CN110803743A - Preparation method of defect-state titanium oxide-aluminum oxide-graphene ceramic electrode - Google Patents
Preparation method of defect-state titanium oxide-aluminum oxide-graphene ceramic electrode Download PDFInfo
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- CN110803743A CN110803743A CN201911120239.1A CN201911120239A CN110803743A CN 110803743 A CN110803743 A CN 110803743A CN 201911120239 A CN201911120239 A CN 201911120239A CN 110803743 A CN110803743 A CN 110803743A
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- 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
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- 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
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- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- 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
Abstract
The invention discloses a preparation method of a defect state titanium oxide-alumina-graphene ceramic electrode, which comprises the following steps: (1) weighing and fully mixing aluminum oxide, titanium oxide, zinc oxide and graphene solid powder according to a certain ratio to obtain a uniform mixture; (2) mixing the mixture with a binder, performing ball milling granulation, and pressing into a polar plate with a specific size; (3) carrying out heat treatment and high-temperature sintering treatment on the formed polar plate; (4) and (4) carrying out fluorination treatment on the sintered polar plate, and drying to obtain the defective titanium oxide-aluminum oxide-graphene ceramic electrode. The invention adopts an in-situ oxygen defect construction technology, and the obtained electrode has high conductivity, good stability and large electrochemical active area, and can be used for large-scale industrial wastewater advanced treatment.
Description
Technical Field
The invention relates to the technical field of electrochemistry and environmental water treatment, in particular to a preparation method of a defect state titanium oxide-aluminum oxide-graphene ceramic electrode.
Background
Among the oxidation technologies for environmental water treatment, electrocatalytic oxidation is an important technology choice. Whereas the choice of anode material is central to the electrocatalytic process. The activity and stability of the anode material not only directly affect the rate and effect of the water treatment process, but also seriously affect the energy consumption, the design and maintenance difficulty of the reactor, and the like.
The electrocatalytic anode used in industrial water treatment process must have three basic conditions of high stability, high catalytic activity and low cost, and particularly, should have good performance in the following aspects:
(1) the mechanical property is stable, and the coating can resist bubble erosion and water flow scouring and is not easy to fall off under the condition of large-amount oxygen evolution on the surface;
(2) stable chemical property, acid corrosion resistance and high potential corrosion resistance, and long service life;
(3) the conductivity is higher, the voltage drop of the pool is reduced, and energy and consumption are saved;
(4) oxygen evolution side reaction is reduced as much as possible, and pollutant degradation selectivity and current efficiency are improved;
(5) the adsorption of pollutants is prevented, and the poisoning and inactivation on the surface of the electrode are prevented.
The metal oxide electrode is the first new type of electrode invented by Beer in 1965, has strong corrosion resistance and Stable shape in the actual use process, and is called a Dimensionally Stable Anode (DSA). Such electrodes have been widely used in organic synthesis, chlor-alkali industry, electroplating industry, and the like. The metal oxide electrode overcomes the defects of poor mechanical strength, high price, poor catalytic performance and the like of the traditional graphite electrode and the traditional noble metal electrode, and has higher development potential in the field of sewage and wastewater treatment.
Through the development of nearly half century, the performance of the metal oxide electrode is greatly improved, the variety is continuously increased, and at present, RuO is mainly used2、IrO2、MnO2、SnO2、PbO2And the like. Wherein RuO2And IrO2Poor oxidation capability and poor pollutant oxidation effect due to low oxygen evolution potentialAnd at the same time, the price is relatively expensive, thereby limiting the application range of the method in the actual industrial sewage treatment. Base metal oxide SnO2、PbO2And MnO2The anode has better corrosion resistance and electrocatalytic activity, and is suitable for being used as an anode surface active layer. Currently, ceramic electrodes are the latest development direction of metal oxide electrodes. The ceramic electrode has the advantages of excellent stability, good mechanical strength and long service life, can be designed into various shapes to adapt to a reactor, and is very suitable for serving as an electrocatalytic anode material for water treatment.
Conductive ceramic electrodes produced from defective titanium oxide were used as bipolar electrode plates for lead-acid batteries for the first time. The defect-state titanium oxide has a crystal lattice structure similar to rutile, is high in conductivity, can reach 300-1500S/cm theoretically in conductivity of different defect-state titanium oxides at normal temperature, and has the characteristic of good chemical stability, so that the defect-state titanium oxide has high industrial application potential. At present, researchers have used defective titanium oxide as an anode material to treat organic wastewater. Treating phenol wastewater by using defect state titanium oxide as an anode, such as gunn and the like; treating 2,4, 6-trinitrophenol wastewater by using a defective titanium oxide electrode; the Linhui and the like use the defective titanium oxide electrode to treat the perfluorooctanoic acid wastewater, and achieve better treatment effect.
The current application methods of the defect state titanium oxide electrode are divided into a defect state titanium oxide pressed electrode and a titanium base coating electrode. For example, patent CN101784487A discloses a defective titanium oxide powder with low resistance and high corrosion resistance, and the defective titanium oxide powder is directly hot-pressed into a plate, although the conductivity is good, the mechanical strength is greatly reduced, which is not beneficial for further processing. CN103303971A discloses a method for preparing an electrode material from titanium powder, which is to form doped solid solution powder in the form of oxide, and although the method improves the conductivity and density of the electrode material, these single-phase solid solutions have problems of poor toughness and poor post-processing property in practical application, like other oxide ceramics.
Another solution is to deposit or spray defective titanium oxide on a metal substrate, for example, CN105058916A has developed an electrode material of a defective titanium oxide intermediate coating, the base material of which is a titanium plate, and the surface active layer and the base layer are bonded by a simple adhesion method; patent CN105967281B develops a method for preparing a titanium-based defective titanium oxide electrode, which comprises the steps of pretreatment of a titanium substrate, transferred arc cleaning, defective titanium oxide spraying and surface oxide sintering electrode, wherein titanium is used as the substrate, and defective titanium oxide powder is sprayed on the titanium substrate by a plasma spraying process to prepare the titanium-based defective titanium oxide coating electrode. However, the above researches have not solved the problems that active free radicals and low-pH solution diffuse to the substrate joint surface along the coating pores during the long-term electrodeposition process, which leads to substrate erosion and even pore erosion, and the anode fails.
Disclosure of Invention
The invention is made in view of the problems in the prior art, and the primary object of the invention is to provide a high-conductivity and corrosion-resistant defective titanium oxide ceramic electrode material aiming at the problems of low mechanical strength, poor toughness, poor post-processing property, easy surface passivation and the like of a defective titanium oxide pressed electrode; the invention aims to provide a preparation method of a defect state titanium oxide-alumina-graphene ceramic electrode, and simultaneously overcomes the defects of high preparation cost, complex process, production danger caused by high-temperature hydrogen operation and the like of the conventional defect state titanium oxide electrode.
In order to achieve the purpose, the technical scheme of the invention is as follows: a preparation method of a defect state titanium oxide-aluminum oxide-graphene ceramic electrode is characterized by comprising the following steps:
(1) mixing aluminum oxide, titanium oxide, zinc oxide and graphene solid powder according to the material ratio to obtain a uniform mixture;
(2) mixing the mixture with a binder, performing ball milling for 6 hours to prepare ceramic powder, and then granulating the obtained ceramic powder, wherein the water content of the granules is controlled to be 5% (weight ratio), and the granularity is 40-80 meshes;
(3) at 1000kg/m2Making the ceramic particles into a ceramic blank plate with the thickness of 5mm in a mould under the pressure of the pressure;
(4) carrying out heat treatment on the ceramic blank plate at 80 ℃ for 24h to remove moisture and organic binder in the blank plate;
(5) sintering the ceramic blank plate after the heat treatment in a vacuum furnace at 1500 ℃ for 12 hours;
(6) dipping the obtained sintered ceramic plate in 5% (weight ratio) ammonium fluoride aqueous solution for fluorination for 24 hours;
(7) drying the fluorinated ceramic plate at 65 ℃ to obtain a defective titanium oxide-aluminum oxide-graphene ceramic electrode;
a second technical means of the present invention is the first technical means, further defined in that the alumina powder, the titania powder, the zinc powder and the zinc oxide powder in the step (1) have particle diameters of 3 μm, 5 μm, 200nm and 20nm, respectively; the weight ratio (alumina: titanium oxide: zinc oxide: graphene) was 65:25:10:2: 0.025.
The second technical means of the present invention is further defined in the first technical means, wherein the binder in the step (2) is polyacrylamide, and the amount of the polyacrylamide added is 0.5% by weight of the powder mixture in the step (1).
In the synthesis formula of the invention, the alumina, titanium oxide, zinc oxide and graphene solid powder respectively play different roles: the aluminum oxide is used as a framework structure of the ceramic composite electrode, provides a basic support for the ceramic composite electrode, has high toughness and good stability, and simultaneously has a large number of Lewis acid active centers, so that the acidic catalytic capability of the ceramic composite electrode can be improved;
titanium oxide is a precursor of defective titanium oxide of a key active catalyst in the ceramic composite electrode, and is gradually reduced into defective titanium oxide in the vacuum roasting process of the step (5);
zinc is a main reducing agent for reducing the defective titanium oxide, and can gradually evaporate on the ceramic blank plate to form steam under the condition of the step (5), so that the titanium oxide can be controllably reduced to be the defective titanium oxide, and the defect that hydrogen is needed to be used as the reducing agent in the traditional preparation process of the defective titanium oxide, and the conventional preparation process has the risk of flammability and explosiveness in hydrogen operation is overcome;
the zinc oxide is a key reduction stabilizer, because the zinc has stronger reducing capability and high volatilization speed at high temperature, the titanium oxide surface is easily reduced rapidly, the reduction inside the particles is insufficient, and the zinc oxide stabilizes the volatilization speed of the zinc, so that the release of zinc vapor is milder and more controllable;
compared with the traditional defect-state titanium oxide hot-pressed ceramic, the graphene provides key electronic conduction capability, avoids the defects of tortuous electronic transmission path, high scattering rate and the like caused by incomplete contact of particles in the traditional defect-state titanium oxide hot-pressed ceramic, and can realize efficient electronic transmission.
The defect-state titanium oxide-aluminum oxide-graphene ceramic electrode prepared by the method can work in various organic and inorganic electrolytes, and has good treatment effect on domestic, industrial and medical sewage; when the defect state titanium oxide-aluminum oxide-graphene ceramic electrode is used for treating sewage, the defect state titanium oxide-aluminum oxide-graphene ceramic electrode is used as an anode, a counter electrode with the same area is used as a cathode, the counter electrode is placed in the sewage, and electrolysis is carried out for a certain time under a certain current density, so that the treatment effect can be achieved.
Compared with the prior art, the invention has the following advantages:
(1) the preparation condition is mild, the dangerous hydrogen operation is avoided, and the controllability of the preparation process is improved;
(2) the zinc powder has low reduction potential, and after the zinc oxide stabilizer is added, both the reduction efficiency and the reduction depth can be taken into consideration, so that the titanium oxide particles can be completely reduced, stable defect states can be obtained inside and outside the particles, and the product purity is high;
(3) the addition of the graphene obviously improves the conductivity of the electrode material, and compared with the traditional defect-state titanium oxide ceramic electrode, the current density can be increased by 40-60 mA/cm2；
(4) The use of the binder improves the toughness of the electrode to the maximum extent and improves the mechanical stability;
(5) the electrode has wide potential window, high oxygen evolution potential, low background current and good selectivity to pollutants;
by adopting the technical scheme, the defect-state titanium oxide-aluminum oxide-graphene ceramic electrode becomes an economic and effective electrode for electrolyzing sewage, which can be used for a long time; the method has the advantages of simple process, reliable principle, low preparation cost, high electrolysis efficiency, good effect, long service life, wide application range and environment-friendly use.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings used in the description of the embodiments section below are briefly described.
FIG. 1 is a diagram of the morphology of the prepared defect state titanium oxide-aluminum oxide-graphene ceramic electrode;
FIG. 2 is a scanning electron microscope image of a defective titania-alumina-graphene ceramic electrode;
FIG. 3 shows the effect of the electrode on the treatment of alkaline residue wastewater (COD concentration change);
FIG. 4 shows the effect of the electrode on aniline wastewater treatment (COD and ammonia nitrogen concentration change).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, specific embodiments of the present invention are described in detail below with reference to the accompanying drawings.
Example 1
The defect state titanium oxide-aluminum oxide-graphene ceramic electrode is prepared by the following steps:
(1) mixing alumina, titanium oxide, zinc oxide and graphene solid powder (wherein the particle sizes of the alumina powder, the titanium oxide powder, the zinc powder and the zinc oxide powder are respectively 3 mu m, 5 mu m, 200nm and 20nm) according to a material ratio (weight ratio) of 65:25:10:2:0.025 to obtain a uniform mixture;
(2) mixing the mixture with 0.5% by mass of a polyacrylamide binder, ball-milling for 6 hours to prepare ceramic powder, and then granulating the obtained ceramic powder, wherein the water content of the granules is controlled to be 5% (by weight), and the granularity is 40-80 meshes;
(3) at 1000kg/m2Making the ceramic particles into a ceramic blank plate with the thickness of 5mm in a mould under the pressure of the pressure;
(4) carrying out heat treatment on the ceramic blank plate at 80 ℃ for 24h to remove moisture and organic binder in the blank;
(5) sintering the ceramic blank plate after the heat treatment in a vacuum furnace at 1500 ℃ for 12 hours;
(6) dipping the obtained sintered ceramic plate in 5% (weight ratio) ammonium fluoride aqueous solution for fluorination for 24 hours;
(7) drying the fluorinated ceramic plate at 65 ℃ to obtain a defective titanium oxide-aluminum oxide-graphene ceramic electrode;
the morphology of the obtained defect-state titanium oxide-aluminum oxide-graphene ceramic electrode is shown in fig. 1, and the microstructure is shown in fig. 2.
Example 2
Specific use method of defect state titanium oxide-aluminum oxide-graphene ceramic electrode
Taking a defective titanium oxide-aluminum oxide-graphene ceramic electrode as an example for treating the alkaline residue wastewater, taking 1L of alkaline residue wastewater of a chemical plant, placing the alkaline residue wastewater in a flat plate type electro-catalytic reactor, taking the defective titanium oxide-aluminum oxide-graphene ceramic electrode as an anode, taking a stainless steel electrode as a cathode, controlling the distance between the anode and the cathode to be 10mm, and controlling the current density to be 20mA/cm2And performing direct current pulse electrolysis on the alkaline residue wastewater for 60min, sampling and analyzing the COD concentration in the water, wherein the COD removal rate is 95.8% as shown in figure 3.
Example 3
Another specific use method of defect state titanium oxide-aluminum oxide-graphene ceramic electrode
Taking a defect state titanium oxide-aluminum oxide-graphene ceramic electrode as an example for treating aniline wastewater, 500mL of aniline wastewater of a chemical plant is taken and placed in a flat plate type electro-catalytic reactor, the defect state titanium oxide-aluminum oxide-graphene ceramic electrode is taken as an anode, a stainless steel electrode is taken as a cathode, the distance between the anode and the cathode is controlled to be 15mm, and the current density is 40mA/cm2And performing direct current pulse electrolysis on the aniline wastewater for 60min, sampling and analyzing COD and ammonia nitrogen concentration in the water, wherein the results are shown in figure 4, the removal rate of the COD is 96.2%, and the removal rate of the ammonia nitrogen is 92.7%.
The above-described embodiments are only intended to specifically illustrate the spirit of the present invention, and the scope of the present invention is not limited thereto, and it is obvious to those skilled in the art that other embodiments can be easily made by changes, substitutions or alterations according to the technical contents disclosed in the present specification, and these other embodiments should be covered within the scope of the present invention.
Claims (3)
1. A preparation method of a defect state titanium oxide-aluminum oxide-graphene ceramic electrode is characterized by comprising the following steps:
(1) mixing aluminum oxide, titanium oxide, zinc oxide and graphene solid powder according to the material ratio to obtain a uniform mixture;
(2) mixing the mixture with a binder, performing ball milling for 6 hours to prepare ceramic powder, and then granulating the obtained ceramic powder, wherein the water content of the granules is controlled to be 5% (weight ratio), and the granularity is 40-80 meshes;
(3) at 1000kg/m2Making the ceramic particles into a ceramic blank plate with the thickness of 5mm in a mould under the pressure of the pressure;
(4) carrying out heat treatment on the ceramic blank plate at 80 ℃ for 24h to remove moisture and organic binder in the blank;
(5) sintering the ceramic blank plate after the heat treatment in a vacuum furnace at 1500 ℃ for 12 hours;
(6) dipping the obtained sintered ceramic plate in 5% (weight ratio) ammonium fluoride aqueous solution for fluorination for 24 hours;
(7) and drying the fluorinated ceramic plate at 65 ℃ to obtain the defect state titanium oxide-aluminum oxide-graphene ceramic electrode.
2. A preparation method of a defect state titanium oxide-aluminum oxide-graphene ceramic electrode is characterized in that the particle diameters of aluminum oxide powder, titanium oxide powder, zinc powder and zinc oxide powder in the step (1) are respectively 3 micrometers, 5 micrometers, 200nm and 20 nm; the weight ratio (alumina: titanium oxide: zinc oxide: graphene) was 65:25:10:2: 0.025.
3. A preparation method of a defect state titanium oxide-alumina-graphene ceramic electrode is characterized in that in the step (2), the adhesive is polyacrylamide, and the addition amount of the adhesive is 0.5% of the weight of the powder mixture in the step (1).
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| CN111384197A (en) * | 2020-03-20 | 2020-07-07 | 杭州高烯科技有限公司 | Defect-state graphene/semiconductor heterojunction photoelectric detector |
| CN112591856A (en) * | 2020-12-04 | 2021-04-02 | 北京师范大学 | Electrocatalytic activity regulation and control method based on inert ion intercalation |
| CN112919700A (en) * | 2020-12-08 | 2021-06-08 | 北京师范大学 | Reactor for advanced treatment of high-salinity organic wastewater by using multistage photoelectric tubes |
| CN112939156A (en) * | 2021-02-05 | 2021-06-11 | 西安交通大学 | Electrochemical reaction system and method with electrode self-repairing function |
| CN114602494A (en) * | 2022-05-12 | 2022-06-10 | 中国环境科学研究院 | Method for preparing multi-metal ozone catalyst by blending-impregnation combined method |
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| CN114602494A (en) * | 2022-05-12 | 2022-06-10 | 中国环境科学研究院 | Method for preparing multi-metal ozone catalyst by blending-impregnation combined method |
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