CN105621541A - Transition-metal doped lead dioxide electrode for wastewater treatment as well as preparation method and application thereof - Google Patents

Transition-metal doped lead dioxide electrode for wastewater treatment as well as preparation method and application thereof Download PDF

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CN105621541A
CN105621541A CN201511030011.5A CN201511030011A CN105621541A CN 105621541 A CN105621541 A CN 105621541A CN 201511030011 A CN201511030011 A CN 201511030011A CN 105621541 A CN105621541 A CN 105621541A
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electrode
lead dioxide
pbo
metal doped
tin
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戴启洲
陈建孟
夏伊静
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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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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    • C23C18/1216—Metal oxides
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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    • C23C28/324—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal matrix material layer comprising a mixture of at least two metals or metal phases or a metal-matrix material with hard embedded particles, e.g. WC-Me
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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
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics

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Abstract

The invention discloses a transition-metal doped lead dioxide electrode for wastewater treatment and a preparation method thereof. The transition-metal doped lead dioxide electrode is prepared through the steps of performing thermal decomposition on a titanium material which serves as a substrate so as to prepare a tin-antimony oxide underlayer, then electroplating an alpha-PbO2 interlayer by use of an alkaline solution and finally preparing a transition-metal doped fluorine-containing beta-PbO2 surface active layer by use of acidic composite electroplating bath. The transition-metal doped lead dioxide electrode prepared by the method has the characteristics of low price, high oxygen evolution potential, high catalytic activity, long service life and the like; the electrode can be used for realizing effective removal of organic pollutants in wastewater through an electrochemical oxidation method, is simple to operate and convenient to manage and has wide social and economic benefits.

Description

A kind of transient metal doped lead dioxide electrode for wastewater treatment and its preparation method and application
(1) technical field
The present invention relates to a kind of transient metal doped lead dioxide electrode for wastewater treatment and preparation method thereof, belong to materials chemistry, Environmental electrochemistry and technical field of waste water processing.
(2) background technology
Electrocatalytic oxidation be the hydroxyl radical free radical produced by anode as primary oxidizers, utilize its strong oxidizing property that the organic pollution of difficult degradation is gradually degraded as organic molecule intermediate, last mineralising is the process of carbon dioxide and water. Electro-catalytic oxidation technology has and does not consume or seldom consume chemical reagent, do not bring the advantages such as secondary pollution, simple to operate, oxidability is strong, reaction condition is gentle, floor space is little, it is efficient environmental contaminants degradation technique, is referred to as environmentally-friendly technique simultaneously. And the key of electro-catalytic oxidation technology and core are in that electrode material performance, in electrochemical reactor, electrode material is to realize electrochemical reaction and improve the key factor of current efficiency, and the difference of electrode material can make the change on the electrochemical reaction rates generation order of magnitude. Therefore, electrode material except preparation cost should cheap as far as possible except, it is necessary to possess conduct electricity very well, oxygen evolution potential is high, stability is good and catalysis activity high.
Research worker has been developed for anode electrode material miscellaneous in decades at this, including graphite electrode, noble metal electrode, boron-doped diamond (BDD) electrode and metal oxide electrode such as RuO2��IrO2��PbO2��SnO2��TiO2Deng. Graphite electrode is the electrode material used the earliest in electrochemical treatment of wastewater method, cheap, but intensity difference, catalysis activity is low, it is impossible to effectively remove or reduce the toxicity of pollutant. The electrode such as precious metals pt, Au is expensive, oxygen evolution potential is low, most electric current all consumes in the process producing oxygen, and is very easily lost its electro catalytic activity by Substances Pollution such as sulfurous organic compound, intermediate oxidation product, CO, causes that current efficiency sharply declines. Boron-doped diamond electrode oxygen evolution potential is high, and catalytic performance is good, but its complicated process of preparation, cost is high, especially for large-area production. Metal oxide electrode has the status that it is special in electrochemical industry, the particularly appearance of DSA electrode (DimensionallyStableAnodes) since realizing industrialization, substantially increase stability and the electrolytic efficiency of electrode, bring a revolution for chlorine industry. By contrast, RuO2��IrO2This kind of metal oxide electrode is inefficient to the catalytic oxidation of organic pollution; TiO2Oxide material is the focus of Recent study, but is more suitable for the electrode material of photocatalytic-oxidation formed material or photochemical catalytic oxidation; Stannic oxide electrode then has an obvious defect: electrode life is too short. And lead dioxide electrode has the advantages such as catalytic performance is good, oxygen evolution potential is high, good conductivity, preparation method are simple, cheap, it it is a kind of electrode material being generally considered application prospect. Lead dioxide electrode is generally prepared by electro-deposition on pottery, Titanium and other metal material matrixes. Due to titanium there are good anti-corrosive properties, thermal conductivity is little, surface is prone to the advantage such as physics and chemical process process, is prepare the desirable matrix material of lead dioxide electrode.
At present, ti-supported lead dioxide electric pole has been successfully applied to the inorganic and aspect such as organic compound electrolysis production and environment pollution control. But in use, researcher finds Ti/PbO2Electrode activity needs further to be improved, and there is also PbO simultaneously2The problems such as active layer is poor with basal body binding force, active layer is unstable, electrode life is short. For this, ti-supported lead dioxide electric pole is improved by some research work further. A kind of method is to introduce stannum, antimony intermediate layer between Titanium base and Lead oxide brown active layer as transition, it is possible to be greatly reduced the internal stress between Lead oxide brown active layer and Titanium base. Another kind of method is to be mixed in electrode active surface layer by some external elements, its objective is to improve the microstructure of electrode electro catalytic activity layer, improves electrode active surface and improves stability. At present, rear-earth-doped electrode can produce many-sided impact, but whole world rare earth reserves are limited at present, and the research and development for rare earth substitute products are extremely urgent. The 4f track special relative to rare earth element, the d track of transition metal also has certain advantage. For this, it is proposed that by transient metal doped in the top layer of lead dioxide electrode, to improve catalysis activity and the service life of electrode.
(3) summary of the invention
The preparation method that it is an object of the invention to provide a kind of lead dioxide electrode for processing used water difficult to degradate, this electrode is the method utilizing electro-deposition, by transient metal doped in the top layer of titanio Lead dioxide anode modifiedby fluorine resin, the transient metal doped lead dioxide electrode cost height low, active, the life-span that prepare are long.
This discovery the technical scheme is that
A kind of transient metal doped lead dioxide electrode for wastewater treatment, described transient metal doped lead dioxide electrode is from inside to outside successively by tin-antimony oxide bottom on Titanium base of Titanium base, heat deposition, the ��-PbO that is electrodeposited on tin-antimony oxide bottom2Intermediate layer and be electrodeposited in ��-PbO2Fluorine-containing ��-the PbO of the containing transition metal on intermediate layer2Active layer forms; Described transition metal is the one or more kinds of combinations in manganese, ferrum, cobalt, nickel, yttrium or zinc, it is preferred to manganese, nickel, cobalt or zinc;
Described transient metal doped lead dioxide electrode is prepared by following methods: Titanium base surface is carried out roughening treatment, Titanium base surface after alligatoring prepares tin-antimony oxide bottom by thermal decomposition method, then through basic plating ��-PbO2Intermediate layer, after through the fluorine-containing ��-PbO of acid composite plating containing transition metal2Active layer, namely prepares described transient metal doped ti-supported lead dioxide electric pole;
Further, the preparation method of described transient metal doped lead dioxide electrode comprises the following steps:
(1) Titanium base pretreatment: Titanium base sand for surface paper polishing, alkali liquor oil removing, with water clean after, it is placed in sulfuric acid solution, etching 10��30min is soaked at 50��70 DEG C of temperature, after cleaning with water, it is placed in again in oxalic acid solution, soak etching 2��5 hours at 70��90 DEG C of temperature, after washing, obtain the Titanium base of pretreatment;
(2) thermal decomposition method prepares tin-antimony oxide bottom: A, be evenly applied to by tin-antimony oxide sol solution on the Titanium base surface of the pretreatment that step (1) obtains, dry 20��30 minutes under 110��130 DEG C of conditions, then thermally decompose 10��15 minutes at 500��550 DEG C of (preferably 515 DEG C) temperature;
After B, repetition A operate 8��15 times, the surface of the electrode slice obtained is uniform tin coating sb oxide sol solution again, at 110��130 DEG C, dry thermal decomposition 60��80 minutes at 20��30 minutes, 500��550 DEG C (preferably 515 DEG C) temperature, prepare the electrode being coated with tin-antimony oxide bottom;
Described tin-antimony oxide sol solution presses following proportions: 5��10gSbCl3, 95��110gSnCl4��5H2O, 240��260mL ethylene glycol, 180��200g citric acid;
Preferred described tin-antimony oxide sol solution presses following proportions: 7.53SbCl3, 104.16gSnCl4��5H2O, 251mL ethylene glycol, 192.14g citric acid;
(3) basic plating ��-PbO2Intermediate layer: being placed in as anode in alkaline Bath using the electrode being coated with tin-antimony oxide bottom that step (2) prepares, do negative electrode with titanium sheet, at temperature 50��65 DEG C (preferably 60 DEG C), electric current density is 3��5mA/cm2(preferred 5mAcm-2) galvanostatic conditions under electro-deposition ��-PbO2Intermediate layer, electroplating time 0.5��2 hour (preferably 1 hour), prepare and be coated with tin-antimony oxide bottom and ��-PbO2The electrode in intermediate layer; Described alkaline Bath is the sodium hydroxide solution dissolved with PbO;
(4) the fluorine-containing ��-PbO of acid composite plating containing transition metal2Active layer: what step (3) obtained is coated with tin-antimony oxide bottom and ��-PbO2The electrode in intermediate layer is placed in as anode in acidic Bath, does negative electrode with titanium sheet, and at temperature 50��90 DEG C (preferably 80 DEG C), electric current density is 10��80mA/cm2(preferred 50mAcm-2) galvanostatic conditions under the fluorine-containing ��-PbO of doping transition metal2Active layer, electroplating time 1.5��2h (preferred 2h), prepare described transient metal doped lead dioxide electrode; Described acidic Bath is by forming preparation as follows: Pb (NO3)2For 0.3molL-1, KF 2H2O is 0.01��0.02molL-1, transition metal nitrate is 0.0015��0.012molL-1, the ptfe emulsion 4��5mLL of mass fraction 60%-1, with nitric acid (concentration is generally 65��68wt%), pH value being adjusted to 1.5��2.0, solvent is water;
Described acidic Bath is preferably by forming preparation as follows: Pb (NO3)2For 0.3molL-1, KF 2H2O is 0.01molL-1, transition metal nitrate is 0.003��0.012molL-1, the ptfe emulsion 4mLL of mass fraction 60%-1, with nitric acid, pH value being adjusted to 1.8, solvent is water.
Titanium base of the present invention can be titanium sheet, titanium net or titanium pipe.
Step of the present invention (1) is operation by the following method preferably: Titanium base sand for surface paper is polishing to Titanium base surface and presents silvery white metallic luster, with deionized water rinsing; Good for the polishing Titanium base cleaned is placed in the NaOH solution that mass fraction is 20��50% (preferably 40%) and soaks 30��60min (preferred 30min), with deionized water rinsing; Then at the H that mass fraction is 20��30% (preferably 20%)2SO4Solution soaks 10��30min (preferred 20min), with deionized water rinsing at 50��70 DEG C of (preferably 60 DEG C) temperature; Last in the oxalic acid solution of 15��20% (preferably 15%) 80 DEG C micro-soak etching 2��5 hours (preferably 3 hours) when boiling, remove oxalic acid and the titanium oxalate of Titanium base surface remaining with substantial amounts of distilled water flushing, obtain the Titanium base of pretreatment; The Titanium base of pretreatment is placed in preserving in the oxalic acid solution of 0.5��1.5% (preferably 1%) stand-by.
Described Titanium base sand for surface paper is polished, and generally first with 120 order coarse sandpapers polishings, then is polishing to Titanium base surface with the fine sandpaper of 600 orders and 1200 orders successively and presents silvery white metallic luster.
In described step (2), tin-antimony oxide sol solution is evenly applied on the Titanium base surface of the pretreatment that step (1) obtains, coating therein can be method centrifugal after brushing, spray or soaking, and this is to well known to a person skilled in the art technology.
In described step (3), described alkaline Bath is by forming preparation as follows: PbO is 0.1molL-1, NaOH is 4��5molL-1(preferred 4.5molL-1), solvent is water.
In described step (4), described transition metal nitrate is the one or more kinds of combinations in manganese nitrate, ferric nitrate, cobalt nitrate, nickel nitrate, Yttrium trinitrate, zinc nitrate, it is preferred to nickel nitrate, zinc nitrate, cobalt nitrate or manganese nitrate.
In described step (3) and (4), during electro-deposition, generally with the titanium sheet of homalographic for negative electrode.
The transient metal doped lead dioxide electrode that the present invention prepares can be used for wastewater treatment, is particularly useful for processing used water difficult to degradate.
Further, transient metal doped lead dioxide electrode prepared by the present invention can be used for the organic wastewater of degradation treatment high-concentration hardly-degradable, such as the waste water containing aspirin, diclofenac sodium.
Further, the method of described application is: with transient metal doped lead dioxide electrode for anode, titanium plate is negative electrode, adopt the organic wastewater of constant current electrolysis degradation treatment high-concentration hardly-degradable, as containing one or more the pharmacy waste water in aspirin, penicillins, cephalosporins, Macrolide, sulfonamides;
Described constant current electrolysis, usual constant current density is 10��80mAcm-2(preferably 30��50mAcm-2), electrolysis time is 1��5 hour.
The present invention utilizes transition metal to ��-PbO2Electrodeposited coating surface texture is transformed, and with tradition lead dioxide electrode compared to the prior art, beneficial effects of the present invention is embodied in:
(1) the transient metal doped lead dioxide electrode prepared by, is followed successively by Titanium base, tin-antimony oxide bottom, ��-PbO from inside to outside2Intermediate layer, transient metal doped fluorine-containing ��-PbO2Surface activity layer
(2) lead dioxide electrode is modified by the present invention by electrode structural designs and surface doping. Adulterate a certain amount of transition metal nitrate in the lead nitrate solution containing fluororesin high molecular polymer, adopts constant current electrochemical deposition method, prepares transient metal doped lead dioxide electrode. Electrode surface PbO is made by the addition of transition metal and high polymer fluororesin2Microgranule dispersion more closely uniformly, is greatly reduced PbO2Internal stress between active layer and Titanium base, is conducive to extending electrode life.
(3) present invention doping by transition metal, not only extends electrode life, also improves the catalysis activity of electrode. PbO is made by adulterating2Crystal particle diameter reduces, and adds the specific surface area of electrode, thus effectively increasing the avtive spot of electrode surface, is conducive to the raising of catalysis activity.
(4) transient metal doped lead dioxide electrode degradable organic pollutant such as pharmacy waste water etc. prepared by the present invention, technique is simple, and removal effect is good, has wide market prospect.
The transient metal doped lead dioxide electrode that the inventive method prepares has the features such as cheap, oxygen evolution potential is high, active strong, the long service life of catalysis. Utilize transient metal doped lead dioxide electrode can realize effective removal of organic pollutants by electrochemical oxidation method, simple to operate, convenient management, there is Social and economic benef@widely.
(4) accompanying drawing explanation
Fig. 1 is the transiting metal nickel doping PbO of embodiment 1 preparation2The undoped p PbO of electrode and comparative example 1 preparation2The SEM figure of electrode, in Fig. 1, a figure is undoped p PbO2Electrode, the big figure in upper left of a figure amplifies 100 times, and the little figure in bottom right of a figure amplifies 5000 times; B figure is the lead dioxide electrode of transiting metal nickel doping, and the big figure in upper left of b figure amplifies 100 times, and the little figure in bottom right of b figure amplifies 5000 times.
Fig. 2 is transiting metal nickel doping PbO prepared by the inventive method2Electrode and undoped p PbO2The XRD figure of electrode, in Fig. 2, (a) figure is undoped p PbO2Electrode, (b) figure is transiting metal nickel doping PbO2Electrode.
Fig. 3 is transiting metal nickel doping PbO prepared by the inventive method2Electrode and undoped p PbO2The CV figure of electrode.
Fig. 4 is transiting metal nickel doping PbO prepared by the inventive method2Electrode and undoped p PbO2Electrode is to 500mgL-1The degradation effect comparison diagram of aspirin, in Fig. 4, a () figure is Aspirin concentrations and the ratio of initial concentration changes over curve chart, and (b) figure is the change curve that the ratio of COD and initial COD changes over curve chart and current efficiency GCE.
(5) detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the invention will be further elaborated, but the present invention is not limited to following embodiment.
Embodiment 1:
A kind of preparation method of transiting metal nickel doping lead dioxide electrode, described nickel doping lead dioxide electrode is with titanium sheet for matrix, titanium sheet is after the pretreatment such as polishing, alkali cleaning oil removing, acid etching technique, pretreated Titanium base prepares tin-antimony oxide bottom by brushing thermal decomposition method, then adopts electrodeposition process to plate ��-PbO successively in the electroplate liquid prepared2Fluorine-containing ��-the PbO of intermediate layer and a certain amount of nickel that adulterates2Active layer.
Specifically comprising the following steps that of described method
(1) Titanium base pretreatment: be 0.1mm by thickness, is of a size of 14cm2The pure titanium sheet of (2cm �� 7cm) is successively with 120#��600#With 1200#Sand papering so that deionized water rinsing is used after presenting silvery white metallic luster in surface; The NaOH solution adopting mass fraction to be 40% soaks 30min, taking-up deionized water rinsing; It is the H of 20% with mass fraction afterwards2SO4Solution soaks 20min under 60 DEG C of conditions, takes out and cleans; Finally under 80 DEG C of conditions, etch 3h with the oxalic acid solution that mass fraction is 15%, remove oxalic acid and the titanium oxalate of Titanium base surface remaining with substantial amounts of distilled water flushing, obtain the Titanium base of pretreatment; Pretreated Titanium base gray pitted skin, is placed in the oxalic acid that mass fraction is 1% and saves backup.
(2) thermal decomposition method prepares tin-antimony oxide bottom: tin-antimony oxide sol solution is uniformly coated on the Titanium base surface of step (1) pretreatment, dry 20 minutes under 130 DEG C of conditions, then in Muffle furnace, thermal decomposition process is carried out 15 minutes under 515 DEG C of conditions, cooling, completes a circulation. So repeat 9 times, the surface of the electrode slice obtained is uniform tin coating sb oxide sol solution again, dry 20 minutes under 130 DEG C of conditions, then in Muffle furnace, thermal decomposition process is carried out 60 minutes under 515 DEG C of conditions, naturally cool to room temperature, after cooling, namely obtain being coated with the electrode of tin-antimony oxide bottom. Tin-antimony oxide sol solution is by forming preparation as follows: 7.53SbCl3, 104.16gSnCl4��5H2O, 251mL ethylene glycol, 192.14g citric acid.
(3) basic plating ��-PbO2Intermediate layer: the electrode being coated with tin-antimony oxide bottom prepared with step (2) is for anode, and the pure titanium sheet of homalographic is negative electrode, is placed in alkaline Bath electro-deposition ��-PbO2Intermediate layer, electrode spacing is 6cm, and controlling bath temperature is 60 DEG C, and electric current density is 5mAcm-2, electroplating time is 1h, prepares and is coated with tin-antimony oxide bottom and ��-PbO2The electrode in intermediate layer; . Described alkaline Bath is by forming preparation as follows: PbO is 0.1molL-1, NaOH is 4.5molL-1, solvent is water.
(4) the fluorine-containing ��-PbO of acid composite plating containing transition metal nickel2Active layer: be coated with tin-antimony oxide bottom and ��-PbO with what prepare in step (3)2The electrode in intermediate layer is anode, and the pure titanium sheet of homalographic is negative electrode, the fluorine-containing ��-PbO of electric deposition nickel doping in acidic Bath2Surface activity layer, electrode spacing is 6cm, and controlling bath temperature is 80 DEG C, and electric current density is 50mAcm-2, electroplating time is 2h, prepares the lead dioxide electrode of transiting metal nickel doping. Described acidic Bath is by forming preparation as follows: Pb (NO3)2For 0.3molL-1, KF 2H2O is 0.01molL-1, Ni (NO3)2��6H2O is 0.003molL-1, fluoro-resin emulsion (PTFE) 4mLL of mass fraction 60%-1, with nitric acid (65wt%), pH value being adjusted to 1.8, solvent is water.
Comparative example 1
Unadulterated ti-supported lead dioxide electric pole
Experimental procedure and condition with embodiment 1, institute the difference is that, in step (4), acidic Bath does not add Ni (NO3)2, acidic Bath is by forming preparation as follows: Pb (NO3)2For 0.3molL-1, KF 2H2O is 0.01molL-1, fluoro-resin emulsion (PTFE) 4mLL of mass fraction 60%-1, with nitric acid (65wt%), pH value being adjusted to 1.8, solvent is water. Other steps and operation are all identical, prepare unadulterated ti-supported lead dioxide electric pole.
The lead dioxide electrode of the transiting metal nickel doping that embodiment 1 prepares and the undoped p PbO of comparative example 1 preparation2The surface topography of electrode is characterized by field emission scanning electron microscope (SEM), sees Fig. 1. In Fig. 1, a figure is undoped p PbO2Electrode, the big figure in upper left of a figure amplifies 100 times, and the little figure in bottom right of a figure amplifies 5000 times; B figure is the lead dioxide electrode of transiting metal nickel doping, and the big figure in upper left of b figure amplifies 100 times, and the little figure in bottom right of b figure amplifies 5000 times. Schemed by a of Fig. 1, b figure compare it can be seen that transiting metal nickel doping after, Lead oxide brown surface even compact more, by amplifying the SEM figure of 5000 times, we are it will be clear that undoped p electrode surface has many cracks, and these cracks can cause that the infiltration of oxygen forms TiO2, thus the internal stress greatly improved between surface activity layer and matrix, reduce electrode life, and after transiting metal nickel doping, the crack of electrode surface greatly reduce, and surface is very fine and close. Therefore, the crack problem of electrode surface can be solved well by the doping of transiting metal nickel, be conducive to improving the service life of electrode.
Fig. 2 is transiting metal nickel doping PbO prepared by the inventive method2Electrode and undoped p PbO2The XRD figure of electrode, in Fig. 2, in Fig. 2, (a) figure is undoped p PbO2Electrode, (b) figure is transiting metal nickel doping PbO2Electrode. As shown in Figure 2, the nickel doping lead dioxide electrode surface activity layer of preparation is all ��-PbO2Tetragonal body crystal structure, its crystallization whereabouts relatively undoped p electrode slightly difference. Oikocryst face �� (200) half-peak breadth of doped electrode and undoped p electrode is brought in Scherrer formula and calculates it can be seen that after a certain amount of nickel that adulterates, PbO2Crystal particle diameter reduces, and contributes to increasing the avtive spot of electrode surface, thus improving the catalysis activity of electrode. It addition, mixing of nickel does not introduce new thing phase, illustrate that nickel is likely in the way of displacement or calking and enters ��-PbO2Lattice, forms solid solution, makes diffraction maximum change.
Linear polarisation curves test condition is: the electrode of preparation is working electrode (10mm �� 10mm), and platinum electrode is auxiliary electrode (10mm �� 15mm), and saturated calomel electrode (SCE) is reference electrode, and electrolyte is 0.5molL-1H2SO4Solution, adopts CHI660c electrochemical workstation. Fig. 3 is transiting metal nickel doping PbO2Electrode and undoped p PbO2The CV figure of electrode, from the figure 3, it may be seen that the doping of nickel can improve the oxygen evolution potential of lead dioxide electrode greatly, is beneficial to the electrocatalytic oxidation activity improving electrode to polluter, improves current efficiency.
With the electrode of above-mentioned preparation for anode, titanium sheet is negative electrode, and electrode area is 14cm2(7cm �� 2cm), supporting electrolyte is 0.1molL-1Anhydrous sodium sulfate, constant current density is 50mAcm-2, electrode spacing is 4cm, and simulated wastewater is 500mgL-1Aspirin, reaction volume is 250mL, under the effect of magnetic agitation, carries out wastewater treatment, and degradation reaction proceeds to not be sampled in the same time analyzing. Fig. 4 is transiting metal nickel doping PbO prepared by the inventive method2Electrode and undoped p PbO2Electrode is to 500mgL-1The degradation effect comparison diagram of aspirin, in Fig. 4, a () figure is Aspirin concentrations and the ratio of initial concentration changes over curve chart, and (b) figure is the change curve that the ratio of COD and initial COD changes over curve chart and current efficiency GCE. As shown in Figure 4, after nickel doping lead dioxide electrode electrochemical degradation aspirin 2.5 hours, the clearance of aspirin is 77.17%, the clearance of COD is 53.26%, and current efficiency (GCE) is 22.30%, and when using undoped p lead dioxide electrode, the clearance of aspirin is 64.07%, the clearance of TOC is 43.53%, and current efficiency (GCE) is 18.22%, illustrates that the removal effect of nickel doping lead dioxide electrode is significantly better than undoped p electrode.
Embodiment 2:
The preparation method of electrode is such as embodiment 1, and institute is the difference is that, in step (4), acidic Bath is that 500mL is mixed with 0.003molL-1Zn(NO3)2��6H2O��0.3molL-1Pb(NO3)2��0.01molL-1KF��2H2O, 2mL mass fraction is the fluoro-resin emulsion (PTFE) of 60%, with nitric acid (65wt%), pH value is adjusted to 1.8, and solvent is water. Prepare zinc doping lead dioxide electrode.
The zinc doping lead dioxide electrode adopting preparation is anode, processes 500mgL-1Aspirin solution, method is embodiment 1 such as, and after reaction carries out 2.5h, the clearance of the aspirin of zinc doping lead dioxide electrode reaches 78.23%, for 1.22 times of undoped p lead dioxide electrode; The clearance of COD is 50.23%, for 1.15 times of undoped p lead dioxide electrode.
Embodiment 3:
The preparation method of electrode is such as embodiment 1, and institute is the difference is that, in step (4), acidic Bath is that 500mL is mixed with 0.012molL-1Mn(NO3)2��0.3molL-1Pb(NO3)2��0.01molL-1KF��2H2O, 2mL mass fraction is the fluoro-resin emulsion (PTFE) of 60%, with nitric acid (65wt%), pH value is adjusted to 1.8, and solvent is water. Prepare additive Mn lead dioxide electrode.
With preparation additive Mn lead dioxide electrode or undoped p lead dioxide electrode for anode, with titanium sheet for negative electrode, electrode area is 14cm2, electrochemical degradation adopts constant-current electrolysis. Constant current density is 30mAcm-2, electrode spacing is 4cm, with containing 0.1molL-1Electrolyte Na2SO41000mgL-1Diclofenac sodium is simulated wastewater, and reaction volume is 250mL, under the effect of magnetic agitation, carries out wastewater treatment, and degradation reaction proceeds to not be sampled in the same time analyzing. After reaction carries out 1h, the clearance of the diclofenac sodium of additive Mn lead dioxide electrode reaches 84.66%, for 1.38 times of undoped p lead dioxide electrode; The clearance of COD is 67.32%, for 1.35 times of undoped p lead dioxide electrode.
Embodiment 4:
The preparation method of electrode is such as embodiment 1, and institute is the difference is that, in step (4), in acidic Bath, transiting metal component is 0.010molL-1Co(NO3)2, prepare cobalt doped lead dioxide electrode.
With preparation cobalt doped lead dioxide electrode or undoped p lead dioxide electrode for anode, with titanium sheet for negative electrode, electrode area is 14cm2, electrochemical degradation adopts constant-current electrolysis. Constant current density is 30mAcm-2, electrode spacing is 4cm, with certain pharmaceutical factory actual waste water (COD6800mgL-1) for processing object, carry out wastewater treatment, and degradation reaction proceeds to not be sampled in the same time analyzing. After reaction carries out 1h, cobalt doped lead dioxide electrode is to 1.78 times that the COD clearance of actual pharmacy waste water is undoped p lead dioxide electrode effect, it is shown that significantly facilitation.

Claims (10)

1. the transient metal doped lead dioxide electrode for wastewater treatment, it is characterised in that described transient metal doped lead dioxide electrode is from inside to outside successively by tin-antimony oxide bottom on Titanium base of Titanium base, heat deposition, the ��-PbO that is electrodeposited on tin-antimony oxide bottom2Intermediate layer and be electrodeposited in ��-PbO2Fluorine-containing ��-the PbO of the containing transition metal on intermediate layer2Active layer forms; Described transition metal is the one or more kinds of combinations in manganese, ferrum, cobalt, nickel, yttrium or zinc.
2. the transient metal doped lead dioxide electrode for wastewater treatment as claimed in claim 1, it is characterised in that described transient metal doped lead dioxide electrode is prepared by following methods: Titanium base surface is carried out roughening treatment, Titanium base surface after alligatoring prepares tin-antimony oxide bottom by thermal decomposition method, then through basic plating ��-PbO2Intermediate layer, after through the fluorine-containing ��-PbO of acid composite plating containing transition metal2Active layer, namely prepares described transient metal doped ti-supported lead dioxide electric pole.
3. the transient metal doped lead dioxide electrode for wastewater treatment as claimed in claim 2, it is characterised in that described transient metal doped lead dioxide electrode is prepared by following steps:
(1) Titanium base pretreatment: Titanium base sand for surface paper polishing, alkali liquor oil removing, with water clean after, it is placed in sulfuric acid solution, etching 10��30min is soaked at 50��70 DEG C of temperature, after cleaning with water, it is placed in again in oxalic acid solution, soak etching 2��5 hours at 70��90 DEG C of temperature, after washing, obtain the Titanium base of pretreatment;
(2) thermal decomposition method prepares tin-antimony oxide bottom: A, be evenly applied to by tin-antimony oxide sol solution on the Titanium base surface of the pretreatment that step (1) obtains, dry 20��30 minutes under 110��130 DEG C of conditions, then thermally decompose 10��15 minutes at 500��550 DEG C of temperature;
After B, repetition A operate 8��15 times, the surface of the electrode slice obtained is uniform tin coating sb oxide sol solution again, at 110��130 DEG C, dry thermal decomposition 60��80 minutes at 20��30 minutes, 500��550 DEG C temperature, prepare the electrode being coated with tin-antimony oxide bottom;
Described tin-antimony oxide sol solution presses following proportions: 5��10gSbCl3, 95��110gSnCl4��5H2O, 240��260mL ethylene glycol, 180��200g citric acid;
(3) basic plating ��-PbO2Intermediate layer: being placed in as anode in alkaline Bath using the electrode being coated with tin-antimony oxide bottom that step (2) prepares, do negative electrode with titanium sheet, temperature 50��65 DEG C, electric current density is 3��5mA/cm2Galvanostatic conditions under electro-deposition ��-PbO2Intermediate layer, electroplating time 0.5��2 hour, prepare and be coated with tin-antimony oxide bottom and ��-PbO2The electrode in intermediate layer; Described alkaline Bath is the sodium hydroxide solution dissolved with PbO;
(4) the fluorine-containing ��-PbO of acid composite plating containing transition metal2Active layer: what step (3) obtained is coated with tin-antimony oxide bottom and ��-PbO2The electrode in intermediate layer is placed in as anode in acidic Bath, does negative electrode with titanium sheet, and temperature 50��90 DEG C, electric current density is 10��80mA/cm2Galvanostatic conditions under the fluorine-containing ��-PbO of doping transition metal2Active layer, electroplating time 1.5��2h, prepare described transient metal doped lead dioxide electrode; Described acidic Bath is by forming preparation as follows: Pb (NO3)2For 0.3molL-1, KF 2H2O is 0.01��0.02molL-1, transition metal nitrate is 0.0015��0.012molL-1, the ptfe emulsion 4��5mLL of mass fraction 60%-1, with nitric acid, pH value being adjusted to 1.5��2.0, solvent is water.
4. the transient metal doped lead dioxide electrode for wastewater treatment as claimed in claim 3, it is characterised in that in described step (2), described tin-antimony oxide sol solution presses following proportions: 7.53SbCl3, 104.16gSnCl4��5H2O, 251mL ethylene glycol, 192.14g citric acid.
5. the transient metal doped lead dioxide electrode for wastewater treatment as claimed in claim 3, it is characterised in that in described step (3), described alkaline Bath is by forming preparation as follows: PbO is 0.1molL-1, NaOH is 4��5molL-1, solvent is water.
6. the transient metal doped lead dioxide electrode for wastewater treatment as claimed in claim 3, it is characterized in that in described step (4), described transition metal nitrate is the one or more kinds of combinations in manganese nitrate, ferric nitrate, cobalt nitrate, nickel nitrate, Yttrium trinitrate, zinc nitrate.
7. the transient metal doped lead dioxide electrode for wastewater treatment as claimed in claim 3, it is characterised in that in described step (4), described transition metal nitrate is nickel nitrate, zinc nitrate, cobalt nitrate or manganese nitrate.
8. the transient metal doped lead dioxide electrode for wastewater treatment as claimed in claim 3, it is characterised in that in described step (4), described acidic Bath is by forming preparation as follows: Pb (NO3)2For 0.3molL-1, KF 2H2O is 0.01molL-1, transition metal nitrate is 0.003��0.012molL-1, the ptfe emulsion 4mLL of mass fraction 60%-1, with nitric acid, pH value being adjusted to 1.8, solvent is water.
9. the application in the organic wastewater of degradation treatment high-concentration hardly-degradable of the transient metal doped lead dioxide electrode for wastewater treatment as described in one of claim 1��8.
10. applying as claimed in claim 9, it is characterised in that the method for described application is: with transient metal doped lead dioxide electrode for anode, titanium plate is negative electrode, adopts the organic wastewater of constant current electrolysis degradation treatment high-concentration hardly-degradable.
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