CN106367779A - Titanium-based porous electrode material and preparation method thereof - Google Patents
Titanium-based porous electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a titanium-based porous electrode material and a preparation method thereof. The titanium-based porous electrode material comprises a tubular matrix, a first coating and a second coating, wherein the surface of the matrix is covered with the first coating and the second coating in sequence; the matrix is made of porous titanium; the first coating is a rhodium oxide layer; and the second coating is equally divided into a tin oxide layer, a germanium oxide layer and a thorium dioxide layer along the surface of the first coating, and the three layers are distributed axially along the matrix. Since the matrix is made of the porous material, the component (rhodium oxide) of the first coating can be uniformly dispersed on the outer surface of the matrix and the inner surfaces of matrix holes, the electrode material is made to have excellent catalytic activity and a good mass transfer effect. The first coating is further coated with the second coating (tin oxide, germanium oxide and thorium dioxide), the corrosion resistance of the electrode material is enhanced, corrosion caused by acid or alkali or salt can be resisted, and the service life of the titanium-based porous electrode material is prolonged accordingly.
Description
Technical field
The present invention relates to a kind of electrode material is and in particular to a kind of porous titanium-matrix electrode material and preparation method thereof.Belong to
Electrochemical material technical field.
Background technology
POROUS TITANIUM is cooperation special process, forms through high temperature sintering, its even structure, a large amount of open pores are distributed with.
Mainly it is used as filter element at present, its filtration resistance is little, long service life, high mechanical strength, easily regenerate.Meanwhile, metallic titanium
Make electrode, and be widely used in electrolytic industry field, it, compared with traditional graphite electrode, lead-containing alloy electrode, has electric current
Density is high, long working life, and corrosion resistance is strong, lightweight, high precision, and matrix can the lot of advantages such as Reusability.Particularly, titanium
Electrode can be used for chlorine industry, production of chloric acid salt industrial, hypochlorite industry and perchlorate etc., being related to of application
The industries such as work, metallurgy, water process, environmental protection, plating and electrolysis organic synthesiss.
Electrode is the core component of electrochemical apparatus, plays a part electric energy and is converted into chemical energy, the therefore quality of electrode
It is directly connected to the efficiency of electrochemical apparatus.Activity and the service life improving electrode material is how transformed by structure and material
There is vital effect.
Content of the invention
The purpose of the present invention is for overcoming above-mentioned the deficiencies in the prior art, providing a kind of porous titanium-matrix electrode material.
Present invention also offers a kind of preparation method of above-mentioned porous titanium-matrix electrode material.
For achieving the above object, the present invention adopts following technical proposals:
A kind of porous titanium-matrix electrode material, the matrix including tubulose and the first coating and second being sequentially coated on its surface
Coating, described matrix is POROUS TITANIUM, and described first coating is rhodium oxide layer, and described second coating is divided into along first coating surface
Three parts, are followed successively by stannic oxide layer, germanium oxide layer and thorium anhydride layer, and this three part is axially distributed along matrix.
Preferably, the gross thickness of described first coating and second coating is 30～80 μm, and both thickness ratio is for 2～3:1.
Preferably, stannic oxide layer, germanium oxide layer are identical with the thickness of thorium anhydride layer.
Preferably, the aperture of described POROUS TITANIUM is 30～100 μm, and porosity is 30～40%.
A kind of preparation method of above-mentioned porous titanium-matrix electrode material, including step:
(1) vacuum-sintering porous titanium tube, and surface preparation is carried out to porous titanium tube, except the oxidation of degreasing and surface
Film, forms the fresh matrix of pitted skin；
(2) prepare rhodium oxide masking liquid, brush rhodium oxide masking liquid on first coating surface, 100～110 DEG C of dryings 2～3 are little
When, heat treatment 2～3 hours under the conditions of 300～400 DEG C, it is cooled to room temperature, forms iridium dioxide coating, this is first coating；
(3) stannum oxide, germanium oxide and thorium anhydride masking liquid are prepared respectively, first coating surface is divided into three parts, successively
Brush three kinds of described masking liquids, 100～110 DEG C of dryings 2～3 hours, under the conditions of 450～550 DEG C, heat treatment 0.5～1 hour, cold
But to room temperature, the stannum oxide of formation, germanium oxide and thorium anhydride coating are axially distributed along matrix, and this is second coating；
Under the conditions of (4) 450～550 DEG C, heat treatment 0.5～1 hour, obtains final product.
Preferably, in step (1), the concrete grammar of surface preparation is: by the porous titanium tube of blasting treatment be placed in from
In sub- water be cleaned by ultrasonic 10～20 minutes, remove moisture after in 50～55 DEG C of acid solution pickling 5～10 minutes, finally go from
It is cleaned by ultrasonic 10～15 minutes in sub- water, be placed in vacuum drying oven and dry；Wherein, acid solution is to be respectively by mass fraction
37% and 98% concentrated hydrochloric acid and concentrated sulphuric acid are prepared according to volume ratio 2:1 and are obtained.
It is further preferred that the concrete grammar of described blasting treatment is: nozzle of sand spraying machine pressure is 0.3～0.5mpa, adopts
With 70～90 mesh al2o3Abrasive material, is sprayed with 60～80 °, and the distance away from POROUS TITANIUM pipe surface for the nozzle is 1～2cm, during process
Between be 5～10s.
Preferably, the masking liquid of step (2) is dispersed in organic solvent for rhodium oxide and obtains, rhodium oxide and organic solvent
Mass ratio be 1:10～30.
Preferably, the masking liquid of step (3) is stannum oxide, germanium oxide or thorium anhydride be dispersed in organic solvent
, the mass ratio of stannum oxide, germanium oxide or thorium anhydride and organic solvent is 1:10～30.
It is further preferred that the process for dispersing employed in step (2) and (3) is ultrasonic disperse 5～10 minutes, described have
Machine solvent is any one in n-butyl alcohol, isopropanol or ethanol.
Beneficial effects of the present invention:
The present invention, with porous titanium tube as matrix, brushes formation first coating and second coating successively on its surface, wherein, the
One coating is rhodium oxide layer, and second coating is divided into three parts along first coating surface, be followed successively by stannic oxide layer, germanium oxide layer and
Thorium anhydride layer, this three part is axially distributed along matrix.Because matrix is porous material, the composition (rhodium oxide) of first coating can
Be dispersed in the outer surface of matrix and matrix internal surface of hole so that the electrode obtained material have excellent catalysis activity and
Good mass transfer effect.Also brush second coating (stannum oxide, germanium oxide and thorium anhydride) outside first coating, enhance electricity
The corrosion resistance of pole material, can keep out the corrosion of acid, alkali or salt, thus improve service life.
Brief description
Fig. 1 is the cross section structure schematic diagram of the present invention；
Wherein, 1 is matrix, and 2 is rhodium oxide layer, and 3 is stannic oxide layer, and 4 is germanium oxide layer, and 5 is thorium anhydride layer.
Specific embodiment
The present invention will be further elaborated with reference to the accompanying drawings and examples it should explanation, and the description below is only
It is to explain the present invention, its content is not defined.
Embodiment 1:
As shown in figure 1, a kind of porous titanium-matrix electrode material of the present invention, matrix 1 including tubulose and be sequentially coated on it
The first coating on surface and second coating, matrix 1 is POROUS TITANIUM, and first coating is rhodium oxide layer 2, and second coating is along first coating
Surface is divided into three parts, is followed successively by stannic oxide layer 3, germanium oxide layer 4 and thorium anhydride layer 5, and this three part is axially divided along matrix 1
Cloth.Wherein, the gross thickness of first coating and second coating is 30 μm, and both thickness ratio is for 2:1.Stannic oxide layer 3, germanium oxide layer 4
Identical with the thickness of thorium anhydride layer 5.The aperture of POROUS TITANIUM is 30 μm, and porosity is 30%.
A kind of preparation method of above-mentioned porous titanium-matrix electrode material, including step:
(1) vacuum-sintering porous titanium tube, and surface preparation is carried out to porous titanium tube, except the oxidation of degreasing and surface
Film, forms the fresh matrix of pitted skin；
(2) prepare rhodium oxide masking liquid, brush rhodium oxide masking liquid, 100 DEG C of dryings 2 hours, 300 DEG C of bars on first coating surface
Heat treatment 2 hours under part, are cooled to room temperature, form iridium dioxide coating, and this is first coating；
(3) stannum oxide, germanium oxide and thorium anhydride masking liquid are prepared respectively, first coating surface is divided into three parts, successively
Brush three kinds of described masking liquids, 100 DEG C of dryings 2 hours, heat treatment 0.5 hour under the conditions of 450 DEG C, it is cooled to room temperature, formation
Stannum oxide, germanium oxide and thorium anhydride coating are axially distributed along matrix, and this is second coating；
Under the conditions of (4) 450 DEG C, heat treatment 0.5 hour, obtains final product.
Wherein, in step (1), the concrete grammar of surface preparation is: the porous titanium tube of blasting treatment is placed in deionization
In water be cleaned by ultrasonic 10 minutes, remove moisture after in 50 DEG C of acid solution pickling 5 minutes, be finally cleaned by ultrasonic in deionized water
10 minutes, it is placed in vacuum drying oven and dries；Wherein, acid solution be by mass fraction be respectively 37% and 98% concentrated hydrochloric acid and
Concentrated sulphuric acid is prepared according to volume ratio 2:1 and is obtained.The concrete grammar of blasting treatment is: nozzle of sand spraying machine pressure is 0.3mpa, adopts
70 mesh al2o3Abrasive material, is sprayed with 60 °, and the distance away from POROUS TITANIUM pipe surface for the nozzle is 1cm, and process time is 5s.
The masking liquid of step (2) is dispersed in organic solvent for rhodium oxide and obtains, the quality of rhodium oxide and organic solvent
Than for 1:10.
The masking liquid of step (3) is stannum oxide, germanium oxide or thorium anhydride are dispersed in organic solvent and obtain, oxidation
The mass ratio of stannum, germanium oxide or thorium anhydride and organic solvent is 1:10.
Process for dispersing employed in step (2) and (3) is ultrasonic disperse 5 minutes, and described organic solvent is isopropanol.
Embodiment 2:
As shown in figure 1, a kind of porous titanium-matrix electrode material of the present invention, matrix 1 including tubulose and be sequentially coated on it
The first coating on surface and second coating, matrix 1 is POROUS TITANIUM, and first coating is rhodium oxide layer 2, and second coating is along first coating
Surface is divided into three parts, is followed successively by stannic oxide layer 3, germanium oxide layer 4 and thorium anhydride layer 5, and this three part is axially divided along matrix 1
Cloth.Wherein, the gross thickness of first coating and second coating is 80 μm, and both thickness ratio is for 3:1.Stannic oxide layer 3, germanium oxide layer 4
Identical with the thickness of thorium anhydride layer 5.The aperture of POROUS TITANIUM is 100 μm, and porosity is 40%.
A kind of preparation method of above-mentioned porous titanium-matrix electrode material, including step:
(1) vacuum-sintering porous titanium tube, and surface preparation is carried out to porous titanium tube, except the oxidation of degreasing and surface
Film, forms the fresh matrix of pitted skin；
(2) prepare rhodium oxide masking liquid, brush rhodium oxide masking liquid, 110 DEG C of dryings 3 hours, 400 DEG C of bars on first coating surface
Heat treatment 3 hours under part, are cooled to room temperature, form iridium dioxide coating, and this is first coating；
(3) stannum oxide, germanium oxide and thorium anhydride masking liquid are prepared respectively, first coating surface is divided into three parts, successively
Brush three kinds of described masking liquids, 110 DEG C of dryings 3 hours, heat treatment 1 hour under the conditions of 550 DEG C, it is cooled to room temperature, the oxygen of formation
Change stannum, germanium oxide and thorium anhydride coating to be axially distributed along matrix, this is second coating；
Under the conditions of (4) 550 DEG C, heat treatment 1 hour, obtains final product.
Wherein, in step (1), the concrete grammar of surface preparation is: the porous titanium tube of blasting treatment is placed in deionization
It is cleaned by ultrasonic 20 minutes in water, remove after moisture pickling 10 minutes in 55 DEG C of acid solution, finally ultrasonic clear in deionized water
Wash 15 minutes, be placed in vacuum drying oven and dry；Wherein, acid solution is by the concentrated hydrochloric acid of mass fraction respectively 37% and 98%
Prepare according to volume ratio 2:1 with concentrated sulphuric acid and obtain.The concrete grammar of blasting treatment is: nozzle of sand spraying machine pressure is 0.5mpa, adopts
With 90 mesh al2o3Abrasive material, is sprayed with 80 °, and the distance away from POROUS TITANIUM pipe surface for the nozzle is 2cm, and process time is 10s.
The masking liquid of step (2) is dispersed in organic solvent for rhodium oxide and obtains, the quality of rhodium oxide and organic solvent
Than for 1:30.
The masking liquid of step (3) is stannum oxide, germanium oxide or thorium anhydride are dispersed in organic solvent and obtain, oxidation
The mass ratio of stannum, germanium oxide or thorium anhydride and organic solvent is 1:30.
Process for dispersing employed in step (2) and (3) is ultrasonic disperse 10 minutes, and described organic solvent is n-butyl alcohol.
Embodiment 3:
As shown in figure 1, a kind of porous titanium-matrix electrode material of the present invention, matrix 1 including tubulose and be sequentially coated on it
The first coating on surface and second coating, matrix 1 is POROUS TITANIUM, and first coating is rhodium oxide layer 2, and second coating is along first coating
Surface is divided into three parts, is followed successively by stannic oxide layer 3, germanium oxide layer 4 and thorium anhydride layer 5, and this three part is axially divided along matrix 1
Cloth.Wherein, the gross thickness of first coating and second coating is 30 μm, and both thickness ratio is for 3:1.Stannic oxide layer 3, germanium oxide layer 4
Identical with the thickness of thorium anhydride layer 5.The aperture of POROUS TITANIUM is 30 μm, and porosity is 40%.
A kind of preparation method of above-mentioned porous titanium-matrix electrode material, including step:
(1) vacuum-sintering porous titanium tube, and surface preparation is carried out to porous titanium tube, except the oxidation of degreasing and surface
Film, forms the fresh matrix of pitted skin；
(2) prepare rhodium oxide masking liquid, brush rhodium oxide masking liquid, 100 DEG C of dryings 3 hours, 300 DEG C of bars on first coating surface
Heat treatment 3 hours under part, are cooled to room temperature, form iridium dioxide coating, and this is first coating；
(3) stannum oxide, germanium oxide and thorium anhydride masking liquid are prepared respectively, first coating surface is divided into three parts, successively
Brush three kinds of described masking liquids, 100 DEG C of dryings 3 hours, heat treatment 1 hour under the conditions of 450 DEG C, it is cooled to room temperature, the oxygen of formation
Change stannum, germanium oxide and thorium anhydride coating to be axially distributed along matrix, this is second coating；
Under the conditions of (4) 450 DEG C, heat treatment 1 hour, obtains final product.
Wherein, in step (1), the concrete grammar of surface preparation is: the porous titanium tube of blasting treatment is placed in deionization
In water be cleaned by ultrasonic 10 minutes, remove moisture after in 55 DEG C of acid solution pickling 5 minutes, be finally cleaned by ultrasonic in deionized water
15 minutes, it is placed in vacuum drying oven and dries；Wherein, acid solution be by mass fraction be respectively 37% and 98% concentrated hydrochloric acid and
Concentrated sulphuric acid is prepared according to volume ratio 2:1 and is obtained.The concrete grammar of blasting treatment is: nozzle of sand spraying machine pressure is 0.3mpa, adopts
90 mesh al2o3Abrasive material, is sprayed with 60 °, and the distance away from POROUS TITANIUM pipe surface for the nozzle is 2cm, and process time is 5s.
The masking liquid of step (2) is dispersed in organic solvent for rhodium oxide and obtains, the quality of rhodium oxide and organic solvent
Than for 1:30.
The masking liquid of step (3) is stannum oxide, germanium oxide or thorium anhydride are dispersed in organic solvent and obtain, oxidation
The mass ratio of stannum, germanium oxide or thorium anhydride and organic solvent is 1:10.
Process for dispersing employed in step (2) and (3) is ultrasonic disperse 10 minutes, and described organic solvent is ethanol.
Embodiment 4:
As shown in figure 1, a kind of porous titanium-matrix electrode material of the present invention, matrix 1 including tubulose and be sequentially coated on it
The first coating on surface and second coating, matrix 1 is POROUS TITANIUM, and first coating is rhodium oxide layer 2, and second coating is along first coating
Surface is divided into three parts, is followed successively by stannic oxide layer 3, germanium oxide layer 4 and thorium anhydride layer 5, and this three part is axially divided along matrix 1
Cloth.Wherein, the gross thickness of first coating and second coating is 80 μm, and both thickness ratio is for 2:1.Stannic oxide layer 3, germanium oxide layer 4
Identical with the thickness of thorium anhydride layer 5.The aperture of POROUS TITANIUM is 100 μm, and porosity is 30%.
A kind of preparation method of above-mentioned porous titanium-matrix electrode material, including step:
(1) vacuum-sintering porous titanium tube, and surface preparation is carried out to porous titanium tube, except the oxidation of degreasing and surface
Film, forms the fresh matrix of pitted skin；
(2) prepare rhodium oxide masking liquid, brush rhodium oxide masking liquid, 110 DEG C of dryings 2 hours, 400 DEG C of bars on first coating surface
Heat treatment 2 hours under part, are cooled to room temperature, form iridium dioxide coating, and this is first coating；
(3) stannum oxide, germanium oxide and thorium anhydride masking liquid are prepared respectively, first coating surface is divided into three parts, successively
Brush three kinds of described masking liquids, 110 DEG C of dryings 2 hours, heat treatment 0.5 hour under the conditions of 550 DEG C, it is cooled to room temperature, formation
Stannum oxide, germanium oxide and thorium anhydride coating are axially distributed along matrix, and this is second coating；
Under the conditions of (4) 550 DEG C, heat treatment 0.5 hour, obtains final product.
Wherein, in step (1), the concrete grammar of surface preparation is: the porous titanium tube of blasting treatment is placed in deionization
It is cleaned by ultrasonic 20 minutes in water, remove after moisture pickling 10 minutes in 50 DEG C of acid solution, finally ultrasonic clear in deionized water
Wash 10 minutes, be placed in vacuum drying oven and dry；Wherein, acid solution is by the concentrated hydrochloric acid of mass fraction respectively 37% and 98%
Prepare according to volume ratio 2:1 with concentrated sulphuric acid and obtain.The concrete grammar of blasting treatment is: nozzle of sand spraying machine pressure is 0.5mpa, adopts
With 70 mesh al2o3Abrasive material, is sprayed with 80 °, and the distance away from POROUS TITANIUM pipe surface for the nozzle is 2cm, and process time is 5s.
The masking liquid of step (2) is dispersed in organic solvent for rhodium oxide and obtains, the quality of rhodium oxide and organic solvent
Than for 1:30.
The masking liquid of step (3) is stannum oxide, germanium oxide or thorium anhydride are dispersed in organic solvent and obtain, oxidation
The mass ratio of stannum, germanium oxide or thorium anhydride and organic solvent is 1:10.
Process for dispersing employed in step (2) and (3) is ultrasonic disperse 10 minutes, and described organic solvent is isopropanol.
Embodiment 5:
As shown in figure 1, a kind of porous titanium-matrix electrode material of the present invention, matrix 1 including tubulose and be sequentially coated on it
The first coating on surface and second coating, matrix 1 is POROUS TITANIUM, and first coating is rhodium oxide layer 2, and second coating is along first coating
Surface is divided into three parts, is followed successively by stannic oxide layer 3, germanium oxide layer 4 and thorium anhydride layer 5, and this three part is axially divided along matrix 1
Cloth.Wherein, the gross thickness of first coating and second coating is 50 μm, and both thickness ratio is for 2.5:1.Stannic oxide layer 3, germanium oxide layer
4 is identical with the thickness of thorium anhydride layer 5.The aperture of POROUS TITANIUM is 80 μm, and porosity is 35%.
A kind of preparation method of above-mentioned porous titanium-matrix electrode material, including step:
(1) vacuum-sintering porous titanium tube, and surface preparation is carried out to porous titanium tube, except the oxidation of degreasing and surface
Film, forms the fresh matrix of pitted skin；
(2) prepare rhodium oxide masking liquid, brush rhodium oxide masking liquid on first coating surface, 105 DEG C of dryings 2.5 hours, 350 DEG C
Under the conditions of heat treatment 2.5 hours, be cooled to room temperature, form iridium dioxide coating, this is first coating；
(3) stannum oxide, germanium oxide and thorium anhydride masking liquid are prepared respectively, first coating surface is divided into three parts, successively
Brush three kinds of described masking liquids, 105 DEG C of dryings 2.5 hours, heat treatment 0.8 hour under the conditions of 500 DEG C, it is cooled to room temperature, formed
Stannum oxide, germanium oxide and thorium anhydride coating be axially distributed along matrix, this is second coating；
Under the conditions of (4) 500 DEG C, heat treatment 0.8 hour, obtains final product.
Wherein, in step (1), the concrete grammar of surface preparation is: the porous titanium tube of blasting treatment is placed in deionization
In water be cleaned by ultrasonic 15 minutes, remove moisture after in 50 DEG C of acid solution pickling 8 minutes, be finally cleaned by ultrasonic in deionized water
12 minutes, it is placed in vacuum drying oven and dries；Wherein, acid solution be by mass fraction be respectively 37% and 98% concentrated hydrochloric acid and
Concentrated sulphuric acid is prepared according to volume ratio 2:1 and is obtained.The concrete grammar of blasting treatment is: nozzle of sand spraying machine pressure is 0.4mpa, adopts
80 mesh al2o3Abrasive material, is sprayed with 70 °, and the distance away from POROUS TITANIUM pipe surface for the nozzle is 2cm, and process time is 8s.
The masking liquid of step (2) is dispersed in organic solvent for rhodium oxide and obtains, the quality of rhodium oxide and organic solvent
Than for 1:20.
The masking liquid of step (3) is stannum oxide, germanium oxide or thorium anhydride are dispersed in organic solvent and obtain, oxidation
The mass ratio of stannum, germanium oxide or thorium anhydride and organic solvent is 1:20.
Process for dispersing employed in step (2) and (3) is ultrasonic disperse 8 minutes, and described organic solvent is n-butyl alcohol.
Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not model is protected to the present invention
The restriction enclosed, on the basis of technical scheme, those skilled in the art do not need to pay creative work and can do
The various modifications going out or deformation are still within protection scope of the present invention.
Claims (10)
1. a kind of porous titanium-matrix electrode material is it is characterised in that including the matrix of tubulose and being sequentially coated on the first of its surface
Coating and second coating, described matrix is POROUS TITANIUM, and described first coating is rhodium oxide layer, and described second coating is along first coating
Surface is divided into three parts, is followed successively by stannic oxide layer, germanium oxide layer and thorium anhydride layer, and this three part is axially distributed along matrix.
2. a kind of porous titanium-matrix electrode material according to claim 1 is it is characterised in that described first coating and second applies
The gross thickness of layer is 30～80 μm, and both thickness ratio is for 2～3:1.
3. a kind of porous titanium-matrix electrode material according to claim 1 it is characterised in that stannic oxide layer, germanium oxide layer and
The thickness of thorium anhydride layer is identical.
4. a kind of porous titanium-matrix electrode material according to claim 1 is it is characterised in that the aperture of described POROUS TITANIUM is 30
～100 μm, porosity is 30～40%.
5. a kind of preparation method of the porous titanium-matrix electrode material any one of Claims 1 to 4 is it is characterised in that wrap
Include step:
(1) vacuum-sintering porous titanium tube, and surface preparation is carried out to porous titanium tube, except the oxide-film of degreasing and surface,
Form the fresh matrix of pitted skin；
(2) prepare rhodium oxide masking liquid, brush rhodium oxide masking liquid on first coating surface, 100～110 DEG C of dryings 2～3 hours, 300
Heat treatment 2～3 hours under the conditions of～400 DEG C, are cooled to room temperature, form iridium dioxide coating, and this is first coating；
(3) stannum oxide, germanium oxide and thorium anhydride masking liquid are prepared respectively, first coating surface is divided into three parts, brushes successively
Three kinds of described masking liquids, 100～110 DEG C of dryings 2～3 hours, under the conditions of 450～550 DEG C, heat treatment 0.5～1 hour, is cooled to
Room temperature, the stannum oxide of formation, germanium oxide and thorium anhydride coating are axially distributed along matrix, and this is second coating；
Under the conditions of (4) 450～550 DEG C, heat treatment 0.5～1 hour, obtains final product.
6. preparation method according to claim 5 is it is characterised in that in step (1), the concrete grammar of surface preparation
It is: the porous titanium tube of blasting treatment is placed in deionized water and is cleaned by ultrasonic 10～20 minutes, at 50～55 DEG C after removing moisture
Acid solution in pickling 5～10 minutes, be finally cleaned by ultrasonic 10～15 minutes in deionized water, be placed in dry in vacuum drying oven and be
Can；Wherein, acid solution is to be prepared according to volume ratio 2:1 by the concentrated hydrochloric acid of mass fraction respectively 37% and 98% and concentrated sulphuric acid
Arrive.
7. preparation method according to claim 6 is it is characterised in that the concrete grammar of described blasting treatment is: sandblasting machine
Nozzle exit pressure is 0.3～0.5mpa, using 70～90 mesh al2o3Abrasive material, is sprayed with 60～80 °, and nozzle is away from porous titanium tube table
The distance in face is 1～2cm, and process time is 5～10s.
8. preparation method according to claim 5 is it is characterised in that the masking liquid of step (2) is dispersed in for rhodium oxide
Obtain in organic solvent, rhodium oxide is 1:10～30 with the mass ratio of organic solvent.
9. preparation method according to claim 5 is it is characterised in that the masking liquid of step (3) is stannum oxide, germanium oxide or two
Thorium oxide is dispersed in organic solvent and obtains, and the mass ratio of stannum oxide, germanium oxide or thorium anhydride and organic solvent is 1:
10～30.
10. preparation method according to claim 8 or claim 9 is it is characterised in that dispersion side employed in step (2) and (3)
Method is ultrasonic disperse 5～10 minutes, and described organic solvent is any one in n-butyl alcohol, isopropanol or ethanol.
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