CN116212928A - Nitrogen-doped carbon nanofiber ozone catalyst, preparation method and application - Google Patents
Nitrogen-doped carbon nanofiber ozone catalyst, preparation method and application Download PDFInfo
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- CN116212928A CN116212928A CN202310214146.5A CN202310214146A CN116212928A CN 116212928 A CN116212928 A CN 116212928A CN 202310214146 A CN202310214146 A CN 202310214146A CN 116212928 A CN116212928 A CN 116212928A
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 45
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004202 carbamide Substances 0.000 claims abstract description 26
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- 238000003763 carbonization Methods 0.000 claims abstract description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 13
- 230000006641 stabilisation Effects 0.000 claims abstract description 11
- 238000011105 stabilization Methods 0.000 claims abstract description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000009987 spinning Methods 0.000 claims description 25
- 239000012300 argon atmosphere Substances 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002121 nanofiber Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 9
- 239000010842 industrial wastewater Substances 0.000 claims description 6
- 229920003169 water-soluble polymer Polymers 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 2
- 239000013043 chemical agent Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 9
- 239000010865 sewage Substances 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- -1 polycyclic aromatic compounds Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- UAADFBBDQUNCJK-UHFFFAOYSA-N copper ozone Chemical compound O=[O+][O-].[Cu] UAADFBBDQUNCJK-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides a nitrogen-doped carbon nanofiber catalyst for ozone catalytic oxidation, which comprises the steps of selecting one or more of water-soluble high polymers such as polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP) and polyethylene oxide (PEO) as a carbon source, preparing an electrostatic spinning precursor solution by taking urea as a nitrogen source and taking water as a solvent, and preparing the nitrogen-doped carbon nanofiber ozone catalyst through electrostatic spinning, high-temperature stabilization and carbonization processes. Adjustment ofThe ratio of the carbon source to the nitrogen source in the precursor solution can be reduced to prepare the nitrogen-doped carbon nanofiber ozone catalyst with the mass fraction of the doped nitrogen element of 0.1-25%. Due to the high-efficiency ozone activating capability of the nitrogen-doped carbon nanofiber catalyst, the catalyst can be used in the fields of treatment of various chemical wastewater, is used for degrading refractory organic matters and the like in the wastewater, and is particularly suitable for BOD (biological oxygen demand) 5 <0.3 of difficult biochemical sewage, can lead the COD of the sewage to be Cr The water content is reduced from 800mg/L to below 30mg/L, so that the standard discharge of the wastewater is realized or the recycling standard of the circulating water is reached.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a nitrogen-doped carbon nanofiber ozone catalyst, a preparation method and application thereof.
Background
In recent years, with the severe environmental situation and the direction of national policies, the standards of sewage discharge and recycling are more and more strict, and sewage treatment is particularly important. Industrial waste water which is difficult to degrade is often produced in the chemical industrial production, and mainly comprises phenols, polycyclic aromatic compounds, thiocyanide and other organic pollutants which are difficult to degrade. The conventional advanced treatment methods such as physical and chemical treatment, biochemical treatment and coagulating sedimentation are used, so that the standard of discharge or recycling is difficult to meet, and the problems of exceeding COD (chemical oxygen demand), high chromaticity, high toxicity and the like are generally presented, so that the effluent needs to be further advanced treated.
Currently, the common advanced treatment methods include adsorption method, ozone oxidation method and catalytic ozone oxidation method. The principle of ozone degradation of organic matters is as follows: under the induction of hydroxyl ions in water, ozone is induced to decompose into hydroxyl free radicals, the hydroxyl free radicals have high oxidation potential and strong oxidation capacity, and the hydroxyl free radicals have no selectivity, can indiscriminately degrade almost all organic matters in the wastewater into carbon dioxide and water, and are particularly suitable for organic matters which are difficult to degrade. The catalytic ozonation aims to initiate the ozone chain reaction under the action of a catalyst to generate more hydroxyl free radicals, and meanwhile, intermediate products possibly serving as free radical inhibitors can be reduced, so that the effective decomposition rate of the ozone and the removal rate of organic matters are improved.
Typical catalytic ozone technology uses homogeneous or heterogeneous metal ion catalysts. Because of the addition or leaching of metal ions, secondary pollution of the wastewater is caused, and other treatment processes are added to remove the metal ions after organic matters are degraded, so that the treatment cost of the wastewater is increased. Meanwhile, the metal ions of the organic catalyst are leached, the ion concentration in the wastewater can be gradually reduced, the catalytic efficiency is reduced, the ozone utilization rate is low, and the cost is high. In addition, the metal ions used for catalysis are often toxic and have negative effects on standard discharge or recycling of wastewater. It is highly desirable to develop efficient nonmetallic ozone catalytic oxidation catalysts. Therefore, the invention provides a nitrogen-doped carbon nanofiber ozone catalyst, a preparation method and application.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a nitrogen-doped carbon nanofiber ozone catalyst, a preparation method and application.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in one aspect, the invention provides a nitrogen-doped carbon nanofiber ozone catalyst, which is prepared by taking one or more of polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP) or polyethylene oxide (PEO) as a carbon source, taking Urea (Urea) as a nitrogen source, and preparing a precursor solution, carrying out electrostatic spinning, stabilizing fibers and carbonizing at a high temperature, wherein the mass fraction of nitrogen element in the ozone catalyst is 0.1-25%.
In another aspect, the invention provides a method for preparing a nitrogen-doped carbon nanofiber ozone catalyst, comprising the following steps:
step one, preparing a precursor solution:
dispersing a water-soluble polymer and urea in water to form a precursor solution for electrostatic spinning, wherein the water-soluble polymer is one or more of polyvinyl alcohol, polyvinylpyrrolidone or polyethylene oxide;
step two, electrostatic spinning:
carrying out electrostatic spinning on the precursor solution obtained in the step one at 80-120 ℃, and receiving polymer nanofibers by using aluminum foil as a receiving plate;
step three, stabilizing the fiber:
placing the polymer nanofiber obtained in the second step into a tube furnace for carbonization, and promoting the stabilization of the polymer nanofiber to obtain a stabilized fiber;
step four, high-temperature carbonization:
and (3) under the protection of argon atmosphere, carbonizing the stable fiber obtained in the step (III) at high temperature by using a tube furnace to obtain the nitrogen-doped carbon nanofiber.
Further, in the first step, the water-soluble polymer and urea are stirred for 4 hours at 60 ℃ during the dispersion in water.
Further, in the second step, the parameters of the electrostatic spinning are as follows: the spinning voltage is 50-70 kV, preferably 55-65 kV; the spinning distance is 10-20 cm, preferably 13-18 cm.
Further, in the third step, the carbonization conditions are as follows: heating rate is 5 ℃/min, carbonization temperature is 250 ℃, and heat preservation time is 2-3 h.
Further, in the fourth step, the carbonization conditions are as follows: heating rate is 5 ℃/min, carbonization temperature is 450 ℃, and heat preservation time is 1-3 h.
In one aspect, the present invention provides the use of a nitrogen-doped carbon nanofiber ozone catalyst for treating industrial wastewater having COD Cr The ozone adding amount is between 60 and 800mg/L, the ozone adding amount is between 15 and 80mg/L, and the residence time in the catalyst layer is between 20 and 80 minutes.
The beneficial effects of the invention are as follows:
1. the nitrogen-doped carbon nanofiber ozone catalyst provided by the invention belongs to a non-metal heterogeneous catalyst, and carbon atoms connected with nitrogen on a carbon nano tube have metal-like catalytic activity due to nitrogen doping. The carbon source and nitrogen source proportion are changed, and the C-N site with catalytic oxidation activity is regulated, so that the nitrogen doped carbon nanofiber ozone catalyst with the mass fraction of doped nitrogen element of 0.1-25% can be prepared, and the catalytic activity can be regulated due to the regulated nitrogen doping amount, so that the catalyst is easy to prepare and has good initiation capability on the chain reaction of ozone;
2. the metal catalyst commonly used in the current ozone oxidation often has the problem that the activity center metal is lost to cause the rapid reduction of the activity. The nitrogen-doped carbon nanofiber ozone catalyst provided by the invention has the advantages that the C-N active site is connected with surrounding atoms through the covalent bond with high electron delocalization, the active site is not easy to run off, and the catalyst stability is good;
3. the nitrogen-doped carbon nanofiber ozone catalyst provided by the invention can be conveniently recycled through filtration after the reaction is finished;
4. the invention provides a method for treating industrial wastewater by catalytic oxidation of ozone, which has the advantages of simple process flow, capability of remarkably improving the capability of degrading CODCr by ozone, great improvement of the utilization rate of ozone and reduction of treatment cost.
Drawings
FIG. 1 is an X-ray photoelectron spectrum of a nitrogen doped carbon nanofiber ozone catalyst;
FIG. 2 is a dispersive energy spectrum of element C, N of a nitrogen-doped carbon nanofiber ozone catalyst;
FIG. 3 is a 1 μm scale electron micrograph of a nitrogen doped carbon nanofiber ozone catalyst;
FIG. 4 is a 10 μm scale electron micrograph of a nitrogen doped carbon nanofiber ozone catalyst;
fig. 5 is a 100 μm scale electron micrograph of a nitrogen-doped carbon nanofiber ozone catalyst.
Detailed Description
In order to solve the problems of secondary pollution of metal ion catalysts, low ozone utilization rate, easy loss of active components of catalysts and the like when the traditional method for catalyzing ozone is used for advanced wastewater treatment, the invention provides an advanced wastewater treatment process taking a nitrogen-doped carbon nanofiber ozone catalyst as a core, and the advanced wastewater treatment process has the advantages of nonmetal catalyst, stable catalyst, difficult loss of active components, simple process flow and capability of remarkably improving the COD degradation of ozone Cr Greatly improves the utilization rate of ozone and reduces the treatment cost.
Example 1
183g of polyvinyl alcohol (PVA) and 0.214g of Urea (Urea) were dissolved in water to prepare a 10wt% aqueous solution as an electrostatic spinning precursor solution, and the precursor solution was stirred at 60℃for 4 hours to obtain a PVA/Urea spinning precursor solution. And (3) carrying out electrostatic spinning at 110 ℃, wherein the spinning voltage is 60kV, the spinning distance is 15cm, and a layer of aluminum foil is paved on a receiving device to serve as a receiving plate. The resulting polymer nanofibers were placed in a tube furnace and subjected to the following fiber stabilization and carbonization processes: raising the temperature from room temperature to 250 ℃ at a heating rate of 5 ℃/min, and preserving the heat for 2 hours; and then heating to 450 ℃ at the same heating rate under the protection of argon atmosphere, preserving heat for 2 hours, and finally cooling to room temperature under the protection of argon atmosphere to obtain the nitrogen-doped carbon nanofiber ozone catalyst. The N doping level was about 0.1%.
Example 2
100g of polyvinyl alcohol (PVA) and 10g of Urea (Urea) are dissolved in water to prepare a 10wt% aqueous solution serving as an electrostatic spinning precursor solution, and the precursor solution is stirred for 4 hours at 60 ℃ to obtain the PVA/Urea spinning precursor solution. And (3) carrying out electrostatic spinning at 110 ℃, wherein the spinning voltage is 60kV, the spinning distance is 15cm, and a layer of aluminum foil is paved on a receiving device to serve as a receiving plate. The resulting polymer nanofibers were placed in a tube furnace and subjected to the following fiber stabilization and carbonization processes: raising the temperature from room temperature to 250 ℃ at a heating rate of 5 ℃/min, and preserving the heat for 2 hours; then under the protection of argon atmosphere, the temperature is raised to 450 ℃ at the same temperature raising rate, the heat is preserved for 2 hours, and finally the nitrogen doped carbon nanofiber ozone catalyst is obtained after cooling to room temperature under the protection of argon atmosphere, wherein the N doping amount is about 7.6%.
Example 3
100g of polyvinyl alcohol (PVA) and 40g of Urea (Urea) are dissolved in water to prepare 10wt% of aqueous solution serving as an electrostatic spinning precursor solution, and the precursor solution is stirred for 4 hours at 60 ℃ to obtain the PVA/Urea spinning precursor solution. And (3) carrying out electrostatic spinning at 110 ℃, wherein the spinning voltage is 70kV, the spinning distance is 18cm, and a layer of aluminum foil is paved on a receiving device to serve as a receiving plate. The resulting polymer nanofibers were placed in a tube furnace and subjected to the following fiber stabilization and carbonization processes: raising the temperature from room temperature to 250 ℃ at a heating rate of 5 ℃/min, and preserving the temperature for 3 hours; then under the protection of argon atmosphere, the temperature is raised to 450 ℃ at the same temperature raising rate, the heat is preserved for 3 hours, and finally the nitrogen doped carbon nanofiber ozone catalyst is obtained after cooling to room temperature under the protection of argon atmosphere, wherein the N doping amount is about 23.0%.
Example 4
100g of polyvinylpyrrolidone (PVP) and 10g of Urea (Urea) are dissolved in water to prepare a 10wt% aqueous solution serving as an electrostatic spinning precursor solution, and the precursor solution is stirred for 4 hours at 60 ℃ to obtain the PVP/Urea spinning precursor solution. And (3) carrying out electrostatic spinning at 90 ℃, wherein the spinning voltage is 60kV, the spinning distance is 15cm, and a layer of aluminum foil is paved on a receiving device to serve as a receiving plate. The resulting polymer nanofibers were placed in a tube furnace and subjected to the following fiber stabilization and carbonization processes: raising the temperature from room temperature to 250 ℃ at a heating rate of 5 ℃/min, and preserving the heat for 2 hours; then under the protection of argon atmosphere, the temperature is raised to 450 ℃ at the same temperature raising rate, the heat is preserved for 2 hours, and finally the nitrogen doped carbon nanofiber ozone catalyst is obtained after cooling to room temperature under the protection of argon atmosphere, wherein the N doping amount is about 20.5%.
Example 5
100g of polyvinylpyrrolidone (PVP) and 1g of Urea (Urea) are dissolved in water to prepare 10wt% aqueous solution serving as electrostatic spinning precursor solution, and the precursor solution is stirred for 3 hours at 60 ℃ to obtain PVP/Urea spinning precursor solution. And (3) carrying out electrostatic spinning at 90 ℃, wherein the spinning voltage is 60kV, the spinning distance is 15cm, and a layer of aluminum foil is paved on a receiving device to serve as a receiving plate. The resulting polymer nanofibers were placed in a tube furnace and subjected to the following fiber stabilization and carbonization processes: raising the temperature from room temperature to 250 ℃ at a heating rate of 5 ℃/min, and preserving the heat for 2 hours; then under the protection of argon atmosphere, the temperature is raised to 450 ℃ at the same temperature raising rate, the heat is preserved for 2 hours, and finally the nitrogen doped carbon nanofiber ozone catalyst is obtained after cooling to room temperature under the protection of argon atmosphere, wherein the N doping amount is about 16.7%.
Example 6
100g of polyethylene oxide (PEO) and 2g of Urea (Urea) were dissolved in water to prepare a 10wt% aqueous solution as an electrospinning precursor solution, and the precursor solution was stirred at 60℃for 4 hours to obtain a PEO/Urea spinning precursor solution. And (3) carrying out electrostatic spinning at 90 ℃, wherein the spinning voltage is 65kV, the spinning distance is 14cm, and a layer of aluminum foil is paved on a receiving device to serve as a receiving plate. The resulting polymer nanofibers were placed in a tube furnace and subjected to the following fiber stabilization and carbonization processes: raising the temperature from room temperature to 250 ℃ at a heating rate of 5 ℃/min, and preserving the temperature for 3 hours; then under the protection of argon atmosphere, the temperature is raised to 450 ℃ at the same temperature raising rate, the heat is preserved for 2 hours, and finally the nitrogen doped carbon nanofiber ozone catalyst is obtained after cooling to room temperature under the protection of argon atmosphere, wherein the N doping amount is about 1.7%.
The nitrogen-doped carbon nanofiber ozone catalysts prepared in examples 1-6 were similar in XPS spectra (fig. 1), C and N element EDS spectra (fig. 2) and morphology structures (fig. 3-5), and the main difference was in the doping amount of nitrogen element, which resulted in different catalytic activities.
Comparative example 1
100g of polyvinyl alcohol (PVA) is dissolved in water to prepare 10wt% aqueous solution serving as electrostatic spinning precursor solution, and the precursor solution is stirred for 4 hours at 60 ℃ to obtain the PVA spinning precursor solution. And (3) carrying out electrostatic spinning at 110 ℃, wherein the spinning voltage is 60kV, the spinning distance is 15cm, and a layer of aluminum foil is paved on a receiving device to serve as a receiving plate. The resulting polymer nanofibers were placed in a tube furnace and subjected to the following fiber stabilization and carbonization processes: raising the temperature from room temperature to 250 ℃ at a heating rate of 5 ℃/min, and preserving the heat for 2 hours; then under the protection of argon atmosphere, the temperature is raised to 450 ℃ at the same temperature raising rate, the heat is preserved for 2 hours, and finally the carbon nanofiber ozone catalyst is obtained after cooling to room temperature under the protection of argon atmosphere.
Industrial wastewater degradation test:
the nitrogen-doped carbon nanofiber ozone catalysts prepared in examples 1 to 6, the nitrogen-free carbon nanofiber ozone catalyst prepared in comparative example 1 and the commercial alumina-supported copper ozone catalyst (supported metal copper ion 0.5%) purchased were respectively packed with the same specification and 50ml of the effective volume of the ozone oxidation reactor. Printing and dyeing wastewater (COD) of certain enterprises under the same process conditions Cr 180-243 mg/L), the ozone adding amount is 40mg/L, and the hydraulic retention time is 30min. The results of the ozone catalytic oxidation effect evaluation are compared with those shown in Table 1.
Table 1 ozone catalyst treatment effect evaluation table
As can be seen from Table 1, the nitrogen-free carbon nanofiber also has certain catalytic activity, the activation of the nitrogen-doped carbon nanofiber catalyst to ozone is obviously enhanced, and COD in the sewage can be obviously improved by ozone Cr Is effective in (1). Meanwhile, the ozone catalytic effect of the nitrogen-doped carbon nanofiber catalysts prepared in examples 1 to 6 is obviously better than that of commercial ozone catalysts, and the nitrogen-doped carbon nanofiber ozone catalysts can enable COD Cr The COD is reduced to below 30mg/L Cr The relative removal rate can reach more than 85 percent.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and all technical solutions belonging to the concept of the present invention belong to the protection scope of the present invention. It should be noted that modifications and adaptations to the invention without departing from the principles thereof are intended to be within the scope of the invention as set forth in the following claims.
Claims (7)
1. The nitrogen-doped carbon nanofiber ozone catalyst is characterized in that the ozone catalyst is prepared by taking one or more of polyvinyl alcohol, polyvinylpyrrolidone or polyethylene oxide as a carbon source and urea as a nitrogen source through the processes of precursor solution preparation, electrostatic spinning, fiber stabilization and high-temperature carbonization, and the mass fraction of nitrogen element in the ozone catalyst is 0.1-25%.
2. The preparation method of the nitrogen-doped carbon nanofiber ozone catalyst is characterized by comprising the following steps of:
step one, preparing a precursor solution:
dispersing a water-soluble polymer and urea in water to form a precursor solution for electrostatic spinning, wherein the water-soluble polymer is one or more of polyvinyl alcohol, polyvinylpyrrolidone or polyethylene oxide;
step two, electrostatic spinning:
carrying out electrostatic spinning on the precursor solution obtained in the step one at 80-120 ℃, and receiving polymer nanofibers by using aluminum foil as a receiving plate;
step three, stabilizing the fiber:
placing the polymer nanofiber obtained in the second step into a tube furnace for carbonization, and promoting the stabilization of the polymer nanofiber to obtain a stabilized fiber;
step four, high-temperature carbonization:
and (3) under the protection of argon atmosphere, carbonizing the stable fiber obtained in the step (III) at high temperature by using a tube furnace to obtain the nitrogen-doped carbon nanofiber.
3. The method for preparing the nitrogen-doped carbon nanofiber ozone catalyst according to claim 2, wherein,
in the first step, the water-soluble polymer and urea are stirred for 4 hours at 60 ℃ in the water dispersing process.
4. The method for preparing the nitrogen-doped carbon nanofiber ozone catalyst according to claim 2, wherein,
in the second step, the parameters of the electrostatic spinning are as follows: the spinning voltage is 50-70 kV, and the spinning distance is 10-20 cm.
5. The method for preparing the nitrogen-doped carbon nanofiber ozone catalyst according to claim 2, wherein,
in the third step, the carbonization conditions are as follows: heating rate is 5 ℃/min, carbonization temperature is 250 ℃, and heat preservation time is 2-3 h.
6. The method for preparing the nitrogen-doped carbon nanofiber ozone catalyst according to claim 2, wherein,
in the fourth step, the carbonization conditions are as follows: heating rate is 5 ℃/min, carbonization temperature is 450 ℃, and heat preservation time is 1-3 h.
7. The nitrogen-doped carbon nanofiber ozone catalyst of claim 1The use of a chemical agent for treating industrial waste water, characterized in that the COD of said industrial waste water Cr The residence time in the catalyst layer is 20-80 min at 60-800 mg/L.
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