CN112657493A - Manufacturing method of carbon nanotube film and continuous flow electro-Fenton system based on limited-area catalyst - Google Patents
Manufacturing method of carbon nanotube film and continuous flow electro-Fenton system based on limited-area catalyst Download PDFInfo
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Abstract
The invention provides a method for manufacturing a carbon nanotube film, which comprises the following steps: s1: providing a carbon nano tube, opening or cutting the carbon nano tube after purification, heating and refluxing the carbon nano tube by using nitric acid, and filtering, washing and freeze-drying the carbon nano tube to obtain CNT; s2: mixing Fe (NO)3)3·9H2Dissolving O in acetone, dispersing the treated CNT in the solution, stirring, ultrasonic treating, continuously stirring until acetone is completely volatilized, raising the temperature of the obtained solid to 120-160 ℃ in air, and maintaining for a periodTime, washing with ultrapure water to obtain Fe2O3Composite material with nanoparticles confined in the CNT tube, denoted Fe2O3-in-CNT; s3: mixing 30mg of Fe2O3Dispersing in-CNT into 30-40 ml of ethanol, performing ultrasonic treatment for 30 minutes by using a probe to obtain a uniform dispersion solution, performing vacuum filtration on the obtained dispersion solution to a polytetrafluoroethylene membrane, and cleaning impurities on the surface by using ultrapure water to obtain the carbon nanotube membrane. The preparation method of the carbon nanotube film has high catalytic activity and good stability.
Description
Technical Field
The invention relates to a method for manufacturing a carbon nanotube film.
Background
The conventional electro-Fenton reaction is usually carried out by Fe2+And Fe3+Activation of in situ generated hydrogen peroxide (H) by cycling2O2) Thereby generating strong oxidant hydroxyl radicals (HO.). However, this process is generally associated with a large accumulation of iron sludge due to its low efficiency under neutral conditions. To overcome the limitations of the electro-Fenton system described above, iron-based catalysts are used for H2O2And HO · generation is widely used as an alternative heterogeneous electro-fenton process. However, these catalysts still have some drawbacks, such as: poor stability, reduced activity, etc., due to leaching of the metal catalyst. Therefore, solving these bottleneck problems for better stability, durability and activity has attracted extensive attention of researchers and has become one of the research hotspots in the field of catalysts.
In view of the above, there is a need for an improvement of the existing electro-fenton reaction apparatus to solve the above problems.
Disclosure of Invention
The invention aims to provide a method for manufacturing a carbon nanotube film, which aims to solve the problems of poor stability, reduced activity and the like caused by leaching of the existing metal catalyst.
In order to achieve the above object, the present invention provides a method for manufacturing a carbon nanotube film, including the steps of:
s1: providing a carbon nano tube, opening or cutting the carbon nano tube after purification, heating and refluxing the carbon nano tube by using nitric acid, and filtering, washing and freeze-drying the carbon nano tube to obtain CNT;
s2: mixing Fe (NO)3)3·9H2Dissolving O in acetone, dispersing the treated CNT in the solution, stirring, ultrasonic treating, and continuously stirring until acetone is completely volatilizedThe obtained solid is heated to 120-160 ℃ in the air and kept for a period of time, and is washed by ultrapure water to obtain Fe2O3Composite material with nanoparticles confined in the CNT tube, denoted Fe2O3-in-CNT；
S3: mixing 30mg of Fe2O3Dispersing in-CNT into 30-40 ml of ethanol, performing ultrasonic treatment for 30 minutes by using a probe to obtain a uniform dispersion solution, performing vacuum filtration on the obtained dispersion solution to a polytetrafluoroethylene membrane, and cleaning impurities on the surface by using ultrapure water to obtain the carbon nanotube membrane.
As a further improvement of the invention, the concentration of the nitric acid in the step S1 is 65-68%.
As a further improvement of the present invention, in step S1, the temperature of the heating reflux is 140 ℃ and the treatment time is 10 hours.
As a further improvement of the invention, the solid obtained in step S2 was raised to 140 ℃ in air at a temperature rise rate of 1 ℃/min and held for 10 hours.
The invention also provides another manufacturing method of the carbon nanotube film, which comprises the following steps:
s1: providing a carbon nano tube, opening or cutting the carbon nano tube after purification, heating and refluxing the carbon nano tube by using nitric acid, and filtering, washing and freeze-drying the carbon nano tube to obtain CNT;
s2: refluxing CNT in nitric acid solution at 110 deg.C for a period of time to obtain carbon nanotube with closed end, and using Fe (NO) to treat the carbon nanotube with closed end3)39H 2O/acetone solution, drying or hydrolyzing or heating, washing with ultrapure water to obtain Fe2O3 composite material (expressed as Fe) supported outside the carbon nanotube2O3-out-CNT；
S3: mixing 30mg of Fe2O3And (3) dispersing-out-CNT into 30-40 ml of ethanol, performing ultrasonic treatment for 30 minutes by using a probe to obtain a uniform dispersion solution, performing vacuum filtration on the obtained dispersion solution to a polytetrafluoroethylene membrane, and cleaning impurities on the surface by using ultrapure water to obtain the carbon nanotube membrane.
As a further improvement of the invention, the concentration of the nitric acid in the step S1 is 65-68%.
As a further improvement of the present invention, in step S1, the temperature of the heating reflux is 140 ℃ and the treatment time is 10 hours.
The invention also provides a continuous flow electro-Fenton system based on the limited-area catalyst, which comprises a filter barrel, a water inlet pool connected with the outlet end of the filter barrel, a peristaltic pump connected with the water inlet pool and the inlet end of the filter barrel, the carbon nanotube membrane arranged in the filter barrel according to any one of claims 1-7, and a titanium sheet arranged at the outlet end of the carbon nanotube membrane close to the filter barrel, wherein the titanium sheet is connected with an anode, and the carbon nanotube membrane is connected with a cathode.
As a further improvement of the invention, Na is placed in the water inlet pool2SiO3The solution acts as an electrolyte.
As a further improvement of the invention, the pH value of the solution in the water inlet pool is 3.6-10.4.
The invention has the beneficial effects that: the carbon nano tube of the invention has limited Fe domain2O3The carbon nanotube film prepared by the nano-particle composite material has high catalytic activity and good stability, and solves the problem that the granular catalyst is difficult to recover; the invention relates to a continuous flow electro-Fenton system based on a limited-area catalyst, which uses Na2SiO3As an electrolyte, H generated in situ can be stabilized2O2Improve H2O2Utilization ratio of (2); the unique microenvironment of the carbon nanotube membrane confinement increases the concentration of local reagents, reduces the mass transfer distance from the diffusion of free radicals to target pollutants, enhances the utilization rate of the free radicals, and can realize the efficiency of efficient Fenton-like reaction; the electro-Fenton technology is combined with the membrane separation technology, and the traditional batch reactor is replaced by the continuous flow design, so that the mass transfer effect in the reaction process is enhanced, and the pollutant degradation efficiency is improved.
Drawings
Fig. 1 is a schematic diagram of the structure of a continuous flow electro-fenton system based on a limited-area catalyst according to the present invention;
FIG. 2 is Fe of example 1 of the present invention2O3-transmission electron microscopy of in-CNT composites;
FIG. 3 is the test results of example 2 of the present invention;
FIG. 4 is a graph showing the effect of tetracycline degradation after 5 cycles in two systems according to example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
The invention provides a continuous flow electro-Fenton system 100 based on a limited-area catalyst, which comprises a filter barrel 1, a water inlet pool 2 connected with the outlet end of the filter barrel 1, a peristaltic pump 3 connected with the water inlet pool 2 and the inlet end of the filter barrel 1, a carbon nano tube membrane 4 arranged in the filter barrel 1, and a titanium sheet 5 arranged at the outlet end of the carbon nano tube membrane 4 close to the filter barrel 1.
The titanium sheet 5 is connected with the anode 6, and the carbon nanotube film 4 is connected with the cathode 7. And the anode 6 and the cathode 7 are respectively connected with the titanium sheet 5 and the carbon nanotube film 4 through titanium rods.
In this embodiment, the carbon nanotube film 4 is a functionalized CNT-confined nano Fe2O3The particles have high catalytic activity and stability.
Na is placed in the water inlet pool 22SiO3The solution acts as an electrolyte. The pH value of the solution in the water inlet pool 2 is 3.6-10.4.
In the continuous flow electro-Fenton system 100 based on the limited-area catalyst, the prepared Fe2O3-in-CNT or Fe2O3-out-CNT film as cathode 7, titanium sheet 5 as anode 6, Na is used2SiO3As an electrolyte (about 10mmol), a solution containing tetracycline is filtered through the filtration bucket 1 by a peristaltic pump 3 at a flow rate of 1.5 to 4.5 ml/min. Setting the voltage of an external direct current power supply to be 1.0-3.0V, adjusting the pH value of the solution to be 3.6-10.4, and under the action of the external voltage, oxygen in the solutionThe gas is reduced to H in situ at the cathode 7 membrane2O2The silicate ions present in the solution stabilize H2O2Preventing it from being reduced to H at the cathode 72O, a large amount of H2O2With Fe in the carbon nanotube film 42O3The nano particles generate Fenton reaction, so that a large amount of oxygen active substances are continuously generated, and the high-efficiency removal of organic matters (tetracycline and bisphenol A) in the water body in the filtering process is realized.
Selection of Na2SiO3As electrolyte to stabilize in situ generated H2O2. Due to shortened migration distance of free radicals (Fe)2O3Limited catalyst), H2O2The yield is increased (due to Na)2SiO3The basic role of CNTs and their excellent oxygen reduction reactivity) and mass transfer enhancement (due to the flow structure and limited pore size of the CNT network) improve electro-fenton performance. Under the action of an external electric field, the method not only contributes to the electroreduction of oxygen, but also contributes to Fe3+/Fe2+The cycle of (2). The invention enhances the utilization rate of free radicals, strengthens the mass transfer efficiency by the design of continuous flow, and can realize the efficiency of high-efficiency electro-Fenton reaction.
The invention also provides a manufacturing method of the carbon nanotube film, which comprises the following steps:
s1: providing a carbon nano tube, opening or cutting the carbon nano tube after purification, heating and refluxing the carbon nano tube by using nitric acid, and filtering, washing and freeze-drying the carbon nano tube to obtain CNT;
s2: mixing Fe (NO)3)3·9H2Dissolving O in acetone, dispersing the treated CNT in the solution, stirring, performing ultrasonic treatment, continuously stirring until acetone is completely volatilized, raising the obtained solid to 120-160 ℃ in the air, keeping the temperature for a period of time, and washing with ultrapure water to obtain Fe2O3Composite material with nanoparticles confined in the CNT tube, denoted Fe2O3-in-CNT；
In another embodiment, step S2 may also be:
s2: refluxing CNT in nitric acid solution at 110 deg.C for a period of time to obtain carbon nanotube with closed end, and using Fe (NO) to treat the carbon nanotube with closed end3)3·9H2Soaking in O/acetone solution, drying or hydrolyzing or heating, washing with ultrapure water to obtain Fe loaded outside the carbon nanotube2O3Composite material, expressed as Fe2O3-out-CNT；
S3: mixing 30mg of Fe2O3-in-CNT or 30mg Fe2O3And (3) dispersing-out-CNT into 30-40 ml of ethanol, performing ultrasonic treatment for 30 minutes by using a probe to obtain a uniform dispersion solution, performing vacuum filtration on the obtained dispersion solution to a polytetrafluoroethylene membrane, and cleaning impurities on the surface by using ultrapure water to obtain the carbon nanotube membrane.
The concentration of nitric acid in the step S1 is 65-68%, the heating reflux temperature is 140 ℃, and the treatment time is 10 hours.
The resulting solid was raised to 140 ℃ in air at a heating rate of 1 ℃/min and held for 10 hours in step S2.
Some specific examples are provided below to further illustrate how to prepare the carbon nanotube film 4 and how to use the continuous flow electro-fenton system 100 based on a limited-area catalyst to remove bisphenol a or tetracycline.
Example 1:
fe2O3-method for preparing in-CNT composite films:
s1: providing carbon nanotubes, purifying the carbon nanotubes, mixing 1g of original carbon nanotubes (the average inner diameter is 9-14 nm, the outer diameter is 15-25 nm) with 250ml of concentrated nitric acid (65-68 wt.%), refluxing the mixture in an oil bath at 140 ℃ for 14h, simultaneously performing magnetic stirring to prevent bumping, cooling the mixture, filtering, repeatedly washing the mixture by using deionized water until the pH is neutral, and then performing freeze drying for 12h to mark the mixture as o-CNT for later use.
S2: 43.32mg Fe (NO) are weighed out3)3·9H2Dissolving O in 20ml acetone, adding 200mg O-CNT, stirring the mixed solution on magnetic stirrer for 1h, performing ultrasonic treatment for 2h, and stirring on magnetic stirrerStirring for about 26h until the solution is completely volatilized. Then heating to 140 ℃ in an oven at the heating rate of 1 ℃/min and keeping for 10h to obtain Fe with the load of 3.0 wt%2O3-in-CNT composite as shown in figure 2.
S3: 30mg of Fe are weighed2O3Adding 30ml of ethanol into the in-CNT, performing ultrasonic treatment for 30 minutes by using a probe to disperse the ethanol, and performing vacuum filtration on the obtained dispersion liquid to obtain a polytetrafluoroethylene membrane with the diameter of 47mm to obtain the carbon nanotube membrane.
Example 2:
a method for removing tetracycline using the limited-area catalyst-based continuous flow electro-fenton system 100:
respectively using carbon nanotube membrane 4 as cathode 7, placing in a filter barrel 1, under the action of applied voltage, adopting continuous flow filtration mode, feeding 40 μmol tetracycline-containing wastewater into the filter barrel 1 along the inlet end of the filter barrel 1 at a flow rate of 1.5mL/min by peristaltic pump 3, and passing through carbon nanotube membrane 4(pH 6.8, applied voltage-2.5V, electrolyte solution is 10mmol sodium sulfate (Na) respectively2SO4) And Na2SiO3) Flows out along the outlet end of the filter barrel 1;
the results of the experiments are shown in FIG. 3, in which Na was used separately2SO4And Na2SiO3As an electrolyte, the tetracycline degradation efficiency in the continuous flow electro-Fenton system 100 based on the limited-area catalyst reaches 97.5% and 62.7% respectively. In addition, with Na2SiO3The oxidation rate constant (k) of tetracycline in the case of electrolytesL) Is 1.02h-1Is Na2SO4Is 1.34 times of the electrolyte. It is clear that in these three systems, Na is used2SiO3The degradation efficiency of the tetracycline is obviously improved when the tetracycline is electrolyte. In addition, the oxidation rate constant k of tetracycline in the zone-limited catalyst-based continuous flow electro-Fenton system 100 is determined under the same conditionsLThe value is 1.65 times higher than that of an open system (1.02 h)-1vs.0.62h-1). This is probably due to the shortened diffusion distance of free radicals in the nano-confinement range and the local enrichment of tetracycline concentration. FIG. 4 shows two system internal circulationsThe degradation effect of tetracycline after 5 cycles of ring, it can be seen from the figure that the catalyst in the confined system can maintain effective catalytic performance, which can be attributed to Fe encapsulated in CNT2O3Can act with the carbon shell to reduce the local work function and promote the migration of electrons from carbon to H2O2Thereby forming active oxygen. In return, the graphitic carbon layer can protect Fe2O3Nanoparticles, preventing corrosion thereof and penetration into the reaction solution. After five cycles, the tetracycline degradation efficiency in the open system decreased significantly due to inevitable iron leakage. The results fully prove that the continuous flow electro-Fenton system 100 based on the limited-area catalyst has the advantages of high treatment efficiency, good stability, environmental protection and the like. Compared with the traditional electro-Fenton system, the system has obvious advantages and can be widely applied to sewage treatment.
Example 3:
a method for removing bisphenol a using the limited-area catalyst-based continuous flow electro-fenton system 100:
fe obtained in example 1 was used2O3An in-CNT electroactive filter membrane is used as a cathode 7, is placed in a filter barrel 1 to be used as the cathode 7, and is used for leading the wastewater containing 40 mu mol of bisphenol A to enter the filter barrel 1 along the inlet end of the filter barrel 1 at the flow rate of 1.5mL/min by a peristaltic pump 3 in a continuous flow filtration mode under the action of an applied voltage and to pass through a carbon nanotube membrane 4 (the pH value is 7.0, the applied voltage is-2.5V, and the electrolyte solution is 10mmol of Na2SiO3) Flows out along the outlet end of the filter barrel 1; after 3 hours of reaction, the degradation rate of bisphenol A was 85.7%.
The carbon nano tube of the invention has limited Fe domain2O3The carbon nanotube film 4 is prepared from the nano-particle composite material, the catalyst has high catalytic activity and good stability, and the problem that the granular catalyst is difficult to recover is solved; the continuous flow electro-Fenton system 100 based on the limited-area catalyst uses Na2SiO3As an electrolyte, H generated in situ can be stabilized2O2Improve H2O2Utilization ratio of (2); the unique microenvironment of the carbon nanotube film 4 confinement increases the local reagent concentration,the mass transfer distance from the free radicals to the target pollutants is reduced, the utilization rate of the free radicals is enhanced, and the efficient Fenton-like reaction efficiency can be realized; the electro-Fenton technology is combined with the membrane separation technology, and the traditional batch reactor is replaced by the continuous flow design, so that the mass transfer effect in the reaction process is enhanced, and the pollutant degradation efficiency is improved.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. A method for manufacturing a carbon nanotube film is characterized by comprising the following steps: the manufacturing method of the carbon nanotube film comprises the following steps:
s1: providing a carbon nano tube, opening or cutting the carbon nano tube after purification, heating and refluxing the carbon nano tube by using nitric acid, and filtering, washing and freeze-drying the carbon nano tube to obtain CNT;
s2: mixing Fe (NO)3)3·9H2Dissolving O in acetone, dispersing the treated CNT in the solution, stirring, performing ultrasonic treatment, continuously stirring until acetone is completely volatilized, raising the obtained solid to 120-160 ℃ in the air, keeping the temperature for a period of time, and washing with ultrapure water to obtain Fe2O3Composite material with nanoparticles confined in the CNT tube, denoted Fe2O3-in-CNT；
S3: mixing 30mg of Fe2O3Dispersing in-CNT into 30-40 ml of ethanol, performing ultrasonic treatment for 30 minutes by using a probe to obtain a uniform dispersion solution, performing vacuum filtration on the obtained dispersion solution to a polytetrafluoroethylene membrane, and cleaning impurities on the surface by using ultrapure water to obtain the carbon nanotube membrane.
2. The method of manufacturing a carbon nanotube film according to claim 1, wherein: the concentration of nitric acid in step S1 is 65% to 68%.
3. The method of manufacturing a carbon nanotube film according to claim 1, wherein: in step S1, the temperature of the heating reflux was 140 ℃ and the treatment time was 10 hours.
4. The method of manufacturing a carbon nanotube film according to claim 2, wherein: the resulting solid was raised to 140 ℃ in air at a heating rate of 1 ℃/min and held for 10 hours in step S2.
5. A method for manufacturing a carbon nanotube film is characterized by comprising the following steps: the manufacturing method of the carbon nanotube film comprises the following steps:
s1: providing a carbon nano tube, opening or cutting the carbon nano tube after purification, heating and refluxing the carbon nano tube by using nitric acid, and filtering, washing and freeze-drying the carbon nano tube to obtain CNT;
s2: refluxing CNT in nitric acid solution at 110 deg.C for a period of time to obtain carbon nanotube with closed end, and using Fe (NO) to treat the carbon nanotube with closed end3)39H 2O/acetone solution, drying or hydrolyzing or heating, washing with ultrapure water to obtain Fe2O3 composite material (expressed as Fe) supported outside the carbon nanotube2O3-out-CNT；
S3: mixing 30mg of Fe2O3And (3) dispersing-out-CNT into 30-40 ml of ethanol, performing ultrasonic treatment for 30 minutes by using a probe to obtain a uniform dispersion solution, performing vacuum filtration on the obtained dispersion solution to a polytetrafluoroethylene membrane, and cleaning impurities on the surface by using ultrapure water to obtain the carbon nanotube membrane.
6. The method of manufacturing a carbon nanotube film according to claim 5, wherein: the concentration of nitric acid in step S1 is 65% to 68%.
7. The method of manufacturing a carbon nanotube film according to claim 5, wherein: in step S1, the temperature of the heating reflux was 140 ℃ and the treatment time was 10 hours.
8. The utility model provides a continuous flow electricity fenton system based on limited area catalyst which characterized in that: the continuous flow electro-Fenton system based on the limited area catalyst comprises a filter barrel, a water inlet pool connected with the outlet end of the filter barrel, a peristaltic pump connected with the water inlet pool and the inlet end of the filter barrel, the carbon nanotube membrane arranged in the filter barrel according to any one of claims 1 to 7, and a titanium sheet arranged at the outlet end of the carbon nanotube membrane close to the filter barrel, wherein the titanium sheet is connected with an anode, and the carbon nanotube membrane is connected with a cathode.
9. The field-limited catalyst-based continuous flow electro-Fenton system of claim 8, wherein: na is placed in the water inlet pool2SiO3The solution acts as an electrolyte.
10. The field-limited catalyst-based continuous flow electro-Fenton system of claim 9, wherein: the pH value of the solution in the water inlet pool is 3.6-10.4.
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