A patterned diamond-based electrochemical oxidation ozone synthesis device and method

Abstract

The application relates to a kind of electrochemical oxidation synthesis ozone device and method based on patterning diamond, belong to electrochemistry technical field, device includes the first shell and second shell connected, the first shell is opened with reaction groove, water is passed to reaction groove in working process;Reaction groove is close to the side of water inlet and is provided with turbulence generator;Patterning diamond anode and patterning cathode are attached to the two sides of proton exchange membrane and constitute electrode group and are arranged in the reaction groove, parallel to the water inlet end and water outlet end of reaction groove and are connected to form straight line;The two sides of electrode group are pressed with metal current collector.The turbulence generator is water wheel or porous microstructure.The application can overcome the problems of poor mechanical strength of traditional through-hole diamond electrode and difficult water and gas transmission on the surface of electrode, while increasing the electrochemical active area of electrode, and thus improving the ozone concentration, reaction efficiency and operating life of the electrochemical oxidation synthesis ozone device.

Description

Technical Field

[0001] This invention belongs to the field of electrochemical technology, and particularly relates to an electrochemical oxidation synthesis device and method based on patterned diamond for ozone synthesis. Background Technology

[0002] Ozone, characterized by its green, non-toxic, self-destructive, environmentally friendly nature and high inactivation efficiency, is an extremely important broad-spectrum disinfectant and bactericide. Electrochemical oxidation synthesis of ozone technology involves the transfer of electrons between water molecules and the surface of an anode material to form ozone molecules. This novel technology, characterized by zero harmful emissions, safe operation, low energy consumption, and suitability for distributed on-site synthesis, is a novel approach. In constructing an electrochemical oxidation synthesis ozone system, the anode material is crucial to system performance. Diamond is derived from SP... 3 The diamond electrode, composed of a stable tetrahedron with strong covalent bonds of hybrid carbon atoms, is environmentally friendly, resistant to strong acids and bases, and chemically stable. Importantly, the diamond electrode possesses an extremely high oxygen evolution potential (2.2~2.6 V vs. SHE), which can significantly suppress oxygen evolution side reactions. Therefore, diamond exhibits excellent potential as an anode material for the electrochemical oxidation synthesis of ozone, demonstrating high efficiency and high stability.

[0003] An electrochemical oxidation ozone synthesis system typically consists of an anode, a proton exchange membrane (PEM), a cathode, and a pure water electrolyte. The anode and cathode are attached to the surface of the PEM, which acts as a medium for ion transport in the solution. While this structure reduces the resistance to ion transport between the electrodes, it increases the resistance to water molecule diffusion to the anode and cathode surfaces, thus hindering ozone molecules from leaving the anode surface. Furthermore, oxygen produced by the anode side reaction and hydrogen produced by the cathode negative reaction tend to remain on the electrode surfaces, reducing the electrode area, increasing the system resistance, and consequently reducing ozone synthesis efficiency and increasing energy consumption. In severe cases, excessively high temperatures at the electrodes and PEM can lead to the failure and destruction of the electrochemical oxidation ozone synthesis device.

[0004] Enhancing the diffusion efficiency of substances on the electrode surface while maintaining low ion transport resistance between the anode and cathode is a key technical challenge for efficient electrochemical oxidation synthesis of ozone. Currently, the most common solution is to use perforated electrodes to construct channels for water molecule supply, ozone molecule and gas exhaust, thus shortening the mass transport distance. For example, Chinese Patent (Publication No.: CN105088267A, Publication Date: November 25, 2015) discloses an electrolytic cell device with separated anode and cathode chambers for ozone electrolytic production, including a conductive diamond membrane anode with perforations, a proton exchange membrane, and a cathode. Water molecules enter the gap between the electrode and the proton exchange membrane from the back of the electrode through the perforations, subsequently undergoing an oxidation reaction to synthesize ozone. Chinese Patent (Publication No.: CN111304678A, Publication Date: June 19, 2020) discloses an electrolytic ozone generator, including an anode, a proton exchange membrane, and a cathode with perforations. Water molecules also flow through the pores on the electrode plate from the back side into the interface between the electrode and the proton exchange membrane for electrolysis and to produce ozone. However, the above structure still has the following shortcomings:

[0005] 1. During assembly, the anode, proton exchange membrane, and cathode are tightly pressed together, with surface pressure exceeding 2.0 MPa. Therefore, although water molecules can flow into the through-holes, transport to the gap between the electrode and the proton exchange membrane remains difficult. Simultaneously, the gas generated by the reaction on the electrode surface cannot be efficiently transported to the through-holes.

[0006] 2. The mechanical strength of diamond electrodes with through holes is reduced. In particular, when using silicon wafers with through holes as the substrate for diamond deposition, the diamond electrode material is very prone to breakage and failure during the assembly and operation of the reaction device, which seriously affects the working life and performance consistency of the electrochemical oxidation synthesis ozone device. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides an electrochemical oxidation ozone synthesis device and method based on patterned diamond.

[0008] An electrochemical oxidation ozone synthesis device based on patterned diamond includes a first shell and a second shell connected together. A reaction tank is provided on the first shell. During operation, water is circulated into the reaction tank. A turbulence generator is provided on the side of the reaction tank near the water inlet. Patterned diamond anodes and patterned cathodes are attached to both sides of a proton exchange membrane to form an electrode assembly, which is arranged in the reaction tank and parallel to the straight line formed by the water inlet and outlet of the reaction tank. The two sides of the electrode assembly are pressed together by a metal current collector.

[0009] The patterned diamond anode, patterned cathode, and proton exchange membrane are of the same size, and the metal current collector is made of one of the following materials: titanium, titanium alloy, stainless steel, or high-nickel-molybdenum corrosion-resistant alloy.

[0010] Both the first and second housings have protrusions on opposite sides to achieve clamping from both sides of the electrode assembly. The height of the protrusions ensures that the patterned diamond anode, proton exchange membrane, and patterned cathode are pressed tightly together.

[0011] The turbulence generator is a water turbine.

[0012] The turbulence generator is a porous microstructure, which is interference-fitted into the pre-reserved mounting position at the front end of the reaction tank. The porous microstructure is made of one of the following materials: silicon dioxide, aluminum oxide, zirconium oxide, magnesium oxide, silicon nitride, boron nitride, aluminum nitride, titanium nitride, silicon carbide, boron carbide, titanium carbide, and zirconium carbide, with a median pore size distribution of 20~200 μm.

[0013] An electrochemical oxidation method for ozone synthesis based on patterned diamond, employing the aforementioned electrochemical oxidation ozone synthesis device based on patterned diamond, specifically includes the following steps:

[0014] S1: Fabrication of patterned diamond electrodes:

[0015] S2: Fabrication of patterned cathode:

[0016] Patterned electrodes are obtained by milling parallel trench arrays with a width and depth of 50~200 μm on the surface of the cathode plate.

[0017] S3: Surface treatment for patterned diamond anodes and patterned cathodes:

[0018] Among them, oxygen plasma or ultraviolet ozone methods are used to treat the diamond film on the surface of the patterned diamond anode and the patterned cathode to make their surfaces hydrophilic.

[0019] S4: Ozone is synthesized by electrochemical oxidation using an ozone synthesis device.

[0020] The patterned diamond electrode is a pyramid-patterned diamond electrode, and its preparation method is as follows:

[0021] S1.1: After ultrasonically cleaning the monocrystalline silicon substrate in acetone, ethanol and water in sequence, dry it with nitrogen gas for later use.

[0022] The monocrystalline silicon substrate is selected with a (100) crystal plane orientation, and the doping type is N-type or P-type, with a doping concentration of 10. 18 ~10 21 atom cm -3 The resistivity is 0.001 ~ 0.05 Ω·cm, and the thickness is 500 μm ~ 5 mm;

[0023] S1.2: The single-crystal silicon substrate cleaned and dried in step S1.1 is etched in a strong alkaline solution of NaOH or KOH, with the temperature of the strong alkaline solution set to 60~90°C. o C, specifically, first treat in concentrated alkali solution for 3~10 min, then treat in dilute alkali solution for 10~60 min;

[0024] The concentrated alkali solution has a mass fraction of 10-30%, the dilute alkali solution has a mass fraction of 0.5-5%, and the dilute alkali solution contains 5-30% isopropanol solution or one of cyclohexanediol, butanol, methanol, ethanol, and propanol.

[0025] S1.3: Place the silicon substrate in the diamond seed solution, and after ultrasonic oscillation for 5-60 min, place it in ethanol and ultrasonic oscillate for 1-10 min, and then dry it with nitrogen gas for later use.

[0026] S1.4: Microwave plasma chemical vapor deposition or hot filament chemical vapor deposition is carried out on a silicon substrate to form a pyramid-patterned diamond electrode with a pyramid-patterned diamond film.

[0027] The patterned diamond electrode is a nanopillar patterned diamond electrode, and the specific preparation method is as follows:

[0028] T1: Clean the monocrystalline silicon substrate by ultrasonic cleaning in acetone, ethanol and water in sequence, and then dry it with nitrogen gas for later use.

[0029] The monocrystalline silicon substrate is selected with a (100) crystal plane orientation, and the doping type is N-type or P-type, with a doping concentration of 10. 18 ~10 21 atom cm -3 The resistivity is 0.001 ~ 0.05 Ω·cm, and the thickness is 500 μm ~ 5 mm;

[0030] T2: The monocrystalline silicon substrate cleaned and dried in step T1 is first treated in an HF solution with a concentration of 2-8 mol / L for 30-300 s, then treated in a mixed solution of HF with a concentration of 2-8 mol / L and AgNO3 with a concentration of 0.001-0.1 mol / L for 1-10 min, then treated in an HF solution with a concentration of 2-8 mol / L and H2O2 solution with a concentration of 0.1-1 mol / L for 3-120 min; finally, treated in a nitric acid solution with a concentration of 0.1 mol / L for 10-30 min.

[0031] Clean with water and dry with nitrogen to form a nanopillar patterned silicon substrate with a nanopillar-shaped surface;

[0032] T3: Place the nanopillar patterned silicon substrate in a diamond seed solution and sonicate for 5-10 min. Then, place the nanopillar patterned silicon substrate in ethanol and sonicate for 1-5 min. Dry it with nitrogen gas for later use.

[0033] T4: Microwave plasma chemical vapor deposition or hot filament chemical vapor deposition is carried out on a nanopillar patterned silicon substrate to form a nanopillar patterned diamond electrode with a nanopillar patterned diamond film.

[0034] Hot-filament chemical vapor deposition consists of two steps: carbonization and growth.

[0035] During the carbonization process, a vacuum is first drawn, followed by the introduction of hydrogen and methane, with a methane / hydrogen flow rate ratio of 0.2-10%. When the gas pressure reaches 1000-4000 Pa, a hot wire current of 180-200 A is applied and maintained for 90-180 min to complete the carbonization step.

[0036] During the growth process, the pyramid-patterned silicon substrate with implanted crystals is placed in a graphite sample stage. First, a vacuum is drawn, and hydrogen, methane, and dopant molecules are introduced. The methane / hydrogen flow rate ratio is 0.5~10%, and the dopant molecule / hydrogen flow rate ratio is 0.25~7.5%. When the gas pressure reaches 1000~4000 Pa, a hot filament current is applied to make the hot filament power 4~8 kW. After 30~600 min of growth, the doping concentration of dopant molecules in the diamond film is adjusted by controlling the power, gas pressure, and flow rate ratio, and the thickness of the diamond film is adjusted by adjusting the growth time.

[0037] The dopant molecules introduced during the deposition process are trimethylborane, diborane, or phosphine.

[0038] By employing the above technical solution, the present invention has at least the following beneficial effects:

[0039] This invention overcomes the problems of poor mechanical strength and difficulty in water and gas transport on the electrode surface of traditional through-hole diamond electrodes, while increasing the electrochemical active area of ​​the electrode, thereby improving the ozone concentration, reaction efficiency, and service life of the electrochemical oxidation ozone synthesis device. Specifically:

[0040] 1. This invention constructs a patterned diamond electrode by etching a pyramid pattern onto a silicon substrate using an alkaline solution or etching a nanopillar pattern onto a silicon substrate using an acid solution. Subsequently, a diamond film is deposited on the silicon substrate via chemical vapor deposition to obtain the patterned diamond electrode. After the patterned diamond electrode is pressed together with a proton exchange membrane, a three-dimensional interconnected microreactor network is formed at the interface. Furthermore, after the surface of the patterned diamond electrode is treated to exhibit hydrophilic properties, water rapidly wets and spreads uniformly along the three-dimensional interconnected microreactor network under capillary force. Simultaneously, the generated ozone and other gases can rapidly escape through the three-dimensional interconnected microreactor network, significantly reducing liquid-gas mass transfer resistance and local overpotential, thereby improving ozone generation efficiency.

[0041] 2. The patterned diamond electrode constructed in this invention possesses a large specific surface area, increasing the number of active sites participating in the electrochemical oxidation reaction and thus increasing the ozone generation efficiency. The patterned diamond electrode does not contain through-hole structures, which helps enhance the mechanical stability of the electrode structure and avoids damage and failure during assembly and use. Simultaneously, this invention reduces drilling or scribing machining steps, lowering manufacturing costs.

[0042] 3. This invention provides an electrochemical oxidation ozone synthesis device based on patterned diamond electrodes, which includes a turbulence generator. When water flows through the turbulence generator, the flow pattern changes from laminar to turbulent, thus reducing dead zones and achieving efficient water mass transfer. Simultaneously, it facilitates the diffusion and escape of gases generated on the reaction site surface, accelerating the regeneration of active sites, thereby improving the efficiency of electrochemical oxidation ozone synthesis. Furthermore, the turbulent water flow promotes efficient heat transfer, accelerates the scouring and removal of deposits on the electrode surface, and extends the operational life of the electrochemical oxidation ozone synthesis device. Attached Figure Description

[0043] Figure 1 This is a schematic diagram of the electrochemical oxidation ozone synthesis device based on patterned diamond provided in Embodiment 1 of the present invention;

[0044] Figure 2 This is a schematic diagram of the second housing of the electrochemical oxidation ozone synthesis device based on patterned diamond provided in Embodiment 1 of the present invention;

[0045] Figure 3 This is a schematic cross-sectional view of the pyramid-patterned diamond anode used in the implementation of the electrochemical oxidation ozone synthesis device based on patterned diamond provided in Embodiment 1 of the present invention.

[0046] Figure 4This is a schematic diagram of the three-dimensional interconnected micro-reaction cavity network formed by pressing a pyramid-patterned diamond anode with a proton exchange membrane during the implementation of the electrochemical oxidation ozone synthesis device based on patterned diamond provided in Embodiment 1 of the present invention.

[0047] Figure 5 This is a schematic diagram of the electrochemical oxidation ozone synthesis device based on patterned diamond provided in Embodiment 4 of the present invention;

[0048] Figure 6 This is a cross-sectional schematic diagram of the nanopillar patterned diamond anode used in the implementation of the electrochemical oxidation ozone synthesis device based on patterned diamond provided in Embodiment 6 of the present invention.

[0049] in:

[0050] 1-Single crystal silicon substrate, 2-Pyramid-shaped surface, 3-Pyramid-patterned diamond film, 4-Nano-pillar-shaped surface, 5-Nano-pillar-patterned diamond film, 6-Proton exchange membrane, 7-Three-dimensional interconnected micro-reaction cavity network, 8-Reaction tank, 9-Patterned diamond anode, 10-Patterned cathode, 11-Anode stainless steel current collector, 12-Cathode stainless steel current collector, 13-Anode boss, 14-Cathode boss, 15-Fixed shaft, 16-Water wheel, 17-Cathode terminal, 18-Anode terminal, 19-First housing, 20-Second housing, 21-Outlet, 22-Inlet, 23-Waterproof gasket, 24-Porous microstructure. Detailed Implementation

[0051] To better explain and facilitate understanding of the present invention, the technical solution and effects of the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0052] Example 1

[0053] like Figures 1-2As shown, this embodiment provides an electrochemical oxidation ozone synthesis device based on patterned diamond, utilizing a patterned diamond anode 9 and a water turbine 16 to enhance mass transfer. Specifically, the electrochemical oxidation ozone synthesis device includes a first housing 19, on which a reaction tank 8 is formed. The two ends of the reaction tank 8 are connected to an inlet 22 and an outlet 21 located outside the first housing 19, respectively. The inlet 22 is connected to a flow-adjustable water pump via a hose, and the pump extends into a water tank. The outlet 21 is connected to a water tank containing ozone water via a hose. The open end of the first housing 19 with the reaction tank 8 is closedly connected to a second housing 20, forming a closed space. A water-resistant gasket 23 is provided between the first housing 19 and the second housing 20 for sealing and water isolation. Specifically, fastening bolts pass sequentially through the second housing 20, the sealing gasket, and the first housing 19, connecting the first housing 19 and the second housing 20, thereby forming a sealed reaction tank 8, providing the space and conditions for the reaction to occur.

[0054] Inside the reaction tank 8, a fixed shaft 15 is provided near the inlet 22, and a water wheel 16 is mounted on the fixed shaft 15 through a shaft hole. In this embodiment, a water wheel 16 is provided between the inlet 22 and the reaction tank 8. The water wheel 16, as a turbulence generator, differs in structure and function from the turbulence generators in the flow box or heat exchange tube of the paper machine. It is an active dynamic turbulence generator used to convert laminar flow into turbulent flow to enhance mass transfer.

[0055] Patterned diamond anode 9 and patterned cathode 10 are disposed inside the reaction tank 8, with the patterned diamond anode 9 positioned close to the first housing 19. A proton exchange membrane 6 is disposed between the patterned diamond anode 9 and the patterned cathode 10, specifically, the proton exchange membrane 6 is attached to the patterned diamond anode 9 and the patterned cathode 10.

[0056] Furthermore, an anode stainless steel current collector 11 is disposed on the side of the patterned diamond anode 9 near the first housing 19. The anode stainless steel current collector 11 is T-shaped, and the size of its contact area with the patterned diamond anode 9 is consistent with that of the patterned diamond anode 9. A cathode stainless steel current collector 12 is disposed on the side of the patterned cathode 10 opposite to the patterned diamond anode 9.

[0057] In this assembly, the first housing 19 and the second housing 20 are respectively provided with an anode boss 13 and a cathode boss 14 on opposite sides. During installation, the anode boss 13, the stainless steel anode current collector 11, the patterned diamond anode 9, the proton exchange membrane 6, the patterned cathode 10, the stainless steel cathode current collector 12, and the cathode boss 14 are stacked sequentially. This ensures good adhesion between the patterned diamond anode 9, the proton exchange membrane 6, and the patterned cathode 10, while maintaining good electrical contact between the stainless steel anode current collector 11 and the patterned diamond anode 9, and between the stainless steel cathode current collector 12 and the patterned cathode 10. The height of the anode boss 13 and the cathode boss 14 must be sufficient to ensure that the patterned diamond anode 9, the proton exchange membrane 6, and the patterned cathode 10 are pressed tightly together.

[0058] The anode boss 13 acts on the anode stainless steel current collector 11, which in turn acts on the patterned diamond anode 9. The patterned diamond anode 9 presses against the proton exchange membrane 6 from one side. The cathode boss 14 acts on the cathode stainless steel current collector 12, which in turn acts on the patterned cathode 10. The patterned cathode 10 presses against the proton exchange membrane 6 from the other side. The inlet of the reaction tank 8 is connected to the inlet 22, and the outlet is connected to the outlet 21.

[0059] The reaction tank 8 is also equipped with a cathode terminal 17 and an anode terminal 18, which are connected to and precisely pressed together with the anode stainless steel current collector 11 and the cathode stainless steel current collector 12, respectively. The electrochemical oxidation ozone synthesis device is driven by a DC, AC, or pulse power supply through the cathode terminal 17 and the anode terminal 18. The electrode group consisting of the patterned diamond anode 9, the proton exchange membrane 6, and the patterned cathode 10 is parallel to the straight line formed by the connection of the inlet 22 and the outlet 21.

[0060] The working principle of the above-mentioned electrochemical oxidation ozone synthesis device based on patterned diamond is as follows:

[0061] During operation, water enters the reaction tank 8 through inlet 22, reacts in the reaction tank 8 to produce ozone, and then flows out through outlet 21. In this embodiment, a water impeller 16 is provided at the connection between inlet 22 and reaction tank 8 as a turbulence generator. After passing through the water impeller 16, the water flow changes from an ordered laminar flow mode to a disordered turbulent flow mode, increasing mass and heat transfer. Subsequently, the water flows to the electrode group composed of patterned diamond anode 9, proton exchange membrane 6, and patterned cathode 10, with the water flow direction parallel to the surface of the electrode group. Furthermore, although the patterned diamond anode 9 and proton exchange membrane 6 are in close contact, the surface of the patterned diamond anode 9 is composed of a patterned diamond film covering the pyramid-shaped surface 2. This surface microscale ridge-valley structure still constructs a three-dimensional interconnected micro-reaction cavity network 7 between them, such as... Figures 3-4As shown. Therefore, water flowing in a disordered turbulent manner can easily enter these reaction volumes. Similarly, a microscale reaction volume is also formed between the patterned cathode 10 and the proton exchange membrane 6, providing conditions for efficient mass transfer of water. In the electrochemical oxidation synthesis of ozone, the space in the reaction tank 8 is filled with water, except for the electrode group consisting of the patterned diamond anode 9, the proton exchange membrane 6, and the patterned cathode 10, as well as the turbulence generator water wheel 16. When the current collector connecting the patterned diamond anode 9 and the patterned cathode 10 is given a certain potential or current, a water oxidation reaction occurs on the surface of the patterned diamond anode 9, producing ozone. The ozone dissolves in the water and then flows into the reaction tank 8 through the three-dimensional interconnected micro-reaction chamber network 7. The reaction on the surface of the patterned diamond anode 9 also produces oxygen. Oxygen has poor solubility in water and will first exist in the form of bubbles in the three-dimensional interconnected micro-reaction chamber network 7. Subsequently, driven by the water flow, the oxygen bubbles flow into the reaction tank 8. Hydrogen gas is generated on the surface of the patterned cathode 10, and the hydrogen bubbles flow into the reaction tank 8 through interconnected microscale reaction volumes. Rapid water and ozone mass transfer accelerates the electrochemical reaction on the electrode surface, while the rapid expulsion of oxygen and hydrogen helps to quickly regenerate the active sites on the electrode surface. Both factors jointly promote the electrochemical oxidation synthesis of ozone. After the reaction, the ozone flows through the reaction tank 8 to the outlet 21 and is discharged, thus achieving the preparation of ozone water.

[0062] A method for electrochemical oxidation synthesis of ozone based on patterned diamond, using the aforementioned electrochemical oxidation ozone synthesis apparatus based on patterned diamond, specifically includes the following steps:

[0063] S1: Preparation of pyramid-patterned diamond anode:

[0064] S1.1: 10 × 20 mm 2 The (001) oriented N-type single-crystal silicon substrate 1 has a doping concentration of 1.0 × 10⁻⁶. 18 atomcm -3 The resistivity is 0.01~0.02 Ω·cm and the thickness is 525 μm. After being ultrasonically cleaned in acetone, ethanol and water in sequence, it is dried with nitrogen gas for later use.

[0065] S1.2: Construct a pyramid pattern on a single-crystal silicon substrate 1.

[0066] The single-crystal silicon substrate 1, which was cleaned and dried in step S1.1, was placed in a 20% KOH solution at a temperature of 80°C. o C water bath treatment for 3 min.

[0067] The monocrystalline silicon substrate 1 was then transferred to a mixed alkaline solution, which in this embodiment consisted of 2% KOH by mass and 10% isopropanol by volume. The mixed alkaline solution was then placed at a temperature of 80°C. o The silicon substrate 1 is heated in a water bath at temperature C. After 40 minutes of heating, the single-crystal silicon substrate 1 is selectively etched to form a pyramid-patterned silicon substrate with a pyramid-shaped surface 2. The size of the pyramid-patterned silicon substrate structure is 3~10 μm.

[0068] S1.3: Place the above pyramid-patterned silicon substrate in a diamond seed solution, and after 30 min of ultrasonic oscillation, place the pyramid-patterned silicon substrate in ethanol and ultrasonically oscillate for 3 min, and then dry it with nitrogen gas for later use.

[0069] In this embodiment, the volumetric mass concentration of the diamond seed solution is 0.025 w / v, and the diamond grain size is 3~4 nm.

[0070] S1.4: Perform hot-wire chemical vapor deposition on a pyramid-patterned silicon substrate.

[0071] Hot-filament chemical vapor deposition consists of two steps: carbonization and growth. During the experiment, 12 tantalum wires were fixed on two molybdenum rod electrodes.

[0072] During the carbonization process, a vacuum is first drawn, followed by the introduction of 400 sccm of hydrogen and 10 sccm of methane. When the pressure reaches 1000 Pa, a hot wire current of 200 A is applied and maintained for 90 min to complete the carbonization step.

[0073] During the growth process, the pyramid-patterned silicon substrate obtained in S1.3 was placed in a graphite sample stage. Since intrinsic diamond is non-conductive, dopant molecules needed to be introduced during the deposition process. Specifically, a vacuum was first created by introducing 400 sccm of hydrogen, 2 sccm of methane, and 6 sccm of trimethylborane as a dopant. When the pressure reached 2000 Pa, a hot filament current was applied, resulting in a hot filament power of 7 kW. After 300 min of growth, a pyramid-patterned diamond electrode was prepared to form the pyramid-patterned diamond film 3, serving as the anode, thus preparing the pyramid-patterned diamond anode. Figure 3 As shown, the thickness of the pyramid-patterned diamond film 3 is 3~3.5 μm.

[0074] S2: Fabrication of patterned titanium cathode:

[0075] In this embodiment, a patterned titanium cathode 10 is obtained by milling a parallel trench array with a width and depth of 200 μm on the surface of a titanium plate. The size of the patterned titanium cathode 10 is the same as that of the pyramid patterned diamond anode.

[0076] S3: Surface treatment for pyramid-patterned diamond anodes and patterned titanium cathodes:

[0077] Pyramid-patterned diamond anodes and patterned titanium cathodes were placed in an ultraviolet ozone instrument and treated for 20 minutes to obtain a hydrophilic surface.

[0078] S4: Electrochemical oxidation synthesis of ozone based on an electrochemical oxidation ozone synthesis device.

[0079] When the electrochemical oxidation ozone synthesis device is operating, a positive potential is applied to the anode terminal 18 and a negative potential is applied to the cathode terminal 17, with an applied current density of 0.5 A or 3.4 A. A water pump supplies power and adjusts the water flow rate to 0.6 L / min or 1.0 L / min, allowing water to flow into the reaction tank 8 through the pump, hose, and inlet 22. Upon entering the reaction tank 8, the water drives the water turbine 16, changing the water flow from laminar to turbulent. Furthermore, the water flows through the side of the electrode assembly consisting of the pyramid-patterned diamond anode, proton exchange membrane 6, and patterned titanium cathode 10 into the three-dimensional interconnected micro-reaction cavity network 7 formed between the pyramid-patterned diamond anode, patterned titanium cathode 10, and proton exchange membrane 6. Due to the hydrophilic surfaces of the pyramid-patterned diamond anode and patterned titanium cathode 10 and the capillary effect, the water can spontaneously wet and rapidly diffuse along the three-dimensional interconnected micro-reaction cavity network 7. On the surface of the pyramid-patterned diamond anode, water undergoes an oxidation reaction, primarily producing ozone; on the surface of the patterned titanium cathode 10, water undergoes a reduction reaction, primarily producing hydrogen. Subsequently, ozone and hydrogen flow together into the outlet 21 and are discharged into the water tank. By measuring the ozone concentration in the water at the outlet 21, the performance of the aforementioned electrochemical oxidation ozone synthesis device can be evaluated.

[0080] Example 2

[0081] This embodiment uses the same electrochemical oxidation ozone synthesis device based on patterned diamond as in Embodiment 1. The only difference is the pyramid patterned diamond electrode. Specifically, the method of constructing the pyramid pattern on the single-crystal silicon substrate 1 is different in this embodiment.

[0082] In terms of implementation, the method for constructing the pyramid pattern on the monocrystalline silicon substrate 1 differs from that in Example 1. The remaining method steps are the same as in Example 1, such as the hot-wire chemical vapor deposition and the electrical and water flow parameters applied by the electrochemical oxidation ozone synthesis device on the pyramid patterned silicon substrate, which are consistent with those in Example 1.

[0083] In this embodiment, the specific steps for constructing the pyramid pattern on the monocrystalline silicon substrate 1 are as follows:

[0084] The monocrystalline silicon substrate 1, which was cleaned and dried in step S1.1, is placed in a 15% KOH solution and heated at a temperature of 80°C. o C water bath treatment for 2 min.

[0085] The monocrystalline silicon substrate 1 was then transferred to a mixed alkaline solution, which in this embodiment consisted of 2% KOH by mass and 15% isopropanol by volume. The mixed alkaline solution was then placed at a temperature of 80°C. o The silicon substrate 1 is heated in a water bath at temperature C. After 10 minutes of heating, the single-crystal silicon substrate 1 is selectively etched to form a pyramid-patterned silicon substrate with a pyramid-shaped surface 2. The size of the pyramid-patterned silicon substrate structure is 1~5 μm.

[0086] Example 3

[0087] This embodiment uses the same electrochemical oxidation ozone synthesis device based on patterned diamond as in Embodiment 1. The only difference is the pyramid patterned diamond electrode. Specifically, the hot-wire chemical vapor deposition method performed on the pyramid patterned silicon substrate is different in this embodiment.

[0088] In terms of implementation, the hot-wire chemical vapor deposition method on the pyramid-patterned silicon substrate differs from that in Example 1. The remaining method steps are the same as in Example 1, such as the pyramid patterning construction method on the single-crystal silicon substrate 1, and the electrical parameters and water flow parameters applied by the electrochemical oxidation ozone synthesis device remain consistent with those in Example 1.

[0089] In this embodiment, hot-wire chemical vapor deposition is performed on a pyramid-patterned silicon substrate. Specifically:

[0090] Hot-filament chemical vapor deposition consists of two steps: carbonization and growth. During the experiment, 12 tantalum wires were fixed on two molybdenum rod electrodes.

[0091] During the carbonization process, a vacuum is first drawn, followed by the introduction of 400 sccm of hydrogen and 20 sccm of methane. When the pressure reaches 1000 Pa, a hot wire current of 180 A is applied and maintained for 100 min to complete the carbonization step.

[0092] During the growth process, the pyramid-patterned silicon substrate obtained in S1.3 was placed in a graphite sample stage. Since intrinsic diamond is non-conductive, dopant molecules needed to be introduced during the deposition process. Specifically, a vacuum was first created by introducing 400 sccm of hydrogen, 2 sccm of methane, and 10 sccm of trimethylborane as a dopant. When the pressure reached 2000 Pa, a hot filament current was applied, resulting in a hot filament power of 7 kW. After 300 min of growth, a pyramid-patterned diamond electrode was prepared to form the pyramid-patterned diamond film 3, serving as the anode, thus preparing the pyramid-patterned diamond anode. Figure 3 As shown, the thickness of the pyramid-patterned diamond film 3 is 2~3 μm.

[0093] Example 4

[0094] like Figure 5 As shown, the only difference between this embodiment and Embodiment 1 is the turbulence generator in the patterned diamond-based electrochemical oxidation ozone synthesis device. The remaining structural configurations and implementation methods of the patterned diamond-based electrochemical oxidation ozone synthesis device are the same as in Embodiment 1. For example, the applied electrical parameters and water flow parameters remain consistent with those in Embodiment 1 during operation. The turbulence generator in this embodiment is a porous microstructure 24, which transforms the water flow from laminar to turbulent. The electrochemical oxidation ozone synthesis device provided in this embodiment is based on a pyramid-patterned diamond electrode and the porous microstructure 24 to enhance mass transfer.

[0095] The porous microstructure 24 is located between the inlet 22 and the reaction tank 8. An installation position is reserved at the front end of the reaction tank 8, and the porous microstructure 24 is assembled onto the installation position of the reaction tank 8 via an interference fit. In this embodiment, the porous microstructure 24 is made of silicon carbide, with a median pore size distribution of 100 μm. During operation, after the water flows through the silicon carbide porous microstructure, the flow pattern changes from laminar to turbulent.

[0096] Example 5

[0097] like Figure 5 As shown, the only difference between this embodiment and Embodiment 1 is the turbulence generator in the patterned diamond-based electrochemical oxidation ozone synthesis device. The remaining structural configurations and implementation methods of the patterned diamond-based electrochemical oxidation ozone synthesis device are the same as in Embodiment 1. For example, the applied electrical parameters and water flow parameters remain consistent with those in Embodiment 1 during operation. In this embodiment, the turbulence generator is a porous microstructure 24, which transforms the water flow from laminar to turbulent. The electrochemical oxidation ozone synthesis device provided in this embodiment is based on a pyramid-patterned diamond electrode and the porous microstructure 24 to enhance mass transfer.

[0098] The porous microstructure 24 is located between the inlet 22 and the reaction tank 8. An installation position is reserved at the front end of the reaction tank 8, and the porous microstructure 24 is assembled onto the installation position of the reaction tank 8 via an interference fit. In this embodiment, the porous microstructure 24 is made of alumina, with a median pore size distribution of 80 μm. During operation, after the water flows through the silicon carbide porous microstructure, the flow pattern changes from laminar to turbulent.

[0099] Example 6

[0100] This embodiment is the same as the electrochemical oxidation ozone synthesis device based on patterned diamond used in Embodiment 1. The only difference is the patterned diamond electrode. In this embodiment, the patterned diamond electrode used as the anode is a nanopillar patterned diamond anode, which is an electrode formed by depositing a nanopillar patterned diamond film 5 on a nanopillar shaped surface 4.

[0101] In terms of implementation, compared with Example 1, the specific preparation method is different due to the different anodes, but the rest of the method steps are the same as in Example 1, such as the applied electrical parameters and water flow parameters being consistent with those in Example 1.

[0102] In this embodiment, the preparation method of the nanopillar patterned diamond anode is as follows:

[0103] T1: 10 × 20 mm 2 The (001) oriented N-type single-crystal silicon substrate 1 has a doping concentration of 1.0 × 10⁻⁶. 19 atomcm -3 The resistivity is 0.01~0.02 Ω·cm and the thickness is 525 μm. After being ultrasonically cleaned in acetone, ethanol and water in sequence, it is dried with nitrogen gas for later use.

[0104] T2: Nanopillar patterning was carried out on a single-crystal silicon substrate 1.

[0105] The single-crystal silicon substrate 1, which was cleaned and dried in step T1, was first treated in HF solution for 30 s, and then treated in a mixed solution of 5 mol / L HF and 0.006 mol / L AgNO3 for 2 min.

[0106] Then, it was treated in a mixed solution of 5 mol / L HF and 0.5 mol / L H2O2 for 5 min.

[0107] Then it was treated in 0.1 mol / L HNO3 solution for 20 min.

[0108] Finally, after washing in water, it is dried with nitrogen gas for later use, forming a nanopillar patterned silicon substrate with a nanopillar-shaped surface 4. As shown in the figure, the length of the nanopillar is 2 μm.

[0109] T3: Place the above-mentioned nanopillar patterned silicon substrate into a diamond seed solution, and after 10 min of ultrasonic oscillation, ultrasonically oscillate the nanopillar patterned silicon substrate in ethanol for 1 min, and then dry it with nitrogen gas for later use.

[0110] In this embodiment, the volumetric mass concentration of the diamond seed solution is 0.025 w / v, and the diamond grain size is 3~4 nm.

[0111] T4: Hot filament chemical vapor deposition is performed on a nanopillar patterned silicon substrate.

[0112] Hot-filament chemical vapor deposition consists of two steps: carbonization and growth. During the experiment, 12 tantalum wires were fixed on two molybdenum rod electrodes.

[0113] During the carbonization process, a vacuum is first drawn, followed by the introduction of 400 sccm of hydrogen and 10 sccm of methane. When the pressure reaches 1000 Pa, a hot wire current of 200 A is applied and maintained for 90 min to complete the carbonization step.

[0114] During the growth process, the nanopillar-patterned silicon substrate obtained in T3 was placed in a graphite sample stage. Since intrinsic diamond is non-conductive, dopant molecules need to be introduced during the deposition process. Specifically, a vacuum was first created by introducing 400 sccm of hydrogen, 2 sccm of methane, and 6 sccm of trimethylborane as a dopant. When the pressure reached 2000 Pa, a hot filament current was applied, resulting in a hot filament power of 7 kW. After 300 min of growth, a nanopillar-patterned diamond anode was prepared, yielding a nanopillar-patterned diamond film 5. Figure 6 As shown, the thickness of the nanopillar patterned diamond film 5 is 3~3.5 μm.

[0115] Example 7

[0116] This embodiment uses the same electrochemical oxidation ozone synthesis device based on patterned diamond as in Embodiment 6, the only difference being the different nanopillar patterned diamond electrodes. Specifically, the method of constructing nanopillar patterns on the single-crystal silicon substrate 1 is different in this embodiment.

[0117] In terms of implementation, the method for constructing nanopillars on the single-crystal silicon substrate 1 differs from that in Example 6. The remaining method steps are the same as in Example 1, such as the hot-filament chemical vapor deposition, the electrical parameters applied by the electrochemical oxidation ozone synthesis device, and the water flow parameters on the nanopillar patterned silicon substrate, which are consistent with those in Example 6.

[0118] In this embodiment, nanopillar patterning is carried out on a single-crystal silicon substrate 1.

[0119] The single-crystal silicon substrate 1, which was cleaned and dried in step T1, was first treated in HF solution for 30 s, and then treated in a mixed solution of 5 mol / L HF and 0.006 mol / L AgNO3 for 1 min.

[0120] Then, it was treated in a mixed solution of 5 mol / L HF and 0.5 mol / L H2O2 for 7 min.

[0121] Then it was treated in 0.1 mol / L HNO3 solution for 20 min.

[0122] Finally, after washing in water, it is dried with nitrogen gas for later use, forming a nanopillar patterned silicon substrate with nanopillar-shaped surface 4. As shown in the figure, the nanopillar length is 3 μm.

[0123] Example 8

[0124] This embodiment uses the same electrochemical oxidation ozone synthesis device based on patterned diamond as in Embodiment 6, the only difference being the different nanopillar patterned diamond electrodes. Specifically, the hot-wire chemical vapor deposition method performed on the nanopillar patterned silicon substrate is different in this embodiment.

[0125] In terms of implementation, the hot-wire chemical vapor deposition method on the nanopillar patterned silicon substrate differs from that in Example 6. The remaining method steps are the same as in Example 6, such as the method for constructing nanopillar patterns on the single-crystal silicon substrate 1, and the electrical parameters and water flow parameters applied by the electrochemical oxidation ozone synthesis device remain consistent with those in Example 6.

[0126] In this embodiment, hot-wire chemical vapor deposition is performed on a nanopillar patterned silicon substrate.

[0127] Hot-filament chemical vapor deposition consists of two steps: carbonization and growth. During the experiment, 12 tantalum wires were fixed on two molybdenum rod electrodes.

[0128] During the carbonization process, a vacuum is first drawn, followed by the introduction of 400 sccm of hydrogen and 15 sccm of methane. When the pressure reaches 1000 Pa, a hot wire current of 180 A is applied and maintained for 100 min to complete the carbonization step.

[0129] During the growth process, the nanopillar-patterned silicon substrate obtained in T3 was placed in a graphite sample stage. Since intrinsic diamond is non-conductive, dopant molecules need to be introduced during the deposition process. Specifically, a vacuum was first created by introducing 400 sccm of hydrogen, 2 sccm of methane, and 9 sccm of trimethylborane as a dopant. When the pressure reached 2000 Pa, a hot filament current was applied, resulting in a hot filament power of 6 kW. After 300 min of growth, a nanopillar-patterned diamond electrode was fabricated, yielding a nanopillar-patterned diamond film 5. Figure 6 As shown, the thickness of the nanopillar patterned diamond film 5 is 2~3 μm.

[0130] Example 9

[0131] The only difference between this embodiment and Embodiment 6 is the turbulence generator in the patterned diamond-based electrochemical oxidation ozone synthesis device. The remaining structural configurations and implementation methods of the patterned diamond-based electrochemical oxidation ozone synthesis device are the same as in Embodiment 6. For example, the applied electrical parameters and water flow parameters remain consistent with those in Embodiment 1 during operation. In this embodiment, the turbulence generator is a porous microstructure 24, which transforms the water flow from laminar to turbulent. The electrochemical oxidation ozone synthesis device provided in this embodiment is based on a nanopillar patterned diamond anode and the porous microstructure 24 to enhance mass transfer.

[0132] The porous microstructure 24 is located between the inlet 22 and the reaction tank 8. An installation position is reserved at the front end of the reaction tank 8, and the porous microstructure 24 is assembled onto the installation position of the reaction tank 8 via an interference fit. In this embodiment, the porous microstructure 24 is made of silica, with a median pore size distribution of 80 μm. During operation, after the water flows through the silica porous microstructure, the flow pattern changes from laminar to turbulent.

[0133] Comparative Example

[0134] In this comparative example, a diamond electrode deposited on a planar silicon substrate surface was used instead of the pyramid-patterned diamond anode provided in Example 1. The cleaning of the planar silicon substrate was consistent with step S1.1 of Example 1. Subsequently, it was treated in a diamond seed solution, with the treatment steps consistent with step S1.3 of Example 1. Finally, a diamond film was chemically vapor-deposited on the planar silicon substrate surface, with the growth steps and parameters consistent with step S1.4 of Example 1. Electrochemical oxidation ozone synthesis was performed using the patterned diamond-based electrochemical oxidation ozone synthesis apparatus provided in Example 1, with the remaining method steps consistent with Example 1, such as the applied electrical parameters and water flow rate parameters during operation of the patterned diamond-based electrochemical oxidation ozone synthesis apparatus, which were consistent with those in Example 1.

[0135] Examples 1, 2, 3, 4, 5, 6, 7, 8, and 9, along with the comparative examples, were compared through experiments. The experimental results are summarized below:

[0136]

[0137] The results show that the ozone concentration and operating life of the examples are significantly higher than those of the comparative example, while the power consumption is significantly lower. At a current of 0.5 A, the ozone concentration of Example 6 is 3 times that of the comparative example, and the operating life of Example 1 is 54 times that of the comparative example. Comparing these examples, Example 7 has the highest ozone concentration and the lowest power consumption, while Example 1 has the longest operating life. The results demonstrate that the electrochemical oxidation ozone synthesis device based on patterned diamond electrodes and a turbulence generator to enhance mass transfer has the advantages of high efficiency, long lifespan, and low energy consumption.

Claims

1. An electrochemical oxidation ozone synthesis device based on patterned diamond, characterized in that: The device includes a first housing and a second housing connected together. A reaction tank is provided on the first housing. During operation, water is supplied to the reaction tank. A turbulence generator is provided on the side of the reaction tank near the water inlet. A patterned diamond anode and a patterned cathode are attached to both sides of the proton exchange membrane to form an electrode assembly, which is arranged in the reaction tank and is parallel to the straight line formed by the water inlet and outlet of the reaction tank. The two sides of the electrode assembly are pressed together by a metal current collector.

2. The ozone synthesis device based on patterned diamond using electrochemical oxidation according to claim 1, characterized in that: The patterned diamond anode, patterned cathode, and proton exchange membrane are of the same size, and the metal current collector is made of one of the following materials: titanium, titanium alloy, stainless steel, or high-nickel-molybdenum corrosion-resistant alloy.

3. The ozone synthesis device based on patterned diamond using electrochemical oxidation according to claim 1, characterized in that: Both the first and second housings have protrusions on opposite sides to achieve clamping from both sides of the electrode assembly. The height of the protrusions ensures that the patterned diamond anode, proton exchange membrane, and patterned cathode are pressed tightly together.

4. The ozone synthesis device based on patterned diamond using electrochemical oxidation according to claim 1, characterized in that: The turbulence generator is a water turbine.

5. The ozone synthesis device based on patterned diamond using electrochemical oxidation according to claim 1, characterized in that: The turbulence generator is a porous microstructure, which is interference-fitted into the pre-reserved mounting position at the front end of the reaction tank. The porous microstructure is made of one of the following materials: silicon dioxide, aluminum oxide, zirconium oxide, magnesium oxide, silicon nitride, boron nitride, aluminum nitride, titanium nitride, silicon carbide, boron carbide, titanium carbide, and zirconium carbide, with a median pore size distribution of 20~200 μm.

6. A method for ozone synthesis by electrochemical oxidation based on patterned diamond, employing the ozone synthesis apparatus for electrochemical oxidation based on patterned diamond as described in any one of claims 1 to 5, characterized in that, Specifically, the following steps are included: S1: Fabrication of patterned diamond electrodes: S2: Fabrication of patterned cathode: Patterned electrodes are obtained by milling parallel trench arrays with a width and depth of 50~200 μm on the surface of the cathode plate. S3: Surface treatment for patterned diamond anodes and patterned cathodes: Among them, oxygen plasma or ultraviolet ozone methods are used to treat the diamond film on the surface of the patterned diamond anode and the patterned cathode to make their surfaces hydrophilic. S4: Ozone is synthesized by electrochemical oxidation using an ozone synthesis device.

7. The method for synthesizing ozone by electrochemical oxidation based on patterned diamond according to claim 6, characterized in that: The patterned diamond electrode is a pyramid-patterned diamond electrode, and its preparation method is as follows: S1.1: After ultrasonically cleaning the monocrystalline silicon substrate in acetone, ethanol and water in sequence, dry it with nitrogen gas for later use. The monocrystalline silicon substrate is selected with a (100) crystal plane orientation, and the doping type is N-type or P-type, with a doping concentration of 10. 18 ~10 21 atomcm -3 The resistivity is 0.001 ~ 0.05 Ω·cm, and the thickness is 500 μm ~ 5 mm; S1.2: The single-crystal silicon substrate cleaned and dried in step S1.1 is etched in a strong alkaline solution of NaOH or KOH, with the temperature of the strong alkaline solution set to 60~90°C. o C, specifically, first treat in concentrated alkali solution for 3~10 min, then treat in dilute alkali solution for 10~60 min; The concentrated alkali solution has a mass fraction of 10-30%, the dilute alkali solution has a mass fraction of 0.5-5%, and the dilute alkali solution contains 5-30% isopropanol solution or one of cyclohexanediol, butanol, methanol, ethanol, and propanol. S1.3: Place the silicon substrate in the diamond seed solution, and after ultrasonic oscillation for 5-60 min, place it in ethanol and ultrasonic oscillate for 1-10 min, and then dry it with nitrogen gas for later use. S1.4: Microwave plasma chemical vapor deposition or hot filament chemical vapor deposition is carried out on a silicon substrate to form a pyramid-patterned diamond electrode with a pyramid-patterned diamond film.

8. The method for synthesizing ozone by electrochemical oxidation based on patterned diamond according to claim 6, characterized in that: The patterned diamond electrode is a nanopillar patterned diamond electrode, and the specific preparation method is as follows: T1: Clean the monocrystalline silicon substrate by ultrasonic cleaning in acetone, ethanol and water in sequence, and then dry it with nitrogen gas for later use. The monocrystalline silicon substrate is selected with a (100) crystal plane orientation, and the doping type is N-type or P-type, with a doping concentration of 10. 18 ~10 21 atomcm -3 The resistivity is 0.001 ~ 0.05 Ω·cm, and the thickness is 500 μm ~ 5 mm; T2: The monocrystalline silicon substrate cleaned and dried in step T1 is first treated in an HF solution with a concentration of 2-8 mol / L for 30-300 s, then treated in a mixed solution of HF with a concentration of 2-8 mol / L and AgNO3 with a concentration of 0.001-0.1 mol / L for 1-10 min, then treated in an HF solution with a concentration of 2-8 mol / L and H2O2 solution with a concentration of 0.1-1 mol / L for 3-120 min; finally, treated in a nitric acid solution with a concentration of 0.1 mol / L for 10-30 min. Clean with water and dry with nitrogen to form a nanopillar patterned silicon substrate with a nanopillar-shaped surface; T3: Place the nanopillar patterned silicon substrate in a diamond seed solution and sonicate for 5-10 min. Then, place the nanopillar patterned silicon substrate in ethanol and sonicate for 1-5 min. Dry it with nitrogen gas for later use. T4: Microwave plasma chemical vapor deposition or hot filament chemical vapor deposition is carried out on a nanopillar patterned silicon substrate to form a nanopillar patterned diamond electrode with a nanopillar patterned diamond film.

9. A method for synthesizing ozone by electrochemical oxidation based on patterned diamond according to claim 7 or 8, characterized in that: Hot-filament chemical vapor deposition consists of two steps: carbonization and growth. During the carbonization process, a vacuum is first drawn, followed by the introduction of hydrogen and methane, with a methane / hydrogen flow rate ratio of 0.2-10%. When the gas pressure reaches 1000-4000 Pa, a hot wire current of 180-200 A is applied and maintained for 90-180 min to complete the carbonization step. During the growth process, the pyramid-patterned silicon substrate with implanted crystals is placed in a graphite sample stage. First, a vacuum is drawn, and hydrogen, methane, and dopant molecules are introduced. The methane / hydrogen flow rate ratio is 0.5~10%, and the dopant molecule / hydrogen flow rate ratio is 0.25~7.5%. When the gas pressure reaches 1000~4000 Pa, a hot filament current is applied to make the hot filament power 4~8 kW. After 30~600 min of growth, the doping concentration of dopant molecules in the diamond film is adjusted by controlling the power, gas pressure, and flow rate ratio, and the thickness of the diamond film is adjusted by adjusting the growth time.

10. The method for synthesizing ozone by electrochemical oxidation based on patterned diamond according to claim 9, characterized in that: The dopant molecules introduced during the deposition process are trimethylborane, diborane, or phosphine.

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