CN107815705A - A kind of titantium hydride nanotube ruthenium titanium oxide coating titanium electrode preparation method - Google Patents

A kind of titantium hydride nanotube ruthenium titanium oxide coating titanium electrode preparation method Download PDF

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CN107815705A
CN107815705A CN201711217048.8A CN201711217048A CN107815705A CN 107815705 A CN107815705 A CN 107815705A CN 201711217048 A CN201711217048 A CN 201711217048A CN 107815705 A CN107815705 A CN 107815705A
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周偎偎
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Xi'an Bo Yue Environmental Protection Technology Co Ltd
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • 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
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
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    • 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
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    • 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
    • C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon

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Abstract

The invention discloses a kind of titantium hydride nanotube ruthenium titanium oxide coating titanium electrode preparation method to comprise the following steps that, step 1, titanium sheet is carried out to blasting treatment, supersound process and chemical polishing processing successively；Step 2, TiO is prepared2Nanotube/Ti electrodes；Step 3, TiH is prepared2Nanotube/Ti electrodes；Step 4, masking liquid is prepared, the TiH that masking liquid is prepared coated in step 3 using spread coating2Nanotube/Ti electrode surfaces, finally obtain titantium hydride nanotube ruthenium titanium oxide coating titanium electrode.TiH prepared by the inventive method2Nanotube has the characteristics of high-sequential, specific surface area is big, therefore, the TiO of acquisition2·RuO2/TiH2Nanotube/Ti electrodes have big electrochemical surface area, with no TiH2Coated electrode (the TiO of nanotube2·RuO2/ Ti electrodes) compared to having more preferable electro catalytic activity.

Description

A kind of titantium hydride nanotube-ruthenium titanium oxide coating titanium electrode preparation method
Technical field
The invention belongs to coated titanium electrode material preparation method technical field, and in particular to a kind of titantium hydride nanotube-ruthenium Titanium oxide coated titanium electrode preparation method.
Background technology
Coated titanium electrode is also known as dimensionally stable anode (DSA), be grow up late 1960s it is a kind of new High performance energy saving electrode material.Even to this day, coated titanium electrode is widely used to the row such as chemical industry, environmental protection, water process, plating Industry.Coated titanium electrode can be classified according in electrochemical reaction Anodic bubbing, and being referred to as chlorine is separated out for anode Chlorine anode is analysed, such as ruthenium system coated titanium electrode；Precipitated oxygen is referred to as analysis oxygen anodes on anode.The preparation work of titanium coating electrode Skill generally comprises the pre-treatment of titanium substrate, acid etch, coating coating, step of thermal oxidation.The ruthenium system titanium coating electrode applied earliest Invented in nineteen sixty-five by H.Beer, this electrode is considered as having high electro catalytic activity in saline electrolysis analysis chlorine reaction and made Use the life-span.Expand with the application of ruthenium system coated titanium electrode, it has been found that such a electrode is in the electrolysis of weak brine solution and alkali Property higher medium in analysis oxygen amount can increase when being electrolysed, on electrode, so as to increase the oxygen content in chlorine；And coating stability (service life) reduces.Therefore, researcher has carried out substantial amounts of improvement in terms of ruthenium system coated titanium electrode1-3.Open and recruit Virtuous grade is to TiO2-RuO2Component ratio is adjusted, and finds TiO2：RuO2=80：When 20, coated electrode performance obtains big carry It is high；New component, such as Sn, Ir, Ta, Co, Sb are introduced in ruthenium titanium coating, be made RuSnTi, RuIrTi, RuIrTa, The multicomponent mixture coating such as RuTiIrSn.Result of study shows that the adjustment of these components makes the oxidation-reduction potential of electrode reduce, change Each oxide component mass fraction in coating has been apt to it so that the comprehensive electrochemical of coated electrode improves.
In terms of improving coating composition, ratio, in recent years, intermediate layer, regulation and control titanium substrate microstructure are being introduced, to carry Also received more and more attention in terms of adhesion between high coating and titanium substrate.It is microcosmic that titanium substrate is regulated and controled by specific method Structure；And suitable intermediate layer is introduced between substrate and coating, it is possible to avoid/reduce the passivation of titanium substrate, improve coating Adhesion 4-6 between substrate.But on the whole, the research report of this respect is less.As far as we know, in titanium-based basal surface Introduce TiH2Nanotube has not been reported as coated titanium electrode intermediate layer.
The content of the invention
It is an object of the invention to provide a kind of titantium hydride nanotube-ruthenium titanium oxide coating titanium electrode preparation method, prepares Obtained titantium hydride nanotube-ruthenium titanium oxide coating titanium electrode has good electrochemical reaction activity and stability.
The technical solution adopted in the present invention is a kind of titantium hydride nanotube-ruthenium titanium oxide coating titanium electrode preparation side Method, comprise the following steps that,
Step 1, titanium sheet is carried out to blasting treatment, supersound process and chemical polishing processing successively；
Step 2, the titanium sheet after being handled using step 1 is anode, using graphite as negative electrode, carries out constant voltage anodic oxidation；Electrolysis Liquid forms：Contain 0.57g~1.72gNH in ethylene glycol solvent per 100mL4F, 0.5g~4gH2O；Anodic oxidation voltage is 10V~30V DC voltage, temperature are room temperature, and mixing speed 1000rpm, anodizing time is 1h~3h, at 450 DEG C Lower annealing 2h, is cooled to room temperature, TiO is prepared2Nanotube/Ti electrodes；
Step 3, using graphite as anode, the TiO that is obtained with step 22Nanotube/Ti electrodes are negative electrode, carry out electrochemistry also It is former；Electrolyte forms：Na containing 3.6g~28.4g in per 100mL water2SO4；Cathodic reduction electric current is 5mAcm-2~ 15mA·cm-2, after mixing speed 1000rpm, cathodic reduction 1h~3h, TiH is prepared2Nanotube/Ti electrodes；
Step 4, masking liquid is prepared, the TiH that masking liquid is prepared coated in step 3 using spread coating2Nanotube/Ti electrodes Surface, then drying, thermal oxide, cooling, complete primary coating；Repetitive coatings, drying, thermal oxide and cooling procedure, until Untill masking liquid is painted with, after the completion of last time coats, 0.5h~2h is calcined at 350 DEG C~550 DEG C, obtains titantium hydride nanometer Pipe-ruthenium titanium oxide coating titanium electrode.
The features of the present invention also resides in,
Ultrasonic procedure in step 1 is：Each ultrasonic 15min in acetone, ethanol successively.
The process of chemical polishing is in step 1：In HF/HNO3/H2Chemical polishing is carried out in O mixed solution, the time is 1min, wherein HF/HNO3/H2O volume ratio is 1：3：6.
The composition of masking liquid is in step 4：Contain in the solvent being made up of 36wt%HCl with n-butanol per 100mL 15.2gRuCl3, 15.2g~75.8g butyl titanates, the volume ratio of 36wt%HCl and n-butanol is 6 in solvent:94.
In step 4, in the TiO being prepared2·RuO2/TiH2In nanotube/Ti coated electrodes, Ru coated weight is： 8g/m2~12g/m2。
Drying temperature is 100 DEG C in step 4, drying time 5min.
The temperature of thermal oxide is 450 DEG C in step 4, thermal oxidation time 5min.
The invention has the advantages that
(1) the inventive method prepares TiH with the methods of template synthesis method, hydro-thermal method2(titantium hydride) nano-tube material is compared, TiH directly can be prepared in Ti (titanium) substrate using anodic oxidation-electrochemical reducing2Nanotube；And the TiH prepared2Nanotube Degree of aggregation is relatively low.Therefore, this method TiH2Nanotube preparation condition is gentle, simple, without high temperature and high pressure；
(2) TiH prepared by the inventive method2Nanotube has the characteristics of high-sequential, specific surface area is big, therefore, obtains TiO2·RuO2/TiH2Nanotube/Ti electrodes have big electrochemical surface area, with no TiH2The coating electricity of nanotube Pole (TiO2·RuO2/ Ti electrodes) compared to having more preferable electro catalytic activity；
(3)TiH2The electric conductivity that material has had so that TiO in itself2·RuO2/TiH2Nanotube/Ti electrodes have more preferable Analysis oxygen, analysis chlorine efficiency；
(4) such a TiH2Nanotube directly grows in Ti substrates, and it has good adhesion between titanium substrate；Separately Outside, TiH2Nanotube has good electric conductivity in itself, can reduce the resistance between titanium substrate and coating, slow down titanium substrate Passivation.In TiH2Nanotube/Ti surfaces form TiO2·RuO2After coating, RuO2TiH may be entered by filling mode2Nanotube Inside, so that TiO2·RuO2Coating and TiH2Adhesion between nanotube/Ti electrodes improves, and causes TiO2·RuO2/ TiH2Nanotube/Ti coated electrodes have more preferable reinforcing life.
Brief description of the drawings
Fig. 1 is the TiO that the inventive method is prepared2·RuO2/TiH2Nanotube/Ti coated electrodes and TiO2·RuO2/ Ti coated electrodes are in 0.5mol/L H2SO4In typical recycling volt-ampere curve comparison diagram；
Fig. 2 is the TiO that the inventive method is prepared2·RuO2/TiH2Nanotube/Ti coated electrodes and TiO2·RuO2/ Typical recycling volt-ampere curve comparison diagram of the Ti coated electrodes in saturation NaCl solution；
Fig. 3 is the TiO that the inventive method is prepared2·RuO2/TiH2Nanotube/Ti coated electrodes and TiO2·RuO2/ Ti coated electrodes are in 0.5mol/L H2SO4In typical linear scanning volt-ampere curve comparison diagram；
Fig. 4 is the TiO that the inventive method is prepared2·RuO2/TiH2Nanotube/Ti coated electrodes and TiO2·RuO2/ Typical linear scanning volt-ampere curve comparison diagram of the Ti coated electrodes in saturation NaCl solution；
Fig. 5 is the TiO that the inventive method is prepared2·RuO2/TiH2Nanotube/Ti coated electrodes and TiO2·RuO2/ The electrode accelerated aging curve comparison figure of Ti coated electrodes.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
A kind of titantium hydride nanotube-ruthenium titanium oxide coating titanium electrode preparation method of the present invention, is comprised the following steps that,
Step 1, titanium sheet is carried out to blasting treatment, supersound process and chemical polishing processing successively；
Ultrasonic procedure in step 1 is：Each ultrasonic 15min in acetone, ethanol successively；
The process of chemical polishing is in step 1：In HF/HNO3/H2Chemical polishing is carried out in O mixed solution, the time is 1min, wherein HF/HNO3/H2O volume ratio is 1：3：6；
Step 2, the titanium sheet after being handled using step 1 is anode, using graphite as negative electrode, carries out constant voltage anodic oxidation；Electrolysis Liquid forms：Contain 0.57g~1.72gNH in ethylene glycol solvent per 100mL4F, 0.5g~4gH2O；Anodic oxidation voltage is 10V~30V DC voltage, temperature are room temperature, and mixing speed 1000rpm, anodizing time is 1h~3h, at 450 DEG C Lower annealing 2h, is cooled to room temperature, TiO is prepared2Nanotube/Ti electrodes；
Step 3, using graphite as anode, the TiO that is obtained with step 22Nanotube/Ti electrodes are negative electrode, carry out electrochemistry also It is former；Electrolyte forms：Na containing 3.6g~28.4g in per 100mL water2SO4；Cathodic reduction electric current is 5mAcm-2~ 15mA·cm-2, after mixing speed 1000rpm, cathodic reduction 1h~3h, TiH is prepared2Nanotube/Ti electrodes；
Step 4, masking liquid is prepared, the TiH that masking liquid is prepared coated in step 3 using spread coating2Nanotube/Ti electrodes Surface, then drying, thermal oxide, cooling, complete primary coating；Repetitive coatings, drying, thermal oxide and cooling procedure, until Untill masking liquid is painted with, after the completion of last time coats, 0.5h~2h is calcined at 350 DEG C~550 DEG C, obtains titantium hydride nanometer Pipe-ruthenium titanium oxide coating titanium electrode；
The composition of masking liquid is in step 4：Contain in the solvent being made up of 36wt%HCl with n-butanol per 100mL 15.2gRuCl3, 15.2g~75.8g butyl titanates, the volume ratio of 36wt%HCl and n-butanol is 6 in solvent:94；
In step 4, in the TiO being prepared2·RuO2/TiH2In nanotube/Ti coated electrodes, Ru coated weight is： 8g/m2~12g/m2；
Drying temperature is 100 DEG C in step 4, drying time 5min；
The temperature of thermal oxide is 450 DEG C in step 4, thermal oxidation time 5min.
Prepared titantium hydride is received using cyclic voltammetry (CV), linear sweep voltammetry (LSV) and accelerated life test Mitron-ruthenium titanium oxide coating titanium electrode (TiO2·RuO2/TiH2Nanotube/Ti coated electrodes) chemical property carry out table Sign, specific experiment condition are as follows：
Working electrode：TiO2·RuO2/TiH2Nanotube/Ti coated electrodes
To electrode：Large area platinum guaze
Reference electrode：Saturated calomel electrode (is tested) only for CV and LSV
Electrolyte：0.5mol/L H2SO4Or saturation NaCl solution, tested for CV and LSV；15wt.%H2SO4Solution is used In accelerating lifetime testing
Temperature：Room temperature
CV and LSV sweep speeds：20mV/s
CV electric potential scanning scopes：0.2-1.2V
LSV electric potential scanning scopes：0-1.5V
Accelerating lifetime testing current density：40000A/m2；Groove pressure rises to 12V and stops experiment.
The present invention is prepared for TiO using anodizing in titanium-based basal surface2Nanotube；And further by electrochemistry also Former method is by TiO2Nanotube is converted into TiH2Nanotube.With TiH2Nanotube/Ti is substrate, and hydrogen is prepared for using thermal decomposition method Change titanium nanotube-ruthenium titanium oxide coating titanium electrode (TiO2·RuO2/TiH2Nanotube/Ti coated electrodes).
As shown in Fig. 1 and Fig. 2 typical recycling volt-ampere curves, in 0.5mol/L H2SO4Solution (see Fig. 1) or saturation NaCl are molten In liquid (see Fig. 2), TiO2·RuO2/TiH2The area that nanotube/Ti coated electrode cyclic voltammetry curves are included is significantly greater than TiO2·RuO2/ Ti coated electrodes, illustrate TiO2·RuO2/TiH2Nanotube/Ti coated electrodes have bigger electrochemical capacitor, There is more preferable electro catalytic activity.
LSV test results as shown in Figures 3 and 4 show：In 0.5mol/L H2SO4Solution (see Fig. 3) or saturation NaCl In solution (see Fig. 4), with not using TiH2Coated electrode (the TiO of nanotube2·RuO2/ Ti electrodes) compare, TiO2·RuO2/ TiH2The take-off potential analysed oxygen on nanotube/Ti electrodes and analyse chlorine does not have significant change, and oxygen evolution potential is about 1.23V, analysis chlorine electricity Position is about 1.07V.But under same potential, TiO2·RuO2/TiH2The electric current of nanotube/Ti coated electrodes analysis oxygen or analysis chlorine is close Degree is much larger than TiO2·RuO2/ Ti electrodes.For example, in the case of analysis oxygen (Fig. 3), during 1.3V, TiO2·RuO2/TiH2Nanotube/Ti Electrode analysis oxygen current density is TiO2·RuO22.2 times of/Ti electrodes；And analyse in the case of chlorine (Fig. 4), during 1.15V, TiO2· RuO2/TiH2Nanotube/Ti electrodes analysis chlorine current density is TiO2·RuO23 times of/Ti electrodes.This further illustrates TiO2· RuO2/TiH2Nanotube/Ti electrodes have preferably analysis oxygen, analysis chlorine efficiency.
As shown in figure 5, accelerating lifetime testing result shows：TiO2·RuO2/TiH2Nanotube/Ti electrodes lose after 4.3h Effect；And TiO2·RuO2/ Ti electrodes failed after 1.1 hours.Illustrate TiO2·RuO2/TiH2Nanotube/Ti electrodes compare TiO2· RuO2/ Ti electrodes have longer reinforcing life.
Embodiment 1
Titanium sheet is carried out to blasting treatment, supersound process and chemical polishing processing successively；Ultrasonic procedure therein is：Exist successively Ultrasonic 15min in acetone, ethanol；The process of chemical polishing is：In HF/HNO3/H2Chemical polishing is carried out in O mixed solution, when Between be 1min, wherein HF/HNO3/H2O volume ratio is 1：3：6；
Using the titanium sheet after processing as anode, using graphite as negative electrode, constant voltage anodic oxidation is carried out, electrolyte composition is every Contain 0.57gNH in 100mL ethylene glycol solvent4F、0.5gH2O, anodic oxidation voltage are 10V DC voltage, and temperature is room Temperature, mixing speed 1000rpm, anodizing time 1h, electrode are annealed after the ultrasonic cleaning of second alcohol and water at 450 DEG C 2h, room temperature is cooled to, TiO is prepared2Nanotube/Ti electrodes；Using large area graphite as anode, with obtained TiO2Nanotube/ Ti electrodes are negative electrode, carry out electrochemical reduction, and electrolyte composition is to contain 3.6g Na per in 100mL aqueous solvents2SO4, negative electrode is also Primary current is 5mAcm-2, after mixing speed 1000rpm, cathodic reduction 1h, TiH is prepared2Nanotube/Ti electrodes；
Masking liquid is prepared, masking liquid is coated in obtained TiH using spread coating2Nanotube/Ti electrode surfaces, then through drying Dry, thermal oxide, cooling, complete primary coating；Repetitive coatings, drying, thermal oxide and cooling procedure, untill masking liquid is painted with. After the completion of last time coats, 0.5h is calcined at 350 DEG C, finally obtains titantium hydride nanotube-ruthenium titanium oxide coating titanium electricity Pole；The composition of wherein masking liquid is：Contain 15.2gRuCl in the solvent being made up of 36wt%HCl and n-butanol per 100mL3、 15.2g butyl titanates, the volume ratio of 36wt%HCl and n-butanol is 6 in solvent:94；In the TiO being prepared2·RuO2/ TiH2In nanotube/Ti coated electrodes, Ru coated weight is：8g/m2；Drying temperature is 100 DEG C, drying time 5min；Hot oxygen The temperature of change is 450 DEG C, thermal oxidation time 5min.
Embodiment 2
Titanium sheet is carried out to blasting treatment, supersound process and chemical polishing processing successively；Ultrasonic procedure therein is：Exist successively Ultrasonic 15min in acetone, ethanol；The process of chemical polishing is：In HF/HNO3/H2Chemical polishing is carried out in O mixed solution, when Between be 1min, wherein HF/HNO3/H2O volume ratio is 1：3：6；
Using the titanium sheet after processing as anode, using large area graphite as negative electrode, constant voltage anodic oxidation, electrolyte composition are carried out To contain 0.86g NH in every 100mL ethylene glycol solvent4F、1gH2O, anodic oxidation voltage are 15V DC voltage, and temperature is Room temperature, mixing speed 1000rpm, anodizing time 1.5h, electrode move back after the ultrasonic cleaning of second alcohol and water at 450 DEG C Fiery 2h, is cooled to room temperature, and TiO is prepared2Nanotube/Ti electrodes；Using large area graphite as anode, with obtained TiO2Nanometer Pipe/Ti electrodes are negative electrode, carry out electrochemical reduction, and electrolyte composition is to contain 7.1g Na per in 100mL aqueous solvents2SO4, negative electrode Reduction current is 7.5mAcm-2, after mixing speed 1000rpm, cathodic reduction 1.5h, TiH is prepared2Nanotube/Ti electricity Pole；
Masking liquid is prepared, masking liquid is coated in obtained TiH using spread coating2Nanotube/Ti electrode surfaces, then through drying Dry, thermal oxide, cooling, complete primary coating；Repetitive coatings, drying, thermal oxide and cooling procedure, untill masking liquid is painted with. After the completion of last time coats, 0.75h is calcined at 400 DEG C, finally obtains titantium hydride nanotube-ruthenium titanium oxide coating titanium electricity Pole；The composition of wherein masking liquid is：Contain 15.2gRuCl in the solvent being made up of 36wt%HCl and n-butanol per 100mL3、 33.3g butyl titanates, the volume ratio of 36wt%HCl and n-butanol is 6 in solvent:94；In the TiO being prepared2·RuO2/ TiH2In nanotube/Ti coated electrodes, Ru coated weight is：8g/m2；Drying temperature is 100 DEG C, drying time 5min；Hot oxygen The temperature of change is 450 DEG C, thermal oxidation time 5min.
Embodiment 3
Titanium sheet is carried out to blasting treatment, supersound process and chemical polishing processing successively；Ultrasonic procedure therein is：Exist successively Ultrasonic 15min in acetone, ethanol；The process of chemical polishing is：In HF/HNO3/H2Chemical polishing is carried out in O mixed solution, when Between be 1min, wherein HF/HNO3/H2O volume ratio is 1：3：6；
Using the titanium sheet after processing as anode, using large area graphite as negative electrode, constant voltage anodic oxidation, electrolyte composition are carried out To contain 1.15g NH in every 100mL ethylene glycol solvent4F、2gH2O, anodic oxidation voltage are 20V DC voltage, and temperature is Room temperature, mixing speed 1000rpm, anodizing time 2h, electrode are annealed after the ultrasonic cleaning of second alcohol and water at 450 DEG C 2h, room temperature is cooled to, TiO is prepared2Nanotube/Ti electrodes；Using large area graphite as anode, with obtained TiO2Nanotube/ Ti electrodes are negative electrode, carry out electrochemical reduction, and electrolyte composition is to contain 14.2g Na per in 100mL aqueous solvents2SO4, negative electrode is also Primary current is 10mAcm-2, after mixing speed 1000rpm, cathodic reduction 2h, TiH is prepared2Nanotube/Ti electrodes；
Masking liquid is prepared, masking liquid is coated in obtained TiH using spread coating2Nanotube/Ti electrode surfaces, then through drying Dry, thermal oxide, cooling, complete primary coating；Repetitive coatings, drying, thermal oxide and cooling procedure, untill masking liquid is painted with. After the completion of last time coats, 1h is calcined at 450 DEG C, finally obtains titantium hydride nanotube-ruthenium titanium oxide coating titanium electrode； The composition of wherein masking liquid is：Contain 15.2gRuCl in the solvent being made up of 36wt%HCl and n-butanol per 100mL3、45.5g Butyl titanate, the volume ratio of 36wt%HCl and n-butanol is 6 in solvent:94；In the TiO being prepared2·RuO2/TiH2Nanometer In pipe/Ti coated electrodes, Ru coated weight is：10g/m2；Drying temperature is 100 DEG C, drying time 5min；The temperature of thermal oxide Spend for 450 DEG C, thermal oxidation time 5min.
Embodiment 4
Titanium sheet is carried out to blasting treatment, supersound process and chemical polishing processing successively；Ultrasonic procedure therein is：Exist successively Ultrasonic 15min in acetone, ethanol；The process of chemical polishing is：In HF/HNO3/H2Chemical polishing is carried out in O mixed solution, when Between be 1min, wherein HF/HNO3/H2O volume ratio is 1：3：6；
Using the titanium sheet after processing as anode, using large area graphite as negative electrode, constant voltage anodic oxidation, electrolyte composition are carried out Contain 1.43gNH in ethylene glycol solvent for every 100mL4F、3gH2O, anodic oxidation voltage are 25V DC voltage, and temperature is Room temperature, mixing speed 1000rpm, anodizing time 2.5h, electrode move back after the ultrasonic cleaning of second alcohol and water at 450 DEG C Fiery 2h, is cooled to room temperature, and TiO is prepared2Nanotube/Ti electrodes；Using large area graphite as anode, with obtained TiO2Nanometer Pipe/Ti electrodes are negative electrode, carry out electrochemical reduction, and electrolyte composition is to contain 21.3g Na per in 100mL aqueous solvents2SO4, it is cloudy Pole reduction current is 12.5mAcm-2, after mixing speed 1000rpm, cathodic reduction 2.5h, TiH is prepared2Nanotube/ Ti electrodes；
Masking liquid is prepared, masking liquid is coated in obtained TiH using spread coating2Nanotube/Ti electrode surfaces, then through drying Dry, thermal oxide, cooling, complete primary coating；Repetitive coatings, drying, thermal oxide and cooling procedure, untill masking liquid is painted with. After the completion of last time coats, 1.5h is calcined at 500 DEG C, finally obtains titantium hydride nanotube-ruthenium titanium oxide coating titanium electricity Pole；The composition of wherein masking liquid is：Contain 15.2gRuCl in the solvent being made up of 36wt%HCl and n-butanol per 100mL3、 60.6g butyl titanates, the volume ratio of 36wt%HCl and n-butanol is 6 in solvent:94；In the TiO being prepared2·RuO2/ TiH2In nanotube/Ti coated electrodes, Ru coated weight is：12g/m2；Drying temperature is 100 DEG C, drying time 5min；Heat The temperature of oxidation is 450 DEG C, thermal oxidation time 5min.
Embodiment 5
Titanium sheet is carried out to blasting treatment, supersound process and chemical polishing processing successively；Ultrasonic procedure therein is：Exist successively Ultrasonic 15min in acetone, ethanol；The process of chemical polishing is：In HF/HNO3/H2Chemical polishing is carried out in O mixed solution, when Between be 1min, wherein HF/HNO3/H2O volume ratio is 1：3：6；
Using the titanium sheet after processing as anode, using large area graphite as negative electrode, constant voltage anodic oxidation, electrolyte composition are carried out Contain 1.72gNH in ethylene glycol solvent for every 100mL4F、4gH2O, anodic oxidation voltage are 30V DC voltage, and temperature is Room temperature, mixing speed 1000rpm, anodizing time 3h, electrode are annealed after the ultrasonic cleaning of second alcohol and water at 450 DEG C 2h, room temperature is cooled to, TiO is prepared2Nanotube/Ti electrodes；Using large area graphite as anode, with obtained TiO2Nanotube/ Ti electrodes are negative electrode, carry out electrochemical reduction, and electrolyte composition is to contain 28.4g Na per in 100mL aqueous solvents2SO4, negative electrode is also Primary current is 15mAcm-2, after mixing speed 1000rpm, cathodic reduction 3h, TiH is prepared2Nanotube/Ti electrodes；
Masking liquid is prepared, masking liquid is coated in obtained TiH using spread coating2Nanotube/Ti electrode surfaces, then through drying Dry, thermal oxide, cooling, complete primary coating；Repetitive coatings, drying, thermal oxide and cooling procedure, untill masking liquid is painted with. After the completion of last time coats, 2h is calcined at 550 DEG C, finally obtains titantium hydride nanotube-ruthenium titanium oxide coating titanium electrode； The composition of wherein masking liquid is：Contain 15.2gRuCl in the solvent being made up of 36wt%HCl and n-butanol per 100mL3、75.8g Butyl titanate, the volume ratio of 36wt%HCl and n-butanol is 6 in solvent:94；In the TiO being prepared2·RuO2/TiH2Nanometer In pipe/Ti coated electrodes, Ru coated weight is：12g/m2；Drying temperature is 100 DEG C, drying time 5min；The temperature of thermal oxide Spend for 450 DEG C, thermal oxidation time 5min.
It is an advantage of the invention that
(1) the inventive method prepares TiH with the methods of template synthesis method, hydro-thermal method2(titantium hydride) nano-tube material is compared, TiH directly can be prepared in Ti (titanium) substrate using anodic oxidation-electrochemical reducing2Nanotube；And the TiH prepared2Nanotube Degree of aggregation is relatively low.Therefore, this method TiH2Nanotube preparation condition is gentle, simple, without high temperature and high pressure；
(2) TiH prepared by the inventive method2Nanotube has the characteristics of high-sequential, specific surface area is big, therefore, obtains TiO2·RuO2/TiH2Nanotube/Ti electrodes have big electrochemical surface area, with no TiH2The coating electricity of nanotube Pole (TiO2·RuO2/ Ti electrodes) compared to having more preferable electro catalytic activity；
(3)TiH2The electric conductivity that material has had so that TiO in itself2·RuO2/TiH2Nanotube/Ti electrodes have more preferable Analysis oxygen, analysis chlorine efficiency；
(4) such a TiH2Nanotube directly grows in Ti substrates, and it has good adhesion between titanium substrate；Separately Outside, TiH2Nanotube has good electric conductivity in itself, can reduce the resistance between titanium substrate and coating, slow down titanium substrate Passivation.In TiH2Nanotube/Ti surfaces form TiO2·RuO2After coating, RuO2TiH may be entered by filling mode2Nanotube Inside, so that TiO2·RuO2Coating and TiH2Adhesion between nanotube/Ti electrodes improves, and causes TiO2·RuO2/ TiH2Nanotube/Ti coated electrodes have more preferable reinforcing life.
Bibliography
1. recruit men of worth, yellow eastern coated titanium electrodes Beijing, metallurgical industry publishing house, 2014,45-71.
2.D.Devilliers,E.Mahe.Modified titanium electrodes:application to Ti/ TiO2/PbO2dimensionally stable anodes.Electrochim.Acta,2010,55:8207-8214.
3.P.Duby.The history of progress in dimensionally stable anodes.JOM, 1993,45:41-43.
4.L.K.Xu,J.D.Scantlebury.A study on the deactivation of an IrO2- Ta2O5coated titanium anode.Corros.Sci.,2003,45:2729-2740.
5.V.Panic,A.Dekanski,V.B.Miskovic-Stankovic,et al.On the deactivation mechanism of RuO2-TiO2/Ti anodes prepared by the sol-gel procedure.J.Electroanal.Chem.,2005,579:67-76.
6.F.Vicent,E.Morallon,C.Quijada,et al.Characterization and stability of doped SnO2anodes.J.Appl.Electrochem.,1998,28:607-612.
7.T.Wu,G.H.Zhao,Y.Z.Lei,et al.Distinctive tin dioxide anode fabricated by pulse electrodeposition:high oxygen evolution potential and efficient electrochemical degradation of fluorobenzene.J.Phys.Chem.C,2011, 115:3888-3898.
8. intermediate layers containing the TiN IrO such as leaf Zhang Jun, sweet Yongping, Zhang Wenkui2-Ta2O5The electrocatalysis characteristic of coating titanium anode China YouSe Acta Metallurgica Sinica, 19:1473-1479.
9.D.Shao,W.Yan,X.L.Li,et al.A highly stable Ti/TiHx/Sb-SnO2anode: preparation,characterization and application.Ind.Chem.Res.2014,53:3898-3907.

Claims (7)

  1. A kind of 1. titantium hydride nanotube-ruthenium titanium oxide coating titanium electrode preparation method, it is characterised in that comprise the following steps that,
    Step 1, titanium sheet is carried out to blasting treatment, supersound process and chemical polishing processing successively；
    Step 2, the titanium sheet after being handled using step 1 is anode, using graphite as negative electrode, carries out constant voltage anodic oxidation；Electrolyte group Turn into：Contain 0.57g~1.72gNH in ethylene glycol solvent per 100mL4F, 0.5g~4gH2O；Anodic oxidation voltage be 10V~ 30V DC voltage, temperature are room temperature, and mixing speed 1000rpm, anodizing time is 1h~3h, is annealed at 450 DEG C 2h, room temperature is cooled to, TiO is prepared2Nanotube/Ti electrodes；
    Step 3, using graphite as anode, the TiO that is obtained with step 22Nanotube/Ti electrodes are negative electrode, carry out electrochemical reduction；Electricity Solution liquid, which forms, is：Na containing 3.6g~28.4g in per 100mL water2SO4；Cathodic reduction electric current is 5mAcm-2~15mA cm-2, after mixing speed 1000rpm, cathodic reduction 1h~3h, TiH is prepared2Nanotube/Ti electrodes；
    Step 4, masking liquid is prepared, the TiH that masking liquid is prepared coated in step 3 using spread coating2Nanotube/Ti electrode surfaces, Then drying, thermal oxide, cooling, primary coating is completed；Repetitive coatings, drying, thermal oxide and cooling procedure, until masking liquid applies Untill complete, after the completion of last time coats, 0.5h~2h calcined at 350 DEG C~550 DEG C, obtains titantium hydride nanotube-ruthenium titanium Oxide coating titanium electrode.
  2. 2. a kind of titantium hydride nanotube-ruthenium titanium oxide coating titanium electrode preparation method according to claim 1, its feature It is, the ultrasonic procedure in step 1 is：Each ultrasonic 15min in acetone, ethanol successively.
  3. 3. a kind of titantium hydride nanotube-ruthenium titanium oxide coating titanium electrode preparation method according to claim 1, its feature It is, the process of chemical polishing is in step 1：In HF/HNO3/H2Carry out chemical polishing in O mixed solution, time 1min, Wherein HF/HNO3/H2O volume ratio is 1：3：6.
  4. 4. a kind of titantium hydride nanotube-ruthenium titanium oxide coating titanium electrode preparation method according to claim 1, its feature It is, the composition of masking liquid is in step 4：Contain in the solvent being made up of 36wt%HCl with n-butanol per 100mL 15.2gRuCl3, 15.2g~75.8g butyl titanates, the volume ratio of 36wt%HCl and n-butanol is 6 in solvent:94.
  5. 5. a kind of titantium hydride nanotube-ruthenium titanium oxide coating titanium electrode preparation method according to claim 1, its feature It is, in step 4, in the TiO being prepared2·RuO2/TiH2In nanotube/Ti coated electrodes, Ru coated weight is：8g/m2 ~12g/m2。
  6. 6. a kind of titantium hydride nanotube-ruthenium titanium oxide coating titanium electrode preparation method according to claim 1, its feature It is, drying temperature is 100 DEG C in step 4, drying time 5min.
  7. 7. a kind of titantium hydride nanotube-ruthenium titanium oxide coating titanium electrode preparation method according to claim 1, its feature It is, the temperature of thermal oxide is 450 DEG C in step 4, thermal oxidation time 5min.
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CN109763146A (en) * 2019-03-27 2019-05-17 贵州省过程工业技术研究中心 A kind of titanium composite material anode preparation method used for aluminium electrolysis
CN112030188A (en) * 2020-09-08 2020-12-04 华北水利水电大学 IrO2 nano-coating anode with TiN nanotube intermediate layer
CN113716658A (en) * 2021-09-27 2021-11-30 大连理工大学 Preparation method of ruthenium, iridium and titanium ternary metal mesh electrode containing nano tip structure
CN113881946A (en) * 2021-11-09 2022-01-04 济南大学 Method for electrochemically preparing titanium hydride electrode
CN118291953A (en) * 2024-04-02 2024-07-05 绵阳宏博环保有限公司 Vanadium and ruthenium modified titanium dioxide electrode and preparation and application methods thereof

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109763146A (en) * 2019-03-27 2019-05-17 贵州省过程工业技术研究中心 A kind of titanium composite material anode preparation method used for aluminium electrolysis
CN109763146B (en) * 2019-03-27 2021-03-26 贵州省过程工业技术研究中心 Preparation method of titanium-based composite material anode for aluminum electrolysis
CN112030188A (en) * 2020-09-08 2020-12-04 华北水利水电大学 IrO2 nano-coating anode with TiN nanotube intermediate layer
CN112030188B (en) * 2020-09-08 2023-06-09 华北水利水电大学 IrO2 nano-coating anode with TiN nano-tube intermediate layer
CN113716658A (en) * 2021-09-27 2021-11-30 大连理工大学 Preparation method of ruthenium, iridium and titanium ternary metal mesh electrode containing nano tip structure
CN113881946A (en) * 2021-11-09 2022-01-04 济南大学 Method for electrochemically preparing titanium hydride electrode
CN113881946B (en) * 2021-11-09 2023-09-19 济南大学 Method for electrochemically preparing titanium hydride electrode
CN118291953A (en) * 2024-04-02 2024-07-05 绵阳宏博环保有限公司 Vanadium and ruthenium modified titanium dioxide electrode and preparation and application methods thereof

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