CN102173449A - Method for preparing nanometer lead dioxide electrode - Google Patents
Method for preparing nanometer lead dioxide electrode Download PDFInfo
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- CN102173449A CN102173449A CN 201110008379 CN201110008379A CN102173449A CN 102173449 A CN102173449 A CN 102173449A CN 201110008379 CN201110008379 CN 201110008379 CN 201110008379 A CN201110008379 A CN 201110008379A CN 102173449 A CN102173449 A CN 102173449A
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Abstract
The invention relates to a method for preparing a nanometer lead dioxide electrode, which comprises the following steps of: firstly, preparing a titanium dioxide nano tube array substrate; secondly, preparing lead dioxide electrodeposition solution; and finally, performing electrodeposition on the titanium dioxide nano tube array substrate to prepare the nanometer lead dioxide electrode. The method has the advantage that: compared with those of the ordinary titanium-base lead dioxide electrode obtained by direct-current deposition, the electro-catalytic activity of the nanometer lead dioxide electrode is improved greatly, and the service life of the nanometer lead dioxide electrode is prolonged greatly. By the method, a new concept is provided for the study of electrodes for water treatment, the study space is broadened, and the technology and the existing doping technology are combined to develop better electrodes; and by the method, the electro-catalytic activity of organic pollutants in oxidized waste water is high, a preparation process is simple, the cost is low, the cost for electrochemical water treatment can be reduced, and economic and social benefits are excellent.
Description
Technical field
The invention belongs to water technology and electrochemical field, relate to the preparation method of nanometer titanium dioxide lead electrode and the application in treatment of Organic Wastewater.
Background technology
Increasing organic wastewater with difficult degradation thereby has proposed challenge for traditional biological treatment, because unlike other compounds in the waste water, these compositions have limited biological degradation or biological utilisation.In order to reach more and more stricter wastewater discharge standard, must seek other treatment technologies.In recent years, emerged in large numbers various new technologies on the Industrial Wastewater Treatment of organic pollutant containing.In the field of waste water treatment of difficult for biological degradation, electrochemical oxidation is considered to a kind of up-and-coming method, and has caused a lot of scholars' research interest.It has that environment compatibility is good, small accommodation area and superpower advantages such as oxidation capacity.
But, than the biologic treating technique of cheapness, electrochemical oxidation technology has tangible mortal wound: the expense height.Be mainly reflected in two aspects: the high and working cost height of the preparation cost of anode material.The exploitation of anode material has been played crucial effects to the cost that reduces electrochemical oxidation technology.The researchist has developed anode material miscellaneous in decades at this, in the hope of improving oxidation capacity and current efficiency, comprises graphite, platinum, iridium dioxide, ruthenium dioxide, tindioxide, plumbic oxide and boron-doped diamond electrode.When using platinum electrode, most electric current can consume in the process that generates oxygen, causes current efficiency low.Iridium dioxide and the organic oxidation susceptibility of ruthenium dioxide electrode pair are on the weak side again.Current research shows, boron-doped diamond electrode can be under the situation that holding current efficient does not significantly reduce the permineralization organic pollutant.But suitable complexity of the preparation technology of kind electrode and cost height are especially for large-area production.Graphite Electrodes is very cheap but their current efficiency is very low, and to be that its overpotential for oxygen evolution is very low cause for this.Stannic oxide electrode does not have this defect, and its overpotential for oxygen evolution is much higher, but it has another obvious defects again: work-ing life is too short.Therefore, a kind of not only strong but also cheap electrode of necessary redevelopment to organic oxidation capacity.Lead dioxide electrode is a kind of possible selection.It has possessed the high oxygen separated overpotential, can produce the characteristics of great amount of hydroxy group free radical and good conductivity.Comparability is in boron-doped diamond electrode, and the catalytic oxidation ability of lead dioxide electrode has just disliked lower, then also needs further to improve its oxidation capacity if will promote on industrial application.In order to address this problem, many documents about the lead dioxide electrode modification have been arranged up to now, mainly the mode by element doping realizes.The unit that is used in the lead dioxide electrode doping vario-property have bismuth, cobalt, cerium, iron, fluorine, PTFE (ptfe emulsion) ... this modification mode lays particular emphasis on and changes electrode active surface layer moiety.In fact, the performance of electrode not only with the active coating moiety, and much relations are arranged with the pattern of electrode surface.
Summary of the invention
The object of the present invention is to provide and a kind ofly have high catalytic activity and than nanometer titanium dioxide lead electrode of long life and preparation method thereof.
To achieve these goals, the present invention is by the following technical solutions:
Present most modes that improve the lead dioxide electrode performances are the various elements that mix, and the present invention has attempted a kind of new mode: also obtain the nanometer titanium dioxide lead electrode with the method for pulse electrodeposition by changing electrode matrix.Its electro catalytic activity of electrode and work-ing life with this method preparation are all improved largely than the common ti-supported lead dioxide electric pole that uses dc electrodeposition to obtain.The electrode that successfully is used for water treatment for research of the present invention provides new approaches, has widened the research space, and exploitation better electrode in the future also can combine present technique and already present doping techniques.
Thinking of the present invention is to seek a kind of new method that improves the lead dioxide electrode electrocatalytic oxidation property from the angle that changes the electrode surface pattern.Most lead dioxide electrodes are the method preparations with galvanic deposit, and it is the most common with metal titanium to be used for the matrix of galvanic deposit.It is this that to prepare ti-supported lead dioxide electric pole by dc electrodeposition on the titanium matrix be a kind of very traditional method.The present invention will change the trial of matrix.Orthotropic high-sequential Nano tube array of titanium dioxide has the specific surface area more much bigger than titanium matrix, can be used as the new mold base of preparation lead dioxide electrode.Nano tube array of titanium dioxide can obtain by the titania based body of anode in fluorine-containing ionogen, and the nanotube that grows can keep more securely attached on the matrix.The nanostructure of nano-tube array has very large surface-to-volume ratio, the exceptional space that this inside that can belong to hollow structure provides.Find no at present bibliographical information directly on Nano tube array of titanium dioxide the load plumbic oxide obtain the nano-electrode of polymolecularity active coating.In case the metal oxide active coating can enter into the inside of titania nanotube, it just can be issued to nano level and high dispersing in the restriction of nanotube.But it is very difficult using traditional dc electrodeposition that plumbic oxide is entered in the titania nanotube, because the surface tension of nanotube is very big.Adopt impulse electrodeposition technology to realize among the present invention.
A kind of preparation method of nanometer titanium dioxide lead electrode comprises step:
(1) preparation Nano tube array of titanium dioxide matrix;
(2) preparation plumbic oxide electrodeposit liquid;
(3) prepared by electrodeposition nanometer titanium dioxide lead electrode on the Nano tube array of titanium dioxide matrix.
The preparation method of described Nano tube array of titanium dioxide matrix comprises step:
(a) at first the titanium sheet is carried out pre-treatment: the titanium sheet of well cutting (thickness 1.0mm, purity 99.5%) carries out oil removal treatment then successively with No. 100, No. 400 and No. 800 sand paper mechanical grinding; Acid cleaning process can be handled 60-90min or 1: 1 and handles 10-15min down for hydrochloric acid 75-85 ℃ with little the boiling of 8%-10% oxalic acid, and distilled water is cleaned the back and dried up with rare gas element such as nitrogen, argon gas etc.;
(b) anodizing: the titanium sheet that pre-treatment is good as anode, platinum as negative electrode, anodizing in fluorine-containing system;
(c) processing of removal fluorion: the anodizing time one arrives, and take out the titanium sheet and clean with a large amount of distilled water immediately; Put it into then and soak 6h-12h in the methyl alcohol;
(d) anneal: unbodied Nano tube array of titanium dioxide places tube furnace, and logical nitrogen in the stove is with 2-4 ℃ of min
-1Temperature rise rate be heated to 450-550 ℃ and keep 1-2h.
The ionogen of described fluorine-containing system is a tart, fills a prescription to be 1.0-1.8wt% hydrofluoric acid/glycol ether, and perhaps this fluorine-containing system is a neutral, fills a prescription to containing 1: 1 glycerol-aqueous solution of 0.25-0.29M Neutral ammonium fluoride.
The anodizing voltage that the fluorine-containing ionogen of described acidity is applied is at 60-70V, anodizing time 8-12h, and temperature is a room temperature.
The anodizing voltage that the fluorine-containing ionogen of described neutrality need apply is 30-40V, anodizing time 6-10h, and temperature is a room temperature.
Described degreaser comprises following component and content thereof:
Sodium hydroxide 20-30g L
-1
Yellow soda ash 25-35g L
-1
Sodium metasilicate or Starso 3-5g L
-1
The use temperature of described degreaser is 80-90 ℃, and be 10-20min heat-up time.
Described oil removing mode is Solvent degreasing or heat alkali liquid oil removing.
Described Solvent degreasing is with organic solvent supersound process 10-20min in ultrasonic tank;
Described organic solvent is selected from acetone, Virahol or methyl alcohol.
Contain 0.1～0.3M HNO in the described plumbic oxide electrodeposit liquid
3, 0.4-0.625M Pb (NO
3)
2With 0.015～0.045MNaF.
Described on the Nano tube array of titanium dioxide matrix prepared by electrodeposition nanometer titanium dioxide lead electrode may further comprise the steps:
(a) earlier with the Nano tube array of titanium dioxide matrix for preparing in the step 1 in 0.8-1.2M (NH
4)
2SO
4In the solution-1.6 to-1.4V (reference electrode the is Ag/AgCl) voltage electroreduction 3～8s;
(b) make up a three-electrode system: the Nano tube array of titanium dioxide matrix with above-mentioned reduction is an anode, and stereotype is a negative electrode, and silver/silver chloride is a reference electrode;
(c) carry out pulse electrodeposition in the electrodeposit liquid of in described step (2), being prepared.
Each recurrence interval of described galvanic deposit will be divided into three sections the working hour: t
1=0.2s, t
2=0.05s and t
e=2s; T wherein
1And t
2The voltage that this two time periods apply is respectively E
1Be 4.5 to 5.5V and E
2Be-0.6 to-0.4V, t
eThe voltage E that applies in time period
eBe 0V; The total time of described galvanic deposit is 55-95min.
As the E that applies 5.0V
1The time, the Pb in the solution
2+The oxidized generation of ion PbO
2Be deposited on the matrix.This voltage is if cross low then difficult deposition plumbic oxide to matrix, too highly then can deposit inhomogeneously, contact angle is very big and grain-size is big.Apply the E of a relative much shorter of time length then
2(-0.5V) can be played the effect to the barrier-layer capacity discharge.If lacked the electrode that this link or time length longly all can occur depositing inhomogeneously, grain-size is big and electrode life is less long.Owing to passed through t
1The oxidation of time period, precipitation, the lead of electrode surface and near solution is by mass consumption, if continuous oxide deposition then the surface evenness of the electrode that makes can be not so good, electrode life is also not all right, because the lead in this case in the main body solution is to be diffused into electrode surface one by one.Therefore, electrodeposition technology of the present invention is at the latter end t in cycle
eDo not apply voltage in the=2s, allow the lead in the solution at a distance fully be diffused near the electrode surface if having time and uniform distribution, for the oxide deposition of next cycle ready.Galvanic deposit total time just can obtain the nanometer titanium dioxide lead electrode behind 55-95min.The active coating deposition of too short then electrode of the time of galvanic deposit is not enough, and long meeting causes the deposition transition, has destroyed the nanostructure of electrode surface, all may cause the electro catalytic activity of electrode to reduce.
The preparation method of common lead dioxide electrode is titanium sheet rather than the Nano tube array of titanium dioxide that matrix uses with the difference of nanometer titanium dioxide lead electrode, and the preparation method of other each steps is identical.
Can see from field emission scanning electron microscope figure (accompanying drawing 2), the Nano tube array of titanium dioxide of growth in situ by marshalling, evenly, periodically extraordinary cylindrical tube is formed.These pipes all extend on the titanium sheet matrix always, and mean inside diameter is about 220nm, and the interstice coverage between the nanometer tube and tube is at 100-300nm.Than the titanium sheet, the Nano tube array of titanium dioxide of this high-sequential has much bigger specific surface area.The inside and outside wall of nanotube all in the load plumbic oxide nanoparticle, the success of pulse electrodeposition method has been described.The pattern of nanotube still remains intact after galvanic deposit, the not blocked or covering sealing of upper end open.Their opening and gap in galvanic deposit become about 90nm after the plumbic oxide, can become micromolecular passage.
X ray diffracting spectrum (accompanying drawing 3) has shown that the main crystalline form of Nano tube array of titanium dioxide matrix is anatase octahedrite (locating for 25.5 °).But, this diffraction peak in load just covered after the plumbic oxide.The plumbous main crystalline form of nanometer titanium dioxide is β-plumbic oxide.Matrix Central Plains belongs to the diffraction peak of metal titanium is covered by the diffraction peak of β-plumbic oxide basically entirely, and is not difficult to find that the latter's diffraction peak is very wide.Existing bibliographical information utilizes the particle of the epitaxial that its particle size of nanometer crystal film that the pulse electrodeposition method obtains obtains than direct current galvanostatic deposition little many.The average particle size particle size of nanometer titanium dioxide lead electrode utilizes Scherrer formula (formula 1) to calculate:
D
(hkl)=κ λ/(β cos θ) (formula 1)
Wherein κ is a shape-dependent constant, and λ is the wavelength (Cu target, K alpha-ray) of X ray, and β is a peak width at half height, and θ is a diffraction angle.The grain-size that calculates is 16.7nm.Littler grain-size has bigger specific surface area, is indicating that the nanometer titanium dioxide lead electrode has more powerful catalytic oxidation ability, will be confirmed in this degradation experiment below.In addition, little grain-size may be improved the corrosion resistance of anode of lead dioxide because surface tissue consolidation more, between crystal grain and the matrix and crystal grain combine closelyr with intergranule, be expected to electrode life improve, this will be confirmed in the accelerated aging experiment.
The accelerated aging experiment is carried out in two electrode systems, makes the work electrode with the electrode for preparing, and platinum electrode is made negative electrode.Ionogen is the 3M sulphuric acid soln, current density 1A cm
-2The accelerated aging of nanometer titanium dioxide lead electrode is about 1.5 times (accompanying drawings 4) of common lead dioxide electrode.Giving between oxide film and the matrix as its unique surface tissue of Nano tube array of titanium dioxide of matrix provides better bonding force, and the result just shows as the prolongation of accelerated aging.Electrode life (SL) under the general current density (i) is with extreme current density (i
a) under accelerated aging between the conversion relation formula as follows:
Wherein the value scope from 1.4 to 2.0 of n, get mean value 1.7 substitutions and calculate.The size of supposing general current density is 15mA cm
-2, the nanometer titanium dioxide lead electrode that calculates so general current density and the work-ing life under the strong acidic condition can be near 3 years in size.
Electrochemical impedance spectroscopy is that a kind of effectively instrument is used for checking the contact that may exist between electrode structure feature and the chemical property.Solution, oxide film and between them the resistance on the interface all can use typical equivalent circuit figure to obtain.R in the accompanying drawing 5
sBe solution resistance, R
CtIt is charge-transfer resistance on the oxide film.C and R
wBe respectively electric double layer capacitance and Wo Baige impedance.The diameter of semicircle is represented the ohmmic drop in the electrochemical impedance spectroscopy.Nanometer titanium dioxide lead electrode ohm in metabisulfite solution is reduced to 82 Ω, and that common plumbic oxide is 177 Ω.Major cause has 4 points: when (i) preparation is as the Nano tube array of titanium dioxide of matrix is annealed in nitrogen atmosphere, and than annealed technology in air atmosphere usually, the electroconductibility of resulting nano-tube array is better.(ii) Nano tube array of titanium dioxide can strengthen electroconductibility under negative bias, by at 1M (NH
4)
2SO
4Middle reduction of following short period of time of negative bias has improved the electroconductibility of nanotube.(iii) the tridimensional network that has of the nano-tube array of high-sequential can make electric charge be delivered to the solution from the direction of matrix along the nanometer pipe range.Therefore can reduce the current loss that electric charge jumps and causes between the nanoparticle border.(iv) metal nanoparticle is deposited on the percolating network that can form conduction on the nano tube structure and has strengthened electronic conduction ability.
This plumbic oxide nano-electrode can be used for handling organic wastewater with difficult degradation thereby.
Described difficult for biological degradation organic pollutant comprises: the azoic dyestuff in the derivative of phenol, phenol, toluene, the dyeing waste water, the polyvinyl alcohol in the textile waste etc.
The Pollutant levels scope is 100-1000mg L in the described organic sewage
-1
Contain a large amount of polyvinyl alcohol in the typical desized wastewater of weaving and printing and dyeing industry discharging as cementing agent.The chemical oxygen demand (COD) concentration of this class waste water is up to every liter of milligram up to ten thousand, and polyvinyl alcohol is wherein maximum contributor.To contain 2g L
-1The 1000mg L of sodium sulfate
-1Polyvinyl alcohol water solution is the degraded object, investigates the electrocatalytic oxidation property difference of two kinds of electrodes.Polyvinyl alcohol is much higher on than common lead dioxide electrode at the clearance on the nanometer titanium dioxide lead electrode, this because the former to produce the avtive spot of hydroxyl radical free radical more, the output of hydroxyl radical free radical is also just higher.And the oxidation capacity of hydroxyl radical free radical is very strong, and it is oxygenant (OH, the E о (OH/H that occurring in nature is only second to fluorine
2O)=2.80Vvs.SHE).In addition, the specific surface area of nanometer titanium dioxide lead electrode is very big, and its tubular structure can make electric charge along the transmission of pipe range direction, and the electric charge that has reduced between the plumbic oxide nanoparticle border jumps, and helps for charge transfer.
The invention has the advantages that:
Also obtain the nanometer titanium dioxide lead electrode with the method for pulse electrodeposition by changing electrode matrix, its electro catalytic activity and work-ing life are all improved largely than the common ti-supported lead dioxide electric pole that uses dc electrodeposition to obtain.The electrode that successfully is used for water treatment for research of the present invention provides new approaches, has widened the research space, and exploitation better electrode in the future also can combine present technique and already present doping techniques.
Plumbic oxide size of particles in the active coating of the nanometer titanium dioxide lead electrode of the present invention preparation be about 10-30nm and high dispersing on the nanotube matrix about caliber 200nm.
The electro catalytic activity height of organic pollutant in the oxidized waste water, preparation technology is simple, and cost is lower, can reduce the cost of electrochemical method water treatment, and economic and social benefit is good.
Description of drawings
Fig. 1 is the synoptic diagram of the pulse electrodeposition vs. electrodeposition time of the embodiment of the invention.
Fig. 2 is the field emission scanning electron microscope photo of the embodiment of the invention, among the figure: (a) Nano tube array of titanium dioxide matrix, (b) nanometer titanium dioxide lead electrode.
Fig. 3 is the X ray diffracting spectrum of the embodiment of the invention, among the figure: (a) Nano tube array of titanium dioxide matrix, (b) nanometer titanium dioxide lead electrode.
Fig. 4 is the nanometer titanium dioxide lead electrode of the embodiment of the invention and the accelerated aging experiment synoptic diagram of common ti-supported lead dioxide electric pole.
Fig. 5 is that the nanometer titanium dioxide lead electrode of the embodiment of the invention 2 and common ti-supported lead dioxide electric pole are at 0.02mol L
-1The electrochemical impedance spectroscopy of testing in the sodium sulfate, voltage are open circuit voltage, range of frequency 0.01-10
5Hz.
Fig. 6 contains 2g L for the embodiment of the invention 2 with nanometer titanium dioxide lead electrode and the degraded of common ti-supported lead dioxide electric pole catalytic oxidation
-1The 1g L of sodium sulfate
-1The Pollutant levels of polyvinyl alcohol water solution change.Current density is stabilized in 15mAcm
-2Constant.
Embodiment
The present invention is further illustrated below in conjunction with the accompanying drawing illustrated embodiment.
Embodiment 1.
The common lead dioxide electrode of prepared by electrodeposition on the titanium matrix:
Cutting titanium plate becomes the titanium sheet of 2cm * 5cm, successively with No. 100, No. 400 and No. 800 sand paperings to bright and do not have a cut.Use acetone and each 15min of pure water ultrasonic cleaning respectively, little boiling handled 1h in 10% oxalic acid then.With distilled water thoroughly clean the back in three-electrode system with it as working electrode, stereotype is a negative electrode, silver/silver chloride is that reference carries out pulse electrodeposition.The pulse in each cycle is divided into three sections, and each section time span and the voltage that applies in the time period are respectively t
0=2s, E
e=0V; t
i=0.2s, E
1=5.0V; t
2=0.05s, E
2=-0.5V.
Prepared by electrodeposition nanometer titanium dioxide lead electrode on the Nano tube array of titanium dioxide matrix:
(1) preparation Nano tube array of titanium dioxide matrix
Cutting titanium plate becomes the titanium sheet of 2cm * 5cm, successively with No. 100, No. 400 and No. 800 sand paperings to bright and do not have a cut.Use acetone and each 15min of pure water ultrasonic cleaning respectively, little boiling handled 1h in 10% oxalic acid then.Thoroughly cleaning the back with distilled water dries up with nitrogen.
Anodizing in the 1.5wt%HF/ glycol ether, voltage constant are at 60V, and the time is 10h;
Anodizing end back is fully cleaned, is put it into then in the methyl alcohol with distilled water and soaked 6 hours;
Take out and put in the tube furnace 1h that anneals under nitrogen atmosphere, 550 ℃ of conditions, temperature rise rate is 2 ℃ of min
-1
(2) preparation plumbic oxide electrodeposit liquid
Preparation contains 0.2M HNO
3, 0.625M Pb (NO
3)
2Deposit fluid with 0.045M NaF.
(3) electrodip process prepares the nanometer titanium dioxide lead electrode
The Nano tube array of titanium dioxide matrix that step (1) is prepared is in 1M (NH earlier
4)
2SO
4In under-1.5V (reference electrode is Ag/AgCl) voltage electroreduction 6s,
Method by pulse electrodeposition prepares the nanometer titanium dioxide lead electrode then: making up a three-electrode system, is working electrode with the Nano tube array of titanium dioxide in three-electrode system, and stereotype is a negative electrode, and silver/silver chloride is that reference carries out pulse electrodeposition.The pulse in each cycle is divided into three sections, and each section time span and the voltage that applies in the time period are respectively t
0=2s, E
e=0V; t
1=0.2s, E
1=5.0V; t
2=0.05s, E
2=-0.5V (accompanying drawing 1).
Just obtained the nanometer titanium dioxide lead electrode behind the galvanic deposit 70min.
Investigate the accelerated aging of two kinds of electrodes:
The accelerated aging test is carried out in two electrode systems, uses nanometer titanium dioxide lead electrode or common lead dioxide electrode as working electrode, and platinum electrode is made counter electrode, ionogen sulphuric acid soln, concentration 3M, 35 ± 1 ℃ of water-bath temperature controls.Current density 1A cm
-2Every certain hour of crossing is noted the groove pressure at interval.After common lead dioxide electrode is modified into the nanometer titanium dioxide lead electrode, 1050 minute (accompanying drawings 4) 710 minute increasing later on of its accelerated aging before improve.
Embodiment 2.:
The method of the common lead dioxide electrode of prepared by electrodeposition is identical with embodiment 1 on the titanium matrix.
Prepared by electrodeposition nanometer titanium dioxide lead electrode on the Nano tube array of titanium dioxide matrix:
(1) successively with the titanium sheet of No. 100, No. 400 and No. 800 sand papering well cuttings (20mm * 50mm * 1mm), until titanium plate surface send evenly, tangible metalluster, the field color that is not polished to can be different with what be polished to, it is complete to make every effort to polish.With 20g L-1 sodium hydroxide, 35g L-1 yellow soda ash and 5g L-1 water glass preparation degreaser, the titanium sheet that polishing is good is put into 90 ℃ of following oil removing 10min of degreaser, and distilled water carries out pickling after cleaning again: putting into water volume ratio is 1: 1 80 ℃ of hydrochloric acid heating 10min down.
Be made into hydrofluoric acid/diethylene glycol solution of 1.4% as the required ionogen of anodizing with the hydrofluoric acid of 80.3g glycol ether and 2.8g 40%.As anode, platinized platinum applies the direct current of 70V as negative electrode, anodizing 8h with the titanium sheet handled.
Take out the back and thoroughly clean electrode surface, dry up surface-moisture, put into methyl alcohol and soak 8h with nitrogen with distilled water.
Put in the retort furnace with 2 ℃ of min
-1Temperature rise rate kept 1 hour after being warming up to 550 ℃, naturally cool to room temperature, obtain the Nano tube array of titanium dioxide matrix.
(2) preparation plumbic oxide electrodeposit liquid
Preparation contains 0.1M HNO
3, 0.5M Pb (NO
3)
2The aqueous solution with 0.02MNaF.
(3) electrodip process prepares the nanometer titanium dioxide lead electrode
The Nano tube array of titanium dioxide matrix that previous step is prepared is as working electrode earlier, and platinum filament is as counter electrode, and silver/silver chloride is as reference electrode, at 1M (NH
4)
2SO
4The aqueous solution in, electroreduction 5s under the-1.5V voltage.
Change over to then and contain 0.1M HNO
3, 0.5M Pb (NO
3)
2, in the aqueous solution of 0.02M NaF, changing counter electrode into stereotype, other electrodes are constant, carry out pulse electrodeposition.The pulse in each cycle is divided into three sections: stop, oxidation and reduction.The voltage that applies in each section time span and time period is identical with embodiment 1.Electrodeposition time always is about 80min.
Measure the electrochemical impedance characteristic and the degradation capability of nanometer titanium dioxide lead electrode and common lead dioxide electrode:
The electrochemical impedance test is to carry out under 20 ± 2 ℃ of conditions, and the used ionogen of system is a 0.02M sodium sulfate, and the voltage that applies is open circuit voltage, and range of frequency is from 0.01Hz to 10
5Hz.The ohmmic drop that can see the nanometer titanium dioxide lead electrode from accompanying drawing 5 only is 46.3% of common lead dioxide electrode.The energy consumption of good conductivity is lower.
Adopt nanometer titanium dioxide lead electrode or common lead dioxide electrode as polyvinyl alcohol (accompanying drawing 6) in the anode catalytic oxidation water, area is 16cm under the liquid
2, negative electrode is the stainless steel of area under the identical liquid, interelectrode distance stuck-at-.5cm, and constant current density is at 15mA cm
-2The starting point concentration of polyvinyl alcohol water solution is 1g L
-1, supporting electrolyte is 2g L
-1Sodium sulfate, liquor capacity 100ml uses magnetic stirrer.The reaction 2.5h after the clearance of polyvinyl alcohol on the nanometer titanium dioxide lead electrode be 87%, the first kernel response rate constant is 0.81, and under the equal conditions on the common lead dioxide electrode clearance of polyvinyl alcohol be 75%, the first kernel response rate constant is 0.55.The former than the latter's catalytic oxidation ability height 47%.
Embodiment 3.
The preparation method of two kinds of electrodes is identical with embodiment 2.Different is in the anodizing process of preparation nanometer titanium dioxide lead electrode, used fluorine-containing ionogen and anodizing condition.Fluorine-containing ionogen is used the ammonium fluoride solution of the 0.27M for preparing in 1: 1 the Glycerine-Aqueous Solution of volume ratio instead.The anodizing condition correspondingly becomes: as anode, platinized platinum applies the direct current of 35V as negative electrode with pretreated titanium sheet, anodizing 6 hours.
The test of wettability is carried out on the contact angle instrument, and the liquid that drips to the survey electrode surface is distilled water.We find contact angle size by more different electrode surface water droplets, because the wettability of two kinds of lead dioxide electrode matrixes differs greatly, so nanometer titanium dioxide lead 41 ° can be more much smaller than 76 ° of common lead dioxide electrode to the contact angle of water.The wetting ability that the former is described is better, and contains hydroxyl in its structural unit of this polymkeric substance of polyvinyl alcohol, and quantity is more, has polarity, so the former can be much better to its absorption property.And good hydrophilicity also helps the formation of hydroxyl radical free radical, also just may obtain higher catalytic oxidation ability.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (10)
1. the preparation method of a nanometer titanium dioxide lead electrode is characterized in that: comprise step:
(1) preparation Nano tube array of titanium dioxide matrix;
(2) preparation plumbic oxide electrodeposit liquid;
(3) prepared by electrodeposition nanometer titanium dioxide lead electrode on the Nano tube array of titanium dioxide matrix.
2. method according to claim 1 is characterized in that: the preparation method of described Nano tube array of titanium dioxide matrix comprises step:
(a) at first the titanium sheet is carried out pre-treatment: the titanium sheet of well cutting is successively used No. 100, No. 400 and No. 800 sand paper mechanical grinding, carries out oil removal treatment then; Acid cleaning process can be handled 60-90min or 1: 1 and handles 10-15min down for hydrochloric acid 75-85 ℃ with little the boiling of 8%-10% oxalic acid, and distilled water is cleaned the back and dried up with rare gas element such as nitrogen, argon gas etc.;
(b) anodizing: the titanium sheet that pre-treatment is good as anode, platinum as negative electrode, anodizing in fluorine-containing system;
(c) processing of removal fluorion: the anodizing time one arrives, and takes out the titanium sheet and cleans with a large amount of distilled water immediately; Put it into then and soak 6h-12h in the methyl alcohol;
(d) anneal: unbodied Nano tube array of titanium dioxide places tube furnace, and logical nitrogen in the stove is with 2-4 ℃ of min
-1Temperature rise rate be heated to 450-550 ℃ and keep 1-2h.
3. method according to claim 2, it is characterized in that: the ionogen of described fluorine-containing system is a tart, prescription is 1.0-1.8wt% hydrofluoric acid/glycol ether, and perhaps this fluorine-containing system is a neutral, fills a prescription to containing 1: 1 glycerol-aqueous solution of 0.25-0.29M Neutral ammonium fluoride.
4. method according to claim 2 is characterized in that: the anodizing voltage that the fluorine-containing ionogen of described acidity is applied is at 60-70V, anodizing time 8-12h, and temperature is a room temperature; Or the anodizing voltage that the fluorine-containing ionogen of described neutrality need apply is 30-40V, anodizing time 6-10h, and temperature is a room temperature.
5. method according to claim 2 is characterized in that: described degreaser comprises following component and content thereof:
Sodium hydroxide 20-30g L
-1
Yellow soda ash 25-35g L
-1
Sodium metasilicate or Starso 3-5g L
-1
6. method according to claim 2 is characterized in that: the use temperature of described degreaser is 80-90 ℃, and be 10-20min heat-up time; Or described oil removing mode is Solvent degreasing or heat alkali liquid oil removing.
7. method according to claim 6 is characterized in that: described Solvent degreasing is for handling 10-20min in organic solvent for ultrasonic in ultrasonic tank; Described organic solvent is selected from acetone, Virahol or methyl alcohol.
8. method according to claim 1 is characterized in that: contain 0.1-0.3MHNO in the described plumbic oxide electrodeposit liquid
3, 0.4-0.625M Pb (NO
3)
2With 0.015-0.045M NaF.
9. method according to claim 1 is characterized in that: described on the Nano tube array of titanium dioxide matrix prepared by electrodeposition nanometer titanium dioxide lead electrode may further comprise the steps:
(a) earlier with the Nano tube array of titanium dioxide matrix for preparing in the step 1 in 0.8-1.2M (NH
4)
2SO
4In the solution-1.6 to-1.4V (reference electrode the is Ag/AgCl) voltage electroreduction 3～8s;
(b) make up a three-electrode system: the Nano tube array of titanium dioxide matrix with above-mentioned reduction is an anode, and stereotype is a negative electrode, and silver/silver chloride is a reference electrode;
(c) carry out pulse electrodeposition in the electrodeposit liquid of in described step (2), being prepared.
10. method according to claim 9 is characterized in that: each recurrence interval of described galvanic deposit will be divided into three sections the working hour: t
1=0.2s, t
2=0.05s and t
e=2s; T wherein
1And t
2The voltage that this two time periods apply is respectively E
1Be 4.5 to 5.5V and E
2Be-0.6 to-0.4V, t
eThe voltage E that applies in time period
eBe 0V; Or the total time of described galvanic deposit is 55-95min.
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