CN113247993A - All-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst and preparation method and application thereof - Google Patents
All-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
Abstract
The invention relates to the technical field of electrocatalysts, and provides an all-solid cobaltosic oxide nanowire array/Ti electrocatalyst and a preparation method and application thereof. The invention takes the titanium mesh as the substrate, which is beneficial to obtaining the all-solid-state mesh material, thereby solving the problem of the traditional powdery Co3O4Easy loss and poor stability; cobalt source, ammonium fluoride, urea and water are used as raw materials, a hydrothermal method is adopted to synthesize basic cobalt carbonate nanowire arrays on a titanium net, and then Co is formed through calcination3O4Nanowire arrays incorporating Co3O4Excellent electrocatalytic performance and the advantage of oriented electron transmission of the nanowire array, and realizes the rapid reduction and dehalogenation of the halogen-containing antibiotics. The results of the examples show that the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst prepared by the invention has excellent stability when being used as an electrocatalytic reduction dehalogenation electrode; and the catalytic degradation efficiency of the chloramphenicol in 30min is 100%.
Description
Technical Field
The invention relates to the technical field of electrocatalysts, in particular to an all-solid cobaltosic oxide nanowire array/Ti electrocatalyst and a preparation method and application thereof.
Background
The problem of massive emissions caused by the abuse of antibiotics seriously threatens the safety of human society. The antibiotic is used as a high-efficiency inhibitor for bacterial growth, is widely applied to the fields of human health, animal husbandry, agriculture and the like, and is used for inactivating or killing microorganisms. In recent years, Chloramphenicol Antibiotics (CAPs), including Chloramphenicol (CAP), Thiamphenicol (TAP), and Florfenicol (FLO) have been used in large quantities in animal husbandry and aquaculture to combat pathogenic bacteria in animals and ensure their smooth growth and avoidance of disease interference. However, the chloramphenicol antibiotics have weak enrichment capacity in soil particles, slow hydrolysis rate, relatively low concentration, accumulative and transfer effects, and easily enter the underground water environment through osmosis, so that the species balance in the underground water environment is damaged. Meanwhile, the long-term accumulation of chloramphenicol antibiotics in the groundwater environment can aggravate the generation of bacterial resistance genes, and the resistance genes are widely spread by human pumping and using groundwater. Therefore, detoxification treatment of antibiotic molecules is very necessary. The traditional oxidation method achieves the effect of removing the organic macromolecules by chain scission, but the generated intermediate product without the halogen groups removed is probably more toxic. Through the halogenous organic matter of electrochemical reduction processing, not only can realize the detoxification of selectivity, make the reaction process cleaner, can also avoid putting into the risk of secondary pollution that the exogenous additive treating agent caused.
The cobalt oxide nano material becomes one of the important materials in the current nano-technology field, and has very wide industrial application value. Co3O4When the catalyst is used as an electrocatalyst for reduction and dehalogenation, halogenated organic molecules can be continuously adsorbed and reduced depending on the valence state change of the catalyst. However, commonly used Co3O4The material is in powder form and existsEasy loss and poor stability, easy secondary pollution and low electrocatalytic activity. Therefore, it is highly desirable to provide Co with high electrocatalytic activity and good stability3O4The electro-catalyst can achieve the purpose of efficiently electro-catalytically degrading the halogen-containing antibiotics in the water.
Disclosure of Invention
The invention aims to provide an all-solid cobaltosic oxide nanowire array/Ti electrocatalyst and a preparation method and application thereof3O4Easy loss and poor stability, and simultaneously realizes the rapid reduction and dehalogenation of the halogen-containing antibiotics.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of an all-solid cobaltosic oxide nanowire array/Ti electrocatalyst, which comprises the following steps:
(1) mixing a titanium mesh serving as a substrate with a cobalt source, ammonium fluoride, urea and water, and then carrying out hydrothermal reaction to obtain a titanium mesh loaded with a cobaltosic oxide nanowire array precursor;
(2) and (2) calcining the titanium mesh loaded with the cobaltosic oxide nanowire array precursor obtained in the step (1) to obtain the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst.
Preferably, the mesh number of the titanium net in the step (1) is 100-120 meshes.
Preferably, the ratio of the amount of cobalt in the cobalt source in step (1) to the amount of ammonium fluoride and urea is 1-5: 2-10: 2-10; the volume ratio of the total mass of the cobalt source, the ammonium fluoride and the urea to the water is (0.4-2.0) g: (30-50) mL.
Preferably, the cobalt source in step (1) comprises cobalt nitrate.
Preferably, the temperature of the hydrothermal reaction in the step (1) is 95-120 ℃, and the time of the hydrothermal reaction is 24-30 h.
Preferably, the calcining temperature in the step (2) is 500-550 ℃.
Preferably, the calcination time in the step (2) is 4-8 h.
The invention provides an all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst prepared by the preparation method in the technical scheme, and the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst comprises a titanium net and a cobaltosic oxide nanowire array loaded on the surface of the titanium net.
The invention also provides the application of the all-solid cobaltosic oxide nanowire array/Ti electrocatalyst in the technical scheme in the electrocatalytic degradation of halogen-containing antibiotics.
Preferably, the halogen-containing antibiotics include chloramphenicol, p-chlorophenol, and florfenicol.
The invention provides a preparation method of an all-solid cobaltosic oxide nanowire array/Ti electrocatalyst, which comprises the following steps: mixing a cobalt source, ammonium fluoride, urea and water by taking a titanium mesh as a substrate, and then carrying out hydrothermal reaction to obtain the titanium mesh loaded with the cobaltosic oxide nanowire array precursor; and calcining the titanium mesh loaded with the cobaltosic oxide nanowire array precursor to obtain the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst. The invention takes a titanium net as a substrate, after a cobalt source, ammonium fluoride, urea and water are added, the titanium net loading the cobaltosic oxide nanowire array precursor is prepared through hydrothermal reaction, and then the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst is prepared through calcination. The invention takes the titanium mesh as the substrate, which is beneficial to obtaining the all-solid-state mesh material, thereby solving the problem of the traditional powdery Co3O4Easy loss and poor stability; cobalt source, ammonium fluoride, urea and water are used as raw materials, a hydrothermal method is adopted to synthesize basic cobalt carbonate nanowire arrays on a titanium net, and then Co is formed through calcination3O4Nanowire arrays incorporating Co3O4Excellent electrocatalytic performance and the advantage of oriented electron transmission of the nanowire array, and realizes the rapid reduction and dehalogenation of the halogen-containing antibiotics. The results of the examples show that the all-solid-state cobaltosic oxide nanowire arrays/Ti electrocatalysts prepared by the invention have Co before and after reaction3O4The material structure of the nanowire array is not changed, which shows that the four oxygen atoms are not changedThe cobaltosic oxide nanowire array/Ti serving as an electrocatalytic reduction dehalogenation electrode has excellent stability; and the catalytic degradation efficiency of the chloramphenicol in 30min is 100%.
Drawings
FIG. 1 is an X-ray photoelectron spectrum of an all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the fully solid cobaltosic oxide nanowire array/Ti electrocatalyst prepared in example 1 according to the invention, magnified 2000 times;
FIG. 3 is a scanning electron microscope image of the all-solid cobaltosic oxide nanowire array/Ti electrocatalyst prepared in example 1 according to the invention, magnified 20000 times;
FIG. 4 is a graph of the catalytic efficiency of the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst prepared in example 1 of the present invention on florfenicol within 0-60 min;
FIG. 5 is a diagram of a reaction device in which an all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst prepared according to the present invention is used as a working electrode for catalytic degradation of halogen-containing antibiotics.
Detailed Description
The invention provides a preparation method of an all-solid cobaltosic oxide nanowire array/Ti electrocatalyst, which comprises the following steps:
(1) mixing a titanium mesh serving as a substrate with a cobalt source, ammonium fluoride, urea and water, and then carrying out hydrothermal reaction to obtain a titanium mesh loaded with a cobaltosic oxide nanowire array precursor;
(2) and (2) calcining the titanium mesh loaded with the cobaltosic oxide nanowire array precursor obtained in the step (1) to obtain the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst.
The method takes a titanium mesh as a substrate, and the titanium mesh is mixed with a cobalt source, ammonium fluoride, urea and water and then subjected to hydrothermal reaction to obtain the titanium mesh loaded with the cobaltosic oxide nanowire array precursor. According to the invention, the basic cobaltous carbonate nanowire array is synthesized on the titanium mesh by mixing the titanium mesh with a cobalt source, ammonium fluoride, urea and water and then carrying out hydrothermal reaction.
The invention takes the titanium mesh as the substrate, and is beneficial to obtainingAll solid state net material, thereby solving the problem of traditional powdery Co3O4Easy loss and poor stability. The source of the titanium mesh is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the invention, the mesh number of the titanium net is preferably 100-120 meshes; the specification of the titanium mesh is preferably 3cm × 4 cm.
The invention preferably pretreats the titanium mesh prior to mixing with a cobalt source, ammonium fluoride, urea and water. In the present invention, the pretreatment preferably includes washing and drying which are sequentially performed. The invention removes impurities such as oil stains on the surface of the titanium mesh by washing, and then removes residual detergent by drying, thereby obtaining a clean titanium mesh substrate. The washing and drying method of the present invention is not particularly limited, and washing and drying methods known to those skilled in the art may be used.
In the present invention, the detergent used for the washing preferably includes acetone, ethanol and deionized water; the washing mode is preferably washing with acetone, ethanol and deionized water in sequence. In the invention, when the specification of the titanium mesh is 3cm × 4cm, the amounts of acetone, ethanol and deionized water are preferably 30-40 mL independently. In the present invention, the washing is preferably performed under the condition of sonication. In the invention, the frequency of the ultrasonic wave is preferably 50-80 kHz, and more preferably 60-70 kHz; the ultrasonic treatment time is preferably 30-45 min, and more preferably 35-40 min. In the present invention, the drying mode is preferably natural airing.
The sources of the cobalt source, ammonium fluoride and urea are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the present invention, the cobalt source preferably comprises cobalt nitrate.
In the present invention, the ratio of the amounts of cobalt, ammonium fluoride and urea in the cobalt source is preferably 1 to 5: 2-10: 2 to 10, more preferably 1:2: 2. In the invention, the ratio of the amounts of the cobalt, the ammonium fluoride and the urea in the cobalt source is preferably controlled in the range, which is favorable for obtaining the nanowire array with uniform appearance.
In the present invention, the volume ratio of the total mass of the cobalt source, ammonium fluoride and urea to water is preferably (0.4 to 2.0) g: (30-50) mL, more preferably 0.4858g:30 mL.
In the invention, the temperature of the hydrothermal reaction is preferably 95-120 ℃, and more preferably 95-110 ℃. According to the invention, the temperature of the hydrothermal reaction is preferably controlled within the range, so that the basic cobalt carbonate nanowire array with uniform appearance can be synthesized on a titanium mesh.
In the invention, the time of the hydrothermal reaction is preferably 24-30 h, and more preferably 24-26 h. In the present invention, the hydrothermal reaction time is preferably controlled within the above range, which is advantageous for ensuring the hydrothermal reaction to be sufficiently performed.
After the titanium mesh loaded with the cobaltosic oxide nanowire array precursor is obtained, the invention calcines the titanium mesh loaded with the cobaltosic oxide nanowire array precursor to obtain the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst. The invention forms Co by calcination3O4Nanowire arrays incorporating Co3O4Excellent electrocatalytic performance and the advantage of oriented electron transmission of the nanowire array, and realizes the rapid reduction and dehalogenation of the halogen-containing antibiotics.
In the invention, the calcination temperature is preferably 500-550 ℃, and more preferably 500-530 ℃; the calcination time is preferably 4-8 h, and more preferably 4-6 h. The invention preferably controls the calcining temperature and time within the range, which is beneficial to obtaining Co with uniform appearance3O4And (4) nanowire arrays.
The invention takes the titanium mesh as the substrate, which is beneficial to obtaining the all-solid-state mesh material, thereby solving the problem of the traditional powdery Co3O4Easy loss and poor stability; cobalt source, ammonium fluoride, urea and water are used as raw materials, a hydrothermal method is adopted to synthesize basic cobalt carbonate nanowire arrays on a titanium net, and then Co is formed through calcination3O4Nanowire arrays incorporating Co3O4Excellent electrocatalytic performance and the advantage of oriented electron transmission of the nanowire array, and realizes the rapid reduction and dehalogenation of the halogen-containing antibiotics.
The invention provides an all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst prepared by the preparation method in the technical scheme, and the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst comprises a titanium net and a cobaltosic oxide nanowire array loaded on the surface of the titanium net.
In the invention, the titanium mesh is used as a substrate, which is beneficial to obtaining a full-solid mesh material, thereby solving the problem of the traditional powdery Co3O4Easy loss and poor stability; the cobaltosic oxide nanowire array is combined with Co3O4Excellent electrocatalytic performance and the advantage of oriented electron transmission of the nanowire array, and realizes the rapid reduction and dehalogenation of the halogen-containing antibiotics.
The invention also provides the application of the all-solid cobaltosic oxide nanowire array/Ti electrocatalyst in the technical scheme in the electrocatalytic degradation of halogen-containing antibiotics.
In the invention, the all-solid cobaltosic oxide nanowire array/Ti electrocatalyst is preferably used as a working electrode for catalyzing and degrading halogen-containing antibiotics.
In the present invention, the reaction device of the all-solid cobaltosic oxide nanowire array/Ti electrocatalyst as the working electrode for catalyzing and degrading the halogen-containing antibiotics is preferably as shown in fig. 5, and the reaction device comprises the all-solid cobaltosic oxide nanowire array/Ti electrocatalyst, a platinum net, Ag/AgCl, a proton exchange membrane, an electrochemical workstation and a reaction solution containing the halogen-containing antibiotics. In the invention, the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst is used as a working electrode, the platinum net is used as a counter electrode, and Ag/AgCl is used as a reference electrode.
The invention has no special limitation on the type of the halogen-containing antibiotics, and the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst provided by the invention is suitable for electrocatalytic degradation of various halogen-containing antibiotics well known to those skilled in the art. In the present invention, the halogen-containing antibiotic preferably comprises chloramphenicol, p-chlorophenol, or florfenicol.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Cutting a commercial black titanium net of 100 meshes into small pieces of 3cm multiplied by 4cm, respectively ultrasonically cleaning the small pieces for 30min by 30mL of acetone, 30mL of ethanol and 30mL of deionized water, wherein the ultrasonic frequency is 50kHz, and then naturally airing to obtain a clean titanium net;
0.291g of Co (NO)3)2·6H2O was dissolved in 30mL of deionized water, then 0.0748g NH was added4F and 0.12g CO (NH)2)2Stirring uniformly to obtain a mixed solution; wherein the ratio of the cobalt nitrate to the ammonium fluoride to the urea is 1mmol:2mmol:2 mmol; the volume ratio of the total mass of the cobalt nitrate, the ammonium fluoride and the urea to the water is 0.4858g:30 mL;
placing the dried titanium mesh in a polytetrafluoroethylene reaction kettle, adding the mixed solution, carrying out hydrothermal reaction at 95 ℃ for 24 hours to obtain the titanium mesh loaded with the cobaltosic oxide nanowire array precursor;
washing the titanium mesh loaded with the cobaltosic oxide nanowire array precursor by using deionized water, then placing the titanium mesh in a muffle furnace, and calcining the titanium mesh at 500 ℃ for 4h to obtain the all-solid cobaltosic oxide nanowire array/Ti electrocatalyst (marked as Co/Ti electrocatalyst)3O4NWs/Ti)。
FIG. 1 is the X-ray photoelectron spectrum of the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst prepared in this example. As can be seen from fig. 1, the material structure of the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst prepared by the present invention is not changed before and after the reaction, which indicates that the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst prepared by the present invention has excellent stability.
Fig. 2 is a scanning electron microscope image of the all-solid cobaltosic oxide nanowire array/Ti electrocatalyst prepared in this example after being amplified by 2000 times, and fig. 3 is a scanning electron microscope image of the all-solid cobaltosic oxide nanowire array/Ti electrocatalyst prepared in this example after being amplified by 20000 times. As can be seen from fig. 2 to 3, the all-solid cobaltosic oxide nanowire array/Ti electrocatalyst prepared in this example has uniform morphology.
Application example 1
Selecting a three-electrode system, applying a voltage of-1.2V in an electrochemical workstation, respectively taking a titanium mesh and the cobaltosic oxide nanowire array/Ti electrocatalyst prepared in example 1 as working electrodes, a platinum mesh as a counter electrode, Ag/AgCl as a reference electrode, and Na with the concentration of 0.1mol/L2SO4The mixed solution of the solution and Florfenicol (FLO) with the concentration of 10mg/L is a reaction solution for electrochemical degradation, and the electro-catalytic reduction dehalogenation of the florfenicol is carried out. The concentration of the florfenicol in the reaction process is tested by using a high performance liquid chromatograph, and the catalytic efficiency of the cobaltosic oxide nanowire array/Ti electrocatalyst prepared in the embodiment 1 on the florfenicol within 0-60 min is obtained through integral calculation, and the result is shown in fig. 4.
As can be seen from FIG. 4, the florfenicol is completely degraded by the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst prepared by the method within 30min, the catalytic efficiency reaches 100%, and the florfenicol catalytic efficiency of the titanium mesh within 30min is only 5%. Thus, the all-solid Co prepared by the invention3O4The nanowire array/Ti electrocatalyst has excellent electrocatalytic performance.
Application example 2
Selecting a three-electrode system, applying a voltage of-1.2V in an electrochemical workstation, taking the cobaltosic oxide nanowire array/Ti electrocatalyst prepared in example 1 as a working electrode, a platinum net as a counter electrode, Ag/AgCl as a reference electrode, and Na with the concentration of 0.1mol/L2SO4The mixed solution of the solution and the chloramphenicol with the concentration of 10mg/L is a reaction solution for electrochemical degradation, and the chloramphenicol is subjected to electrocatalytic reduction dehalogenation. The concentration of chloramphenicol in the reaction process was measured by a high performance liquid chromatograph, and the catalytic effect of the cobaltosic oxide nanowire array/Ti electrocatalyst prepared in example 1 on chloramphenicol within 30min was obtained by integral calculationThe ratio was 100%.
Application example 3
Selecting a three-electrode system, applying a voltage of-1.2V in an electrochemical workstation, taking the cobaltosic oxide nanowire array/Ti electrocatalyst prepared in example 1 as a working electrode, a platinum net as a counter electrode, Ag/AgCl as a reference electrode, and Na with the concentration of 0.1mol/L2SO4The mixed solution of the solution and the parachlorophenol with the concentration of 20mg/L is a reaction solution for electrochemical degradation, an electrocatalytic reduction dehalogenation experiment of the parachlorophenol is carried out, a high performance liquid chromatograph is used for testing the concentration of the parachlorophenol in the reaction process, and the catalytic efficiency of the cobaltosic oxide nanowire array/Ti electrocatalyst prepared in the embodiment 1 on the parachlorophenol is 76% within 2h through integral calculation.
Example 2
Cutting a commercial black titanium net of 100 meshes into small pieces of 3cm multiplied by 4cm, respectively ultrasonically cleaning the small pieces for 30min by 30mL of acetone, 30mL of ethanol and 30mL of deionized water, wherein the ultrasonic frequency is 50kHz, and then naturally airing to obtain a clean titanium net;
1.455g of Co (NO)3)2·6H2O was dissolved in 30mL of deionized water and then 0.374g NH was added4F and 0.6g CO (NH)2)2Stirring uniformly to obtain a mixed solution; wherein the ratio of the cobalt nitrate to the ammonium fluoride to the urea is 5mmol:10mmol:10 mmol; the volume ratio of the total mass of the cobalt nitrate, the ammonium fluoride and the urea to the water is 2.429g:30 mL;
placing the dried titanium mesh in a polytetrafluoroethylene reaction kettle, adding the mixed solution, carrying out hydrothermal reaction at 95 ℃ for 24 hours to obtain the titanium mesh loaded with the cobaltosic oxide nanowire array precursor;
and washing the titanium mesh loaded with the cobaltosic oxide nanowire array precursor by using deionized water, then placing the titanium mesh in a muffle furnace, and calcining the titanium mesh at 500 ℃ for 4 hours to obtain the all-solid cobaltosic oxide nanowire array/Ti electrocatalyst.
Application example 4
The tricobalt tetraoxide nanowire array prepared in example 2 was selected to be-Ti electrocatalyst as working electrode, platinum net as counter electrode, Ag/AgCl as reference electrode, Na with concentration of 0.1mol/L2SO4The mixed solution of the solution and the chloramphenicol with the concentration of 10mg/L is a reaction solution for electrochemical degradation, and the chloramphenicol is subjected to electrocatalytic reduction dehalogenation. The concentration of chloramphenicol in the reaction process was measured by a high performance liquid chromatograph, and the catalytic efficiency of the cobaltosic oxide nanowire array/Ti electrocatalyst prepared in example 2 for chloramphenicol was 60% within 30min, which was obtained by integral calculation.
Example 3
Cutting a commercial black titanium net of 100 meshes into small pieces of 3cm multiplied by 4cm, respectively ultrasonically cleaning the small pieces for 30min by 30mL of acetone, 30mL of ethanol and 30mL of deionized water, wherein the ultrasonic frequency is 50kHz, and then naturally airing to obtain a clean titanium net;
0.291g of Co (NO)3)2·6H2O was dissolved in 30mL of deionized water, then 0.0748g NH was added4F and 0.12g CO (NH)2)2Stirring uniformly to obtain a mixed solution; wherein the ratio of the cobalt nitrate to the ammonium fluoride to the urea is 1mmol:2mmol:2 mmol; the volume ratio of the total mass of the cobalt nitrate, the ammonium fluoride and the urea to the water is 0.4858g:30 mL;
placing the dried titanium mesh in a polytetrafluoroethylene reaction kettle, adding the mixed solution, carrying out hydrothermal reaction at 100 ℃, and reacting for 26 hours to obtain the titanium mesh loaded with the cobaltosic oxide nanowire array precursor;
and (3) washing the titanium mesh loaded with the cobaltosic oxide nanowire array precursor with deionized water, then placing the titanium mesh in a muffle furnace, and calcining the titanium mesh at 520 ℃ for 6 hours to obtain the all-solid cobaltosic oxide nanowire array/Ti electrocatalyst.
Application example 5
A three-electrode system was selected, a voltage of-1.2V was applied in an electrochemical workstation, the cobaltosic oxide nanowire array/Ti electrocatalyst prepared in example 3 was used as a working electrode, a platinum mesh was used as a counter electrode, Ag/AgCl was used as a reference electrode, and Na with a concentration of 0.1mol/L was used2SO4The mixed solution of the solution and the chloramphenicol with the concentration of 10mg/L is a reaction solution for electrochemical degradation, and the chloramphenicol is carried outCarrying out electrocatalytic reduction dehalogenation. The concentration of chloramphenicol in the reaction process was measured by a high performance liquid chromatograph, and the catalytic efficiency of the cobaltosic oxide nanowire array/Ti electrocatalyst prepared in example 3 for chloramphenicol was 100% in 30min, which was obtained by integral calculation.
As can be seen from the above examples, the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst prepared by the invention solves the problem of the traditional powdery Co3O4Easy loss and poor stability, and simultaneously realizes the rapid reduction and dehalogenation of the halogen-containing antibiotics. In addition, the cobaltosic oxide nanowire array/Ti electrocatalyst prepared by the invention has 100% catalytic efficiency on chloramphenicol within 30 min.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of an all-solid cobaltosic oxide nanowire array/Ti electrocatalyst comprises the following steps:
(1) mixing a titanium mesh serving as a substrate with a cobalt source, ammonium fluoride, urea and water, and then carrying out hydrothermal reaction to obtain a titanium mesh loaded with a cobaltosic oxide nanowire array precursor;
(2) and (2) calcining the titanium mesh loaded with the cobaltosic oxide nanowire array precursor obtained in the step (1) to obtain the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst.
2. The method according to claim 1, wherein the titanium mesh in step (1) has a mesh size of 100 to 120 meshes.
3. The method according to claim 1, wherein the ratio of the amounts of cobalt in the cobalt source to the amounts of ammonium fluoride and urea in step (1) is 1-5: 2-10: 2-10; the volume ratio of the total mass of the cobalt source, the ammonium fluoride and the urea to the water is (0.4-2.0) g: (30-50) mL.
4. The production method according to claim 1 or 3, wherein the cobalt source in the step (1) comprises cobalt nitrate.
5. The preparation method according to claim 1, wherein the temperature of the hydrothermal reaction in the step (1) is 95-120 ℃, and the time of the hydrothermal reaction is 24-30 h.
6. The method according to claim 1, wherein the calcination temperature in the step (2) is 500 to 550 ℃.
7. The preparation method of claim 1 or 6, wherein the calcination time in the step (2) is 4-8 h.
8. The all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst prepared by the preparation method of any one of claims 1 to 7, wherein the all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst comprises a titanium mesh and a cobaltosic oxide nanowire array loaded on the surface of the titanium mesh.
9. Use of the all-solid-state cobaltosic oxide nanowire arrays/Ti electrocatalysts of claim 8 for the electrocatalytic degradation of halogen-containing antibiotics.
10. The use of an all-solid-state cobaltosic oxide nanowire array/Ti electrocatalyst according to claim 9 for the electrocatalytic degradation of halogen-containing antibiotics, wherein said halogen-containing antibiotics comprise chloramphenicol, p-chlorophenol, or florfenicol.
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