CN101857288B - Preparation method of titanium-based titanium dioxide nanotube stannic oxide electrode - Google Patents
Preparation method of titanium-based titanium dioxide nanotube stannic oxide electrode Download PDFInfo
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Abstract
The invention relates to a preparation method of a titanium-based titanium dioxide nanotube stannic oxide electrode, belonging to the technical field of electro-catalysis electrode preparation. The method comprises the following steps: firstly adopting an anodic oxidation method to prepare a titanium dioxide nanotube on a titanium matrix, thus improving the specific surface area of the titanium matrix; and depositing stibium and tin in the titanium dioxide nanotube by an electro-deposition method successively, and performing thermal oxidation to lead the stibium doped stannic oxide to be bonded firmly with the titanium dioxide nanotubes directly connected with the titanium matrix. The stannic oxide crystal particles prepared by the electro-deposition method are dispersed evenly, and the electrode surface is compact and has no crack. The method overcomes the defect that crack is generated on the surface of the electrode prepared by the traditional brush coating thermal decomposition method. The electrode prepared by the invention has high potential for oxygen evolution, high electric catalytic activity and long service life and the like; the preparation process is easily controlled, has low cost and lower equipment requirements; and the prepared electrode can effectively treat pollutants that are poorly biodegradable.
Description
Technical field
The invention belongs to the preparation method of electro catalytic electrode preparing technical field, particularly a kind of titanium-based titanium dioxide nanotube stannic oxide electrode.
Background technology
Electrochemical oxidation process is with its high efficiency, and the characteristics of environment compatibility and friendly have caused people's extensive concern.Electrochemical oxidation is reagent with the electronics mainly, does not need to add any chemical reagent, has avoided the secondary pollution problem that caused by other interpolation medicament, and electrochemical oxidation generally just can carry out at normal temperatures and pressures, is a kind of energy-conservation green technology.Handle in the process of organic waste water at electrochemical oxidation process, electrode not only plays a part transmission current, but also organic degraded is played katalysis.Therefore, the quality that electrode materials is selected directly affects the height of organic matter degradation efficient.When the Applied Electrochemistry technology, the major influence factors that consider is electroconductibility, stability and the catalytic performance of electrode materials.
Titanium base stannic oxide electrode has caused that the investigator greatly pays close attention in recent years.Discover that titanium base SnO2 electrode all has good electrocatalysis because of its oxygen evolution potential height to organism anodic oxidation and wastewater treatment.But adopt traditional law system to be equipped with titanium base SnO2 electrode and have a series of problem: at first, the SnO2 coatingsurface is prone to the crack, causes the passivation of titanium matrix easily, and its stability is bad, easily comes off; Secondly, SnO2 is a semi-conductor, and normal temperature resistance is very big.This also is the biggest obstacle that early stage SnO2 electrode is promoted the use of.Mix antimony titanium base SnO2 electrode and overcome the defective of caking power difference to a certain extent, electroconductibility increases, but still does not have really to solve the problem of electrode passivation and inactivation defective.Extra some special metals of doping or non-metallic element can be used in to mix in the antimony titanium base SnO2 electrode and increase its work-ing life, but also may have some restrictions.For example the mix Ti/SnO2-Sb electrode of Ir, because the low oxygen evolution potential of IrO2 can reduce the working efficiency and the electrochemical catalysis ability of electrode, its energy consumption also can increase because of the generation of oxygen evolution reaction.Explanation utilizes the titanium base stannic oxide electrode of traditional brushing thermal decomposition method preparation thus, has that electrode life is low, the defective of the easy inactivation of electrode.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of titanium-based titanium dioxide nanotube stannic oxide electrode, optimize electrode performance, effectively improve electrode life and electrocatalysis characteristic by improving its preparation method.
The technical solution that realizes the object of the invention is: a kind of preparation method of titanium-based titanium dioxide nanotube stannic oxide electrode, adopt anodic oxidation, galvanic deposit and thermal oxidation method to make titanium-based titanium dioxide nanotube stannic oxide electrode, specifically may further comprise the steps:
The first step: adopt anonizing on the titanium matrix, to prepare titania nanotube:
Titanium plate surface is polished smooth, clean up the back as anode, with stainless steel as negative electrode, the control volts DS, in Potassium monofluoride, hydrogen fluoride and vitriolic electrolytic solution, carry out anodic oxidation, the titanium matrix after the anodic oxidation is taken out, rinse well, treat air-dry post-heating roasting, make titanium-based titanium dioxide nanotube;
Second step: adopt galvanic deposit and thermal oxidation method on titanium-based titanium dioxide nanotube, to prepare the tindioxide coating:
To prepare the titanium matrix of titania nanotube as negative electrode, with stainless steel as anode, constant current density, galvanic deposit antimony, galvanic deposit tin in tin tetrachloride and vitriolic mixing solutions then in the mixing solutions of butter of antimony and citric acid earlier, by this step, repeat galvanic deposit antimony and tin, the titanium matrix after the galvanic deposit is taken out, rinse well, treat air-dry post-heating roasting, make titanium-based titanium dioxide nanotube stannic oxide electrode.
The present invention compared with prior art, its remarkable advantage: the titania nanotube marshalling that the present invention adopts anonizing to prepare on the titanium matrix, high-sequential, improved the specific surface area of titanium matrix, can increase the charge capacity of catalytic active substance, be deposited on antimony and tin in the titania nanotube successively by electrodip process, through thermooxidizing, antimony-doped stannic oxide can form good Solid solution with titanium dioxide, make the titania nanotube mortise that antimony-doped stannic oxide and titanium matrix directly link to each other, and the tindioxide crystal grain for preparing by electrodip process is uniformly dispersed, the electrode surface densification, compact, leakless, because of making electrode surface, solvent evaporation produces fissured defective when having overcome traditional brushing thermal decomposition method and preparing electrode, thereby avoided electrolytic solution by permeating the crack, slowed down the passivation of titanium matrix the erosion that the titanium matrix causes.
The present invention compares with traditional method for preparing titanium base stannic oxide electrode and has the following advantages: preparation method's operation of the present invention is easy to control, and cost is low, and equipment requirements is lower; Improve the surface tissue of stannic oxide electrode, both can increase the catalytic activity of electrode, can increase the work-ing life of electrode again; The titanium-based titanium dioxide nanotube stannic oxide electrode surface compact leakless of preparation, coating difficult drop-off, its reinforcing life are more than 15 times of titanium base stannic oxide electrode that tradition is brushed the thermal decomposition method preparation, have improved the stability of electrode greatly; Its oxygen evolution potential exceeds more than the 0.3V than traditional titanium base stannic oxide electrode, and electrocatalysis characteristic is greatly improved.
Description of drawings
Fig. 1 is the SEM figure of titanium-based titanium dioxide nanotube stannic oxide electrode of the present invention.
Fig. 2 is the XRD spectra of titanium-based titanium dioxide nanotube stannic oxide electrode of the present invention.
Embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.
The preparation method of titanium-based titanium dioxide nanotube stannic oxide electrode of the present invention adopts anodic oxidation, galvanic deposit and thermal oxidation method to make titanium-based titanium dioxide nanotube stannic oxide electrode, specifically may further comprise the steps:
The first step: adopt anonizing on the titanium matrix, to prepare titania nanotube:
Titanium plate surface is polished smooth, clean up the back as anode, with stainless steel as negative electrode, volts DS is controlled at 20～25V, at Potassium monofluoride, carry out anodic oxidation in hydrogen fluoride and the vitriolic electrolytic solution, electrolytic solution is 0.07～0.08mol/L Potassium monofluoride, 0.07～0.08mol/L hydrogen fluoride and 0.95～1.05mol/L vitriolic mixing solutions, anodizing time is 40～70min, titanium matrix after the anodic oxidation is taken out, rinse well, treat air-dry post-heating roasting, the temperature that adds thermal bake-out is 500～550 ℃, temperature rise rate is 1～2 ℃/min, and roasting 3～5 hours makes titanium-based titanium dioxide nanotube;
Second step: adopt galvanic deposit and thermal oxidation method on titanium-based titanium dioxide nanotube, to prepare the tindioxide coating:
As negative electrode, as anode, constant current density is 2～4mA/cm with stainless steel with the titanium matrix that prepared titania nanotube
2Elder generation's galvanic deposit antimony in the mixing solutions of butter of antimony and citric acid, galvanic deposit tin in tin tetrachloride and vitriolic mixing solutions then, by this step, repeat galvanic deposit antimony and tin, the composition of the mixing solutions of butter of antimony and citric acid is 0.01～0.015mol/L butter of antimony and 0.05～0.1mol/L citric acid, the time of galvanic deposit antimony is 0.5～1min, the composition of tin tetrachloride and vitriolic mixing solutions is 0.1～0.2mol/L tin tetrachloride and 0.05～0.1mol/L sulfuric acid, the time of galvanic deposit tin is 25～40min, and the number of times that repeats galvanic deposit antimony and tin is 1～3 time, and the titanium matrix after the galvanic deposit is taken out, rinse well, treat air-dry post-heating roasting, the temperature that adds thermal bake-out is 500～550 ℃, and temperature rise rate is 1～5 ℃/min, roasting 4～6 hours makes titanium-based titanium dioxide nanotube stannic oxide electrode.
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1
The titanium plate is cut into size 1.0cm * 3.0cm, until metalluster, remove the greasy dirt on the titanium matrix surface, in the solution of 18wt%HCl, suitably heat 15min again and remove zone of oxidation, be placed in the distilled water standby with distilled water flushing with sand papering titanium surface.With the titanium plate handled well as anode, onesize stainless steel plate is as negative electrode, electrolytic solution is 0.07mol/L Potassium monofluoride, 0.08mol/L hydrogen fluoride and 0.95mol/L vitriolic mixing solutions, and the control electrode spacing is 1cm, and volts DS is 20V, behind the anodic oxidation 60min, take out sample, use deionized water rinsing, be placed on behind the natural air drying in the retort furnace, roasting is 3 hours after adopting 1 ℃/min of temperature programming to be heated to 500 ℃, makes titanium-based titanium dioxide nanotube.As negative electrode, onesize stainless steel is as anode with the titanium matrix that prepared titania nanotube, and control current density is 3mA/cm
2The galvanic deposit antimony 1min in the mixing solutions of 0.01mol/L butter of antimony and 0.05mol/L citric acid of elder generation, galvanic deposit tin 35min in 0.1mol/L tin tetrachloride and 0.05mol/L vitriolic mixing solutions then, by this step, galvanic deposit antimony and tin 1 time, titanium matrix after the galvanic deposit is taken out, clean with distilled water flushing, after treating natural air drying, be placed in the retort furnace, adopt 1 ℃/min of temperature programming to be heated to 500 ℃ of rear oxidation roastings 4 hours, promptly make titanium-based titanium dioxide nanotube stannic oxide electrode (TiO
2-NTs/SnO
2-Sb).
By scanning electronic microscope (SEM) to TiO
2-NTs/SnO
2-Sb electrode surface pattern characterizes, and sees accompanying drawing 1, and electrode surface is fine and close compact as can be seen, leakless.
Adopt X diffraction analysis method (XRD) to TiO
2-NTs/SnO
2-Sb electrode structure characterizes, and sees accompanying drawing 2.Can analyze SnO
2Crystalline structure, only detect a spot of titanium diffraction peak, surperficial SnO is described
2Coating has well covered the titanium matrix.
With TiO
2-NTs/SnO
2The titanium base stannic oxide electrode (Ti/SnO of-Sb electrode and traditional technology preparation
2-Sb) at 0.1molL
-1H
2SO
4In the solution, at 100mA/cm
2The current density condition under strengthen accelerated aging test, draw TiO
2-NTs/SnO
2The reinforcing life of-Sb electrode reaches 62h, is Ti/SnO
2More than 15 times of-Sb reinforcing life.
With TiO
2-NTs/SnO
2The Ti/SnO of-Sb electrode and traditional technology preparation
2-Sb electrode is measured at acidity, neutrality and alkaline condition respectively and is analysed the oxygen polarization curve, and the result who obtains oxygen evolution potential is as shown in table 1.
The oxygen evolution potential of two kinds of electrodes of table 1 in 3 kinds of media
Embodiment 2
The pre-treatment step of titanium plate is identical with case study on implementation 1.With the titanium plate handled well as anode, onesize stainless steel plate is as negative electrode, electrolytic solution is 0.08mol/L Potassium monofluoride, 0.07mol/L hydrogen fluoride and 1.05mol/L vitriolic mixing solutions, the control electrode spacing is 1cm, and volts DS is 25V, behind the anodic oxidation 40min, use deionized water rinsing, be placed on behind the natural air drying in the retort furnace, roasting was 3 hours after 2 ℃/min of employing temperature programming was heated to 550 ℃, made titanium-based titanium dioxide nanotube.As negative electrode, onesize stainless steel is as anode with the titanium matrix that prepared titania nanotube, and control current density is 4mA/cm
2The galvanic deposit antimony 0.5min in the mixing solutions of 0.015mol/L butter of antimony and 0.1mol/L citric acid of elder generation, galvanic deposit tin 25min in 0.2mol/L tin tetrachloride and 0.1mol/L vitriolic mixing solutions then, by this step, galvanic deposit antimony and tin 2 times take out the titanium matrix after the galvanic deposit, clean with distilled water flushing, after treating natural air drying, be placed in the retort furnace, adopt 5 ℃/min of temperature programming to be heated to 550 ℃ of rear oxidation roastings 5 hours.The various performances of the titanium-based titanium dioxide nanotube stannic oxide electrode that makes are close with case study on implementation 1, and its reinforcing life reaches 68h, and the oxygen evolution potential under acidity, neutrality and alkaline condition is respectively 2.18V, 2.06V and 1.6V.
Embodiment 3
The pre-treatment step of titanium plate is identical with case study on implementation 1.With the titanium plate handled well as anode, onesize stainless steel plate is as negative electrode, electrolytic solution is 0.075mol/L Potassium monofluoride, 0.075mol/L hydrogen fluoride and 1mol/L vitriolic mixing solutions, the control electrode spacing is 1cm, and volts DS is 20V, behind the anodic oxidation 70min, use deionized water rinsing, be placed on behind the natural air drying in the retort furnace, roasting was 5 hours after 1 ℃/min of employing temperature programming was heated to 500 ℃, made titanium-based titanium dioxide nanotube.As negative electrode, onesize stainless steel is as anode with the titanium matrix that prepared titania nanotube, and control current density is 2mA/cm
2The galvanic deposit antimony 0.5min in the mixing solutions of 0.015mol/L butter of antimony and 0.1mol/L citric acid of elder generation, galvanic deposit tin 40min in 0.1mol/L tin tetrachloride and 0.05mol/L vitriolic mixing solutions then, by this step, galvanic deposit antimony and tin 3 times take out the titanium matrix after the galvanic deposit, clean with distilled water flushing, after treating natural air drying, be placed in the retort furnace, adopt 2 ℃/min of temperature programming to be heated to 550 ℃ of rear oxidation roastings 6 hours.The various performances of the titanium-based titanium dioxide nanotube stannic oxide electrode that makes are close with case study on implementation 1, and its reinforcing life reaches 64h, and the oxygen evolution potential under acidity, neutrality and alkaline condition is respectively 2.15V, 2.05V and 1.55V.
Embodiment 4
Adopt the titanium-based titanium dioxide nanotube stannic oxide electrode (TiO of preparation in the case study on implementation 1,2 and 3
2-NTs/SnO
2-Sb) and the titanium base stannic oxide electrode (Ti/SnO of traditional technology preparation
2-Sb) the electrocatalysis degradation effect to Cyclotrimethylene trinitramine (RDX) compares.
Compound concentration is each 100mL of RDX simulated wastewater of 20mg/L, and each adds 50mM Na
2SO
4As ionogen, respectively with TiO
2-NTs/SnO
2-Sb and Ti/SnO
2Electrode is as anode, and stainless steel is as negative electrode, and current density is 50mA/cm
2, the electrocatalysis degradation property of two kinds of electrode pair RDX of comparison under identical electrolytic condition.Draw: the TiO in the case study on implementation 1,2 and 3
2-NTs/SnO
2The degradation property of-Sb electrode pair RDX obviously is better than the Ti/SnO of traditional technology preparation
2Electrode, behind the electrolysis 3h, the clearance of RDX is respectively 95%, 96.1% and 96.8%, and the clearance of TOC is respectively 75.2%, 76.1% and 77.3%.And Ti/SnO
2The clearance of electrode pair RDX is 83.2%, and the clearance of TOC only is 58.6%.The TiO of preparation is described
2-NTs/SnO
2-Sb electrode electro catalytic activity is higher, is used for electrolysis treatment waste water, and its energy consumption will obviously reduce.
Claims (5)
1. the preparation method of a titanium-based titanium dioxide nanotube stannic oxide electrode is characterized in that adopting anodic oxidation, galvanic deposit and thermal oxidation method to make titanium-based titanium dioxide nanotube stannic oxide electrode, specifically may further comprise the steps:
The first step: adopt anonizing on the titanium matrix, to prepare titania nanotube:
Titanium plate surface is polished smooth, clean up the back as anode, with stainless steel as negative electrode, the control volts DS, in Potassium monofluoride, hydrogen fluoride and vitriolic electrolytic solution, carry out anodic oxidation, the titanium matrix after the anodic oxidation is taken out, rinse well, treat air-dry post-heating roasting, make titanium-based titanium dioxide nanotube;
Second step: adopt galvanic deposit and thermal oxidation method on titanium-based titanium dioxide nanotube, to prepare the tindioxide coating:
To prepare the titanium matrix of titania nanotube as negative electrode, with stainless steel as anode, constant current density, galvanic deposit antimony, galvanic deposit tin in tin tetrachloride and vitriolic mixing solutions then in the mixing solutions of butter of antimony and citric acid earlier, by this step, repeat galvanic deposit antimony and tin, the titanium matrix after the galvanic deposit is taken out, rinse well, treat air-dry post-heating roasting, make titanium-based titanium dioxide nanotube stannic oxide electrode.
2. preparation method according to claim 1, it is characterized in that: the volts DS of control described in the first step is 20～25V, anodizing time is 40～70min, and electrolytic solution is 0.07～0.08mol/L Potassium monofluoride, 0.07～0.08mol/L hydrogen fluoride and 0.95～1.05mol/L vitriolic mixing solutions.
3. preparation method according to claim 1 is characterized in that: the temperature that adds thermal bake-out described in the first step is 500～550 ℃, and temperature rise rate is 1～2 ℃/min, roasting 3～5 hours.
4. preparation method according to claim 1 is characterized in that: constant current density is 2～4mA/cm described in second step
2The composition of the mixing solutions of butter of antimony and citric acid is 0.01～0.015mol/L butter of antimony and 0.05～0.1mol/L citric acid; The time of galvanic deposit antimony is 0.5～1min; The composition of tin tetrachloride and vitriolic mixing solutions is 0.1～0.2mol/L tin tetrachloride and 0.05～0.1mol/L sulfuric acid; The time of galvanic deposit tin is 25～40min; The number of times that repeats galvanic deposit antimony and tin is 1～3 time.
5. preparation method according to claim 1 is characterized in that: the temperature that adds thermal bake-out described in second step is 500～550 ℃, and temperature rise rate is 1～5 ℃/min, roasting 4～6 hours.
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Inventor after: Han Weiqing Inventor after: Wei Kajia Inventor after: Chen Yong Inventor after: Wang Lianjun Inventor after: Hong Lei Inventor after: Xue Hongmin Inventor after: Sun Xiuyun Inventor after: Li Jiansheng Inventor after: Liu Xiaodong Inventor before: Han Weiqing Inventor before: Chen Yong Inventor before: Wang Lianjun Inventor before: Hong Lei Inventor before: Xue Hongmin Inventor before: Sun Xiuyun Inventor before: Li Jiansheng Inventor before: Liu Xiaodong |