CN114101660B - Diamond particle with core-shell structure and preparation method and application thereof - Google Patents
Diamond particle with core-shell structure and preparation method and application thereof Download PDFInfo
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- CN114101660B CN114101660B CN202111106655.3A CN202111106655A CN114101660B CN 114101660 B CN114101660 B CN 114101660B CN 202111106655 A CN202111106655 A CN 202111106655A CN 114101660 B CN114101660 B CN 114101660B
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 96
- 239000010432 diamond Substances 0.000 title claims abstract description 96
- 239000002245 particle Substances 0.000 title claims abstract description 58
- 239000011258 core-shell material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011162 core material Substances 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052796 boron Inorganic materials 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 239000011574 phosphorus Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 27
- 238000005530 etching Methods 0.000 claims description 20
- 239000002113 nanodiamond Substances 0.000 claims description 19
- 238000012986 modification Methods 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 12
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 11
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000085 borane Inorganic materials 0.000 claims description 5
- 238000004050 hot filament vapor deposition Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000001020 plasma etching Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000000835 electrochemical detection Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- 230000008021 deposition Effects 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 7
- 239000008103 glucose Substances 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000003115 supporting electrolyte Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5001—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with carbon or carbonisable materials
- C04B41/5002—Diamond
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
-
- 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
-
- 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
-
- 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
- C23C16/44—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 method of coating
- C23C16/4417—Methods specially adapted for coating powder
Abstract
The invention discloses a diamond particle with a core-shell structure and a preparation method and application thereof, wherein the diamond particle with the core-shell structure comprises a core material and an outer shell layer coating the core material, the core material is selected from metal or ceramic materials with a three-dimensional structure, the size of the core material is 200nm-30mm, the outer shell is a doped diamond film, and doping elements are selected from one or more of boron, nitrogen, phosphorus and lithium; according to the invention, the carbide or metal with a three-dimensional structure is used as a core material, the polycrystalline doped diamond film is grown on the surface of the carbide or metal, and finally the obtained doped diamond particles have excellent conductivity, high specific surface area, no toxicity to the environment and high signal to noise ratio.
Description
Technical Field
The invention belongs to the technical field of diamond electrode preparation, and particularly relates to diamond particles with a core-shell structure, and a preparation method and application thereof.
Background
The diamond film electrode is a material with excellent physical and chemical properties, high mechanical strength, excellent chemical stability and electrochemical properties, no obvious change on the surface of the electrode under high-intensity current load, and the like, so that the diamond film electrode has wide prospect in electrochemical application. The boron doped diamond electrode obtained by doping boron elements 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 semiconductor or the conductor is deposited on the surface of certain electrode matrixes such as titanium sheets, silicon wafers, graphite and the like is an important 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 electrode (BDD) 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 electrochemical oxidation treatment of sewage.
The traditional flat electrode belongs to a two-dimensional electrode, the real electrode area is similar to the apparent electrode area, and the mass transfer efficiency of the electrode surface is severely restricted by the low specific surface area of the electrode.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide diamond particles with a core-shell structure, and a preparation method and application thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
The invention relates to a diamond particle with a core-shell structure, which comprises a core material and an outer shell layer coating the core material, wherein the core material is selected from ceramic materials or metals with three-dimensional structures, the size of the core material is 200nm-30mm, the outer shell is a diamond film, and doping elements are selected from one or more of boron, nitrogen, phosphorus and lithium, preferably boron.
Preferably, the core material is selected from a ceramic material or metal of an irregular or regular three-dimensional structure, wherein the ceramic material is selected from A1 2 O 3 、ZrO 2 、SiC、Si 3 N 4 、BN、B 4 C、AlN、WC、Cr 7 C 3 At least one of the metals is selected fromOne of nickel, niobium, copper, titanium, cobalt, tungsten, molybdenum, chromium, iron, or an alloy thereof.
Preferably, the core material is selected from silicon carbide or titanium with a particle size of 0.5-10 mm, preferably 3-5 mm, and the core material has a spherical structure.
Through a large number of experiments, the inventor finds that when silicon carbide and titanium with spherical structures with the particle diameters within 0.5-10 mm are selected as core materials, the conductivity and the catalytic activity of the finally obtained doped diamond particles are greatly superior to those of core materials with other structures, other sizes and other materials.
Preferably, the thickness of the doped diamond film is 5nm-20 μm, preferably 1-2 μm.
Preferably, the doping mode of the doped diamond film comprises one or more of constant doping, multi-layer changing doping and gradient doping.
In a preferred scheme, the doped diamond film is a doped diamond film with a porous structure, and the pore diameter of the pores in the doped diamond film is 10nm-200nm.
Preferably, the doping concentration of the doped diamond film is more than 10 21 cm -3 Preferably 10 21 cm -3～ 10 22 cm -3 。
When the content of the doped diamond film is controlled within the above range, the properties of the finally obtained doped diamond particles are optimal, since when the doping concentration is more than 10 18 cm -3 When the insulating diamond has semiconductor property, when the insulating diamond is more than 10 21 cm -3 When the metal-like properties are obtained, however, too much doping will cause the diamond lattice to be broken due to the difference in lattice coefficients between the doping element and the diamond, producing impurity phases (e.g. sp 2 ) Resulting in the loss of some of the good properties of diamond such as high hardness, high strength, inert surfaces, while controlling the doping concentration in the boron doped diamond film within the above ranges will achieve optimal performance in conjunction with the core material.
The inventors found that by setting the doped diamond film in the above range, diamond particles of core-shell structure having the most excellent properties can be obtained with completely uniform coating.
The micropores are arranged on the surface of the doped diamond film, so that the specific surface area of the particles can be further increased, and the performance of the particles can be improved.
In a preferred scheme, the surface of the coating layer is provided with a modification layer, and the modification layer is one or a combination of a plurality of end group modification, metal modification, carbon material modification and organic matter modification.
By providing the modifying layer on the surface of the coating layer, the electrocatalytic activity of the modifying layer particles can be further improved.
The invention relates to a preparation method of doped diamond particles with a core-shell structure, which comprises the following steps: firstly, planting nano diamond seed crystals on the surface of a core material, and then, carrying out chemical vapor deposition on the core material planted with the diamond seed crystals to grow a boron-doped diamond film so as to obtain diamond particles with a core-shell structure, wherein during chemical vapor deposition, the mass flow ratio of the gas is hydrogen: methane: doping gas source = 98:2:0.3-0.6, the growth pressure is 2-5Kpa, the growth temperature is 800-850 ℃, the number of times of growth is 2-6 times, preferably 5 times, each time of growth is 1 time, the core material is taken out, the core material is shaken and then continues to grow, the time of single growth is 3-6 hours, and the doping air source is at least one of phosphine, ammonia and borane.
The inventor finds that the carrier particles can be better coated by growing for multiple times after each growth for 3-6 hours, namely cooling, taking out the carrier particles, heating to the target temperature, and finally obtaining the doped diamond particles with optimal performance.
In a preferred scheme, the chemical vapor deposition is hot filament chemical vapor deposition, and the temperature of the hot filament is 2500-2700 ℃.
In a preferred scheme, etching the doped diamond particles to obtain a doped diamond film with a porous structure; the etching treatment process comprises at least one of high-temperature atmosphere etching treatment, high-temperature metal etching treatment and plasma etching.
Further preferably, the high-temperature metal etching treatment comprises the following steps: firstly, sputtering metallic nickel on the surface of the boron-doped diamond film by adopting a magnetron sputtering method, and then performing heat treatment.
In addition, according to the practical application condition, boiling nitric acid solution is adopted to remove nickel particles in the holes after the heat treatment is finished.
Still further preferably, the process parameters of the sputtered metallic nickel are: argon is introduced to adjust the air pressure to be 1-3 Pa, the sputtering current is 250-350 mA, and the sputtering time is 10-30 s; the thickness of the sputtered Ni layer is 5-10nm, and the air pressure is maintained at 7-15 kpa.
Still more preferably, the temperature of the heat treatment is 800-900 ℃, the heat treatment time is 3-5H, and the mass flow ratio of the introduced atmosphere is H 2 :Ar＝1.5。
Still more preferably, the nitric acid solution is prepared from concentrated nitric acid and water according to a ratio of 1-4: mixing in a volume ratio of 4.
In a preferred scheme, the process of planting the nano diamond seed crystal on the surface of the core material comprises the following steps: immersing the core material into a nano-diamond-containing suspension for ultrasonic vibration for more than or equal to 30min, and finally cleaning and drying to obtain the nano-diamond-containing suspension, wherein the mass fraction of the nano diamond in the nano-diamond-containing suspension is 0.01-0.1wt%.
The invention also provides an application of the doped diamond particles with the core-shell structure, wherein the doped diamond particles are used as electrodes for one of electrochemical sewage purification treatment, electrochemical biosensors, electrochemical synthesis, electrochemical detection fields and ozone generators.
Advantageous effects
According to the invention, carbide or metal with a three-dimensional structure is used as a core material, a carbon material/boron-doped diamond composite electrode is used as a core material on the surface of the carbide or metal, a polycrystalline doped diamond film grows on the surface of the carbide or metal, and finally the obtained doped diamond particles have excellent conductivity, high specific surface area, no toxicity to the environment and high signal to noise ratio.
The inventors have unexpectedly found that when silicon carbide and titanium having spherical structures with particle diameters within 2-8 mm are selected as core materials, the conductivity and catalytic activity of the finally obtained doped diamond particles are significantly better than those of other core materials having other structures and other sizes and other materials.
The invention adopts vapor deposition mode in the growth process, taking boron doped film as an example, the vapor deposition is used for preparing the polycrystalline diamond by methane (CH) 4 ) Hydrocarbon such as acetylene, hydrogen (H) 2 ) The boron-doped diamond film prepared by the vapor deposition method has higher uniformity of doping B and is easy to prepare a high-B film, and the boron-doped diamond film has the most excellent performance by adopting a mode of multiple growth and effectively controlling the crystal structure, the thickness of the film and the doping amount.
Drawings
FIG. 1 is a schematic diagram of an ozone generator. In the figure, 1, an upper shell; 2. a lower housing; 3. a suction cup; 4. a slot-type clamping shell; 5. a diamond anode; 6. an isolation net; 7. a mesh cathode; 8. a sealing body; 9. an electrode wire.
Detailed Description
Example 1
3mm spherical silicon carbide is used as a core material, immersed into a suspension containing nano diamond, subjected to ultrasonic vibration for 30min, and cleaned and dried. And (3) putting the nano diamond into the suspension containing the nano diamond, wherein the mass fraction of the nano diamond is 0.01wt%.
Adopting hot filament CVD to deposit boron doped diamond film, and the deposition technological parameters are as follows: the distance between the hot wires is 6mm, the growth temperature is 800 ℃, the hot wire temperature is 2200 ℃, the deposition pressure is 3KPa, and the thickness of the diamond film is 1 mu m by controlling the deposition time; during the chemical vapor deposition, the mass flow ratio of the passing gas is hydrogen: methane: borane=98: 2:0.3, the growth pressure is 2Kpa, the growth times are 2 times, the carrier particles are taken out every time of growth, the carrier particles are shaken and then continue to grow, and the time of single growth is 6 hours.
The boron-doped diamond particle electrode prepared in the step is wrapped by polytetrafluoroethylene in a total of 100g and is connected with a positive electrode, a stainless steel electrode is used as a negative electrode, and the electrode is connected with a power supply and then placed in an electrolytic tank with a capacity of 1L, wherein the initial COD in the tank is about 9000mg/L glucose solution. Setting the current density in the degradation process to 200mA/cm 2 The supporting electrolyte is sodium sulfate, the concentration is 0.1mol/L, the PH is regulated to be neutral, and the rotating speed of the stirring magnetic rotor is 200 revolutions/min. The COD degradation rate of the solution reaches 99.9 percent after degradation for 4 hours, and the ton water energy consumption is 21.9kwh/m 3 。
Example 2
Otherwise, the same conditions as in the examples were used, except that the core material used was silicon carbide of 5mm spherical structure,
the boron-doped diamond particles prepared in the step are wrapped by polytetrafluoroethylene in a total of 100g and are connected with a positive electrode, a stainless steel electrode is used as a negative electrode, and after a power supply is connected, the boron-doped diamond particles are placed in an electrolytic tank with a capacity of 1L, and glucose solution with initial COD of 9000mg/L is placed in the tank. Setting the current density in the degradation process to 200mA/cm 2 The supporting electrolyte is sodium sulfate, the concentration is 0.1mol/L, the PH is regulated to be neutral, and the rotating speed of the stirring magnetic rotor is 200 revolutions/min. The COD degradation rate of the solution reaches 99.9% after 4.5 hours of degradation, and the ton water energy consumption is 24.6kwh/m3.
Example 3
Otherwise, the same conditions as in the examples were applied, except that the core material used was a square structure of silicon carbide with a side length of 1mm
The boron-doped diamond particle electrode prepared in the step is wrapped by polytetrafluoroethylene in 100g and connected with a positive electrode, a stainless steel electrode is used as a negative electrode, and after a power supply is connected, the boron-doped diamond particle electrode is placed in an electrolytic tank with the capacity of 1L, and glucose solution with the initial COD of 9000mg/L is placed in the tank. Setting the current density in the degradation process to 200mA/cm 2 The supporting electrolyte is sodium sulfate, the concentration is 0.1mol/L, the PH is regulated to be neutral, and the rotating speed of the stirring magnetic rotor is 200 revolutions/min. The COD degradation rate of the solution reaches 99.9% after 5 hours of degradation, and the ton water energy consumption is 27.3kwh/m3.
Example 4
Titanium with a spherical structure of 5mm is used as a core material, immersed into suspension containing nano diamond, subjected to ultrasonic vibration for 30min, and cleaned and dried. And (3) putting the nano diamond into the suspension containing the nano diamond, wherein the mass fraction of the nano diamond is 0.1wt%.
Adopting hot filament CVD to deposit boron doped diamond film, and the deposition technological parameters are as follows: the distance between the hot wires is 6mm, the growth temperature is 850 ℃, the hot wire temperature is 2200 ℃, the deposition pressure is 4KPa, and the gas ratio is hydrogen: methane: borane=98: 2:0.5, obtaining the thickness of the diamond film by controlling the deposition time to be 2 mu m; the growth times are 4 times, the carrier particles are taken out after each growth time, the carrier particles are shaken and then continue to grow, the single growth time is 4 hours,
(4) Etching the boron-doped diamond particles to obtain a boron-doped diamond film with a porous structure; the etching treatment process comprises the following steps: sputtering metallic nickel on the surface of the boron-doped diamond film by adopting a magnetron sputtering method, wherein the technological parameters of sputtering the metallic nickel are as follows: argon is introduced to adjust the air pressure to 3Pa, the sputtering current is 350mA, and the sputtering time is 10s; sputtering Ni layer with thickness of 7nm, then heat treating, maintaining air pressure at 12kpa, heat treating temperature at 900 deg.C, heat treating time at 3H, and introducing atmosphere with mass flow ratio of H 2 Ar=1.5. After the heat treatment is completed.
The prepared boron-doped diamond particles are used for detecting glucose on a CHI 660E electrochemical workstation, and the cyclic voltammetry test result shows that the detection sensitivity of the composite electrode can reach 1130 mu AmM -1 cm -2 And 420 mu AmM -1 cm -2 The concentration range of the detectable glucose is 0.1 mu M-4mM and 4mM-10mM, the stability of the composite electrode is high, and the accuracy of the detection sensitivity can still be kept more than 81.55% in the continuous one-month time current detection process.
Comparative example 1
Other conditions are the same as in example 2, except that the core material is directly used to detect glucose on the CHI 660E electrochemical workstation, and the cyclic voltammetry test result shows that the detection sensitivity of the composite electrode can reach 2200 mu AmM-1cm < -2 >, and the concentration range of the detectable glucose is 3 mu M-5mM.
Example 5
Immersing silicon carbide with a spherical structure of 5mm as a core material into suspension containing nano diamond, carrying out ultrasonic vibration for 30min, cleaning and drying. And (3) putting the nano diamond into the suspension containing the nano diamond, wherein the mass fraction of the nano diamond is 0.1wt%.
Adopting hot filament CVD to deposit boron doped diamond film, and the deposition technological parameters are as follows: the distance between the hot wires is 6mm, the growth temperature is 800-850 ℃, the hot wire temperature is 2200 ℃, the deposition pressure is 4KPa, and the gas proportion is hydrogen: methane: borane=98: 2:0.5, obtaining the thickness of the diamond film by controlling the deposition time to be 2 mu m; the growth times are 4 times, the carrier particles are taken out after each growth time, the carrier particles are shaken and then continue to grow, the single growth time is 4 hours,
(4) Etching the boron-doped diamond particles to obtain a boron-doped diamond film with a porous structure; the etching treatment process comprises the following steps: the plasma method is adopted for etching, and the specific etching steps of the boron-doped diamond film with the porous structure are as follows: and etching the prepared boron-doped diamond particles by adopting an automatically-adjusted oxygen plasma etching instrument. The etching process parameters are as follows: the etching power is 100W, the gas volume flow rate of oxygen is 20sccm, and the system pressure is maintained at 455+/-5 Pa. The etching temperature is 700 ℃ and the etching time is 2min.
Taking the prepared boron-doped diamond particles as a working electrode; titanium mesh is used as a cathode; the working electrode and the cathode electrode are separated by an insulating isolation net (made of tetrafluoroethylene) and are arranged in an ozone generator (figure 1), and the inventor finds that the current density is maintained at 100mAcm when the ozone generator is used for preparing ozone by electrolyzing water as the electrode 2 The solubility of the prepared ozone water is 6.80mg L-1 measured by a potassium iodide titration method after electrolysis for 45min, and is 1.39 times of that of the ozone prepared by the traditional electrolysis method.
Example 6
Otherwise, as in example 5, except that silicon carbide having a square structure with a core material of 5mm in side length was used as a working electrode in an ozone generator and electrolyzed water as an electrode to produce ozone, the inventors found that the current density was maintained at 100mA cm- 2 The solubility of the prepared ozone water is 4.2mg L-1 measured by a potassium iodide titration method after electrolysis for 45min, which is 1.1 times of that of the ozone prepared by the traditional electrolysis method.
Claims (9)
1. A preparation method of doped diamond particles with a core-shell structure is characterized by comprising the following steps: the method comprises the following steps: firstly, planting nano diamond seed crystals on the surface of a core material, and then, carrying out chemical vapor deposition on the core material planted with the diamond seed crystals to grow a doped diamond film so as to obtain doped diamond particles with a core-shell structure, wherein the mass flow ratio of the gas during chemical vapor deposition is hydrogen: methane: doping gas source = 98:2:0.3-0.6, the growth pressure is 2-5Kpa, the growth temperature is 800-850 ℃, the number of times of growth is 2-6, each time of growth is 1 time, the core material is taken out, the core material is shaken and then continues to grow, the single growth time is 3-6 hours, and the doping air source is at least one of phosphine, ammonia and borane;
the doped diamond particles with the core-shell structure comprise a core material and an outer shell layer coating the core material, wherein the core material is selected from silicon carbide or titanium with the particle size of 0.5-10 mm, the core material is of a spherical structure, the outer shell is a doped diamond film, and the doping elements are selected from one or more of boron, nitrogen and phosphorus;
the thickness of the doped diamond film is 5nm-20 mu m, and the crystal structure is polycrystal;
the doping concentration of the doped diamond film is 10 21 cm -3 ~10 22 cm -3 。
2. The method for preparing the core-shell structured doped diamond particles according to claim 1, wherein the method comprises the following steps: the chemical vapor deposition is hot filament chemical vapor deposition, and the temperature of the hot filament is 2500-2700 ℃.
3. The method for preparing the core-shell structured doped diamond particles according to claim 1, wherein the method comprises the following steps:
etching the doped diamond particles to obtain a doped diamond film with a porous structure; the etching treatment process comprises at least one of high-temperature atmosphere etching treatment, high-temperature metal treatment etching and plasma etching.
4. A core-shell structured doped diamond according to claim 1The preparation method of the stone particles is characterized in that: the core material is selected from a ceramic material or metal with an irregular or regular three-dimensional structure, wherein the ceramic material is selected from A1 2 O 3 、ZrO 2 、SiC、 Si 3 N 4 、BN、B 4 C、AlN、WC、Cr 7 C 3 The metal is selected from one of nickel, niobium, copper, titanium, cobalt, tungsten, molybdenum, chromium and iron or one of alloys thereof.
5. The method for preparing the core-shell structured doped diamond particles according to claim 1, wherein the method comprises the following steps:
the doping mode of the doped diamond film comprises one or more of constant doping, multi-layer changing doping and gradient doping.
6. The method for preparing the core-shell structured doped diamond particles according to claim 1, wherein the method comprises the following steps:
the doped diamond film is of a porous structure, and the pore diameter of the pores in the doped diamond film is 10nm-200nm.
7. The method for preparing the core-shell structured doped diamond particles according to claim 1, wherein the method comprises the following steps: the surface of the shell layer is provided with a modification layer, and the modification layer is one or a combination of a plurality of metal modification, carbon material modification and organic matter modification.
8. The method for preparing the core-shell structured doped diamond particles according to claim 1, wherein the method comprises the following steps: the surface of the shell layer is provided with a modification layer, and the modification layer is selected from end group modification.
9. The use of a core-shell structured doped diamond particle prepared by the preparation method according to any one of claims 1 to 8, wherein: the doped diamond particles are used as electrodes for one of electrochemical sewage purification treatment, electrochemical biosensors, electrochemical synthesis, electrochemical detection fields and ozone generators.
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