CN113517446B - Preparation of active porous Co-Cu-Ti by 3D technology4O7Method for compounding three-dimensional electrode and application - Google Patents

Preparation of active porous Co-Cu-Ti by 3D technology4O7Method for compounding three-dimensional electrode and application Download PDF

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CN113517446B
CN113517446B CN202110388940.2A CN202110388940A CN113517446B CN 113517446 B CN113517446 B CN 113517446B CN 202110388940 A CN202110388940 A CN 202110388940A CN 113517446 B CN113517446 B CN 113517446B
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powder
printing
electrode
porous
precursor
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CN113517446A (en
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何忠艳
吕斯濠
李威
林辉
杨立辉
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Dongguan University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/005—Combined electrochemical biological processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8684—Negative electrodes
    • 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

Abstract

The invention discloses a method for preparing active porous Co-Cu-Ti by using a 3D technology4O7The Co-Cu precursor and the modified Ti are prepared by the method, the electrochemical performance of the Co-Cu precursor is better than that of the simple Co and Cu, and the Co-Cu precursor and the modified Ti are used4O7The powder is uniformly mixed by adopting a mechanical mixing method, a dissolution precipitation method or a solvent evaporation method, and the Co-Cu precursor and the modified Ti4O7The powder is tightly compounded by hydroxyl groups to obtain Co-Cu-Ti4O7Composite powder, and printing porous Co-Cu-Ti by using 3D technology4O7Compounding three-dimensional electrode, and mixing porous Co-Cu-Ti4O7The composite three-dimensional electrode enhances activation treatment, so that the active sites on the surface of the printed electrode are further increased, and the active porous Co-Cu-Ti is obtained4O7The composite three-dimensional electrode is applied to sewage treatment, and can greatly improve the sewage purification effect.

Description

Preparation of active porous Co-Cu-Ti by 3D technology4O7Method for compounding three-dimensional electrode and application
Technical Field
The invention relates to the technical field of electrochemical electrode manufacturing, in particular to a method for preparing active porous Co-Cu-Ti by using a 3D technology4O7A method for compounding three-dimensional electrodes and application.
Background
The organic pollutants contained in the sewage contain abundant chemical energy which is 9-10 times of the energy required by the water treatment process. The realization of sewage treatment energy self-supply or energy production and the promotion of the development of water treatment to the direction of resource utilization and sustainability are important directions of the current water treatment technology innovation.
Microbial Fuel Cell (MFC) technology converts chemical energy of organic matter in sewage into directly usable electric energy by using microbes as catalysts, has the advantages of wide substrate utilization range, small influence of temperature, high energy conversion rate and the like, and has recently received wide attention of domestic and foreign scholars. At present, the output current of the MFC is low, and the MFC belongs to the main problem that low-grade electric energy is difficult to directly utilize and is restricted in large-scale application. The essential of the MFC electricity generation is that microorganisms on the anode catalyze decomposition of organic matters and transfer of electrons to the electrode (anode) is realized, so the microbial load and the electron transfer rate are key problems influencing the electricity generation of the MFC. The anode material not only directly influences the attachment and growth of microbial cells on the electrode, determines the microbial load of the electrode, influences the formation and structure of an electrode biofilm, and further influences the direct/indirect transfer rate of electrons from the microbes to the electrode, so that the anode material is an extremely important factor for determining the electricity generation performance of the MFC.
Titanium suboxide is known to have excellent electrochemical performance, so that the titanium suboxide has a promoting effect on refractory organics when being used as an anode material in electrochemical advanced oxidation. Also, the copper or cobalt-based nanostructure has rich oxidation states, and can effectively perform redox charge transfer, thereby realizing higher energy density, so that the copper or cobalt is also used as an anode material in electrochemical advanced oxidation. And researches show that the electrochemical performances of the copper cobalt oxide, the sulfide, the selenide and the hydroxide are respectively superior to those of the corresponding single copper or cobalt compound. Therefore, how to combine copper, cobalt and titanium suboxide to be applied to the anode of the battery to exert the maximum characteristics becomes a problem to be solved in the field.
Disclosure of Invention
In view of the foregoing, the present invention is directed to the prior artThe main purpose of the present invention is to provide a method for preparing active porous Co-Cu-Ti by using 3D technology4O7The method and application of the composite three-dimensional electrode combine copper, cobalt and titanium suboxide to be applied to the anode of the battery to exert the maximum characteristics of the battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
active porous Co-Cu-Ti prepared by using 3D technology4O7The method for compounding the three-dimensional electrode comprises the following steps;
(1) preparation of Co-Cu precursor: dissolving soluble copper salt and soluble cobalt salt in water, carrying out hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain a Co-Cu precursor;
(2) selecting materials: selecting nano-grade Ti4O7The powder is taken as a raw material;
(3) modification treatment: taking 2 parts by weight of Ti4O7Mixing the powder and 0.2-0.5 part of absolute ethyl alcohol in a container; heating the mixed liquid in the container to be dry by using a heating magnetic stirrer at the temperature of 90 ℃; then placing the mixture into an oven, setting the temperature of the oven to be 60 ℃ and baking the mixture for 10 hours; then putting the baked powder into a ball mill for grinding to obtain modified Ti powder4O7Powder; modified Ti4O7The surface of the modified material is provided with hydroxyl groups by absolute ethyl alcohol;
(4) mixing materials: modified Ti in mass percent4O745-65% of powder, 10-15% of high molecular binder epoxy resin and 25-40% of Co-Cu precursor; subjecting the modified Ti4O7Mixing the powder, the high-molecular binder epoxy resin and the Co-Cu precursor according to mass percent, and then putting the mixture into a ball mill for mechanical mixing and grinding to modify Ti4O7The powder, the high molecular binder epoxy resin and the Co-Cu precursor are completely and uniformly mixed; and Co-Cu precursor and modified Ti4O7Epoxy of powder via hydroxyl group and high molecular adhesiveThe resin is tightly compounded to obtain Co-Cu-Ti4O7Compounding powder;
(5)3D modeling: drawing a three-dimensional model electrode to be printed by using three-dimensional drawing software and setting 3D printing parameters;
(6) laying printing powder: mixing the Co-Cu-Ti obtained in (3)4O7The composite powder is laid in the area between a lifting platform and a scraping plate in the 3D printer and is ready for Co-Cu-Ti4O7After the composite powder is paved, a scraper plate is used for scraping Co-Cu-Ti with the thickness exceeding the set thickness4O7Scraping the composite powder to obtain printing powder layers with set thickness, wherein the thickness of each printing powder layer is consistent and is 0.1mm-0.2 mm;
(7) laser scanning: a laser head in the 3D printer emits a laser beam to scan the printing powder layer according to a set program, so that the scanned printing powder in the area is mutually combined, the laser preheating temperature is 50-70 ℃, the sintering temperature is 1200-1600 ℃, the laser power is 5-10W, the scanning interval is 0.1-0.2 mm, and the scanning speed is 1500-2000 mm/s;
(8) descending the platform: after scanning a layer of printing powder layer, a lifting platform in the 3D printer descends the height of the single printing powder layer according to a set program; then, the steps of laying and printing powder, scanning laser and descending a platform are sequentially repeated until a plurality of layers of printing powder layers are sintered into the three-dimensional model electrode drawn in the step (5);
(9) excess material removal: taking out the electrode after 3D printing, washing with water, removing the unprinted powder on the electrode to obtain the porous Co-Cu-Ti4O7Compounding a three-dimensional electrode;
(10) enhancing the activity: porous Co-Cu-Ti4O7The composite three-dimensional electrode is placed into a solution containing active substances to be soaked for 1-5 h, and freeze drying treatment is carried out for 10-30 h to obtain the porous Co-Cu-Ti doped with the active components4O7A composite three-dimensional electrode precursor; then porous Co-Cu-Ti4O7Carrying out heat treatment on the composite three-dimensional electrode precursor to obtain active porous Co-Cu-Ti4O7And compounding the three-dimensional electrode.
Utilize 3Preparation of active porous Co-Cu-Ti by D technology4O7The method for compounding the three-dimensional electrode comprises the following steps;
(1) preparation of Co-Cu precursor: dissolving soluble copper salt and soluble cobalt salt in water, carrying out hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain a Co-Cu precursor;
(2) selecting materials: selecting nano-grade Ti4O7The powder is taken as a raw material;
(3) modification treatment: taking 2 parts by weight of Ti4O7Mixing the powder and 0.2-0.5 part of absolute ethyl alcohol in a container; heating the mixed liquid in the container to be dry by using a heating magnetic stirrer at the temperature of 90 ℃; then placing the mixture into an oven, setting the temperature of the oven to be 60 ℃ and baking the mixture for 10 hours; then putting the baked powder into a ball mill for grinding to obtain modified Ti powder4O7Powder; modified Ti4O7The surface of the modified material is provided with hydroxyl groups by absolute ethyl alcohol;
(4) mixing materials: modified Ti in mass percent4O7The mass percent of the powder is 40-60%, the mass percent of the polymer nylon 12 is 10-15%, the mass percent of the Co-Cu precursor is 25-35%, and the mass percent of the absolute ethyl alcohol is 5-10%; subjecting the modified Ti4O7Mixing the powder, the polymer nylon 12, the Co-Cu precursor and absolute ethyl alcohol according to mass percent, heating for fusion and stirring to fully dissolve the polymer nylon 12 into the absolute ethyl alcohol, reacting the modified Ti4O7 with the absolute ethyl alcohol again to increase the number of hydroxyl groups, and modifying the modified Ti4O7 with the hydroxyl groups4O7The powder, the polymer nylon 12 and the Co-Cu precursor are tightly compounded to obtain a mixture; in the cooling process of the mixture, the solubility of the polymer nylon 12 in absolute ethyl alcohol is reduced, ceramic particles are taken as cores to be separated out, finally, the residual absolute ethyl alcohol is filtered and recovered, and the residual mixture is dried and sieved to obtain the polymer coated ceramic Co-Cu-Ti4O7Compounding powder;
(5)3D modeling: drawing a three-dimensional model electrode to be printed by using three-dimensional drawing software and setting 3D printing parameters;
(6) laying printing powder: coating the polymer obtained in the step (3) with ceramic Co-Cu-Ti4O7The composite powder is laid in the area between a lifting platform and a scraper plate in the 3D printer and ceramic Co-Cu-Ti is coated with a polymer4O7After the composite powder is paved, a scraper plate is utilized to coat the polymer film-coated ceramic Co-Cu-Ti with the thickness exceeding the set thickness4O7Scraping the composite powder to obtain printing powder layers with set thickness, wherein the thickness of each printing powder layer is consistent and is 0.1mm-0.2 mm;
(7) laser scanning: a laser head in the 3D printer emits a laser beam to scan the printing powder layer according to a set program, so that the scanned printing powder in the area is mutually combined, the laser preheating temperature is 50-70 ℃, the sintering temperature is 1200-1600 ℃, the laser power is 5-10W, the scanning interval is 0.1-0.2 mm, and the scanning speed is 1500-2000 mm/s;
(8) descending the platform: after scanning a layer of printing powder layer, a lifting platform in the 3D printer descends the height of the single printing powder layer according to a set program; then, the steps of laying and printing powder, scanning laser and descending a platform are sequentially repeated until a plurality of layers of printing powder layers are sintered into the three-dimensional model electrode drawn in the step (5);
(9) excess material removal: taking out the electrode after 3D printing, washing with water, removing the powder not printed on the electrode to obtain the polymer film porous Co-Cu-Ti4O7Compounding a three-dimensional electrode;
(10) enhancing the activity: coating polymer with porous Co-Cu-Ti4O7The composite three-dimensional electrode is placed into a solution containing active substances to be soaked for 1-5 h, and freeze drying treatment is carried out for 10-30 h to obtain the active component doped polymer coating porous Co-Cu-Ti4O7A composite three-dimensional electrode precursor; then coating the polymer with porous Co-Cu-Ti4O7Carrying out heat treatment on the composite three-dimensional electrode precursor to obtain the polymer coated active porous Co-Cu-Ti4O7And compounding the three-dimensional electrode.
Prepared by using 3D technologyActive porous Co-Cu-Ti4O7The method for compounding the three-dimensional electrode comprises the following steps;
(1) preparation of Co-Cu precursor: dissolving soluble copper salt and soluble cobalt salt in water, carrying out hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain a Co-Cu precursor;
(2) selecting materials: selecting nano-grade Ti4O7The powder is taken as a raw material;
(3) modification treatment: taking 2 parts by weight of Ti4O7Mixing the powder and 0.2-0.5 part of absolute ethyl alcohol in a container; heating the mixed liquid in the container to be dry by using a heating magnetic stirrer at the temperature of 90 ℃; then placing the mixture into an oven, setting the temperature of the oven to be 60 ℃ and baking the mixture for 10 hours; then putting the baked powder into a ball mill for grinding to obtain modified Ti powder4O7Powder; modified Ti4O7The surface of the modified material is provided with hydroxyl groups by absolute ethyl alcohol;
(4) mixing materials: modified Ti in mass percent4O740-60% of powder, 10-15% of stearic acid powder, 25-35% of Co-Cu precursor and 5-10% of absolute ethyl alcohol; subjecting the modified Ti4O7Mixing the powder, the stearic acid powder, the Co-Cu precursor and the absolute ethyl alcohol according to mass percent, putting the mixture into a ball mill for high-speed ball milling to ensure that the stearic acid is fully dissolved in the absolute ethyl alcohol, and the absolute ethyl alcohol is used for carrying out modification treatment on the Ti4O7Reacting to increase the number of hydroxyl groups which will modify the treated Ti4O7Tightly compounding the powder, stearic acid and a Co-Cu precursor to obtain a mixture; heating and stirring the obtained mixture to evaporate the mixture to obtain the required mixed material, drying, grinding and sieving the mixed material to obtain the stearic acid coated Co-Cu-Ti4O7Compounding powder;
(5)3D modeling: drawing a three-dimensional model electrode to be printed by using three-dimensional drawing software and setting 3D printing parameters;
(6) laying printing powder: coating the polymer obtained in the step (3) with ceramic Co-Cu-Ti4O7The composite powder is laid in the area between a lifting platform and a scraping plate in the 3D printer and Co-Cu-Ti is coated with a film to be stearic acid4O7After the composite powder is paved, a scraper plate is utilized to coat the stearic acid with the thickness exceeding the set thickness with Co-Cu-Ti4O7Scraping the composite powder to obtain printing powder layers with set thickness, wherein the thickness of each printing powder layer is consistent and is 0.1mm-0.2 mm;
(7) laser scanning: a laser head in the 3D printer emits a laser beam to scan the printing powder layer according to a set program, so that the scanned printing powder in the area is mutually combined, the laser preheating temperature is 50-70 ℃, the sintering temperature is 1200-1600 ℃, the laser power is 5-10W, the scanning interval is 0.1-0.2 mm, and the scanning speed is 1500-2000 mm/s;
(8) descending the platform: after scanning a layer of printing powder layer, a lifting platform in the 3D printer descends the height of the single printing powder layer according to a set program; then, the steps of laying and printing powder, scanning laser and descending a platform are sequentially repeated until a plurality of layers of printing powder layers are sintered into the three-dimensional model electrode drawn in the step (5);
(9) excess material removal: taking out the electrode after 3D printing, washing with water, removing the powder not printed on the electrode to obtain the stearic acid coated porous Co-Cu-Ti4O7Compounding a three-dimensional electrode;
(10) enhancing the activity: coating stearic acid with porous Co-Cu-Ti4O7The composite three-dimensional electrode is placed into a solution containing active substances to be soaked for 1-5 h, and freeze drying treatment is carried out for 10-30 h to obtain the stearic acid coated porous Co-Cu-Ti doped with the active components4O7A composite three-dimensional electrode precursor; then coating stearic acid with a porous Co-Cu-Ti4O7Carrying out heat treatment on the composite three-dimensional electrode precursor to obtain stearic acid coated active porous Co-Cu-Ti4O7And compounding the three-dimensional electrode.
Preferably, the activated porous Co-Cu-Ti is printed4O7Soaking the composite three-dimensional electrode in ammonia water for treatmentThe porous structure is abundant.
As a preferable scheme, the concentration of the ammonia water is 0.2 wt% -20 wt%, and the soaking treatment time is 1-40 hours.
As a preferable scheme, the soluble copper salt is copper nitrate, and the soluble cobalt salt is cobalt nitrate; the mol ratio of the soluble copper salt to the soluble cobalt salt is 1 (0.5-2).
As a preferable scheme, in the hydrothermal reaction process, the temperature is 150-200 ℃ and the time is 6-14 h.
Preferably, the active substance is tetraphenylboron, tetraphenylboron-phosphorus, melamine, ammonium molybdate, iron acetylacetonate, nickel acetylacetonate, and the concentration of the solution is in the range of 1 wt% to 80 wt%.
As a preferable scheme, the heat treatment process is as follows: in a tubular furnace, firstly heating to 200-900 ℃ at the speed of 1-20 ℃/min, keeping the temperature for 0.5-15 h, then heating to 900-1800 ℃ at the speed of 1-20 ℃/min, keeping the temperature for 0.5-15 h, and finally cooling to room temperature at the speed of 1-20 ℃/min.
Active porous Co-Cu-Ti prepared by using 3D technology preparation method4O7Application of composite three-dimensional electrode, namely active porous Co-Cu-Ti4O7The composite three-dimensional electrode is used as an anode of a microbial fuel cell and is used in sewage treatment.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and particularly, as can be seen from the technical scheme,
Co-Cu precursor and modified Ti are prepared by preparing Co-Cu precursor which has better electrochemical performance compared with simple Co and Cu4O7The powder is uniformly mixed by adopting a mechanical mixing method, a dissolution precipitation method or a solvent evaporation method, and the Co-Cu precursor and the modified Ti4O7The powder is tightly compounded by hydroxyl groups to obtain Co-Cu-Ti4O7Composite powder, and printing porous Co-Cu-Ti by using 3D technology4O7Compounding three-dimensional electrode, and mixing porous Co-Cu-Ti4O7The composite three-dimensional electrode enhances the activation treatment to lead the printing to be carried outFurther increasing the active sites on the surface of the electrode to obtain active porous Co-Cu-Ti4O7A composite three-dimensional electrode prepared by mixing Co, Cu and Ti4O7The three materials are well combined, the characteristics of the three materials are furthest exerted, and the three materials are applied to sewage treatment, so that the effect of purifying sewage can be greatly improved.
To more clearly illustrate the structural features and effects of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Drawings
FIG. 1 shows active porous Co-Cu-Ti prepared by the present invention4O7A schematic diagram and a partial enlarged view of a composite three-dimensional electrode structure;
FIG. 2 shows active porous Co-Cu-Ti prepared by the present invention4O7Composite three-dimensional electrode and Ti4O7Faradaic efficiency of the electrodes is plotted against the faradaic efficiency.
Detailed Description
The first embodiment:
active porous Co-Cu-Ti prepared by using 3D technology4O7The method for compounding the three-dimensional electrode comprises the following steps;
(1) preparation of Co-Cu precursor: and dissolving soluble copper salt and soluble cobalt salt in water, carrying out hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain the Co-Cu precursor. The soluble cobalt salt is cobalt nitrate; the mol ratio of the soluble copper salt to the soluble cobalt salt is 1 (0.5-2). In the hydrothermal reaction process, the temperature is 150-200 ℃ and the time is 6-14 h.
Specifically, firstly, 2mmol of Cu (NO3)2 and 2mmol of Co (NO3) 2.6H 2O are dissolved in 40mL of water, a hydrothermal reaction is carried out after magnetic stirring is carried out for 20min, the mixture is transferred into a 50mL polytetrafluoroethylene-lined stainless steel autoclave for a first hydrothermal reaction, the hydrothermal reaction temperature is 180 ℃, the hydrothermal reaction time is 10H, a sample after the hydrothermal reaction is taken out and cooled, and then the sample is centrifuged, washed and dried in vacuum at 60 ℃ for 12H, so that the Co-Cu precursor is obtained.
(2) Selecting materials: selecting nano-grade Ti4O7Powder ofIs taken as a raw material; the purity of the product is more than 99.99 percent, and the product is Ti4O7The powder is Ti with the pore size of 60-100 mu m4O7A porous powder.
(3) Modification treatment: taking 2 parts by weight of Ti4O7Mixing the powder and 0.2-0.5 part of absolute ethyl alcohol in a container; heating the mixed liquid in the container to be dry by using a heating magnetic stirrer at the temperature of 90 ℃; then placing the mixture into an oven, setting the temperature of the oven to be 60 ℃ and baking the mixture for 10 hours; then putting the baked powder into a ball mill for grinding, and grinding the ground Ti4O7The powder is finer; the obtained powder is modified Ti4O7Powder; modified Ti4O7The surface of the modified material is provided with hydroxyl groups by absolute ethyl alcohol.
(4) Mixing materials: modified Ti in mass percent4O745-65% of powder, 10-15% of high molecular binder epoxy resin and 25-40% of Co-Cu precursor; subjecting the modified Ti4O7Mixing the powder, the high-molecular binder epoxy resin and the Co-Cu precursor according to mass percent, and then putting the mixture into a ball mill for mechanical mixing and grinding to modify Ti4O7The powder, the high molecular binder epoxy resin and the Co-Cu precursor are completely and uniformly mixed; and Co-Cu precursor and modified Ti4O7The powder is tightly compounded with a macromolecular binder epoxy resin through hydroxyl groups to obtain Co-Cu-Ti4O7And (3) compounding the powder. The method has the advantages of simple operation, low requirement on equipment and short powder preparation period, and mixed powder meeting SLS forming requirements can be prepared when fully mixed.
(5)3D modeling: and drawing the three-dimensional model electrode to be printed by using three-dimensional drawing software and setting 3D printing parameters.
(6) Laying printing powder: mixing the Co-Cu-Ti obtained in (3)4O7The composite powder is laid in the area between a lifting platform and a scraping plate in the 3D printer and is ready for Co-Cu-Ti4O7After the composite powder is laid, the composite powder is utilizedThe scraper plate will exceed the Co-Cu-Ti with set thickness4O7And scraping the composite powder to obtain a printing powder layer with a set thickness, wherein the thickness of each printing powder layer is consistent and is 0.1-0.2 mm. Do benefit to the 3D printer, can accomplish automatic shop's powder, and the powder bed thickness of laying can accurate control.
(7) Laser scanning: a laser head in the 3D printer emits a laser beam to scan the printing powder layer according to a set program, so that the scanned printing powder in the area is mutually combined, the laser preheating temperature is 50-70 ℃, the sintering temperature is 1200-1600 ℃, the laser power is 5-10W, the scanning interval is 0.1-0.2 mm, and the scanning speed is 1500-2000 mm/s; and sintering the scanned powder by using laser, and sintering and connecting the sintered powder.
(8) Descending the platform: after scanning a layer of printing powder layer, a lifting platform in the 3D printer descends the height of the single printing powder layer according to a set program; and then, repeating the steps of laying printing powder, scanning laser and descending the platform in sequence until a plurality of layers of printing powder layers are sintered into the three-dimensional model electrode drawn in the step (5).
(9) Excess material removal: taking out the electrode after 3D printing, washing with water, removing the unprinted powder on the electrode to obtain the porous Co-Cu-Ti4O7Compounding a three-dimensional electrode;
(10) enhancing the activity: porous Co-Cu-Ti4O7The composite three-dimensional electrode is placed into a solution containing active substances to be soaked for 1-5 h, and freeze drying treatment is carried out for 10-30 h to obtain the porous Co-Cu-Ti doped with the active components4O7A composite three-dimensional electrode precursor; then porous Co-Cu-Ti4O7Carrying out heat treatment on the composite three-dimensional electrode precursor to obtain active porous Co-Cu-Ti4O7And compounding the three-dimensional electrode. The active substances are tetraphenyl boron, tetraphenyl boron phosphorus, melamine, ammonium molybdate, iron acetylacetonate and nickel acetylacetonate, and the concentration range of the solution is 1-80 wt%. The heat treatment process comprises the following steps: in a tubular furnace, firstly heating to 200-900 ℃ at the speed of 1-20 ℃/min, keeping the temperature for 0.5-15 h, then heating to 900-1800 ℃ at the speed of 1-20 ℃/min, keeping the temperature for 0.5-15 h, and finally heating at the speed of 1-20 ℃/minThe rate was reduced to room temperature. Through this step, the number of activated carbon sites on the electrode surface increases and the chemical reaction becomes more active.
Second embodiment:
active porous Co-Cu-Ti prepared by using 3D technology4O7The method for compounding the three-dimensional electrode comprises the following steps;
(1) preparation of Co-Cu precursor: dissolving soluble copper salt and soluble cobalt salt in water, carrying out hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain a Co-Cu precursor;
(2) selecting materials: selecting nano-grade Ti4O7The powder is taken as a raw material;
(3) modification treatment: taking 2 parts by weight of Ti4O7Mixing the powder and 0.2-0.5 part of absolute ethyl alcohol in a container; heating the mixed liquid in the container to be dry by using a heating magnetic stirrer at the temperature of 90 ℃; then placing the mixture into an oven, setting the temperature of the oven to be 60 ℃ and baking the mixture for 10 hours; then putting the baked powder into a ball mill for grinding to obtain modified Ti powder4O7Powder; modified Ti4O7The surface of the modified material is provided with hydroxyl groups by absolute ethyl alcohol;
(4) mixing materials: modified Ti in mass percent4O7The mass percent of the powder is 40-60%, the mass percent of the polymer nylon 12 is 10-15%, the mass percent of the Co-Cu precursor is 25-35%, and the mass percent of the absolute ethyl alcohol is 5-10%; subjecting the modified Ti4O7Mixing the powder, the polymer nylon 12, the Co-Cu precursor and the absolute ethyl alcohol according to mass percent, heating for fusion and stirring to fully dissolve the polymer nylon 12 into the absolute ethyl alcohol, and then modifying the modified Ti by the absolute ethyl alcohol again4O7Reacting to increase the number of hydroxyl groups which will modify the treated Ti4O7The powder, the polymer nylon 12 and the Co-Cu precursor are tightly compounded to obtain a mixture; during the cooling of the mixture, the solubility of the polymer nylon 12 in absolute ethyl alcohol is reduced, and ceramic particles are taken as cores to be separated out, and the maximumThen, the residual absolute ethyl alcohol is filtered and recovered, and the residual mixture is dried and sieved to obtain the polymer coated ceramic Co-Cu-Ti4O7Compounding powder;
(5)3D modeling: drawing a three-dimensional model electrode to be printed by using three-dimensional drawing software and setting 3D printing parameters;
(6) laying printing powder: coating the polymer obtained in the step (3) with ceramic Co-Cu-Ti4O7The composite powder is laid in the area between a lifting platform and a scraper plate in the 3D printer and ceramic Co-Cu-Ti is coated with a polymer4O7After the composite powder is paved, a scraper plate is utilized to coat the polymer film-coated ceramic Co-Cu-Ti with the thickness exceeding the set thickness4O7Scraping the composite powder to obtain printing powder layers with set thickness, wherein the thickness of each printing powder layer is consistent and is 0.1mm-0.2 mm;
(7) laser scanning: a laser head in the 3D printer emits a laser beam to scan the printing powder layer according to a set program, so that the scanned printing powder in the area is mutually combined, the laser preheating temperature is 50-70 ℃, the sintering temperature is 1200-1600 ℃, the laser power is 5-10W, the scanning interval is 0.1-0.2 mm, and the scanning speed is 1500-2000 mm/s;
(8) descending the platform: after scanning a layer of printing powder layer, a lifting platform in the 3D printer descends the height of the single printing powder layer according to a set program; then, the steps of laying and printing powder, scanning laser and descending a platform are sequentially repeated until a plurality of layers of printing powder layers are sintered into the three-dimensional model electrode drawn in the step (5);
(9) excess material removal: taking out the electrode after 3D printing, washing with water, removing the powder not printed on the electrode to obtain the polymer film porous Co-Cu-Ti4O7Compounding a three-dimensional electrode;
(10) enhancing the activity: coating polymer with porous Co-Cu-Ti4O7The composite three-dimensional electrode is placed into a solution containing active substances to be soaked for 1-5 h, and freeze drying treatment is carried out for 10-30 h to obtain the active component doped polymer coating porous Co-Cu-Ti4O7A composite three-dimensional electrode precursor; then coating the polymer with a filmPorous Co-Cu-Ti4O7Carrying out heat treatment on the composite three-dimensional electrode precursor to obtain the polymer coated active porous Co-Cu-Ti4O7And compounding the three-dimensional electrode.
The second example is different from the first example in the step (4) of mixing, and the second example adopts the coating Co-Cu-Ti prepared by the' dissolving precipitation method4O7The composite powder has better fluidity and more uniform components, is not easy to generate segregation phenomenon in the powder laying and sintering processes, has small shrinkage deformation of the electrode during post-treatment, and has more uniform internal tissues.
The third embodiment:
active porous Co-Cu-Ti prepared by using 3D technology4O7The method for compounding the three-dimensional electrode comprises the following steps;
(1) preparation of Co-Cu precursor: dissolving soluble copper salt and soluble cobalt salt in water, carrying out hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain a Co-Cu precursor;
(2) selecting materials: selecting nano-grade Ti4O7The powder is taken as a raw material;
(3) modification treatment: taking 2 parts by weight of Ti4O7Mixing the powder and 0.2-0.5 part of absolute ethyl alcohol in a container; heating the mixed liquid in the container to be dry by using a heating magnetic stirrer at the temperature of 90 ℃; then placing the mixture into an oven, setting the temperature of the oven to be 60 ℃ and baking the mixture for 10 hours; then putting the baked powder into a ball mill for grinding to obtain modified Ti powder4O7Powder; modified Ti4O7The surface of the modified material is provided with hydroxyl groups by absolute ethyl alcohol;
(4) mixing materials: modified Ti in mass percent4O740-60% of powder, 10-15% of stearic acid powder, 25-35% of Co-Cu precursor and 5-10% of absolute ethyl alcohol; subjecting the modified Ti4O7Mixing the powder, the stearic acid powder, the Co-Cu precursor and the absolute ethyl alcohol according to mass percentageMixing, high-speed ball milling in ball mill to dissolve stearic acid in absolute alcohol, and modifying Ti with absolute alcohol4O7Reacting to increase the number of hydroxyl groups which will modify the treated Ti4O7Tightly compounding the powder, stearic acid and a Co-Cu precursor to obtain a mixture; heating and stirring the obtained mixture to evaporate the mixture to obtain the required mixed material, drying, grinding and sieving the mixed material to obtain the stearic acid coated Co-Cu-Ti4O7Compounding powder;
(5)3D modeling: drawing a three-dimensional model electrode to be printed by using three-dimensional drawing software and setting 3D printing parameters;
(6) laying printing powder: coating the polymer obtained in the step (3) with ceramic Co-Cu-Ti4O7The composite powder is laid in the area between a lifting platform and a scraping plate in the 3D printer and Co-Cu-Ti is coated with a film to be stearic acid4O7After the composite powder is paved, a scraper plate is utilized to coat the stearic acid with the thickness exceeding the set thickness with Co-Cu-Ti4O7Scraping the composite powder to obtain printing powder layers with set thickness, wherein the thickness of each printing powder layer is consistent and is 0.1mm-0.2 mm;
(7) laser scanning: a laser head in the 3D printer emits a laser beam to scan the printing powder layer according to a set program, so that the scanned printing powder in the area is mutually combined, the laser preheating temperature is 50-70 ℃, the sintering temperature is 1200-1600 ℃, the laser power is 5-10W, the scanning interval is 0.1-0.2 mm, and the scanning speed is 1500-2000 mm/s;
(8) descending the platform: after scanning a layer of printing powder layer, a lifting platform in the 3D printer descends the height of the single printing powder layer according to a set program; then, the steps of laying and printing powder, scanning laser and descending a platform are sequentially repeated until a plurality of layers of printing powder layers are sintered into the three-dimensional model electrode drawn in the step (5);
(9) excess material removal: taking out the electrode after 3D printing, washing with water, removing the powder not printed on the electrode to obtain the stearic acid coated porous Co-Cu-Ti4O7Compounding a three-dimensional electrode;
(10) enhancing the activity: coating stearic acid with porous Co-Cu-Ti4O7The composite three-dimensional electrode is placed into a solution containing active substances to be soaked for 1-5 h, and freeze drying treatment is carried out for 10-30 h to obtain the stearic acid coated porous Co-Cu-Ti doped with the active components4O7A composite three-dimensional electrode precursor; then coating stearic acid with a porous Co-Cu-Ti4O7Carrying out heat treatment on the composite three-dimensional electrode precursor to obtain stearic acid coated active porous Co-Cu-Ti4O7And compounding the three-dimensional electrode.
The third example is different from the first and second examples in the step (4) of mixing, and the Co-Cu-Ti prepared by the "solvent evaporation method" in the third example4O7The composite powder is approximately spherical, and stearic acid is uniformly coated on each composite powder, so that the prepared composite ceramic powder has good fluidity.
The number of layers of the printing electrodes can be controlled by a 3D printing technology, and electrodes with different thicknesses can be prepared; by adjusting the printing speed, electrodes with different widths can be obtained; by the 3D printing technology, rich pore channel structures can be realized, and the electrolyte can be permeated conveniently; the 3D printing ceramic material is rapidly developed at present, has the advantages of high precision, short period, relatively low personalized manufacturing cost and the like, and provides great convenience for being put into engineering production.
In the laser sintering process of the mechanically mixed powder of the first embodiment, since Ti4O7The powder, Co-Cu precursor and polymer binder are randomly distributed, so that the polymer melt is oriented to Co-Cu-Ti4O7The infiltration and spreading process of the surface of the composite powder also has the bonding process between the surfaces of the same kind of macromolecules. In contrast, in the laser sintering process of the second embodiment solution precipitation method, since Co-Cu-Ti4O7The composite powder particles are completely coated by the polymer binder, so that the polymer binder is basically scanned during laser scanning, and only the similar surfaces of the polymers are bonded. Because the bonding rate between the same kind of substances is far greater than the infiltration and bonding rate between the heterogeneous substances, the same kind and content of substances are usedWhen the adhesive is used, the sintering rate of the dissolving precipitation method is higher than that of the mechanical mixed powder. In addition, compared with mechanical mixed powder, the powder laser selective sintering forming effect of the dissolution precipitation method is good, but the preparation period of the powder is long, and the requirement on equipment is high. And Co-Cu-Ti obtained by the solvent evaporation method in the third example4O7The composite powder is more spherical and fuller, the flowability is better, and the surface active points of the electrode manufactured subsequently are more.
Three examples printed the activated porous Co-Cu-Ti4O7The composite three-dimensional electrode is soaked in ammonia water for treatment to obtain rich pore structures. Optionally, the concentration of the ammonia water is 0.2 wt% to 20 wt%, and the soaking time is 1 to 40 hours. Specifically, active porous Co-Cu-Ti is used in three examples4O7The composite three-dimensional electrode was placed in 20 wt% ammonia water and soaked for 7 hours.
FIG. 1 shows an active porous Co-Cu-Ti4O7The composite three-dimensional electrode is prepared by a 3D technology preparation method, and active porous Co-Cu-Ti is prepared by4O7The composite three-dimensional electrode is used as an anode of a microbial fuel cell and is used in sewage treatment. And in active porous Co-Cu-Ti4O7The surface and the cross section of the composite three-dimensional electrode have mesopores of 5-50 micrometers, and the porosity of the composite three-dimensional electrode is about 94.0-97.8%. The pore structure has good conductivity and biocompatibility; can obviously improve the bacteria carrying capacity and the electron transmission rate of the microbial electrochemical system.
Comparative example:
FIG. 2 shows active porous Co-Cu-Ti prepared by the present invention4O7Composite three-dimensional electrode and Ti4O7Electrode at 0.1M KHCO3CO in solution2And (4) testing the performance of the reduction catalyst. As can be seen from FIG. 2, active porous Co-Cu-Ti4O7Composite three-dimensional electrode in CO2The Faraday efficiency in the reaction of reducing to generate CO is obviously higher than that of simple substance Ti4O7Control sample of electrode. After optimization, the Faraday efficiency reaches 88.5 percent, and the current density reaches 12.2mA cm < -2 >, which indicates that the active porous Co-Cu-Ti4O7The composite three-dimensional electrode has excellent performance of electrochemically reducing carbon dioxide to generate synthesis gas, which can be attributed to the following two points that firstly, the multi-level pore structure promotes the permeation of electrolyte and accelerates the transmission of ions; second, the Co-Cu precursor and the activity enhancing treatment impart catalytically active sites to the electrode.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.

Claims (10)

1. Active porous Co-Cu-Ti prepared by using 3D technology4O7The method for compounding the three-dimensional electrode is characterized by comprising the following steps: comprises the following steps;
(1) preparation of Co-Cu precursor: dissolving soluble copper salt and soluble cobalt salt in water, carrying out hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain a Co-Cu precursor;
(2) selecting materials: selecting nano-grade Ti4O7The powder is taken as a raw material;
(3) modification treatment: taking 2 parts by weight of Ti4O7Mixing the powder and 0.2-0.5 part of absolute ethyl alcohol in a container; heating the mixed liquid in the container to be dry by using a heating magnetic stirrer at the temperature of 90 ℃; then putting the mixture into an oven, setting the temperature of the oven to be 60 ℃ and baking the mixture for 10 hours; then putting the baked powder into a ball mill for grinding to obtain modified Ti powder4O7Powder; modified Ti4O7The surface of the modified material is provided with hydroxyl groups by absolute ethyl alcohol;
(4) mixing materials: modified Ti in mass percent4O745-65% of powder, 10-15% of high molecular binder epoxy resin and 25-40% of Co-Cu precursor; subjecting the modified Ti4O7Powder, high molecular binder epoxy resin and Co-Cu precursorMixing according to the mass percentage, and then putting the mixture into a ball mill for mechanical mixing and grinding to modify Ti4O7The powder, the high molecular binder epoxy resin and the Co-Cu precursor are completely and uniformly mixed; and Co-Cu precursor and modified Ti4O7The powder is tightly compounded with a macromolecular binder epoxy resin through hydroxyl groups to obtain Co-Cu-Ti4O7Compounding powder;
(5)3D modeling: drawing a three-dimensional model electrode to be printed by using three-dimensional drawing software and setting 3D printing parameters;
(6) laying printing powder: mixing the Co-Cu-Ti obtained in (3)4O7The composite powder is laid in the area between a lifting platform and a scraping plate in the 3D printer and is ready for Co-Cu-Ti4O7After the composite powder is paved, a scraper plate is used for scraping Co-Cu-Ti with the thickness exceeding the set thickness4O7Scraping the composite powder to obtain printing powder layers with set thickness, wherein the thickness of each printing powder layer is consistent and is 0.1mm-0.2 mm;
(7) laser scanning: a laser head in the 3D printer emits a laser beam to scan the printing powder layer according to a set program, so that the scanned printing powder in the area is mutually combined, the laser preheating temperature is 50-70 ℃, the sintering temperature is 1200-1600 ℃, the laser power is 5-10W, the scanning interval is 0.1-0.2 mm, and the scanning speed is 1500-2000 mm/s;
(8) descending the platform: after scanning a layer of printing powder layer, a lifting platform in the 3D printer descends the height of the single printing powder layer according to a set program; then, the steps of laying and printing powder, scanning laser and descending a platform are sequentially repeated until a plurality of layers of printing powder layers are sintered into the three-dimensional model electrode drawn in the step (5);
(9) excess material removal: taking out the electrode after 3D printing, washing with water, removing the unprinted powder on the electrode to obtain the porous Co-Cu-Ti4O7Compounding a three-dimensional electrode;
(10) enhancing the activity: porous Co-Cu-Ti4O7The composite three-dimensional electrode is placed into a solution containing active substances to be soaked for 1-5 h, and is subjected to freeze drying treatment for 10-30 h to obtain the doped materialPorous Co-Cu-Ti with active component4O7A composite three-dimensional electrode precursor; then porous Co-Cu-Ti4O7Carrying out heat treatment on the composite three-dimensional electrode precursor to obtain active porous Co-Cu-Ti4O7And compounding the three-dimensional electrode.
2. Active porous Co-Cu-Ti prepared by using 3D technology4O7The method for compounding the three-dimensional electrode is characterized by comprising the following steps: comprises the following steps;
(1) preparation of Co-Cu precursor: dissolving soluble copper salt and soluble cobalt salt in water, carrying out hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain a Co-Cu precursor;
(2) selecting materials: selecting nano-grade Ti4O7The powder is taken as a raw material;
(3) modification treatment: taking 2 parts by weight of Ti4O7Mixing the powder and 0.2-0.5 part of absolute ethyl alcohol in a container; heating the mixed liquid in the container to be dry by using a heating magnetic stirrer at the temperature of 90 ℃; then putting the mixture into an oven, setting the temperature of the oven to be 60 ℃ and baking the mixture for 10 hours; then putting the baked powder into a ball mill for grinding to obtain modified Ti powder4O7Powder; modified Ti4O7The surface of the modified material is provided with hydroxyl groups by absolute ethyl alcohol;
(4) mixing materials: modified Ti in mass percent4O7The mass percent of the powder is 40-60%, the mass percent of the polymer nylon 12 is 10-15%, the mass percent of the Co-Cu precursor is 25-35%, and the mass percent of the absolute ethyl alcohol is 5-10%; subjecting the modified Ti4O7Mixing the powder, the polymer nylon 12, the Co-Cu precursor and the absolute ethyl alcohol according to mass percent, heating for fusion and stirring to fully dissolve the polymer nylon 12 into the absolute ethyl alcohol, and then modifying the modified Ti by the absolute ethyl alcohol again4O7Reacting to increase the number of hydroxyl groups which will modify the treated Ti4O7Powder, Polymer Nylon 12 and Co-Cu precursor compactCompounding to obtain a mixture; in the cooling process of the mixture, the solubility of the polymer nylon 12 in absolute ethyl alcohol is reduced, ceramic particles are taken as cores to be separated out, finally, the residual absolute ethyl alcohol is filtered and recovered, and the residual mixture is dried and sieved to obtain the polymer coated ceramic Co-Cu-Ti4O7Compounding powder;
(5)3D modeling: drawing a three-dimensional model electrode to be printed by using three-dimensional drawing software and setting 3D printing parameters;
(6) laying printing powder: coating the polymer obtained in the step (3) with ceramic Co-Cu-Ti4O7The composite powder is laid in the area between a lifting platform and a scraper plate in the 3D printer and ceramic Co-Cu-Ti is coated with a polymer4O7After the composite powder is paved, a scraper plate is utilized to coat the polymer film-coated ceramic Co-Cu-Ti with the thickness exceeding the set thickness4O7Scraping the composite powder to obtain printing powder layers with set thickness, wherein the thickness of each printing powder layer is consistent and is 0.1mm-0.2 mm;
(7) laser scanning: a laser head in the 3D printer emits a laser beam to scan the printing powder layer according to a set program, so that the scanned printing powder in the area is mutually combined, the laser preheating temperature is 50-70 ℃, the sintering temperature is 1200-1600 ℃, the laser power is 5-10W, the scanning interval is 0.1-0.2 mm, and the scanning speed is 1500-2000 mm/s;
(8) descending the platform: after scanning a layer of printing powder layer, a lifting platform in the 3D printer descends the height of the single printing powder layer according to a set program; then, the steps of laying and printing powder, scanning laser and descending a platform are sequentially repeated until a plurality of layers of printing powder layers are sintered into the three-dimensional model electrode drawn in the step (5);
(9) excess material removal: taking out the electrode after 3D printing, washing with water, removing the powder not printed on the electrode to obtain the polymer film porous Co-Cu-Ti4O7Compounding a three-dimensional electrode;
(10) enhancing the activity: coating polymer with porous Co-Cu-Ti4O7The composite three-dimensional electrode is placed into a solution containing active substances to be soaked for 1-5 hours, and freeze drying treatment is carried out for 10-3 hours0h to obtain the porous Co-Cu-Ti doped with the active component polymer coating film4O7A composite three-dimensional electrode precursor; then coating the polymer with porous Co-Cu-Ti4O7Carrying out heat treatment on the composite three-dimensional electrode precursor to obtain the polymer coated active porous Co-Cu-Ti4O7And compounding the three-dimensional electrode.
3. Active porous Co-Cu-Ti prepared by using 3D technology4O7The method for compounding the three-dimensional electrode is characterized by comprising the following steps: comprises the following steps;
(1) preparation of Co-Cu precursor: dissolving soluble copper salt and soluble cobalt salt in water, carrying out hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying to obtain a Co-Cu precursor;
(2) selecting materials: selecting nano-grade Ti4O7The powder is taken as a raw material;
(3) modification treatment: taking 2 parts by weight of Ti4O7Mixing the powder and 0.2-0.5 part of absolute ethyl alcohol in a container; heating the mixed liquid in the container to be dry by using a heating magnetic stirrer at the temperature of 90 ℃; then putting the mixture into an oven, setting the temperature of the oven to be 60 ℃ and baking the mixture for 10 hours; then putting the baked powder into a ball mill for grinding to obtain modified Ti powder4O7Powder; modified Ti4O7The surface of the modified material is provided with hydroxyl groups by absolute ethyl alcohol;
(4) mixing materials: modified Ti in mass percent4O740-60% of powder, 10-15% of stearic acid powder, 25-35% of Co-Cu precursor and 5-10% of absolute ethyl alcohol; subjecting the modified Ti4O7Mixing the powder, the stearic acid powder, the Co-Cu precursor and the absolute ethyl alcohol according to mass percent, putting the mixture into a ball mill for high-speed ball milling to ensure that the stearic acid is fully dissolved in the absolute ethyl alcohol, and the absolute ethyl alcohol is used for carrying out modification treatment on the Ti4O7Reacting to increase the number of hydroxyl groups which will modify the treated Ti4O7Tightly compounding the powder, stearic acid and a Co-Cu precursor to obtain a mixture; heating and stirring the obtained mixture to evaporate the mixture to obtain the required mixed material, drying, grinding and sieving the mixed material to obtain the stearic acid coated Co-Cu-Ti4O7Compounding powder;
(5)3D modeling: drawing a three-dimensional model electrode to be printed by using three-dimensional drawing software and setting 3D printing parameters;
(6) laying printing powder: coating the polymer obtained in the step (3) with ceramic Co-Cu-Ti4O7The composite powder is laid in the area between a lifting platform and a scraping plate in the 3D printer and Co-Cu-Ti is coated with a film to be stearic acid4O7After the composite powder is paved, a scraper plate is utilized to coat the stearic acid with the thickness exceeding the set thickness with Co-Cu-Ti4O7Scraping the composite powder to obtain printing powder layers with set thickness, wherein the thickness of each printing powder layer is consistent and is 0.1mm-0.2 mm;
(7) laser scanning: a laser head in the 3D printer emits a laser beam to scan the printing powder layer according to a set program, so that the scanned printing powder in the area is mutually combined, the laser preheating temperature is 50-70 ℃, the sintering temperature is 1200-1600 ℃, the laser power is 5-10W, the scanning interval is 0.1-0.2 mm, and the scanning speed is 1500-2000 mm/s;
(8) descending the platform: after scanning a layer of printing powder layer, a lifting platform in the 3D printer descends the height of the single printing powder layer according to a set program; then, the steps of laying and printing powder, scanning laser and descending a platform are sequentially repeated until a plurality of layers of printing powder layers are sintered into the three-dimensional model electrode drawn in the step (5);
(9) excess material removal: taking out the electrode after 3D printing, washing with water, removing the powder not printed on the electrode to obtain the stearic acid coated porous Co-Cu-Ti4O7Compounding a three-dimensional electrode;
(10) enhancing the activity: coating stearic acid with porous Co-Cu-Ti4O7The composite three-dimensional electrode is placed into a solution containing active substances to be soaked for 1-5 h, and freeze drying treatment is carried out for 10-30 h to obtain the stearic acid coated porous Co-Cu doped with the active components-Ti4O7A composite three-dimensional electrode precursor; then coating stearic acid with a porous Co-Cu-Ti4O7Carrying out heat treatment on the composite three-dimensional electrode precursor to obtain stearic acid coating active porous Co-Cu-Ti4O7And compounding the three-dimensional electrode.
4. Preparation of active porous Co-Cu-Ti with 3D technology according to any of claims 1-34O7The method for compounding the three-dimensional electrode is characterized by comprising the following steps: the activated porous Co-Cu-Ti printed4O7The composite three-dimensional electrode is soaked in ammonia water for treatment to obtain rich pore structures.
5. Preparation of active porous Co-Cu-Ti with 3D technology according to claim 44O7The method for compounding the three-dimensional electrode is characterized by comprising the following steps: the concentration of the ammonia water is 0.2 wt% -20 wt%, and the soaking treatment time is 1-40 hours.
6. Preparation of active porous Co-Cu-Ti with 3D technology according to any of claims 1-34O7The method for compounding the three-dimensional electrode is characterized by comprising the following steps: the soluble copper salt is copper nitrate, and the soluble cobalt salt is cobalt nitrate; the mol ratio of the soluble copper salt to the soluble cobalt salt is 1 (0.5-2).
7. Preparation of active porous Co-Cu-Ti with 3D technology according to any of claims 1-34O7The method for compounding the three-dimensional electrode is characterized by comprising the following steps: in the hydrothermal reaction process, the temperature is 150-200 ℃ and the time is 6-14 h.
8. Preparation of active porous Co-Cu-Ti with 3D technology according to any of claims 1-34O7The method for compounding the three-dimensional electrode is characterized by comprising the following steps: the active substances are tetraphenyl boron, tetraphenyl boron phosphorus, melamine, ammonium molybdate, iron acetylacetonate and nickel acetylacetonate, and the concentration range of the solution is 1-80 wt%.
9. Preparation of active porous Co-Cu-Ti with 3D technology according to any of claims 1-34O7The method for compounding the three-dimensional electrode is characterized by comprising the following steps: the heat treatment process comprises the following steps: in a tubular furnace, firstly heating to 200-900 ℃ at the speed of 1-20 ℃/min, keeping the temperature for 0.5-15 h, then heating to 900-1800 ℃ at the speed of 1-20 ℃/min, keeping the temperature for 0.5-15 h, and finally cooling to room temperature at the speed of 1-20 ℃/min.
10. Active porous Co-Cu-Ti obtained by the preparation method according to any one of claims 1 to 3 by using 3D technology4O7The application of the composite three-dimensional electrode is characterized in that: mixing active porous Co-Cu-Ti4O7The composite three-dimensional electrode is used as an anode of a microbial fuel cell and is used in sewage treatment.
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