CN105239094A - Graphene and lanthanum-doped modified titanium-based lead dioxide electrode and preparation method thereof - Google Patents
Graphene and lanthanum-doped modified titanium-based lead dioxide electrode and preparation method thereof Download PDFInfo
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- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 title claims abstract description 144
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 150000003608 titanium Chemical class 0.000 title abstract 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000010936 titanium Substances 0.000 claims abstract description 72
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 72
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 51
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 51
- 230000008021 deposition Effects 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 43
- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 19
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 15
- 239000010439 graphite Substances 0.000 claims abstract description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 60
- 238000000151 deposition Methods 0.000 claims description 43
- 230000004048 modification Effects 0.000 claims description 41
- 239000011248 coating agent Substances 0.000 claims description 39
- 238000000576 coating method Methods 0.000 claims description 39
- 238000012986 modification Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 235000006408 oxalic acid Nutrition 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 238000005530 etching Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000004070 electrodeposition Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000002203 pretreatment Methods 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 6
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract 1
- 229940012189 methyl orange Drugs 0.000 abstract 1
- 238000012797 qualification Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 229910006531 α-PbO2 Inorganic materials 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 19
- 229910006529 α-PbO Inorganic materials 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
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- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 239000003115 supporting electrolyte Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
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- 239000002245 particle Substances 0.000 description 2
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- 238000005411 Van der Waals force Methods 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
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- 239000013067 intermediate product Substances 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
The application discloses a graphene and lanthanum doped modified titanium-based lead dioxide electrode, which comprises a titanium substrate; a bottom layer of tin antimony oxide thermally deposited on the titanium substrate; graphene and lanthanum modified beta-PbO electrodeposited on tin antimony oxide underlayer2An active layer; compared with the prior art, the titanium-based lead dioxide electrode has the advantages that the removal effect on methyl orange can be improved by 15.6% under the condition that the service life of the titanium-based lead dioxide electrode is at least maintained; the application also discloses a preparation method of the titanium-based lead dioxide electrode, which comprises the steps of taking the titanium substrate on which the tin-antimony oxide bottom layer is thermally deposited as an anode, taking graphite with equal area as a cathode, and electrodepositing beta-PbO in acidic deposition liquid2The acid deposition solution contains graphene, lanthanum nitrate, lead nitrate, nitric acid and a surfactant; the preparation method eliminates alpha-PbO2The preparation process of the layer simplifies the preparation method of the titanium-based lead dioxide electrode and lays a foundation for improving the qualification rate of finished products of electrode products.
Description
Technical field
The present invention is electrochemical water treatment technology, relates to catalytic oxidation and water-treatment technology field, is specifically related to a kind ofly mix ti-supported lead dioxide electric pole of Graphene and lanthanum modification and preparation method thereof.
Background technology
Catalytic oxidation has advantages such as consuming chemical reagent is few, convenient operation and control.As the Typical Representative of insoluble anode, ti-supported lead dioxide electric pole is the electro catalytic electrode with greater advantage of generally acknowledging at present, ti-supported lead dioxide electric pole in aqueous electrolysis time have that oxygen evolution potential is high, oxidation capacity is strong, solidity to corrosion is good, good conductivity, by characteristics such as larger current, so be just used as insoluble anode in electrolytic industry a long time ago.At present, ti-supported lead dioxide electric pole is widely used in the electrolytic preparation of each type organic and inorganics, and in all kinds of organic sewage treatment process.Although ti-supported lead dioxide electric pole has above-mentioned multiple advantages, it still has larger improvement space, and as the electrode for catalytic oxidation, it should possess following several performances:
1, high catalytic activity, namely can realize required catalyzed reaction, and suppressing does not need or harmful side reaction;
2, satisfactory stability, namely the effect of impurity and intermediate product can be tolerated and unlikely contaminated or poisoning quickly and inactivation, and in the potential range realizing catalyzed reaction, catalytic surface is unlikely to lose catalytic activity too early because of electrochemical reaction, good mechanical-physical character should be had in addition, as upper layer does not come off, do not dissolve.
The part that ti-supported lead dioxide electric pole works is for being in the β-PbO on ti-supported lead dioxide electric pole top layer
2layer, but at present, by β-PbO
2the layer electrode be deposited directly on titanium base does not still have actual use value, and this is due to β-PbO
2the sticking power of layer on Titanium base is low, easily peel off, and in electrolytic process, the life-span is short, and for this reason, people are at Titanium base and β-PbO
2between be provided with middle layer, middle layer is played β-PbO on the one hand
2layer is bonded on matrix well, effectively can slow down the corrosion of Titanium base on the other hand.
At present, middle layer is generally multilayered structure, and the outermost layer in middle layer is α-PbO
2layer, α-PbO
2the skin of layer is β-PbO
2layer.Comprise α-PbO
2the introducing in the middle layer of layer, effectively enhances the stability of ti-supported lead dioxide electric pole, but also makes its manufacturing process complicated simultaneously, inhibit the raising of the product qualified rate of ti-supported lead dioxide electric pole product.
The catalytic oxidation effect improving ti-supported lead dioxide electric pole is the Main way that people study; On the basis at least ensureing the existing effect of ti-supported lead dioxide electric pole, simplify its manufacturing process, improve the product qualified rate of product, reduce its manufacturing cost, expand another direction that its use range becomes people's research.
Summary of the invention
First the object of the application is to provide a kind of ti-supported lead dioxide electric pole mixing Graphene and lanthanum modification, this ti-supported lead dioxide electric pole compared to existing technology, when at least keeping its work-ing life, under identical voltage, its catalytic oxidation effect obtains and effectively improves, and can improve 15.6% to the removal effect of tropeolin-D.
Concrete scheme of the present invention is as follows: a kind of ti-supported lead dioxide electric pole mixing Graphene and lanthanum modification, comprises
Titanium base;
The tin-antimony oxide bottom of heat deposition on Titanium base;
The Graphene of galvanic deposit on tin-antimony oxide bottom and the β-PbO of lanthanum modification
2active coating.
Titanium base can be the materials such as titanium silk, titanium pipe, titanium net or titanium plate.
The ti-supported lead dioxide electric pole that the present invention mixes Graphene and lanthanum modification has following features and advantage:
(1), using titanium as matrix, tin-antimony oxide layer is bottom, not containing α-PbO
2middle layer, the β-PbO of Direct precipitation doped graphene and lanthanum outside tin-antimony oxide layer
2active coating.
(2), the present invention is by the doping of Graphene and lanthanum, improve electro catalytic activity, adopt the present invention to mix the ti-supported lead dioxide electric pole By Electro-catalytic Oxidation Process tropeolin-D of Graphene and lanthanum modification, its electric degradation property can improve 15.6% than common ti-supported lead dioxide electric pole.
(3), the present invention mixes the level at least maintaining common ti-supported lead dioxide electric in prior art work-ing life of the ti-supported lead dioxide electric pole of Graphene and lanthanum modification, and in some circumstances, the work-ing life of electrode can improve 11.2%.
The ti-supported lead dioxide electric pole that the present invention mixes Graphene and lanthanum modification has These characteristics and advantage, be due to:
Graphene, as two-dimension nano materials, has the mechanics of many excellences, electricity and chemical property; Lanthanum, as rare earth element, has special 4f electronic structure, and very easily deformation, easily enter PbO in the mode of calking or displacement
2intracell.Due to These characteristics, by Graphene and La doped to settled layer β-PbO
2in after, the surface topography of electrode is changed comparatively large, electrode surface particle diminishes, and improves microtexture and the catalytic effect of electrode, and the electric degradation property of electrode is improved; Make β-PbO simultaneously
2active coating and tin-antimony oxide bottom are provided with better binding ability, are eliminating α-PbO
2when layer, at least maintain the level of prior art the work-ing life of electrode, and be improved the work-ing life of electrode in some circumstances.
The present invention mixes the ti-supported lead dioxide electric pole of Graphene and lanthanum modification successfully by α-PbO
2middle layer is cancelled, and improves electrocatalysis characteristic under the condition ensureing its work-ing life, for ti-supported lead dioxide electric pole is at the electrolytic preparation of electrolytic industry and each type organic and inorganics, especially lays a good foundation in the extensive use of sewage treatment process.
Secondly, the object of the application is to provide a kind of above-mentioned preparation method mixing the ti-supported lead dioxide electric pole of Graphene and lanthanum modification, and this preparation method eliminates α-PbO
2the preparation section of layer, simplifies the preparation method of ti-supported lead dioxide electric pole, for the product qualified rate improving electrode product is laid a good foundation.
Concrete scheme of the present invention is as follows: the preparation method mixing the ti-supported lead dioxide electric pole of Graphene and lanthanum modification, comprises the steps:
Step 1, pre-treatment is carried out to Titanium base; Very ripe to the pre-treatment of Titanium base in prior art, repeat no more;
Step 2, heat deposition tin-antimony oxide bottom; In prior art, the technology of heat deposition tin-antimony oxide bottom is very ripe, repeats no more;
Step 3, β-PbO in tin-antimony oxide bottom substrates Graphene and lanthanum modification
2active coating: heat deposition is had the Titanium base of tin-antimony oxide bottom as anode, the graphite of homalographic as negative electrode, galvanic deposit β-PbO in acid deposition liquid
2active coating, the current density of galvanic deposit is 0.5 ~ 1A/dm
2, electrodeposition temperature is 40 ~ 60 DEG C, and electrodeposition time is 0.5 ~ 1 hour; Containing Graphene, lanthanum nitrate, lead nitrate, nitric acid and tensio-active agent in described acid deposition liquid.
This preparation method directly carries out β-PbO on the Titanium base that heat deposition has tin-antimony oxide bottom
2the deposition of active coating, eliminates α-PbO
2the preparation section of layer, simplify the preparation method of ti-supported lead dioxide electric pole, the simplification of preparation method can make the preparation efficiency of ti-supported lead dioxide electric pole be improved, owing to eliminating α-PbO
2the preparation section of layer, also eliminates in this operation the processing parameter needing to adjust and control accordingly, is conducive to the raising of the product qualified rate of product, and reduces production cost thus.
Acid deposition liquid preferably adopts deionization to prepare, wherein containing Graphene 0.005 ~ 0.02g/L, lanthanum nitrate 1.7 ~ 2.6g/L, lead nitrate 100 ~ 132g/L, Sodium dodecylbenzene sulfonate 0.05 ~ 0.1g/L, nitric acid 5 ~ 8g/L.
In preparation method of the present invention, in the acid deposition liquid adopted, add tensio-active agent; Because Graphene inside also exists stronger Van der Waals force, can not stable dispersion in a solvent, add tensio-active agent in acid deposition liquid after, Graphene can be made more easily to disperse in a solvent, to adapt to the needs of galvanic deposit.
Tensio-active agent in acid deposition liquid preferentially adopts Sodium dodecylbenzene sulfonate, and Sodium dodecylbenzene sulfonate has good dispersiveness to Graphene, disperses in a solvent with can making graphene uniform, makes the electrode structure made even.
In the prior art, to the pre-treatment of Titanium base and the heat deposition technology of tin-antimony oxide bottom very ripe, needs of the present invention can be met, embody further for enabling advantage of the present invention, prior art is screened, have chosen and be more applicable to preparation process of the present invention, specific as follows:
Wherein, the pretreatment process of Titanium base is: by Titanium base sanding and polishing, until it presents argenteous true qualities, after deionized water rinsing, is placed in acetone supersound process 3 ~ 5 minutes, wipe oil; Then the Titanium base after oil removal treatment is placed in deionized water for ultrasonic process 3 ~ 5 minutes, removes acetone and other impurity; After finally completing etching processing in oxalic acid etching liquid, taking-up is placed in oxalic acid conserving liquid and preserves stand-by; Described etching processing is that Titanium base is placed in oxalic acid etching liquid, etching 50 ~ 70 minutes under 90 DEG C to micro-condition of boiling;
The flow process of heat deposition tin-antimony oxide bottom is: tin tetrachloride and butter of antimony are dissolved in concentrated hydrochloric acid and propyl carbinol mixing solutions and make coating liquid, coating liquid is coated on the surface of the Titanium base that preservation is stand-by in step (1), then dries 5 ~ 10 minutes at 100 ~ 130 DEG C in air dry oven; After repeating above coating, drying step 7 ~ 9 times, the Titanium base of oven dry to be placed at retort furnace 450 ~ 550 DEG C roasting 50 ~ 70 minutes, to take out and naturally cool to room temperature.
Oxalic acid etching liquid preferably adopts deionized water to prepare, and wherein concentration of oxalic acid is 80 ~ 120g/L; Oxalic acid conserving liquid preferably adopts deionized water to prepare, and wherein concentration of oxalic acid is 8 ~ 12g/L.
Coating liquid preferably adopts hydrochloric acid to prepare, wherein containing 65 ~ 100g/L hydrogenchloride, 620 ~ 670g/L propyl carbinol, 130 ~ 200g/L tin tetrachloride and 20 ~ 40g/L butter of antimony.
Graphene and lanthanum element are creatively blended in electrodeposit liquid by the preparation method that the present invention mixes the ti-supported lead dioxide electric pole of Graphene and lanthanum modification, make Graphene and lanthanum element successfully with β-PbO
2active coating becomes a community, and this preparation method is owing to eliminating α-PbO
2the preparation flow of layer, also synchronously eliminates the control of the corresponding process parameters in this flow process, simplifies the manufacturing process of electrode, adds the technology controlling and process point of the rare and lanthanum element of graphite in the present invention, but it is just at β-PbO
2increase reference mark in the preparation flow of active coating, compare and cancel whole α-PbO
2the preparation flow of layer still decreases controlling the size of process point, the difficulty of technology controlling and process is reduced, the fluctuation of technology controlling and process is more tended to be steady, the favourable raising with the product qualified rate of product, the raising of product qualified rate makes the manufacturing cost of the ti-supported lead dioxide electric pole mixing Graphene and lanthanum modification be reduced, and enhances its market competitiveness.
Accompanying drawing explanation
Fig. 1 is the structural representation that the present invention mixes the ti-supported lead dioxide electric pole of Graphene and lanthanum modification.
Fig. 2, Fig. 3 and Fig. 4 are embodiment 1 adopt the present invention to mix scanning electron microscope (SEM) photograph that the made 1# of the preparation method of the ti-supported lead dioxide electric pole of Graphene and lanthanum modification mixes the ti-supported lead dioxide electric pole of Graphene and lanthanum modification respectively, and magnification is respectively 5000,3000 and 1000 times.
Fig. 5, Fig. 6 and Fig. 7 are the scanning electron microscope (SEM) photograph of the common ti-supported lead dioxide electric pole of 1# that comparative example 1 adopts prior art made respectively, and magnification is respectively 5000,3000 and 1000 times.
Mark in figure:
1. Titanium base, 2. tin-antimony oxide bottom, the β-PbO of 3. Graphene and lanthanum modification
2active coating.
Embodiment
Embodiment 1:
1# mixes the ti-supported lead dioxide electric pole of Graphene and lanthanum modification, consults Fig. 1, and its concrete structure comprises:
Titanium base 1;
The tin-antimony oxide bottom 2 of heat deposition on Titanium base;
The Graphene of galvanic deposit on tin-antimony oxide bottom and the β-PbO of lanthanum modification
2active coating 3.
In the present embodiment, Titanium base adopts titanium silk.
The concrete preparation method that 1# mixes the ti-supported lead dioxide electric pole of Graphene and lanthanum modification is as follows:
(1) pre-treatment of Titanium base: with titanium silk as Titanium base, first with flint paper, sanding and polishing is carried out to titanium silk, until it presents silvery white metal light, after deionized water rinsing; The titanium silk crossed by sanding and polishing is placed in acetone supersound process 4 minutes, wipe oil; Then the titanium silk after oil removal treatment is placed in deionized water for ultrasonic process 4 minutes, removes acetone and other impurity; Finally titanium silk is immersed in oxalic acid etching liquid and etches, etch under micro-condition of boiling after 1 hour and take out, be placed in oxalic acid conserving liquid preserve stand-by by completing the titanium silk after etching; Described oxalic acid etching liquid adopts in ionized water formulated, and concentration of oxalic acid is 100g/L; Described oxalic acid conserving liquid adopts in ionized water formulated, and concentration of oxalic acid is 10g/L.
(2) heat deposition tin-antimony oxide bottom: tin tetrachloride and butter of antimony are dissolved in concentrated hydrochloric acid and propyl carbinol mixing solutions and make coating liquid, coating liquid is coated on the titanium silk after processing in above-mentioned (1) on the surface, dry 8 minutes at 120 DEG C in air dry oven, coating drying like this repeats 8 times, again the titanium silk of oven dry to be placed at retort furnace 500 DEG C roasting 1 hour, after taking-up, to naturally cool to room temperature; Coating liquid adopts mass concentration to be that 37% concentrated hydrochloric acid is formulated, wherein containing 87g/L hydrogenchloride, 650g/L propyl carbinol, 170g/L tin tetrachloride and 30g/L butter of antimony.
(3) β-PbO of galvanic deposit Graphene and lanthanum modification
2active coating: above-mentioned heat deposition is had the Titanium base of tin-antimony oxide bottom as anode, the graphite of homalographic as negative electrode, galvanic deposit β-PbO in acid deposition liquid
2active coating, obtained 1# mixes the ti-supported lead dioxide electric pole of Graphene and lanthanum modification; Acid deposition liquid adopts deionized water formulated, containing Graphene 0.005g/L, lanthanum nitrate 1.7g/L, lead nitrate 100g/L, Sodium dodecylbenzene sulfonate 0.05g/L, nitric acid 5g/L; The current density of galvanic deposit is 0.5A/dm
2, electrodeposition temperature is 40 DEG C, and electrodeposition time is 0.5 hour.
Ti-supported lead dioxide electric pole 1# being mixed to Graphene and lanthanum modification detects: 1# is mixed the ti-supported lead dioxide electric pole of Graphene and lanthanum modification as anode, and electrode surface area is 1cm
2the graphite of homalographic is as negative electrode, interpole gap is 2cm, tropeolin-D in catalytic oxidation water, the concentration of tropeolin-D is that the sodium sulfate of 10mg/L, 5g/L does supporting electrolyte, the volume of solution is 100mL, catalytic oxidation voltage is 5V, and temperature is 30 DEG C, and reacting the clearance of tropeolin-D after 30 minutes is 83%; Adopt this electrode to be that anode carries out accelerated life test, in the sulphuric acid soln of 1mol/L, temperature is 60 DEG C, 100A/dm
2current density under the weightlessness of electrolysis 5 hours rear electrodes be 1.7mg/cm
2.
Ti-supported lead dioxide electric pole 1# being mixed to Graphene and lanthanum modification carries out electron-microscope scanning, and display is as Fig. 2, Fig. 3 and Fig. 4, and Fig. 2, Fig. 3 and Fig. 4 are respectively the scanning electron microscope (SEM) photograph that magnification is 5000,3000 and 1000 times.
Comparative example 1:
The common ti-supported lead dioxide electric pole of 1#, its concrete structure comprises:
Titanium base;
The tin-antimony oxide bottom of heat deposition on Titanium base;
α-the PbO of galvanic deposit on tin-antimony oxide bottom
2layer;
Galvanic deposit is at α-PbO
2β-PbO on layer
2active coating.
In this comparative example, Titanium base adopts titanium silk, identical with embodiment 1.
The concrete preparation method of the common ti-supported lead dioxide electric pole of 1# is as follows:
(1) pre-treatment of Titanium base: identical with the pre-treatment step of the Titanium base in embodiment 1;
(2) heat deposition tin-antimony oxide bottom: identical with the step of the heat deposition tin-antimony oxide bottom in embodiment 1;
(3) galvanic deposit α-PbO
2middle layer: heat deposition is had the Titanium base of tin-antimony oxide bottom as anode, the graphite of homalographic as negative electrode, galvanic deposit α-PbO in the sodium hydroxide solution being dissolved with PbO
2middle layer, PbO concentration 220g/L, naoh concentration 130g/L; The current density of galvanic deposit is 3mA/cm
2, depositing temperature is 50 DEG C, and depositing time is 1.5 hours;
(4) galvanic deposit β-PbO
2active coating: galvanic deposit is had α-PbO
2the Titanium base in middle layer as anode, the graphite of homalographic as negative electrode, galvanic deposit β-PbO in acid deposition liquid
2active coating, the obtained common ti-supported lead dioxide electric pole of 1#; Acid deposition liquid contains lead nitrate 100g/L, nitric acid 5g/L; The current density of galvanic deposit is 0.5A/dm
2, electrodeposition temperature is 40 DEG C, and electrodeposition time is 0.5 hour.
Detect the common ti-supported lead dioxide electric pole of 1#: using common for 1# ti-supported lead dioxide electric pole as anode, electrode surface area is 1cm
2the graphite of homalographic is as negative electrode, interpole gap is 2cm, tropeolin-D in catalytic oxidation water, the concentration of tropeolin-D is that the sodium sulfate of 10mg/L, 5g/L does supporting electrolyte, the volume of solution is 100mL, catalytic oxidation voltage is 5V, and temperature is 30 DEG C, and reacting the clearance of tropeolin-D after 30 minutes is 73%; Common for this 1# ti-supported lead dioxide electric pole is carried out accelerated life test as anode, and in the sulphuric acid soln of 1mol/L, temperature is 60 DEG C, 100A/dm
2current density under the weightlessness of electrolysis 5 hours rear electrodes be 1.9mg/cm
2.
Carry out electron-microscope scanning to the common ti-supported lead dioxide electric pole of 1#, display is as Fig. 5, Fig. 6 and Fig. 7, and Fig. 5, Fig. 6 and Fig. 7 are respectively the scanning electron microscope (SEM) photograph that magnification is 5000,3000 and 1000 times.
Scanning electron microscope (SEM) photograph shows, through the rare and lanthanum of graphite to β-PbO
2the doping vario-property of active coating, the surface topography of electrode obtains larger change, and electrode surface particle diminishes, the fine uniform more that structure becomes, and the compactness of microtexture increases, and reduces β-PbO
2the internal stress of active coating, improves β-PbO
2the stability of active coating, β-PbO
2active coating and tin-antimony oxide bottom are provided with better binding ability, and the work-ing life of modified electrode is extended; Simultaneously due to the good electric property that graphite is rare, make the β-PbO of modified electrode
2the loading capacity of active coating is increased, and in use, discharge capacity that can be larger, when being used to dispose of sewage, can produce more O
2, O
3deng oxidizing species, enhance wastewater treatment efficiency.
The detected result display of above embodiment 1 and comparative example 1:
The ti-supported lead dioxide electric pole mixing Graphene and lanthanum modification through the 1# of Graphene and lanthanum modification is provided with larger progress compared with the common ti-supported lead dioxide electric pole of 1#: the removal effect of tropeolin-D improves 13.7%, and the life-span of the same terms lower electrode improves 11.2%.
Embodiment 2:
2# mixes the ti-supported lead dioxide electric pole of Graphene and lanthanum modification, and it is identical with the structure of the ti-supported lead dioxide electric pole of lanthanum modification that this electrode and the 1# of embodiment 1 mix Graphene.
In the present embodiment, Titanium base adopts titanium silk.
The concrete preparation method that 2# mixes the ti-supported lead dioxide electric pole of Graphene and lanthanum modification is as follows:
(1) pre-treatment of Titanium base: identical with the pre-treatment step of embodiment 1;
(2) heat deposition tin-antimony oxide bottom: identical with the step of the heat deposition tin-antimony oxide bottom of embodiment 1;
(3) β-PbO of galvanic deposit Graphene and lanthanum modification
2active coating: above-mentioned heat deposition is had the Titanium base of tin-antimony oxide bottom as anode, the graphite of homalographic as negative electrode, galvanic deposit β-PbO in acid deposition liquid
2active coating, obtained 2# mixes the ti-supported lead dioxide electric pole of Graphene and lanthanum modification; Acid deposition liquid adopts deionized water formulated, containing Graphene 0.02g/L, lanthanum nitrate 2.6g/L, lead nitrate 132g/L, Sodium dodecylbenzene sulfonate 0.1g/L, nitric acid 8g/L; The current density of galvanic deposit is 1A/dm
2, electrodeposition temperature is 60 DEG C, and electrodeposition time is 1 hour.
Ti-supported lead dioxide electric pole 2# being mixed to Graphene and lanthanum modification detects: 2# is mixed the ti-supported lead dioxide electric pole of Graphene and lanthanum modification as anode, and electrode surface area is 1cm
2the graphite of homalographic is as negative electrode, interpole gap is 2cm, tropeolin-D in catalytic oxidation water, the concentration of tropeolin-D is that the sodium sulfate of 10mg/L, 5g/L does supporting electrolyte, the volume of solution is 100mL, catalytic oxidation voltage is 5V, and temperature is 30 DEG C, and reacting the clearance of tropeolin-D after 30 minutes is 89%; Adopt this electrode to be that anode carries out accelerated life test, in the sulphuric acid soln of 1mol/L, temperature is 60 DEG C, 100A/dm
2current density under the weightlessness of electrolysis 5 hours rear electrodes be 1.8mg/cm
2.
Comparative example 2:
The common ti-supported lead dioxide electric pole of 2#, this electrode is identical with the structure of the common ti-supported lead dioxide electric pole of the 1# of comparative example 1
In this comparative example, Titanium base adopts titanium silk, identical with embodiment 2.
The concrete preparation method of the common ti-supported lead dioxide electric pole of 2# is as follows:
(1) pre-treatment of Titanium base: identical with the pre-treatment step of the Titanium base in embodiment 2;
(2) heat deposition tin-antimony oxide bottom: identical with the step of the heat deposition tin-antimony oxide bottom in embodiment 2;
(3) galvanic deposit α-PbO
2middle layer: with the galvanic deposit α-PbO in comparative example 1
2the step in middle layer is identical;
(4) galvanic deposit β-PbO
2active coating: galvanic deposit is had α-PbO
2the Titanium base in middle layer as anode, the graphite of homalographic as negative electrode, galvanic deposit β-PbO in acid deposition liquid
2active coating, the obtained common ti-supported lead dioxide electric pole of 2#; Acid deposition liquid adopts deionized water formulated, and acid deposition liquid contains lead nitrate 132g/L, nitric acid 8g/L; The current density of galvanic deposit is 1.0A/dm
2, electrodeposition temperature is 60 DEG C, and electrodeposition time is 1 hour.
Detect the common ti-supported lead dioxide electric pole of 2#: using common for 2# ti-supported lead dioxide electric pole as anode, electrode surface area is 1cm
2the graphite of homalographic is as negative electrode, interpole gap is 2cm, tropeolin-D in catalytic oxidation water, the concentration of tropeolin-D is that the sodium sulfate of 10mg/L, 5g/L does supporting electrolyte, the volume of solution is 100mL, catalytic oxidation voltage is 5V, and temperature is 30 DEG C, and reacting the clearance of tropeolin-D after 30 minutes is 77%; Common for this 2# ti-supported lead dioxide electric pole is carried out accelerated life test as anode, and in the sulphuric acid soln of 1mol/L, temperature is 60 DEG C, 100A/dm
2current density under the weightlessness of electrolysis 5 hours rear electrodes be 1.8mg/cm
2.
The detected result display of above embodiment 2 and comparative example 2:
The ti-supported lead dioxide electric pole mixing Graphene and lanthanum modification through the 2# of Graphene and lanthanum modification is provided with larger progress compared with the common ti-supported lead dioxide electric pole of 2#: the removal effect of tropeolin-D improves 15.6%, and the life-span of the same terms lower electrode is identical.
The Graphene adopted in above embodiment is purchased from Nanjing Ji Cang nanosecond science and technology company limited, and model is JCG-6-5, concrete specification and parameter as follows:
Outward appearance is random flaky texture, flit size 5um, microplate thickness 5 ~ 8nm, thermal conductivity 400w/ (m*k), specific conductivity 1000S/cm, carbon content > 99.5%.
Claims (6)
1. mix a ti-supported lead dioxide electric pole for Graphene and lanthanum modification, it is characterized in that, comprise
Titanium base;
The tin-antimony oxide bottom of heat deposition on Titanium base;
The Graphene of galvanic deposit on tin-antimony oxide bottom and the β-PbO of lanthanum modification
2active coating.
2. the preparation method mixing the ti-supported lead dioxide electric pole of Graphene and lanthanum modification according to claim 1, is characterized in that, comprise the steps:
Step 1, pre-treatment is carried out to Titanium base;
Step 2, heat deposition tin-antimony oxide bottom;
β-the PbO that step 3, galvanic deposit Graphene and lanthanum are modified
2active coating: heat deposition is had the Titanium base of tin-antimony oxide bottom as anode, the graphite of homalographic as negative electrode, galvanic deposit β-PbO in acid deposition liquid
2active coating, the current density of galvanic deposit is 0.5 ~ 1A/dm
2, electrodeposition temperature is 40 ~ 60 DEG C, and electrodeposition time is 0.5 ~ 1 hour; Containing Graphene, lanthanum nitrate, lead nitrate, nitric acid and tensio-active agent in described acid deposition liquid.
3. preparation method according to claim 2, is characterized in that,
Described acid deposition liquid adopts deionized water preparation, wherein containing Graphene 0.005 ~ 0.02g/L, lanthanum nitrate 1.7 ~ 2.6g/L, lead nitrate 100 ~ 132g/L, Sodium dodecylbenzene sulfonate 0.05 ~ 0.1g/L, nitric acid 5 ~ 8g/L.
4. the preparation method according to Claims 2 or 3, is characterized in that,
The idiographic flow of described step 1 is: by Titanium base sanding and polishing, until it presents argenteous true qualities, after deionized water rinsing, is placed in acetone supersound process 3 ~ 5 minutes, wipe oil; Then the Titanium base after oil removal treatment is placed in deionized water for ultrasonic process 3 ~ 5 minutes, removes acetone and other impurity; After finally completing etching processing in oxalic acid etching liquid, taking-up is placed in oxalic acid conserving liquid and preserves stand-by; Described etching processing is that Titanium base is placed in oxalic acid etching liquid, etching 50 ~ 70 minutes under 90 DEG C to micro-condition of boiling;
The idiographic flow of described step 2 is: tin tetrachloride and butter of antimony are dissolved in concentrated hydrochloric acid and propyl carbinol mixing solutions and make coating liquid, coating liquid is coated on the surface of the Titanium base that preservation is stand-by in step (1), then dries 5 ~ 10 minutes at 100 ~ 130 DEG C in air dry oven; After repeating above coating, drying step 7 ~ 9 times, at the Titanium base of oven dry being placed in retort furnace 450 ~ 550 DEG C, roasting is after 50 ~ 70 minutes, takes out and naturally cools to room temperature.
5. preparation method according to claim 4, is characterized in that, described oxalic acid etching liquid adopts deionized water formulated, and wherein concentration of oxalic acid is 80 ~ 120g/L; Described oxalic acid conserving liquid adopts deionized water formulated, and wherein concentration of oxalic acid is 8 ~ 12g/L.
6. preparation method according to claim 4, is characterized in that, described coating liquid adopts hydrochloric acid to prepare, wherein containing 65 ~ 100g/L hydrogenchloride, 620 ~ 670g/L propyl carbinol, 130 ~ 200g/L tin tetrachloride and 20 ~ 40g/L butter of antimony.
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