CN115417477B - Nb is printed to 3D 2 O 5 -TiO 2 Preparation method and application of porous electrode - Google Patents
Nb is printed to 3D 2 O 5 -TiO 2 Preparation method and application of porous electrode Download PDFInfo
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- CN115417477B CN115417477B CN202211141967.2A CN202211141967A CN115417477B CN 115417477 B CN115417477 B CN 115417477B CN 202211141967 A CN202211141967 A CN 202211141967A CN 115417477 B CN115417477 B CN 115417477B
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- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000010146 3D printing Methods 0.000 claims abstract description 32
- AYIRNRDRBQJXIF-NXEZZACHSA-N (-)-Florfenicol Chemical compound CS(=O)(=O)C1=CC=C([C@@H](O)[C@@H](CF)NC(=O)C(Cl)Cl)C=C1 AYIRNRDRBQJXIF-NXEZZACHSA-N 0.000 claims abstract description 26
- 229960003760 florfenicol Drugs 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
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- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
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- 239000007772 electrode material Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 238000007639 printing Methods 0.000 claims description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003344 environmental pollutant Substances 0.000 claims description 12
- 231100000719 pollutant Toxicity 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000003115 biocidal effect Effects 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 3
- 230000007480 spreading Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XZUAPPXGIFNDRA-UHFFFAOYSA-N ethane-1,2-diamine;hydrate Chemical compound O.NCCN XZUAPPXGIFNDRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 239000003242 anti bacterial agent Substances 0.000 abstract description 5
- 229940088710 antibiotic agent Drugs 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 19
- 239000012071 phase Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 239000004408 titanium dioxide Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 238000005245 sintering Methods 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 108010077805 Bacterial Proteins Proteins 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000282806 Rhinoceros Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001243 protein synthesis Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
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- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
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- 241000894007 species Species 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to the technical field of organic wastewater treatment and the field of 3D printing of metal powder, in particular to a Nb 2 O 5 ‑TiO 2 Preparation method and application of electrode, and 3D printing Nb 2 O 5 ‑TiO 2 The electrode can be used for electrocatalytic oxidation degradation of organic pollutants such as antibiotics florfenicol in wastewater. The 3D printing Nb prepared by the invention 2 O 5 ‑TiO 2 The porous electrode can realize the industrial effective purification of the florfenicol, wherein the decomposition efficiency of the florfenicol dye at ppm level is more than 99.9% in 120 min.
Description
Technical Field
The invention relates to the technical field of organic wastewater treatment and the field of 3D printing of metal powder, in particular to a Nb 2 O 5 -TiO 2 Preparation method and application of electrode, and 3D printing Nb 2 O 5 -TiO 2 The electrode can be used for electrocatalytic oxidation degradation of organic pollutants such as antibiotics florfenicol in wastewater.
Background
Florfenicol is one of broad-spectrum halogenated antibiotics, has an inhibiting effect on transpeptidation in the bacterial protein synthesis process, and is the type with the largest using amount of antibiotics for livestock in China. It is also used in many countries to control several bacterial diseases in humans and animals. Florfenicol inhibits a wide variety of gram-positive and gram-negative bacteria, including most anaerobic bacteria, and therefore cannot be effectively removed by conventional water treatment techniques, particularly biological treatment. However, the antibacterial properties and persistent C-F bonds of florfenicol lead to incomplete degradation thereof and subsequent accumulation in aquatic or sedimentary environments, which may lead to the development and spread of antibiotic resistance. In particular, low concentrations of florfenicol are not effectively degraded by conventional water treatment techniques and the degradation products may be as active and or toxic as the parent compound. Therefore, the high-efficiency energy-saving advanced treatment technology has important significance for degrading low-concentration antibiotic pollutants and eliminating antibiotic drug resistance and guaranteeing water safety.
In recent studies, advanced Oxidation Processes (AOPs) have demonstrated the remediation of organic contaminants in water and the mineralization of various types of microcontaminants. Microcontacts can be selectively attacked and degraded by the strongly oxidizing species (hydroxyl radicals (·oh)) produced by AOPs. OH reacts with micro-pollutants in the water throughout the mineralization process and converts into non-toxic byproducts (CO 2 、H 2 O and inorganic). In AOPs, electrochemical oxidation processes produce highly reactive OH and sulfate radicals (SO 4 The-, has a significant effect in drug degradation and mineralization and has attracted more and more attention. Electrochemical oxidation is an attractive technique, especially for difficult to biodegrade contaminants, because they are free of chemicals, do not produce waste (e.g., sludge), operate at room temperature, and can be powered by renewable energy sources. There is some evidence concerning the reaction mechanism of electrochemical oxidation using inactive electrodes that the formation of OH at the anode surface promotes complete mineralization of micro-pollutants in water.
On the other hand, 3D printing technology has been rapidly developed in recent years, and printing precision, material properties and the like have also been remarkably improved. Currently, 3D printing is used in combination with catalysis of monolithic catalysts, reactors, mixers and auxiliary equipment. For example, metal oxides can integrate other materials into the catalytic system by adding active ingredients to the printed material, and can control the overall structure of the catalyst or reactor, such as a micron-sized multichannel structure catalyst, by computer-aided printing to promote mass transfer processes while improving reaction efficiency. In addition, 3D printing techniques can also assist the electrodes in reducing concentration polarization effects of the transmission-limited reactions.
Nb as an important n-type semiconductor having a wide bandgap of about 3.4eV 2 O 5 In the aspects of gas sensors, catalysts, optical and electrochromic devices and the likeIs widely applied. The doped material has high specific surface area, high porosity, high refractive index, excellent chemical stability and corrosion resistance. It has now been found that Nb 2 O 5 Exist in different polymorphic forms: TT-Nb 2 O 5 (pseudo hexagonal), T-Nb 2 O 5 (rhombic), M-Nb 2 O 5 (orthogonalization) and H-Nb 2 O 5 (monoclinic). Of these phases, the H phase is the most stable phase, while the TT phase is the least stable phase, and is easily converted to the H phase by heat treatment under high temperature sintering conditions. Wherein Nb in H phase 2 O 5 Has higher thermodynamic performance and better electrochemical performance, but the specific surface area is compared with the Nb of TT phase 2 O 5 Will be reduced.
In summary, the project aims to prepare a titanium-based metal anode with a porous structure through a metal powder 3D printing system, and adopts an electric advanced oxidation technology to decompose the florfenicol with low concentration in a water body efficiently, so that the florfenicol is converted into substances harmless to the environment and human bodies.
Disclosure of Invention
The invention aims to provide a 3D printing Nb 2 O 5 ＝TiO 2 The preparation method of the porous electrode comprises the following steps:
(1) Ti powder with particle size of 15-53um and Nb by ultrasonic treatment 2 O 5 The powder is dispersed to the concentration C with the same mass according to the proportion alpha 1 1 Adding lithium hydroxide solution into ethylenediamine water solution to change system concentration into C 2 Stirring was carried out under magnetic stirring for 24h. And obtaining mixed powder through centrifugal separation treatment, and drying in an oven.
(2) Opening and downloading a porous mesh structure electrode drawing file drawn in advance by using metal powder 3D printing equipment, and setting a printing method M 1 The cooling water instrument and the argon gas valve are opened to reduce the content of dissolved oxygen in the printing chamber to 200ppm. And starting the laser equipment, and printing after the laser equipment is preheated.
(3) And cutting the printed 3D titanium-based electrode material from the printing substrate. The electrode material is placed in absolute ethyl alcohol for ultrasonic treatment for 10 to 15 minutes, and the ultrasonic treatment is repeated for 2 to 3 times.
(4) And (3) respectively soaking the electrode material obtained in the step (3) in a 4wt% sodium hydroxide solution and a 10wt% oxalic acid solution, heating, removing surface oil stains and surface oxide films, and washing away oxalic acid remained on the surface of the electrode by ultrasonic treatment.
(5) Placing the electrode material obtained in the step (4) in a tube furnace to raise the temperature A by programming 1 Is sintered and cooled to normal temperature at a rate of 1 ℃/min. And cleaning the electrode surface by ultrasonic treatment.
(6) Concentration is C 3 The pollutants are added into an electrolytic tank with the reaction volume of 100ml, the electrode material obtained in the step (5) is taken as an anode, and stainless steel is taken as a cathode. The current density was set to I1, and the concentration of the contaminant obtained by the reaction was detected by high performance liquid chromatograph.
In the method of the present invention, in the step (1), the concentration C 1 6.0 to 8.0mol/L.
The method according to the invention, in step (1), the ratio α 1 0.5 to 5.0 percent.
In the method of the present invention, in the step (1), the concentration C 2 1.0 to 2.0mol/L.
The method of the present invention, in step (2), the printing method M 1 The method comprises the following steps: the scanning strategy adopts X, Y direction equidistant rotation 90 DEG alternate scanning, the scanning speed range is 900-1200 mm/s, the laser power range is 190-220W, the scanning distance is 0.07-0.11 mm, the powder spreading layer thickness is 0.05mm, and the laser peak power is 100%.
In the method according to the present invention, in the step (5), the temperature programming method A 1 In the first stage, the temperature is raised to 450-500 ℃ at normal temperature, and the temperature raising time is 30-40 min; the second stage keeps the temperature in the furnace at 450-500 ℃ for 2h.
In the method of the present invention, in the step (6), the concentration C 3 2 to 20ppm.
In the method of the present invention, in the step (6), the current density I 1 Is 5-30 mA/cm 2 。
Compared with the existing titanium dioxide anode, the invention has the following advantages:
1. the 3D printing Nb prepared by the invention 2 O 5 -TiO 2 Compared with the existing titanium dioxide electrode, the porous electrode has the characteristics of adjustable structure, flexible operation, strong applicability and the like, and can be used for industrial production and laboratory research.
2. The 3D printing Nb prepared by the invention 2 O 5 -TiO 2 Compared with the traditional preparation method of the titanium dioxide electrode, the porous electrode has lower manufacturing cost and higher structural precision.
3. The 3D printing Nb prepared by the invention 2 O 5 -TiO 2 Compared with the existing titanium dioxide electrode, the porous electrode has high specific surface area and higher mass transfer rate.
4. The 3D printing Nb prepared by the invention 2 O 5 -TiO 2 Compared with the existing titanium dioxide electrode, the porous electrode has the characteristics of small influence (such as pH and the like) caused by environmental change and stronger adaptability.
5. The 3D printing Nb prepared by the invention 2 O 5 -TiO 2 The porous electrode can realize the industrial effective purification of the florfenicol, wherein the decomposition efficiency of the florfenicol dye at ppm level is more than 99.9% in 120 min.
Drawings
FIG. 1 is a graph showing degradation data of florfenicol by titanium-based electrodes with different doping ratios in an embodiment of the present invention.
FIG. 2 is a 3D printed Nb in an embodiment of the present invention 2 O 5 -TiO 2 A physical representation of a porous electrode material.
FIG. 3 is a 3D printed Nb in an embodiment of the present invention 2 O 5 -TiO 2 SEM scanning electron micrographs of porous electrode materials.
FIG. 4 is a 3D printed Nb in an embodiment of the present invention 2 O 5 -TiO 2 XRD characterization of porous electrode material.
Detailed Description
The invention provides a 3D printing Nb 2 O 5 -TiO 2 A preparation method and application of a porous electrode,the present invention will be described in further detail with reference to examples below in order to make the objects, technical solutions and effects of the present invention more clear and distinct. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. FIG. 1 is a graph showing degradation data of florfenicol by titanium-based electrodes with different doping ratios in an embodiment of the present invention. FIG. 2 is a 3D printed Nb in an embodiment of the present invention 2 O 5 -TiO 2 A physical representation of a porous electrode material. FIG. 3 is a 3D printed Nb in an embodiment of the present invention 2 O 5 -TiO 2 SEM scanning electron micrographs of porous electrode materials. FIG. 4 is a 3D printed Nb in an embodiment of the present invention 2 O 5 -TiO 2 XRD characterization of porous electrode material.
[ example 1 ]: printing Nb with 3D provided by the invention 2 O 5 -TiO 2 Porous electrode electrocatalytic oxidative degradation of florfenicol
The preparation method of the material and the process for degrading florfenicol comprise the following steps:
(1) Weighing 116.4g of pure Ti powder and 3.6g of Nb 2 O 5 The powder was dispersed in 120ml of a 40% ethylenediamine aqueous solution by ultrasonic treatment, and a lithium hydroxide solution was added so that the system concentration became 1.6mol/L, followed by stirring under magnetic stirring for 24 hours. The mixed powder was obtained by centrifugal separation and dried in an oven at 50℃for 3 hours.
(2) And (3) passing the dried powder obtained in the step (4) through a 200-mesh screen mesh, and shaking the mixed powder on a shaker until the mixed powder is completely screened into a stainless steel disc with powder in the lower part.
(3) The Hanbang SLM150 metal powder 3D printing equipment is selected, a metal printing substrate of the printing equipment is installed and leveled, the printing substrate is parallel to a bottom plate of a printing room, and a silica gel scraping strip is installed to be parallel to the printing substrate and descends to a position just attached to the printing substrate.
(4) Pouring the mixed powder obtained in the step (3) into a powder tank of a 3D printer, and adjusting the powder tank to a proper position for powder paving operation.
(5) The cooling water instrument and the argon gas valve are opened to reduce the oxygen content in the printing chamber to 200ppm, a porous net structure electrode drawing file drawn by Rhinoceros in advance is opened and downloaded (a scanning strategy adopts X, Y direction equidistant rotation 90 DEG alternate scanning, the scanning speed range is 900-1200 mm/s, the laser power range is 190-220W, the scanning interval is 0.07-0.11 mm, the powder spreading layer thickness is 0.05 mm), the laser peak power is set to 100%, and printing can be performed after the laser is opened.
(6) And cutting the printed 3D titanium-based electrode material from the printing substrate. The electrode material is placed in absolute ethyl alcohol for ultrasonic treatment for 10 to 15 minutes, and the ultrasonic treatment is repeated for 2 to 3 times.
(7) Heating for 0.5h by using a 4wt% sodium hydroxide solution at 90 ℃ to remove residual oil stains on the surface of the electrode material in the step (6), boiling for 2h by using a 10wt% oxalic acid solution at 90 ℃ to remove an oxide film on the surface of the electrode, and placing the electrode into an ultrasonic cleaner to clean with ultrapure water for 5min to wash away residual oxalic acid on the surface of the electrode.
(8) Placing the electrode material obtained in the step (7) in a tube furnace, and setting a temperature programming method for sintering: in the first stage, the temperature is raised to 500 ℃ at normal temperature, and the temperature raising time is 40min; the second stage keeps the temperature in the furnace at 500 ℃ for 2 hours. And cooling the electrode material to normal temperature at a cooling rate of 1 ℃/min. And cleaning the electrode surface by ultrasonic treatment.
(9) The florfenicol solution with the concentration of 5ppm is added into an electrolytic tank with the reaction volume of 100ml, the electrode material obtained in the step (8) is taken as an anode, and stainless steel is taken as a cathode. The current density was set at 20mA/cm 2 1ml of the reaction solution was placed in a liquid phase flask at 0, 5, 10, 20, 30, 45, 60, 90, 120min from the start of the reaction, and 15. Mu.l of methanol was added to terminate the reaction in the liquid phase flask.
(10) And (3) placing the liquid phase bottle obtained in the step (9) in an automatic sample injection chamber of a high performance liquid chromatograph, and detecting the concentration of pollutants in the liquid phase bottle.
As shown in FIG. 1, the 3D printed Nb prepared by the invention 2 O 5 -TiO 2 The porous electrode has a current density of 20mA/cm 2 Under the condition of (1), the degradation efficiency of the mg/L-level florfenicol dye is over 99.9 percent within 120min, and the industrial effective purification of the florfenicol can be realized. At the position ofThis, nb is printed for 3D 2 O 5 -TiO 2 Porous electrode contains 0, 0.5%, 1%, 3%, 5% Nb 2 O 5 Gradient analysis of doping ratio, selection of 3% Nb 2 O 5 Doping ratio 3D printed Nb 2 O 5 -TiO 2 The porous electrode is the most optimal condition. At the same time compare non-3D printed TiO 2 Electrode and 3D printing TiO 2 The degradation effect of the electrode on florfenicol pollutants is found out, and 3D printing TiO is found out 2 The degradation efficiency of the electrode to florfenicol pollutants is higher than that of non-3D printing TiO 2 An electrode.
FIG. 2 is a 3D printed Nb 2 O 5 -TiO 2 Physical diagram of porous electrode, 3D printing Nb prepared by the invention 2 O 5 -TiO 2 The porous electrode material has a higher specific surface area, reduced concentration polarization effect of transport-limiting reactions, and higher OH yield than 2D electrode materials.
(11) In commercial TiO 2 The electrode repeats the operations from step (9) to step (10) with the aim of comparing the two to obtain the material of the invention compared with commercial TiO 2 The degradation rate of the electrode to florfenicol is greatly improved.
In view of the above-mentioned different crystal phases Nb 2 O 5 The invention provides a brand new 3D printing Nb 2 O 5 Doped TiO 2 The porous electrode can degrade antibiotics and other pollutants in the wastewater with high efficiency. Under the condition of externally adding lithium hydroxide, laser rapid sweeping and heating in the 3D printing process is utilized to ensure that the original TT phase Nb 2 O 5 The surface phase transformation is changed into H-phase Nb with more ordered crystal structure and better thermodynamic property and electrochemical property 2 O 5 Wherein the presence of Li atoms contributes to the enhancement of H-phase Nb 2 O 5 Is a crystal of (a) is a crystal of (b). The obtained electrode material is sintered by a tube furnace, and Ti is converted into anatase phase TiO 2 At the same time, due to the diffusion of Li atoms, nb 2 O 5 The interlayer distance expansion is shown to generate a cavity, a nano-pore structure is formed, and the specific surface area of the electrode material is increased. 3D printed H phase Nb 2 O 5 Doped TiO 2 The porous electrode can generate high-oxidation-capability OH under the condition of externally applied voltage so as to effectively degrade pollutants such as florfenicol in wastewater, compared with non-printed Nb 2 O 5 -TiO 2 The electrode material after 3D printing has higher mass transfer capability, greatly improves the degradation rate of pollutants, has good thermodynamic performance and electrochemical performance, and prolongs the service life of the electrode.
The 3D printing Nb prepared by the invention 2 O 5 -TiO 2 Compared with the existing titanium dioxide electrode, the porous electrode has the characteristics of adjustable structure, flexible operation, strong applicability and the like, and can be used for industrial production and laboratory research. The 3D printing Nb prepared by the invention 2 O 5 -TiO 2 Compared with the traditional preparation method of the titanium dioxide electrode, the porous electrode has lower manufacturing cost and higher structural precision. The 3D printing Nb prepared by the invention 2 O 5 -TiO 2 Compared with the existing titanium dioxide electrode, the porous electrode has a high specific surface area and a high mass transfer rate. The 3D printing Nb prepared by the invention 2 O 5 -TiO 2 Compared with the existing titanium dioxide electrode, the porous electrode has the characteristics of small influence (such as pH and the like) caused by environmental change and stronger adaptability. The 3D printing Nb prepared by the invention 2 O 5 -TiO 2 The porous electrode can realize the industrial effective purification of the florfenicol, wherein the decomposition efficiency of the florfenicol dye at ppm level is more than 99.9% in 120 min.
Claims (3)
1. Nb is printed to 3D 2 O 5 -TiO 2 The preparation method of the porous electrode comprises the following steps:
(1) Ti powder and Nb powder having particle diameters of 15-53 μm are treated by ultrasonic treatment 2 O 5 Dispersing the powder into ethylenediamine water solution with the concentration of 6.0-8.0 mol/L and the same mass according to the proportion of 0.5-5.0%, adding lithium hydroxide solution to change the system concentration into 1.0-2.0 mol/L, stirring for 24 hours under the magnetic stirring condition, obtaining mixed powder through centrifugal separation treatment, and drying in a drying oven;
(2) Opening and downloading a porous mesh structure electrode drawing file drawn in advance by using metal powder 3D printing equipment, and setting a printing method M 1 Opening a cooling water meter and an argon gas valve to reduce the content of dissolved oxygen in a printing chamber to 200ppm, wherein the printing method M 1 The scanning strategy adopts X, Y direction equidistant rotation 90 degrees for alternating scanning, the scanning speed range is 900-1200 mm/s, the laser power range is 190-220W, the scanning distance is 0.07-0.11 mm, the powder spreading layer thickness is 0.05mm, and the laser peak power is 100%;
(3) Cutting the 3D titanium-based electrode material from the printing substrate, placing the electrode material into absolute ethyl alcohol, performing ultrasonic treatment for 10-15 min, and repeating for 2-3 times;
(4) Respectively soaking the electrode material obtained in the step (3) in a 4wt% sodium hydroxide solution and a 10wt% oxalic acid solution, heating, removing surface oil stains and surface oxide films, and washing away oxalic acid remained on the surface of the electrode through ultrasonic treatment;
(5) Placing the electrode material obtained in the step (4) in a tube furnace to raise the temperature A by programming 1 Is sintered by the method of (2), is cooled to normal temperature at a speed of 1 ℃/min, and is cleaned on the surface of the electrode by ultrasonic treatment, wherein the temperature programming method A 1 In the first stage, the temperature is raised to 450-500 ℃ at normal temperature, and the temperature raising time is 30-40 min; the second stage keeps the temperature in the furnace at 450-500 ℃ for 2h.
2. A wastewater treatment method using Nb prepared by 3D printing according to claim 1 2 O 5 -TiO 2 The electrode electrocatalytic oxidation degrades organic pollutants in the wastewater,
adding pollutants with the concentration of 2-20 ppm into an electrolytic tank with the reaction volume of 100ml, and printing prepared Nb in 3D 2 O 5 -TiO 2 The electrode material is anode, stainless steel is cathode, and the current density is set to 5-30 mA/cm 2 And detecting the concentration of the pollutant obtained by the reaction by using a high performance liquid chromatograph.
3. The wastewater treatment process of claim 2, wherein the organic contaminant is the antibiotic florfenicol.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101399371A (en) * | 2007-09-26 | 2009-04-01 | 株式会社东芝 | Non-aqueous electrolyte battery and battery pack |
| CN101485015A (en) * | 2006-06-05 | 2009-07-15 | T/J技术公司 | Alkali metal titanates and methods for their synthesis |
| CN101807688A (en) * | 2010-04-26 | 2010-08-18 | 安徽工业大学 | Niobium-doped lithium titanate anode material for lithium ion battery and method for preparing same |
| CN105552346A (en) * | 2016-02-26 | 2016-05-04 | 南阳师范学院 | Titanium niobate/carbon composite electrode material and preparation method thereof |
| CN107615427A (en) * | 2015-04-09 | 2018-01-19 | 林科闯 | Electrode material and energy storage devices |
| CN111926208A (en) * | 2020-08-27 | 2020-11-13 | 北京科技大学 | Method for preparing niobium-based alloy with superfine oxide dispersed phase |
| CN113264574A (en) * | 2021-04-22 | 2021-08-17 | 东莞理工学院 | Ni-Fe/MoS2Preparation method of electrode and application of electrode in degradation of florfenicol pollutants |
| CN114614168A (en) * | 2022-03-29 | 2022-06-10 | 江南大学 | Preparation method and application of aluminum-air battery anode composite slurry |
-
2022
- 2022-09-19 CN CN202211141967.2A patent/CN115417477B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101485015A (en) * | 2006-06-05 | 2009-07-15 | T/J技术公司 | Alkali metal titanates and methods for their synthesis |
| CN101399371A (en) * | 2007-09-26 | 2009-04-01 | 株式会社东芝 | Non-aqueous electrolyte battery and battery pack |
| CN101807688A (en) * | 2010-04-26 | 2010-08-18 | 安徽工业大学 | Niobium-doped lithium titanate anode material for lithium ion battery and method for preparing same |
| CN107615427A (en) * | 2015-04-09 | 2018-01-19 | 林科闯 | Electrode material and energy storage devices |
| CN105552346A (en) * | 2016-02-26 | 2016-05-04 | 南阳师范学院 | Titanium niobate/carbon composite electrode material and preparation method thereof |
| CN111926208A (en) * | 2020-08-27 | 2020-11-13 | 北京科技大学 | Method for preparing niobium-based alloy with superfine oxide dispersed phase |
| CN113264574A (en) * | 2021-04-22 | 2021-08-17 | 东莞理工学院 | Ni-Fe/MoS2Preparation method of electrode and application of electrode in degradation of florfenicol pollutants |
| CN114614168A (en) * | 2022-03-29 | 2022-06-10 | 江南大学 | Preparation method and application of aluminum-air battery anode composite slurry |
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