CN115404459A - Distributed boron-doped diamond/metal-based composite material and preparation method and application thereof - Google Patents
Distributed boron-doped diamond/metal-based composite material and preparation method and application thereof Download PDFInfo
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- CN115404459A CN115404459A CN202211088307.2A CN202211088307A CN115404459A CN 115404459 A CN115404459 A CN 115404459A CN 202211088307 A CN202211088307 A CN 202211088307A CN 115404459 A CN115404459 A CN 115404459A
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- boron
- doped diamond
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- distributed
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 105
- 239000010432 diamond Substances 0.000 title claims abstract description 105
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 61
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
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- 239000011248 coating agent Substances 0.000 claims abstract description 41
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- 238000000034 method Methods 0.000 claims description 26
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- 239000011156 metal matrix composite Substances 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 238000005530 etching Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
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- 239000010949 copper Substances 0.000 claims description 12
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- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
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- 239000010703 silicon Substances 0.000 description 4
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- INOIOAWTVPHTCJ-UHFFFAOYSA-N 6-acetamido-4-hydroxy-3-[[4-(2-sulfooxyethylsulfonyl)phenyl]diazenyl]naphthalene-2-sulfonic acid Chemical compound CC(=O)NC1=CC=C2C=C(C(N=NC3=CC=C(C=C3)S(=O)(=O)CCOS(O)(=O)=O)=C(O)C2=C1)S(O)(=O)=O INOIOAWTVPHTCJ-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/271—Diamond only using hot filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
- B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
- B22F7/064—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts using an intermediate powder layer
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/278—Diamond only doping or introduction of a secondary phase in the diamond
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a distributed boron-doped diamond/metal-based composite material and a preparation method and application thereof, wherein the distributed boron-doped diamond/metal-based composite material comprises a metal sheet and a plurality of boron-doped diamond electrode plates distributed on the surface of the metal sheet at intervals, wherein a lead suboxide coating is arranged between the metal sheet and the boron-doped diamond electrode plates; the lead suboxide coating is completely coated on the surface of the metal sheet, or a plurality of lead suboxide coatings are arranged on the surface of the metal sheet at intervals; the invention provides a distributed boron-doped diamond/metal-based composite material for the first time, which is formed by combining a plurality of boron-doped diamond electrode plates, has good conductivity and larger electrochemical active area compared with single BDD, has better corrosion resistance effect compared with the single BDD, and has longer service life.
Description
Technical Field
The invention relates to a distributed boron-doped diamond/metal-based composite material and a preparation method and application thereof, belonging to the field of
Background
Diamond is a material with excellent physical and chemical properties, has the characteristics of high mechanical strength, excellent chemical stability and performance, no obvious change on the surface of an electrode under the action of high-strength current load and the like, and has wide prospects in the aspect of electrochemical application. Boron element is doped in the growth process of the diamond film, so that the prepared boron-doped diamond film is changed into a semiconductor or a conductor with metal property, and the boron-doped diamond electrode obtained by depositing the boron-doped diamond film on the surface of certain electrode substrates such as titanium sheets, silicon wafers, graphite and the like is the key point in the fields of sewage purification treatment, electrochemical biosensors and the like in recent years. Compared with the traditional electrode, the boron-doped diamond film electrode has the advantages of wide window, small background current, good electrochemical stability, good mechanical property, strong corrosion resistance, good conductivity and the like, and has good prospect in the field of treating sewage by electrochemical oxidation.
The traditional single-layer electrode for growing boron-doped diamond on a titanium sheet or a silicon sheet is prone to film falling due to mismatching of thermal expansion coefficients, and the further development of the boron-doped diamond film electrode is limited due to insufficient conductivity of the silicon sheet.
The continuous progress of electrochemical processes and the emergence of new electrode materials and electrode structures in recent years have provided newer and more effective solutions to electrochemical research. The multilayer composite electrode material has better conductivity and longer electrode service life compared with a single-layer electrode. Compared with the process production size limited by a single-layer electrode, the size of the multi-layer composite electrode is larger, the multi-electrode combination obtains larger specific surface area, so that the electrochemical activity is stronger, the efficiency is higher, the application range of the electrode is expanded while the excellent electrochemical performance is considered, and the multi-layer composite electrode can be applied to more fields.
However, no multi-electrode combination has been reported at present.
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention aims to provide a distributed boron-doped diamond/metal matrix composite material with long service life, high conductivity and higher electrochemical activity.
The second purpose of the invention is to provide a preparation method of the distributed boron-doped diamond/metal matrix composite material.
The third purpose of the invention is to provide the application of the distributed boron-doped diamond/metal matrix composite material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a distributed boron-doped diamond/metal-based composite material, which comprises a metal sheet and a plurality of boron-doped diamond electrode plates distributed on the surface of the metal sheet at intervals, wherein a lead suboxide coating is arranged between the metal sheet and the boron-doped diamond electrode plates.
The invention provides a distributed boron-doped diamond/metal-based composite material for the first time, which is formed by combining a plurality of boron-doped diamond electrode plates, has good conductivity and larger electrochemical active area compared with single BDD, has better corrosion resistance effect compared with the single BDD, and has longer service life; and a lead suboxide coating with excellent conductivity is introduced between the metal sheet and the boron-doped diamond electrode sheet, so that the metal sheet and the boron-doped diamond electrode sheet are firmly connected by sintering and welding on the basis of ensuring the conductivity.
Preferably, the lead suboxide coating is completely coated on the surface of the metal sheet, or a plurality of lead suboxide coatings are arranged on the surface of the metal sheet at intervals.
The inventor finds that when the lead suboxide coating is completely coated on the surface of the metal sheet and then a plurality of boron-doped diamond electrode plates are arranged on the lead suboxide coating, the lead suboxide can act together with the BDD to enable the lead suboxide coating to have a larger active area, and when a plurality of lead suboxide coatings are arranged on the surface of the metal sheet at intervals and then a corresponding number of boron-doped diamond electrode plates are arranged on the surfaces of the plurality of lead suboxide coatings, the boron-doped diamond electrode plates can obtain a higher oxidation potential.
Preferably, the thickness of the lead suboxide coating is 500nm-200 μm, preferably 50-150 μm, and the inventor finds that the thickness of the lead suboxide coating needs to be effectively controlled, and the excessive thickness and the excessive thinness can influence the binding force.
In a preferred scheme, the metal sheet is selected from one of a titanium-clad copper sheet, a tantalum-clad copper sheet, a titanium sheet, a niobium sheet, a tantalum sheet and a zirconium sheet.
Preferably, the structure of the metal sheet is selected from one of a continuous plate-shaped structure, a net-shaped structure, a discontinuous frame structure, a columnar structure, a barrel-shaped structure, an irregular three-dimensional structure and a regular three-dimensional structure.
In a preferred scheme, the boron-doped diamond electrode plates are arranged on the surface of the metal sheet in an array arrangement mode.
The inventor finds that the boron-doped diamond electrode plates are arranged in various array modes according to requirements, so that the optimal electrode unit radiation range, the higher electrocatalytic activity area and the higher current efficiency can be obtained.
In a preferred scheme, the boron-doped diamond electrode plate consists of a substrate and a boron-doped diamond film layer arranged on the surface of the substrate.
Further preferably, the substrate is selected from one of metal nickel, niobium, tantalum, zirconium, copper, titanium, cobalt, tungsten, molybdenum, chromium, iron or one of metal alloys; or the substrate is selected from ceramic Si and Al 2 O 3 、ZrO 2 、SiC、Si 3 N 4 、BN、B 4 C、AlN、TiB 2 、TiN、WC、Cr 7 C 3 、Ti 2 GeC、Ti 2 AlC and Ti 2 AlN、Ti 3 SiC 2 、Ti 3 GeC 2 、Ti 3 AlC 2 、Ti 4 AlC 3 、BaPO 3 Or doped ceramics therein.
Further preferably, the substrate structure is at least one selected from a three-dimensional continuous network structure, a two-dimensional continuous net structure, a two-dimensional closed flat plate structure, a one-dimensional filament shape, a one-dimensional linear shape, a one-dimensional rod shape and a zero-dimensional particle shape.
Further preferably, the thickness of the boron-doped diamond film layer is 5-20 μm.
Further preferably, the mass fraction of the boron element in the boron-doped diamond film layer is 2-10 per mill.
In the invention, the shape of the boron-doped diamond electrode plate is not limited, and can be triangular, square, circular, star-shaped or other regular or irregular shapes,
in the invention, the boron-doped diamond electrode plates with different shapes and used as leftover materials in production can be welded in a combined way on the substrate, and the materials are recycled.
The invention relates to a preparation method of a distributed boron-doped diamond/metal-based composite material, which comprises the following steps: and uniformly arranging the coating containing the lead suboxide on the metal sheet, then placing the substrate exposed surface of the boron-doped diamond electrode sheet facing the coating containing the lead suboxide on the metal sheet containing the coating containing the lead suboxide, drying and sintering to obtain the distributed boron-doped diamond/metal-based composite material.
In a preferred embodiment, the preparation method of the coating containing lead suboxide comprises the following steps: mixing anhydrous ethanol, water, lead monoxide, sintering aid and binder, and stirring at 80-120 deg.C for 30-90 min.
Further preferably, the mass ratio of the absolute ethyl alcohol, the water and the lead suboxide is (1-3) to (7-10) to (8-11). In actual operation, the water used is deionized water.
Further preferably, the sintering aid is selected from Al powder, ti powder and TiC 2 Powder, pbO 2 Powder, tiB 2 At least one of the powders, wherein the addition amount of the sintering aid is 2-10 wt.% of the mass of the lead sub-oxide.
Further preferably, the binder is selected from at least one of polyvinyl alcohol, polyethylene glycol and nafion, and the addition amount of the binder is 2-10 wt% of the mass of the lead sub-oxide.
In the actual operation process, when the arrangement mode that the lead suboxide coating is completely coated on the surface of the metal sheet is adopted, the coating containing the lead suboxide can be uniformly arranged on the metal sheet in one or more modes of dipping, spin coating, roll coating, spraying and brush coating, when a plurality of lead suboxide coatings are arranged on the surface of the metal sheet at intervals, and then a corresponding number of boron-doped diamond electrode plates are arranged on the surfaces of the plurality of lead suboxide coatings, the coating containing the lead suboxide is uniformly arranged on the metal sheet in one mode of spraying or brush coating.
Then, the exposed surface of the substrate of the boron-doped diamond electrode plate faces the coating containing the lead suboxide and is placed on a metal sheet containing the coating containing the lead suboxide, and a clamp is adopted to fix the boron-doped diamond electrode plate.
In a preferable scheme, the drying temperature is 60-90 ℃, and the drying time is 5-24h.
Preferably, the sintering process comprises: heating to 300-450 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 1h-3h, heating to 500-750 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 1h-4h, controlling the vacuum degree to be 1000-6000pa, and controlling the flow of argon atmosphere to be 20-100sccm.
The inventors have found that the above-described temperature raising process provides good bonding of the electrode sheet to the lead oxide coating and the metal sheet, which may be affected if the sintering process of the present invention is not followed.
In a preferred scheme, the boron-doped diamond electrode plate is obtained by the following steps: firstly, etching the substrate, then planting nano diamond seed crystals on the surface of the etched substrate, and finally growing a boron-doped diamond layer on the etched surface of the substrate by adopting hot filament chemical vapor deposition.
The inventor finds that the etching treatment can remove the surface oxidation film and the surface oil stain, increase the specific surface area of the substrate, enhance the binding force and enable the electrode plate to be better sintered and welded.
Further preferably, when the substrate is ceramic, firstly, the substrate is subjected to ultrasonic cleaning, and then the substrate is subjected to heating and etching treatment for 0.5-2h by using an alkali solution in a water bath at 50-90 ℃, wherein the mass fraction of the alkali in the alkali solution is 5% -20%, and the alkali is selected from at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide; when the substrate is metal, firstly carrying out ultrasonic cleaning on the substrate, and then carrying out water bath heating and etching treatment on the substrate for 1-3h at 70-100 ℃ by using oxalic acid solution, wherein the mass fraction of oxalic acid in the oxalic acid solution is 5% -15%.
Further preferably, the process of carrying out the seed crystal planting of the nanodiamond on the surface of the substrate comprises the following steps: and vertically suspending and immersing the substrate in a suspension containing the nano-diamond seed crystals, performing ultrasonic oscillation for more than or equal to 15min, and finally cleaning and drying the substrate by using alcohol, wherein the grain size of the nano-diamond seed crystals is 5-20nm, and the mass concentration of the nano-diamond seed crystals in the suspension is 1-5%.
Further preferably, the process of growing the boron-doped diamond layer on the etching surface of the substrate by hot filament chemical vapor deposition comprises the following steps: the mass flow ratio of the introduced gas is hydrogen: methane: boron-doped gas source =100: (1-5): (0.1-2.5), the growth pressure is 2-5Kpa, the growth temperature is 600-950 ℃, the growth times are 1-3, and the time of single growth is 5-24h.
The invention relates to application of a distributed boron-doped diamond/metal-based composite material, which is applied to the fields of electrochemical synthesis, electrochemical sewage purification treatment, electrochemical detection and electrochemical biosensors.
The invention discloses an application of a distributed boron-doped diamond/metal-based composite material, which is applied to electrochemical resource regeneration and recycling, wherein the distributed boron-doped diamond/metal-based composite material is used as an anode, an anode region regenerates at least one of permanganate, persulfate, hypochlorite, ozone and hydrogen peroxide, a cathode region recovers at least one of gold, silver, aluminum, zinc, copper, chromium, nickel and palladium, and an ion exchange membrane is arranged between the cathode and the anode.
Advantageous effects
1. Compared with the process production size limited by a single-layer electrode, the size of the multi-layer composite electrode is larger, and the electrochemical activity is stronger and the efficiency is higher due to the larger specific surface area obtained by combining multiple electrodes.
2. The lead suboxide has a ceramic phase and is low in preparation temperature, the lead suboxide is used as the intermediate layer coating, the phenomenon that a film is easy to fall off due to mismatching of thermal expansion coefficients is prevented, the defect of insufficient conductivity of a silicon wafer is made up, and the conductivity, corrosion resistance and other properties of the composite material are improved.
3. The lead suboxide is sintered at high temperature and reacts with the substrate to form oxide substances, so that the bonding capacity of the substrate to the boron-doped diamond film is improved, and the lead suboxide conductive intermediate layer plays a role of a bonding bridge between the substrate and the boron-doped diamond electrode plate.
Drawings
Fig. 1 is a schematic diagram of a distributed boron-doped diamond/metal matrix composite prepared in example 1, wherein the schematic diagram sequentially shows from top to bottom: the electrode plate is made of boron-doped diamond, a lead suboxide middle layer and a metal sheet.
Fig. 2 is a schematic diagram of the distributed boron-doped diamond/metal matrix composite material according to embodiment 2, in which: the electrode plate is made of boron-doped diamond, a lead suboxide middle layer and a metal sheet.
Detailed Description
Example 1
Using monocrystalline silicon ceramic as a substrate, firstly carrying out ultrasonic cleaning on the substrate, and heating and etching the silicon carbide substrate in a water bath at 70 ℃ for 0.5h by using a sodium hydroxide solution with the mass fraction of 5%;
the boron-doped diamond layer grows by adopting hot wire chemical vapor deposition, and the specific process comprises the following steps: the mass flow ratio of the introduced gas is hydrogen: methane: boron-doped gas source =100:2:0.6, the growth pressure is 3Kpa, the growth temperature is 750 ℃, the growth times are 3 times, and the single growth time is 12 hours; one surface of the boron-doped diamond electrode slice is a substrate with one surface of a boron-doped diamond film layer exposed;
stirring absolute ethyl alcohol, deionized water, lead suboxide, al powder, a binder and polyvinyl alcohol at 100 ℃ for 60min to obtain the lead suboxide conductive intermediate layer coating. Wherein the mass ratio of the absolute ethyl alcohol to the deionized water to the lead suboxide is 2.
Preparing a distributed boron-doped diamond/titanium-based composite electrode by adopting a thermal decomposition method, uniformly brushing the prepared coating of the lead suboxide conductive intermediate layer on a titanium sheet, then facing the exposed substrate of the prepared boron-doped diamond electrode sheet to the intermediate layer of the suboxide, and fixing the electrode sheet by a clamp; and (4) transferring the coating into an oven to dry for 12 hours at the temperature of 60 ℃ for standby, wherein the thickness of the intermediate layer of the sub-oxide coating is 100 mu m.
And (3) performing segmented high-temperature sintering on the prepared sample: the first-stage sintering temperature is 300 ℃, and the sintering time is 2 hours; the second-stage sintering temperature is 500 ℃, the sintering time is 3h, the heating rate is 5 ℃/min, the vacuum degree is 3000pa, and the argon atmosphere flow is 70sccm; the distributed boron-doped diamond/titanium-based composite electrode obtained by sintering is firmly combined and has no shedding phenomenon.
Packaging the prepared distributed boron-doped diamond/titanium-based composite electrode, using a stainless steel electrode as a negative electrode, and preparing 1L of electrolyte Na with initial concentration of 100mg/L 2 SO 4 Placing reactive orange X-GN simulated dye wastewater with concentration of 0.1mol/L on a magnetic stirrer, adjusting rotation speed to 200r/min, and maintaining current density of 100mA/cm in degradation process 2 And degrading for 2h, wherein the chroma removal rate of the dye reaches 98 percent, and the degradation is basically complete. The removal rate of degraded TOC in 2h is 40%, the energy consumption is 46.379KJ, and the unit TOC removal energy consumption is 7.976KJ/KgTOC. The degradation effect is obviously better than that of a single boron-doped diamond electrode under the same area.
Example 2
Taking zirconia ceramic as a substrate, firstly carrying out ultrasonic cleaning on the substrate, and heating and etching the silicon carbide substrate in a water bath at 70 ℃ for 0.5h by using a sodium hydroxide solution with the mass fraction of 5%;
the boron-doped diamond layer grows by adopting hot wire chemical vapor deposition, and the specific process comprises the following steps: the mass flow ratio of the introduced gas is hydrogen: methane: boron-doped gas source =100:3:0.8, the growth pressure is 3Kpa, the growth temperature is 700 ℃, the growth times are 3 times, and the single growth time is 20 hours; one surface of the boron-doped diamond electrode plate is provided with a substrate with one exposed surface of the boron-doped diamond film layer;
stirring absolute ethyl alcohol, deionized water, lead suboxide, al powder, a binder and polyvinyl alcohol at 100 ℃ for 60min to obtain the lead suboxide conductive intermediate layer coating. Wherein the mass ratio of the absolute ethyl alcohol to the deionized water to the lead suboxide is 2.
Preparing a distributed boron-doped diamond/titanium-based composite electrode by adopting a thermal decomposition method, locally brushing the prepared lead suboxide conductive intermediate layer coating on a titanium sheet according to the distribution mode of boron-doped diamond, then facing the exposed substrate of the prepared boron-doped diamond electrode sheet to the intermediate layer of the suboxide, and fixing the electrode sheet by a clamp; and (4) transferring the coating into an oven to dry for 12 hours at the temperature of 60 ℃ for standby, wherein the thickness of the intermediate layer of the sub-oxide coating is 70 mu m.
And (3) sintering the prepared sample at high temperature: the first-stage sintering temperature is 300 ℃, and the sintering time is 2h; the second-stage sintering temperature is 500 ℃, the sintering time is 3h, the heating rate is 5 ℃/min, the vacuum degree is 3000pa, and the argon atmosphere flow is 70sccm; the distributed boron-doped diamond/titanium-based composite electrode obtained by sintering is firmly combined and has no shedding phenomenon.
Packaging the prepared distributed boron-doped diamond/titanium-based composite electrode, using a stainless steel electrode as a negative electrode, and preparing 1L of electrolyte Na with initial concentration of 100mg/L 2 SO 4 The reactive orange X-GN simulated dye wastewater with the concentration of 0.1mol/L is put on a magnetic stirrer, the rotating speed is adjusted to be 200r/min, and the current density is kept to be 100mA/cm in the degradation process 2 And degrading for 2h, wherein the chroma removal rate of the dye reaches 96 percent, and the degradation is basically complete. The removal rate of degraded TOC in 2h is 37.650 percent, the energy consumption is 49.519KJ, and the unit TOC removal energy consumption is 8.03KJ/KgTOC. The degradation effect is obvious because of the single boron-doped diamond electrode under the same area.
Example 3
The electrode prepared in the embodiment 1 is used for degrading PCB copper etching waste liquid, the prepared distributed boron-doped diamond and metal-based composite electrode is taken as an anode, copper is taken as a cathode, a cation exchange membrane is arranged between the cathode and the anode, and gauze is coated outside the cation exchange membrane and used for filtering particle impurities in the waste liquid; the conditions of the electrolysis parameters are as follows: the current is 60A, the voltage is 23V, the current density is 200A/m < 2 >, the inter-polar distance is 50mm, and the area ratio of a cathode electrode to an anode electrode is 2; SO in etching waste liquid 4 2- The concentration of (A) is 232g/L, the concentration of copper ions is 180g/L, and the etching speed is 10.0 mu m/min; electrolyzing the etching waste liquid until the content of copper ions is reduced to about 40g/L, and then, obviously separating out red copper simple substances on a cathode; detection S 2 O 8 2- The output condition is calculated to obtain that the current efficiency of persulfate generated by the anodic oxidation of the system is about 80 percent, and S 2 O 8 2- The regeneration and copper recovery effects are obvious.
Comparative example 1
The other conditions were the same as in example 1 except that the intermediate lead suboxide coating was not provided and sintering was carried out directly, and BDD was hardly bonded to the titanium substrate and dropped significantly.
Comparative example 2
The other conditions are the same as the embodiment 1, only the intermediate conductive coating is titanium suboxide, the bonding force between the sintered boron-doped diamond electrode and the metal substrate is not strong, the boron-doped diamond electrode is easy to peel off after being stressed, and the degradation effect is far inferior to that of the embodiment 1.
Comparative example 3
The other conditions are the same as the example 2, only the temperature rise rate is too fast at 20 ℃/min during high-temperature sintering, the lead suboxide formed by sintering has poor cohesiveness, the bonding force between the boron-doped diamond and the metal substrate is not strong, the boron-doped diamond is easy to fall off, and the degradation effect is far inferior to the example 2.
Claims (11)
1. A distributed boron-doped diamond/metal matrix composite material is characterized in that: the distributed boron-doped diamond/metal matrix composite material comprises a metal sheet and a plurality of boron-doped diamond electrode sheets distributed on the surface of the metal sheet at intervals, wherein a lead suboxide coating is arranged between the metal sheet and the boron-doped diamond electrode sheets.
2. The distributed boron-doped diamond/metal matrix composite according to claim 1, wherein: the lead suboxide coating is completely coated on the surface of the metal sheet, or a plurality of lead suboxide coatings are arranged on the surface of the metal sheet at intervals; the thickness of the lead suboxide coating is 500nm-200 μm.
3. The distributed boron-doped diamond/metal matrix composite according to claim 1, wherein:
the metal sheet is selected from one of a titanium-coated copper sheet, a tantalum-coated copper sheet, a titanium sheet, a niobium sheet, a tantalum sheet and a zirconium sheet;
the structure of the metal sheet is selected from one of a continuous plate-shaped structure, a reticular structure, a discontinuous frame structure, a columnar structure, a barrel-shaped structure, an irregular three-dimensional structure and a regular three-dimensional structure;
the boron-doped diamond electrode slice consists of a substrate and a boron-doped diamond film layer arranged on the surface of the substrate;
the boron diamond electrode plates are arranged on the surface of the metal sheet in an array arrangement mode.
4. The distributed boron-doped gold of claim 3The diamond/metal matrix composite material is characterized in that: the substrate is selected from one of metal nickel, niobium, tantalum, zirconium, copper, titanium, cobalt, tungsten, molybdenum, chromium and iron or one of metal alloys; or the substrate is selected from ceramic Si and Al 2 O 3 、ZrO 2 、SiC、Si 3 N 4 、BN、B 4 C、AlN、TiB 2 、TiN、WC、Cr 7 C 3 、Ti 2 GeC、Ti 2 AlC and Ti 2 AlN、Ti 3 SiC 2 、Ti 3 GeC 2 、Ti 3 AlC 2 、Ti 4 AlC 3 、BaPO 3 One or a doped ceramic therein;
the substrate structure is at least one selected from a three-dimensional continuous network structure, a two-dimensional continuous net structure, a two-dimensional closed flat plate structure, a one-dimensional filiform structure, a one-dimensional linear structure, a one-dimensional rod shape and a zero-dimensional particle shape;
the thickness of the boron-doped diamond film layer is 5-20 mu m;
the mass fraction of boron element in the boron-doped diamond film layer is 2-10 per mill.
5. The method of preparing a distributed boron-doped diamond/metal matrix composite as claimed in any one of claims 1 to 4, wherein: and uniformly arranging the coating containing the lead suboxide on the metal sheet, then placing the substrate exposed surface of the boron-doped diamond electrode sheet facing the coating containing the lead suboxide on the metal sheet containing the coating containing the lead suboxide, drying and sintering to obtain the distributed boron-doped diamond/metal-based composite material.
6. The method for preparing the distributed boron-doped diamond/metal matrix composite material according to claim 5, wherein the method comprises the following steps: the preparation method of the coating containing lead suboxide comprises the following steps: mixing absolute ethanol, water, lead monoxide, sintering aid and binder, and stirring at 80-120 deg.C for 30-90min to obtain the final product;
wherein the mass ratio of the absolute ethyl alcohol to the water to the lead monoxide is (1-3) to (7-10) to (8-11);
the sintering aid is selected from Al powder, ti powder and TiC 2 Powder, pbO 2 Powder, tiB 2 At least one of powders, wherein the addition amount of the sintering aid is 2-10 wt.% of the mass of the lead suboxide;
the adhesive is selected from at least one of polyvinyl alcohol, polyethylene glycol and nafion, and the addition amount of the adhesive is 2-10 wt.% of the mass of the lead suboxide.
7. The method for preparing the distributed boron-doped diamond/metal matrix composite material according to claim 6, wherein the method comprises the following steps:
the drying temperature is 60-90 ℃, and the drying time is 5-24h;
the sintering process comprises the following steps: the temperature is raised to 300-450 ℃ by adopting the heating rate of 5-10 ℃/min, the temperature is preserved for 1-3h, then the temperature is raised to 500-750 ℃ by adopting the heating rate of 5-10 ℃/min, the temperature is preserved for 1-4 h, the vacuum degree is controlled to be 1000-6000pa, and the argon atmosphere flow is controlled to be 20-100sccm.
8. The method for preparing the distributed boron-doped diamond/metal matrix composite material according to claim 6, wherein the method comprises the following steps: the boron-doped diamond electrode slice is obtained by the following steps: firstly, etching the substrate, then planting nano diamond seed crystals on the surface of the etched substrate, and finally growing a boron-doped diamond layer on the etching surface of the substrate by adopting hot filament chemical vapor deposition.
9. The method for preparing the distributed boron-doped diamond/metal matrix composite material according to claim 8, wherein the method comprises the following steps:
when the substrate is ceramic, firstly, ultrasonically cleaning the substrate, and then, heating and etching the substrate for 0.5-2h in a water bath at 50-90 ℃ by using an alkali solution, wherein the mass fraction of the alkali in the alkali solution is 5% -20%, and the alkali is selected from at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide; when the substrate is metal, firstly carrying out ultrasonic cleaning on the substrate, and then carrying out water bath heating and etching treatment on the substrate for 1-3h at 70-100 ℃ by using oxalic acid solution, wherein the mass fraction of oxalic acid in the oxalic acid solution is 5% -15%;
the process of carrying out the nano diamond seed crystal planting on the surface of the substrate comprises the following steps: vertically suspending and immersing a substrate in a turbid liquid containing nano diamond seed crystals, carrying out ultrasonic oscillation for more than or equal to 15min, finally cleaning with alcohol, and drying to obtain the nano diamond seed crystals, wherein the grain size of the nano diamond seed crystals is 5-20nm, and the mass concentration of the nano diamond seed crystals in the turbid liquid is 1-5%;
the process of growing the boron-doped diamond layer on the etching surface of the substrate by adopting hot wire chemical vapor deposition comprises the following steps: the mass flow ratio of the introduced gas is hydrogen: methane: boron-doped gas source =100: (1-5): (0.1-2.5), the growth pressure is 2-5Kpa, the growth temperature is 600-950 ℃, the growth times are 1-3, and the single growth time is 5-24h.
10. Use of a distributed boron doped diamond/metal matrix composite according to any one of claims 1 to 5, wherein: the distributed boron-doped diamond/metal matrix composite material is applied to one of the fields of electrochemical synthesis, electrochemical sewage purification treatment, electrochemical detection and electrochemical biosensors.
11. Use of a distributed boron doped diamond/metal matrix composite according to any one of claims 1 to 5, wherein: the distributed boron-doped diamond/metal-based composite material is applied to electrochemical resource regeneration and recycling, wherein the distributed boron-doped diamond/metal-based composite material is used as an anode, resources of an anode region regenerate at least one of permanganate, persulfate, hypochlorite, ozone and hydrogen peroxide, resources of a cathode region recover at least one of gold, silver, aluminum, zinc, copper, chromium, nickel and palladium, and an ion exchange membrane is arranged between the cathode and the anode.
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