CN104386785A - Preparation method for molybdenum-antimony co-doped titanium-based stannic oxide electrocatalysis electrode - Google Patents
Preparation method for molybdenum-antimony co-doped titanium-based stannic oxide electrocatalysis electrode Download PDFInfo
- Publication number
- CN104386785A CN104386785A CN201410512990.7A CN201410512990A CN104386785A CN 104386785 A CN104386785 A CN 104386785A CN 201410512990 A CN201410512990 A CN 201410512990A CN 104386785 A CN104386785 A CN 104386785A
- Authority
- CN
- China
- Prior art keywords
- electrode
- preparation
- titanium base
- antimony
- molybdenum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000010936 titanium Substances 0.000 title claims abstract description 66
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- WYWFMUBFNXLFJK-UHFFFAOYSA-N [Mo].[Sb] Chemical compound [Mo].[Sb] WYWFMUBFNXLFJK-UHFFFAOYSA-N 0.000 title abstract 4
- 238000000034 method Methods 0.000 claims abstract description 42
- 230000003197 catalytic effect Effects 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- 239000002585 base Substances 0.000 claims description 49
- 229910052787 antimony Inorganic materials 0.000 claims description 48
- 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
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 32
- 229910052750 molybdenum Inorganic materials 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 24
- 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
- 229910052718 tin Inorganic materials 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 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
- 239000012153 distilled water Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000007669 thermal treatment Methods 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
- 238000006731 degradation reaction Methods 0.000 abstract description 16
- 230000015556 catabolic process Effects 0.000 abstract description 13
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract description 2
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 abstract 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000003618 dip coating Methods 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 150000002989 phenols Chemical class 0.000 abstract 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 239000000985 reactive dye Substances 0.000 description 8
- 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
- 230000010718 Oxidation Activity Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000002441 X-ray diffraction Methods 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
- 239000000126 substance Substances 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 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
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 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
- 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 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
- 239000008151 electrolyte solution 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
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a preparation method for a molybdenum-antimony co-doped titanium-based stannic oxide electrocatalysis electrode, and belongs to the technical field of catalytic electrodes. The preparation method comprises: firstly using a sol-gel process for preparing the molybdenum-antimony co-doped titanium-based stannic oxide electrocatalysis electrode, concretely pretreating a titanium matrix, taking SnCl4.5H2O, Sb2O3 and (NH4)6Mo7O24 as raw materials, and preparing a sol according to the Sn:Sb:Mo atomic ratio of 100:3:1-3, employing a dipping-pulling process dip-coating technology, controlling the dipping time and the pulling speed, employing gradient-program heating sintering processing, and controlling the heat treatment temperature and the heat treatment time of each heating stage, so as to prepare the molybdenum-antimony co-doped titanium-based stannic oxide electrocatalysis electrode. The prepared electrode is relatively low in cost, uniform and dense in surface, good in stability and relatively strong in degradation capability on phenols, caprolactam, reactive black KN-B and other organic pollutants with different structures.
Description
Technical field
The present invention relates to the preparation method of a kind of molybdenum, antimony codoped titanium base tindioxide electro catalytic electrode, belong 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 pollutant has been there is in sewage, conventional physics, chemical process are difficult to these organism of process, and may secondary pollution problems be produced, traditional bioremediation can only remove the biological organism mixed in water body effectively.Electro-catalytic oxidation technology is more thorough owing to having degradation of organic substances, and the features such as 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 that electrochemistry is in the application of field of Environment Protection, the anode material manufacturing 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, overcomes the shortcoming that conventional graphite electrodes, lead dioxide electrode etc. exist, solves the problem of anode dissolution, avoids and produces pollution to electrolytic solution and cathode product, become electrochemical industry and the widely used electrode materials of field of Environment Protection.In all kinds of DSA electrode, Ti/RuO
2, Ti/IrO
2the low current efficiency that causes of electrode oxygen evolution potential is not high, and Ru, Ir all belong to precious metal, and this type of electrode preparation cost is higher.Ti/PbO
2can there is coating dissolution in anode, the lead ion of generation can pollute in electrolytic process.Ti/SnO
2electro catalytic activity and the corrosion resistance nature of-Sb electrode are fine, and there is higher oxygen evolution potential, it is a kind of electrocatalytic oxidation polarizing electrode of good performance, its many organic substance of can degrading in the short period of time, the process therefore studying tin antimony oxide coated electrode pair research waste water has very significance.The rare earth doped Ti/SnO that had many scholars to prepare in recent years
2-Sb electrode, and study its best preparation technology and electrocatalytic oxidation property thereof, although obtained electrode performance makes moderate progress, general rare earth element is expensive, and the cost of molybdenum is lower, wide material sources, and effectively can improve Ti/SnO
2the performance of-Sb electrode, therefore the present invention proposes a kind of novel Mo, antimony codoped titanium base tindioxide electro catalytic electrode and preparation method thereof of introducing molybdenum element first.
Summary of the invention
Goal of the invention
In order to solve the problem, the invention provides the preparation method of a kind of novel Mo, antimony codoped titanium base tindioxide 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 codoped titanium base tindioxide electro catalytic electrode, is characterized in that: step is as follows:
(1) pre-treatment of Titanium base: Titanium base 120# and 240# water-proof abrasive paper are polished, then be 40%NaOH solution alkali cleaning oil removing 1h at 80 DEG C by mass concentration, be that 10 ~ 15% oxalic acid solutions etch 1h at slight boiling condition by mass concentration again after cleaning, with being kept in ultrapure water after distilled water cleaning;
(2) colloidal sol preparation: take ethanol as solvent, dissolves SnCl
45H
2o, Sb
2o
3, (NH
4)
6mo
7o
24raw material, adds complexing agent citric acid and ethylene glycol, after raw material dissolves completely, fully stir 1h 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 handled well, blots the moisture of matrix surface attachment, then carries out lift film with Best-Effort request machine;
(4) sintering processes: above-mentioned coating application procedures carries out 10 ~ 15 times, last heat treatment process adopts ladder temperature programming sintering processes electrode.
Step (2) Raw is that 100:3:1 ~ 3 are added by the atomic ratio of Sn, Sb, Mo, and above-mentioned element source is SnCl
45H
2o, Sb
2o
3(NH
4)
6mo
7o
24raw material; With citric acid and ethylene glycol for 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), lift painting membrane process is: Titanium base does not flood 10min in colloidal sol, lifts out colloidal sol with 1mm/min speed; In air dry oven, carry out drying after each film, drying temperature is 100 ~ 120 DEG C, and time of drying is 10 ~ 15min; In room temperature cooling 10min after drying, then heat-treat in electric furnace, thermal treatment temp 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, is then warming up to 400 DEG C of insulation 20min with 3 DEG C/min, then is incubated 2h at being warming up to 600 DEG C with 1 DEG C/min, finally obtain the target electrode of adulterating.
Advantage and effect
Tool of the present invention has the following advantages and beneficial effect:
(1) novel Mo of the present invention, antimony codoped titanium base tindioxide electro catalytic electrode preparation method simply controlled (schema is shown in Fig. 1), be conducive to manufacturing and designing related electrode Preparation equipment, is easy to the preparation of mass-producing electrode.
(2) the method for the invention is prepared novel Mo, antimony codoped titanium base tindioxide electro catalytic electrode top 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 codoped do not change tindioxide four directions Rutile Type crystalline structure (X-ray diffraction spectrogram is shown in Fig. 5).
(3) the method for the invention prepare novel Mo, antimony codoped titanium base tindioxide electro catalytic electrode Pyrogentisinic Acid, the number of chemical structure such as hexanolactam and Reactive dye red M-3BE organism all there is oxidation activity, can effectively destroy its structure, and can effective intermediates, process is comparatively thoroughly (see experimental example).
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of novel Mo, antimony codoped titanium base tindioxide electro catalytic electrode;
Novel Mo, antimony codoped titanium base tindioxide electro catalytic electrode 2000 times of scanning electron microscope images of Fig. 2 to be the atomic ratio of Sn, Sb, Mo be 100:3:1;
Novel Mo, antimony codoped titanium base tindioxide electro catalytic electrode 2000 times of scanning electron microscope images of Fig. 3 to be the atomic ratio of Sn, Sb, Mo be 100:3:2;
Novel Mo, antimony codoped titanium base tindioxide electro catalytic electrode 2000 times of scanning electron microscope images of Fig. 4 to be the atomic ratio of Sn, Sb, Mo be 100:3:3;
Fig. 5 is the atomic ratio of Sn, Sb, Mo is the novel Mo of 100:3:1, the X-ray diffraction spectrogram of antimony codoped titanium base tindioxide electro catalytic electrode;
Fig. 6 is phenol molecular structure;
The novel Mo of Fig. 7 to be the atomic ratio of Sn, Sb, Mo be 100:3:1, antimony codoped titanium base tindioxide electro catalytic electrode Pyrogentisinic Acid and COD clearance are with degradation time Changing Pattern figure;
Fig. 8 is hexanolactam molecular structure;
The novel Mo of Fig. 9 to be the atomic ratio of Sn, Sb, Mo be 100:3:1, antimony codoped titanium base tindioxide electro catalytic electrode to COD clearance in hexanolactam electrochemical degradation process with degradation time Changing Pattern figure;
Figure 10 is Reactive dye red M-3BE molecular structure;
The novel Mo of Figure 11 to be the atomic ratio of Sn, Sb, Mo be 100:3:1, antimony codoped titanium base tindioxide electro catalytic electrode to Reactive dye red M-3BE and COD clearance with degradation time Changing Pattern figure.
Embodiment
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 codoped titanium base tindioxide electro catalytic electrode, and as shown in Figure 1, the method step is as follows:
(1) pre-treatment of Titanium base: Titanium base 120# and 240# water-proof abrasive paper are polished, then be that 40%NaOH solution is at 80 DEG C of alkali cleaning oil removing 1h by mass concentration, be that 10 ~ 15% oxalic acid solutions etch 1h at slight boiling condition by mass concentration again after cleaning, be kept in ultrapure water with after distilled water cleaning.
(2) colloidal sol preparation: take ethanol as solvent, be 100:3:1 ~ 3 by the atomic molar ratio of Sn, Sb, Mo, above-mentioned element source is SnCl
45H
2o, Sb
2o
3, (NH
4)
6mo
7o
24deng 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 after dissolving completely Deng raw material, then in 60 DEG C of water-baths still aging 2h.
(3) coating preparation: take out the above-mentioned titanium electrode substrate handled well, blots the moisture of matrix surface attachment, then carries out lift film with Best-Effort request machine; Titanium base does not flood 10min in colloidal sol, lifts out colloidal sol with 1mm/min speed; In air dry oven, carry out drying after each film, drying temperature is 100 ~ 120 DEG C, and time of drying is 10 ~ 15min; In room temperature cooling 10min after drying, then heat-treat in electric furnace, thermal treatment temp is 450 ~ 500 DEG C, and heat treatment time is 10min.
(4) sintering processes: above-mentioned coating application procedures 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, is then warming up to 400 DEG C of insulation 20min with 3 DEG C/min, then is incubated 2h at being warming up to 600 DEG C with 1 DEG C/min, finally obtain the target electrode of adulterating.
The surface Scanning Electron MIcrosope 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 codoped titanium base tindioxide electro catalytic electrode, step is as follows:
(1) pre-treatment of Titanium base: Titanium base 120# and 240# water-proof abrasive paper are polished, then uses 40%NaOH solution at 80 DEG C of alkali cleaning oil removing 1h, etches 1h again after cleaning with 10% oxalic acid solution at slight boiling condition, is kept in ultrapure water with after distilled water cleaning.
(2) colloidal sol preparation: take ethanol as solvent, be 100:3:1 by the atomic molar ratio of Sn, Sb, Mo, above-mentioned element source is SnCl
45H
2o, Sb
2o
3, (NH
4)
6mo
7o
24deng 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 after dissolving completely Deng raw material, then in 60 DEG C of water-baths still aging 2h.
(3) coating preparation: take out the above-mentioned titanium electrode substrate handled well, blots the moisture of matrix surface attachment, then carries out lift film with Best-Effort request machine; Titanium base does not flood 10min in colloidal sol, lifts out colloidal sol with 1mm/min speed; In air dry oven, carry out drying after each film, drying temperature is 100 DEG C, and time of drying is 15min; In room temperature cooling 10min after drying, then heat-treat in electric furnace, thermal treatment temp is 500 DEG C, and heat treatment time is 10min.
(4) sintering processes: above-mentioned coating application procedures 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, is then warming up to 400 DEG C of insulation 20min with 3 DEG C/min, then is incubated 2h at being warming up to 600 DEG C with 1 DEG C/min, finally obtain the target electrode of adulterating.
Embodiment 2:
A preparation method for novel Mo, antimony codoped titanium base tindioxide electro catalytic electrode, step is as follows:
(1) pre-treatment of Titanium base: Titanium base 120# and 240# water-proof abrasive paper are polished, then uses 40%NaOH solution at 80 DEG C of alkali cleaning oil removing 1h, etches 1h again after cleaning with 15% oxalic acid solution at slight boiling condition, is kept in ultrapure water with after distilled water cleaning.
(2) colloidal sol preparation: take ethanol as solvent, be 100:3:2 by the atomic molar ratio of Sn, Sb, Mo, above-mentioned element source is SnCl
45H
2o, Sb
2o
3, (NH
4)
6mo
7o
24deng 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 after dissolving completely Deng raw material, then in 60 DEG C of water-baths still aging 2h.
(3) coating preparation: take out the above-mentioned titanium electrode substrate handled well, blots the moisture of matrix surface attachment, then carries out lift film with Best-Effort request machine; Titanium base does not flood 10min in colloidal sol, lifts out colloidal sol with 1mm/min speed; In air dry oven, carry out drying after each film, drying temperature is 120 DEG C, and time of drying is 10min; In room temperature cooling 10min after drying, then heat-treat in electric furnace, thermal treatment temp is 450 DEG C, and heat treatment time is 10min.
(4) sintering processes: above-mentioned coating application procedures 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, is then warming up to 400 DEG C of insulation 20min with 3 DEG C/min, then is incubated 2h at being warming up to 600 DEG C with 1 DEG C/min, finally obtain the target electrode of adulterating.
Embodiment 3:
A preparation method for novel Mo, antimony codoped titanium base tindioxide electro catalytic electrode, step is as follows:
(1) pre-treatment of Titanium base: Titanium base 120# and 240# water-proof abrasive paper are polished, then uses 40%NaOH solution at 80 DEG C of alkali cleaning oil removing 1h, etches 1h again after cleaning with 12% oxalic acid solution at slight boiling condition, is kept in ultrapure water with after distilled water cleaning.
(2) colloidal sol preparation: take ethanol as solvent, be 100:3:3 by the atomic molar ratio of Sn, Sb, Mo, above-mentioned element source is SnCl
45H
2o, Sb
2o
3, (NH
4)
6mo
7o
24deng 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 after dissolving completely Deng raw material, then in 60 DEG C of water-baths still aging 2h.
(3) coating preparation: take out the above-mentioned titanium electrode substrate handled well, blots the moisture of matrix surface attachment, then carries out lift film with Best-Effort request machine; Titanium base does not flood 10min in colloidal sol, lifts out colloidal sol with 1mm/min speed; In air dry oven, carry out drying after each film, drying temperature is 110 DEG C, and time of drying is 12min; In room temperature cooling 10min after drying, then heat-treat in electric furnace, thermal treatment temp is 480 DEG C, and heat treatment time is 10min.
(4) sintering processes: above-mentioned coating application procedures 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, is then warming up to 400 DEG C of insulation 20min with 3 DEG C/min, then is incubated 2h at being warming up to 600 DEG C with 1 DEG C/min, finally obtain the target electrode of adulterating.
experimental example:
Experimental example 1: novel Mo, the antimony codoped titanium base tindioxide electro catalytic electrode degradation of phenol simulated wastewater of preparation in embodiment 1,2 and 3.
Degradation condition: simulated wastewater volume 400ml, current density 10mA/cm
2, initial phenol concentration 100mg/L, ionogen 0.25mol/L sodium sulfate, configuration of electrodes is anode two negative electrode, adjacent electrode spacing 20mm, the effective working area 40cm of electrode
2.Magnetic stirrer is adopted in electrocatalysis electrolytic experiment process.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 codoped titanium base tindioxide electro catalytic electrode Pyrogentisinic Acid catalytic oxidation activity prepared by the inventive method are higher, reach 99.6%, 99.6%, 98.1%, COD clearance respectively through 3.5h electrocatalysis oxidation reaction phenol clearance and reach 90.2%, 90.2%, 84.0% respectively.
Experimental example 2: the novel Mo of preparation in embodiment 1, antimony codoped titanium base tindioxide electro catalytic electrode degraded hexanolactam simulated wastewater.
Degradation condition: simulated wastewater volume 400ml, current density 10mA/cm
2, hexanolactam starting point concentration 100mg/L, ionogen 0.25mol/L sodium sulfate, configuration of electrodes is anode two negative electrode, adjacent electrode spacing 20mm, the effective working area 40cm of electrode
2.Magnetic stirrer is adopted in electrocatalysis electrolytic experiment process.Hexanolactam molecular structure as shown in Figure 8, in hexanolactam electrochemical degradation process, COD clearance is shown in Fig. 9 with degradation time change curve, novel Mo, antimony codoped titanium base tindioxide electro catalytic electrode prepared by the inventive method are higher to hexanolactam catalytic oxidation activity, and in 3.5h electrocatalysis oxidation reaction hexanolactam electrochemical degradation process, COD clearance reaches 91.5%.
Experimental example 3: novel Mo, the black KN-B simulated wastewater of antimony codoped titanium base tindioxide electro catalytic electrode degrading activity of preparation in embodiment 1.
Degradation condition: simulated wastewater volume 400ml, current density 20mA/cm
2, dyestuff starting point concentration 100mg/L, ionogen 0.25mol/L sodium sulfate, configuration of electrodes is anode two negative electrode, adjacent electrode spacing 20mm, the effective working area 40cm of electrode
2.Magnetic stirrer is adopted in electrocatalysis electrolytic experiment process.Reactive dye red M-3BE molecular structure as shown in Figure 10, Reactive dye red M-3BE and COD clearance are shown in Figure 11 with degradation time change curve, the inventive method prepares novel Mo, antimony codoped titanium base tindioxide electro catalytic electrode is higher to Reactive dye red M-3BE catalytic oxidation activity, reach 100%, COD clearance through 3.0h electrocatalysis oxidation reaction Reactive dye red M-3BE clearance and reach 74.6%.
Conclusion: the present invention adopts sol-gel method to prepare molybdenum, antimony codoped titanium base tindioxide electro catalytic electrode first, obtained electrode cost compared with the noble coatings such as ruthenium, iridium electrode is low, and electrode surface even compact, good stability, the organic pollutant of the multiple different structures such as Pyrogentisinic Acid, hexanolactam and Reactive dye red M-3BE all has stronger degradation capability.
Claims (4)
1. a preparation method for molybdenum, antimony codoped titanium base tindioxide electro catalytic electrode, is characterized in that: step is as follows:
(1) pre-treatment of Titanium base: Titanium base 120# and 240# water-proof abrasive paper are polished, then be 40%NaOH solution alkali cleaning oil removing 1h at 80 DEG C by mass concentration, be that 10 ~ 15% oxalic acid solutions etch 1h at slight boiling condition by mass concentration again after cleaning, with being kept in ultrapure water after distilled water cleaning;
(2) colloidal sol preparation: take ethanol as solvent, dissolves SnCl
45H
2o, Sb
2o
3, (NH
4)
6mo
7o
24raw material, adds complexing agent citric acid and ethylene glycol, after raw material dissolves completely, fully stir 1h 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 handled well, blots the moisture of matrix surface attachment, then carries out lift film with Best-Effort request machine;
(4) sintering processes: above-mentioned coating application procedures carries out 10 ~ 15 times, last heat treatment process adopts ladder temperature programming sintering processes electrode.
2. the preparation method of molybdenum according to claim 1, antimony codoped titanium base tindioxide electro catalytic electrode, is characterized in that: step (2) Raw is that 100:3:1 ~ 3 are added by the atomic ratio of Sn, Sb, Mo, and above-mentioned element source is SnCl
45H
2o, Sb
2o
3(NH
4)
6mo
7o
24raw material; With citric acid and ethylene glycol for 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.
3. the preparation method of molybdenum according to claim 1, antimony codoped titanium base tindioxide electro catalytic electrode, is characterized in that: in step (3), lift painting membrane process is: Titanium base does not flood 10min in colloidal sol, lifts out colloidal sol with 1mm/min speed; In air dry oven, carry out drying after each film, drying temperature is 100 ~ 120 DEG C, and time of drying is 10 ~ 15min; In room temperature cooling 10min after drying, then heat-treat in electric furnace, thermal treatment temp is 450 ~ 500 DEG C, and heat treatment time is 10min.
4. the preparation method of molybdenum according to claim 1, antimony codoped titanium base tindioxide electro catalytic electrode, it is characterized in that: 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, then 400 DEG C of insulation 20min are warming up to 3 DEG C/min, be incubated 2h at being warming up to 600 DEG C with 1 DEG C/min again, finally obtain the target electrode of adulterating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410512990.7A CN104386785B (en) | 2014-09-29 | 2014-09-29 | The preparation method of molybdenum, antimony codope titanium base tin ash electro catalytic electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410512990.7A CN104386785B (en) | 2014-09-29 | 2014-09-29 | The preparation method of molybdenum, antimony codope titanium base tin ash electro catalytic electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104386785A true CN104386785A (en) | 2015-03-04 |
| CN104386785B CN104386785B (en) | 2016-05-25 |
Family
ID=52604767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410512990.7A Active CN104386785B (en) | 2014-09-29 | 2014-09-29 | The preparation method of molybdenum, antimony codope titanium base tin ash electro catalytic electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104386785B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732605A (en) * | 2016-12-27 | 2017-05-31 | 上海应用技术大学 | A kind of non-noble metal oxide catalyst and preparation method with water resistant protective layer |
| CN108390070A (en) * | 2018-02-10 | 2018-08-10 | 浩发环保科技（深圳）有限公司 | Tin-antimony oxide anode material coating and preparation method thereof, flow battery Ti-base Sn-Sb oxide electrode |
| CN109594066A (en) * | 2018-12-18 | 2019-04-09 | 福建浩达智能科技股份有限公司 | A kind of preparation method of the super nanocrystalline titanium anode coating of hyperoxia |
| CN109772295A (en) * | 2019-03-11 | 2019-05-21 | 中南大学 | A kind of bismuth tungstate modification antimony-doped stannic oxide composite photoelectric catalysis electrode, preparation method and application |
| CN110670091A (en) * | 2019-09-30 | 2020-01-10 | 中国科学院过程工程研究所 | Coating composition of dimensionally stable electrode, preparation method and application |
| CN112626549A (en) * | 2020-12-15 | 2021-04-09 | 哈尔滨工业大学 | Titanium-doped tin dioxide electrocatalytic material, preparation method thereof and application of electrocatalytic nitrogen fixation |
-
2014
- 2014-09-29 CN CN201410512990.7A patent/CN104386785B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 刘淼等: "改性 Ti /SnO2-Sb电极降解硝基苯废水", 《高等学校化学学报》, vol. 34, no. 8, 31 August 2013 (2013-08-31), pages 1899 - 1906 * |
| 葛伟青等: "Mo掺杂Ti/Sb-SnO2电极处理含油废水的实验研究", 《唐山学院学报》, vol. 26, no. 6, 30 November 2013 (2013-11-30), pages 63 - 64 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732605A (en) * | 2016-12-27 | 2017-05-31 | 上海应用技术大学 | A kind of non-noble metal oxide catalyst and preparation method with water resistant protective layer |
| CN106732605B (en) * | 2016-12-27 | 2019-03-15 | 上海应用技术大学 | A kind of non-noble metal oxide catalyst and preparation method with water resistant protective layer |
| CN108390070A (en) * | 2018-02-10 | 2018-08-10 | 浩发环保科技（深圳）有限公司 | Tin-antimony oxide anode material coating and preparation method thereof, flow battery Ti-base Sn-Sb oxide electrode |
| CN108390070B (en) * | 2018-02-10 | 2021-02-12 | 浩发环保科技（深圳）有限公司 | Tin-antimony oxide anode material coating, preparation method thereof and titanium-based tin-antimony oxide electrode of flow battery |
| CN109594066A (en) * | 2018-12-18 | 2019-04-09 | 福建浩达智能科技股份有限公司 | A kind of preparation method of the super nanocrystalline titanium anode coating of hyperoxia |
| CN109772295A (en) * | 2019-03-11 | 2019-05-21 | 中南大学 | A kind of bismuth tungstate modification antimony-doped stannic oxide composite photoelectric catalysis electrode, preparation method and application |
| CN110670091A (en) * | 2019-09-30 | 2020-01-10 | 中国科学院过程工程研究所 | Coating composition of dimensionally stable electrode, preparation method and application |
| CN112626549A (en) * | 2020-12-15 | 2021-04-09 | 哈尔滨工业大学 | Titanium-doped tin dioxide electrocatalytic material, preparation method thereof and application of electrocatalytic nitrogen fixation |
| CN112626549B (en) * | 2020-12-15 | 2022-02-25 | 哈尔滨工业大学 | Titanium-doped tin dioxide electrocatalytic material, preparation method thereof and application of electrocatalytic nitrogen fixation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104386785B (en) | 2016-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104386785B (en) | The preparation method of molybdenum, antimony codope titanium base tin ash electro catalytic electrode | |
| An et al. | The synthesis and characterization of Ti/SnO2–Sb2O3/PbO2 electrodes: the influence of morphology caused by different electrochemical deposition time | |
| Lim et al. | Influence of the Sb content in Ti/SnO2-Sb electrodes on the electrocatalytic behaviour for the degradation of organic matter | |
| CN103014755B (en) | Fabrication method of long-life titanium base electrode | |
| CN107020074A (en) | A kind of electro-catalysis POROUS TITANIUM filter membrane with micro-nano structure and preparation method thereof | |
| CN102304724B (en) | Preparation method of rare earth Pr (praseodymium)-Dy (dysprosium) doped nanometer titanium-based tin dioxide-antimony double coating electrode | |
| CN104973662B (en) | Oxide anode for treatment of ship domestic sewage and preparation method thereof | |
| CN110803743B (en) | Preparation method of defect-state titanium oxide-aluminum oxide-graphene ceramic electrode | |
| CN109292918B (en) | Preparation method of DSA electrode | |
| CN111099702A (en) | Preparation method of titanium anode for water treatment | |
| CN103253743A (en) | Preparation method and application of Fe-doped PTFE-PbO2/TiO2-NTs/Ti electrode | |
| CN104016449A (en) | Preparation and application of Sb-Ni-Nd co-doping SnO2 high catalytic activity positive electrode | |
| CN110272100A (en) | Ti4O7Preparation method of ceramic microfiltration membrane electrode of coating | |
| CN103159299A (en) | Porous titanium film photoelectrically-catalytic waste water reaction device | |
| CN108217852A (en) | High life, high catalytic activity lead dioxide electrode | |
| CN108130582A (en) | A kind of preparation method of 2.5 dimension anodes of high catalytic activity carried magnetic particle | |
| CN105692798A (en) | Electrocatalytic oxidation reaction device for treating degradation-resistant organic wastewater | |
| CN104528887A (en) | Preparation method of Ti/SnO2-Sb thin film electrode for sewage deep treatment | |
| CN113716658B (en) | Preparation method of ruthenium, iridium and titanium ternary metal mesh electrode containing nano tip structure | |
| CN101956194A (en) | Method for preparing TiO2 thin film modified titanium-based beta-PbO2 photoelectrode | |
| CN110980890A (en) | Titanium-based lead dioxide electrode for degrading rhodamine B and preparation method and application thereof | |
| CN110655150B (en) | Titanium-based tin oxide anode electrode and preparation method thereof | |
| CN109824126B (en) | Tin oxide anode electrode with high oxygen evolution potential and preparation method | |
| KR20190067354A (en) | method for manufacturing graphene complex electrolysis electrodes for wastewater processing and sterilization | |
| CN112499729A (en) | Electrode with active layer containing S-doped GO and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230728 Address after: Room A203, No. 400-11 (1-201), Wisdom Second Street, Hunnan District, Shenyang City, Liaoning Province, 110000 Patentee after: Shenyang Baiyi Boshuo Technology Co.,Ltd. Address before: 110870 No. 111 Shenyang West Road, Shenyang economic and Technological Development Zone, Liaoning Patentee before: SHENYANG University OF TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231222 Address after: No. 400-11, Zhihui Second Street, Hunnan District, Shenyang, Liaoning 110167 (1-301) Patentee after: SHENYANG INDUSTRIAL TECHNOLOGY INSTITUTE OF LANJIN ENVIRONMENTAL PROTECTION INDUSTRY Co.,Ltd. Address before: Room A203, No. 400-11 (1-201), Wisdom Second Street, Hunnan District, Shenyang City, Liaoning Province, 110000 Patentee before: Shenyang Baiyi Boshuo Technology Co.,Ltd. |