CN109967078B - Preparation method of morphology-controllable carbon nanotube-based gas catalytic membrane - Google Patents
Preparation method of morphology-controllable carbon nanotube-based gas catalytic membrane Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 62
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 62
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 45
- 239000012528 membrane Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
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- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 5
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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Abstract
The invention discloses a preparation method of a carbon nanotube-based gas catalytic membrane with controllable morphology. Firstly, carrying out ultrasonic cleaning treatment on a porous support body membrane; then placing the support body in a reactor, and preparing carbon nanotube films with different appearances by changing the reaction conditions of chemical vapor deposition and the placing mode of the support body; and finally, loading a catalytic active component on the carbon nanotube film by adopting an atomic layer deposition method, thus preparing the catalytic film. The method has the advantages of simple and practical process, low cost and no pollution, and can realize the growth position of the carbon nano tube on the target base material and the controllable appearance by changing the preparation conditions. The prepared catalytic membrane can synchronously realize the separation and catalytic degradation of gas pollutants and has good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of catalytic membrane preparation, and particularly relates to a preparation method of a carbon nanotube-based gas catalytic membrane with controllable morphology.
Background
Volatile organic compounds generally refer to organic compounds that can be volatilized at normal temperature and pressure, and are one of the main causes of air pollution. At present, a chemical catalysis method is mainly adopted for treating volatile organic compounds, wherein the chemical catalysis method is to catalyze and degrade the volatile organic compounds into nontoxic carbon dioxide and water through a proper catalyst, the catalytic effect is best by noble metals such as platinum and palladium, but the noble metal catalyst is high in cost, so that the catalyst is usually loaded on a carrier with a large specific surface area, and the use cost is reduced through high dispersion of the noble metals on the surface of the carrier. Carbon nanotubes are widely used as carriers to load various catalysts due to their good chemical stability and large specific surface area.
The fine particulate matter PM2.5 refers to particulate matter with an aerodynamic equivalent diameter of 2.5 μm or less in the ambient air. Medical studies have clearly shown that prolonged exposure to PM2.5 can cause a variety of acute and chronic diseases including cardiovascular disease. The treatment method for fine particles in the air is mainly a membrane separation method. In recent years, ceramic membranes have been widely used in the field of gas-solid separation due to their special porous structure and good mechanical properties, but due to the limitations of the manufacturing process of ceramic membranes, it is difficult to produce a small pore structure, and carbon nanotubes can be interlaced into a network due to their large aspect ratio, and have been developed for the production of composite membranes having porous ceramic as a support, carbon nanotubes as channels, and surface modification.
The chemical vapor deposition method is a technology which is easy to produce carbon nanotubes on a large scale and has lower cost, meanwhile, the chemical vapor deposition method has simple process conditions, and can better control the appearance of the carbon nanotubes by changing different condition parameters, so that the carbon nanotubes have different use advantages: for example, when the carbon nano tubes in the directional arrangement are used as the membrane, the gas flux is large, and the low pressure drop during the filtration can be ensured; the net-shaped interlaced carbon nano tubes can ensure smaller aperture and improve the filtration efficiency; the spiral carbon nano tube has large specific surface area, and can provide more adsorption sites for the catalyst when being used as a carrier, thereby improving the catalytic efficiency.
Based on the market demand of air pollution treatment materials, a ceramic membrane with a porous structure is used as a support body, carbon nano tubes with different morphologies are prepared on the surface of the ceramic membrane, the pore structure of the membrane material is regulated and controlled, the specific surface area of the support body is increased, and then a catalyst is loaded on the carbon nano tubes, so that the high-efficiency gas purification membrane with the functions of catalysis and separation can be prepared. The catalytic membrane material can synchronously and efficiently remove PM2.5 and catalytically degrade gas pollutants such as formaldehyde, toluene and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon nano tube gas catalytic membrane based on controllable morphology, which has the advantages of simple operation steps, low cost and strong practicability.
The invention is realized by the following technical scheme:
a preparation method of a morphology-controllable carbon nanotube-based gas catalytic membrane comprises the following steps:
(1) pretreatment of the support body: putting the support body into ethanol, ultrasonically cleaning for 10-20min, removing impurities in the sintering preparation process of the support body, and drying in an oven at 70-90 ℃ for 1-2 h;
(2) preparing a ferrocene ethanol solution, and uniformly mixing by ultrasonic to form a reaction solution;
(3) the support body processed in the step (1) is placed in a reactor in a mode of being parallel to the radial cross section of the reactor, or the support body is placed in the reactor in a mode of being perpendicular to the radial cross section of the reactor, an inlet and an outlet are sealed by gaskets, protective gas is introduced, the temperature is raised to the reaction temperature of 800-;
(4) sucking a proper amount of the reaction liquid prepared in the step (2) by using an injector, fixing the reaction liquid on an injector propeller, and setting the propelling speed to ensure that the reaction liquid is injected into a reactor in the tubular furnace at a constant speed;
(5) the reaction is carried out under a protective atmosphere with a certain gas velocity: the gas velocity is selectable in three ranges of 0.9-1.5 cm/s and 1.5-9 cm/s, 9-15 cm/s, the constant temperature reaction is maintained for 2-4 h, the support body for growing the carbon nano tube is taken out after the reaction is finished and naturally cooled to the room temperature;
(6) and (4) putting the support body obtained in the step (5) into a beaker, ultrasonically cleaning the support body for 20-40 min by using dilute nitric acid with the mass fraction of 10-15%, then cleaning the support body in deionized water to be neutral, and drying the support body.
(7) And (4) placing the carbon nanotube film obtained in the step (6) in an atomic layer deposition device, and depositing the catalytic active component at the temperature of 200-280 ℃ for 40-60 cycles.
Preferably:
in the step (1), the support body is a sheet-shaped porous material, such as an alumina ceramic sheet, a silicon carbide ceramic membrane, a porous metal sheet and the like, and the aperture of the support body is 10-50 μm.
In the step (2), the concentration of the ferrocene ethanol solution is 0.05-0.12 mol/L; the ultrasonic power is 100-300W, and the ultrasonic time is 10-20 min.
In the step (3), the protective gas is high-purity argon or high-purity nitrogen, and the gas speed is 6-9 cm/s.
In the step (4), the reaction liquid amount sucked by the injector is 40-50 mL, and the propelling speed is 0.5-2.0 mm/min; continuous injection, or 2 s post injection each time with 15 s pause in circulation.
In the step (5), the gas speed of the protective gas is selected according to the following principle: preparing the carbon nanotube film in the oriented arrangement, wherein the gas velocity is selected to be 0.9-1.5 cm/s, so that the oriented flow of the carbon source under the action of gas is ensured, and the carbon source generation and deposition speeds are approximately balanced; preparing a reticular interlaced carbon nanotube film, wherein the gas speed is selected to be 1.5-9 cm/s, the flow speed of a carbon source under the action of gas is ensured to be in a lower range, and the high yield of deposition is realized; the gas velocity should be selected from 9-15 cm/s to prepare the spiral carbon nanotube film, and the carbon source generation is higher than the deposition velocity in the flowing process of the carbon source gas.
In the step (6), the drying temperature is 70-90 ℃, and the drying is carried out for 2-3 h.
In the step (7), the catalytic active component is noble metal Pt, Pd, Ag, or nickel oxide, manganese dioxide metal oxide.
The invention has the beneficial effects that:
the method has the advantages of simple and practical process, low cost and no pollution, and can control the appearance and the growth position of the carbon nano tube by changing the reaction conditions and the placing mode of the support body. The prepared catalytic membrane can be widely applied to the fields of gas pollutant treatment and purification, catalyst carriers and the like, and has good application prospect.
Drawings
FIG. 1 is an electron microscope image of carbon nanotube films of different morphologies in examples 1-3; (a) a carbon nanotube film (b) in which carbon nanotubes are aligned, a carbon nanotube film (c) in which carbon nanotubes are interlaced in a network shape, and a carbon nanotube film in a spiral shape.
Fig. 2 is a graph of the retention data for PM2.5 for the carbon nanotube film of example 1.
Detailed Description
The present invention will be further explained with reference to examples. The following examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1
Putting the silicon carbide support body with the thickness of 3 mm into absolute ethyl alcohol, ultrasonically cleaning the silicon carbide support body for 10 min by using 100W power, and then drying the silicon carbide support body for 1 h at the temperature of 80 ℃; preparing 100 ml of 0.05 mol/L ferrocene ethanol solution, and carrying out ultrasonic treatment for 30 min at 100W power to uniformly mix the solution; sealing the front and back parts of the treated silicon carbide by using a graphite gasket, placing the silicon carbide in the reactor in parallel to the radial cross section of the reactor, screwing flanges of an air inlet and an air outlet of the reactor by using a tetrafluoro gasket as a sealing ring, and introducing argon; the argon gas speed is 7.5 cm/s, the temperature is raised to 800 ℃ at 5 ℃/min, and then the temperature is kept; changing the gas velocity of argon gas to be 0.9 cm/s, sucking the prepared 40 mL reaction liquid by an injector, injecting the reaction liquid into a reactor at a propelling speed of 0.5 mm/min, reacting at constant temperature for 2h, and stopping heat preservation; naturally cooling to room temperature, closing argon and a tube furnace power supply, and taking out the silicon carbide growing into the directionally arranged carbon nano tubes; placing the carbon nano tube/silicon carbide film into a flask, adding a dilute nitric acid solution with the mass fraction of 10%, ultrasonically cleaning for 20min, washing with deionized water, placing into an oven to be dried for 2h at the temperature of 80 ℃, placing the treated carbon nano tube/silicon carbide film into an atomic layer deposition device, and depositing for 60 times at the temperature of 200 ℃ to loadPalladium metal, and obtaining the catalytic membrane (the carbon nano tubes are in directional arrangement). The carbon nano tubes which are directionally arranged grow on the surface of the silicon carbide and are distributed uniformly without the phenomenon of local abnormal density or local non-growth to form the carbon nano tube with the length of 10 mu m; raman spectrum at 1580 cm-1And 1355 cm-1The strong peaks show that the prepared carbon nano tube is a multi-wall carbon nano tube, and through the test of gas flux and aperture, the average aperture of the silicon carbide ceramic support body is about 30 mu m before the carbon nano tube grows, and the gas flux is 800 m3/m2H KPa, pore size of support after growth about 11 μm, gas flux 450 m3/m2h.KPa, the catalytic membrane has a retention rate of more than 95% for PM2.5, the catalytic effect on formaldehyde at room temperature can reach 60%, and the catalytic effect on toluene can reach 50%.
Example 2
Putting a 4 mm-thick sheet-shaped silicon carbide support body into absolute ethyl alcohol, ultrasonically cleaning for 10 min by 200W power, and drying at the temperature of 70 ℃ for 1.5 h; preparing 80 ml of 0.06 mol/L ferrocene ethanol solution, and carrying out ultrasonic treatment for 20min at 200W power to uniformly mix the solution; placing the treated support body in a reactor perpendicular to the radial cross section of the reactor, screwing flanges of an air inlet and an air outlet of the reactor by taking a tetrafluoro gasket as a sealing ring, and introducing high-purity nitrogen; the nitrogen gas speed is 9 cm/s, the temperature is raised to 850 ℃ at the speed of 6 ℃/min, and then the temperature is preserved; changing the nitrogen gas speed to 4.5 cm/s, injecting the prepared 50 mL of reaction liquid into a reactor at a constant speed, wherein the propelling speed is 1.5 mm/min, reacting at constant temperature for 3h, and stopping heat preservation; naturally cooling to room temperature, closing the nitrogen and the power supply of the tube furnace, and taking out the silicon carbide film after reaction; putting the silicon carbide film into a flask, adding a dilute nitric acid solution with the mass fraction of 10%, ultrasonically cleaning for 30 min, then washing with deionized water, drying at 75 ℃ for 2.5 h, then putting the treated silicon carbide film into an atomic layer deposition device, and depositing the loaded metal platinum for 50 times at 280 ℃ to obtain the catalytic film (the carbon nano tubes are meshed and interwoven). The surface of the silicon carbide ceramic support grows net-shaped interwoven carbon nano tubes which are obtained by scanning electron microscope, Raman spectrum and thermal weight characterization, and the pore channels also growThe coiled carbon nano-tube appears, and the Raman spectrum is 1580 cm-1And 1355 cm-1The strong peaks show that the prepared carbon nano tube is a multi-wall carbon nano tube, and through the test of gas flux and aperture, the average aperture of the silicon carbide support body is about 26 mu m before the carbon nano tube grows, and the gas flux is 680 m3/m2h.KPa, pore size after reaction of about 7 μm, gas flux of 250 m3/m2h.KPa, the catalytic membrane has a retention rate of more than 98% for PM2.5, a catalytic effect on formaldehyde at room temperature can reach more than 55%, and a catalytic effect on toluene can reach 60%.
Example 3
Putting a sheet-shaped alumina support body with the thickness of 3 mm into absolute ethyl alcohol, ultrasonically cleaning for 10 min by 300W power, and drying for 1 h by a drying oven at the temperature of 90 ℃; 60 ml of 0.09 mol/L ferrocene ethanol solution is prepared and is uniformly mixed by ultrasonic treatment for 30 min with 100W power; weighing 0.1 g of ferrocene powder, coating the ferrocene powder on the surface of alumina, placing a graphite gasket in front of the alumina, placing the graphite gasket in the reactor in parallel to the radial cross section of the reactor, screwing flanges of an air inlet and an air outlet of the reactor by taking a tetrafluoro gasket as a sealing ring, introducing high-purity nitrogen at the nitrogen gas speed of 6 cm/s, heating to 900 ℃ at the speed of 6 ℃/min, and then preserving heat; changing the nitrogen gas speed to 15 cm/s, sucking 50 mL of mixed solution by an injector, injecting the mixed solution into the reactor at a constant speed, wherein the propelling speed is 2.0 mm/min, stopping for 15 s after each injection for 2 s, and performing circular injection; reacting at constant temperature for 4 h, and stopping heating; naturally cooling to room temperature, closing the nitrogen and the power supply of the tube furnace, and taking out the alumina film for growing the carbon nano tube after reaction; putting the catalytic membrane into a flask, adding a dilute nitric acid solution with the mass fraction of 10.5%, ultrasonically cleaning for 40 min, then washing with ionized water, drying in an oven at 90 ℃ for 2h, then putting an aluminum oxide membrane into an atomic layer deposition device, and depositing the loaded metal Ag for 60 times at 250 ℃ to obtain the catalytic membrane (the carbon nano tube is spiral). Scanning electron microscope, Raman spectrum, and thermal mass spectrum, wherein helical carbon nanotubes are grown on the surface of the alumina ceramic support, and interlaced carbon nanotubes are grown in the pore channels, and the Raman spectrum is 1580 cm-1And 1355 cm-1The strong peaks show that the prepared carbon nano-tube is a multi-wall carbon nano-tube, andand through the test of gas flux and aperture, the average aperture of the alumina ceramic support is about 15 μm and the gas flux is 300 m before the carbon nano tube grows3/m2H KPa, pore size of support after growth of about 4 μm, gas flux of 90 m3/m2h.KPa, the catalytic membrane has a retention rate of more than 99% for PM2.5, a catalytic effect on formaldehyde at room temperature can reach more than 55%, and a catalytic effect on toluene can reach 46%.
Example 4
Putting a sheet-shaped alumina support body with the thickness of 3 mm into absolute ethyl alcohol, ultrasonically cleaning the support body for 20min by using 100W power, and drying the support body for 1 h by using an oven at the temperature of 85 ℃; 50 ml of 0.1 mol/L ferrocene ethanol solution is prepared and is subjected to ultrasonic treatment for 30 min at the power of 100W to be uniformly mixed to prepare reaction liquid; placing alumina in a reactor perpendicular to the radial cross section of the reactor, screwing flanges of an air inlet and an air outlet of the reactor by taking a tetrafluoro gasket as a sealing ring, introducing high-purity nitrogen at the speed of 9 cm/s, heating to 850 ℃ at the speed of 8 ℃/min, and then preserving heat; changing the nitrogen gas speed to 4.5 cm/s, sucking 50 mL of mixed solution by an injector, and injecting the mixed solution into the reactor at a constant speed, wherein the propelling speed is 2.0 mm/min; after reacting for 3 hours at constant temperature, stopping heating; naturally cooling to room temperature, closing the nitrogen and the power supply of the tube furnace, and taking out the alumina film for growing the carbon nano tube after reaction; putting the catalytic membrane into a flask, adding a dilute nitric acid solution with the mass fraction of 10%, ultrasonically cleaning for 30 min, then washing with ionized water, drying in an oven at 90 ℃ for 2h, then putting an aluminum oxide membrane into an atomic layer deposition device, and depositing the nickel oxide load for 60 times at 200 ℃ to obtain the catalytic membrane (the carbon nano tubes are meshed and interwoven). Scanning electron microscope, Raman spectrum, and thermal mass spectrum, wherein helical carbon nanotubes are grown on the surface of the alumina ceramic support, and interlaced carbon nanotubes are grown in the pore channels, and the Raman spectrum is 1580 cm-1And 1355 cm-1The strong peaks show that the prepared carbon nano tube is a multi-wall carbon nano tube, and through the test of gas flux and aperture, the average aperture of the alumina ceramic support body is about 12 mu m before the carbon nano tube grows, and the gas flux is 280 m3/m2H KPa, pore size of support after growth about 3 μm, gas flux 90 m3/m2h.KPa, the catalytic membrane has a retention rate of more than 99% for PM2.5, the catalytic effect on formaldehyde at room temperature can reach more than 30%, and the catalytic effect on toluene can reach 28%.
Example 5
Putting a sheet-shaped silicon carbide support body with the thickness of 3 mm into absolute ethyl alcohol, ultrasonically cleaning the sheet-shaped silicon carbide support body for 10 min by using 100W power, and then drying the sheet-shaped silicon carbide support body for 2h at 80 ℃; 40 ml of 0.12 mol/L ferrocene ethanol solution is prepared and is subjected to ultrasonic treatment for 30 min at the power of 100W to be uniformly mixed to prepare reaction liquid; sealing the front and back parts of the treated silicon carbide by using a graphite gasket, placing the silicon carbide in the reactor in parallel to the radial cross section of the reactor, screwing flanges of an air inlet and an air outlet of the reactor by using a tetrafluoro gasket as a sealing ring, and introducing argon; the argon gas speed is 7.5 cm/s, the temperature is raised to 800 ℃ at 5 ℃/min, and then the temperature is kept; changing the gas velocity of argon gas to be 0.9 cm/s, injecting the prepared 40 mL reaction solution into a reactor at the propelling speed of 0.5 mm/min, reacting at constant temperature for 2h, and stopping heat preservation; naturally cooling to room temperature, closing argon and a tube furnace power supply, and taking out the silicon carbide growing into the directionally arranged carbon nano tubes; putting the carbon nano tube/silicon carbide film into a flask, adding a dilute nitric acid solution with the mass fraction of 15%, ultrasonically cleaning for 30 min, washing with deionized water, putting the washed carbon nano tube/silicon carbide film into an oven, drying for 3h at 70 ℃, putting the treated carbon nano tube/silicon carbide film into an atomic layer deposition device, and depositing manganese dioxide load for 60 times at 220 ℃ to obtain the catalytic film (the carbon nano tubes are in directional arrangement). The carbon nano tubes which are directionally arranged grow on the surface of the silicon carbide and are distributed uniformly without the phenomenon of local abnormal density or local non-growth to form the carbon nano tube with the length of 10 mu m; raman spectrum at 1580 cm-1And 1355 cm-1The strong peaks show that the prepared carbon nano tube is a multi-wall carbon nano tube, and through the test of gas flux and aperture, the average aperture of the silicon carbide ceramic support body is about 30 mu m before the carbon nano tube grows, and the gas flux is 800 m3/m2H KPa, pore size of support after growth about 11 μm, gas flux 450 m3/m2h.KPa, the catalytic film has a retention rate of more than 95% for PM2.5, the catalytic effect on formaldehyde at room temperature can reach 20%, and tolueneThe catalytic effect can reach 20%.
Claims (5)
1. A preparation method of a morphology-controllable carbon nanotube-based gas catalytic membrane is characterized by comprising the following steps:
(1) pretreatment of the support body: putting the support body into ethanol, ultrasonically cleaning for 10-20min, removing impurities in the sintering preparation process of the support body, and drying in an oven at 70-90 ℃ for 1-2 h; the support body is a sheet-shaped porous material and is selected from an alumina ceramic sheet, a silicon carbide ceramic membrane and a porous metal sheet, and the aperture of the support body is 10-50 mu m;
(2) preparing a ferrocene ethanol solution, and uniformly mixing by ultrasonic to form a reaction solution;
(3) selecting a proper placing mode for the support body treated in the step (1): the support body is placed in the reactor in parallel with the radial cross section of the reactor, or the support body is placed in the reactor in perpendicular to the radial cross section of the reactor, the inlet and the outlet are sealed by gaskets, protective gas is introduced, the temperature is raised to the reaction temperature of 800-900 ℃ at the speed of 5-8 ℃/min, and then the temperature is preserved; the protective gas is high-purity argon or high-purity nitrogen, and the gas speed is 6-9 cm/s;
(4) sucking a proper amount of the reaction liquid prepared in the step (2) by using an injector, fixing the reaction liquid on an injector propeller, and setting the propelling speed to ensure that the reaction liquid is injected into a reactor in the tubular furnace at a constant speed; stopping the circulation injection for 15 s after each injection for 2 s;
(5) the reaction is carried out under a protective atmosphere with a certain gas velocity: maintaining constant temperature reaction for 2-4 h, naturally cooling to room temperature after the reaction is finished, and taking out the support body for growing the carbon nano tube; the selection of the protective gas speed follows the following principle: preparing a carbon nanotube film in an oriented arrangement, wherein the gas velocity is 0.9-1.5 cm/s, so that the oriented flow of a carbon source under the action of gas is ensured, and the carbon source generation and deposition speeds are close to balance; preparing a reticular interlaced carbon nanotube film, wherein the gas velocity is 1.5-9 cm/s, the flow velocity of a carbon source under the action of gas is ensured to be in a lower range, and the high yield of deposition is realized; preparing a spiral carbon nanotube film, wherein the gas velocity is 9-15 cm/s, and the carbon source generation is higher than the deposition velocity in the flowing process of the carbon source gas;
(6) putting the support body obtained in the step (5) into a beaker, ultrasonically cleaning the support body for 20-40 min by using dilute nitric acid with the mass fraction of 10-15%, then cleaning the support body to be neutral by using deionized water, and drying the support body;
(7) placing the carbon nanotube film obtained in the step (6) in an atomic layer deposition device, depositing catalytic active components at the temperature of 200-280 ℃, and performing deposition for 40-60 times of circulation; the catalytic active component is noble metal Pt or Pd, or nickel oxide, manganese dioxide.
2. The method for preparing a morphology-controllable carbon nanotube-based gas catalytic membrane according to claim 1, wherein in the step (2), the concentration of the ferrocene ethanol solution is 0.05-0.12 mol/L; the ultrasonic power is 100-300W, and the ultrasonic time is 10-20 min.
3. The method for preparing a morphology-controllable carbon nanotube-based gas catalytic membrane according to claim 1, wherein in the step (4), the amount of the reaction solution sucked by the injector is 40-50 mL, and the propelling speed is 0.5-2.0 mm/min; continuous injection.
4. The preparation method of the morphology-controllable carbon nanotube-based gas catalytic membrane according to claim 1, wherein the drying temperature in the step (6) is 70-90 ℃ and the drying time is 2-3 h.
5. The method for preparing a morphology-controllable carbon nanotube-based gas-catalyzed film according to claim 1, wherein in the step (7), the catalytically active component is Ag.
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