# US 12,759,906 B2 · Boron-doped diamond electrode with ultra-high specific surface area, and preparation method therefor and application thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,759,906 B2 - Document ID: US12759906B2 - Status: Granted - Kind: B2 - Application number: 17/924,682 - Filed: 2021-05-10 - Published: 2023-06-15 - Granted: 2026-10-13 - Earliest claimed: 2020-05-11 - Assignees: Nanjing Zuanxin Dianhuaxue Technology Co., Ltd. - Applicants: Nanjing Zuanxin Dianhuaxue Technology Co., Ltd. - Inventors: Qiuping Wei; Li Ma; Kechao Zhou; Lifeng Wang; Baofeng Wang; Haiping Shi - Web page: https://patentgrep.com/patent/US12759906B2 ## CPC - C02F 1/46109: {Electrodes} - C25B 11/059: Silicon - C25B 11/083: Diamond - C02F 2001/46147: {Diamond coating} - C02F 1/4672: {by electrooxydation} - C02F 2303/04: Disinfection - C02F: TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE (separation in general B01D; special arrangements on waterborne vessels of installations for treating water, waste water or sewage, e.g. for producing fresh water, B63J; adding materials to water to prevent corrosion C23F; treating radioactively-contaminated liquids G21F9/04; regeneration of reactants for recirculation into processes, see the relevant places for the processes) - C25B: ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR (anodic or cathodic protection C23F13/00; single-crystal growth C30B) ## Abstract A boron-doped diamond electrode with an ultra-high specific surface area, and a preparation method therefor and the application thereof are provided. The boron-doped diamond electrode includes a substrate and an electrode working layer arranged on a surface thereof, the substrate is polysilicon or monocrystal silicon with a high specific surface area, and the electrode working layer is a boron-doped diamond layer. The polysilicon with a high specific surface area is obtained by anisotropic etching and/or isotropic etching, and the monocrystal silicon with a high specific surface area is obtained by anisotropic etching. The boron-doped diamond layer includes a highly conductive layer, a corrosion-resistant layer, and a strongly electrocatalytically active layer, which have different boron contents. Compared with a traditional plate electrode, the present disclosure has a low cost and an extremely high specific surface area, provides a larger current intensity with a lower current density, and has broad application prospects. ## Claims ### Claim 1 A boron-doped diamond electrode, comprising a substrate and an electrode working layer, wherein a surface of the substrate is covered by the electrode working layer; the substrate is a polysilicon or a monocrystal silicon; the electrode working layer is a boron-doped diamond layer; the polysilicon is obtained by carrying out an anisotropic etching and/or an isotropic etching on a surface of the polysilicon; and the monocrystal silicon is obtained by carrying out the anisotropic etching on a surface of the monocrystal silicon; wherein the boron-doped diamond layer comprises a boron-doped diamond conductive layer, a boron-doped diamond corrosion-resistant layer, and a boron-doped diamond electrocatalytically active layer, and the boron-doped diamond conductive layer, the boron-doped diamond corrosion-resistant layer, and the boron-doped diamond electrocatalytically active layer have different boron contents and are successively deposited on the surface of the substrate; wherein in the boron-doped diamond conductive layer, a B/C is 20000 ppm-33333 ppm in an atomic ratio; in the boron-doped diamond corrosion-resistant layer, a B/C is 0 ppm-10000 ppm in the atomic ratio; and in the boron-doped diamond electrocatalytically active layer, a B/C is 10000 ppm-20000 ppm in the atomic ratio. ### Claim 2 (depends on 1) The boron-doped diamond electrode according to claim 1, wherein the substrate is the polysilicon; the polysilicon is obtained by carrying out the isotropic etching on the surface of the polysilicon; the substrate is in a shape of a column, a cylinder, or a flat plate; and the substrate is a three-dimensional continuous network structure, a two-dimensional continuous network structure, or a two-dimensional closed flat plate structure. ### Claim 3 (depends on 2) The boron-doped diamond electrode according to claim 2, wherein the boron-doped diamond layer has a thickness of 5 μm-2 mm; the boron-doped diamond electrocatalytically active layer accounts for 40%-60% of the boron-doped diamond layer in the thickness; and micro holes and/or sharp cones are distributed on a surface of the boron-doped diamond layer. ### Claim 4 (depends on 1) The boron-doped diamond electrode according to claim 1, wherein the boron-doped diamond layer has a thickness of 5 μm-2 mm; the boron-doped diamond electrocatalytically active layer accounts for 40%-60% of the boron-doped diamond layer in the thickness; and micro holes and/or sharp cones are distributed on a surface of the boron-doped diamond layer. ### Claim 5 A boron-doped diamond electrode, comprising a substrate and an electrode working layer, wherein a surface of the substrate is covered by the electrode working layer; the substrate is a polysilicon or a monocrystal silicon; the electrode working layer is a boron-doped diamond layer; the polysilicon is obtained by carrying out an anisotropic etching and/or an isotropic etching on a surface of the polysilicon; and the monocrystal silicon is obtained by carrying out the anisotropic etching on a surface of the monocrystal silicon; wherein the boron-doped diamond layer comprises a boron-doped diamond conductive layer, a boron-doped diamond corrosion-resistant layer, and a boron-doped diamond electrocatalytically active layer, and the boron-doped diamond conductive layer, the boron-doped diamond corrosion-resistant layer, and the boron-doped diamond electrocatalytically active layer have different boron contents and are successively deposited on the surface of the substrate; wherein the boron-doped diamond layer has a thickness of 5 μm-2 mm; the boron-doped diamond electrocatalytically active layer accounts for 40%-60% of the boron-doped diamond layer in the thickness; and micro holes and/or sharp cones are distributed on a surface of the boron-doped diamond layer. ### Claim 6 (depends on 5) The boron-doped diamond electrode with according to claim 5, wherein the substrate is the polysilicon; the polysilicon is obtained by carrying out the isotropic etching on the surface of the polysilicon; the substrate is in a shape of a column, a cylinder, or a flat plate; and the substrate is a three-dimensional continuous network structure, a two-dimensional continuous network structure, or a two-dimensional closed flat plate structure. ### Claim 7 (depends on 1) A method for preparing the boron-doped diamond electrode according to claim 1, comprising the following steps: step I: pretreating the substrate carrying out the anisotropic etching or/and the isotropic etching on a surface of a polysilicon substrate material to obtain the polysilicon; and carrying out the anisotropic etching on a surface of a monocrystal silicon substrate material to obtain the monocrystal silicon; step II: planting seed crystals on the surface of the substrate placing the polysilicon or the monocrystal silicon obtained in the step I in a suspension containing mixed particles of a nanocrystal diamond and/or a microcrystal diamond, and carrying out an ultrasonic treatment and a drying to obtain the polysilicon or the monocrystal silicon with the nanocrystal diamond and/or the microcrystal diamond adsorbed on the surface of the polysilicon and the surface of the monocrystal silicon; step III: depositing the boron-doped diamond layer placing the polysilicon or the monocrystal silicon obtained in the step II in a chemical vapor deposition furnace, injecting a carbon containing gas and a boron containing gas, and sequentially carrying out three stages of a deposition to obtain the boron-doped diamond layer, wherein during a first stage of the deposition, the boron containing gas is controlled to account for 0.03%-0.05% of a total mass flow of a gas in the chemical vapor deposition furnace; during a second stage of the deposition, the boron containing gas is controlled to account for 0%-0.015% of the total mass flow of the gas in the chemical vapor deposition furnace, and during a third stage of the deposition, the boron containing gas is controlled to account for 0.015%-0.03% of the total mass flow of the gas in the chemical vapor deposition furnace; and step IV: a high-temperature treatment carrying out a heat treatment on the polysilicon or the monocrystal silicon with the boron-doped diamond layer deposited, wherein a temperature of the heat treatment is 400° C.-1200° C., a time of the heat treatment is 5 min-110 min, a pressure in the chemical vapor deposition furnace is 10 Pa-105 Pa, and an atmosphere of the heat treatment contains an etching gas. ### Claim 8 (depends on 7) The method for preparing the boron-doped diamond electrode according to claim 7, wherein in the step I, a specific process of carrying out the anisotropic etching on the surface of the polysilicon substrate material is: soaking the polysilicon substrate material in an anisotropic etching solution at 20° C.-90° C. for 10 min-180 min, and cleaning and drying the polysilicon substrate material; and the anisotropic etching solution is one of: a sodium hydroxide solution, a potassium hydroxide solution, a mixed solution of sodium hydroxide and sodium hypochlorite, a tetramethyl ammonium hydroxide solution, a mixed solution of tetramethyl ammonium hydroxide and isopropanol, a mixed solution of the tetramethyl ammonium hydroxide and polyethylene glycol octyl phenyl ether, a mixed solution of the tetramethyl ammonium hydroxide and ammonium persulfate, a mixed solution of the tetramethyl ammonium hydroxide, the polyethylene glycol octyl phenyl ether, and the isopropanol, a mixed solution of ethylenediamine, pyrocatechol, and water, and ethylenediamine phosphoquinone. ### Claim 9 (depends on 7) The method for preparing the boron-doped diamond electrode according to claim 7, wherein in the step I, a specific process of carrying out the isotropic etching on the surface of the polysilicon substrate material is: soaking the polysilicon substrate material in an isotropic etching solution at 0° C.-90° C. for 10 s-130 min, and cleaning and drying the polysilicon substrate material; and the isotropic etching solution is one of a mixed solution of hydrofluoric acid and nitric acid, a mixed solution of the hydrofluoric acid, the nitric acid, and acetic acid, and a mixed solution of the hydrofluoric acid and the acetic acid. ### Claim 10 (depends on 7) The method for preparing the boron-doped diamond electrode according to claim 7, wherein in the step II, a mass fraction of the mixed particles in the suspension containing the mixed particles of the nanocrystal diamond and/or the microcrystal diamond is 0.01%-0.05%; in the step II, a time of the ultrasonic treatment is 5 min-30 min; in the step III, the carbon containing gas accounts for 0.5%-10.0% of the total mass flow of the gas in the chemical vapor deposition furnace during the three stages of the deposition; and in the step III, the first stage of the deposition is carried out at 600° C.-1000° C. and 103 Pa-104 Pa for less than or equal to 18 h; the second stage of the deposition is carried out at 600° C.-1000° C. and 103 Pa-104 Pa for less than or equal to 18 h; and the third stage of the deposition is carried out at 600° C.-1000° C. and 103 Pa-104 Pa for less than or equal to 18 h. ### Claim 11 (depends on 7) The method for preparing the boron-doped diamond electrode according to claim 7, wherein the substrate is the polysilicon; the polysilicon is obtained by carrying out the isotropic etching on the surface of the polysilicon; the substrate is in a shape of a column, a cylinder, or a flat plate; and the substrate is a three-dimensional continuous network structure, a two-dimensional continuous network structure, or a two-dimensional closed flat plate structure. ### Claim 12 (depends on 7) The method for preparing the boron-doped diamond electrode according to claim 7, wherein the boron-doped diamond layer has a thickness of 5 μm-2 mm; the boron-doped diamond electrocatalytically active layer accounts for 40%-60% of the boron-doped diamond layer in the thickness; and micro holes and/or sharp cones are distributed on a surface of the boron-doped diamond layer. ### Claim 13 (depends on 1) A method of a use of the boron-doped diamond electrode according to claim 1, wherein the boron-doped diamond electrode is used in an electrochemical oxidation treatment of a wastewater, a sterilization and a disinfection of a various daily water, a removal of organic pollutants, or ozone generators, or electrochemical biosensors.