CN115490304B - Preparation method and application of cerium dioxide doped titanium nanotube electrode - Google Patents
Preparation method and application of cerium dioxide doped titanium nanotube electrode Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 99
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 83
- 239000002071 nanotube Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title description 5
- 230000015556 catabolic process Effects 0.000 claims abstract description 82
- 238000006731 degradation reaction Methods 0.000 claims abstract description 82
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 43
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002351 wastewater Substances 0.000 claims abstract description 34
- 230000003647 oxidation Effects 0.000 claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 238000004070 electrodeposition Methods 0.000 claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- CQPFMGBJSMSXLP-ZAGWXBKKSA-M Acid orange 7 Chemical compound OC1=C(C2=CC=CC=C2C=C1)/N=N/C1=CC=C(C=C1)S(=O)(=O)[O-].[Na+] CQPFMGBJSMSXLP-ZAGWXBKKSA-M 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 9
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005530 etching Methods 0.000 claims abstract description 7
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 49
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 29
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 29
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- 238000010525 oxidative degradation reaction Methods 0.000 claims description 19
- 229910052697 platinum Inorganic materials 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- -1 cerium ions Chemical class 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 238000003837 high-temperature calcination Methods 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
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- 230000000694 effects Effects 0.000 abstract description 16
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
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- 238000005516 engineering process Methods 0.000 description 8
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- 239000002105 nanoparticle Substances 0.000 description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 229910003460 diamond Inorganic materials 0.000 description 6
- 239000010432 diamond Substances 0.000 description 6
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- 238000002484 cyclic voltammetry Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
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- 230000008859 change Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- 244000137852 Petrea volubilis Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
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- 150000003608 titanium Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
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- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Abstract
The invention discloses a preparation method and application of a cerium oxide doped titanium nanotube electrode, wherein the preparation process comprises the steps of etching a titanium sheet to serve as an electrode anode and carrying out anodic oxidation; then taking the anodized electrode as an anode, reacting at constant voltage, and calcining the obtained electrode at high temperature to obtain a titanium dioxide nanotube electrode; preparing a solution containing one or two of cerium sulfate and cerium nitrate as an electrodeposition solution, performing electrochemical deposition with constant potential by taking the electrode as a working electrode, and annealing and calcining the obtained electrode to obtain the cerium oxide doped titanium nanotube electrode. The preparation process is safe, the cost is low, and experiments prove that the electrode prepared by the invention has good conductivity, high oxygen evolution potential, excellent electrochemical oxidation activity, pollutant degradation capability and high stability, has good degradation and mineralization effects on simulated dye wastewater, especially acid orange 7-containing wastewater, and has wide application prospects.
Description
Technical Field
The invention belongs to the field of electrochemical oxidative degradation of pollutants, and particularly relates to a preparation method of a cerium oxide doped titanium nanotube electrode and application of the cerium oxide doped titanium nanotube electrode in electrochemical oxidation.
Background
The textile and printing industry, as a major consumer of industrial water, generates large amounts of wastewater every day. The dye wastewater has the characteristics of complex components, high concentration of organic matters, large pH change, difficult biodegradation and the like, so that the treatment of the dye wastewater is always a difficult problem in the environmental field. The dye wastewater contains a large amount of benzene, anthracene, amine compounds, polycyclic aromatic hydrocarbon, azo substances and other organic pollutants with a three-effect, has toxic action on microorganisms in water, and is more harmful to life and health of human beings. In addition, the dye wastewater has high chromaticity, and the pollution can destroy the self-cleaning function of the water body, interfere the growth of aquatic organisms and seriously destroy ecological balance.
At present, the treatment of dye wastewater mainly comprises a physical adsorption method, a membrane separation method, biodegradation and advanced oxidation technology. The adsorption technology is convenient to operate, but the manufacturing cost of the adsorption material is high, the regeneration is difficult, and the adsorption material is difficult to be used for treating a large amount of wastewater; the separation effect of the membrane separation technology depends on the performance of the semipermeable membrane, the dye wastewater has complex components, the pollution problem of the semipermeable membrane exists in the treatment process, and the service life is reduced; the application of the advanced oxidation technology has the problems of secondary pollution, high energy consumption, high operation cost and the like, and industrial operation is difficult to realize. The electrochemical oxidation technology has the characteristics of no secondary pollution, small equipment occupation area, easiness in automation, high reaction efficiency, low toxicity of reaction products and the like, and has good development prospect in the treatment of dye wastewater.
In the anode materials used at present for electrochemical oxidation, the electrochemical oxidation performance of the boron-doped diamond electrode and the steady-state electrode is better. Common commercialized electrodes have low cost, but poor oxidizing capability, and cannot meet the wastewater degradation requirement. However, the boron-doped diamond electrode material has high cost and complex preparation process, and cannot be produced in large scale; the steady-state electrode active layer is easy to fall off, so that the electrode is deactivated, and metals such as lead metal and the like which can cause heavy pollution are generally required to be doped, so that the electrode has potential harm to the environment. There is therefore an urgent need to develop new electrodes with high electrocatalytic activity, high chemical stability, low cost and no environmental hazard.
Disclosure of Invention
The invention aims to: aiming at the problems existing in the prior art, the invention provides a preparation method of a cerium oxide doped titanium nanotube electrode with good electrocatalytic oxidation capability, low cost and high efficiency.
The invention also provides application of the cerium oxide doped titanium nanotube electrode.
The technical scheme is as follows: in order to achieve the above object, the preparation method of the cerium oxide doped titanium nanotube electrode of the present invention comprises the following steps:
(1) Polishing a titanium plate, a titanium rod or a titanium mesh into titanium sheets, and etching the titanium sheets by adopting concentrated sulfuric acid and/or concentrated nitric acid mixed solution; soaking the etched titanium sheet in ultrasonic waves and drying;
(2) Taking the electrode obtained in the step (1) as an anode, taking a platinum sheet electrode as a cathode, configuring anode oxidation electrolyte, performing anodic oxidation, taking out the anode electrode after the reaction is finished, washing and drying;
(3) Preparing ethylene glycol solution containing phosphoric acid as electrolyte, taking the electrode obtained in the step (2) as an anode, taking a platinum sheet electrode as a cathode, reacting at constant voltage, and calcining the obtained electrode at high temperature to obtain the titanium dioxide nanotube electrode, namely TiO 2 An NTA electrode;
(4) Preparing a solution containing one or two of cerium sulfate and cerium nitrate as an electrodeposition solution, and using the electrode obtained in the step (3) as an electrodeThe electrode is prepared by performing electrochemical deposition with a constant potential by using a platinum sheet electrode as a reference electrode and a saturated calomel electrode as a counter electrode, and annealing and calcining the obtained electrode to obtain a cerium oxide doped titanium nanotube electrode, namely CeO 2 /TiO 2 NTA。
Wherein, in the step (1), a mixed solution of concentrated sulfuric acid and concentrated nitric acid with the molar ratio of 1:1-1:3 is prepared, and the titanium sheet is etched at the temperature of 40-60 ℃.
Wherein the anodic oxidation electrolyte in the step (2) contains 0.1-0.75wt% of ammonium fluoride and 1-3wt% of H 2 Ethylene glycol solution of O.
Preferably, the mass fraction of ammonium fluoride in the anodic oxidation electrolyte is 0.25wt% and the mass fraction of water is 2wt%.
Wherein, the anodic oxidation in the step (2) adopts a constant voltage method, and the anodic oxidation is carried out for 2-6h under 50-70V.
Preferably, the voltage is 50V and the optimal reaction time is 5h.
Preferably, the mass fraction of phosphoric acid in the solution prepared in step (3) is 0.1 to 0.5wt%.
Wherein the reaction in the step (3) is carried out for 1-2h under the constant voltage of 50-70V.
Wherein the high-temperature calcination in the step (3) is carried out for 2-3 hours at the temperature of 450-800 ℃.
Wherein the concentration of cerium ions in the electrodeposition solution in the step (4) is 1-10mmol/L.
Preferably, the electrochemical deposition in the step (4) has a potential of 0.4-1.2V Vs SCE and a reaction time of 5-30min, and the annealing calcination is performed at 450-800 ℃ for 1-2h.
The application of the cerium oxide doped titanium nanotube electrode prepared by the preparation method in electrochemical oxidative degradation of acid orange 7 dye (AO 7) wastewater.
Further, the specific steps of the application are as follows: taking acid orange 7-containing wastewater solution as electrolyte, taking a cerium oxide doped titanium nanotube electrode as an anode, taking a platinum sheet electrode as a cathode, and carrying out degradation treatment under constant current density, wherein the current density is 1-20 mA/cm 2 Is constant in (2)Under the current condition, the electrolyte is sodium sulfate with the concentration of 0.01-0.1 mol/L, the stirring speed is 500-1000r/min, and the reaction time is 1-2h.
The invention provides a cerium dioxide doped titanium nanotube electrode, which is prepared by taking a titanium plate as a substrate, and sequentially carrying out polishing, acidification etching, anodic oxidation, anodic reoxidation, high-temperature calcination, electrodeposition and annealing on the substrate. Specifically, the titanium plate is used as a substrate, and the substrate sequentially removes oxides and irregular particles on the surface of titanium metal through sanding, concentrated sulfuric acid/concentrated nitric acid acidification and etching processes, so that the subsequent generation of the titanium nanotubes is more uniform; then, the electrode plate is anodized in electrolyte solution containing glycol and fluoride ions to generate a titanium nanotube structure; oxidizing again in the solution containing phosphoric acid and ethylene glycol to make the surface structure of the electrode more stable; preparing a modified titanium nanotube crystal phase through a high-temperature calcination process; then taking the electrode as an anode, and carrying out electrodeposition in electrolyte containing trivalent cerium under constant potential to realize cerium metal doping; the doped cerium metal is converted into a cerium oxide nanoparticle form by a high temperature annealing process. The specific surface area of the electrode material can be obviously increased by the titanium nano tube, a special electron action mechanism can be formed by doping the cerium oxide nano particles and the titanium nano tube, and meanwhile, oxygen vacancies and defects are introduced on the surface of the electrode by introducing the cerium oxide nano particles, so that OH is more easily generated, and the electrochemical oxidation reaction process is facilitated. Further, experiments prove that the electrocatalytic oxidation process of the electrode prepared by the invention mainly realizes the degradation of pollutants through the efficient oxidation of hydroxyl radicals, and in addition, the electrochemical analysis shows that the electrode prepared by the invention has an oxygen evolution potential higher than that of a BDD electrode and has stronger electrocatalytic oxidation potential. The invention aims at electrochemical oxidative degradation of dye pollutants, and provides an electrocatalytic anode electrode which is low in cost, high in efficiency and good in electrocatalytic activity.
The cerium dioxide doped titanium nanotube electrode prepared by the invention can quickly oxidize and degrade typical dye AO7 wastewater in the solution in a conventional electrocatalytic reactor, has obvious solution decoloring effect after being treated for a period of time, and has better effect on removing COD. Compared with the commercialized electrode widely applied at present, the electrode provided by the invention has optimal electrochemical oxidation activity on typical dye AO7 wastewater, is low in cost, has wide sources of raw materials, does not need large-scale equipment in the preparation process, and is expected to be widely applied to the field of electrochemical treatment of dye wastewater treatment.
According to the invention, the titanium plate is used as a substrate, and the substrate sequentially removes oxides and irregular particles on the surface of titanium metal through sand paper polishing, concentrated sulfuric acid/concentrated nitric acid acidification and etching processes, so that the subsequent generation of the titanium nanotubes is more uniform; then, the electrode plate is anodized in electrolyte solution containing glycol and fluoride ions to generate a titanium nanotube structure; oxidizing again in the solution containing phosphoric acid and ethylene glycol to make the surface structure of the electrode more stable; preparing a modified titanium nanotube crystal phase through a high-temperature calcination process; then taking the electrode as an anode, and carrying out electrodeposition in electrolyte containing trivalent cerium under constant potential to realize cerium metal doping; the doped cerium metal is converted into a cerium oxide nanoparticle form by a high temperature annealing process. The specific surface area of the electrode material can be obviously increased by the titanium nano tube, a special electron action mechanism can be formed by doping the cerium oxide nano particles and the titanium nano tube, and meanwhile, oxygen vacancies and defects are introduced on the surface of the electrode by introducing the cerium oxide nano particles, so that OH is more easily generated, and the electrochemical oxidation reaction process is facilitated.
The catalyst with high catalytic effect is produced by using the titanium plate and cerium metal as raw materials through a series of specific reaction processes, and the catalyst has better catalytic effect than the existing commercial electrode through degradation experiments of pollutants and electrochemical characterization data.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
1. the preparation process is simple and safe, the prepared electrode has the advantages of low cost, good conductivity and corrosion resistance, and meanwhile, the specific surface area of the electrode and the charge transfer efficiency are increased through a simple anodizing process, so that the conductivity of the electrode is improved.
2. The preparation of the titanium nanotube is realized through an anodic oxidation technology, the stability of the electrode is improved based on the anodic reoxidation and high-temperature annealing technology with phosphoric acid as a stabilizer, the doping of cerium oxide is realized through an electrochemical deposition technology, more oxygen vacancies are introduced, and the oxygen evolution potential, the catalytic activity and the conductivity of the electrode are increased, so that the electrode has higher electrochemical oxidation activity and pollutant degradation capability.
3. Experiments prove that the electrode has good electrochemical oxidation potential and good capacitance characteristic. Meanwhile, the electrode prepared by the invention can efficiently degrade the typical dye AO7 through an electrochemical oxidation process, and has good mineralization effect (shown by COD) on AO7 solution.
4. Compared with several common commercial electrodes, the electrode prepared by the invention has optimal electrocatalytic activity and pollutant degradation capability to typical dye AO7, and simultaneously has simpler preparation process, more environmental friendliness and good application potential.
Drawings
FIG. 1 shows CeO in example 1 of the present invention 2 /TiO 2 The NTA electrode is used for comparing the simulated dye wastewater degradation effects of acid orange 7 at different current densities;
FIG. 2 shows CeO in example 1 of the present invention 2 /TiO 2 The NTA electrode is used for comparing the simulated dye wastewater degradation effect of the acid orange 7 under different electrolyte concentrations;
FIG. 3 shows CeO in example 1 of the present invention 2 /TiO 2 The degradation effect changes with the times when the NTA electrode electrolyzes AO7 for a plurality of times;
FIG. 4 is a comparison of the degradation effect of the electrodes of example 1 of the present invention on AO7 dye wastewater in comparative examples 8 to 12;
FIG. 5 is a linear sweep voltammogram of the electrodes of example 1 and comparative example 13 of the present invention;
FIG. 6 shows cyclic voltammograms of different electrodes in example 1 and comparative examples 13 to 15 of the present invention.
Detailed Description
The invention is further illustrated by the following examples.
The experimental methods described in the examples, unless otherwise specified, are all conventional; the reagents and materials, unless otherwise specified, are commercially available.
Boron diamond electrode (BDD), titanium-based tin antimony (Ti/SnO) 2 -Sb 2 O 5 ) Titanium-based iridium tantalum ruthenium iridium (Ti/IrO) 2 -Ta 2 O 5 ) Titanium-based ruthenium iridium (Ti/RuO) 2 -IrO 2 ) Ti/pt are commercially available.
Example 1
Firstly, preparing an electrode, wherein the electrode is prepared by the following steps: (1) Grinding the titanium plate into titanium sheets by sand paper, preparing a concentrated sulfuric acid/concentrated nitric acid mixed solution with the molar ratio of 1:2, and etching the titanium sheets at 50 ℃. And (3) sequentially placing the etched titanium sheet in acetone and ethanol solution, soaking and ultrasonic treating for 60 minutes, and then placing in a 60 ℃ oven for drying for 12 hours. (2) Preparing an anodic oxidation electrolyte containing 0.25wt% of ammonium fluoride and 2wt% of H 2 The ethylene glycol solution of O was placed in a polytetrafluoroethylene beaker. Taking the electrode treated in the step (1), taking the electrode as an anode, taking a platinum sheet electrode as a cathode, taking the solution as an electrolyte, performing anodic oxidation for 5 hours at 50V by adopting a constant voltage method, taking out the anode electrode after the reaction is finished, flushing the surface of the electrode obtained after anodic oxidation by ethanol, flushing by ultrapure water, and drying. (3) Preparing ethylene glycol solution containing 0.25wt% of phosphoric acid as electrolyte, taking the obtained electrode as an anode, taking a platinum sheet electrode as a cathode, reacting for 1h under constant voltage of 50V, then placing the obtained electrode into a muffle furnace, and calcining at 500 ℃ for 2h at high temperature to obtain the titanium dioxide nanotube electrode, namely TiO 2 NTA electrode. (4) Preparing cerium nitrate aqueous solution containing 5mmol/L as electrodeposition solution, taking the electrode as a working electrode, taking a platinum sheet electrode as a reference electrode, taking a saturated calomel electrode as a counter electrode to perform electrochemical deposition with constant potential, wherein the potential is 0.8V Vs. SCE, and the reaction time is 15min. Annealing and calcining the obtained electrode for 2 hours at 500 ℃ to obtain the cerium oxide doped titanium nanotube electrode, namely CeO 2 /TiO 2 NTA。
Test 1: electrochemical oxidative degradation of acid orange 7 mimics dye waste water: configuration contains 50mg/L of acidityOrange 7 (AO 7) simulated dye wastewater solution. 200mL of simulated dye wastewater is taken as electrolyte in an electrochemical reactor, a cerium oxide doped titanium nanotube electrode is taken as an anode, a platinum sheet electrode is taken as a cathode, the reaction is carried out under constant current density, and the current density is 10mA/cm 2 The electrolyte is 0.05mol/L sodium sulfate, the stirring speed is 500r/min, and the reaction time is 2h. And (3) measuring the concentration of AO7 and COD in the water sample after the reaction, wherein the concentration of AO7 is detected by an ultraviolet spectrophotometer. As a result, the degradation rate of AO7 reaches 90.12% after the reaction is carried out for 2 hours, and the COD degradation rate reaches 82.18%.
Test 2: the three-electrode cyclic voltammetry test system is adopted, and the above-mentioned electrode CeO is adopted respectively 2 /TiO 2 NTA electrode and TiO 2 NTA electrode is used as working electrode, saturated calomel electrode is used as reference electrode, platinum electrode is used as counter electrode, test electrolyte solution is 0.05mol/L sodium sulfate solution, scanning speed is 100mV/s, and potential window is-0.5-1.5V vs. SCE. The test results are shown in FIG. 5. As can be seen from FIG. 5, ceO 2 The CV curve of the doped electrode is approximately rectangular, which shows CeO 2 /TiO 2 The NTA electrode has excellent capacitance characteristics and higher electrocatalytic oxidation-reduction activity.
Test 3: the three-electrode linear volt-ampere test system is adopted, and the prepared electrode CeO is adopted respectively 2 /TiO 2 NTA electrode or other electrodes are used as working electrodes, saturated calomel electrode is used as reference electrode, platinum electrode is used as counter electrode, test electrolyte solution is sulfuric acid solution of 0.5mol/L, scanning speed is 5mV/min, and potential window is 0-4.0V vs. The test results are shown in FIG. 6. CeO can be obtained from the analysis of FIG. 6 2 /TiO 2 The NTA electrode has a higher oxygen evolution potential (i.e., the diagonal portion of the LSV curve extends to a potential corresponding to the coordinate where it intersects the X-axis), which is shown to be significantly higher on the far right side than the other electrodes.
Example 2
The preparation method of the cerium oxide doped titanium nanotube electrode is the same as that of example 1. Electrochemical degradation the current density in this example was changed to 1mA/cm 2 Other reaction conditions were the same as described in example 1And the same is true. The reaction is carried out for 2 hours, the degradation rate of AO7 is 46.53 percent, and the COD degradation rate is 37.78 percent.
Example 3
The preparation method of the cerium oxide doped titanium nanotube electrode is the same as that of example 1, and the current density in this example is changed to 2.5mA/cm 2 Other reaction conditions were the same as described in example 1. The reaction is carried out for 2 hours, the degradation rate of AO7 is 58.65 percent, and the COD degradation rate reaches 48.42 percent.
Example 4
The preparation method of the cerium oxide doped titanium nanotube electrode is the same as that of example 1, and the current density in this example is changed to 5mA/cm 2 Other reaction conditions were the same as described in example 1. The reaction is carried out for 2 hours, the degradation rate of AO7 is 76.87%, and the COD degradation rate reaches 61.37%.
Example 5
The preparation method of the cerium oxide doped titanium nanotube electrode is the same as that of example 1, and the current density in this example is changed to 20mA/cm 2 Other reaction conditions were the same as described in example 1. The reaction is carried out for 2 hours, the degradation rate of AO7 is 94.28 percent, and the COD degradation rate reaches 84.21 percent.
Example 6
The preparation method of the cerium oxide doped titanium nanotube electrode was the same as in example 1, and the electrolyte concentration in this example was changed to 0.01mol/L, and the other reaction conditions were the same as those described in example 1. The degradation rate of AO7 is 74.79% after 2 hours of reaction, and the COD degradation rate reaches 64.12%.
Example 7
The preparation method of the cerium oxide doped titanium nanotube electrode was the same as in example 1, and the electrolyte concentration in this example was changed to 0.025mol/L, and the other reaction conditions were the same as those described in example 1. The reaction is carried out for 2 hours, the degradation rate of AO7 is 83.89 percent, and the COD degradation rate reaches 71.45 percent.
Example 8
The preparation method of the cerium oxide doped titanium nanotube electrode is the same as that of example 1, the electrolyte concentration in the example is changed to 0.075mol/L, and other reaction conditions are the same as those described in example 1. The reaction is carried out for 2 hours, the degradation rate of AO7 is 92.15 percent, and the COD degradation rate is 83.13 percent.
Example 9
The preparation method of the cerium oxide doped titanium nanotube electrode was the same as in example 1, and the electrolyte concentration in this example was changed to 0.1mol/L, and the other reaction conditions were the same as those described in example 1. The degradation rate of AO7 is 92.88 percent after 2 hours of reaction, and the COD degradation rate reaches 84.25 percent.
From examples 1 to 9, with reference to fig. 1 and fig. 2, it can be seen that the prepared cerium oxide doped titanium nanotube electrode has a good electrochemical oxidative degradation effect on acid orange 7 simulated dye wastewater, and meanwhile, electrochemical oxidative degradation parameters such as current density, electrolyte concentration and the like are found to have a great influence on the electrochemical oxidation process, and the reasons of the electrochemical oxidative degradation parameters include influence of factors such as conductivity, competing reaction and the like are analyzed. Considering both economic and degradation efficiency factors, the reaction cost is significantly increased due to the increase of the current density and the electrolyte concentration, when the current density is more than 10mA/cm 2 After the electrolyte concentration is more than 0.05mol/L, the AO7 degradation rate is hardly improved or the improvement amplitude is small, so that the optimal parameters of the electrochemical oxidation process are determined as follows: optimal degradation current density of 10mA/cm 2 The optimum electrolyte concentration was 0.05mol/L sodium sulfate solution, and this parameter was the parameter in example 1.
Example 10
The parameters of the preparation method of the cerium oxide doped titanium nanotube electrode and the electrochemical oxidative degradation AO7 simulated dye wastewater are the same as in example 1. To determine the stability of the electrode, the electrodes prepared in example 1 were used to repeat 7 AO7 degradation experiments, in which the AO7 degradation rates were 90.12, 89.99, 89.56, 89.29, 89.17, 88.26, 87.97% and COD degradation rates were 82.18, 82.07, 82.00, 81.89, 81.58, 81.40%, respectively, with the other parameters unchanged.
As can be seen from the degradation rate of AO7 and COD in the embodiment 10 in combination with the attached figure 3, the electrode prepared by the invention has good degradation effect on the AO7 simulated dye wastewater after 7 times of recycling, which indicates that the electrode has good stability and good application potential in the treatment of actual wastewater.
Comparative example 1
By adopting the method of example 1, the electrode preparation process is only (1), steps (2), (3) and (4) are not performed, the obtained electrode is a titanium sheet electrode, the electrode does not contain a titanium nanotube structure and does not contain cerium oxide particle doping, and the electrochemical oxidative degradation process is the same as that of example 1. The degradation rate of AO7 reaches 10.15% after 2 hours of reaction, and the COD degradation rate reaches 3.57%.
Comparative example 2
By adopting the method of example 1, the electrode preparation process is only (1) and (4), steps (2) and (3) are not performed, the obtained electrode is the cerium oxide doped Ti/CeO2 electrode, the electrode does not contain a titanium nanotube structure, and the electrochemical oxidative degradation process is the same as that of example 1. The degradation rate of AO7 reaches 32.15% after 2 hours of reaction, and the COD degradation rate reaches 22.57%.
Comparative example 3
By adopting the method of example 1, the electrode preparation process is only carried out by (1) and (2) and steps (3) and (4) are not carried out, the obtained electrode is the titanium nanotube electrode, the electrode is not subjected to the anode stabilization process and does not contain cerium oxide particle doping, and the electrochemical oxidative degradation process is the same as that of example 1. The degradation rate of AO7 reaches 50.14% after 2 hours of reaction, and the COD degradation rate reaches 42.57%.
Comparative example 4
By the method of example 1, the electrode preparation process is only carried out by (1) (2) (3) and step (4) is not carried out, and the obtained electrode is the titanium dioxide nanotube electrode which is subjected to anode stabilization and is not subjected to electrodeposition, namely TiO 2 The process of electrochemical oxidative degradation of the NTA electrode was the same as in example 1. After 2 hours of reaction, the degradation rate of AO7 reaches 65.56%, and the COD degradation rate reaches 57.13%.
Comparative example 5
By adopting the method of example 1, the electrode preparation process is only carried out by (1) (2) (4), step (3) is not carried out, and the obtained electrode is the ceria-doped electrode which is not subjected to the anode stabilization process, and the electrochemical oxidative degradation process is the same as that of example 1. After 2 hours of reaction, the degradation rate of AO7 reaches 71.15%, and the COD degradation rate reaches 61.34%.
Comparative example 6
The electrode preparation process was carried out by the method of example 1, with steps (1) and (2) being omitted, and steps (3) and (4) being omitted, the electrode obtained was unstableDeposited titanium dioxide nanotube electrode, designated Un-TiO 2 The process of electrochemical oxidative degradation of the NTA electrode was the same as in example 1. For determining the electrode stability, un-TiO was used with the other degradation parameters unchanged 2 The NTA electrode repeatedly carries out 7 times of AO7 degradation experiments, wherein the degradation rates of AO7 in the 7 times of experiments are respectively 50.14, 45.15, 40.48, 33.47, 31.27, 30.18 and 21.18 percent, and the COD degradation rates are respectively 42.57, 35.25, 30.15, 25.45, 23.28 and 15.18 percent.
Comparative example 7
The method of example 1 is adopted, the electrode preparation process is only carried out through (1) (2) (3) and step (4) is not carried out, and the obtained electrode is the titanium dioxide nanotube electrode which is subjected to anode stabilization and is not electrodeposited, namely TiO 2 The process of electrochemical oxidative degradation of the NTA electrode was the same as in example 1. For determining the electrode stability, un-TiO was used with the other degradation parameters unchanged 2 The NTA electrode repeatedly carries out 7 times of AO7 degradation experiments, wherein the degradation rates of AO7 in the 7 times of experiments are 65.56, 64.32, 63.17, 62.52, 60.25, 58.17 and 56.15 percent respectively, and the COD degradation rates are 57.13, 56.25, 55.12, 54.27, 53.15 and 52.18 percent respectively.
It is known from the combination of example 1 and comparative examples 1 to 5 that the steps (2), (3) and (4) according to the present invention can significantly improve the catalytic ability of the electrode, and that none of the four key steps of electrode preparation can be replaced, but the performance of the electrode is significantly reduced without any step. The purpose of step (2) is mainly to produce a titanium nanotube structure on the electrode surface, and the results of comparative examples 1-2 and example 1 show that the electrode catalytic ability suddenly drops without going through step (2), which proves the necessity of step (2); the purpose of the step (3) is mainly to stabilize the electrode, remove surface impurities and the like. It is apparent from comparative examples 6 to 7 that the stability of the electrode after the step (3) was significantly improved and the catalytic performance was also increased. Electrodes prepared without step (3) (4), i.e. Un-TiO 2 The degradation rate of AO7 and COD of NTA electrode after multiple reactions become low, which shows that TiO 2 NTA electrodes have poor stability, and the surface structure of the electrodes is destroyed after multiple reactions. The step (4) aims at doping cerium oxide nano particles, introducing oxygen vacancies and improvingElectrode catalytic activity and electrode stability. In combination with example 1, comparative example 4 shows that step (4) can significantly improve catalyst performance, and also improves electrode stability after doping cerium oxide nanoparticles as shown in example 10 and comparative example 7.
Comparative example 8
The method of example 1 was used to change the anode of step (2) to a boron doped diamond electrode (BDD), and the other reaction conditions were the same as those described in example 1 for the electrochemical degradation of acid orange 7 to simulate dye wastewater. The reaction is carried out for 2 hours, the degradation rate of AO7 is 78.12 percent, and the COD degradation rate is 71.03 percent. The AO7 degradation rate is shown in figure 4.
Comparative example 9
The method of example 1 was used to change the anode in step (2) to titanium-based tin antimony (Ti/SnO 2 -Sb 2 O 5 ) The electrode, other reaction conditions were the same as described in example 1 for the electrochemical degradation of acid orange 7 to simulate dye wastewater. The reaction is carried out for 2 hours, the degradation rate of AO7 is 64.52 percent, and the COD degradation rate is 55.98 percent. The AO7 degradation rate is shown in figure 4.
Comparative example 10
The procedure of example 1 was used to modify the anode of step (2) to be titanium-based iridium tantalum ruthenium iridium (Ti/IrO) 2 -Ta 2 O 5 ) The electrode, other reaction conditions were the same as described in example 1 for the electrochemical degradation of acid orange 7 to simulate dye wastewater. The reaction is carried out for 2 hours, the degradation rate of AO7 is 59.64 percent, and the COD degradation rate is 51.98 percent. The AO7 degradation rate is shown in figure 4.
Comparative example 11
The procedure of example 1 was employed to modify the anode of step (2) to be titanium-based ruthenium iridium (Ti/RuO) 2 -IrO 2 ) The electrode, other reaction conditions were the same as described in example 1 for the electrochemical degradation of acid orange 7 to simulate dye wastewater. The reaction is carried out for 2 hours, the degradation rate of AO7 is 45.52 percent, and the COD degradation rate is 51.21 percent. The AO7 degradation rate is shown in figure 4.
Comparative example 12
The method of example 1 was used to change the anode of step (2) to a platinum sheet electrode (Ti/Pt), and the other reaction conditions were the same as those described in example 1 for the electrochemical degradation of acid orange 7 to simulate dye wastewater. The reaction is carried out for 2 hours, the degradation rate of AO7 is 35.52 percent, and the COD degradation rate is 26.85 percent. The AO7 degradation rate is shown in figure 4.
From example 1 and comparative examples 8-12, and with reference to fig. 4, it can be seen that the electrode provided by the invention has the best degradation effect on AO7 simulated dye wastewater, has oxidation catalytic capability exceeding that of various commercial electrodes on the market, and has better performance than the currently accepted boron-doped diamond electrode (electrode with accepted performance tip in the field) with excellent electrochemical oxidation performance, thus indicating that the electrochemical oxidation treatment of dye wastewater has good application prospect.
Comparative example 13
By the method of example 1, the electrode preparation process is carried out only by (1) (2) (3) and step (4) is not carried out, and the obtained electrode is the titanium dioxide nanotube electrode which is not electrodeposited after anode stabilization, namely TiO 2 NTA electrode. The three electrode cyclic voltammetry test system of test 2 of example 1 was used as TiO 2 NTA is a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum electrode is used as a counter electrode, the test electrolyte solution is 0.05mol/L sodium sulfate solution, the scanning speed is 100mV/s, and the potential window is-0.5-1.5V vs. The test results are shown in FIG. 5.
Cyclic voltammetry analysis can be used to test the electrochemically active surface area of the electrode. Example 1 and comparative example 13 As can be seen from the accompanying FIG. 5, tiO 2 The cyclic voltammogram of NTA shows a triangular shape, which is due to the higher resistance of the anode, resulting in a higher current density during electrolysis. CeO (CeO) 2 The CV curve of the electrode obtained after doping is rectangular, which indicates CeO 2 /TiO 2 NTA electrode has excellent capacitance characteristic and CeO 2 Doping increases the conductivity of the electrode, and has higher electrocatalytic oxidation-reduction activity and pollutant degradation potential.
Comparative example 14
By the method of example 1, the electrode preparation process is carried out only by (1) (2) (3) and step (4) is not carried out, and the obtained electrode is the titanium dioxide nanotube electrode which is not electrodeposited after anode stabilization, namely TiO 2 NTA electrode. The three-electrode linear voltammetry test system of test 3 of example 1 was used as TiO 2 NTA electrode asThe working electrode, the saturated calomel electrode is used as a reference electrode, the platinum electrode is used as a counter electrode, the test electrolyte solution is 0.5mol/L sulfuric acid solution, the scanning speed is 5mV/min, and the potential window is 0-4.0V vs. The test results are shown in FIG. 6.
Comparative example 15
The three electrode linear voltammetry system of test 3 of example 1 was used with commercial electrodes used in comparative examples 8-12, namely boron diamond electrode (BDD), titanium based tin antimony (Ti/SnO 2 -Sb 2 O 5 ) Titanium-based iridium tantalum ruthenium iridium (Ti/IrO) 2 -Ta 2 O 5 ) Titanium-based ruthenium iridium (Ti/RuO) 2 -IrO 2 ) The method is characterized in that a platinum sheet electrode (Ti/Pt) is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum electrode is used as a counter electrode, a test electrolyte solution is 0.5mol/L sulfuric acid solution, the scanning speed is 5mV/min, and the potential window is 0-4.0V vs. The test results are shown in FIG. 6.
As can be seen from comparative examples 13 to 15 in combination with FIG. 6, some side reactions occur during electrocatalytic oxidation, with oxygen evolution side reactions being most pronounced. In general, the more susceptible the oxygen evolution side reaction is, the lower the current efficiency for treating the contaminants is, the lower the electrocatalytic activity is exhibited by the electrode, and thus the electrode for electrocatalytic oxidative degradation of the contaminants is required to have a higher oxygen evolution potential, thereby reducing the occurrence of oxygen evolution side reactions. FIG. 6 is CeO 2 /TiO 2 NTA、TiO 2 NTA and commercial electrode BDD, ti/SnO 2 -Sb 2 O 5 、Ti/IrO 2 -Ta 2 O 5 、Ti/RuO 2 -IrO 2 Linear voltammograms of Ti/Pt and CeO can be obtained by graph analysis 2 /TiO 2 The oxygen evolution potential of the NTA electrode is highest and obviously higher than that of TiO 2 NTA and BDD electrodes are significantly higher than other commercial electrodes. This indicates CeO 2 /TiO 2 The NTA electrode has higher electrocatalytic oxidation capability and better pollutant degradation potential.
Example 11
The preparation of example 1 was used, except that:
preparing concentrated sulfuric acid and concentrated nitric acid with the molar ratio of 1:1 in the step (1)The solution was mixed and the titanium sheet was etched at 40 ℃. The anodic oxidation electrolyte in the step (2) contains 0.1wt% of ammonium fluoride and 1wt% of H 2 A glycol solution of O; the anodic oxidation was carried out by a constant voltage method at 50V for 6 hours. The reaction at the constant voltage in the step (3) is carried out for 2 hours at the constant voltage of 50V; the high-temperature calcination is high-temperature calcination at 450 ℃ for 3 hours. The concentration of cerium ions in the electrodeposition solution in the step (4) is 1mmol/L; the potential of the electrochemical deposition was 0.4V Vs SCE, the reaction time was 30min, and the annealing calcination was performed at 450℃for 2h. The electrochemical oxidative degradation process was the same as in example 1.
Example 12
The preparation of example 1 was used, except that: in the step (1), a mixed solution of concentrated sulfuric acid and concentrated nitric acid with a molar ratio of 1:3 is prepared, and the titanium sheet is etched at 60 ℃. The anodic oxidation electrolyte in the step (2) contains 0.75 weight percent of ammonium fluoride and 3 weight percent of H 2 A glycol solution of O; the anodic oxidation was carried out by a constant voltage method at 70V for 2 hours. The reaction at the constant voltage in the step (3) is carried out for 1h at the constant voltage of 70V; the high temperature calcination is carried out at 800 ℃ for 2 hours. The concentration of cerium ions in the electrodeposition solution in the step (4) is 10mmol/L; the electrochemical deposition potential was 1.2V Vs SCE, the reaction time was 5min, and the annealing calcination was performed at 800℃for 1h. The electrochemical oxidative degradation process was the same as in example 1.
Claims (10)
1. The preparation method of the cerium oxide doped titanium nanotube electrode is characterized by comprising the following steps of:
(1) Polishing a titanium plate, a titanium rod or a titanium mesh into titanium sheets, and etching the titanium sheets by adopting a mixed solution of concentrated sulfuric acid and concentrated nitric acid; immersing the etched titanium sheet in ultrasonic waves and drying to serve as an electrode anode;
(2) Taking the electrode obtained in the step (1) as an anode, taking a platinum sheet electrode as a cathode, configuring anode oxidation electrolyte, performing anodic oxidation, taking out the anode electrode after the reaction is finished, washing and drying;
(3) Taking the electrode obtained in the step (2) as an anode, taking a platinum sheet electrode as a cathode, and reacting at a constant voltage to obtainThe titanium dioxide nanotube electrode is obtained by high-temperature calcination of the electrode, namely TiO 2 An NTA electrode;
(4) Preparing a solution containing one or two of cerium sulfate and cerium nitrate as an electrodeposition solution, performing electrochemical deposition with the electrode obtained in the step (3) as a working electrode, a platinum sheet electrode as a reference electrode and a saturated calomel electrode as a counter electrode at constant potential, annealing and calcining the obtained electrode to obtain the cerium oxide doped titanium nanotube electrode, namely CeO 2 /TiO 2 NTA。
2. The method for preparing a cerium oxide doped titanium nanotube electrode according to claim 1, wherein a mixed solution of concentrated sulfuric acid and concentrated nitric acid with a molar ratio of 1:1-1:3 is prepared in the step (1), and the titanium sheet is etched at 40-60 ℃.
3. The method for preparing a cerium oxide doped titanium nanotube electrode according to claim 1, wherein the anodic oxidation electrolyte in the step (2) is 0.1-0.75wt% of ammonium fluoride and 1-3wt% of H 2 Ethylene glycol solution of O.
4. The method for preparing a ceria-doped titanium nanotube electrode according to claim 1, wherein the anodic oxidation in step (2) is performed by a constant voltage method at 50 to 70V for 2 to 6 hours.
5. The method for preparing a cerium oxide doped titanium nanotube electrode according to claim 1, wherein the reaction at the constant voltage of step (3) is performed for 1-2 hours at a constant voltage of 50-70V.
6. The method for preparing a cerium oxide doped titanium nanotube electrode according to claim 1, wherein the high-temperature calcination in the step (3) is performed at a temperature of 450-800 ℃ for 2-3 hours.
7. The method for preparing a cerium oxide doped titanium nanotube electrode according to claim 1, wherein the concentration of cerium ions in the electrodeposition solution in the step (4) is 1-10mmol/L.
8. The method for preparing a cerium oxide doped titanium nanotube electrode according to claim 1, wherein the electrochemical deposition potential in the step (4) is 0.4-1.2V Vs. SCE, the reaction time is 5-30min, and the annealing calcination is performed at 450-800 ℃ for 1-2h.
9. Use of a ceria-doped titanium nanotube electrode prepared by the preparation method of claim 1 in electrochemical oxidative degradation of acid orange 7 dye wastewater.
10. The use according to claim 9, characterized in that the specific steps of the use are as follows: taking acid orange 7-containing wastewater solution as electrolyte, taking a cerium oxide doped titanium nanotube electrode as an anode, taking a platinum sheet electrode as a cathode, and carrying out degradation treatment under constant current density, wherein the current density is 1-20 mA/cm 2 The electrolyte is 0.01-0.1 mol/L sodium sulfate, the stirring speed is 500-1000r/min, and the reaction time is 1-2h.
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| CN104577139A (en) * | 2015-01-21 | 2015-04-29 | 苏州大学 | Photo-responsive titania nanotube-supported catalyst electrode and preparation method thereof |
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| CN104577139A (en) * | 2015-01-21 | 2015-04-29 | 苏州大学 | Photo-responsive titania nanotube-supported catalyst electrode and preparation method thereof |
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