CN114560536A - Terbium rhenium modified Ti/RuO2Dimensionally stable anode, preparation method and application - Google Patents
Terbium rhenium modified Ti/RuO2Dimensionally stable anode, preparation method and application Download PDFInfo
- Publication number
- CN114560536A CN114560536A CN202210230963.5A CN202210230963A CN114560536A CN 114560536 A CN114560536 A CN 114560536A CN 202210230963 A CN202210230963 A CN 202210230963A CN 114560536 A CN114560536 A CN 114560536A
- Authority
- CN
- China
- Prior art keywords
- terbium
- ruo
- rhenium
- substrate
- modified
- 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
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
- C02F1/46—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
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Electrochemistry (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a terbium rhenium modified Ti/RuO2The dimensionally stable anode comprises a Ti substrate, wherein RuO is arranged on the surface of the Ti substrate2Coating of RuO therein2The coating contains terbium oxide and rhenium oxide; RuO2In the coating, the molar ratio of the sum of terbium and rhenium to Ru is 0.12-0.24: 1. also discloses a preparation method of the dimensionally stable anode and application of the dimensionally stable anode in membrane filtration concentrated solution of landfill leachate in electrochemical catalytic oxidation treatment. The invention relates to a terbium-rhenium modified Ti/RuO2The dimensionally stable anode has the advantages of high catalytic activity and good stability, and can realize environment-friendly and efficient treatment of wastewater.
Description
Technical Field
The invention relates to terbium rhenium modified Ti/RuO2A dimensionally stable anode, a preparation method and application thereof,belongs to the technical field of electrode materials and wastewater treatment.
Background
At present, the most common method for disposing the landfill leachate is a biochemical treatment combined membrane group treatment process. Compared with the landfill leachate, the landfill leachate concentrated solution after membrane interception has higher concentrations of organic pollutants, inorganic salts and non-metallic ions and poorer biodegradability. The landfill leachate membrane filtration concentrated solution has the following characteristics: (1) the components are complex, the concentration of organic pollutants is high, the COD is usually 1000-5000 mg/L, and the highest COD can reach more than 20000 mg/L. (2) The inorganic salt has high component content and the conductivity is up to 20000-50000 mu S/cm except for conventional Na+、K+In addition, it also contains trace Pb2+、Cu2+And the heavy metal ions are equal. (3) The concentrated chloride ion has the corrosion problem. (4) The biodegradability is poor, the BOD/COD is generally less than 0.1, and most of the substances are difficult to biodegrade. (5) the concentrated solution is brownish black, and the hardness is usually 1000-2500 mg/L.
The landfill leachate membrane filtration concentrated solution adopts a recharge landfill yard body, the concentrated solution is repeatedly recharged and vicious circulated for a long time, so that the concentration of salt-enriched and refractory organic matters in the leachate is increased, and the activity of biological flora is reduced during biochemical treatment, so that the treatment capacity of the existing equipment is gradually reduced, and the leachate is gradually accumulated to form new environmental safety hidden troubles. The main methods in the field of landfill leachate concentrated solution treatment, which are being tried, include evaporation or mechanical compression and re-evaporation, submerged combustion, membrane group re-concentration and decrement and the like. The methods generally have the defects of high energy consumption and low efficiency, the operation of the process can be interrupted due to blockage, and concentrated solution with higher concentration and higher treatment difficulty can be generated. How to keep the leachate treatment facility to operate stably for a long time, solve the contradiction that the production amount of the landfill leachate is not adaptive to the actual treatment capacity, improve the treatment capacity and consume the accumulated leachate, and are in need of various landfill sites.
The electrochemical advanced oxidation technology has the characteristics of high COD removal efficiency, no secondary pollution, environmental protection and the like. The anode material is the core of electrochemical wastewater treatment, and the main types of the anode material comprise a metal electrode, a graphite electrode, a titanium-based oxide electrode, a boron-doped diamond electrode (BDD) and the like.Noble metal oxide RuO2The catalyst is in a rutile structure and has excellent catalytic activity. Titanium-based RuO2The electrode has the advantages of high catalytic activity, long service life, good corrosion resistance and the like, and has wide application prospect in the wastewater treatment process.
Disclosure of Invention
The invention aims to: aiming at the problems, the invention provides a terbium rhenium modified Ti/RuO2Dimensionally stable anode, preparation method and application thereof, Ti/RuO of the invention2The dimensionally stable anode has the advantages of high catalytic activity and good stability, and can realize environment-friendly and efficient treatment of wastewater.
The technical scheme adopted by the invention is as follows:
terbium rhenium modified Ti/RuO2The dimensionally stable anode comprises a Ti substrate, wherein RuO is arranged on the surface of the Ti substrate2Coating of RuO therein2The coating contains terbium oxide and rhenium oxide.
In the present invention, RuO2The main component in the coating is ruthenium dioxide, and the ruthenium dioxide is modified by oxides of terbium and rhenium, wherein the terbium belongs to rare earth elements and has a 4f electronic structure, and the rhenium belongs to transition metal elements and has d and f electronic structures, so that Ti/RuO can be improved2Dimensionally stabilizing the catalytic activity and stability of the anode.
Preferably, the RuO2In the coating, the molar ratio of the sum of terbium and rhenium to Ru is 0.12-0.24: 1.
In the above scheme, the effect of terbium and rhenium is on RuO2The coating is modified, if the addition amount of terbium and rhenium is too much (the molar ratio is more than 0.24: 1), the terbium and rhenium can not play a role in modification, and RuO2More performances of terbium and rhenium are presented in the coating, and the effects of improving catalytic activity and the like cannot be achieved; on the other hand, if the amount of terbium and rhenium is too small (molar ratio less than 0.12: 1), the modification effect and the improvement effect of the catalytic activity are also not achieved.
Preferably, the molar ratio of terbium to rhenium is 0.1-10: 1.
preferably, the RuO2The thickness of the coating is 3-10 um.
In the scheme, if the thickness of the coating is too thin, the catalytic effect of the dimensionally stable anode is poor; the cost is increased when the coating thickness is too thick, and the catalytic activity cannot be increased continuously when the coating thickness is a certain thickness; RuO2The thickness of the coating is 3-10 um, and the coating has high catalytic activity.
Preferably, the RuO2In the coating, RuO2Terbium oxide and rhenium oxide were uniformly distributed.
Preferably, the oxide of terbium is Tb2O3And/or Tb4O7The oxide of rhenium being ReO3And/or Re2O3And/or ReO2And/or Re2O。
Preferably, the Ti substrate is a titanium sheet or a titanium mesh.
Preferably, the Ti substrate is ground and etched.
Terbium rhenium modified Ti/RuO2The preparation method of the dimensionally stable anode comprises the following steps:
step a: mixing isopropanol and concentrated hydrochloric acid to form a mixed solution, adding ruthenium trichloride, terbium trichloride and rhenium trichloride into the mixed solution, and stirring and ultrasonically treating the mixed solution to form uniform coating liquid, wherein the molar ratio of the sum of terbium and rhenium to Ru is 0.12-0.24: 1;
step b: pretreating a Ti substrate;
step c: coating the coating liquid on the surface of a Ti substrate, and then drying and calcining;
step d: after cooling, repeating the step c for a plurality of times to enable the coating to reach the required thickness;
step e: sintering the anode obtained in the step d at 450-550 ℃ for 2-3 h to obtain terbium rhenium modified Ti/RuO2And (4) dimensionally stabilizing the anode.
Preferably, in step a, the volume ratio of the isopropanol to the concentrated hydrochloric acid is 8-10: 1.
preferably, in step b, the pretreatment process of the Ti substrate is: sanding the Ti substrate by using sand paper until the Ti substrate presents uniform metal luster; sequentially and respectively carrying out ultrasonic treatment on the Ti substrate in acetone, NaOH solution and distilled water for 10-15 min; and putting the Ti substrate into an oxalic acid solution, and etching for 1-3 hours at the temperature of 80-90 ℃ to enable the Ti substrate to present a gray pitted surface without metallic luster.
In the scheme, RuO can be improved by polishing and etching2The adhesion of the coating on the Ti substrate improves the dimensionally stable anode performance.
Preferably, in the step c, the temperature in the drying process is controlled to be 60-90 ℃, and the drying time is 15-20 min; the temperature of the calcination process is controlled to be 450-550 ℃, and the calcination time is 10-15 min.
The terbium rhenium modified Ti/RuO2The application of the dimensionally stable anode is used for treating the membrane filtration concentrated solution of the landfill leachate by electrochemical catalytic oxidation.
Preferably, the electrocatalytic oxidation treatment is carried out under conditions of pH 5 to 7.
The invention relates to terbium rhenium modified Ti/RuO2A dimensionally stable anode, a preparation method and application.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. terbium rhenium modified Ti/RuO2The dimensionally stable anode has high catalytic activity and good stability;
2. can realize the environmental protection and high-efficiency treatment of the wastewater, and is particularly suitable for the wastewater with high COD and high ammonia nitrogen content.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
Example 1
In this example, a Tb-Re-modified Ti/RuO2The preparation method of the dimensionally stable anode comprises the following steps:
step a: mixing isopropanol and concentrated hydrochloric acid in a volume ratio of 8: 1, adding ruthenium trichloride, terbium trichloride and rhenium trichloride into the mixed solution, stirring and carrying out ultrasonic treatment for 30 minutes to form uniform coating liquid, wherein the molar ratio of the sum of terbium and rhenium to Ru is 0.12: 1, molar ratio of terbium to rhenium of 10: 1;
step b: the Ti substrate is a titanium sheet, and is pretreated, wherein the pretreatment process comprises the following steps: sanding the Ti substrate by using sand paper until the Ti substrate presents uniform metal luster; sequentially performing ultrasonic treatment on a Ti substrate in acetone, 20 wt% NaOH solution and distilled water for 10min respectively; putting the Ti substrate into oxalic acid solution, and etching for 1h at 80 ℃ to enable the Ti substrate to present a gray pitted surface without metallic luster;
step c: uniformly brushing the coating liquid on two surfaces of a Ti substrate, drying in an oven at 60 ℃ for 20min, and calcining in a muffle furnace at 450 ℃ for 15 min;
step d: after cooling, repeating step c for a plurality of times to make the thickness of the coating layer be 3 um;
step e: d, sintering the anode obtained in the step d in a muffle furnace at 550 ℃ for 2 hours, cooling to room temperature, and taking out to obtain terbium rhenium modified Ti/RuO2And (5) dimensionally stabilizing the anode.
The preparation of this example yielded a terbium rhenium modified Ti/RuO2And (5) dimensionally stabilizing the anode.
Example 2
In this example, a Tb-Re-modified Ti/RuO2The preparation method of the dimensionally stable anode comprises the following steps:
step a: mixing isopropanol and concentrated hydrochloric acid in a volume ratio of 10: 1, adding ruthenium trichloride, terbium trichloride and rhenium trichloride into the mixed solution, stirring and carrying out ultrasonic treatment for 30 minutes to form uniform coating liquid, wherein the molar ratio of the sum of terbium and rhenium to Ru is 0.24: 1, the molar ratio of terbium to rhenium is 0.1: 1;
step b: the Ti substrate is a titanium sheet, and is pretreated, wherein the pretreatment process comprises the following steps: sanding the Ti substrate by using sand paper until the Ti substrate presents uniform metal luster; sequentially performing ultrasonic treatment on a Ti substrate in acetone, 20 wt% NaOH solution and distilled water for 15min respectively; putting the Ti substrate into oxalic acid solution, and etching for 3 hours at 90 ℃ to enable the Ti substrate to present a gray pitted surface without metallic luster;
step c: uniformly brushing the coating liquid on two surfaces of a Ti substrate, drying in an oven at 90 ℃ for 15min, and calcining in a muffle at 550 ℃ for 10 min;
step d: after cooling, repeating the step c for a plurality of times to ensure that the thickness of the coating is 10 um;
step e: d, sintering the anode obtained in the step d in a muffle furnace at 450 ℃ for 2h, cooling to room temperature, and taking out to obtain terbium rhenium modified Ti/RuO2And (5) dimensionally stabilizing the anode.
The preparation of this example yielded a terbium rhenium modified Ti/RuO2And (5) dimensionally stabilizing the anode.
Example 3
In this example, a Tb-Re-modified Ti/RuO2The preparation method of the dimensionally stable anode comprises the following steps:
step a: mixing isopropanol and concentrated hydrochloric acid in a volume ratio of 9: 1, adding ruthenium trichloride, terbium trichloride and rhenium trichloride into the mixed solution, stirring and carrying out ultrasonic treatment for 30 minutes to form uniform coating liquid, wherein the molar ratio of the sum of terbium and rhenium to Ru is 0.18: 1, the molar ratio of terbium to rhenium is 1: 1;
step b: the Ti substrate is a titanium sheet, and is pretreated, wherein the pretreatment process comprises the following steps: sanding the Ti substrate by using sand paper until the Ti substrate presents uniform metal luster; sequentially performing ultrasonic treatment on a Ti substrate in acetone, 20 wt% NaOH solution and distilled water for 12min respectively; putting the Ti substrate into oxalic acid solution, and etching for 2 hours at 85 ℃ to enable the Ti substrate to present a gray pitted surface without metal luster;
step c: uniformly brushing the coating liquid on two surfaces of a Ti substrate, drying in a 75 ℃ oven for 18min, and calcining in a 500 ℃ muffle furnace for 12 min;
step d: after cooling, repeating step c for a plurality of times to make the thickness of the coating be 6 um;
step e: d, sintering the anode obtained in the step d in a muffle furnace at 500 ℃ for 2.5h, cooling to room temperature and taking out to obtain terbium rhenium modified Ti/RuO2And (4) dimensionally stabilizing the anode.
The preparation of this example yielded a terbium rhenium modified Ti/RuO2And (4) dimensionally stabilizing the anode.
Example 4
The true bookExample A Terbium rhenium modified Ti/RuO2The preparation method of the dimensionally stable anode comprises the following steps:
a, step a: mixing isopropanol and concentrated hydrochloric acid in a volume ratio of 9: 1, adding ruthenium trichloride, terbium trichloride and rhenium trichloride into the mixed solution, stirring and carrying out ultrasonic treatment for 30 minutes to form uniform coating liquid, wherein the molar ratio of the sum of terbium and rhenium to Ru is 0.24: 1, the molar ratio of terbium to rhenium is 0.5: 1;
step b: the Ti substrate is a titanium sheet, and is pretreated, wherein the pretreatment process comprises the following steps: sanding the Ti substrate by using sand paper until the Ti substrate presents uniform metal luster; sequentially performing ultrasonic treatment on a Ti substrate in acetone, 20 wt% NaOH solution and distilled water for 12min respectively; putting the Ti substrate into oxalic acid solution, and etching for 2h at 90 ℃ to enable the Ti substrate to present a gray pitted surface without metal luster;
step c: uniformly brushing the coating liquid on two sides of a Ti substrate, drying in an oven at 70 ℃ for 15min, and calcining in a muffle furnace at 500 ℃ for 15 min;
step d: after cooling, repeating step c for a plurality of times to make the thickness of the coating layer be 8 um;
step e: d, sintering the anode obtained in the step d in a muffle furnace at 550 ℃ for 2 hours, cooling to room temperature, and taking out to obtain terbium rhenium modified Ti/RuO2And (5) dimensionally stabilizing the anode.
The preparation of this example yielded a terbium rhenium modified Ti/RuO2And (4) dimensionally stabilizing the anode.
Example 5
This example is different from example 4 in that the Ti substrate in this example is a titanium mesh.
Examples 6 to 9
Examples 6-9 differ from example 4 in that the molar ratio of the sum of terbium and rhenium to Ru in step a of examples 6-9 was 0.12: 1. 0.15: 1. 0.18: 1. 0.21: 1.
comparative example 1
This comparative example differs from example 4 in that the molar ratio of the sum of terbium and rhenium to Ru in step a is 0.09: 1, obtaining a terbium rhenium modified Ti/RuO2And (5) dimensionally stabilizing the anode.
Comparative example 2
This comparative example differs from example 4 in that the molar ratio of the sum of terbium and rhenium to Ru in step a is 0.06: 1, obtaining a terbium rhenium modified Ti/RuO2And (5) dimensionally stabilizing the anode.
Comparative example 3
This comparative example differs from example 4 in that the molar ratio of the sum of terbium and rhenium to Ru in step a is 0.03: 1, obtaining a terbium rhenium modified Ti/RuO2Dimensionally stable anode
Comparative example 4
This comparative example differs from example 4 in that only ruthenium trichloride was added in step a, giving unmodified Ti/RuO2And (5) dimensionally stabilizing the anode.
Comparative example 5
This comparative example differs from example 4 in that the molar ratio of the sum of terbium and rhenium to Ru in step a is 0.3: 1, obtaining a terbium rhenium modified Ti/RuO2And (5) dimensionally stabilizing the anode.
Comparative example 6
This comparative example differs from example 4 in that the molar ratio of the sum of terbium and rhenium to Ru in step a is 0.4: 1, obtaining a terbium rhenium modified Ti/RuO2And (4) dimensionally stabilizing the anode.
Comparative example 7
This comparative example differs from example 4 in that the molar ratio of the sum of terbium and rhenium to Ru in step a is 0.5: 1, obtaining a terbium rhenium modified Ti/RuO2And (5) dimensionally stabilizing the anode.
Comparative example 8
This comparative example differs from example 4 in that the molar ratio of the sum of terbium and rhenium to Ru in step a is 0.6: 1, obtaining a terbium rhenium modified Ti/RuO2And (5) dimensionally stabilizing the anode.
Comparative example 9
This comparative example differs from example 4 in that the molar ratio of the sum of terbium and rhenium to Ru in step a was 1: 1, obtaining a terbium rhenium modified Ti/RuO2And (5) dimensionally stabilizing the anode.
Comparative example 10
This comparative example differs from example 4 in that no terbium trichloride was added in step a, the molar ratio of rhenium to Ru was 0.24: 1, obtainingTo obtain a rhenium modified Ti/RuO2And (5) dimensionally stabilizing the anode.
Comparative example 11
The comparative example differs from example 4 in that rhenium trichloride is not added in step a and the molar ratio of terbium to Ru is 0.24: 1, obtaining a terbium modified Ti/RuO2And (4) dimensionally stabilizing the anode.
The dimensionally stable anode obtained in the above examples and comparative examples is used for carrying out electrochemical catalytic oxidation treatment on the membrane filtration concentrated solution of the landfill leachate at the current density of 30mAcm-2And the pH value is 6, the treatment is carried out for 2.5h at 25 ℃, the initial COD of the percolate membrane filtration concentrated solution is 10547mg/L, the initial ammonia nitrogen content is 886mg/L, and the results are shown in the following table:
as can be seen from the above examples and comparative examples, the terbium rhenium modified Ti/RuO of the present invention2The dimensionally stable anode has good catalytic activity, the removal rate of COD can reach more than 99%, and the removal rate of ammonia nitrogen can reach more than 94%; when the molar ratio of the sum of terbium and rhenium to Ru is less than 0.12, as compared with example 6 by comparative examples 1-3: 1, the catalytic performance of the dimensionally stable anode is reduced rapidly; from examples 4, 6 to 9, it can be seen that when the molar ratio of the sum of terbium and rhenium to Ru is in the range from 0.12 to 0.24: 1, along with the increase of the total content of terbium and rhenium, the dimensionally stable anode catalytic performance is increased, but when reaching a certain point (0.18: 1), the dimensionally stable anode catalytic performance is continuously increased, and the dimensionally stable anode catalytic performance is reduced; by comparing comparative examples 5-9 with example 4, and continuing to increase the total terbium and rhenium content, the catalytic performance of the dimensionally stable anode began to drop dramatically, since too much terbium and rhenium was added to adversely affect the RuO2The catalytic performance of (2). By comparing comparative examples 10-11 with example 4, it can be seen that the Ti/RuO modified with terbium rhenium2Terbium or rhenium modified Ti/RuO alone, in comparison to dimensionally stable anodes2The catalytic performance of the dimensionally stable anode is worse, which shows that two elements of terbium rhenium are modified Ti/RuO than one element2The effect of the dimensionally stable anode is better; by comparing comparative example 4 with the examples, it can be seen that the modified Ti/RuO is comparable to that of the unmodified one2Terbium rhenium modified Ti/RuO with dimensionally stable anode phase ratio2The catalytic performance of the dimensionally stable anode is greatly improved; by comparison of examples 4-5, the Ti substrate is a titanium mesh with slightly better catalytic performance than the titanium sheet due to the larger contact area of the mesh anode and better catalytic effect.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification, and to any novel method or process steps or any novel combination of steps disclosed.
Claims (10)
1. Terbium rhenium modified Ti/RuO2A dimensionally stable anode characterized by: comprises a Ti substrate, wherein the surface of the Ti substrate is provided with RuO2Coating of RuO therein2The coating contains terbium oxide and rhenium oxide.
2. The terbium rhenium modified Ti/RuO of claim 12A dimensionally stable anode characterized by: the RuO2In the coating, the molar ratio of the sum of terbium and rhenium to Ru is 0.12-0.24: 1.
3. the terbium rhenium modified Ti/RuO of claim 12A dimensionally stable anode characterized by: the molar ratio of terbium to rhenium is 0.1-10: 1.
4. the terbium rhenium modified Ti/RuO of claim 12A dimensionally stable anode characterized by: the RuO2The thickness of the coating is 3-10 um.
5. The terbium rhenium modified Ti/RuO of claim 12A dimensionally stable anode characterized by: the RuO2In the coating, RuO2Terbium oxide and rhenium oxide were uniformly distributed.
6. The terbium rhenium modified Ti/RuO of claim 12A dimensionally stable anode characterized by: the Ti substrate is a titanium sheet or a titanium mesh.
7. Terbium rhenium modified Ti/RuO2The preparation method of the dimensionally stable anode is characterized by comprising the following steps: the method comprises the following steps:
step a: mixing isopropanol and concentrated hydrochloric acid to form a mixed solution, adding ruthenium trichloride, terbium trichloride and rhenium trichloride into the mixed solution, and stirring and ultrasonically treating the mixed solution to form uniform coating liquid, wherein the molar ratio of the sum of terbium and rhenium to Ru is 0.12-0.24: 1;
step b: pretreating a Ti substrate;
step c: coating the coating liquid on the surface of a Ti substrate, and then drying and calcining;
step d: after cooling, repeating the step c for a plurality of times to enable the coating to reach the required thickness;
step e: sintering the anode obtained in the step d at 450-550 ℃ for 2-3 h to obtain terbium rhenium modified Ti/RuO2And (5) dimensionally stabilizing the anode.
8. The terbium rhenium modified Ti/RuO of claim 72The preparation method of the dimensionally stable anode is characterized by comprising the following steps: in the step a, the volume ratio of the isopropanol to the concentrated hydrochloric acid is 8-10: 1.
9. the terbium rhenium modified Ti/RuO of claim 72The preparation method of the dimensionally stable anode is characterized by comprising the following steps: in the step b, the pretreatment process of the Ti substrate comprises the following steps: sanding the Ti substrate by using sand paper until the Ti substrate presents uniform metal luster; sequentially and respectively carrying out ultrasonic treatment on the Ti substrate in acetone, NaOH solution and distilled water for 10-15 min; and (3) putting the Ti substrate into an oxalic acid solution, and etching for 1-3h at the temperature of 80-90 ℃ to enable the Ti substrate to present a gray pitted surface without metallic luster.
10. The terbium rhenium modified Ti/RuO according to any one of claims 1 to 62The application of the dimensionally stable anode is characterized in that: the method is used for treating the garbage percolate membrane filtration concentrated solution by electrochemical catalytic oxidation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210230963.5A CN114560536B (en) | 2022-03-09 | 2022-03-09 | Terbium-rhenium modified Ti/RuO 2 Dimensionally stable anode, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210230963.5A CN114560536B (en) | 2022-03-09 | 2022-03-09 | Terbium-rhenium modified Ti/RuO 2 Dimensionally stable anode, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114560536A true CN114560536A (en) | 2022-05-31 |
| CN114560536B CN114560536B (en) | 2023-07-28 |
Family
ID=81717442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210230963.5A Active CN114560536B (en) | 2022-03-09 | 2022-03-09 | Terbium-rhenium modified Ti/RuO 2 Dimensionally stable anode, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114560536B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3701724A (en) * | 1968-10-18 | 1972-10-31 | Ici Ltd | Electrodes for electrochemical processes |
| CA1124210A (en) * | 1976-03-31 | 1982-05-25 | Placido M. Spaziante | Sintered electrodes with electrocatalytic coating |
| US20030085199A1 (en) * | 2001-11-08 | 2003-05-08 | Korea Atomic Energy Research Institute & Technology Winners Co., Ltd. | Method for manufacturing catalytic oxide anode using high temperature sintering |
| CN101914782A (en) * | 2010-07-27 | 2010-12-15 | 武汉大学 | Metallic oxide anode suitable for Fenton system and preparation method thereof |
| US20120103828A1 (en) * | 2010-10-28 | 2012-05-03 | Bayer Materialscience Ag | Electrode for electrolytic chlorine production |
| CN102477565A (en) * | 2010-11-29 | 2012-05-30 | 淮南师范学院 | Preparation of high-catalytic activity Ti-based electrodes, Ti/nanoTiO2-RE2O3 and Ti/nanoTiO2-ZrO2 |
| CN104662721A (en) * | 2012-08-03 | 2015-05-27 | 庄信万丰股份有限公司 | Air-breathing cathode for metal-air batteries |
| CN110129821A (en) * | 2019-05-10 | 2019-08-16 | 上海氯碱化工股份有限公司 | Tin, Sb doped titanium-based ruthenic oxide coated electrode preparation method |
| JP2019163524A (en) * | 2018-03-20 | 2019-09-26 | 旭化成株式会社 | Electrolytic tank manufacturing method |
| JP2019179592A (en) * | 2018-03-30 | 2019-10-17 | Fdk株式会社 | Manufacturing method of catalyst for air secondary battery, manufacturing method of air secondary battery, catalyst for air secondary battery, and air secondary battery |
-
2022
- 2022-03-09 CN CN202210230963.5A patent/CN114560536B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3701724A (en) * | 1968-10-18 | 1972-10-31 | Ici Ltd | Electrodes for electrochemical processes |
| CA1124210A (en) * | 1976-03-31 | 1982-05-25 | Placido M. Spaziante | Sintered electrodes with electrocatalytic coating |
| US20030085199A1 (en) * | 2001-11-08 | 2003-05-08 | Korea Atomic Energy Research Institute & Technology Winners Co., Ltd. | Method for manufacturing catalytic oxide anode using high temperature sintering |
| CN101914782A (en) * | 2010-07-27 | 2010-12-15 | 武汉大学 | Metallic oxide anode suitable for Fenton system and preparation method thereof |
| US20120103828A1 (en) * | 2010-10-28 | 2012-05-03 | Bayer Materialscience Ag | Electrode for electrolytic chlorine production |
| CN102477565A (en) * | 2010-11-29 | 2012-05-30 | 淮南师范学院 | Preparation of high-catalytic activity Ti-based electrodes, Ti/nanoTiO2-RE2O3 and Ti/nanoTiO2-ZrO2 |
| CN104662721A (en) * | 2012-08-03 | 2015-05-27 | 庄信万丰股份有限公司 | Air-breathing cathode for metal-air batteries |
| JP2019163524A (en) * | 2018-03-20 | 2019-09-26 | 旭化成株式会社 | Electrolytic tank manufacturing method |
| JP2019179592A (en) * | 2018-03-30 | 2019-10-17 | Fdk株式会社 | Manufacturing method of catalyst for air secondary battery, manufacturing method of air secondary battery, catalyst for air secondary battery, and air secondary battery |
| CN110129821A (en) * | 2019-05-10 | 2019-08-16 | 上海氯碱化工股份有限公司 | Tin, Sb doped titanium-based ruthenic oxide coated electrode preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 戴红等: "钛基钌系氧化物涂层阳极电催化水处理活性与失活", 《贵金属》 * |
| 戴红等: "钛基钌系氧化物涂层阳极电催化水处理活性与失活", 《贵金属》, 30 August 2019 (2019-08-30), pages 2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114560536B (en) | 2023-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2018023912A1 (en) | Indium-doped titanium-based lead dioxide electrode, and manufacturing method thereof and application of same | |
| CN110820030B (en) | Titanium-based PbO for preparing conducting ceramic membrane intermediate layer based on in-situ thermal reaction2Anode preparation method | |
| CN105621541A (en) | Transition-metal doped lead dioxide electrode for wastewater treatment as well as preparation method and application thereof | |
| CN113690455B (en) | Long-life anode electrode material and preparation method thereof | |
| CN106745557B (en) | Titanium-based tin iridium oxide electrode and preparation method thereof | |
| Ma et al. | Electrochemical removal of ammonia in coking wastewater using Ti/SnO2+ Sb/PbO2 anode | |
| CN111634982B (en) | Preparation method of anode material for efficient phenol wastewater degradation | |
| CN111254435A (en) | Ti/Sb-SnO2/PVDF-CNT-PbO2Electrode and method for producing same | |
| CN115626693B (en) | Lead-antimony coated titanium anode plate with intermediate layer and preparation method and application thereof | |
| CN114560536B (en) | Terbium-rhenium modified Ti/RuO 2 Dimensionally stable anode, preparation method and application | |
| CN112267114A (en) | Method for improving compactness and corrosion resistance of hydrotalcite coating on surface of magnesium alloy | |
| CN114538571A (en) | Praseodymium and niobium modified Ti/RuO2Dimensionally stable anode, preparation method and application | |
| Chen et al. | Electrosynthesis and physicochemical properties of α–PbO2–CeO2–TiO2 composite electrodes | |
| CN111607805B (en) | High-life anode material | |
| CN115159633A (en) | Method for manufacturing titanium-based iridium tantalum tin coating electrode for high-salt organic wastewater | |
| CN113149141B (en) | Graphite-phase carbon nitride modified lead dioxide electrode and preparation method and application thereof | |
| CN111943327B (en) | Having RuO for acidic wastewater treatment2-IrO2Electrode material of intermediate layer and preparation method | |
| CN113233549A (en) | Nano lead dioxide electrode and preparation method and application thereof | |
| CN109504987B (en) | Titanium-based composite anode for electrolytic manganese and preparation method and application thereof | |
| CN117285125B (en) | Preparation method and application of doped modified lead dioxide electrode for wastewater treatment | |
| CN114751489B (en) | Gradient porous titanium-based/lead dioxide composite electrode and preparation method thereof | |
| Zhang et al. | Effect of current density on the performance of electrodeposited Ti/Sb–SnO2 electrode from methanesulfonate medium | |
| CN115650376B (en) | DSA electrode based on phenolic resin assistance and preparation method and application thereof | |
| CN115094475B (en) | Electrode material with high-performance oxygen evolution catalytic activity and preparation method thereof | |
| CN113186557A (en) | In-situ preparation method of water electrolysis oxygen evolution catalytic electrode, electrode and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |