CN115417477A - 3D printing Nb 2 O 5 -TiO 2 Preparation method and application of porous electrode - Google Patents
3D printing Nb 2 O 5 -TiO 2 Preparation method and application of porous electrode Download PDFInfo
- Publication number
- CN115417477A CN115417477A CN202211141967.2A CN202211141967A CN115417477A CN 115417477 A CN115417477 A CN 115417477A CN 202211141967 A CN202211141967 A CN 202211141967A CN 115417477 A CN115417477 A CN 115417477A
- Authority
- CN
- China
- Prior art keywords
- printing
- electrode
- tio
- concentration
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000010146 3D printing Methods 0.000 title claims abstract description 45
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 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 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 230000003115 biocidal effect Effects 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 239000002351 wastewater Substances 0.000 claims abstract description 5
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 32
- 239000007772 electrode material Substances 0.000 claims description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000007639 printing Methods 0.000 claims description 16
- 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
- 239000000243 solution Substances 0.000 claims description 11
- 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
- 239000003344 environmental pollutant Substances 0.000 claims description 9
- 231100000719 pollutant Toxicity 0.000 claims description 9
- 230000008569 process Effects 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
- 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
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 5
- 239000000356 contaminant Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000005245 sintering Methods 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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 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
- 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
- 239000000758 substrate Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000000593 degrading effect Effects 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
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000009303 advanced oxidation process reaction Methods 0.000 description 4
- 230000033558 biomineral tissue development Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010030 laminating Methods 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
- 230000002085 persistent effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of organic wastewater treatment and the field of metal powder 3D printing, in particular to 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 degrading organic pollutants such as antibiotic florfenicol in wastewater by electrocatalytic oxidation. 3D printing Nb prepared by the invention 2 O 5 ‑TiO 2 The porous electrode can decompose ppm-level florfenicol dye in 120min with the decomposition efficiency of more than 99.9 percent, and the industrial effective purification of the florfenicol can be realized.
Description
Technical Field
The invention relates to the technical field of organic wastewater treatment and the field of metal powder 3D printing, in particular to 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 degrading organic pollutants such as antibiotic florfenicol in wastewater by electrocatalytic oxidation.
Background
Florfenicol is one of broad-spectrum halogenated antibiotics, has an inhibiting effect on transpeptidation in the process of synthesizing bacterial protein, and is the class with the most use amount of antibiotics for livestock in China. It is also used in many countries to control several bacterial diseases in humans and animals. Florfenicol has an inhibitory effect against a variety of gram-positive and gram-negative bacteria, and also includes most anaerobic bacteria, and thus cannot be effectively removed by conventional water treatment techniques, especially biological treatment. However, the antibacterial nature and persistent C-F bond of florfenicol results in its incomplete degradation and subsequent build-up in aquatic or sedimentary environments, which can 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 efficient and energy-saving advanced treatment technology has important significance for the degradation of low-concentration antibiotic pollutants and the elimination of antibiotic drug resistance and the guarantee of water safety.
In recent studies, advanced Oxidation Processes (AOPs) have demonstrated remediation of organic contaminants in water and mineralization of various types of micropollutants. The micropollutants can be selectively attacked and degraded by the strongly oxidizing species (hydroxyl radicals (. OH)) produced by the AOPs. OH reacts with micropollutants in the water throughout the mineralization process and is converted to non-toxic by-products (CO) 2 、H 2 O and inorganic). In AOPs, electrochemical oxidation processes generate highly reactive OH and Sulfate (SO) radicals due to their ability to generate 4 Has attracted increasing attention because of the marked effects of- (meth-) on drug degradation and mineralization. Electrochemical oxidation is an attractive technology, particularly for pollutants that are difficult to biodegrade, because they are chemical free, do not produce waste (e.g., sludge), operate at room temperature, and can be powered by renewable energy sources. There is some evidence that the reaction mechanism involving electrochemical oxidation using inactive electrodes suggests that the formation of OH on the anode surface promotes micro-contamination in waterComplete mineralization of the material.
On the other hand, in recent years, 3D printing technology is rapidly developed, and printing precision, material performance and other aspects are also remarkably improved. Currently, 3D printing is used in conjunction with the catalysis of monolithic catalysts, reactors, mixers, and ancillary equipment. For example, metal oxides can incorporate other materials into a catalytic system by adding active ingredients to the printed materials, and can control the overall structure of a catalyst or reactor, such as a micron-sized multi-channel structured catalyst, by computer-aided printing to facilitate mass transfer processes while increasing reaction efficiency. In addition, the 3D printing technology can also assist the electrode to reduce the concentration polarization effect of the transmission limiting reaction.
Nb, an important n-type semiconductor having a wide bandgap of about 3.4eV 2 O 5 The method has wide application in gas sensors, catalysts, optical and electrochromic devices and the like. The doped material has the advantages of high specific surface area, high porosity, high refractive index, excellent chemical stability and corrosion resistance, and is particularly attractive. It has now been found that Nb 2 O 5 In different polymorphic forms: TT-Nb 2 O 5 (pseudo-hexagonal), T-Nb 2 O 5 (orthorhombic), M-Nb 2 O 5 (orthogonal) and H-Nb 2 O 5 (monoclinic). Among these phases, the H phase is the most stable phase, and the TT phase is the most unstable phase, and is easily transformed into the H phase by heat treatment under high-temperature sintering conditions. Wherein, nb of H phase 2 O 5 Nb with higher thermodynamic performance and better electrochemical performance, but specific surface area is compared with TT phase 2 O 5 There will be a reduction.
In conclusion, the titanium-based metal anode with the porous structure is prepared by the metal powder 3D printing system, and the florfenicol with low concentration in the water body is efficiently decomposed by adopting the electric advanced oxidation technology, so that the florfenicol is converted into substances harmless to the environment and the human body.
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) Subjecting Ti powder having a particle size of 15-53um and Nb to ultrasonic treatment 2 O 5 The powder is dispersed according to the proportion alpha 1 to the concentration C with the same mass 1 Adding a lithium hydroxide solution to the aqueous solution of ethylenediamine to convert the system concentration to C 2 Stirring for 24h under magnetic stirring. And then the mixed powder is obtained through centrifugal separation treatment and is dried in an oven.
(2) Opening and downloading a pre-drawn porous mesh structure electrode drawing file by using metal powder 3D printing equipment, and setting a printing method M 1 And opening the cooling water instrument and the argon gas valve to reduce the content of dissolved oxygen in the printing chamber to 200ppm. And starting the laser equipment, and printing after preheating.
(3) And cutting the printed 3D titanium-based electrode material from the printed substrate. The electrode material is placed in absolute ethyl alcohol for ultrasonic treatment for 10-15 min, and the ultrasonic treatment is repeated for 2-3 times.
(4) And (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 a surface oxidation film, and washing away the oxalic acid remaining on the surface of the electrode through ultrasonic treatment.
(5) Placing the electrode material obtained in the step (4) in a tube furnace to be heated by a program A 1 Sintering and cooling to normal temperature at the speed of 1 ℃/min. And then the surface of the electrode is cleaned by ultrasonic treatment.
(6) To a concentration of C 3 The contaminants of (2) were charged into an electrolytic cell having a reaction volume of 100ml, and the electrode material obtained in step (5) was used as an anode and stainless steel as a cathode. The current density was set to I1, and the concentration of the contaminant obtained by the reaction was detected by a high performance liquid chromatograph.
The method of the present invention, step (1), the concentration C 1 6.0 to 8.0mol/L.
The method of the present invention, step (1), wherein the ratio α is 1 0.5 to 5.0 percent.
The method of the present invention, step (1), the concentration C 2 Is 1.0 to 2.0mol/L.
The method and the steps of the invention(2) In the printing method M 1 Comprises the following steps: the scanning strategy adopts the alternative scanning of rotating 90 degrees in the X direction and the Y direction at equal intervals, 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 layer thickness is 0.05mm, and the laser peak power is 100%.
The method of the present invention, step (5), the temperature-programmed 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; in the second stage, the temperature in the furnace is kept between 450 and 500 ℃, and the holding time is 2 hours.
The method of the present invention, step (6), the concentration C 3 2 to 20ppm.
The method of the present invention, step (6), the current density I 1 Is 5 to 30mA/cm 2 。
Compared with the existing titanium dioxide anode, the invention has the following advantages:
1. 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. 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. 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. 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 of environmental change (such as pH value) and stronger adaptability.
5. 3D printing Nb prepared by the invention 2 O 5 -TiO 2 The porous electrode can decompose ppm-level florfenicol dye in 120min with the decomposition efficiency of more than 99.9 percent, and the industrialization of the florfenicol can be realizedAnd (4) effective purification.
Drawings
FIG. 1 is a graph of data on the degradation of florfenicol by titanium-based electrodes with different doping ratios in the embodiment of the invention.
FIG. 2 shows an example of 3D printing Nb 2 O 5 -TiO 2 Physical diagram of porous electrode material.
FIG. 3 shows an example of 3D printing Nb 2 O 5 -TiO 2 SEM scanning electron micrograph of the porous electrode material.
FIG. 4 shows a 3D printing Nb in the embodiment of the invention 2 O 5 -TiO 2 XRD characterization pattern of porous electrode material.
Detailed Description
The invention provides a 3D printing Nb 2 O 5 -TiO 2 The preparation method and application of the porous electrode are further described in detail with reference to the examples below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. FIG. 1 is a graph of data on the degradation of florfenicol by titanium-based electrodes with different doping ratios in the example of the present invention. FIG. 2 shows a 3D printing Nb in the embodiment of the invention 2 O 5 -TiO 2 Physical diagram of porous electrode material. FIG. 3 shows an example of 3D printing Nb 2 O 5 -TiO 2 SEM scanning electron micrograph of the porous electrode material. FIG. 4 shows an Nb for 3D printing in an embodiment of the invention 2 O 5 -TiO 2 XRD characterization pattern of porous electrode material.
[ example 1 ] of the present invention: 3D printing Nb provided by the invention 2 O 5 -TiO 2 Porous electrode electrocatalytic oxidation degradation florfenicol
The preparation method of the material and the process for degrading florfenicol by using the material comprise the following steps:
(1) A mass of 116.4g of pure Ti powder and 3.6g of Nb were weighed 2 O 5 The powder was dispersed into 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 inStirring for 24h under magnetic stirring. Then the mixed powder is obtained by centrifugal separation treatment and is dried for 3 hours in an oven at 50 ℃.
(2) And (5) sieving the dried powder obtained in the step (4) by a 200-mesh sieve, and shaking on a shaker until the mixed powder is completely sieved into a stainless steel disc containing the powder at the lower part.
(3) Choose for use Hanbang SLM150 metal powder 3D printing apparatus, the metal of installation printing apparatus prints the base plate and carries out the leveling, makes and prints base plate and printing room bottom plate parallel, and installation silica gel scrapes the strip and makes it parallel with printing the base plate and descend to just with the position of printing the base plate laminating.
(4) And (4) pouring the mixed powder obtained in the step (3) into a powder groove of a 3D printer, and adjusting the powder groove to a proper position for powder paving operation.
(5) Opening a cooling water instrument and an argon gas valve to reduce the oxygen content in the printing chamber to 200ppm, opening and downloading a porous reticular structure electrode drawing file drawn by Rhinoceros in advance (the scanning strategy adopts X and Y directions to rotate by 90 degrees at equal intervals for 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 layer thickness is 0.05 mm), setting the laser peak power to be 100%, and printing can be carried out after the laser is opened.
(6) And cutting the printed 3D titanium-based electrode material from the printed substrate. The electrode material is placed in absolute ethyl alcohol for ultrasonic treatment for 10-15 min, and the ultrasonic treatment is repeated for 2-3 times.
(7) And (3) heating the electrode material in the step (6) at 90 ℃ for 0.5h by using a 4wt% sodium hydroxide solution to remove residual oil stains on the surface of the electrode material, boiling the electrode material for 2h at 90 ℃ by using a 10wt% oxalic acid solution to remove an oxide film on the surface of the electrode, and cleaning the electrode material in an ultrasonic cleaner by using ultrapure water for 5min to remove 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; in the second stage, the temperature in the furnace is kept at 500 ℃ and the holding time is 2h. And the electrode material is cooled to normal temperature at the cooling rate of 1 ℃/min. And then the surface of the electrode is cleaned by ultrasonic treatment.
(9) Adding the florfenicol solution with the concentration of 5ppm into an electrolytic bath with the reaction volume of 100ml, and taking the electrode material obtained in the step (8) as an anode and stainless steel as a cathode. The current density was set at 20mA/cm 2 1ml of the reaction solution was placed in a liquid bottle at 0, 5, 10, 20, 30, 45, 60, 90, 120min after the start of the reaction, and 15. Mu.l of methanol was added to the liquid bottle to terminate the reaction.
(10) And (4) placing the liquid phase bottle obtained in the step (9) into an automatic sample introduction chamber of a high performance liquid chromatograph, and detecting the concentration of the pollutants in the liquid phase bottle.
As shown in FIG. 1, the 3D printing Nb prepared by the invention 2 O 5 -TiO 2 The porous electrode has a current density of 20mA/cm 2 Under the condition, the degradation efficiency of mg/L florfenicol dye is more than 99.9 percent within 120min, and the industrial effective purification of the florfenicol can be realized. Here, nb is printed for 3D 2 O 5 -TiO 2 The porous electrode is made of Nb with the content of 0, 0.5%, 1%, 3% and 5% 2 O 5 The doping ratio was subjected to gradient analysis to select 3% of Nb 2 O 5 Doping ratio 3D printing Nb 2 O 5 -TiO 2 The porous electrode is the most optimal condition. Simultaneously compares the TiO printed by non-3D 2 Electrode and 3D printing TiO 2 Degradation effect of the electrode on florfenicol pollutants, 3D printing of TiO was found 2 The degradation efficiency of the electrode on florfenicol pollutants is higher than that of non-3D printed TiO 2 And an electrode.
FIG. 2 is a 3D printing Nb 2 O 5 -TiO 2 Material graph of porous electrode, 3D printing Nb prepared by the invention 2 O 5 -TiO 2 Compared with a 2D electrode material, the porous electrode material has higher specific surface area, reduces the concentration polarization effect of transmission limitation reaction and has higher OH generation amount.
(11) With commercial TiO 2 The electrode repeats the operations from step (9) to step (10) above, aiming at obtaining a comparison of the two, the material of the invention is compared with commercial TiO 2 The degradation rate of the electrode to florfenicol is greatly improved.
In view of the above different crystal phases Nb 2 O 5 The invention provides a brand new 3D printing Nb 2 O 5 Doped TiO 2 2 The porous electrode can efficiently degrade the pollutants such as antibiotics in the wastewater. Under the condition of adding lithium hydroxide externally, laser in the 3D printing process is used for rapidly scanning and heating, so that the original TT-phase Nb is 2 O 5 H-phase Nb with more ordered surface phase change crystal structure and better thermodynamic and electrochemical properties 2 O 5 Wherein the presence of Li atoms is advantageous for increasing the H phase Nb 2 O 5 The crystallinity of (a). The obtained electrode material is sintered in a tubular furnace to convert Ti into anatase phase TiO 2 At the same time, nb is caused by diffusion of Li atoms 2 O 5 The interlayer distance is expanded to generate a cavity, a nano-pore structure is formed, and the specific surface area of the electrode material is increased. H-phase Nb obtained by 3D printing 2 O 5 Doped TiO 2 2 The porous electrode can generate OH with strong oxidizing power under the condition of applied voltage so as to effectively degrade florfenicol and other pollutants in wastewater, compared with non-printed Nb 2 O 5 -TiO 2 The electrode material after 3D printing has higher mass transfer capacity, greatly improves the degradation rate of pollutants, has good thermodynamic property and electrochemical property, and prolongs the service life of the electrode.
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. 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. 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 high mass transfer rate. 3D printing Nb prepared by the invention 2 O 5 -TiO 2 Compared with the existing titanium dioxide electrode, the porous electrode has the advantages of small influence of environmental change (such as pH value and the like) and adaptabilityAnd the characteristics are stronger. 3D printing Nb prepared by the invention 2 O 5 -TiO 2 The porous electrode can realize the decomposition efficiency of ppm-level florfenicol dye over 99.9 percent within 120min, and can realize the industrialized effective purification of the florfenicol.
Claims (10)
1. 3D prints Nb 2 O 5 -TiO 2 The preparation method of the porous electrode comprises the following steps:
(1) Subjecting Ti powder having a particle size of 15-53 μm and Nb to ultrasonic treatment 2 O 5 Powder in proportion of alpha 1 Dispersed to the same mass concentration of C 1 Adding a lithium hydroxide solution to the aqueous solution of ethylenediamine to convert the concentration of the system to C 2 Stirring for 24 hours under the condition of magnetic stirring, then performing centrifugal separation treatment to obtain mixed powder, and drying in an oven;
(2) Opening and downloading a pre-drawn porous mesh structure electrode drawing file by using metal powder 3D printing equipment, and setting a printing method M 1 Opening a cooling water instrument and an argon gas valve to reduce the content of dissolved oxygen in the printing chamber to 200ppm;
(3) Cutting the printed 3D titanium-based electrode material from the printing substrate, placing the electrode material in absolute ethyl alcohol for 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 a surface oxidation film, and washing off residual oxalic acid on the surface of the electrode through ultrasonic treatment;
(5) Placing the electrode material obtained in the step (4) into a tube furnace to be heated by a program A 1 The method of (3) is carried out sintering, the temperature is reduced to normal temperature at the speed of 1 ℃/min, and then the surface of the electrode is cleaned by ultrasonic treatment.
2. The method of claim 1, step (1), wherein the concentration C is 1 6.0 to 8.0mol/L.
3. The method of claim 1, step (1), wherein the ratio a 1 0.5 to 5.0 percent.
4. The method of claim 1, step (1), wherein the concentration C is 2 Is 1.0 to 2.0mol/L.
5. The method according to claim 1, step (2), the printing method M 1 Comprises the following steps: the scanning strategy adopts the alternative scanning of rotating 90 degrees in the X direction and the Y direction at equal intervals, 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 layer thickness is 0.05mm, and the laser peak power is 100%.
6. The method of claim 1, step (5), the temperature-programmed 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; in the second stage, the temperature in the furnace is kept between 450 and 500 ℃, and the holding time is 2 hours.
7. A wastewater treatment method using Nb prepared by 3D printing according to any one of claims 1 to 6 2 O 5 -TiO 2 The electrode electrocatalytic oxidation degrades the organic pollutants in the wastewater,
at a concentration of C 3 Into an electrolytic cell having a reaction volume of 100ml, and 3D printing the prepared Nb 2 O 5 -TiO 2 The electrode material is an anode, the stainless steel is a cathode, and the current density is set as I 1 And detecting the concentration of the pollutants obtained by the reaction by using a high performance liquid chromatograph.
8. The method of claim 7, said concentration C 3 2 to 20ppm.
9. The method of claim 7, the current density I 1 Is 5 to 30mA/cm 2 。
10. The wastewater treatment process of claim 7, wherein the organic contaminant is the antibiotic florfenicol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211141967.2A CN115417477B (en) | 2022-09-19 | 2022-09-19 | Nb is printed to 3D 2 O 5 -TiO 2 Preparation method and application of porous electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211141967.2A CN115417477B (en) | 2022-09-19 | 2022-09-19 | Nb is printed to 3D 2 O 5 -TiO 2 Preparation method and application of porous electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115417477A true CN115417477A (en) | 2022-12-02 |
| CN115417477B CN115417477B (en) | 2023-11-03 |
Family
ID=84204544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211141967.2A Active CN115417477B (en) | 2022-09-19 | 2022-09-19 | Nb is printed to 3D 2 O 5 -TiO 2 Preparation method and application of porous electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115417477B (en) |
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115417477B (en) | 2023-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111672335B (en) | Preparation method and application of CuO @ CuS/PVDF water treatment composite membrane | |
| CN101343746A (en) | Titanium oxide nano wire film on metallic titanium surface and manufacture method thereof | |
| CN102874960A (en) | Device and method for treating high-salinity and degradation-resistant organic industrial waste water by performing photoelectrical synchro coupling and catalytic oxidation on three-dimensional particles | |
| Jing et al. | Treatment of organic matter and ammonia nitrogen in wastewater by electrocatalytic oxidation: a review of anode material preparation | |
| CN113929187B (en) | Anode electrochemical oxidation water treatment method by coupling active chlorine with hydroxyl radical | |
| CN112958092B (en) | Activated persulfate catalyst and preparation method and application thereof | |
| CN113060800A (en) | Preparation method and application of bimetal oxide modified foamed nickel composite electrode | |
| CN113165916A (en) | Device for purifying a fluid, in particular waste water | |
| CN110560130A (en) | preparation method of cerium dioxide nanosphere-carbon nitride composite visible-light-driven photocatalyst | |
| CN113353932A (en) | Hierarchical pore charcoal electrocatalyst prepared from pitaya peel and preparation method and application thereof | |
| CN113683239B (en) | Heterogeneous photocatalyst and tubular membrane electrode coupling device and organic matter degradation method | |
| Bukhari et al. | Effects of Different Parameters on Photocatalytic Oxidation of Slaughterhouse Wastewater Using TiO | |
| Almasi et al. | Photocatalytic activity and water purification performance of in situ and ex situ synthesized bacterial cellulose‐CuO nanohybrids | |
| Chen et al. | Complete removal of 4-fluorophenol using a novel optical fiber photocatalysis–biodegradation–ion-adsorption system | |
| CN111229200B (en) | Bismuth oxide modified Ti 3+ Self-doping TiO 2 Preparation method of heterojunction photocatalyst | |
| CN115417477B (en) | Nb is printed to 3D 2 O 5 -TiO 2 Preparation method and application of porous electrode | |
| KR100926126B1 (en) | Method for preparing integral nanotube photocatalyst, apparatus and method for reducing hexavalent chrominum | |
| CN111545211A (en) | Graphene oxide-lanthanum oxide-cobalt hydroxide composite material, and synthesis method and application thereof | |
| CN115382551B (en) | Three-dimensional carbonaceous functional cathode material based on potassium ferrate modification, and preparation method and application thereof | |
| CN114984980B (en) | Dual-function FeCo 2 O 4 CdS tubular micromotor, and preparation method and application thereof | |
| CN116655068A (en) | Internal aeration type electro-Fenton device and method for treating antibiotic wastewater | |
| CN113354059B (en) | Method for promoting ferric iron/hydrogen peroxide system to degrade environmental pollutants by using amorphous red phosphorus | |
| CN109675546A (en) | Zine stannate nano cube/graphene aerogel sunlight catalytic agent preparation method for Ciprofloxacin Hydrochloride waste water of degrading | |
| CN116216665B (en) | Method for degrading trimethoprim by using advanced oxidation technology | |
| CN111573818A (en) | Ozone catalytic membrane reactor assembly and application method thereof in water treatment engineering |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |