CN104846357B - A kind of preparation method of metal oxides coating of anode - Google Patents
A kind of preparation method of metal oxides coating of anode Download PDFInfo
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- CN104846357B CN104846357B CN201510284290.1A CN201510284290A CN104846357B CN 104846357 B CN104846357 B CN 104846357B CN 201510284290 A CN201510284290 A CN 201510284290A CN 104846357 B CN104846357 B CN 104846357B
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Abstract
The invention belongs to electrochemical technology field; it is related to a kind of preparation method of metal oxides coating of anode; the anode prepared using atmospheric plasma auxiliary is applied to the degraded of electrolytic seawater sewage, prevents the Electrochemical Engineering occasion such as marine biofouling and cathodic protection, and preparation method includes that prepared by substrate pretreatment, masking liquid and coated anode prepares three steps：In conventional equipment, plasma discharge electric current and jet gun rate travel are first adjusted to setting value, pretreatment substrate surface on cover type injection prepare masking liquid after substrate is put into drying baker in dry, coating is formed on the surface of the substrate, then the electric discharge of using plasma jet is aoxidized to coating surface；, then be put into substrate in sintering furnace and sinter by the step of repeating injection, drying and plasma oxidation 68 times, completes coated anode and prepares；Its preparation process is simple, principle reliability, energy consumption is small, efficiency high, and the anode stability of preparation is good, and long service life is environment-friendly.
Description
Technical field：
The invention belongs to electrochemical technology field, it is related to a kind of preparation method of metal oxides coating of anode, using normal
Anode prepared by pressure plasmaassisted is applied to the degraded of electrolytic seawater sewage, prevents the electricity such as marine biofouling and cathodic protection
Chemical Engineering occasion.
Background technology：
At present, worked on the marine facilities such as ship, oil platform and island, in the sewage for producing of living containing largely having
Machine thing, these organic matters trigger eutrophication, change the living environment of marine organisms, have a negative impact to marine environment.
In the prior art, it is general using with flexibility ratio multi-functional, high, pollution-free or of low pollution, easily controllable and economy electrification
Learn means of the oxidizing process as treatment sewage；The key of this electrochemical oxidation process treatment sanitary sewage is anode material, anode
Material directly affects efficiency and the life-span of decomposition apparatus, should have good analysis chlorine activity, current efficiency and stability；Titanium-based
Oxide body coated electrode is to apply a kind of more novel electrode in nearly 2 years, is urged with electricity by the coating on Titanium base surface
Prepared by the method for changing the platinum-group metal oxide coatings of activity, have compared with traditional Ti/Pt (titanium/platinum) electrode preferably steady
Qualitative and corrosion resistance.Metal oxides coating of anode is typically prepared using traditional thermolysis process, and detailed process is will be molten
Metal chloride brushing of the solution in ethanol water first dries matrix 10-20min in matrix surface at 100-130 DEG C, then
Air cooling matrix under normal temperature is taken out at 450-550 DEG C after high temperature sintering matrix 10-20min, brushed repeatedly, dry, sintered and air cooling
The step of matrix, is until the coating of metal oxides carrying capacity of matrix reaches 10-30g/m2Afterwards, matrix is sintered at 450-550 DEG C
60-120min, obtains metal oxides coating of anode, and the purpose that matrix is sintered at 450 DEG C -550 DEG C is to promote ruthenium and iridium etc.
Element forms oxide；The mode of production of this batch discontinuous is deposited in the preparation process brushed repeatedly, dry, sinter and cool down
Many in time loss, energy ezpenditure is high, the low problem of production efficiency；As the plasma of the 4th state material there is particle to move
The characteristics of energy is greatly and chemical property is active, is widely used to the fields such as the energy, material and environment, and plasma discharge can be by gold
Category oxide-coated surface and its inside oxygen ionization into oxygen atom or oxonium ion with strong oxidizing property so that improve oxygen with
The reaction probabilities of the element such as ruthenium and iridium, therefore, using plasma replaces metal oxides coating of anode in the prior art to prepare
During drying, sintering and refrigerating work procedure, be conducive to the oxide of coating of metal oxides surface and its inside to form height and urge
Change activity, the preparation method of the metal oxides coating of anode has the advantages that energy consumption is small, continuous production and efficiency is high, Hen You societies
Meeting and economic worth, have a extensive future.
The content of the invention：
It is an object of the invention to the defect for overcoming prior art to exist, seek to design a kind of energy consumption is small, production is continuous and
The preparation method of the metal oxides coating of anode of efficiency high
To achieve these goals, the preparation method of metal oxides coating of anode of the present invention is located in advance including substrate
Prepared by reason, masking liquid and coated anode prepares three steps：
(1), substrate pretreatment：From technical pure titanium plate as base material, substrate is placed after conventional blasting treatment
Acid etching 1 hour, treats that substrate surface is coarse in the oxalic acid aqueous solution that mass percent concentration is 10% and temperature is 90-100 DEG C
Degree Ra uses industrial alcohol washes 2-3 times again after being drawn off being cleaned by ultrasonic totally with distilled water when being 1.5-3.5 μm, then dries
Substrate and to immerse sealing preserve in absolute alcohol cylinder stand-by, completes substrate pretreatment；
(2), prepared by masking liquid：According to the value requirement of the mol ratio of Ir, Ru, Ta, Sb, Ti and Sn in coating of metal oxides
Measure the IrO of corresponding volume2、RuO2、Ta2O5、SbO2、TiO2And SnO2The aqueous solution is mixed, and obtains mixed liquor, then in mixed liquor
According to 1：The weight of 1.5-3 adds the n-butanol aqueous solution that mass percent concentration is 99% than proportioning, by gold in mixed liquor
Belong to magnetic agitation mixed liquor after total ion concentration is adjusted to 0.2-0.35mol/L and, to its uniform mixing, masking liquid is obtained；
(3), prepared by coated anode：In conventional equipment, it is 3-4A, jet gun movement first to set plasma discharge electric current
Speed is 100-600mm/min, step (1) pretreatment substrate surface on cover type injecting step (2) prepare masking liquid after
100 DEG C of temperature control dries 10min during substrate is put into drying baker, and coating, then using plasma jet are formed on the surface of the substrate
Electric discharge is aoxidized to coating surface；The step of repeating above-mentioned injection, drying and plasma oxidation 6-8 times, then by substrate
It is put into 550 DEG C of sintering furnace and sinters 1-1.2h, completes coated anode and prepare.
Substrate material of the present invention is Titanium of the mass percent purity more than 99%, and shapes of substrates includes net
Shape, tabular, tubulose and bar-shaped；IrO of the coating of metal oxides being related to by setting weight than proportioning2、RuO2、Ta2O5、SbO2、
TiO2、SnO2In one-component or multicomponent compound constitute.
The present invention compared with prior art, coats mixed metal oxide coating, using plasma in conductive substrates
Instead of the drying in metal oxides coating of anode preparation process, sintering and refrigerating work procedure, be conducive to coating of metal oxides table
The oxide of face and its inside forms high catalytic activity；Its preparation process is simple, principle reliability, energy consumption is small, efficiency high, preparation
Anode stability is good, and long service life is environment-friendly.
Brief description of the drawings：
Fig. 1 is the cyclic voltammetry curve comparison diagram of the anode that the present invention is prepared with prior art.
Fig. 2 is the cyclic voltammetric electricity comparison diagram of the anode that the present invention is prepared with prior art.
Fig. 3 is the ultraviolet spectra comparison diagram of the anode that the present invention is prepared with prior art.
Fig. 4 is the COD change comparison diagram of the anode that the present invention is prepared with prior art.
Fig. 5 is the service life comparison diagram of the anode that the present invention is prepared with prior art.
Specific embodiment：
Below by embodiment and with reference to accompanying drawing, the invention will be further described.
Embodiment 1：
The preparation method of the metal oxides coating of anode that the present embodiment is related to includes that substrate pretreatment, masking liquid are prepared and applied
Layer anode prepares three steps：
(1), substrate pretreatment：Choose the TA2 industry that the generous size of length is 140mm × 110mm × 3mm and purity is 99%
Titanium board uses granularity to carry out sandblasting to titanium plate substrate and removed with distilled water flushing for 120 μm of diamond dust as base material
Remove to remain sand grains and metal fillings on the surface of the substrate, titanium plate substrate is put into after carrying out oil removing in acetone soln, be positioned over matter
Acid etching 1 hour in the oxalic acid aqueous solution that amount percent concentration is 10% and temperature is 90 DEG C, treats that substrate surface roughness Ra is 3.5
μm when be drawn off with distilled water be cleaned by ultrasonic it is clean after again with industrial alcohol washes 2-3 time, immersed without watery wine after drying substrate
Sealing preserve is stand-by in smart cylinder, completes substrate pretreatment；
(2), prepared by masking liquid：According to Ru：Ir：Sb is 1：1：0.5 mol ratio measures the H of corresponding volume2IrCl6·6H2O、
RuCl3Mixed liquor is configured with the Sb aqueous solution, then the n-butanol water that 100ml mass percent concentrations are 99% is added in mixed liquor
Solution, magnetic agitation mixed liquor is completed to its uniform mixing after metal ion total concentration in mixed liquor is adjusted to 0.3mol/L
It is prepared by masking liquid；
(3), prepared by coated anode：In conventional equipment and instrument, it is 3A, jet gun movement to set plasma discharge electric current
Speed is 400mm/min, by titanium plate after the masking liquid that prepared by injecting step (2) on the titanium plate substrate surface of step (1) pretreatment
Substrate is put into 100 DEG C of drying 10min of temperature control in drying baker, and coating, plasma discharge current settings are formed on titanium plate substrate surface
It is 3A, jet gun rate travel is set as 400mm/min, then the electric discharge of using plasma jet is aoxidized to coating surface；
, then be put into titanium plate substrate in 550 DEG C of sintering furnace by the step of repeating above-mentioned injection, drying and plasma oxidation 6-8 times
Sintering 1-1.2h, completes coated anode and prepares.
The present embodiment prepares coating of metal oxides sun respectively according to the technique of traditional thermolysis process and the present embodiment
Pole is simultaneously represented with a and b respectively, is the electro catalytic activity of test a and b, using Parstat2273 work stations in three-electrode cell
In carry out electro-chemical test, it is 1cm to set working electrode test area2, auxiliary electrode is platinum niobium electrode, and reference electrode is saturation
Calomel electrode, electrolyte is 1molL-1H2SO4The aqueous solution, test temperature is 25 ± 0.5 DEG C, by a and b difference in the electrolytic solution
Tested after immersion 2h, to a under the conditions of cyclic voltammetry scope is -2.0-2.0V and sweep speed is 20mVs-1
Carry out 20 circulations respectively with b, last cyclic voltammetry curve is integrated, try to achieve cyclic voltammetric electricity Q, anode surface
Number of active sites is directly proportional to cyclic voltammetric electricity Q, and surface-active points are bigger, and explanation electro catalytic activity is higher, as shown in Figure 1
Ti/RuO2-IrO2In-Sb cyclic voltammetry curve comparison diagrams, the intensified electrolysis current strength of a and b increases with the increase of current potential
Plus, b is consistently greater than a, as shown in Fig. 2 cyclic voltammetric electricity of the cyclic voltammetric electricity of b more than a, shows the surface-active point of b
Surface-active of the number more than a is counted, and illustrates the catalysis activity of the catalysis activity higher than a of b.
In order to test the effect of a and b degraded sewage in the present embodiment, the methylene blue for being respectively configured 400ml0.1mM is water-soluble
Liquid simultaneously adds NaCl that mass percent concentration is 1% as electrolyte, and negative electrode is titanium plate, and pole plate spacing is 1cm, current density
It is 50mA/cm2, interception size for 2*2cm each 1 piece of a and b put into the aqueous solution of methylene blue for having configured respectively in be electrolysed 1h,
With ultraviolet specrophotometer respectively test electrolysis a and b after aqueous solution of methylene blue Methylene Blue content, as shown in figure 3,
The colour developing group characteristic peak of the methylene blue of a and b disappears substantially in 580-680nm wave bands, and aqueous solution of methylene blue is changed into nothing
Color, the characteristic peak reduction amplitude of the methylene blue benzene ring structure of b is significantly greater than the characteristic peak reduction width of a near 280nm wavelength
Degree；It is respectively configured the D/W of 400ml2g/L and adds NaCl that mass percent concentration is 3% as electrolyte,
Negative electrode is stainless steel plate, and pole plate spacing is 1cm, and current density is 10mA/cm2, interception size is each 1 piece point of a and b of 2*2cm
It is electrolysed in the D/W that Tou Ru do not configured, the D/W of electrolysis a and b is repeatedly extracted in electrolytic process simultaneously
COD value therein is tested respectively, as shown in figure 4, COD value is reduced with the extension of degradation time, COD value is in 1200-
The degradation rate of a and b is essentially identical when in the range of 2000mg/L, and less than after 1200mg/L, the degradation rate of b is more than a to COD value
Degradation rate, average current efficiency improves 17%, illustrate b than a degrade sewage effect is good, the time is short.
The present embodiment is the service life for testing a and b, detects the stabilization of a and b respectively using intensified electrolysis life test method
Property, in 40 DEG C of 1mol/L H2SO4Anodic current density as 1A/cm is set in the aqueous solution2, titanium plate is between auxiliary cathode, pole plate
Away from being 2cm, a and b being electrolysed respectively, electrolysis being stopped when tank voltage rises to 10V, the electrolysis duration now is respectively a and b
The intensified electrolysis life-span, according to intensified electrolysis life-span and service life conversion formula：T1=(i2/i1)2* t2, calculates a and b respectively
Actual life, t1 represents service life in formula, and unit is h, and t2 represents the intensified electrolysis life-span, and unit is h, and i2 represents strong
Change electrolytic current density, unit is mA/cm2, and i1 represents actually used current density unit for mA/cm2, as shown in figure 5, a
Service life is 277h, and the service life of b is 424h, and the service life extension more than 50% of the service life than a of b illustrates b's
Stability it is stronger, service life is longer.
Embodiment 2：
The preparation method of the metal oxides coating of anode that the present embodiment is related to includes that substrate pretreatment, masking liquid are prepared and applied
Layer anode prepares three steps：
(1), substrate pretreatment：The TA2 technical pures titanium plate of 140mm × 110mm × 3mm is chosen as base material, is used
Granularity is that 120 μm of diamond dust carries out sandblasting to titanium plate substrate and removes residual sand grains on the surface of the substrate with distilled water flushing
And metal fillings, titanium plate substrate is put into acetone soln (concentration parameter) after oil removing, it is 10% to be positioned over mass percent concentration
With acid etching 1 hour in the oxalic acid aqueous solution that temperature is 100 DEG C, it is drawn off when substrate surface roughness Ra is 1.5 μm with steaming
Distilled water uses industrial alcohol washes 2-3 times again after being cleaned by ultrasonic totally, and immersing sealing preserve in absolute alcohol cylinder after drying substrate treats
With completion substrate pretreatment；
(2), prepared by masking liquid：According to Ru：Ir：Sb is 1：1：0.5 mol ratio measures the H of corresponding volume2IrCl6·6H2O、
RuCl3Mixed liquor is configured with the Sb aqueous solution, then the n-butanol water that 100ml mass percent concentrations are 99% is added in mixed liquor
Solution, magnetic agitation mixed liquor is completed to its uniform mixing after metal ion total concentration in mixed liquor is adjusted to 0.35mol/L
It is prepared by masking liquid；
(3), prepared by coated anode：It is 4A to set plasma discharge electric current, and jet gun rate travel is 100mm/min,
Titanium plate substrate is put into 100 in drying baker after the masking liquid that on the titanium plate substrate surface of step (1) pretreatment prepared by injecting step (2)
DEG C drying 10min, forms coating on titanium plate substrate surface, plasma discharge current settings are 4A, the setting of jet gun rate travel
It is 100mm/min, the electric discharge of using plasma jet is aoxidized to coating surface, repeats above-mentioned injection, drying and plasma
The step of body is aoxidized 6 times, titanium plate substrate is put into 1h is sintered in 550 DEG C of sintering furnace, is completed coated anode and is prepared.
Embodiment 3：
The preparation method of the metal oxides coating of anode that the present embodiment is related to includes that substrate pretreatment, masking liquid are prepared and applied
Layer anode prepares three steps：
(1), substrate pretreatment：The TA2 technical pures titanium plate of 140mm × 110mm × 3mm is chosen as base material, is used
Granularity is that 120 μm of diamond dust carries out sandblasting to titanium plate substrate and removes residual sand grains on the surface of the substrate with distilled water flushing
And metal fillings, titanium plate substrate is put into acetone soln (concentration parameter) after oil removing, it is 10% to be positioned over mass percent concentration
With acid etching 1 hour in the oxalic acid aqueous solution that temperature is 92 DEG C, it is drawn off using distilled water when substrate surface roughness Ra is 2 μm
Industrial alcohol washes are used again 2-3 times, sealing preserve is stand-by in immersion absolute alcohol cylinder after drying substrate, complete after ultrasonic cleaning is clean
Into substrate pretreatment；
(2), prepared by masking liquid：According to Ru：Ir：Sb is 1：1：0.5 mol ratio measures the H of corresponding volume2IrCl6·6H2O、
RuCl3Mixed liquor is configured with the Sb aqueous solution, then the n-butanol water that 100ml mass percent concentrations are 99% is added in mixed liquor
Solution, magnetic agitation mixed liquor is completed to its uniform mixing after metal ion total concentration in mixed liquor is adjusted to 0.2mol/L
It is prepared by masking liquid.
(3), prepared by coated anode：It is 3.5A to set plasma discharge electric current, and jet gun rate travel is 600mm/min,
Step (1) pretreatment titanium plate substrate surface on injecting step (2) prepare masking liquid after titanium plate substrate is put into drying baker
100 DEG C of drying 10min, form coating on titanium plate substrate surface, plasma discharge current settings are 3.5A, jet gun rate travel
It is set as 600mm/min, the electric discharge of using plasma jet is aoxidized to coating surface, is repeated above-mentioned injection, is dried and wait
The step of gas ions are aoxidized 8 times, titanium plate substrate is put into 1.2h is sintered in 550 DEG C of sintering furnace, is completed coated anode and is prepared.
Claims (1)
1. a kind of preparation method of metal oxides coating of anode, it is characterised in that preparation method includes substrate pretreatment, masking liquid
Prepare and coated anode prepares three steps：
(1), substrate pretreatment：From technical pure titanium plate as base material, substrate is positioned over matter after conventional blasting treatment
Amount percent concentration is 10% and temperature is acid etching 1 hour in 90-100 DEG C of oxalic acid aqueous solution, treats substrate surface roughness Ra
For 1.5-3.5 μm when be drawn off with distilled water be cleaned by ultrasonic it is clean after again with industrial alcohol washes 2-3 times, then dry substrate
And it is stand-by to immerse sealing preserve in absolute alcohol cylinder, substrate pretreatment is completed；
(2), prepared by masking liquid：Value requirement according to the mol ratio of Ir, Ru, Ta, Sb, Ti and Sn in coating of metal oxides is measured
The IrO of corresponding volume2、RuO2、Ta2O5、SbO2、TiO2And SnO2The aqueous solution is mixed, and obtains mixed liquor, then pressed in mixed liquor
According to 1：The weight of 1.5-3 than proportioning add mass percent concentration be 99% n-butanol aqueous solution, by metal in mixed liquor from
Sub- total concentration be adjusted to 0.2-0.35mol/L after magnetic agitation mixed liquor to its uniform mixing, be obtained masking liquid；
(3), prepared by coated anode：In conventional equipment, it is 3-4A, jet gun rate travel first to set plasma discharge electric current
It is 100-600mm/min, by base after the masking liquid that prepared by cover type injecting step (2) on the substrate surface of step (1) pretreatment
Bottom is put into 100 DEG C of drying 10min of temperature control in drying baker, and coating, then the electric discharge of using plasma jet are formed on the surface of the substrate
Coating surface is aoxidized；, then be put into for substrate by the step of repeating above-mentioned injection, drying and plasma oxidation 6-8 times
1-1.2h is sintered in 550 DEG C of sintering furnace, coated anode is completed and is prepared；The substrate material is more than for mass percent purity
99% Titanium, shapes of substrates includes netted, tabular, tubulose and bar-shaped；The coating of metal oxides is by setting weight ratio
The IrO of proportioning2、RuO2、Ta2O5、SbO2、TiO2、SnO2In one-component or multicomponent compound constitute.
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| CN105967281B (en) * | 2016-06-16 | 2019-01-25 | 中国船舶重工集团公司第七二五研究所 | A kind of titanium-based Asia Titanium oxide electrode preparation method |
| CN108660443B (en) * | 2018-06-04 | 2020-05-22 | 中大立信（北京）技术发展有限公司 | Preparation method and application of stannic oxide electrode |
| CN110015721B (en) * | 2019-04-24 | 2021-12-21 | 无锡小天鹅电器有限公司 | Method for producing electrocatalytic coatings using plasma |
| CN113773055A (en) * | 2021-10-15 | 2021-12-10 | 中国船舶重工集团公司第七二五研究所 | Preparation method of metal oxide coating electrode |
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| CN1888141A (en) * | 2006-05-24 | 2007-01-03 | 中国船舶重工集团公司第七二五研究所 | Sea water pollution resisting oxide anode and its prepn |
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| JP2979691B2 (en) * | 1991-04-02 | 1999-11-15 | ダイソー株式会社 | Manufacturing method of anode for oxygen generation |
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| CN1888141A (en) * | 2006-05-24 | 2007-01-03 | 中国船舶重工集团公司第七二五研究所 | Sea water pollution resisting oxide anode and its prepn |
Non-Patent Citations (1)
| Title |
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| IrO2复合涂层电极的研究进展;汪广进等;《中国腐蚀与防护学报》;20120430;第32卷(第2期);第85-88页 * |
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