 500℃. After natural cooling, an electrode with a piezoelectric composite catalytic film (i.e. an electrode with an Sb-SnO2 / t-BaTiO3 catalytic film layer) is obtained.

[0223] In step 1) and step 2), the heating rate is 10℃ / min.

[0224] According to scanning electron microscopy and electrochemical workstation (Gamry 600+), the thickness of the piezoelectric composite catalytic membrane in this embodiment was measured to be 0.22 μm; the particle size of Sb-SnO2 / t-BaTiO3 in step 2) was 80-100 nm, and the piezoelectric composite catalytic membrane was assembled from particulate materials; the electrochemical impedance of the electrode containing the piezoelectric composite catalytic membrane in this embodiment was 223 Ω.

[0225] Example 8

[0226] This embodiment provides a method for preparing an electrode, which differs from Embodiment 5 in that the amount of Sb-SnO2 / t-BaTiO3 in step 3) is replaced with 0.05g, and includes the following steps:

[0227] 1) Take 1g of c-BaTiO3 (i.e., cubic phase barium titanate, trade name: nano barium titanate, CAS number: 12047-27-7, average particle size: about 50nm, purchased from Aladdin Company) and place it in a ceramic boat. Then place it in a muffle furnace and calcine it at 500℃ in an air atmosphere for 2 hours. After natural cooling to a temperature below 40℃, take it out and grind it for 20-30 minutes to obtain calcined barium titanate (i.e., t-BaTiO3).

[0228] 2) Disperse the t-BaTiO3 from step 1) in 100 mL of anhydrous ethanol by ultrasonication to obtain an ethanol solution of 0.1 g / L t-BaTiO3;

[0229] Add 10 mL of 0.45 g / L SnCl4 ethanol solution and 0.1 mL of 0.98 g / L SbCl3 ethanol solution dropwise to 100 mL of 0.1 g / L t-BaTiO3 ethanol solution, and stir for 1 h; then add 10 mL of 1 M ammonia water, maintain stirring for 8 h, centrifuge, wash, dry at 80 °C, and calcine at 500 °C in air for 1 h to obtain composite piezoelectric catalyst material (i.e., Sb-SnO2 / t-BaTiO3 solid powder);

[0230] 3) Take 0.05g of Sb-SnO2 / t-BaTiO3 and place it in 1.5mL of ethanol aqueous solution containing 0.05% (w / w) Nafion (ethanol volume fraction 50%, purchased from Aladdin Reagent Company). After sonication for 10min and uniform dispersion, a suspension containing composite piezoelectric catalyst material (i.e., a suspension containing Sb-SnO2 / t-BaTiO3) is obtained.

[0231] 4) Drop-coat 0.375 mL of the Sb-SnO2 / t-BaTiO3 suspension from step 3) onto a 3 cm × 5 cm ITO conductive glass (thickness: 1.5 mm), and then dry it at 105 °C for 1 h. Repeat the drop-coating and drying operation 4 times to obtain an ITO conductive glass with an Sb-SnO2 / t-BaTiO3 coating.

[0232] 5) Place the ITO conductive glass with Sb-SnO2 / t-BaTiO3 coating from step 4) in a muffle furnace and calcine it for 2 hours under an air atmosphere and a temperature of 500℃. After natural cooling, an electrode with a piezoelectric composite catalytic film (i.e. an electrode with an Sb-SnO2 / t-BaTiO3 catalytic film layer) is obtained.

[0233] In step 1) and step 2), the heating rate is 10℃ / min.

[0234] According to scanning electron microscopy and electrochemical workstation (Gamry 600+), the thickness of the piezoelectric composite catalytic membrane in this embodiment was measured to be 0.10 μm; the particle size of Sb-SnO2 / t-BaTiO3 in step 2) was 80-100 nm, and the piezoelectric composite catalytic membrane was assembled from particulate materials; the electrochemical impedance of the electrode containing the piezoelectric composite catalytic membrane in this embodiment was 121 Ω.

[0235] Material characterization and properties

[0236] 1. The X-ray diffraction patterns of c-BaTiO3 (commercial product) and calcined barium titanate powder (t-BaTiO3) obtained by calcining c-BaTiO3 (commercial product) in air at 500°C for 2 hours were tested. The test results are as follows: Figure 1 As shown.

[0237] Depend on Figure 1 It can be seen that c-BaTiO3 (commercial product) has only one obvious characteristic peak at 2θ in the range of 44-46°. However, after c-BaTiO3 (commercial product) is calcined at 500°, the original single peak at 2θ in the range of 44-46° splits into two peaks. This indicates that c-BaTiO3 (commercial product) can be converted into tetragonal phase crystal t-BaTiO3 after calcination at 500° for 2 hours.

[0238] 2. X-ray diffraction patterns of the electrode containing the piezoelectric catalytic membrane in Example 2 and the electrode containing the piezoelectric composite catalytic membrane in Example 6, as shown. Figure 2 As shown. The X-ray photoelectron spectroscopy (XPS) of the electrode containing the piezoelectric composite catalytic film in Example 6 is as follows. Figure 3 As shown; where a is a narrow scan XPS image and b is an XPS image with a binding energy of 524 eV to 542 eV.

[0239] Depend on Figure 2 and Figure 3 It can be known that: Figure 2 Combination Figure 1 In Example 2, the BaTiO3 composition on the electrode containing the piezoelectric catalytic membrane and in Example 6, the electrode containing the piezoelectric composite catalytic membrane, is tetragonal t-BaTiO3 (i.e., 2θ has a double peak at 44-46°).

[0240] X-ray photoelectron spectroscopy analysis revealed that the electrode sample containing the piezoelectric composite catalytic film in Example 6 exhibited distinct characteristic peaks at 495.0 eV and 486.6 eV, which were attributed to Sn, respectively. 4+ 3D 3 / 2 and Sn 4+ 3D 5 / 2 Characteristic peaks; distinct characteristic peaks appeared at 539.8 eV and 530.4 eV, which were attributed to Sb, respectively. 3+ 3D 3 / 2 and Sb 3+ 3D 5 / 2 The characteristic peaks indicate that the piezoelectric composite catalytic membrane in Example 6 is actually a composite material with the co-catalyst Sb-SnO2 loaded on the surface of t-BaTiO3.

[0241] 3. Electron microscopy (EMS) samples were prepared at the junction of the ITO conductive glass and the piezoelectric catalytic film of the electrode containing the t-BaTiO3 catalytic film from Example 2. Scanning electron microscopy (SEM) tests were then performed on these samples. Figure 4 As shown; where a is a scanning electron microscope (SEM) image of the cross-section of the sample tested by electron microscopy; b and c are SEM images of the piezoelectric catalytic film obtained at higher magnification. A transmission electron microscope (TEM) image of the Sb-SnO2 / t-BaTiO3 solid powder in Example 6 is shown below. Figure 5 As shown; where a is a transmission electron microscope (TEM) image of Sb-SnO2 / t-BaTiO3 (the circled area in the figure is the region containing the Sb-SnO2 component); b is a high-resolution TEM image obtained by further magnification of the region containing Sb-SnO2.

[0242] Depend on Figure 4 and Figure 5 It can be seen that: according to Figure 4 It can be seen that in Example 2, the t-BaTiO3 piezoelectric anodic catalyst film was immobilized on ITO conductive glass, and the thickness of the piezoelectric catalyst film was about 3.3 μm. Figure 4 c shows that the piezoelectric material t-BaTiO3 is spherical (i.e. granular), with a particle size distribution of 40nm to 150nm and an average particle size of about 90nm.

[0243] Figure 5 As can be seen from the example, the piezoelectric composite catalytic membrane in Example 6 is based on t-BaTiO3 as the main material, and t-BaTiO3 is also granular (particle size: 40nm~120nm), with a small amount of Sb-SnO2 uniformly dispersed and loaded on the surface of t-BaTiO3.

[0244] The analysis results, combining XRD and XPS spectra, and by Figure 5 b and Figure 4 C-analysis revealed that the co-catalyst Sb-SnO2 was successfully loaded onto the surface of t-BaTiO3. Both Sb-SnO2 and t-BaTiO3 exhibited granular structures, with t-BaTiO3 having a particle size of approximately 50 nm, while the Sb-SnO2 component had a particle size of 2–5 nm. The SnO2-Sb... {200} =0.245nm indicates that Sb doping affects the {200} crystal plane spacing (0.25nm) of pure SnO2, showing that Sb is doped in the SnO2 phase.

[0245] 4. The composite piezoelectric catalytic material (i.e., Sb-SnO2 / t-BaTiO3 solid powder) in Example 6 was tested using a plasma mass spectrometer (ICPS 7500, manufacturer: Shimadzu, Japan). The test and analysis showed that the SnO2 content was 0.4 at% (mass fraction) and the Sb doping amount was 0.01 at% (mass fraction).

[0246] 5. Piezoelectric microscopy-piezoelectric response diagrams and butterfly plots of the electrode containing the t-BaTiO3 catalytic film in Example 2 and the electrode containing the Sb-SnO2 / t-BaTiO3 catalytic film in Example 6, as shown in the figure. Figure 6 As shown; where a is the piezoelectric micrograph of the electrode containing the t-BaTiO3 catalytic membrane in Example 2, b is the piezoelectric micrograph of the electrode containing the Sb-SnO2 / t-BaTiO3 catalytic membrane in Example 6, c is the butterfly diagram of the electrode containing the t-BaTiO3 catalytic membrane in Example 2, and d is the butterfly diagram of the electrode containing the Sb-SnO2 / t-BaTiO3 catalytic membrane in Example 6. The EIS-Nyquist spectra (i.e., Nyquist spectra in electrochemical impedance spectroscopy) and equivalent circuit diagrams of the electrodes containing the t-BaTiO3 catalytic membrane in Example 2 and the electrodes containing the Sb-SnO2 / t-BaTiO3 catalytic membrane in Example 6 are shown below. Figure 7 As shown; where a is the EIS-Nyquist spectrum; b is the equivalent circuit fitted by ZSimWin software, where Rs, Rct, CPE and Zw are the solution resistance, charge transfer resistance, double-layer capacitance and Warburg impedance, respectively.

[0247] Depend on Figure 6 and Figure 7 It can be seen that the piezoelectric response of the electrode containing the t-BaTiO3 catalytic film in Example 2 (see...) Figure 6 a) The piezoelectric constant is based on Figure 6 c is calculated to be 358 pm / V. The piezoelectric response of the electrode containing the Sb-SnO2 / t-BaTiO3 catalytic film in Example 6 (see...) Figure 6 b) The piezoelectric constant is based on Figure 6 d is calculated to be 271 pm / V.

[0248] Based on the above test results and analysis, it can be seen that the electrode containing the t-BaTiO3 catalytic film in Example 2 and the electrode containing the Sb-SnO2 / t-BaTiO3 catalytic film layer in Example 6 both exhibit piezoelectric activity. Compared with the electrode containing the t-BaTiO3 catalytic film in Example 2 (impedance: 2580Ω), the impedance value of the electrode containing the Sb-SnO2 / t-BaTiO3 catalytic film layer in Example 6 is 317Ω, and the impedance of the electrode containing the Sb-SnO2 / t-BaTiO3 piezoelectric catalytic film is reduced by 87.7%. This indicates that the loading of the co-catalyst Sb-SnO2 is beneficial to reducing the resistance of the piezoelectric catalytic film, enhancing its conductivity, and facilitating current generation.

[0249] Example 9

[0250] This embodiment provides a single-chamber piezoelectric fuel cell, which includes: an electrode containing a piezoelectric catalytic membrane (i.e., an electrode containing a t-BaTiO3 catalytic membrane layer, the anode) as in Example 2, a platinum sheet with dimensions of 3cm×5cm×1.5mm (i.e., cathode), wires, a container with dimensions of 5cm×5cm×7cm, and an ultrasonic machine (i.e., an ultrasonic generator).

[0251] The anode and cathode are arranged in parallel inside the container, and the distance between the cathode and anode is 4 cm.

[0252] The cathode and anode are connected by a wire;

[0253] The container is located inside the ultrasonic generator, enabling the ultrasonic generator to provide mechanical energy to the fuel cell.

[0254] The single-chamber piezoelectric fuel cell in this embodiment also includes: being connected to an external circuit (including other electronic components) by wires;

[0255] The electrolyte is placed inside the container, with the anode and cathode immersed in the electrolyte.

[0256] This embodiment also provides a method for using a single-chamber piezoelectric fuel cell for wastewater treatment, including the following steps:

[0257] 1) Construction of a single-chamber piezoelectric fuel cell: The electrode containing the piezoelectric catalytic membrane (i.e. the electrode containing the t-BaTiO3 catalytic membrane layer) in Example 2 is used as the anode of the fuel cell, and a platinum sheet with a specification of 3cm×5cm×1.5mm is used as the cathode electrode. The electrode distance is set to 4cm, and the cathode and anode are connected by wires to form an external circuit.

[0258] Add 60 mL of organic wastewater containing methylene blue as the electrolyte to a container with dimensions of 5 cm × 5 cm × 7 cm.

[0259] Place the above container in an ultrasonic machine containing water as a medium;

[0260] 2) Driving a single-chamber piezoelectric fuel cell: The ultrasonic machine is set to a working power of 100W and a frequency of 40kHz. The ultrasonic waves generated by the machine are used to drive the piezoelectric catalytic reaction in the single-chamber piezoelectric fuel cell, thereby realizing power generation and organic wastewater treatment.

[0261] In step 1), the concentration of methylene blue in the organic wastewater containing methylene blue is 0.1 g / L to 1 g / L; the concentration of potassium sulfate in the organic wastewater containing methylene blue in step 1) is 0.5 mol / L.

[0262] The piezoelectric catalytic reaction in step 2) is carried out at room temperature and pressure (i.e., temperature of 20-25°C, pressure of 0.1 MPa, and air atmosphere); the ultrasonic or piezoelectric catalytic reaction takes 2 hours.

[0263] Performance testing of single-chamber piezoelectric fuel cells for wastewater treatment and power generation

[0264] Keeping other factors constant, four single-chamber piezoelectric fuel cells were constructed by replacing the organic wastewater with methylene blue concentrations of 1 g / L, 0.6 g / L, 0.3 g / L, and 0.1 g / L, respectively, and the wastewater was treated under the same conditions.

[0265] Meanwhile, the four single-chamber piezoelectric fuel cells were connected to an electrochemical workstation (Gamry 6000+) to test and monitor the electrical energy generated and the degradation rate of methylene blue.

[0266] The test results above show that: single-chamber piezoelectric fuel cells with methylene blue concentrations of 1 g / L, 0.6 g / L, 0.3 g / L, and 0.1 g / L in organic wastewater containing methylene blue, under ultrasonic conditions (100 W, 40 kHz) and ambient pressure, exhibited methylene blue degradation rates of 86.1 mg / L, 69.6 mg / L, 44.8 mg / L, and 21.4 mg / L after 2 hours of piezoelectric catalytic reaction.

[0267] Within 2 hours of the reaction, the current generated by the corresponding single-chamber piezoelectric fuel cell first increases rapidly, and then the current tends to stabilize, with the stable current being maintained at approximately 2.45 μA, 1.78 μA, 1.12 μA and 0.83 μA.

[0268] Based on the above results, the single-chamber piezoelectric fuel cell (i.e., piezoelectric reactor) in this embodiment can not only effectively degrade organic pollutants and generate electricity, but also the higher the concentration of methylene blue, the greater the current, proving that methylene blue plays the role of "fuel", and the power generation performance of the battery is positively correlated with methylene blue.

[0269] Example 10

[0270] This embodiment provides a dual-chamber piezoelectric fuel cell, which includes: an electrode containing a piezoelectric catalytic membrane (i.e., an electrode containing a t-BaTiO3 catalytic membrane layer, the anode) as in Example 2, a platinum sheet with dimensions of 3cm×5cm×1.5mm (i.e., cathode), wires, a PVDF microfiltration membrane with a membrane pore size of 0.22μm (i.e., a separator, PVDF refers to polyvinylidene fluoride), a container with dimensions of 5cm×5cm×7cm, and an ultrasonic machine (i.e., an ultrasonic generator);

[0271] The diaphragm is located inside the container and is used to divide the container into two spaces of equal volume (i.e., the cathode chamber and the anode chamber).

[0272] The anode and cathode are arranged parallel to each other inside the container, with the cathode placed inside the cathode chamber and the anode placed inside the anode chamber. The distance between the cathode and anode is 4 cm. The cathode and anode are connected by a wire.

[0273] The container is located inside the ultrasonic generator, enabling the ultrasonic generator to provide mechanical energy to the fuel cell.

[0274] The dual-chamber piezoelectric fuel cell in this embodiment also includes: being connected to an external circuit (including other electronic components) by wires;

[0275] The electrolyte is placed inside the container, and the anode and cathode are placed in the electrolyte;

[0276] Two partitions are installed on the top of the anode chamber and the top of the cathode chamber, respectively, to isolate them from the external environment and provide conditions for creating an oxygen-free or oxygen-rich space.

[0277] This embodiment also provides a method for using a dual-chamber piezoelectric fuel cell for wastewater treatment, including the following steps:

[0278] 1) Construction of a dual-chamber piezoelectric fuel cell: A PVDF microfiltration membrane with a pore size of 0.22 μm is installed inside the container, dividing the container into two spaces of equal volume (i.e., the cathode chamber and the anode chamber);

[0279] The electrode containing the piezoelectric catalytic membrane (i.e. the electrode containing the t-BaTiO3 catalytic membrane layer) in Example 2 is used as the anode of the fuel cell, and a platinum sheet with a size of 3cm×5cm×1.5mm is used as the cathode electrode. The anode and cathode are placed in parallel, and the distance between the two electrodes is controlled to be 4cm. The cathode and anode are connected by wires to form an external circuit.

[0280] A partition, installed on top of the anode and cathode chambers, is used to isolate the anode chamber from the external environment, providing conditions for creating an oxygen-free space;

[0281] Add 30 mL of tricyclazole-containing organic wastewater to the anode chamber and introduce nitrogen gas (flow rate: 100 mL / min) into the anode chamber to create an anaerobic environment;

[0282] Add 30 mL of 0.5 mol / L sodium sulfate solution (solvent is water) to the cathode chamber, and introduce oxygen into the cathode chamber (flow rate: 100 mL / min) to create an oxygen-saturated environment. The dissolved oxygen concentration of the solution in the anode chamber is 11.2 mg / L.

[0283] Place the above container in an ultrasonic machine containing water as a medium;

[0284] 2) Driving the dual-chamber piezoelectric fuel cell: Set the working power of the ultrasonic machine to 100W and the frequency to 40kHz, and use the ultrasonic waves generated by it to drive the piezoelectric catalytic reaction in the dual-chamber piezoelectric fuel cell to achieve power generation and organic wastewater treatment.

[0285] In step 1), the concentration of tricyclazole in the organic wastewater containing tricyclazole is 0.1 g / L to 1 g / L.

[0286] The piezoelectric catalytic reaction in step 2) is carried out at room temperature and pressure (i.e., temperature of 20-25℃ and pressure of 0.1MPa); the ultrasonic or piezoelectric catalytic reaction takes 2 hours.

[0287] Performance testing of dual-chamber piezoelectric fuel cells for wastewater treatment and power generation

[0288] Keeping other factors constant, three types of dual-chamber piezoelectric fuel cells were constructed by replacing the tricyclazole-containing organic wastewater with tricyclazole concentrations of 1 g / L, 0.6 g / L, 0.3 g / L, and 0.1 g / L, respectively, and the wastewater was treated under the same conditions.

[0289] Meanwhile, the above four types of dual-chamber piezoelectric fuel cells were connected to an electrochemical workstation (Gamry 600+) to test and monitor the electrical energy generated and the degradation rate of methylene blue.

[0290] The test results above show that for dual-chamber piezoelectric fuel cells with tricyclic azole concentrations of 1 g / L, 0.6 g / L, 0.3 g / L, and 0.1 g / L, the degradation amounts of tricyclic azole after 2 hours of piezoelectric catalytic reaction driven by an ultrasonic machine with a working power of 100 W and a frequency of 40 kHz at room temperature and pressure were 106.5 mg / L, 87.1 mg / L, 54.8 mg / L, and 24.6 mg / L, respectively.

[0291] Within 2 hours of the reaction, the current generated by the corresponding dual-chamber piezoelectric fuel cell first increases rapidly, and then the current tends to stabilize, with the stable current being basically maintained at 2.93μA, 2.12μA, 1.29μA and 1.05μA.

[0292] Based on the above results, the dual-chamber piezoelectric fuel cell (i.e., piezoelectric reactor) in this embodiment can not only effectively degrade organic pollutants and generate electricity, but also the higher the tricyclic azole concentration, the greater the current, proving that tricyclic azole plays the role of "fuel", and the power generation performance of the battery is positively correlated with tricyclic azole.

[0293] Furthermore, the dual-chamber piezoelectric fuel cell in this embodiment has better degradation efficiency for organic pollutants and higher power generation efficiency than the stable single-chamber piezoelectric fuel cell in Example 9.

[0294] Example 11

[0295] The working principle of a piezoelectric fuel cell is described using this embodiment as an example. A schematic diagram of the dual-chamber piezoelectric fuel cell in this embodiment is shown below. Figure 8 As shown.

[0296] Depend on Figure 8 It can be seen that: in this embodiment, the dual-chamber piezoelectric fuel cell uses an electrode containing an Sb-SnO2 / t-BaTiO3 catalytic membrane as the anode, a 0.5 mol / L sodium sulfate aqueous solution as the anode, a PVDF membrane with a pore size of 0.22 μm as the separator, a 0.5 mol / L sodium sulfate aqueous solution as the electrolyte, and tricyclic azole organic pollutant as the "fuel"; the anode chamber is an oxygen-free environment; and the cathode chamber is an oxygen-rich environment.

[0297] The working principle of the dual-chamber piezoelectric fuel cell in this embodiment is as follows: A Sb-SnO2 / t-BaTiO3 piezoelectric catalytic membrane with ITO conductive glass as the substrate is designed as the piezoelectric anode; driven by external mechanical energy (e.g., kinetic energy provided by ultrasound), organic pollutants in wastewater act as "fuel," and the electrons they release are captured by the piezoelectric anode, and then reach the cathode through an external circuit driven by the piezoelectric potential; subsequently, electrons on the cathode are captured by hydrogen ions or oxygen molecules in the cathode chamber to undergo a reduction reaction; thus, it can both degrade organic wastewater and effectively utilize external mechanical energy and the chemical energy in organic wastewater to generate electricity.

[0298] This embodiment provides a dual-chamber piezoelectric fuel cell (see...). Figure 8 This includes: the electrode (i.e., the anode) containing the Sb-SnO2 / t-BaTiO3 catalytic film layer as described in Example 6.

[0299] The following components are required: a platinum sheet (cathode) with dimensions of 3cm×5cm×1.5mm, wires, a PVDF microfiltration membrane (diaphragm, PVDF refers to polyvinylidene fluoride) with a pore size of 0.22μm, a container with dimensions of 5cm×5cm×7cm, and an ultrasonic machine (ultrasonic generator).

[0300] The diaphragm is located inside the container and is used to divide the container into two spaces of equal volume (i.e., the cathode chamber and the anode chamber).

[0301] The anode and cathode are arranged parallel to each other inside the container, with the cathode placed inside the cathode chamber and the anode placed inside the anode chamber. The distance between the cathode and anode is 4 cm. The cathode and anode are connected by a wire.

[0302] The container is located inside the ultrasonic generator, enabling the ultrasonic generator to provide mechanical energy to the fuel cell.

[0303] The dual-chamber piezoelectric fuel cell in this embodiment also includes: being connected to an external circuit (including other electronic components) by wires;

[0304] The electrolyte is placed inside the container, and the anode and cathode are placed in the electrolyte;

[0305] Two partitions are installed on the top of the anode chamber and the top of the cathode chamber, respectively, to isolate them from the external environment and provide conditions for creating an oxygen-free or oxygen-rich space.

[0306] This embodiment provides a method capable of simultaneously treating organic wastewater and generating electricity (see...). Figure 8 The process includes the following steps:

[0307] 1) Construction of a dual-chamber piezoelectric fuel cell: A PVDF microfiltration membrane with a pore size of 0.22 μm is installed inside the container, dividing the container into two spaces of equal volume (i.e., the cathode chamber and the anode chamber);

[0308] The electrode containing the Sb-SnO2 / t-BaTiO3 catalytic film layer in Example 6 was used as the anode of the fuel cell, and a platinum sheet with a size of 3cm×5cm×1.5mm was used as the cathode electrode. The anode and cathode were placed in parallel, with a distance of 4cm between the two electrodes, and the cathode and anode were connected by wires to form an external circuit.

[0309] A partition, which is installed at the top of the anode chamber and the top of the cathode chamber, is used to isolate them from the external environment;

[0310] Add 30 mL of tricyclazole-containing organic wastewater to the anode chamber and introduce nitrogen gas (flow rate: 100 mL / min) into the anode chamber to create an anaerobic environment;

[0311] Add 30 mL of 0.5 mol / L sodium sulfate solution (solvent is water) to the cathode chamber, and introduce oxygen into the cathode chamber (flow rate: 100 mL / min) to create an oxygen-saturated environment. The dissolved oxygen concentration of the solution in the anode chamber is 11.2 mg / L.

[0312] Place the above container in an ultrasonic machine containing water as a medium;

[0313] 2) Driving the dual-chamber piezoelectric fuel cell: Set the working power of the ultrasonic machine to 100W and the frequency to 40kHz, and use the ultrasonic waves generated by it to drive the piezoelectric catalytic reaction in the dual-chamber piezoelectric fuel cell to achieve power generation and organic wastewater treatment.

[0314] In step 1), the tricyclazole concentration in the organic wastewater containing tricyclazole is 0.1 g / L to 1 g / L.

[0315] The piezoelectric catalytic reaction in step 2) is carried out at room temperature and pressure (i.e., temperature of 20-25℃ and pressure of 0.1MPa); the ultrasonic or piezoelectric catalytic reaction takes 2 hours.

[0316] Performance testing of dual-chamber piezoelectric fuel cells for wastewater treatment and power generation

[0317] Keeping other factors constant, three types of dual-chamber piezoelectric fuel cells were constructed by replacing the tricyclazole-containing organic wastewater with tricyclazole concentrations of 1 g / L, 0.6 g / L, 0.3 g / L, and 0.1 g / L, respectively, and the wastewater was treated under the same conditions.

[0318] Meanwhile, the above four types of dual-chamber piezoelectric fuel cells were connected to an electrochemical workstation (Gamry 6000+) to test and monitor the electrical energy generated and the degradation rate of methylene blue.

[0319] The test results above show that for dual-chamber piezoelectric fuel cells with tricyclic azole concentrations of 1 g / L, 0.6 g / L, 0.3 g / L, and 0.1 g / L, the degradation amounts of tricyclic azole after 2 hours of piezoelectric catalytic reaction driven by an ultrasonic machine with a working power of 100 W and a frequency of 40 kHz at room temperature and pressure were 123.2 mg / L, 103.6 mg / L, 63.9 mg / L, and 30.3 mg / L, respectively.

[0320] Within 2 hours of the reaction, the current generated by the corresponding dual-chamber piezoelectric fuel cell first increases rapidly, and then the current tends to stabilize, with the stable current being basically maintained at 3.37μA, 2.38μA, 1.47μA and 1.19μA.

[0321] Based on the above results, the pollutant degradation efficiency and power generation efficiency of the dual-chamber piezoelectric fuel cell equipped with Sb-SnO2 / t-BaTiO3 piezoelectric anode are higher than those of the dual-chamber piezoelectric fuel cell equipped with t-BaTiO3 piezoelectric anode, indicating that Sb-SnO2 plays the role of a co-catalyst.

[0322] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. An application of a piezoelectric fuel cell in the treatment of organic wastewater containing tricyclic azole, characterized in that, The piezoelectric fuel cell includes: a container, a device for providing mechanical energy, a cathode, an anode, and organic wastewater containing tricyclazole; the impedance of the anode is 100 Ω to 400 Ω. Both the cathode and anode are placed in the container. The anode includes a conductive substrate and a catalytic film immobilized on the conductive substrate. The thickness of the catalytic film is 0.10 μm to 0.45 μm. The catalytic film comprises granular tetragonal BaTiO3 with a particle size of 40 nm to 120 nm. The X-ray diffraction pattern of the tetragonal BaTiO3 has two characteristic peaks at a 2θ position of 44.5° to 45.5°. The catalytic film also includes Sb-doped SnO2 loaded on the surface of the granular tetragonal BaTiO3. The particle size of the Sb-doped SnO2 is 1 nm to 10 nm, the mass ratio of Sb to SnO2 in the Sb-doped SnO2 is 0.2:100 to 0.5:100, the mass fraction of Sb-doped SnO2 in the catalytic film is 0.3% to 0.6%, and the loading of the catalytic film in the anode is 0.05 mg / cm³. 2 ~4 mg / cm 2 Furthermore, the anode is placed in the electrolyte of organic wastewater containing tricyclazole; The method for preparing the anode includes the following steps: 1) The cubic phase barium titanate was calcined to obtain the tetragonal phase BaTiO3; 2) The tetragonal BaTiO3 is dispersed in an organic reagent to obtain a suspension of tetragonal BaTiO3; 3) After mixing the tetragonal BaTiO3 suspension with SnCl4 solution and SbCl3 solution, alkali was added and the mixture was calcined to obtain a composite material in which Sb-doped SnO2 was loaded on the surface of tetragonal BaTiO3. 4) The composite material and the adhesive are mixed and drip-coated onto a conductive substrate to obtain an anode containing a catalytic film.

2. The application according to claim 1, characterized in that: The piezoelectric fuel cell also includes a membrane and a separator, and the membrane separates the container into a cathode chamber and an anode chamber.

3. The application according to claim 1, characterized in that: The device that provides mechanical energy is at least one of a mixer, an ultrasonic machine, a vibrator, and a pump.

4. A method capable of simultaneously treating organic wastewater containing tricyclazole and generating electricity, characterized in that, Includes the following steps: Organic wastewater containing tricyclazole is added to the container, and the anode of the piezoelectric fuel cell is placed in the organic wastewater containing tricyclazole. By connecting the anode and cathode of the piezoelectric fuel cell and turning on the device that provides mechanical energy, it is possible to simultaneously treat organic wastewater containing tricyclazole and generate electricity. The piezoelectric fuel cell includes: a container, a device for providing mechanical energy, a cathode, an anode, and organic wastewater containing tricyclazole; the impedance of the anode is 100 Ω to 400 Ω. Both the cathode and anode are placed in the container. The anode includes a conductive substrate and a catalytic film immobilized on the conductive substrate. The thickness of the catalytic film is 0.10 μm to 0.45 μm. The catalytic film comprises granular tetragonal BaTiO3 with a particle size of 40 nm to 120 nm. The X-ray diffraction pattern of the tetragonal BaTiO3 has two characteristic peaks at a 2θ position of 44.5° to 45.5°. The catalytic film also includes Sb-doped SnO2 loaded on the surface of the granular tetragonal BaTiO3. The particle size of the Sb-doped SnO2 is 1 nm to 10 nm, the mass ratio of Sb to SnO2 in the Sb-doped SnO2 is 0.2:100 to 0.5:100, the mass fraction of Sb-doped SnO2 in the catalytic film is 0.3% to 0.6%, and the loading of the catalytic film in the anode is 0.05 mg / cm³. 2 ~4 mg / cm 2 Furthermore, the anode is placed in the electrolyte of organic wastewater containing tricyclazole; The method for preparing the anode includes the following steps: 1) The cubic phase barium titanate was calcined to obtain the tetragonal phase BaTiO3; 2) The tetragonal BaTiO3 is dispersed in an organic reagent to obtain a suspension of tetragonal BaTiO3; 3) After mixing the tetragonal BaTiO3 suspension with SnCl4 solution and SbCl3 solution, alkali was added and the mixture was calcined to obtain a composite material in which Sb-doped SnO2 was loaded on the surface of tetragonal BaTiO3. 4) The composite material and the adhesive are mixed and drip-coated onto a conductive substrate to obtain an anode containing a catalytic film.

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