CN109701510A - A kind of preparation method of Magneli phase oxidation titanium mesopore surfaces - Google Patents
A kind of preparation method of Magneli phase oxidation titanium mesopore surfaces Download PDFInfo
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- CN109701510A CN109701510A CN201910079744.XA CN201910079744A CN109701510A CN 109701510 A CN109701510 A CN 109701510A CN 201910079744 A CN201910079744 A CN 201910079744A CN 109701510 A CN109701510 A CN 109701510A
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Abstract
The present invention relates to inorganic nano material science and technology fields, more particularly to a kind of preparation method of Magneli phase oxidation titanium mesopore surfaces, first in the electrolytic solution by the submergence of the titanium-based material as anode, then apply certain voltage between a cathode and an anode, carry out cathode glow discharging in the electrolytic solution and generate plasma；Plasma electrolysis water generates hydrogen atom, high energy electron, and the substance near plasma carries out hydrogenation reduction treatment in situ；The synergistic effect of plasma deoxidization processing and anodic oxidation reactions, it is mesoporous that induction titanium substrate surface is grown into out Magneli phase oxidation titanium；After providing discharge time, titanium substrate surface generates the mesoporous thin layer of certain thickness grey Magneli phase oxidation titanium, i.e. the Magneli phase oxidation titanium mesopore surfaces.The synergistic effect with anodic oxidation reactions is handled by plasma deoxidization, grows Magneli phase oxidation titanium meso-hole structure in titanium-based material spatial induction.
Description
Technical field
The present invention relates to inorganic nano material science and technology fields, and in particular to a kind of mesoporous table of Magneli phase oxidation titanium
The preparation method in face.
Background technique
Titanium dioxide is as a kind of typical semiconductor light-catalyst, because it is with green, cheap, stable chemical performance
Feature is widely used the fields such as Photocatalyzed Hydrogen Production, solar battery, sewage treatment1-3.With most of semiconductor catalysts
Equally, titanium dioxide optical catalyst only absorbs ultraviolet light, extremely low for visible light utilization efficiency.Many methods can be by dioxy at present
Change titanium and be reduced into black or grey titanium dioxide, realizes visible absorption enhancing, it is seen that photo-catalysis capability is promoted.These methods
There are hydrogenation treatment, thermit reaction, laser plasma processing etc.4-6.But the above method exist energy consumption is high, it is complicated for operation not
Foot, as hydrogenation treatment generally requires to be passed through hydrogen for a long time under high-temperature and high-pressure conditions；Laser plasma processing generally requires
High power pulsed laser causes production cost expensive, is unfavorable for large-scale industrial application as excitaton source.
TinO2n-1(4 < n < 10) are a series of Magneli phase meso-porous titanium oxides, and numerous outstanding physical properties are as magnetized
Coefficient, specific conductance, photo absorption performance and than hot property, therefore be widely used in photocatalytic degradation, cathodic protection, at waste liquid
Reason, photoelectricity polaron, the fields such as memory material7,8.Wherein Ti4O7It is a kind of mixed valence compound, by Ti4+(3d0) and Ti3+
(3d1) uniformly form, experiments have shown that Ti4O7It is a kind of catalyst with high visible catalytic performance.Preparation Magneli at present
Phase meso-porous titanium oxide usually requires reducibility gas (H2/NH3) high-temperature process, cumbersome synthesis step, time-consuming technique stream
Journey, the factors such as equipment valuableness limit its large-scale application, such as Chinese patent: application number: 201210295358.2；Application
Number: 201410254580.7.Because the invention is a kind of simple, quickly and effectively method come synthesize stablize, high photocatalysis performance
Magneli phase meso-porous titanium oxide it is significant.
On the other hand, the optically catalytic TiO 2 technology of practical application is put at present, mainly includes floating type titanium dioxide
Two kinds of catalyst, load type photocatalytic material.In practical applications, above two material, which shows good photocatalytic degradation, has
Machine physical performance, but still Shortcomings.Wherein floating type titanium deoxide catalyst has the disadvantage that a) catalyst fines separation
Recycling is difficult, be easy to cause secondary pollution of water；B) titania powder cannot reuse；C) stability is poor, and easily occurs
Blocking filtering device.The shortcomings that support type photocatalysis net is: a) titanium dioxide dispersion degree reduces, small with reactant contact area；
B) supporting substrates can not be often heat-treated, and cannot form effective composite crystalline structure；C) supporting substrates binding force is bad, easily quilt
Oil pollution, service life is not high.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of Magneli phases
The preparation method on medium pore of titania surface, cathode glow discharging generates the plasma of strong reducing property in electrolyte liquid phase environment
Anodic oxidation reactions, the synergistic effect of plasma deoxidization processing and anodic oxidation reactions, in titanium-based occur for body, titanium-based material anode
Material spatial induction grows Magneli phase oxidation titanium meso-hole structure.
The purpose of the invention is achieved by the following technical solution: a kind of preparation side of Magneli phase oxidation titanium mesopore surfaces
Method first in the electrolytic solution by the submergence of the titanium-based material as anode, and the end of cathode substrate is immersed in electrolyte, then
Apply certain voltage between a cathode and an anode, carries out cathode glow discharging in the electrolytic solution and generate plasma；Plasma
Electrolysis water generates hydrogen atom, high energy electron, and the substance near plasma carries out hydrogenation reduction treatment in situ；Plasma is also
The synergistic effect of original place reason and anodic oxidation reactions, it is mesoporous that induction titanium substrate surface is grown into out Magneli phase oxidation titanium；Rule
After determining discharge time, the titanium substrate surface generation mesoporous thin layer of certain thickness grey Magneli phase oxidation titanium, i.e., described
Magneli phase oxidation titanium mesopore surfaces.The present invention in electrolyte liquid phase environment cathode glow discharging generate strong reducing property etc.
Anodic oxidation reactions occur for gas ions, titanium-based material anode, and plasma deoxidization handles the synergistic effect with anodic oxidation reactions,
Titanium-based material spatial induction grows Magneli phase oxidation titanium meso-hole structure, can control surface plasma by regulating and controlling discharge power
Modifies object phase component.
Plasma electrolysis water generate hydrogen atom, high energy electron, these high active substances have strong reducing property, can equity from
Substance near daughter carries out hydrogenation reduction treatment in situ.The synergistic effect of plasma deoxidization processing and anodic oxidation reactions,
Specifically, due to applying certain voltage, cathode substrate generates glow discharge plasma, at the same time, anode titanium substrate surface
Anodic oxidation reactions occur.Since titanium-based material is within plasma deoxidization sphere of action, cause titanium substrate surface by anodic oxygen
Change reaction generate noncrystalline medium pore of titania structure while, also will receive by plasma generate hydrogen atom, electronics hydrogen
Change reduction, induction is generated in amorphous titanium mesopore surfaces has Lacking oxygen, titanous Ti3+Lattice defect, namely
Magneli phase oxidation titanium.Therefore under the reduction treatment of plasma and anodic oxidation synergistic effect, anode titanium substrate surface is raw
Grow Magneli phase oxidation titanium mesopore surfaces.
Preferably, the titanium-based material is pure titanium and/or titanium alloy；The specification of the titanium-based material is titanium foil, titanium plate, foam
Titanium, titanium net, stud, titanium silk, or the multi-factor structure material of pure titanium or titanium alloy is plated in metal, nonmetallic surface.More preferably,
The titanium-based material is pure titanium, and the specification of the titanium-based material is titanium net or titanium foam.
Preferably, the cathode substrate be rod-shaped conductor, the rod-shaped conductor be gold, silver, copper, iron, tin, titanium, aluminium, tungsten,
One of nickel, platinum, magnesium, chromium, cobalt, zinc, carbon, silicon, Germanium, the rodlike conductor diameter of cathode are 0.1-10mm.It is rodlike to lead
The part of body and electrolyte contacts generates plasma, it is preferred that rod-shaped conductor is copper rod, stud, aluminium bar or tungsten bar, cathode base
Material can be multiple, multiple cathode substrates be uniformly distributed with around titanium-based material.
Preferably, in discharge process, the temperature of the electrolyte is controlled at 70-100 DEG C, and the discharge voltage is >=
200v, the discharge power of the plasma are 0.2-200KW.
The temperature for controlling electrolyte in discharge process by the water-bath circulatory system, makes the temperature of electrolyte in discharge process
In be maintained within the scope of 70-100 DEG C, keep discharge process stablize carry out.When temperature be lower than 70 DEG C, cathode glow will not be generated
Discharge plasma, temperature are higher than 100 DEG C, and water comes to life, and influence experiment safety, under the premise of guaranteeing safety, temperature
Degree is higher, and obtained product catalyst performance is better.More preferably, the temperature of electrolyte is maintained at 80-90 during discharge
Within the scope of DEG C.When discharge power is lower than 0.2KW, electrolyte can not discharge.Plasma discharge voltage includes DC voltage, exchange
Voltage, pulse voltage, preferentially select pulse voltage, and the pulse voltage is 200-1000V, pulse repetition frequency 100-
5000Hz.The regulation discharge time is 0.1-72 hours, and discharge time and discharge power are negatively correlated.
Preferably, the electrolyte is uniformly mixed to obtain by a certain amount of acid solution with water, and the acid solution is nitre
At least one of acid, sulfuric acid, hydrochloric acid and hydrofluoric acid solution, the hydrogen ion concentration of the electrolyte are 0.01-10mol/
L, the conductivity of the electrolyte are 0.1-100mS/cm at 25 DEG C.
The conductivity of electrolyte is proportional to hydrogen ion concentration, and hydrogen ion concentration is bigger, and conductivity is bigger, the electricity of water
Hinder smaller, the amounts of hydrogen being electrolysed is about more, therefore the preferred present invention uses acidic electrolysis bath, when conductivity is in 0.1-100ms/
When cm range, the amounts of hydrogen of generation is the most suitable.
Preferably, the distance between the cathode substrate and titanium-based material are >=5mm.
Preferably, the object of the Magneli phase oxidation titanium mesopore surfaces is mutually Ti4O7、Ti5O9、Ti6O11、Ti7O13、
Ti8O15、Ti9O17Or Ti10O19At least one of.Wherein Ti4O7For main component, object can control by regulating and controlling discharge power
Phase component, and power is bigger, TinO2n-1Middle n value is bigger.
Preferably, the mesoporous thin layer of the grey Magneli phase oxidation titanium with a thickness of 0.01-800um.It is discharged by control
Voltage, discharge time can regulate and control the thickness, and the thickness of the mesoporous thin layer of Magneli phase oxidation titanium and discharge voltage, put
The electric time is positively correlated.
Preferably, the Magneli phase oxidation titanium mesopore surfaces include secondary structure, and wherein primary structure is 20-50nm
Size it is mesoporous, secondary structure is to be attached to the Titanium dioxide nanoparticle that the partial size of the mesoporous inner wall is 1-5nm.Mesopore size
Can be regulated and controled by discharge voltage, discharge power and plasma electron density, specifically with discharge voltage, discharge power, etc.
Gas ions electron density is positively correlated；Secondary structure is the Titanium dioxide nanoparticle for being attached to the 1-5nm of mesoporous inner wall, the nanometer
Particle has highlight catalytic active.
Preferably, the Magneli phase oxidation titanium mesopore surfaces have lattice defect, and include at least Lacking oxygen and/or
One of titanous.The concentration of the lattice defect can be adjusted by plasma electron density, discharge power, discharge time
Control, specially the concentration of lattice defect is positively correlated with plasma electron density, discharge power, discharge time.Described
Magneli phase oxidation titanium mesopore surfaces, photocatalytic activity can be optimized by regulating and controlling lattice surface defect density, specially
Photocatalytic activity is positively correlated with lattice surface defect density.
The beneficial effects of the present invention are: present invention cathode glow discharging in electrolyte liquid phase environment generates strong reducing property
Plasma, anodic oxidation reactions occur for titanium-based material anode, and plasma deoxidization processing cooperates with work with anodic oxidation reactions
With, titanium-based material spatial induction grow Magneli phase oxidation titanium meso-hole structure, by regulate and control discharge power can control surface etc.
The modifies object phase component of ion.
The synergistic effect with anodic oxidation reactions is handled by plasma deoxidization in the present invention, specifically, due to applying
Certain voltage, cathode substrate generate glow discharge plasma, and at the same time, it is anti-that anodic oxidation occurs for anode titanium substrate surface
It answers.Since titanium-based material is within plasma deoxidization sphere of action, titanium substrate surface is caused to be generated non-knot by anodic oxidation reactions
While brilliant medium pore of titania structure, the hydro-reduction effect of the hydrogen atom, electronics that are generated by plasma, induction also will receive
Generating in amorphous titanium mesopore surfaces has Lacking oxygen, titanous Ti3+Lattice defect namely Magneli phase oxidation titanium.
Therefore under the reduction treatment of plasma and anodic oxidation synergistic effect, anode titanium substrate surface grows Magneli phase oxygen
Change titanium mesopore surfaces.
The method that the present invention uses cathode glow discharging plasma hydrogenation to handle for the first time, it is in situ in one step of titanium substrate surface
It is prepared for Magneli phase oxidation titanium Ti4O7It is mesoporous.The Magneli phase oxidation titanium Ti4O7It is mesoporous that there is anti-oxidant, anti-corruption
It loses, the feature that large specific surface area and visible light absorption capacity are strong, it is living to show excellent visible light catalytic in practical applications
Property and good stability.
Relative to the method that tradition prepares Magneli phase oxidation titanium, the method for the present invention has the advantage that the method for the present invention
Complicated high-temperature calcination processing is carried out it is not necessary that reducing agent is added, it is easy to operate, highly-safe, low in cost, environmentally protective, suitable
Large scale preparation high-performance Magneli phase oxidation titanium.The surface mesoporous with Magneli phase oxidation titanium prepared by the present invention has
High visible light catalytic activity can be directly applied to water body, air environment, it is not necessary that titanium dioxide is carried out load coating film treatment, because
This significantly shortens manufacturing cycle, reduces production cost.
The Magneli phase oxidation titanium of method preparation of the invention can be applicable to inert electrode, catalyst carrier, lithium battery,
Thermoelectricity and photoelectric material, electrode protection and photocatalytic degradation of organic matter field.
Detailed description of the invention
Fig. 1 liquid glow discharge plasma acts on the schematic illustration of titanium-based material；
Fig. 2 Experimental equipment；
Fig. 3 Magneli phase oxidation titanium Ti4O7The scanning electron microscope (SEM) photograph of mesopore surfaces；
In the case of Fig. 4 difference discharge time, Magneli phase oxidation titanium Ti obtained4O7The ultraviolet-visible of mesopore surfaces is unrestrained
Reflectance spectrum figure；
In the case of Fig. 5 difference discharge time, Magneli phase oxidation titanium Ti obtained4O7Visible Light Induced Photocatalytic sieve of mesopore surfaces
The curve graph of red bright B.
Specific embodiment
For the ease of the understanding of those skilled in the art, the present invention is made below with reference to examples and drawings 1-5 further
Explanation, the content that embodiment refers to not is limitation of the invention.
Embodiment 1
It is 40min in discharge time, discharge power is obtained under the conditions of being 420W to have Magneli phase oxidation titanium Ti4O7It is situated between
The titanium net of hole surface.
The nitric acid solution of 4mL 0.1mol/L is instilled in 50mL deionized water, is sufficiently stirred to obtain electrolyte.By 10mL
The nitric acid solution of 0.1mol/L instills in 60mL deionized water, is sufficiently stirred to obtain buffer.
As shown in Fig. 2, two stud cathodes are symmetrically disposed at titanium net anode two sides, parallel discharge system is formed, it is used
Two stud cathode diameters be 4mm, length 20cm.Two stud cathodes are inserted in alundum tube, and only length is
The conical tip part of 0.8cm is not coated by alundum tube, and titanium net anode used, specification is 0.1*2*2cm3, titanium net checkerwork cell is big
Small is 2*3mm2, grid thickness is 1mm.
Electrolyte is poured into electrolytic cell, in stud cathode and titanium net anode submergence electrolyte.It is 600V, frequency by voltage
Stud cathode and titanium net anode both ends are applied to for the pulse voltage of 1kHz.It is just generated when electrolyte temperature reaches 80 DEG C or so
Cathode glow discharging plasma opens the water-bath circulatory system at this time to maintain electrolyte temperature to stablize.Steady glow is generated to put
When electro-plasma, electric current is shown as 0.7A, i.e. discharge power is 420W.Due to that can cause to damage to electrolyte in discharge process
Consumption, so needing to be added buffer in electrolytic cell to supplement electrolyte, the flow velocity that buffer is added is 1mL/min.
It discharges after 40min, stops electric discharge, titanium net is washed with deionized water and obtains target with Magneli phase oxidation
Titanium Ti4O7The titanium net catalyst (GT-40) of mesopore surfaces.
Embodiment 2
It is 60min in discharge time, discharge power is obtained under the conditions of being 420W to have Magneli phase oxidation titanium Ti4O7It is situated between
The titanium net of hole surface.
The nitric acid solution of 4mL 0.1mol/L is instilled in 50mL deionized water, is sufficiently stirred to obtain electrolyte.By 10mL
The nitric acid solution of 0.1mol/L instills in 60mL deionized water, is sufficiently stirred to obtain buffer.
As shown in Fig. 2, two stud cathodes are symmetrically disposed at titanium net anode two sides, parallel discharge system is formed, it is used
Two stud cathode diameters be 4mm, length 20cm.Two stud cathodes are inserted in alundum tube, and only length is
The conical tip part of 0.8cm is not coated by alundum tube, and titanium net anode used, specification is 0.1*2*2cm3, titanium net checkerwork cell is big
Small is 2*3mm2, grid thickness is 1mm.
Electrolyte is poured into electrolytic cell, in stud cathode and titanium net anode submergence electrolyte.It is 600V, frequency by voltage
Stud cathode and titanium net anode both ends are applied to for the pulse voltage of 1kHz.It is just generated when electrolyte temperature reaches 80 DEG C or so
Cathode glow discharging plasma opens the water-bath circulatory system at this time to maintain electrolyte temperature to stablize.Steady glow is generated to put
When electro-plasma, electric current is shown as 0.7A, i.e. discharge power is 420W.Due to that can cause to damage to electrolyte in discharge process
Consumption, so needing to be added buffer in electrolytic cell to supplement electrolyte, the flow velocity that buffer is added is 1mL/min
It discharges after 60min, stops electric discharge, titanium net is washed with deionized water and obtains target with Magneli phase oxidation
Titanium Ti4O7The titanium net (GT-60) of mesopore surfaces.
Embodiment 3
It is 80min in discharge time, discharge power is obtained under the conditions of being 420W to have Magneli phase oxidation titanium Ti4O7It is situated between
The titanium net of hole surface.
The nitric acid solution of 4mL 0.1mol/L is instilled in 50mL deionized water, is sufficiently stirred to obtain electrolyte.By 10mL
The nitric acid solution of 0.1mol/L instills in 60mL deionized water, is sufficiently stirred to obtain buffer.
As shown in Fig. 2, two stud cathodes are symmetrically disposed at titanium net anode two sides, parallel discharge system is formed, it is used
Two stud cathode diameters be 4mm, length 20cm.Two stud cathodes are inserted in alundum tube, and only length is
The conical tip part of 0.8cm is not coated by alundum tube, and titanium net anode used, specification is 0.1*2*2cm3, titanium net checkerwork cell is big
Small is 2*3mm2, grid thickness is 1mm.
Electrolyte is poured into electrolytic cell, in stud cathode and titanium net anode submergence electrolyte.It is 600V, frequency by voltage
Stud cathode and titanium net anode both ends are applied to for the pulse voltage of 1kHz.It is just generated when electrolyte temperature reaches 80 DEG C or so
Cathode glow discharging plasma opens the water-bath circulatory system at this time to maintain electrolyte temperature to stablize.Steady glow is generated to put
When electro-plasma, electric current is shown as 0.7A, i.e. discharge power is 420W.Due to that can cause to damage to electrolyte in discharge process
Consumption, so needing to be added buffer in electrolytic cell to supplement electrolyte, the flow velocity that buffer is added is 1mL/min.
It discharges after 80min, stops electric discharge, titanium net is washed with deionized water and obtains target with Magneli phase oxidation
Titanium Ti4O7The titanium net (GT-80) of mesopore surfaces.
Embodiment 4
It is 120min in discharge time, discharge power is obtained under the conditions of being 420W to have Magneli phase oxidation titanium Ti4O7
The titanium net of mesopore surfaces.
The nitric acid solution of 4mL 0.1mol/L is instilled in 50mL deionized water, is sufficiently stirred to obtain electrolyte.By 10mL
The nitric acid solution of 0.1mol/L instills in 60mL deionized water, is sufficiently stirred to obtain buffer.
As shown in Fig. 2, two stud cathodes are symmetrically disposed at titanium net anode two sides, parallel discharge system is formed, it is used
Two stud cathode diameters be 4mm, length 20cm.Two stud cathodes are inserted in alundum tube, and only length is
The conical tip part of 0.8cm is not coated by alundum tube, and titanium net anode used, specification is 0.1*2*2cm3, titanium net checkerwork cell is big
Small is 2*3mm2, grid thickness is 1mm.
Electrolyte is poured into electrolytic cell, in stud cathode and titanium net anode submergence electrolyte.It is 600V, frequency by voltage
Stud cathode and titanium net anode both ends are applied to for the pulse voltage of 1kHz.It is just generated when electrolyte temperature reaches 80 DEG C or so
Cathode glow discharging plasma opens the water-bath circulatory system at this time to maintain electrolyte temperature to stablize.Steady glow is generated to put
When electro-plasma, electric current is shown as 0.7A, i.e. discharge power is 420W.Due to that can cause to damage to electrolyte in discharge process
Consumption, so needing to be added buffer in electrolytic cell to supplement electrolyte, the flow velocity that buffer is added is 1mL/min
It discharges after 120min, stops electric discharge, titanium net is washed with deionized water and obtains target with Magneli phase oxidation
Titanium Ti4O7The titanium net (GT-120) of mesopore surfaces.
Embodiment 5
UV-Vis reflective spectrum test: there is Magneli phase oxidation titanium Ti by prepared by embodiment 1-44O7It is mesoporous
The titanium net on surface carries out UV-Vis reflective spectrum test, figure 4, it is seen that having Magneli phase oxidation titanium
Ti4O7The titanium net of mesopore surfaces have excellent visible absorption, illustrate cathode plasma hydro-reduction processing can effectively into
Row surface Lacking oxygen, titanous Ti3+Lattice defect doping.
Embodiment 6
The experiment of degradation dye, rhodamine B (RhB) under visible light conditions.
Specific steps are as follows: will have Magneli phase oxidation titanium Ti first4O7The titanium net 1cm of mesopore surfaces2It is dense to be placed in 10ml
Degree is that stirring 10min obtains mixed liquor in the rhodamine B solution of 20ppm.Then mixing is placed in dark place and is sufficiently mixed 30min,
To reach adsorption equilibrium.
Using the 300W xenon lamp with 420nm edge filter as visible light source, it is placed in above mixed liquor at 20cm, then
Carry out photocatalytic degradation experiment.
500ul is sampled from mixed liquor every 10min, with the specific peak absorbance at UV-vis absorption spectrum 552nm
Intensity is sampling the concentration in liquid to characterize rhodamine B.It is bent to draw rhodamine B degradation, as shown in Figure 5, the results showed that surface
Modified titanium oxide catalytic effect is substantially better than commercial oxidation titanium.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. a kind of preparation method of Magneli phase oxidation titanium mesopore surfaces, it is characterised in that: first by the titanium-based material as anode
Submergence in the electrolytic solution, and the end of cathode substrate is immersed in electrolyte, is then applied between a cathode and an anode certain
Voltage carries out cathode glow discharging in the electrolytic solution and generates plasma；Plasma electrolysis water generates hydrogen atom, high energy electricity
Son, the substance near plasma carry out hydrogenation reduction treatment in situ；Plasma deoxidization processing and anodic oxidation reactions
Synergistic effect, it is mesoporous that induction titanium substrate surface is grown into out Magneli phase oxidation titanium；After providing discharge time, titanium-based
Material surface generates the mesoporous thin layer of certain thickness grey Magneli phase oxidation titanium, the i.e. mesoporous table of Magneli phase oxidation titanium
Face.
2. the preparation method of Magneli phase oxidation titanium mesopore surfaces according to claim 1, it is characterised in that: the titanium
Substrate is pure titanium and/or titanium alloy；The specification of the titanium-based material be titanium foil, titanium plate, titanium foam, titanium net, stud, titanium silk, or
Metal, nonmetallic surface plate the multi-factor structure material of pure titanium or titanium alloy.
3. the preparation method of Magneli phase oxidation titanium mesopore surfaces according to claim 1, it is characterised in that: the yin
Pole substrate be rod-shaped conductor, the rod-shaped conductor be gold, silver, copper, iron, tin, titanium, aluminium, tungsten, nickel, platinum, magnesium, chromium, cobalt, zinc, carbon,
One of silicon, Germanium, the rodlike conductor diameter of cathode are 0.1-10mm.
4. the preparation method of Magneli phase oxidation titanium mesopore surfaces according to claim 1, it is characterised in that: discharged
Cheng Zhong, the temperature of the electrolyte are controlled at 70-100 DEG C, and the discharge voltage is >=200v, the electric discharge function of the plasma
Rate is 0.2-200KW.
5. the preparation method of Magneli phase oxidation titanium mesopore surfaces according to claim 1, it is characterised in that: the electricity
Solution liquid is uniformly mixed to obtain by a certain amount of acid solution with water, and the acid solution is nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid
The hydrogen ion concentration of at least one of solution, the electrolyte is 0.01-10mol/l, and the conductivity of the electrolyte exists
25 DEG C are 0.1-100mS/cm.
6. the preparation method of Magneli phase oxidation titanium mesopore surfaces according to claim 1, it is characterised in that: the yin
The distance between pole substrate and titanium-based material are >=5mm.
7. the preparation method of Magneli phase oxidation titanium mesopore surfaces according to claim 1, it is characterised in that: described
The object of Magneli phase oxidation titanium mesopore surfaces is mutually Ti4O7、Ti5O9、Ti6O11、Ti7O13、Ti8O15、Ti9O17Or Ti10O19In
It is at least one.
8. the preparation method of Magneli phase oxidation titanium mesopore surfaces according to claim 1, it is characterised in that: the ash
The mesoporous thin layer of color Magneli phase oxidation titanium with a thickness of 0.01-800um.
9. the preparation method of Magneli phase oxidation titanium mesopore surfaces according to claim 1, it is characterised in that: described
Magneli phase oxidation titanium mesopore surfaces include secondary structure, and wherein primary structure is mesoporous, the secondary structure of 20-50nm size
To be attached to the Titanium dioxide nanoparticle that the partial size of the mesoporous inner wall is 1-5nm.
10. the preparation method of Magneli phase oxidation titanium mesopore surfaces according to claim 1, it is characterised in that: described
Magneli phase oxidation titanium mesopore surfaces have lattice defect, and include at least one of Lacking oxygen and/or titanous.
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| CN114275857A (en) * | 2021-12-06 | 2022-04-05 | 澳门大学 | Electrochemical wastewater treatment device and application thereof |
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