CN106277216A - Indium doping ti-supported lead dioxide electric pole and its preparation method and application - Google Patents
Indium doping ti-supported lead dioxide electric pole and its preparation method and application Download PDFInfo
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- CN106277216A CN106277216A CN201610644677.8A CN201610644677A CN106277216A CN 106277216 A CN106277216 A CN 106277216A CN 201610644677 A CN201610644677 A CN 201610644677A CN 106277216 A CN106277216 A CN 106277216A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention provides a kind of In doped titanium-base lead dioxide electrode and preparation method thereof, and the application in the degradation treatment of the pharmacy waste water of high concentration difficult for biological degradation, described electrode, with titanium as matrix, is coated with tin-antimony oxide bottom, α PbO from Titanium base the most successively2Intermediate layer, the fluorine-containing β PbO of doping In2Active layer；Lead dioxide electrode is modified by the present invention by electrode structural designs and surface doping, makes electrode surface PbO by the addition of main group metal In and high polymer fluororesin2Microgranule dispersion more closely uniformly, significantly improves structure and the character of electrode surface, makes PbO2Internal stress between active layer and Titanium base reduces, and therefore, the electrode prepared has higher oxygen evolution potential and electrochemical stability, effectively extends electrode life；This electrode catalyst performance is good, and service life is long, practical, it is easy to preparation, has wide market prospect.
Description
(1) technical field
The present invention relates to a kind of main group metal indium (In) doped titanium-base lead dioxide electrode and its preparation method and application, should
Electrode has high catalytic performance, can be applicable to the electrochemical degradation of difficult for biological degradation pharmacy waste water, belongs to electrochemical techniques and ring
Protect technical field of waste water processing.
(2) background technology
Along with the high speed development of society, in industrial wastewater, the quantity of biodegradable organic compounds grows with each passing day with kind, this
A little poisonous and hazardous high concentration hard-degraded organic waste waters propose challenge greatly to traditional biological treatment.The most more allusion quotation
Type is pharmacy waste water, and such waste component is complicated, be difficult to degrade, and is the difficult point that processes of domestic and international water and focus.Therefore, in order to
Reach the strictest wastewater discharge standard, need badly and to develop that new good reliability, effect be high, the sewage disposal skill of low cost
Art.In recent years, in the treatment of Organic Wastewater containing difficult for biological degradation, electrochemical oxidation process does not consumes because it has or seldom consumes
Chemical reagent, the advantages such as secondary pollution, simple to operate, oxidability is strong, reaction condition is gentle, floor space is little are not brought to form
For study hotspot.And the key of electrochemical water treatment technology and core are anode material performance.Anode material is except being prepared as
Should the cheapest outside, it is necessary to possess features such as conducting electricity very well, oxygen evolution potential is high and catalysis activity is good, to be applied to give up
The electrochemicial oxidation of organic pollutants.
Research worker has been developed for anode material miscellaneous in decades at this, including platinum, graphite, titanium dioxide
Ruthenium, iridium dioxide, tin ash, Lead oxide brown and boron-doped diamond electrode.Platinum electrode is expensive, and oxygen evolution potential is low, greatly
The current drain of part is producing the process of oxygen, causes current efficiency low；Graphite electrode is cheap, but analysis oxygen electricity equally
Position is low；Ruthenic oxide and iridium dioxide electrode are the most on the weak side to organic oxidation susceptibility；Stannic oxide electrode has one significantly
Defect: electrode life is the shortest；The complicated process of preparation of boron-doped diamond electrode, cost is high, especially to large-area production
For.By contrast, lead dioxide electrode has good conductivity, low cost, preparation method is simple, oxygen evolution potential is high, energy of oxidation
The advantages such as power is strong, are a kind of electrode materials being generally considered application prospect.Lead dioxide electrode is generally at pottery, Titanium
And prepared by electro-deposition on other metal material matrixes.Owing to titanium has good anti-corrosive properties, cheap, thermal conductance
Rate is little, surface is prone to physics and the advantage such as chemical process process, is to prepare the preferable matrix material of lead dioxide electrode.At present,
Ti-supported lead dioxide electric pole has been successfully applied to the aspects such as inorganic and organic compound electrolysis production, environment pollution control.But
It is during the use of ti-supported lead dioxide electric pole, there is PbO2Active layer is combined with matrix not closely, PbO2Active layer planted agent
The problems such as power is big, easy peeling, have impact on catalysis activity and the stability of electrode.To this end, some research work are to titanio titanium dioxide
Lead electrode improves further.A kind of method is to introduce stannum, antimony intermediate layer between Titanium base and Lead oxide brown active layer as mistake
Cross layer, the internal stress between Lead oxide brown active layer and Titanium base can be greatly reduced.Another kind of method is in electroplate liquid
Adding NaF, politef (PTFE), prepare Lead dioxide anode modifiedby fluorine resin, it is little that prepared electrode has internal stress, adhesion
The advantages such as good, length electrode life.
Research about lead dioxide electrode shows, although these lead dioxide electrodes improved have stronger stability
And electrocatalysis, but still need to improve electrode catalyst activity and current efficiency further.
(3) summary of the invention
To PbO2Electrode carries out structure design and surface doping is modified, utilizes simple electro-deposition method, by plating
Adulterate in liquid Main Group Metal Elements In, can realize the transformation of electrode surface structures, while improving electrocatalysis characteristic, further
Improve its oxygen evolution potential and stability, a kind of novel electrode with superior electrocatalysis characteristic will certainly be obtained, for organic dirt
Research and the application of dye thing, the particularly electrocatalytic oxidation method of difficult for biological degradation pollutant have great significance.
Therefore, it is an object of the invention to provide and a kind of there is the long-life Pharmaceutical Wastewater Treatment of can be used for of oxygen evolution potential
Novel I n doped titanium-base lead dioxide electrode and preparation method and application.
For achieving the above object, this discovery the technical scheme is that
A kind of In doped titanium-base lead dioxide electrode, described electrode, with titanium as matrix, depends on from Titanium base from the inside to the outside
Secondary it is coated with tin-antimony oxide bottom, α-PbO2Intermediate layer, the fluorine-containing β-PbO of doping In2Active layer.
The preparation method of In doped titanium-base lead dioxide electrode of the present invention includes: carried out at roughening on Titanium base surface
Tin-antimony oxide bottom is prepared by thermal decomposition method, then through basic plating α-PbO in reason, Titanium base surface after roughening2In
Interbed, after through the fluorine-containing β-PbO of acid composite plating doping In2Active layer, i.e. prepares described In doped titanium-base titanium dioxide
Lead electrode.
In the present invention, described Titanium base can be titanium sheet, titanium net or titanium pipe.
Further, the preparation method of described In doped titanium-base lead dioxide electrode is carried out as follows:
(1) Titanium base pretreatment (surface coarsening process):
Titanium base sand for surface paper is polished, alkali liquor oil removing, after cleaning with water, is placed in sulfuric acid solution, at 50～70 DEG C
Soak etching 10～60min, after cleaning with water, then be placed in oxalic acid solution, at 70～90 DEG C, soak etching 2～5h, use water
Pretreated Titanium base is obtained after cleaning；
(2) thermal decomposition method prepares tin-antimony oxide bottom:
A: tin-antimony oxide sol solution is evenly applied to the pretreated Titanium base surface that step (1) obtains, puts
In tubular type Muffle furnace, under 130 DEG C of constant temperatures, dry 20min, then be warming up to 515 DEG C of thermal decomposition process 15min, cooling, complete
Become an operation cycle；
B: the operation cycle 8 described in repetition A～15 times, the most uniformly tin coating sb oxide sol solution, baking
After Gan at 500～550 DEG C thermal decomposition process 60～80min, prepare after cooling and be coated with the electrode of tin-antimony oxide bottom；
Described tin-antimony oxide sol solution is obtained by the material mixed preparing of following weight portion: SbCl35～10 parts,
SnCl4·5H2O 95～110 parts, ethylene glycol 268～290 parts, citric acid 180～200 parts；
Preferably, described tin-antimony oxide sol solution is obtained by the material mixed preparing of following weight portion: SbCl3
7.53 parts, SnCl4·5H2O 104.16 parts, ethylene glycol 280 parts, citric acid 192.14 parts；
(3) basic plating α-PbO2Intermediate layer:
With step (2) prepare the electrode being coated with tin-antimony oxide bottom as anode, titanium sheet is negative electrode, is placed in basic plating
Constant current electro-deposition α-PbO in liquid2Intermediate layer, operating condition is: temperature 50～65 DEG C (preferably 60 DEG C), electric current density 3～
5mA/cm2(preferably 5mA/cm2), sedimentation time 0.5～2h (preferably 1h)；Prepare and be coated with tin-antimony oxide bottom and α-PbO2In
The electrode of interbed；
Described alkaline Bath by forming preparation: PbO 0.1mol/L, NaOH 4～5mol/L as follows, solvent is water；
(4) the fluorine-containing β-PbO of acid composite plating doping In2Active layer:
It is coated with tin-antimony oxide bottom and α-PbO with what step (3) prepared2The electrode in intermediate layer is anode, and titanium sheet is
Negative electrode, is placed in the fluorine-containing β-PbO of constant current doping In in acidic Bath2Surface activity layer, operating condition is: temperature
50～90 DEG C of (preferably 80 DEG C), electric current densities 10～80mA/cm2(preferably 50mA/cm2), sedimentation time 1.5～2h (preferably 2h),
Prepare described In doped titanium-base lead dioxide electrode；
Described acidic Bath is prepared as follows:
First by following composition preparation mixed liquor: Pb (NO3)2 0.3mol/L、KF·2H2O 0.01～0.02mol/L, In
(NO3)30.0015～0.012mol/L, 60wt% ptfe emulsion 4～5mL/L, solvent is water；The mixing that will prepare
Liquid nitre acid for adjusting pH value is 1.5～2.0, obtains described acidic Bath；
Preferably, described acidic Bath is prepared as follows:
First by following composition preparation mixed liquor: Pb (NO3)2 0.3mol/L、KF·2H2O 0.01mol/L、In(NO3)30.003mol/L, 60wt% ptfe emulsion 4mL/L, solvent is water；The mixed liquor nitre acid for adjusting pH value that will prepare
It is 1.8, obtains described acidic Bath；
Described 60wt% ptfe emulsion can be the most commercially available.
Further, in preparation method of the present invention, described step (1) operates by the following method:
By Titanium base sand papering so that it is after surface presents silvery white metallic luster, use deionized water rinsing；To beat again
The Titanium base that milled is cleaned is placed in 20wt%～50wt% (preferably 40wt%) NaOH solution, soaks 30～60min (preferably
30min) oil removing, uses deionized water rinsing；It is subsequently placed in 20wt%～30wt% (preferably 20wt%) H2SO4In solution, 50～
Soak etching 10～60min (preferably 20min) under 70 DEG C (preferably 60 DEG C), use deionized water rinsing；Then be placed in 15wt%～
In 20wt% (preferably 15wt%) oxalic acid solution, under 70～90 DEG C (preferably 80 DEG C), soak etching 2～5h (preferably 3h), finally
Remove oxalic acid and the titanium oxalate of Titanium base surface remaining with a large amount of distilled water flushings, obtain pretreated Titanium base；Gained warp
The Titanium base gray pitted skin of pretreatment, is stored in 0.5wt%～1.5wt% oxalic acid solution, standby.
In step (1), described Titanium base sand for surface paper is polished, and the most first with 120 mesh coarse sandpaper polishings, then uses successively
600 mesh, the fine sandpaper of 1200 mesh are polishing to Titanium base surface and present silvery white metallic luster.
In described step (2), tin-antimony oxide sol solution is evenly applied to pretreated Titanium base surface, described
Coating method can be brush, spray or soak after be centrifuged, this is to well known to a person skilled in the art technology.
In doped titanium-base lead dioxide electrode of the present invention catalysis activity is strong, and oxygen evolution potential is high, and stability is good, makes
Use the life-span long, can be applicable to the degradation treatment of the pharmacy waste water of high concentration difficult for biological degradation；The method of described application is: with this
Bright In doped titanium-base lead dioxide electrode is anode, and titanium plate is negative electrode, uses constant-current electrolysis pharmacy waste water.
The present invention utilizes major element In to β-PbO2Electrodeposited coating surface texture is transformed, with tradition lead dioxide electrode
Compared to the prior art, beneficial effects of the present invention is embodied in:
(1) lead dioxide electrode is modified by the present invention by electrode structural designs and surface doping: containing fluorine tree
Adulterate in the lead nitrate solution of fat high molecular polymer a certain amount of main group metal In, uses constant current electrochemical deposition method,
Preparation Ti/Sn-SbOx/α-PbO2/In-β-PbO2Electrode.Electrode table is made by the addition of main group metal In and high polymer fluororesin
Face PbO2Microgranule dispersion more closely uniformly, significantly improves structure and the character of electrode surface, makes PbO2Active layer and titanio
Internal stress between body reduces, and therefore, the electrode prepared has higher oxygen evolution potential and electrochemical stability, effectively prolongs
Grow electrode life.
(2) present invention doping by main group metal In, not only increases the catalysis activity of electrode, also extends the electrode longevity
Life.By the improvement of surface texture, PbO2Crystal particle diameter reduces, and adds the specific surface area of electrode, thus effectively increases electricity
The avtive spot on surface, pole, compared with undoped p lead dioxide electrode, the catalysis activity of modified electrode significantly improves.
(3) what the present invention prepared has both oxygen evolution potential, the Lead oxide brown electricity of high service life and high catalytic activity
Pole has efficient removal effect for the pharmacy waste water of difficult for biological degradation.
(4) this electrode catalyst performance is good, and service life is long, practical, it is easy to preparation, has wide market prospect.
(4) accompanying drawing explanation
Fig. 1 a is the In doping PbO of embodiment 1 preparation2SEM figure (amplifying 100 times) of electrode；
Fig. 1 b is the In doping PbO of embodiment 1 preparation2SEM figure (amplifying 500 times) of electrode；
Fig. 2 is the In doping PbO of embodiment 1 preparation2The PbO of undoped p In of electrode and comparative example 1 preparation2The XRD of electrode
Figure, wherein, (a) figure is the PbO of undoped p In2Electrode, (b) figure is In doping PbO2Electrode；
Fig. 3 is the In doping PbO of embodiment 1 preparation2The PbO of undoped p In of electrode and comparative example 1 preparation2The pole of electrode
Change curve chart；
Fig. 4 a is In doping PbO in embodiment 22Electrode and the PbO of undoped p In2The electrode fall to 500mg/L aspirin
Solve effect (clearance of aspirin) comparison diagram；
Fig. 4 b is In doping PbO in embodiment 22Electrode and the PbO of undoped p In2The electrode fall to 500mg/L aspirin
Solve effect (clearance of COD and current efficiency) comparison diagram.
(5) detailed description of the invention
Below by specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited in
This.
Used below to 60wt% ptfe emulsion reach Science and Technology Ltd. purchased from Hangzhou is omnipotent.
Embodiment 1
The preparation of In doped titanium-base lead dioxide electrode:
(1) Titanium base pretreatment: be 0.1mm, a size of 14cm by thickness2The pure titanium sheet of (7cm × 2cm) is successively with 120
Sand papering to the Titanium base of mesh, 600 mesh and 1200 mesh presents silvery white metallic luster, with deionized water rinsing；By polishing well
The titanium sheet cleaned is placed in the NaOH solution that mass fraction is 40% immersion 30min, uses deionized water rinsing；Then at 60 DEG C of bars
Under part, in H2SO4Solution (mass fraction is 20%) soaks 20min, takes out and be washed with deionized water only；Last at oxalic acid solution
In (mass fraction is 15%), under the conditions of 80 DEG C, soak etching 3h, remove Titanium base surface remaining with substantial amounts of distilled water flushing
Oxalic acid and titanium oxalate, obtain the Titanium base of pretreatment.Titanium base gray pitted skin after pretreatment, being placed on mass fraction is
The oxalic acid of 1% saves backup.
(2) thermal decomposition method prepares tin-antimony oxide bottom: tin-antimony oxide sol solution is evenly applied to step (1) pre-
The Titanium base surface processed, is then placed in tubular type Muffle furnace, dries 20 minutes, then by electric furnace liter under 130 DEG C of constant temperatures
Warm to 515 DEG C, thermal decomposition process 15 minutes at this temperature, cooling, complete a circulation.Repeat above-mentioned operation 9 times, obtain
Electrode slice brushing stannum antimony sol gel solution again, thermal decomposition process 60 minutes under 515 DEG C of high temperature again after drying, after cooling
I.e. obtain being coated with the electrode of tin-antimony oxide bottom.
Wherein, tin-antimony oxide sol solution is by forming preparation as follows: 7.53g SbCl3, 104.16g SnCl4·5H2O,
251mL ethylene glycol, 192.14g citric acid.
(3) basic plating α-PbO2Layer: with step (2) prepare the electrode being coated with tin-antimony oxide bottom as anode, etc.
The titanium sheet of area is negative electrode, is placed in constant current electro-deposition α-PbO in alkaline Bath2Intermediate layer, during electro-deposition, electrode spacing is
6cm, temperature is 60 DEG C, and electric current density is 5mA cm-2, sedimentation time is 1 hour, prepare be coated with tin-antimony oxide bottom and α-
PbO2The electrode in intermediate layer.
Wherein, described alkaline Bath is 0.1mol L by forming preparation: PbO as follows-1, NaOH is 4.5mol L-1, molten
Agent is water.
(4) the fluorine-containing β-PbO of acid composite plating doping In2Active layer: be coated with the oxidation of stannum antimony with prepare in step (3)
Thing bottom and α-PbO2The electrode in intermediate layer is anode, and the titanium sheet of homalographic is negative electrode, and in acidic Bath, constant current electricity sinks
Fluorine-containing β-the PbO of long-pending doping In2Surface activity layer, during electro-deposition, electrode spacing is 6cm, and temperature is 80 DEG C, and electric current density is
50mA cm-2, sedimentation time is 2 hours, prepares product I n doped titanium-base lead dioxide electrode.
Wherein, described acidic Bath is prepared as follows: first by following composition preparation mixed liquor: Pb (NO3)2For
0.3mol L-1, KF 2H2O is 0.01mol L-1, In (NO3)3For 0.003mol L-1, the politef of mass fraction 60%
Emulsion (PTFE) 4mL L-1, solvent is water, obtains mixed liquor；The mixed liquor HNO that will prepare3PH value is adjusted to 1.8, to obtain final product
Acidic Bath.
Comparative example 1
The ti-supported lead dioxide electric pole of undoped p In
Experimental procedure and condition with embodiment 1, except that, in step (4), acidic Bath does not adds In
(NO3)3, acidic Bath is prepared as follows: first prepare mixed liquor by following composition: Pb (NO3)2For 0.3mol L-1,
KF·2H2O is 0.01mol L-1, ptfe emulsion (PTFE) the 4mL L of mass fraction 60%-1, solvent is water, is mixed
Close liquid；The mixed liquor HNO that will prepare3PH value is adjusted to 1.8, obtains acidic Bath.Other steps and operation are homogeneous
With, prepare the ti-supported lead dioxide electric pole of undoped p In.
The In doping PbO that embodiment 1 prepares2Electrode, is characterized by field emission scanning electron microscope (SEM), sees
Fig. 1 a, 1b.Knowable to Fig. 1 a, 1b, the electrode surface of preparation presents obvious tetrahedron solid crystalline structure, and crystal grain distribution causes
Close uniformly, grain diameter is about 35 μm.Fig. 2 is In doping PbO2Electrode and the PbO of undoped p In2The XRD figure of electrode, contrast β-
PbO2Standard card can find, the In doping lead dioxide electrode surface activity layer of preparation is all β-PbO2Tetragonal body crystal knot
Degree of crystallinity and crystallization whereabouts slightly difference after structure, and doping In.By oikocryst face β (200) of doped electrode and undoped p electrode half
Peak width is brought in Scherrer formula calculating and understands, after doping In, and PbO2Crystal particle diameter reduces, and contributes to increasing the work of electrode surface
Property site, thus improve electrode catalysis activity.It addition, the incorporation of In does not introduce new thing phase, illustrate that In may be with displacement
Or the mode of calking enters β-PbO2Lattice, forms solid solution, makes diffraction maximum change.
Three-electrode electro Chemical is used to measure system, in CHI660c electrochemical workstation, respectively with the In doping two of preparation
The lead dioxide electrode of lead dioxide electrode and undoped p In is working electrode (10mm × 10mm), and platinum electrode is auxiliary electrode
(10mm × 15mm), saturated calomel electrode (SCE) is reference electrode, at 0.5mol L-1H2SO4Solution measures the pole of electrode
Change curve, see Fig. 3.The oxygen evolution potential of the lead dioxide electrode recording In doping is about 2.08V, higher than the titanium dioxide of undoped p In
Lead electrode (1.99V).During electrocatalytic oxidation, oxygen evolution reaction is a main competition side reaction, can cause electric energy wave
Take and reduce electric current effective rate of utilization, and higher oxygen evolution potential can effectively suppress to analyse the probability of happening of oxygen side reaction, therefore, high
Oxygen evolution potential is conducive to improving current efficiency.
Embodiment 2
Utilize the dioxy of undoped p In of In doping lead dioxide electrode that embodiment 1 prepares and comparative example 1 preparation
Change lead electrode electrocatalytic oxidation degraded aspirin.
Lead oxide brown electricity with undoped p In prepared by In doping lead dioxide electrode or the comparative example 1 of embodiment 1 preparation
Extremely anode, titanium sheet is negative electrode, and electrode area is 14cm2, electrochemical degradation uses constant-current electrolysis.Constant current density is
50mA cm-2, electrode spacing is 4cm.With containing 0.1mol L-1Electrolyte Na2SO4500mg L-1Aspirin is useless for simulation
Water, reaction volume is 250mL, under the effect of magnetic agitation, carries out waste water process, and when degradation reaction proceeds to difference
It is sampled quarter analyzing.The situation of change of the concentration of aspirin high performance liquid chromatograph (HPLC) measures the most in the same time, always
The situation of change of organic carbon content (TOC) TOC analyzer measures, and experimental result is shown in Fig. 4 a, 4b.Fig. 4 a, 4b are In doping
PbO2Electrode and undoped p PbO2Electrode is to 500mg L-1The degradation effect comparison diagram of aspirin, Fig. 4 a is going of aspirin
Except rate, Fig. 4 b is the clearance of TOC.
From Fig. 4 a, 4b, after In doping lead dioxide electrode electrochemical degradation aspirin 2.5 hours, Ah Si
The clearance of woods reaches 76.45%, and the clearance of COD also reaches 52.09%, and when using the lead dioxide electrode of undoped p In,
The clearance of aspirin is 64.07%, and the clearance of COD is 43.53%, and the removal effect of In doping lead dioxide electrode is described
Fruit is significantly better than undoped p electrode.Further, by current efficiency during two electrode degrading aspirin of contrast, it appeared that
In degradation process, the current efficiency of In doping lead dioxide electrode is above the current efficiency of the lead dioxide electrode of undoped p In.
Additionally, In doped electrode is also degraded by we, the safety of aspirin detects.Pass through plasma chromatography
Issuable toxic metal ions in electrolysis is detected by instrument (ICP-MS), such as Pb, Ti, Sn, Sb and In etc., ties from experiment
Fruit understands, and does not detect that the existence of Ti, Sn, Sb and In ion, the concentration of Pb ion are in the waste water solution after process
0.005mg L-1, far below the discharge standard (≤0.1mg L of lead ion-1).Therefore, the lead dioxide electrode that In adulterates is utilized
During degraded aspirin, there is the highest safety.
Claims (10)
1. an In doped titanium-base lead dioxide electrode, it is characterised in that described electrode with titanium as matrix, from Titanium base by
Interior to being coated with tin-antimony oxide bottom, α-PbO successively outward2Intermediate layer, the fluorine-containing β-PbO of doping In2Active layer.
2. In doped titanium-base lead dioxide electrode as claimed in claim 1, it is characterised in that described Titanium base be titanium sheet,
Titanium net or titanium pipe.
3. the preparation method of In doped titanium-base lead dioxide electrode as claimed in claim 1, it is characterised in that described preparation
Method includes:
(1) Titanium base surface is carried out roughening treatment, obtain the Titanium base of roughened process；
(2) tin-antimony oxide bottom is prepared by thermal decomposition method in the Titanium base surface in the roughened process of step (1) gained, obtains
It is coated with the electrode of tin-antimony oxide bottom；
(3) step (2) gained is coated with the electrode of tin-antimony oxide bottom through basic plating α-PbO2Intermediate layer, obtains being coated with stannum antimony
Oxide underlayer and α-PbO2The electrode in intermediate layer；
(4) step (3) gained is coated with tin-antimony oxide bottom and α-PbO2The electrode in intermediate layer is through acid composite plating doping In's
Fluorine-containing β-PbO2Active layer, i.e. prepares described In doped titanium-base lead dioxide electrode.
4. preparation method as claimed in claim 3, it is characterised in that the operational approach of described step (1) is:
Titanium base sand for surface paper is polished, alkali liquor oil removing, after cleaning with water, is placed in sulfuric acid solution, soaks at 50～70 DEG C
Etching 10～60min, after cleaning with water, then is placed in oxalic acid solution, soaks etching 2～5h, clean with water at 70～90 DEG C
After obtain the Titanium base of roughened process.
5. preparation method as claimed in claim 4, it is characterised in that the operational approach of described step (1) is:
By Titanium base sand papering so that it is after surface presents silvery white metallic luster, use deionized water rinsing；Again by polishing well
The Titanium base cleaned is placed in 20wt%～50wt%NaOH solution, soaks 30～60min oil removings, uses deionized water rinsing；So
It is placed on 20wt%～30wt%H2SO4In solution, at 50～70 DEG C, soak etching 10～60min, use deionized water rinsing；
Then it is placed in 15wt%～20wt% oxalic acid solution, at 70～90 DEG C, soaks etching 2～5h, finally remove with distilled water flushing
Remove oxalic acid and the titanium oxalate of Titanium base surface remaining, obtain the Titanium base of roughened process, be stored in 0.5wt%～1.5wt%
In oxalic acid solution, standby.
6. preparation method as claimed in claim 3, it is characterised in that the operational approach of described step (2) is:
A: tin-antimony oxide sol solution is evenly applied to the Titanium base surface of the roughened process that step (1) obtains, is placed in
In tubular type Muffle furnace, under 130 DEG C of constant temperatures, dry 20min, then be warming up to 515 DEG C of thermal decomposition process 15min, cooling, complete
One operation cycle；
B: the operation cycle 8 described in repetition A～15 times, the most uniform tin coating sb oxide sol solution, after drying
Thermal decomposition process 60～80min at 500～550 DEG C, prepare the electrode being coated with tin-antimony oxide bottom after cooling；
Described tin-antimony oxide sol solution is obtained by the material mixed preparing of following weight portion: SbCl35～10 parts, SnCl4·
5H2O 95～110 parts, ethylene glycol 268～290 parts, citric acid 180～200 parts.
7. preparation method as claimed in claim 3, it is characterised in that the operational approach of described step (3) is:
With step (2) prepare the electrode being coated with tin-antimony oxide bottom as anode, titanium sheet is negative electrode, is placed in alkaline Bath
Constant current electro-deposition α-PbO2Intermediate layer, operating condition is: temperature 50～65 DEG C, electric current density 3～5mA/cm2, sedimentation time
0.5～2h；Prepare and be coated with tin-antimony oxide bottom and α-PbO2The electrode in intermediate layer；
Described alkaline Bath by forming preparation: PbO 0.1mol/L, NaOH 4～5mol/L as follows, solvent is water.
8. preparation method as claimed in claim 3, it is characterised in that the operational approach of described step (4) is:
It is coated with tin-antimony oxide bottom and α-PbO with what step (3) prepared2The electrode in intermediate layer is anode, and titanium sheet is negative electrode, puts
Fluorine-containing β-the PbO of constant current doping In in acidic Bath2Surface activity layer, operating condition is: temperature 50～90
DEG C, electric current density 10～80mA/cm2, sedimentation time 1.5～2h, prepare described In doped titanium-base lead dioxide electrode；
Described acidic Bath is prepared as follows and is obtained:
First by following composition preparation mixed liquor: Pb (NO3)2 0.3mol/L、KF·2H2O 0.01～0.02mol/L, In (NO3)30.0015～0.012mol/L, 60wt% ptfe emulsion 4～5mL/L, solvent is water；The mixed liquor prepared is used
Nitre acid for adjusting pH value is 1.5～2.0, obtains described acidic Bath.
9. In doped titanium-base lead dioxide electrode as claimed in claim 1 is in the fall of the pharmacy waste water of high concentration difficult for biological degradation
Application in solution process.
Apply the most as claimed in claim 9, it is characterised in that with described In doped titanium-base lead dioxide electrode as anode,
Titanium plate is negative electrode, uses constant-current electrolysis pharmacy waste water.
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