CN114134542B - Porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode and preparation method thereof - Google Patents
Porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode and preparation method thereof Download PDFInfo
- Publication number
- CN114134542B CN114134542B CN202111492152.4A CN202111492152A CN114134542B CN 114134542 B CN114134542 B CN 114134542B CN 202111492152 A CN202111492152 A CN 202111492152A CN 114134542 B CN114134542 B CN 114134542B
- Authority
- CN
- China
- Prior art keywords
- porous titanium
- amorphous metal
- metal oxide
- layer
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 123
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000010936 titanium Substances 0.000 title claims abstract description 118
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 114
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 105
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 105
- 239000005300 metallic glass Substances 0.000 title claims abstract description 55
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 52
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 74
- 238000000576 coating method Methods 0.000 claims abstract description 74
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 230000003647 oxidation Effects 0.000 claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 20
- 238000004070 electrodeposition Methods 0.000 claims abstract description 16
- 229910003134 ZrOx Inorganic materials 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims description 64
- 239000011159 matrix material Substances 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 230000002378 acidificating effect Effects 0.000 claims description 26
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 15
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 14
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 14
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 14
- 239000011684 sodium molybdate Substances 0.000 claims description 14
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002109 single walled nanotube Substances 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 59
- 239000000243 solution Substances 0.000 description 30
- 239000011572 manganese Substances 0.000 description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 12
- 238000005488 sandblasting Methods 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000009854 hydrometallurgy Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910006529 α-PbO Inorganic materials 0.000 description 3
- 229910006654 β-PbO2 Inorganic materials 0.000 description 3
- 229910020935 Sn-Sb Inorganic materials 0.000 description 2
- 229910008757 Sn—Sb Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- -1 fluoride ions Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- 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
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
- C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention relates to a porous titanium-based carbon nano tube reinforced amorphous metal oxide coating electrode and a preparation method thereof, belonging to the technical field of anode plates. The invention relates to a porous titanium-based carbon nanotube reinforced amorphous metal oxide coating electrode, which comprises a porous titanium substrate, a conductive metal oxidation intermediate layer and an amorphous metal active layer which are sequentially arranged from inside to outside, wherein the conductive metal oxidation intermediate layer is a Sn-Ru-Ti-TaO x layer prepared by thermal decomposition, and the amorphous metal active layer is a carbon nanotube reinforced Mn-Mo-Ni-ZrOx oxide layer obtained by pulse electrodeposition and thermal oxidation treatment. The electrode has the characteristics of low noble metal consumption, high electrocatalytic activity, good conductivity, strong anodic oxidation resistance, long service life, low production cost and the like.
Description
Technical Field
The invention relates to a porous titanium-based carbon nano tube reinforced amorphous metal oxide coating electrode and a preparation method thereof, and belongs to the technical field of electrodes.
Background
In the hydrometallurgical production of high purity metal products, more than 95% of the electricity consumption is concentrated on the electrolytic cell, the unit of electricity consumption depends on the current efficiency and cell voltage, and electricity saving requires a reduction in cell voltage while improving current efficiency. However, the current efficiency is influenced by factors such as process conditions, ore sources and the like, so that the difficulty of further improvement is high; thus reducing the tank voltage is the dominant direction of reducing power consumption. The cell voltage is related to the magnitude of the oxygen evolution overpotential of the anode material. In the traditional industry, lead-silver alloy is adopted as an anode, the anode overvoltage is caused by oxygen precipitation on the anode, the value of the anode overvoltage is about 0.86V, and the anode overvoltage accounts for about 18% of the total voltage of the anode, and is a main source of useless electricity consumption. The electrode is an important component part of hydrometallurgy industry and electrochemistry industry, and the preparation of the electrode material with high performance and long service life is extremely important for energy conservation and consumption reduction. The kinetics of the electrode reaction, the structural form and service life of the electrode, the production and maintenance modes and the like are greatly dependent on the preparation materials and the functional structure of the electrode. In particular, in the structural design of the electrode, the electrode material is closely related to the conductivity, the electrocatalytic activity and the service life of the electrode material, and the novel electrode material with excellent development performance can greatly expand and deepen the application of the electrode in hydrometallurgy industry and electrochemical industry.
In the prior art, the carbon fiber/alpha-PbO 2/β-PbO2/RuO2-MnO2 electrode and the electrode which takes titanium as a matrix and is coated with PbO 2 or SeO 2 all have the problems of higher manufacturing cost, shorter service life of the electrode and narrower application range.
The causes of failure of titanium-based oxide coated anodes can be broadly divided into two aspects: (1) Is the loss of active oxide, including chemical corrosion, electrochemical corrosion, erosion, etc.; (2) Due to passivation of the titanium matrix and passivation mechanism of forming a void layer, an oxide layer with high resistance is formed on the surface of the electrode to form a p-n junction, including chemical damage of matrix metal, impact of internal precipitated gas and the like.
Disclosure of Invention
Aiming at the problems of the existing titanium-based oxide coating anode, the invention provides a porous titanium-based carbon nano tube reinforced amorphous metal oxide coating electrode and a preparation method thereof, wherein the electrode has an oxide with electrocatalytic activity and electrochemical corrosion resistance, is an adhesive which can form a solid solution with the oxide with electrocatalytic activity, and has strong adhesive force with a titanium matrix; the composite carbon nano tube is adopted to strengthen the electrode, the conductivity is good, the specific surface area is large, the strength, the elasticity and the fatigue resistance are good, the amorphous metal oxide coating carbon nano tube is used to strengthen the Mn-Mo-Ni-ZrOx oxide layer, in the random arrangement of atoms, the carbon nano tube is disordered in long range and has an irregularly spaced and short-range ordered entity, the long-range disordered and short-range ordered internal structural characteristics enable the carbon nano tube to strengthen the Mn-Mo-Ni-ZrOx oxide layer to have macroscopic conductivity and surface active sites, the electrocatalytic performance of the electrode is greatly improved, the efficient catalysis is realized, and compared with a crystalline structure, the carbon nano tube is used to strengthen the amorphous Mn-Mo-Ni-ZrOx oxide layer, has lower internal energy and viscosity coefficient, has larger interatomic force and specific surface area, and is strong in corrosion resistance and stable in chemical property.
The porous titanium-based carbon nanotube reinforced amorphous metal oxide coating electrode comprises a porous titanium substrate, a conductive metal oxidation intermediate layer and an amorphous metal active layer which are sequentially arranged from inside to outside, wherein the conductive metal oxidation intermediate layer is a Sn-Ru-Ti-TaO x layer prepared by thermal decomposition, and the amorphous metal active layer is a carbon nanotube reinforced Mn-Mo-Ni-ZrOx oxide layer obtained by pulse electrodeposition and thermal oxidation treatment;
The pore diameter of the porous titanium matrix is 10-100 mu m, and the pore depth is 1-50 mu m;
The Sn, ru, ti and Ta in the Sn-Ru-Ti-TaO x layer have the molar ratio of 60-80:5-10:1-10:1-5 and the thickness of 50-200 mu m;
The molar ratio of Mn, mo, ni and Zr in the carbon nano tube reinforced Mn-Mo-Ni-ZrOx oxide layer is 60-80:10-20:5-15:1-5, and the thickness is 200-800 mu m.
The preparation method of the porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode comprises the following specific steps:
(1) Removing an oxide layer on the surface of the porous titanium matrix by sand blasting, and then placing the porous titanium matrix in hydrochloric acid solution for activation treatment for 30-120 min to form a rough surface, so that the activity specific surface of the titanium matrix is increased, the adhesion of a later-stage oxide coating is facilitated, and the activated porous titanium matrix is obtained; preferably, the mass concentration of the hydrochloric acid solution is 10-30%, and the activation treatment temperature is 20-60 ℃;
(2) Coating the conductive layer coating liquid on the surface of the activated porous titanium substrate, drying, placing the activated porous titanium substrate at the temperature of 300-700 ℃ for thermal decomposition and oxidation for 5-20min, and repeatedly performing coating, drying and thermal decomposition and oxidation treatment to obtain a conductive metal oxide intermediate layer; wherein the conducting layer coating liquid contains SnCl 4、RuCl3, butyl titanate and TaCl 5;
(3) Activated carbon nanotubes are obtained by activating the carbon nanotubes by concentrated nitric acid and sodium hydroxide solution in sequence, the activated carbon nanotubes are dispersed into an acidic composite solution, the carbon nanotubes are subjected to ultrasonic modification for 10-20min at the temperature of 20-60 ℃, solid-liquid separation and drying treatment are carried out, and the carbon nanotubes are repeatedly modified for 6-10 times to obtain the composite carbon nanotubes; wherein the acidic composite solution contains n-butanol 、HNO3、Mn(NO3)2、Na2MoO4、Ni(NO3)2、Zr(NO3)2 and a complexing agent; concentrated nitric acid is a commercial product, and the mass concentration of the sodium hydroxide solution is 10-30%;
(4) Placing the porous titanium matrix coated with the conductive metal oxidation intermediate layer into an acidic composite electroplating solution, taking a titanium mesh as a cathode, and performing pulse electrodeposition for 0.5-2h under the stirring condition at the temperature of 40-90 ℃ to obtain a composite carbon nano tube coating containing nano crystalline and/or amorphous Mn, mo, ni and Zr reinforcement; wherein the acidic composite plating solution contains composite carbon nanotubes, HNO 3、Mn(NO3)2、Na2MoO4、Ni(NO3)2 and Zr (NO 3)2;
(5) Placing the porous titanium substrate deposited with the reinforced composite carbon nano tube coating on the porous titanium substrate at the temperature of 150-300 ℃ for thermal oxidation treatment for 60-120min to convert the reinforced composite carbon nano tube coating into an amorphous metal active layer Mn-Mo-Ni-ZrO x, and thermally decomposing to promote the mutual diffusion of amorphous oxides and improve the bonding force between the amorphous oxides, thus obtaining the multi-Kong Taiji carbon nano tube reinforced amorphous metal oxide coated electrode;
Preferably, the sand blasting pressure is 0.2-0.6Mpa, the angle between the nozzle and the titanium matrix is 45-80 degrees, and the sand blasting material is 30-200 meshes of SiC or Al 2O3 particles;
The organic solvent of the conducting layer coating liquid in the step (2) is one or more of ethanol, glycol, isopropanol and n-butanol;
The carbon nano tube in the step (3) is a single-walled carbon nano tube, the diameter is 1-2nm, and the length is 1-50nm; the acidic composite solution contains 5-20g/L of n-butanol 100-200 g/L、HNO3 80-160g/L、Mn(NO3)2 5-30g/L、Na2MoO4 5-20g/L、Ni(NO3)2 2-10g/L、Zr(NO3)2 2-4g/L、 complexing agent;
the complexing agent is ethylenediamine tetraacetic acid and/or acetylacetone;
The step (4) of acidic composite plating solution contains composite carbon nano tubes 10-30g/L、HNO3 40-100g/L、Mn(NO3)2 5-20g/L、 Na2MoO41-10g/L、Ni(NO3)2 1-10g/L and Zr (NO 3)2 1-10g/L;
The solution temperature of the pulse electrodeposition is 40-90 ℃, the current density is 0.2-1.4A/dm 2, and the duty ratio is 30-60%.
The beneficial effects of the invention are as follows:
(1) The conductive metal oxide intermediate layer Sn-Ru-Ti-TaO x prepared by thermal decomposition in the porous titanium-based carbon nano tube reinforced amorphous metal oxide coating electrode can form Ti/Sn mixed crystal represented by Ti 0.6Sn0.4）O2 with a titanium substrate, so that the bonding force between the conductive layer and the substrate is greatly enhanced, sn and Ru and Ti have similar atomic radiuses and the same rutile structure, a solid solution structure is easy to form, sn and Ru have similar electronegativity, and Sn 4+ is in the highest valence state and has better chemical stability;
(2) The amorphous Mn-Mo-Ni-ZrOx metal active layer obtained by pulse electrodeposition and thermal oxidation treatment in the porous titanium-based carbon nanotube reinforced amorphous metal oxide coating electrode is more uniformly distributed in a porous state; the amorphous short-range ordered structure generates a large number of active sites on the surface, so that the charge transfer rate is improved, the relative number of coordination unsaturated metal sites available for reaction in the amorphous metal oxide is obviously increased compared with that of crystalline materials, and the catalytic activity of the novel electrode is greatly improved; the nano structure has strong corrosion resistance and good electrochemical stability, and can reduce the overpotential of oxygen/chlorine evolution in the electrolysis process when being used as a composite anode;
(3) The introduction of the carbon nano tube in the porous titanium-based carbon nano tube reinforced amorphous metal oxide coating electrode reduces the internal stress in the coating, avoids the generation of coating cracks, and greatly improves the conductivity of the composite coating, and the service life of the porous titanium-based carbon nano tube reinforced amorphous metal oxide coating electrode is prolonged by more than 1 time compared with that of the traditional anode plate represented by lead because the carbon nano tube is a conductor material with excellent corrosion resistance; working in solutions containing chloride and fluoride ions, has good corrosion resistance, and can produce high-grade metal products without lead, which is impossible to achieve with lead electrodes;
(4) The porous titanium-based carbon nano tube reinforced amorphous metal oxide coated electrode has the characteristics of low noble metal consumption, high electrocatalytic activity, good conductivity, strong anodic oxidation resistance, long service life, low production cost and the like;
(5) The porous titanium-based carbon nano tube reinforced amorphous metal oxide coated electrode can be widely applied to hydrometallurgy industry, sewage treatment, organic electrosynthesis, and other electrochemical engineering, and can be used as an anode or a cathode.
Drawings
FIG. 1 is a schematic diagram of a porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode structure;
FIG. 2 is an SEM image of a porous titanium substrate of example 1;
FIG. 3 is a conductive metal oxide interlayer of example 1;
fig. 4 is a schematic diagram of a modified carbon nanotube of example 1, (1) an original carbon nanotube, (2) an activated carbon nanotube, and (3) a composite adsorbed carbon nanotube.
Fig. 5 is an SEM image of the metal oxide active layer of example 1.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
Example 1: a porous titanium-based carbon nano tube reinforced amorphous metal oxide coating electrode (see figure 1) comprises a porous titanium substrate, a conductive metal oxidation intermediate layer and an amorphous metal active layer which are sequentially arranged from inside to outside, wherein the conductive metal oxidation intermediate layer is an Sn-Ru-Ti-TaO x layer prepared by thermal decomposition, and the amorphous metal active layer is a carbon nano tube reinforced Mn-Mo-Ni-ZrOx oxide layer obtained by pulse electrodeposition and thermal oxidation treatment;
The total thickness of the composite electrode material is 2.5mm, the thickness of the porous titanium matrix is 2mm, the pore diameter of the porous titanium matrix is 20 mu m, and the pore depth is 5-10 mu m; the mol ratio of Sn, ru, ti and Ta in the Sn-Ru-Ti-TaO x layer is 8:2:1:1, and the thickness is 50 μm; the molar ratio of Mn, mo, ni and Zr in the carbon nano tube reinforced Mn-Mo-Ni-ZrOx oxide layer is 6:2:2:1, and the thickness is 200 mu m;
the preparation method of the porous titanium-based carbon nano tube reinforced amorphous metal oxide coating electrode comprises the following specific steps:
(1) Performing sand blasting on a porous titanium matrix by adopting 40-mesh SiC to remove an oxide layer on the surface of the porous titanium matrix, then placing the porous titanium matrix in a hydrochloric acid solution with the mass concentration of 20%, and performing activation treatment at the temperature of 40 ℃ for 60min to form a rough surface, so that the activity specific surface of the titanium matrix is increased, the adhesion of a later-stage oxide coating is facilitated, and the activated porous titanium matrix is obtained; wherein the sand blasting pressure is 0.2Mpa, the angle between the nozzle and the titanium substrate is 60 degrees, and the surface of the titanium sheet after sand blasting is matt tingling gray;
(2) Coating the conductive layer coating liquid on the surface of the activated porous titanium substrate, drying at 120 ℃ for 5min, then carrying out thermal decomposition and oxidation at 500 ℃ for 10min, and repeating the coating, drying and thermal decomposition and oxidation treatment for 6 times to obtain a conductive metal oxide intermediate layer; wherein the conductive layer coating liquid contains 0.9mol/L SnCl 4, 0.225mol/L RuCl 3, 0.1125mol/L butyl titanate (C 16H36 OTi) and 0.1125mol/L TaCl 5; the preparation method of the conducting layer coating liquid comprises the steps of sequentially adding SnCl 4、RuCl3, butyl titanate and TaCl 5 into 20mL of commercial concentrated hydrochloric acid, ultrasonically mixing and dissolving for 20min, filtering by using 1PS liquid phase test paper to remove water, and adding n-butanol to 100mL;
(3) The method comprises the steps of sequentially carrying out activating treatment on carbon nanotubes (large specific surface area single-wall carbon nanotubes with the diameter of 2nm and the length of 5-20 nm) by using commercially available concentrated nitric acid for 5min and activating treatment by using sodium hydroxide solution with the mass concentration of 20% for 5min to obtain activated carbon nanotubes, dispersing the activated carbon nanotubes into an acidic composite solution, carrying out ultrasonic modification at the temperature of 40 ℃ for 10min, carrying out solid-liquid separation, carrying out drying treatment at the temperature of 80 ℃, and repeatedly carrying out modification on the carbon nanotubes for 6 times to obtain the composite carbon nanotubes; wherein the acidic composite solution contains n-butanol 100g/L、HNO3 80g/L、Mn(NO3)2 15g/L、Na2MoO4 10g/L、Ni(NO3)2 4g/L、Zr(NO3)2 2g/L and complexing agent ethylenediamine tetraacetic acid 10g/L;
(4) Placing a porous titanium matrix coated with a conductive metal oxidation interlayer Sn-Ru-Ti-TaO x into an acidic composite electroplating solution, taking a titanium mesh as a cathode, and performing pulse electrodeposition for 40min under the stirring condition of the temperature of 60 ℃ and the speed of 200r/min to obtain a composite carbon nano tube coating containing nano crystalline and/or amorphous Mn, mo, ni and Zr enhancement; wherein the acidic composite plating solution contains composite carbon nano tube 10g/L、HNO3 60g/L、Mn(NO3)2 12g/L、Na2MoO4 8g/L、Ni(NO3)2 2g/L and Zr (NO 3)2 1g/L; the current density of pulse electrodeposition is 0.2A/dm 2, and the duty ratio is 30%;
(5) Placing the porous titanium substrate deposited with the reinforced composite carbon nano tube coating on the porous titanium substrate at 180 ℃ for thermal oxidation treatment for 90min to convert the reinforced composite carbon nano tube coating into an amorphous metal active layer Mn-Mo-Ni-ZrO x, wherein the thermal decomposition promotes the mutual diffusion of amorphous oxides and improves the bonding force between the amorphous oxides, thus obtaining the multi Kong Taiji carbon nano tube reinforced amorphous metal oxide coated electrode;
The SEM image of the porous titanium substrate of this embodiment is shown in fig. 2, the conductive metal oxide intermediate layer is shown in fig. 3, the modified carbon nanotube schematic diagram is shown in fig. 4, the metal oxide active layer is shown in fig. 5, and as can be seen from fig. 2-5, the surface structure of the porous titanium substrate is loose, has a large surface area, and the internal structure is in a sheet-like staggered superposition, so that more binding sites and more active substances can be provided, the mechanical strength is ensured, and the self weight of the substrate is reduced; the surface of the conductive oxide intermediate layer is flat, the definition of the whole surface is consistent, which shows that the conductivity is good, the crystal grain size is 5-20 mu m, and the gap width among the crystal grains is basically consistent; the surface of the activated carbon nano tube becomes rough, and metal ions are uniformly attached to the tube wall after repeated modification treatment for many times; the surface of the active layer is formed by stacking rice-shaped particles with the particle size of 20-60nm, and the arrangement is tight;
The porous titanium-based carbon nanotube reinforced amorphous metal oxide coating electrode prepared in the embodiment is in manganese electrolyte, the electrolysis condition is that the concentration of manganese ions in the cathode electrolyte is 0.9mol/L, the concentration of ammonium chloride is 2.4 mol/L, the pH is 6.80, the concentration of hydrochloric acid in the anode electrolyte is 1.5mol/L, the concentration of ammonium chloride is 1 mol/L, the concentration of fluoride is less than 100mg/L, the electrolysis temperature is 15 ℃, metal manganese is electrodeposited by adopting an anion membrane electrolytic tank, the electric efficiency of the electrode is improved by 6% compared with that of a traditional Ti/Sn-Sb/alpha-PbO 2/β-PbO2 anode plate, and the service life is prolonged by 1 time.
Example 2: the porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode of this example was substantially the same as example 1, except that: the total thickness of the composite electrode material is 6mm, the thickness of the porous titanium matrix is 5mm, the pore diameter of the porous titanium matrix is 30 mu m, and the pore depth is 10-30 mu m; the mol ratio of Sn, ru, ti and Ta in the Sn-Ru-Ti-TaO x layer is 10:2:2:1, and the thickness is 80 mu m; the molar ratio of Mn, mo, ni and Zr in the carbon nano tube reinforced Mn-Mo-Ni-ZrOx oxide layer is 6:3:2:1, and the thickness is 420 mu m;
the preparation method of the porous titanium-based carbon nano tube reinforced amorphous metal oxide coating electrode comprises the following specific steps:
(1) Adopting 60 mesh SiC to carry out sand blasting on a porous titanium substrate to remove an oxide layer on the surface of the porous titanium substrate, then placing the porous titanium substrate in hydrochloric acid solution with the mass concentration of 25%, and carrying out activation treatment for 45min at the temperature of 25 ℃ to form a rough surface, so that the activity specific surface of the titanium substrate is increased, the adhesion of a later-stage oxide coating is facilitated, and the activated porous titanium substrate is obtained; wherein the sand blasting pressure is 0.3Mpa, the angle between the nozzle and the titanium substrate is 75 degrees, and the surface of the titanium sheet after sand blasting is matt tingling gray;
(2) Coating the conductive layer coating liquid on the surface of the activated porous titanium substrate, drying at 120 ℃ for 3min, then carrying out thermal decomposition and oxidation at 600 ℃ for 8min, and repeating the coating, drying and thermal decomposition and oxidation treatment for 8 times to obtain a conductive metal oxide intermediate layer; wherein the conducting layer coating liquid contains 1.0mol/L SnCl 4, 0.20mol/L RuCl 3, 0.20mol/L butyl titanate (C 16H36 OTi) and 0.10mol/L TaCl 5; the preparation method of the conducting layer coating liquid comprises the steps of sequentially adding SnCl 4、RuCl3, butyl titanate and TaCl 5 into 30mL of commercial concentrated hydrochloric acid, ultrasonically mixing and dissolving for 30min, filtering by using 1PS liquid phase test paper to remove water, and adding n-butanol to 100mL;
(3) The method comprises the steps of sequentially carrying out activating treatment on carbon nanotubes (large specific surface area single-wall carbon nanotubes with the diameter of 2nm and the length of 10-20 nm) by using commercially available concentrated nitric acid for 10min and activating treatment by using sodium hydroxide solution with the mass concentration of 20% for 10min to obtain activated carbon nanotubes, dispersing the activated carbon nanotubes into an acidic composite solution, carrying out ultrasonic modification at the temperature of 50 ℃ for 15min, carrying out solid-liquid separation, carrying out drying treatment at the temperature of 100 ℃, and repeatedly carrying out 8 times of modification on the carbon nanotubes to obtain composite carbon nanotubes; wherein the acidic composite solution contains n-butanol 120g/L、HNO3 100g/L、Mn(NO3)2 20g/L、 Na2MoO4 10g/L、Ni(NO3)2 6g/L、Zr(NO3)2 3g/L and complexing agent acetylacetone 20g/L;
(4) Placing a porous titanium matrix coated with a conductive metal oxidation interlayer Sn-Ru-Ti-TaO x into an acidic composite electroplating solution, taking a titanium mesh as a cathode, and performing pulse electrodeposition for 80min under the stirring condition of the temperature of 45 ℃ and the speed of 200r/min to obtain a composite carbon nano tube coating containing nano crystalline and/or amorphous Mn, mo, ni and Zr enhancement; wherein the acidic composite plating solution contains composite carbon nano tube 20g/L、HNO3 80g/L、Mn(NO3)2 8g/L、 Na2MoO4 6g/L、Ni(NO3)2 4g/L and Zr (NO 3)2 g/L; the current density of pulse electrodeposition is 0.3A/dm 2, and the duty ratio is 40%;
(5) Placing the porous titanium substrate deposited with the reinforced composite carbon nano tube coating on the porous titanium substrate at 200 ℃ for thermal oxidation treatment for 120min to convert the reinforced composite carbon nano tube coating into an amorphous metal active layer Mn-Mo-Ni-ZrO x, wherein the thermal decomposition promotes the mutual diffusion of amorphous oxides and improves the bonding force between the amorphous oxides, thus obtaining the multi Kong Taiji carbon nano tube reinforced amorphous metal oxide coated electrode;
The porous titanium-based carbon nanotube reinforced amorphous metal oxide coating electrode prepared in the embodiment is in manganese electrolyte, the electrolysis condition is that the concentration of manganese ions in the cathode electrolyte is 1.2mol/L, the concentration of ammonium chloride is 2.0 mol/L, the pH value is 7.0, the concentration of hydrochloric acid in the anode electrolyte is 1.2mol/L, the concentration of ammonium chloride is 1.2mol/L, the concentration of fluoride is less than 200mg/L, the electrolysis temperature is 5 ℃, and metal manganese is electrodeposited by adopting an anion membrane electrolytic tank, so that the electric efficiency of the electrode is improved by 11% compared with that of a traditional graphite anode plate, and the pollution to the electrolyte can be effectively reduced.
Example 3: the porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode of this example was substantially the same as example 1, except that: the total thickness of the composite electrode material is 11.4mm, the thickness of the porous titanium matrix is 10mm, the pore diameter of the porous titanium matrix is 50 mu m, and the pore depth is 20-40 mu m; the mol ratio of Sn, ru, ti and Ta in the Sn-Ru-Ti-TaO x layer is 12:3:2:1, and the thickness is 100 mu m; the molar ratio of Mn, mo, ni and Zr in the carbon nano tube reinforced Mn-Mo-Ni-ZrOx oxide layer is 8:4:2:1, and the thickness is 600 mu m;
the preparation method of the porous titanium-based carbon nano tube reinforced amorphous metal oxide coating electrode comprises the following specific steps:
(1) Adopting 100 meshes of Al 2O3 to carry out sand blasting on a porous titanium substrate to remove an oxide layer on the surface of the porous titanium substrate, then placing the porous titanium substrate in a hydrochloric acid solution with the mass concentration of 30%, and carrying out activation treatment for 40min at the temperature of 20 ℃ to form a rough surface, so that the activity specific surface of the titanium substrate is increased, the adhesion of a later-stage oxide coating is facilitated, and the activated porous titanium substrate is obtained; wherein the sand blasting pressure is 0.4Mpa, the angle between the nozzle and the titanium substrate is 45 degrees, and the surface of the titanium sheet after sand blasting is matt tingling gray;
(2) Coating the conductive layer coating liquid on the surface of the activated porous titanium substrate, drying at 150 ℃ for 5min, then carrying out thermal decomposition and oxidation at 650 ℃ for 10min, and repeating the coating, drying and thermal decomposition and oxidation treatment for 6 times to obtain a conductive metal oxide intermediate layer, wherein the particle size of the conductive layer is 20-40 mu m; wherein the conducting layer coating liquid contains 1.2mol/L of SnCl 4, 0.30mol/L of RuCl 3, 0.20mol/L of butyl titanate (C 16H36 OTi) and 0.10mol/L of TaCl 5; the preparation method of the conducting layer coating liquid comprises the steps of sequentially adding SnCl 4、RuCl3, butyl titanate and TaCl 5 into 40mL of commercial concentrated hydrochloric acid, ultrasonically mixing and dissolving for 40min, filtering by using 1PS liquid phase test paper to remove water, and adding n-butanol to 100mL;
(3) The method comprises the steps of sequentially carrying out activating treatment on carbon nanotubes (large specific surface area single-wall carbon nanotubes with the diameter of 2nm and the length of 5-20 nm) by using commercially available concentrated nitric acid for 8min and activating treatment by using sodium hydroxide solution with the mass concentration of 20% for 8min to obtain activated carbon nanotubes, dispersing the activated carbon nanotubes into an acidic composite solution, carrying out ultrasonic modification at the temperature of 45 ℃ for 20min, carrying out solid-liquid separation, carrying out drying treatment at the temperature of 90 ℃, and repeatedly carrying out 10 times of modification on the carbon nanotubes to obtain composite carbon nanotubes; wherein the acidic composite solution contains n-butanol 130g/L、HNO3 120g/L、Mn(NO3)2 25g/L、 Na2MoO4 15g/L、Ni(NO3)2 8g/L、Zr(NO3)2 4g/L and complexing agent ethylenediamine tetraacetic acid 15 g/L;
(4) Placing a porous titanium matrix coated with a conductive metal oxidation interlayer Sn-Ru-Ti-TaO x into an acidic composite electroplating solution, taking a titanium mesh as a cathode, and performing pulse electrodeposition for 120min under the stirring condition of the temperature of 70 ℃ and the speed of 300r/min to obtain a composite carbon nano tube coating containing nano crystalline and/or amorphous Mn, mo, ni and Zr enhancement; wherein the acidic composite plating solution contains composite carbon nano tube 25g/L、HNO3 90g/L、Mn(NO3)2 10g/L、 Na2MoO4 8g/L、Ni(NO3)2 6g/L and Zr (NO 3)2 g/L; the current density of pulse electrodeposition is 0.4A/dm 2, and the duty ratio is 50%;
(5) Placing the porous titanium substrate deposited with the reinforced composite carbon nano tube coating on the porous titanium substrate at 300 ℃ for thermal oxidation treatment for 120min to convert the reinforced composite carbon nano tube coating into an amorphous metal active layer Mn-Mo-Ni-ZrO x, wherein the thermal decomposition promotes the mutual diffusion of amorphous oxides and improves the bonding force between the amorphous oxides, thus obtaining the multi Kong Taiji carbon nano tube reinforced amorphous metal oxide coated electrode;
The porous titanium-based carbon nanotube reinforced amorphous metal oxide coating electrode prepared in the embodiment is in manganese electrolyte, the electrolysis condition is that the concentration of manganese ions in the cathode electrolyte is 1.2mol/L, the concentration of ammonium chloride is 2.0 mol/L, the pH is 7.0, the concentration of hydrochloric acid in the anode electrolyte is 1.2mol/L, the concentration of ammonium chloride is 1.2mol/L, the concentration of fluoride is less than 200mg/L, the electrolysis temperature is 5 ℃, metal manganese is electrodeposited by adopting an anion membrane electrolytic tank, the electric efficiency of the electrode is improved by 8% compared with that of a traditional Ti/Sn-Sb/alpha-PbO 2/β-PbO2 anode plate, and the service life is prolonged by 1.1 times.
The electrode obtained by the preparation method has the advantages of low noble metal consumption, high electrocatalytic activity, good conductivity, strong corrosion resistance, long service life and low production cost, and the novel electrode obtained by the preparation method can be widely applied to hydrometallurgy industry, sewage treatment, organic electrosynthesis, and other electrochemical engineering. Can be used as an anode or a cathode.
While the present invention has been described in detail with reference to the drawings, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (8)
1. A porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode characterized by: the preparation method comprises a porous titanium substrate, a conductive metal oxidation intermediate layer and an amorphous metal active layer which are sequentially arranged from inside to outside, wherein the conductive metal oxidation intermediate layer is a Sn-Ru-Ti-TaO x layer prepared by thermal decomposition, and the amorphous metal active layer is a carbon nano tube reinforced Mn-Mo-Ni-ZrOx oxide layer obtained by pulse electrodeposition and thermal oxidation treatment;
the preparation method of the porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode comprises the following specific steps:
(1) Removing an oxide layer on the surface of the porous titanium substrate, and then placing the porous titanium substrate in a hydrochloric acid solution for activation treatment for 30-120 min to obtain an activated porous titanium substrate;
(2) Coating the conductive layer coating liquid on the surface of the activated porous titanium substrate, drying, placing the activated porous titanium substrate at the temperature of 300-700 ℃ for thermal decomposition and oxidation for 5-20min, and repeatedly performing coating, drying and thermal decomposition and oxidation treatment to obtain a conductive metal oxide intermediate layer; wherein the conducting layer coating liquid contains SnCl 4、RuCl3, butyl titanate and TaCl 5;
(3) Activated carbon nanotubes are obtained by activating the carbon nanotubes by concentrated nitric acid and sodium hydroxide solution in sequence, the activated carbon nanotubes are dispersed into an acidic composite solution, the carbon nanotubes are subjected to ultrasonic modification for 10-20min at the temperature of 20-60 ℃, solid-liquid separation and drying treatment are carried out, and the carbon nanotubes are repeatedly modified for 6-10 times to obtain the composite carbon nanotubes; the acidic composite solution contains 5-20g/L of n-butanol 100-200 g/L、HNO3 80-160g/L、Mn(NO3)2 5-30g/L、Na2MoO4 5-20g/L、Ni(NO3)2 2-10g/L、Zr(NO3)2 2-4g/L、 complexing agent; the complexing agent is ethylenediamine tetraacetic acid and/or acetylacetone;
(4) Placing the porous titanium matrix coated with the conductive metal oxidation intermediate layer into an acidic composite electroplating solution, taking a titanium mesh as a cathode, and performing pulse electrodeposition for 0.5-2h under the stirring condition at the temperature of 40-90 ℃ to obtain a reinforced composite carbon nano tube coating; the acidic composite plating solution contains composite carbon nano tubes 10-30g/L、HNO3 40-100g/L、Mn(NO3)2 5-20g/L、Na2MoO4 1-10g/L、Ni(NO3)2 1-10g/L and Zr (NO 3)2 1-20g/L;
(5) And (3) placing the porous titanium substrate deposited with the reinforced composite carbon nano tube coating on the porous titanium substrate at the temperature of 150-300 ℃ for thermal oxidation treatment for 60-120min to convert the reinforced composite carbon nano tube coating into an amorphous metal active layer, thus obtaining the multi Kong Taiji carbon nano tube reinforced amorphous metal oxide coating electrode.
2. The porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode of claim 1, wherein: the pore diameter of the porous titanium matrix is 10-100 μm, and the pore depth is 1-50 μm.
3. The porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode of claim 1, wherein: the mol ratio of Sn, ru, ti and Ta in the Sn-Ru-Ti-TaO x layer is 60-80:5-10:1-10:1-5, and the thickness is 50-200 mu m.
4. The porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode of claim 3, wherein: the molar ratio of Mn, mo, ni and Zr in the carbon nano tube reinforced Mn-Mo-Ni-ZrOx oxide layer is 60-80:10-20:5-15:1-5, and the thickness is 200-800 mu m.
5. The method for preparing the porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode according to any one of claims 1 to 4, which is characterized by comprising the following specific steps:
(1) Removing an oxide layer on the surface of the porous titanium substrate, and then placing the porous titanium substrate in a hydrochloric acid solution for activation treatment for 30-120 min to obtain an activated porous titanium substrate;
(2) Coating the conductive layer coating liquid on the surface of the activated porous titanium substrate, drying, placing the activated porous titanium substrate at the temperature of 300-700 ℃ for thermal decomposition and oxidation for 5-20min, and repeatedly performing coating, drying and thermal decomposition and oxidation treatment to obtain a conductive metal oxide intermediate layer; wherein the conducting layer coating liquid contains SnCl 4、RuCl3, butyl titanate and TaCl 5;
(3) Activated carbon nanotubes are obtained by activating the carbon nanotubes by concentrated nitric acid and sodium hydroxide solution in sequence, the activated carbon nanotubes are dispersed into an acidic composite solution, the carbon nanotubes are subjected to ultrasonic modification for 10-20min at the temperature of 20-60 ℃, solid-liquid separation and drying treatment are carried out, and the carbon nanotubes are repeatedly modified for 6-10 times to obtain the composite carbon nanotubes; the acidic composite solution contains 5-20g/L of n-butanol 100-200 g/L、HNO3 80-160g/L、Mn(NO3)2 5-30g/L、Na2MoO4 5-20g/L、Ni(NO3)2 2-10g/L、Zr(NO3)2 2-4g/L、 complexing agent; the complexing agent is ethylenediamine tetraacetic acid and/or acetylacetone;
(4) Placing the porous titanium matrix coated with the conductive metal oxidation intermediate layer into an acidic composite electroplating solution, taking a titanium mesh as a cathode, and performing pulse electrodeposition for 0.5-2h under the stirring condition at the temperature of 40-90 ℃ to obtain a reinforced composite carbon nano tube coating; the acidic composite plating solution contains composite carbon nano tubes 10-30g/L、HNO3 40-100g/L、Mn(NO3)2 5-20g/L、Na2MoO4 1-10g/L、Ni(NO3)2 1-10g/L and Zr (NO 3)2 1-20g/L;
(5) And (3) placing the porous titanium substrate deposited with the reinforced composite carbon nano tube coating on the porous titanium substrate at the temperature of 150-300 ℃ for thermal oxidation treatment for 60-120min to convert the reinforced composite carbon nano tube coating into an amorphous metal active layer, thus obtaining the multi Kong Taiji carbon nano tube reinforced amorphous metal oxide coating electrode.
6. The method for preparing the porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode according to claim 5, wherein the method comprises the following steps: the organic solvent of the conductive layer coating liquid in the step (2) is one or more of ethanol, glycol, isopropanol and n-butanol.
7. The method for preparing the porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode according to claim 5, wherein the method comprises the following steps: the carbon nanotubes in the step (3) are single-walled carbon nanotubes.
8. The method for preparing the porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode according to claim 5, wherein the method comprises the following steps: the current density of the pulse electrodeposition is 0.2-1.4A/dm 2, and the duty ratio is 30-60%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111492152.4A CN114134542B (en) | 2021-12-08 | 2021-12-08 | Porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111492152.4A CN114134542B (en) | 2021-12-08 | 2021-12-08 | Porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114134542A CN114134542A (en) | 2022-03-04 |
| CN114134542B true CN114134542B (en) | 2024-05-10 |
Family
ID=80385098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111492152.4A Active CN114134542B (en) | 2021-12-08 | 2021-12-08 | Porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114134542B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3731285A1 (en) * | 1987-09-17 | 1989-04-06 | Conradty Metallelek | Dimensionally stable anode, method for manufacturing it, and use thereof |
| JP2006083462A (en) * | 2004-09-17 | 2006-03-30 | Tama Kagaku Kogyo Kk | Electrode for electrolysis, and method for producing aqueous solution of quaternary ammonium hydroxide with the use of the electrode |
| CN102051634A (en) * | 2011-01-26 | 2011-05-11 | 西北有色金属研究院 | Titanium electrode material with porous titanium as substrate and preparation method of titanium electrode material |
| CN104593818A (en) * | 2014-12-24 | 2015-05-06 | 中南大学 | Titanium-based composite anode as well as preparation method and application thereof |
| CN105110425A (en) * | 2015-09-01 | 2015-12-02 | 上海应用技术学院 | Preparation method of carbon-nanotube-modified three-dimensional porous-titanium-base lead dioxide electrode |
| CN106048690A (en) * | 2016-07-20 | 2016-10-26 | 中南大学 | Titanium-based titanium dioxide nanotube composite anode and preparation method thereof |
| CN107245729A (en) * | 2017-06-21 | 2017-10-13 | 昆明理工大学 | Manganese electrodeposition carbon fiber-based graded composite anode material and preparation method thereof |
| CN108677221A (en) * | 2018-06-13 | 2018-10-19 | 昆明理工大学 | A kind of titanium-based β-MnO2Composite coating anode and preparation method thereof |
| CN108690919A (en) * | 2018-05-15 | 2018-10-23 | 昆明理工大学 | A kind of method that nano metallurgical method prepares carbon nanotube and/or graphene enhancing lead base composite anode |
| CN109023436A (en) * | 2018-07-23 | 2018-12-18 | 昆明理工大学 | A kind of titanium-based β-MnO2-RuO2Composite coating anode plate and the preparation method and application thereof |
| CN109628957A (en) * | 2018-12-27 | 2019-04-16 | 西安泰金工业电化学技术有限公司 | A kind of preparation method of Zinc electrolysis titanium-based nano composite anode |
-
2021
- 2021-12-08 CN CN202111492152.4A patent/CN114134542B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3731285A1 (en) * | 1987-09-17 | 1989-04-06 | Conradty Metallelek | Dimensionally stable anode, method for manufacturing it, and use thereof |
| JP2006083462A (en) * | 2004-09-17 | 2006-03-30 | Tama Kagaku Kogyo Kk | Electrode for electrolysis, and method for producing aqueous solution of quaternary ammonium hydroxide with the use of the electrode |
| CN102051634A (en) * | 2011-01-26 | 2011-05-11 | 西北有色金属研究院 | Titanium electrode material with porous titanium as substrate and preparation method of titanium electrode material |
| CN104593818A (en) * | 2014-12-24 | 2015-05-06 | 中南大学 | Titanium-based composite anode as well as preparation method and application thereof |
| CN105110425A (en) * | 2015-09-01 | 2015-12-02 | 上海应用技术学院 | Preparation method of carbon-nanotube-modified three-dimensional porous-titanium-base lead dioxide electrode |
| CN106048690A (en) * | 2016-07-20 | 2016-10-26 | 中南大学 | Titanium-based titanium dioxide nanotube composite anode and preparation method thereof |
| CN107245729A (en) * | 2017-06-21 | 2017-10-13 | 昆明理工大学 | Manganese electrodeposition carbon fiber-based graded composite anode material and preparation method thereof |
| CN108690919A (en) * | 2018-05-15 | 2018-10-23 | 昆明理工大学 | A kind of method that nano metallurgical method prepares carbon nanotube and/or graphene enhancing lead base composite anode |
| CN108677221A (en) * | 2018-06-13 | 2018-10-19 | 昆明理工大学 | A kind of titanium-based β-MnO2Composite coating anode and preparation method thereof |
| CN109023436A (en) * | 2018-07-23 | 2018-12-18 | 昆明理工大学 | A kind of titanium-based β-MnO2-RuO2Composite coating anode plate and the preparation method and application thereof |
| CN109628957A (en) * | 2018-12-27 | 2019-04-16 | 西安泰金工业电化学技术有限公司 | A kind of preparation method of Zinc electrolysis titanium-based nano composite anode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114134542A (en) | 2022-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109023436B (en) | Titanium-based β -MnO2-RuO2Composite coating anode plate and preparation method and application thereof | |
| CN108677221B (en) | Titanium-based β -MnO2Composite coating anode and preparation method thereof | |
| CN104495811A (en) | Graphene composite material and preparation method thereof | |
| Wang et al. | Preparation of nanostructured Cu (OH) 2 and CuO electrocatalysts for water oxidation by electrophoresis deposition | |
| CN106087002B (en) | A kind of preparation method of the compound hydrogen-precipitating electrodes of 3D structures Ni/rGO | |
| CN101113525A (en) | Pt-TiO2/Ti combination electrode and method for making same | |
| CN115244220A (en) | Alkaline water electrolysis method and anode for alkaline water electrolysis | |
| CN105239095A (en) | Method for preparing Ti/Sb-SnO2/Nd-nano TiO2-PbO2 electrode and degrading reactive blue 117 through Ti/Sb-SnO2/Nd-nano TiO2-PbO2 electrode | |
| CN112195482B (en) | Composite titanium anode plate and preparation method thereof | |
| CN114134542B (en) | Porous titanium-based carbon nanotube reinforced amorphous metal oxide coated electrode and preparation method thereof | |
| CN112877711B (en) | Ni-NiO/C core-shell structure nano material electrocatalyst and preparation method thereof | |
| Xu et al. | Research progress of metal oxide as cathode materials for hydrogen evolution | |
| CN101511469A (en) | Nanometer powder catalyst and preparation method thereof | |
| CN115466986B (en) | Electrode for producing hydrogen by waste water electrolysis and preparation method and application thereof | |
| CN116446014A (en) | Composite electroplating solution, nickel-based composite material, and preparation method and application thereof | |
| CN113430555B (en) | Iridium oxide-platinum composite nano catalyst, preparation method and application thereof | |
| CN108301013A (en) | A kind of preparation method for the modified anode of lead dioxide generating ozone | |
| CN111186883B (en) | Novel preparation technology of lead dioxide electrode modified by titanium tetroxide nanotube | |
| CN111926345B (en) | IrO2-Ta2O5 anode with TiN nanotube interlayer | |
| CN113529133A (en) | Preparation method of self-supporting type bifunctional catalytic electrode | |
| CN113233549A (en) | Nano lead dioxide electrode and preparation method and application thereof | |
| CA3081715A1 (en) | Porous ni electrodes and a method of fabrication thereof | |
| KR102251850B1 (en) | Catalyst coated electrode, catalyst paste composition and methods of manufacturing thereof | |
| JP3921300B2 (en) | Hydrogen generator | |
| CN112030188B (en) | IrO2 nano-coating anode with TiN nano-tube intermediate layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |