CN106283105A - A kind of Ni interlayer that adds prepares low energy consumption, long-life titanio PbO2the method of anode - Google Patents
A kind of Ni interlayer that adds prepares low energy consumption, long-life titanio PbO2the method of anode Download PDFInfo
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- CN106283105A CN106283105A CN201610702861.3A CN201610702861A CN106283105A CN 106283105 A CN106283105 A CN 106283105A CN 201610702861 A CN201610702861 A CN 201610702861A CN 106283105 A CN106283105 A CN 106283105A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000011229 interlayer Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 27
- 241000292525 Titanio Species 0.000 title claims abstract description 18
- 238000005265 energy consumption Methods 0.000 title claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000010936 titanium Substances 0.000 claims abstract description 57
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000010410 layer Substances 0.000 claims abstract description 27
- 238000004070 electrodeposition Methods 0.000 claims abstract description 21
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- -1 hydroxyl radical free radical Chemical class 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 18
- 229910006654 β-PbO2 Inorganic materials 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007832 Na2SO4 Substances 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000010405 anode material Substances 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 239000002608 ionic liquid Substances 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 239000002932 luster Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 abstract description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910006531 α-PbO2 Inorganic materials 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical group Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 208000036626 Mental retardation Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- B01J35/33—
-
- 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
- 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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
-
- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
Abstract
The invention discloses one and prepare low energy consumption, long-life Ti/Ni/PbO by adding Ni interlayer2The method of dimensional stable anode, by carrying out negative electrode electro-deposition nickel dam to the titanium plate surface good through oil removing and acid corroding pretreatment, it is achieved with the strong bonded of titanio material, it will be apparent that promote anodic oxidation and prepare β PbO2Active layer, effectively prevents Oxygen anodic evolution and generates during hydroxyl radical free radical active oxygen and become TiO to anode colonization of moving to the interior2And cause anode to lose efficacy, serve the effect of oxygen barrier；The Ni interlayer of satisfactory electrical conductivity makes the tank voltage of electrochemical process significantly reduce simultaneously, and energy expenditure rate significantly improves, and increases anode electrode service life.
Description
Technical field
The invention belongs to lead dioxide electrode preparing technical field, add Ni interlayer particularly to one and prepare mental retardation
Consumption, long-life titanio PbO2The method of anode.
Background technology
PbO2There is the electric conductivity that metalloid is excellent, there is good corrosion resistance, preferable electro-catalysis in aqueous
Performance, overpotential for oxygen evolution are high, cheap for manufacturing cost, and become one and be widely used in many inorganic and organic compound electrolysis life
Produce, electrochemical oxidation removes one of anode materials such as dirty Organic substance in water.PbO2Mainly there is rhombic system (α-PbO2) and four directions system
(β-PbO2) two class formations, both compare, α-PbO2Poorly conductive, catalysis activity low, stability is preferable；And β-PbO2Electric conductivity
High, catalysis activity height, the most typically uses the β-PbO of the tetragonal crystalline structure that catalytic performance is higher2As electro-catalysis anode material
Material.In order to eliminate PbO2Electrodeposition distorts the defect such as big, fragile, difficult processing, select close with its thermal coefficient of expansion and against corrosion, lead
The best titanio material, becomes the common practice.Ti/β-PbO2Anode is usually in acid condition with Anodic oxygen
The technology changed is prepared from Ti substrate surface.Relatively big yet with the internal stress of intrinsic in Lead oxide brown preparation process, electrolysis
During because of nascent oxygen atom can be diffused into matrix surface formed TiO2Insulating barrier, often results in disbonding etc. and lost efficacy.For
Improvement disadvantages described above, it is thus achieved that high performance PbO2Anode electrode, adds intermediate layer modification and is proved to be an effective technology
Approach, up to the present, intermediate layer modified layer mainly has two kinds, and (1) is to use the noble metals such as Pt, Au；(2) oxidation of stannum antimony is added
The coatings such as thing.Generally it is generally at Titanium base and β-PbO2Between surface layer use brushing method thermal decomposition prepare oxide coating or
Electro-deposition precious metal adds intermediate layer, reduces the internal stress between titanio material and surface activity layer, strengthens β-PbO2Plating
Adhesion between layer and Titanium base, but brushing pyrolysismethod to prepare intermediate layer process loaded down with trivial details, complicated wayward, and deposit
Precious metal intermediate layer then significantly increases electrode fabrication cost, is still difficult to fundamentally solve β-PbO2Coating working life
Short, poor stability and the big problem of energy consumption.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, it is an object of the invention to provide a kind of Ni interlayer that adds and prepare low
Cost, low energy consumption, long-life titanio PbO2The method of anode, prepares uncomplicated realizing electrode, effectively controls cost, can be very well
Ground reduces the electric energy loss in application of electrode and extends electrode life, promotes PbO further2The industrialization of anode material should
With；This is high based on metallic nickel not only electrical conductivity, and has certain catalysis activity (realizing chemistry plating continuously), is exactly i.e. raw
Become nickel oxide also to belong to semi-conducting material and there is certain catalysis activity, also can effectively stop active oxygen to internal diffusion；Although punching
Hitting nickel plating is the easily optional process for surface preparation of passivating material such as rustless steel, titanium alloy, but not yet has as electrode intermediate layer
The precedent of application, the present invention then hinders performance imagination from its catalytic performance and oxygen and proposes, it was found that its low energy consumption, long-life spy
Property.
To achieve these goals, the technical solution used in the present invention is:
A kind of Ni interlayer that adds prepares low energy consumption, long-life titanio PbO2The method of anode, follows the steps below:
(1) pretreatment of Titanium base；
(2) preparation of Ni interlayer: with pretreated Titanium base as negative electrode, the nickel plate of two pieces of homalographics is anode, puts
In with mixing tank liquor that sulphuric acid nickel salt is main salt, carry out electro-deposition, take out the titanium-matrix electrode in plated nickel intermediate layer afterwards, with steaming
Distilled water is by clean for Ti/Ni (represent and be plated with Ni layer on Titanium base) electrode clean, and cold wind dries up, and obtains being combined good with base material titanium
Good, the Ni interlayer of surface compact, uniform color；
(3)β-PbO2The preparation of active layer: be anode by the Ti/Ni of the band " Ni interlayer " obtained in (2), the faces such as two pieces
Long-pending corrosion resistant plate is negative electrode, is placed in containing main salt Pb (NO3)2, pH adjusting agent HNO3And in the mixed solution of other auxiliary additive
Carrying out electroxidation to prepare, clean to prepared anode distilled water flushing afterwards, cold wind dries up, obtain surface compact, uniformly,
Stability and the best active Ti/Ni/ β-PbO2Dimensional stable anode material.
Here, Ti/Ni material refers to be plated with the electrode material to be oxidized of Ni layer on Titanium base；It is plated with Ni interlayer
Ti/Ni material refer to the Ni intermediate layer material that is plated on Ti.
The pretreatment of described Titanium base includes cutting polishing, oil removing alkali cleaning and oxalic acid three links of etching, titanium plate after process
Surface forms rough pitted skin layer, gray, loses metallic luster, it is thus achieved that without greasy dirt and the clean surface of oxide skin.
In the preparation process of described Ni interlayer, in order to ensure to be well combined, optional charged lower groove carries out electro-deposition.
In the preparation process of described Ni interlayer, mixing tank liquor is mainly by NiSO4·7H2O、Na2SO4·10H2O、H3BO3、
NaCl is constituted.
Described NiSO4·7H2The concentration of O is 140～200g/L, Na2SO4·10H2The concentration of O is 50～80g/L, H3BO3
Concentration be 20～35g/L, the concentration of NaCl is 5～15g/L.
The pH value of described mixing tank liquor is 4～6, and electrodeposition temperature controls at 18～40 DEG C, electric current density be 0.5～
1.2A/dm2, the distance of negative electrode and anode is 1～3cm.
Described Ni interlayer THICKNESS CONTROL is in 7～10 μm.
Described β-PbO2In the preparation of active layer, Pb (NO3)2Solution concentration is 0.4～0.6mol/L, passes through pH adjusting agent
HNO3Consumption control electroxidation mixed solution pH value 2～4, electrodeposition temperature is 30～50 DEG C, electrodeposition time be 30～
90min, electric current density is 10～20mA/cm2。
Described β-PbO2In the preparation of active layer, auxiliary additive is ionic liquid, and ionic liquid can be 1-ethyl-3-
Methyl-imidazoles tetrafluoroborate is additive, and its concentration is 5～50mg/L.
Compared with prior art, the present invention uses cathodic electrodeposition to prepare Ni interlayer on Titanium base, the most again profit
Ti/Ni/PbO is prepared with anodizing technology2Anode.Nickel intermediate prepared by electrodeposition process simplifies in preparing with brushing method
The loaded down with trivial details link of mesosome, reduce the cost using other precious metals as intermediate.And do not add under the same terms
Ti/PbO prepared by mesosome2Dimensional stable anode is compared, Ti/Ni/PbO2Dimensional stable anode crystallization is thinner, crystallization degree is more preferable, electro-catalysis is alive
Property is higher, service life is longer, less at electrocatalytic oxidation organic wastewater and electrolytic synthesis time institute consuming electric power.
Accompanying drawing explanation
Fig. 1 is Ti/PbO2Electrode and Ti/Ni/PbO2The diffraction spectra schematic diagram of electrode.
Fig. 2 is Ti/PbO2Electrode and Ti/Ni/PbO2The surface topography contrast schematic diagram of electrode, wherein figure (a) is Ti/
PbO2Electrode surface pattern, figure (b) is Ti/Ni/PbO2Electrode surface pattern.
Fig. 3 is Ti/PbO2Electrode and Ti/Ni/PbO2Electrode is at 1M H2SO4Middle accelerated aging contrast schematic diagram.
Detailed description of the invention
Embodiments of the present invention are described in detail below in conjunction with the accompanying drawings with embodiment.
Embodiment 1
Initially with being negative electrode through polishing, alkali cleaning, the titanium plate of pickling, the nickel plate of homalographic size is anode, uses the moon
Ni interlayer is prepared in pole electro-deposition, and the most again with Ti/Ni electrode material as anode, the rustless steel of homalographic size is negative electrode, sun
Pole electroxidation prepares β-PbO2Active layer, thus obtain Ti/Ni/PbO2Dimensional stable anode.The electrodeposition condition of nickel intermediate is such as
Under: NiSO4·7H2O 180g/L、Na2SO4·10H20 65g/L、H3BO330g/L, NaCl g/L 10g/L is electronickelling groove
Liquid, control temperature be 25 ± 5 DEG C, electrodeposition time be 45min, electric current density be 1A/dm2, bath pH value be 4.7.β-PbO2Live
Property layer electrodeposition condition is as follows: Pb (NO3)2: 0.45mol/L, HNO31.4mL/L, pH value is 2.4, with ionic liquid for 1-second
Base-3-methyl-imidazoles tetrafluoroborate is additive, and its concentration is 30mg/L；Electrodeposition temperature is 40 ± 5 DEG C, during electro-deposition
Between be 60min, electric current density is 20mA/cm2.Ti/Ni/PbO by preparation2Electrode is clean with distilled water flushing, and cold wind dries up,
Obtain surface compact, uniform Ti/Ni/PbO2Dimensional stable anode, carries out XRD Yu SEM phenetic analysis (Fig. 1 and 2) to its surface, with
Ti/PbO2Dimensional stable anode is compared, Ti/Ni/PbO2β-the PbO of electrode2Active layer crystallization is preferable, homogeneous grain size, surface compact
More smooth, without packing phenomenon.
Ti/Ni/PbO with embodiment 1 preparation2Electrode is clean with distilled water flushing, and cold wind dries up, obtain surface compact,
Uniform Ti/Ni/PbO2Anode.By Ti/Ni/PbO2Electrode material is 150mL for volume, and initial concentration is 100mg/L phenol
The oxidative degradation of simulated wastewater processes, and after 180min, phenol clearance is 95.02%, and COD clearance is 54.19%, and electric energy
Average power consumption be about: 0.004 degree, and Ti/PbO under the same terms2Phenol clearance after 180min after handled by electrode material
Being 93.12%, COD clearance is 49.66%, and the average power consumption of electric energy is: 0.007 degree, as shown in table 1.
Table 1Ti/PbO2Electrode and Ti/Ni/PbO2The phenol that 100mg/L phenol synthetic water is degraded 3 hours by electrode is removed
Rate, COD clearance and institute's consuming electric power contrast
It can thus be appreciated that the addition in Ni intermediate layer adds the electric conductivity of electrode, improve the catalysis activity of electrode, very great Cheng
The loss of the electric energy reduced on degree.
Ti/Ni/PbO with embodiment 1 preparation2Electrode is clean with distilled water flushing, and cold wind dries up, obtain surface compact,
Uniform Ti/Ni/PbO2Anode.The accelerated life test electrode material to preparing is used to carry out stability test, Ti/
Ni/PbO2For working electrode, the titanium plate of homalographic size is to electrode, and saturated calomel electrode is reference electrode.Test is at electric current
Density is 1A/cm2, electrolyte is 1M H2SO4, temperature is carried out under conditions of being 50 DEG C, and recording electrode current potential is with the testing time
Change, the criterion that the sudden change flex point of electrode potential time graph is inactivated as electrode.Experimental result is as it is shown on figure 3, can
To find out, Ti/Ni/PbO2The accelerated test life-span of electrode is 47h, is without intermediate layer of nickel Ti/PbO21.7 times of electrode, it is seen that
The electrode life using the method for the invention to prepare is substantially better than the Ti base PbO not adding intermediate2Anode.
The one implementing the present invention above to be provided prepares low energy consumption, long-life Ti/Ni/ by adding Ni interlayer
PbO2Dimensional stable anode is described in detail, and applies specific embodiment and carry out principle and the embodiment of the present invention in literary composition
Illustrating, the explanation of above example is only intended to help to understand method and the core concept thereof of the present invention；And for this area
Those skilled in the art, according to the thought of the present invention, the most all will change, therefore this theory
Bright book content should not be construed as limitation of the present invention.
Claims (10)
1. an interpolation Ni interlayer prepares low energy consumption, long-life titanio PbO2The method of anode, it is characterised in that according to following
Step is carried out:
(1) pretreatment of Titanium base；
(2) preparation of Ni interlayer: with pretreated Titanium base as negative electrode, the nickel plate of two pieces of homalographics is anode, be placed in
Sulphuric acid nickel salt be main salt mixing tank liquor in carry out electro-deposition, take out titanium-matrix electrode afterwards, clean up with distilled water, cold wind blows
Dry, obtain being well combined with base material, the Ni interlayer of surface compact, uniform color；
(3)β-PbO2The preparation of active layer: be plated with Ni interlayer Ti/Ni material as anode, two blocks of rustless steels of homalographic
Plate is negative electrode, is placed in containing main salt Pb (NO3)2, pH adjusting agent HNO3And the mixed solution of other auxiliary additive carries out electroxidation
Preparation, clean to prepared anode distilled water flushing afterwards, cold wind dries up, and obtains surface compact, uniform, stability and work
Ti/Ni/ β-the PbO that property is the best2Dimensional stable anode material.
Add Ni interlayer the most according to claim 1 and prepare low energy consumption, long-life titanio PbO2The method of anode, its feature
Being, the pretreatment of described Titanium base includes cutting polishing, oil removing alkali cleaning and oxalic acid three links of etching, titanium plate surface after process
Form rough pitted skin layer, gray, lose metallic luster, it is thus achieved that without greasy dirt and the clean surface of oxide skin.
Add Ni interlayer the most according to claim 1 and prepare low energy consumption, long-life titanio PbO2The method of anode, its feature
It is, in the preparation process of described Ni interlayer, in order to ensure to be well combined, selects charged lower groove to carry out electro-deposition.
Add Ni interlayer the most according to claim 1 and prepare low energy consumption, long-life titanio PbO2The method of anode, its feature
Being, in the preparation process of described Ni interlayer, mixing tank liquor is by NiSO4·7H2O、Na2SO4·10H2O、H3BO3, NaCl structure
Become.
Add Ni interlayer the most according to claim 4 and prepare low energy consumption, long-life titanio PbO2The method of anode, its feature
It is, described NiSO4·7H2The concentration of O is 140～200g/L, Na2SO4·10H2The concentration of O is 50～80g/L, H3BO3's
Concentration is 20～35g/L, and the concentration of NaCl is 5～15g/L.
Add Ni interlayer the most according to claim 4 and prepare low energy consumption, long-life titanio PbO2The method of anode, its feature
Being, the pH value of described mixing tank liquor is 4～6, and electrodeposition temperature controls at 18～40 DEG C, and electric current density is 0.5～1.2A/
dm2, the distance of negative electrode and anode is 1～3cm.
Add Ni interlayer the most according to claim 1 and prepare low energy consumption, long-life titanio PbO2The method of anode, its feature
Being, described Ni interlayer THICKNESS CONTROL is in 7～10 μm.
Add Ni interlayer the most according to claim 1 and prepare low energy consumption, long-life titanio PbO2The method of anode, its feature
It is, described β-PbO2In the preparation of active layer, Pb (NO3)2Solution concentration is 0.4～0.6mol/L, by pH adjusting agent HNO3
Consumption control electroxidation mixed solution pH value 2～4, electrodeposition temperature is 30～50 DEG C, electrodeposition time be 30～
90min, electric current density is 10～20mA/cm2。
Add Ni interlayer the most according to claim 1 and prepare low energy consumption, long-life titanio PbO2The method of anode, its feature
It is, described β-PbO2In the preparation of active layer, auxiliary additive is ionic liquid.
Add Ni interlayer the most according to claim 9 and prepare low energy consumption, long-life titanio PbO2The method of anode, its feature
Be, described ionic liquid be 1-ethyl-3-methyl-imidazoles tetrafluoroborate be additive, its concentration is 5～50mg/L.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108505083A (en) * | 2018-04-28 | 2018-09-07 | 西安建筑科技大学 | A kind of addition modified manganese dioxide middle layer preparation titanium-based β-PbO2The method of anode |
| CN108823613A (en) * | 2018-05-24 | 2018-11-16 | 西安建筑科技大学 | A kind of preparation method of lightweight hot pressing clad with metal foil base lead dioxide electrode |
| CN109457279A (en) * | 2018-12-24 | 2019-03-12 | 西安建筑科技大学 | It adds nickel composite interlayer and prepares low energy consumption, long-life titanium-based PbO2The method of anode |
| CN109778100A (en) * | 2019-04-01 | 2019-05-21 | 西安建筑科技大学 | One kind is lengthened the life the steady PbO of energy saving shape2The electric-arc thermal spray coating preparation method of anode middle layer |
| CN110820030A (en) * | 2019-11-14 | 2020-02-21 | 西安建筑科技大学 | Titanium-based PbO for preparing conducting ceramic membrane intermediate layer based on in-situ thermal reaction2Anode preparation method |
| CN111962121A (en) * | 2020-08-19 | 2020-11-20 | 西安交通大学 | Method for quickly constructing titanium substrate three-dimensional porous lead dioxide active layer |
| EP4012073A4 (en) * | 2019-08-07 | 2022-11-23 | Seoul National University R & DB Foundation | Electrode structures for electrochemical reaction, and electrochemical reaction systems including same |
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| CN103700813A (en) * | 2013-11-07 | 2014-04-02 | 西安建筑科技大学 | New method for preparing Ti base PbO2 dimensionally-stable anode |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108505083A (en) * | 2018-04-28 | 2018-09-07 | 西安建筑科技大学 | A kind of addition modified manganese dioxide middle layer preparation titanium-based β-PbO2The method of anode |
| CN108823613A (en) * | 2018-05-24 | 2018-11-16 | 西安建筑科技大学 | A kind of preparation method of lightweight hot pressing clad with metal foil base lead dioxide electrode |
| CN109457279A (en) * | 2018-12-24 | 2019-03-12 | 西安建筑科技大学 | It adds nickel composite interlayer and prepares low energy consumption, long-life titanium-based PbO2The method of anode |
| CN109778100A (en) * | 2019-04-01 | 2019-05-21 | 西安建筑科技大学 | One kind is lengthened the life the steady PbO of energy saving shape2The electric-arc thermal spray coating preparation method of anode middle layer |
| EP4012073A4 (en) * | 2019-08-07 | 2022-11-23 | Seoul National University R & DB Foundation | Electrode structures for electrochemical reaction, and electrochemical reaction systems including same |
| CN110820030A (en) * | 2019-11-14 | 2020-02-21 | 西安建筑科技大学 | Titanium-based PbO for preparing conducting ceramic membrane intermediate layer based on in-situ thermal reaction2Anode preparation method |
| CN110820030B (en) * | 2019-11-14 | 2021-06-15 | 西安建筑科技大学 | Titanium-based PbO for preparing conducting ceramic membrane intermediate layer based on in-situ thermal reaction2Anode preparation method |
| CN111962121A (en) * | 2020-08-19 | 2020-11-20 | 西安交通大学 | Method for quickly constructing titanium substrate three-dimensional porous lead dioxide active layer |
| CN111962121B (en) * | 2020-08-19 | 2021-11-19 | 西安交通大学 | Method for quickly constructing titanium substrate three-dimensional porous lead dioxide active layer |
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