CN104386785B - The preparation method of molybdenum, antimony codope titanium base tin ash electro catalytic electrode - Google Patents
The preparation method of molybdenum, antimony codope titanium base tin ash electro catalytic electrode Download PDFInfo
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- CN104386785B CN104386785B CN201410512990.7A CN201410512990A CN104386785B CN 104386785 B CN104386785 B CN 104386785B CN 201410512990 A CN201410512990 A CN 201410512990A CN 104386785 B CN104386785 B CN 104386785B
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- 239000010936 titanium Substances 0.000 title claims abstract description 63
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 57
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 50
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 37
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 33
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000011733 molybdenum Substances 0.000 title claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000011159 matrix material Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 claims abstract description 8
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 239000002585 base Substances 0.000 claims description 28
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 abstract description 22
- 238000006731 degradation reaction Methods 0.000 abstract description 16
- 230000015556 catabolic process Effects 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 2
- 238000003618 dip coating Methods 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 5
- 230000010718 Oxidation Activity Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
Abstract
The preparation method who the invention discloses a kind of molybdenum, antimony codope titanium base tin ash electro catalytic electrode, belongs to catalysis electrode technical field. Adopt first sol-gel process to prepare molybdenum, antimony codope titanium base tin ash electro catalytic electrode, first titanium matrix is carried out to pretreatment, with SnCl4·5H2O、Sb2O3、(NH4)6Mo7O24For raw material, Sn, Sb, Mo prepare colloidal sol by atomic ratio 100:3:1 ~ 3, adopt dip-coating method to lift technology for coating, control dip time and pull rate, adopt ladder temperature programming sintering processes, control heat treatment temperature and the heat treatment time of each temperature rise period, prepare novel Mo, antimony codope titanium base tin ash electro catalytic electrode. The electrode cost making in the present invention is lower, electrode surface even compact, good stability, and the organic pollution of the multiple different structures such as Pyrogentisinic Acid, caprolactam and active black KN-B all has stronger degradation capability.
Description
Technical field
The preparation method who the present invention relates to a kind of molybdenum, antimony codope titanium base tin ash electro catalytic electrode, belongs to catalysis electrode technical field.
Background technology
Along with industrial expansion, the mankind are more serious to the pollution level of water body, increasing bio-refractory and bio-toxicity organic pollution in sewage, are there is, conventional physics, chemical method are difficult to process these organic matters, and may produce secondary pollution problems, traditional bioremediation can only be removed the biological organic matter mixing in water body effectively. The features such as electro-catalytic oxidation technology is more thorough owing to having degradation of organic substances, and efficiency is high, easy and simple to handle, cause extensive concern in water treatment field in recent years.
Electrode is the core of electrocatalysis oxidation reaction equipment, and in order to promote the application of electrochemistry at field of Environment Protection, the anode material that manufactures the good combination properties such as electro catalytic activity is high, good stability, long service life becomes study hotspot gradually. The appearance of DSA electrode, has overcome the shortcoming that conventional graphite electrode, lead dioxide electrode etc. exist, and has solved the problem of anodic solution, has avoided electrolyte and cathode product to produce pollution, becomes the widely used electrode material of electrochemical industry and field of Environment Protection. In all kinds of DSA electrodes, Ti/RuO2、Ti/IrO2The low current efficiency that causes of electrode oxygen evolution potential is not high, and Ru, Ir all belong to noble metal, and this type of electrode preparation cost is higher. Ti/PbO2Can there is coating and dissolve in anode, the lead ion of generation can pollute in electrolytic process. Ti/SnO2Electro catalytic activity and the decay resistance of-Sb electrode are fine, and there is higher oxygen evolution potential, it is a kind of well behaved electrocatalytic oxidation polarizing electrode, its many organic substances of can degrading in the short period of time, the processing of therefore studying tin antimony oxide coated electrode pair research waste water has very significance. There are in recent years many scholars to prepare rare earth doped Ti/SnO2-Sb electrode, and study its best preparation technology and electrocatalytic oxidation property thereof, although the electrode performance making makes moderate progress, general rare earth element is expensive, and the cost of molybdenum is lower, wide material sources, and can effectively improve Ti/SnO2The performance of-Sb electrode, therefore the present invention proposes a kind of novel Mo of introducing molybdenum element, antimony codope titanium base tin ash electro catalytic electrode and preparation method thereof first.
Summary of the invention
Goal of the invention
In order to address the above problem, the invention provides the preparation method of a kind of novel Mo, antimony codope titanium base tin ash electro catalytic electrode, can be used for treatment of Organic Wastewater.
Technical scheme
The present invention is achieved through the following technical solutions:
A preparation method for molybdenum, antimony codope titanium base tin ash electro catalytic electrode, is characterized in that: step is as follows:
(1) pretreatment of titanium matrix: titanium matrix is polished with 120# and 240# water-proof abrasive paper, then be 40%NaOH solution alkali cleaning oil removing 1h at 80 DEG C by mass concentration, after cleaning, be that 10 ~ 15% oxalic acid solutions are at slight boiling condition etching 1h, with being kept in ultra-pure water after distilled water cleaning by mass concentration again;
(2) colloidal sol preparation: taking ethanol as solvent, dissolve SnCl4·5H2O、Sb2O3、(NH4)6Mo7O24Raw material, adds complexing agent citric acid and ethylene glycol, fully stirs 1h after raw material dissolves completely in 60 DEG C of water-baths, then in 60 DEG C of water-baths still aging 2h;
(3) coating preparation: take out the above-mentioned titanium electrode substrate of handling well, blot the moisture that matrix surface adheres to, then lift film with dipping pulling machine;
(4) sintering processes: above-mentioned coating coating procedure carries out 10 ~ 15 times, last heat treatment process adopts ladder temperature programming sintering processes electrode.
Step (2) Raw is that add 100:3:1 ~ 3 by the atomic ratio of Sn, Sb, Mo, and above-mentioned element source is SnCl4·5H2O、Sb2O3(NH4)6Mo7O24Raw material; Taking citric acid and ethylene glycol as complexing agent, wherein the mol ratio of metal ion, citric acid and ethylene glycol is 1:3:3; Metal ion refers to the summation of Sn, Sb, Mo ion.
In step (3), lifting painting membrane process is: titanium matrix does not flood 10min in colloidal sol, lifts out colloidal sol with 1mm/min speed; After each film, in air dry oven, be dried, baking temperature is 100 ~ 120 DEG C, and be 10 ~ 15min drying time; After dry, in the cooling 10min of room temperature, then heat-treat in electric furnace, heat treatment temperature is 450 ~ 500 DEG C, and heat treatment time is 10min.
In step (4), ladder Temperature Programmed Processes is: be warming up to 200 DEG C of insulation 20min by room temperature with 10 DEG C/min, be then warming up to 400 DEG C of insulation 20min with 3 DEG C/min, then be warming up at 600 DEG C and be incubated 2h with 1 DEG C/min, finally obtain the target electrode of doping.
Advantage and effect
Tool of the present invention has the following advantages and beneficial effect:
(1) novel Mo of the present invention, antimony codope titanium base tin ash electro catalytic electrode preparation method simply controlled (flow chart is shown in Fig. 1), be conducive to manufacture and design related electrode Preparation equipment, is easy to the preparation of scale electrode.
(2) the method for the invention is prepared novel Mo, antimony codope titanium base tin ash electro catalytic electrode face coat particle are slightly reunited, particle size and be evenly distributed that (scanning electron microscope image is shown in Fig. 2, Fig. 3, Fig. 4), molybdenum, antimony codope do not change tin ash four directions Rutile Type crystal structure (X-ray diffraction spectrogram is shown in Fig. 5).
(3) organic matter of the number of chemical structures such as the method for the invention is prepared novel Mo, antimony codope titanium base tin ash electro catalytic electrode Pyrogentisinic Acid, caprolactam and active black KN-B all has oxidation activity, can effectively destroy its structure, and effective intermediates, process comparatively thoroughly (seeing experimental example).
Brief description of the drawings
Fig. 1 is the preparation flow figure of novel Mo, antimony codope titanium base tin ash electro catalytic electrode;
Fig. 2 is novel Mo, 2000 times of scanning electron microscope images of antimony codope titanium base tin ash electro catalytic electrode that the atomic ratio of Sn, Sb, Mo is 100:3:1;
Fig. 3 is novel Mo, 2000 times of scanning electron microscope images of antimony codope titanium base tin ash electro catalytic electrode that the atomic ratio of Sn, Sb, Mo is 100:3:2;
Fig. 4 is novel Mo, 2000 times of scanning electron microscope images of antimony codope titanium base tin ash electro catalytic electrode that the atomic ratio of Sn, Sb, Mo is 100:3:3;
Fig. 5 is the atomic ratio of Sn, Sb, the Mo novel Mo that is 100:3:1, the X-ray diffraction spectrogram of antimony codope titanium base tin ash electro catalytic electrode;
Fig. 6 is phenol molecular structure;
Fig. 7 is that the atomic ratio of Sn, Sb, Mo be 100:3:1 novel Mo, antimony codope titanium base tin ash electro catalytic electrode Pyrogentisinic Acid and COD clearance is with degradation time Changing Pattern figure;
Fig. 8 is caprolactam molecular structure;
Fig. 9 be the atomic ratio of Sn, Sb, the Mo novel Mo that is 100:3:1, antimony codope titanium base tin ash electro catalytic electrode to COD clearance in caprolactam electrochemical degradation process with degradation time Changing Pattern figure;
Figure 10 is active black KN-B molecular structure;
Figure 11 is the atomic ratio of Sn, Sb, the Mo novel Mo that is 100:3:1, antimony codope titanium base tin ash electro catalytic electrode to active black KN-B and COD clearance with degradation time Changing Pattern figure.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is described further:
The present invention is the preparation method of a kind of novel Mo, antimony codope titanium base tin ash electro catalytic electrode, and as shown in Figure 1, the method step is as follows:
(1) pretreatment of titanium matrix: titanium matrix is polished with 120# and 240# water-proof abrasive paper, then be that 40%NaOH solution is at 80 DEG C of alkali cleaning oil removing 1h by mass concentration, after cleaning, be that 10 ~ 15% oxalic acid solutions are at slight boiling condition etching 1h, with being kept in ultra-pure water after distilled water cleaning by mass concentration again.
(2) colloidal sol preparation: taking ethanol as solvent, than being 100:3:1 ~ 3, above-mentioned element source is SnCl by the atomic molar of Sn, Sb, Mo4·5H2O、Sb2O3、(NH4)6Mo7O24Deng raw material, add complexing agent citric acid and ethylene glycol, wherein the mol ratio of metal ion, citric acid and ethylene glycol is 1:3:3; Metal ion refers to the summation of Sn, Sb, Mo ion. In 60 DEG C of water-baths, fully stir 1h Deng raw material after dissolving completely, then in 60 DEG C of water-baths still aging 2h.
(3) coating preparation: take out the above-mentioned titanium electrode substrate of handling well, blot the moisture that matrix surface adheres to, then lift film with dipping pulling machine; Titanium matrix does not flood 10min in colloidal sol, lifts out colloidal sol with 1mm/min speed; After each film, in air dry oven, be dried, baking temperature is 100 ~ 120 DEG C, and be 10 ~ 15min drying time; After dry, in the cooling 10min of room temperature, then heat-treat in electric furnace, heat treatment temperature is 450 ~ 500 DEG C, and heat treatment time is 10min.
(4) sintering processes: above-mentioned coating coating procedure carries out 10 ~ 15 times, last heat treatment process adopts ladder temperature programming sintering processes electrode; Ladder temperature programming temperature-rise period is: be warming up to 200 DEG C of insulation 20min by room temperature with 10 DEG C/min, be then warming up to 400 DEG C of insulation 20min with 3 DEG C/min, then be warming up at 600 DEG C and be incubated 2h with 1 DEG C/min, finally obtain the target electrode of doping.
The surface scan electron microscope image of this electrode and X-ray diffraction spectrogram are as Figure 2-Figure 5.
Embodiment:
Embodiment 1:
A preparation method for novel Mo, antimony codope titanium base tin ash electro catalytic electrode, step is as follows:
(1) pretreatment of titanium matrix: titanium matrix is polished with 120# and 240# water-proof abrasive paper, then uses 40%NaOH solution at 80 DEG C of alkali cleaning oil removing 1h, uses 10% oxalic acid solution at slight boiling condition etching 1h after cleaning again, after cleaning, is kept in ultra-pure water with distilled water.
(2) colloidal sol preparation: taking ethanol as solvent, than being 100:3:1, above-mentioned element source is SnCl by the atomic molar of Sn, Sb, Mo4·5H2O、Sb2O3、(NH4)6Mo7O24Deng raw material, add complexing agent citric acid and ethylene glycol, wherein the mol ratio of metal ion, citric acid and ethylene glycol is 1:3:3. In 60 DEG C of water-baths, fully stir 1h Deng raw material after dissolving completely, then in 60 DEG C of water-baths still aging 2h.
(3) coating preparation: take out the above-mentioned titanium electrode substrate of handling well, blot the moisture that matrix surface adheres to, then lift film with dipping pulling machine; Titanium matrix does not flood 10min in colloidal sol, lifts out colloidal sol with 1mm/min speed; After each film, in air dry oven, be dried, baking temperature is 100 DEG C, and be 15min drying time; After dry, in the cooling 10min of room temperature, then heat-treat in electric furnace, heat treatment temperature is 500 DEG C, and heat treatment time is 10min.
(4) sintering processes: above-mentioned coating coating procedure carries out 10 times, last heat treatment process adopts ladder temperature programming sintering processes electrode; Ladder temperature programming temperature-rise period is: be warming up to 200 DEG C of insulation 20min by room temperature with 10 DEG C/min, be then warming up to 400 DEG C of insulation 20min with 3 DEG C/min, then be warming up at 600 DEG C and be incubated 2h with 1 DEG C/min, finally obtain the target electrode of doping.
Embodiment 2:
A preparation method for novel Mo, antimony codope titanium base tin ash electro catalytic electrode, step is as follows:
(1) pretreatment of titanium matrix: titanium matrix is polished with 120# and 240# water-proof abrasive paper, then uses 40%NaOH solution at 80 DEG C of alkali cleaning oil removing 1h, uses 15% oxalic acid solution at slight boiling condition etching 1h after cleaning again, after cleaning, is kept in ultra-pure water with distilled water.
(2) colloidal sol preparation: taking ethanol as solvent, than being 100:3:2, above-mentioned element source is SnCl by the atomic molar of Sn, Sb, Mo4·5H2O、Sb2O3、(NH4)6Mo7O24Deng raw material, add complexing agent citric acid and ethylene glycol, wherein the mol ratio of metal ion, citric acid and ethylene glycol is 1:3:3. In 60 DEG C of water-baths, fully stir 1h Deng raw material after dissolving completely, then in 60 DEG C of water-baths still aging 2h.
(3) coating preparation: take out the above-mentioned titanium electrode substrate of handling well, blot the moisture that matrix surface adheres to, then lift film with dipping pulling machine; Titanium matrix does not flood 10min in colloidal sol, lifts out colloidal sol with 1mm/min speed; After each film, in air dry oven, be dried, baking temperature is 120 DEG C, and be 10min drying time; After dry, in the cooling 10min of room temperature, then heat-treat in electric furnace, heat treatment temperature is 450 DEG C, and heat treatment time is 10min.
(4) sintering processes: above-mentioned coating coating procedure carries out 15 times, last heat treatment process adopts ladder temperature programming sintering processes electrode; Ladder temperature programming temperature-rise period is: be warming up to 200 DEG C of insulation 20min by room temperature with 10 DEG C/min, be then warming up to 400 DEG C of insulation 20min with 3 DEG C/min, then be warming up at 600 DEG C and be incubated 2h with 1 DEG C/min, finally obtain the target electrode of doping.
Embodiment 3:
A preparation method for novel Mo, antimony codope titanium base tin ash electro catalytic electrode, step is as follows:
(1) pretreatment of titanium matrix: titanium matrix is polished with 120# and 240# water-proof abrasive paper, then uses 40%NaOH solution at 80 DEG C of alkali cleaning oil removing 1h, uses 12% oxalic acid solution at slight boiling condition etching 1h after cleaning again, after cleaning, is kept in ultra-pure water with distilled water.
(2) colloidal sol preparation: taking ethanol as solvent, than being 100:3:3, above-mentioned element source is SnCl by the atomic molar of Sn, Sb, Mo4·5H2O、Sb2O3、(NH4)6Mo7O24Deng raw material, add complexing agent citric acid and ethylene glycol, wherein the mol ratio of metal ion, citric acid and ethylene glycol is 1:3:3. In 60 DEG C of water-baths, fully stir 1h Deng raw material after dissolving completely, then in 60 DEG C of water-baths still aging 2h.
(3) coating preparation: take out the above-mentioned titanium electrode substrate of handling well, blot the moisture that matrix surface adheres to, then lift film with dipping pulling machine; Titanium matrix does not flood 10min in colloidal sol, lifts out colloidal sol with 1mm/min speed; After each film, in air dry oven, be dried, baking temperature is 110 DEG C, and be 12min drying time; After dry, in the cooling 10min of room temperature, then heat-treat in electric furnace, heat treatment temperature is 480 DEG C, and heat treatment time is 10min.
(4) sintering processes: above-mentioned coating coating procedure carries out 13 times, last heat treatment process adopts ladder temperature programming sintering processes electrode; Ladder temperature programming temperature-rise period is: be warming up to 200 DEG C of insulation 20min by room temperature with 10 DEG C/min, be then warming up to 400 DEG C of insulation 20min with 3 DEG C/min, then be warming up at 600 DEG C and be incubated 2h with 1 DEG C/min, finally obtain the target electrode of doping.
Experimental example:
Novel Mo, the antimony codope titanium base tin ash electro catalytic electrode degradation of phenol simulated wastewater of preparation in experimental example 1: embodiment 1,2 and 3.
Degradation condition: simulated wastewater volume 400ml, current density 10mA/cm2, initial phenol concentration 100mg/L, electrolyte 0.25mol/L sodium sulphate, configuration of electrodes is anode two negative electrodes, adjacent electrode spacing 20mm, the effective work area 40cm of electrode2. In electro-catalysis electrolytic experiment process, adopt magnetic stirrer to stir. Phenol molecular structure as shown in Figure 6, phenol and COD clearance are shown in Fig. 7 with degradation time change curve, novel Mo, antimony codope titanium base tin ash electro catalytic electrode Pyrogentisinic Acid catalytic oxidation activity prepared by the inventive method are higher, reach respectively 99.6%, 99.6%, 98.1% through 3.5h electrocatalysis oxidation reaction phenol clearance, COD clearance reaches respectively 90.2%, 90.2%, 84.0%.
The novel Mo of preparation, antimony codope titanium base tin ash electro catalytic electrode degraded caprolactam simulated wastewater in experimental example 2: embodiment 1.
Degradation condition: simulated wastewater volume 400ml, current density 10mA/cm2, caprolactam initial concentration 100mg/L, electrolyte 0.25mol/L sodium sulphate, configuration of electrodes is anode two negative electrodes, adjacent electrode spacing 20mm, the effective work area 40cm of electrode2. In electro-catalysis electrolytic experiment process, adopt magnetic stirrer to stir. Caprolactam molecular structure as shown in Figure 8, in caprolactam electrochemical degradation process, COD clearance is shown in Fig. 9 with degradation time change curve, novel Mo, antimony codope titanium base tin ash electro catalytic electrode prepared by the inventive method are higher to caprolactam catalytic oxidation activity, reach 91.5% through COD clearance in 3.5h electrocatalysis oxidation reaction caprolactam electrochemical degradation process.
Novel Mo, the black KN-B simulated wastewater of antimony codope titanium base tin ash electro catalytic electrode degrading activity of preparation in experimental example 3: embodiment 1.
Degradation condition: simulated wastewater volume 400ml, current density 20mA/cm2, dyestuff initial concentration 100mg/L, electrolyte 0.25mol/L sodium sulphate, configuration of electrodes is anode two negative electrodes, adjacent electrode spacing 20mm, the effective work area 40cm of electrode2. In electro-catalysis electrolytic experiment process, adopt magnetic stirrer to stir. Active black KN-B molecular structure as shown in figure 10, active black KN-B and COD clearance are shown in Figure 11 with degradation time change curve, the inventive method is prepared novel Mo, antimony codope titanium base tin ash electro catalytic electrode is higher to active black KN-B catalytic oxidation activity, reach 100%, COD clearance through 3.0h electrocatalysis oxidation reaction active black KN-B clearance and reach 74.6%.
Conclusion: the present invention adopts sol-gel process to prepare molybdenum, antimony codope titanium base tin ash electro catalytic electrode first, the electrode making cost compared with the noble coatings such as ruthenium, iridium electrode is low, and electrode surface even compact, good stability, the organic pollution of the multiple different structures such as Pyrogentisinic Acid, caprolactam and active black KN-B all has stronger degradation capability.
Claims (1)
1. a preparation method for molybdenum, antimony codope titanium base tin ash electro catalytic electrode, is characterized in that: step is as follows:
(1) pretreatment of titanium matrix: titanium matrix is polished with 120# and 240# water-proof abrasive paper, then be 40%NaOH solution alkali cleaning oil removing 1h at 80 DEG C by mass concentration, after cleaning, be that 10 ~ 15% oxalic acid solutions are at slight boiling condition etching 1h, with being kept in ultra-pure water after distilled water cleaning by mass concentration again;
(2) colloidal sol preparation: taking ethanol as solvent, dissolve SnCl4·5H2O、Sb2O3、(NH4)6Mo7O24Raw material, adds complexing agent citric acid and ethylene glycol, fully stirs 1h after raw material dissolves completely in 60 DEG C of water-baths, then in 60 DEG C of water-baths still aging 2h;
(3) coating preparation: take out the above-mentioned titanium electrode substrate of handling well, blot the moisture that matrix surface adheres to, then lift film with dipping pulling machine;
(4) sintering processes: above-mentioned coating coating procedure carries out 10 ~ 15 times, last heat treatment process adopts ladder temperature programming sintering processes electrode;
Step (2) Raw is that add 100:3:1 ~ 3 by the atomic ratio of Sn, Sb, Mo; Taking citric acid and ethylene glycol as complexing agent, wherein the mol ratio of metal ion, citric acid and ethylene glycol is 1:3:3; Metal ion refers to the summation of Sn, Sb, Mo ion;
In step (3), lifting painting membrane process is: titanium matrix does not flood 10min in colloidal sol, lifts out colloidal sol with 1mm/min speed; After each film, in air dry oven, be dried, baking temperature is 100 ~ 120 DEG C, and be 10 ~ 15min drying time; After dry, in the cooling 10min of room temperature, then heat-treat in electric furnace, heat treatment temperature is 450 ~ 500 DEG C, and heat treatment time is 10min;
In step (4), ladder Temperature Programmed Processes is: be warming up to 200 DEG C of insulation 20min by room temperature with 10 DEG C/min, be then warming up to 400 DEG C of insulation 20min with 3 DEG C/min, then be warming up at 600 DEG C and be incubated 2h with 1 DEG C/min, finally obtain the target electrode of doping.
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