CN109967078A - A kind of preparation method of the carbon nanotube base gas catalysis film of morphology controllable - Google Patents
A kind of preparation method of the carbon nanotube base gas catalysis film of morphology controllable Download PDFInfo
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- CN109967078A CN109967078A CN201910233008.5A CN201910233008A CN109967078A CN 109967078 A CN109967078 A CN 109967078A CN 201910233008 A CN201910233008 A CN 201910233008A CN 109967078 A CN109967078 A CN 109967078A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 56
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000002238 carbon nanotube film Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 19
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 10
- 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 10
- 238000000151 deposition Methods 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- BGOFCVIGEYGEOF-UJPOAAIJSA-N helicin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=CC=C1C=O BGOFCVIGEYGEOF-UJPOAAIJSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- -1 manganese dioxide metal oxide Chemical class 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 23
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 238000004506 ultrasonic cleaning Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 230000004907 flux Effects 0.000 description 16
- 238000001237 Raman spectrum Methods 0.000 description 10
- 229960004756 ethanol Drugs 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 229930040373 Paraformaldehyde Natural products 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 239000002048 multi walled nanotube Substances 0.000 description 5
- 229920002866 paraformaldehyde Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 208000030090 Acute Disease Diseases 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 208000017667 Chronic Disease Diseases 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
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- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
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- B01J35/59—
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- 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
- B01J37/06—Washing
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- 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
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- 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
- B01J37/34—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
-
- 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
- B01J37/34—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
- B01J37/347—Ionic or cathodic spraying; Electric discharge
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Abstract
The invention discloses a kind of preparation methods of the carbon nanotube base gas catalysis film of morphology controllable.Ultrasonic cleaning processing is carried out to porous supporting body diaphragm first；Supporter is placed in reactor again, the carbon nano-tube film of different-shape is prepared by the modes of emplacement of the reaction condition and supporter of changing chemical vapor deposition；Atomic layer deposition method supporting catalytic active component over the carbon nanotube film is finally used, catalytic membrane can be prepared.Present invention process is simple and practical, at low cost, pollution-free, carbon nanotube can be realized in target substrate growth position, itself morphology controllable by changing preparation condition.Prepared catalytic membrane can synchronize separation and the catalytic degradation realized to gas pollutant, have good industrial application prospect.
Description
Technical field
The invention belongs to catalytic membrane preparation technical field, the carbon nanotube base gas catalysis film of specially a kind of morphology controllable
Preparation method.
Background technique
One of the main reason for volatile organic matter refers to the organic matter that can be volatilized at normal temperatures and pressures, is air pollution.
Chemical catalysis is mainly used for the improvement of volatile organic matter at present, chemical catalysis refers to through suitable catalyst, will
Volatile organic matter is degraded by catalytic to nontoxic carbon dioxide and water, and catalytic effect is best with noble metal platinum, palladium etc., but noble metal
Catalyst higher cost, therefore often catalyst is supported on the carrier of large specific surface area, by noble metal in carrier surface
High dispersive reduces use cost.And carbon nanotube is then because its good chemical stability and big specific surface area are widely used as carrying
Body loads all kinds of catalyst.
Fine particle PM2.5 refers to particulate matter of the aerodynamics equivalent diameter less than or equal to 2.5 μm in surrounding air.
Medical research clearly indicates that is exposed under PM2.5 environment a variety of acute and chronic diseases that can cause including cardiovascular disease for a long time
Disease.Administering method for fine particle in air is mainly membrane separation process.In recent years, ceramic membrane is because of its special porous structure
With good mechanical performance, and it is widely used in gas solid separation field, but ceramic membrane is because of the limitation of its manufacturing process, it is difficult to prepare
Lesser pore structure out, and carbon nanotube is because of its biggish draw ratio, can be interweaved networking, and be exploited for preparation with
Porous ceramics is the composite membrane of supporter, carbon nanotube as duct and surface modification.
Chemical vapour deposition technique is to be easy to be mass produced carbon nanotube and a kind of lower-cost technology, while chemical gas
Phase sedimentation process conditions are simple, can preferably control the pattern of carbon nanotube by changing different conditional parameters, make carbon
Nanotube has different use advantages: when the carbon nanotube such as aligned is used as film, gas flux is big, it is ensured that filtering
When low pressure drop；The carbon nanotube of netted intertexture can guarantee lesser aperture, improve the efficiency of filtering；Spiral helicine carbon is received
Mitron large specific surface area when as carrier, can provide more adsorption sites for catalyst, improve catalytic efficiency.
Based on the market demand of air pollution treatment material, using the ceramic membrane of porous structure as supporter, in its surface system
The carbon nanotube of standby different-shape out, regulates and controls membrane material pore structure, increases the specific surface area of supporter, then on the carbon nanotubes into
The load of row catalyst can prepare the efficient gas purification membrane with catalysis, separation function.The catalytic membrane material can synchronize
The efficiently gas pollutants such as removal PM2.5, catalytic degradation formaldehyde, toluene.
Summary of the invention
It is simple, at low cost, practical based on pattern that the problem to be solved by the invention is to provide a kind of operating procedures
The preparation method of controllable carbon nanotube gas catalytic membrane.
The invention is realized by the following technical scheme:
A kind of preparation method of the carbon nanotube base gas catalysis film of morphology controllable, includes the following steps:
(1) pretreatment of supporter: being put into ultrasonic cleaning 10-20 min in ethyl alcohol for supporter, removes supporter sintering preparation
Impurity in the process, in an oven with 70-90 DEG C of baking 1-2 h；
(2) ferrocene ethanol solution is prepared, ultrasonic mixing is formed uniformly reaction solution；
(3) step (1) treated supporter is selected suitable modes of emplacement: supporter is parallel to reactor radial cross-section
It puts in the reactor or supporter is placed in the reactor perpendicular to reactor radial cross-section, inlet and outlet washer sealing,
It is passed through protective gas, is kept the temperature after being warming up to 800-900 DEG C of reaction temperature with the speed of 5-8 DEG C/min；
(4) prepared reaction solution in appropriate step (2) is drawn with syringe, be fixed on syringe propeller, setting promotes
Speed, it is ensured that reaction solution at the uniform velocity injects in the reactor in tube furnace；
(5) reacted under the protective atmosphere of certain gas velocity: gas velocity is in 0.9-1.5 cm/s, 1.5-9 cm/s 9-15 cm/s
It is optional within the scope of three, isothermal reaction 2-4 h is maintained, after reaction cooled to room temperature, takes out growth carbon nanotube
Supporter；
(6) supporter of step (5) is put into beaker, is that 10-15 % dust technology is cleaned by ultrasonic 20-40 with mass fraction
Min, then with cleaning in deionized water to drying after neutrality.
(7) carbon nano-tube film of step (6) is placed in apparatus for atomic layer deposition, the depositing catalytic at 200-280 DEG C
Active component deposits 40-60 circulation.
It is preferred:
In step (1), the support body is sheet-like porous material, such as alumina ceramic plate, silicon carbide ceramics diaphragm, porous metals
Piece etc., the aperture of supporter are 10-50 μm.
In step (2), the ferrocene ethanol solution concentration is 0.05-0.12 mol/L；Ultrasonic power is 100-300
W, ultrasonic time are 10-20 min.
In step (3), the protective gas is high-purity argon gas or high pure nitrogen, and gas velocity is 6-9 cm/s.
In step (4), the load responsive fluid that syringe is drawn is 40-50 mL, and fltting speed is 0.5-2.0 mm/min；Even
15 s circulation of pausing after continuous injection or 2 s of every injection is injected.
In step (5), the protective gas gas velocity selection should follow following principle: prepare the carbon nanotube aligned
Film, gas velocity should select 0.9-1.5 cm/s, guarantee directed flow of the carbon source under gas effect, carbon source generates and deposition velocity connects
Nearly balance；The carbon nano-tube film of netted intertexture is prepared, gas velocity should select 1.5-9 cm/s, guarantee stream of the carbon source under gas effect
Dynamic speed realizes the high yield of deposition in a lower range；Spiral helicine carbon nano-tube film is prepared, gas velocity should select 9-15
Cm/s, guarantee carbon source gas flow process in, carbon source generate be higher than deposition velocity.
Drying temperature is 70-90 DEG C in step (6), dries 2-3h.
In step (7), catalytic active component is precious metals pt, Pd, Ag or nickel oxide, manganese dioxide metal oxide.
Beneficial effects of the present invention:
Present invention process is simple and practical, at low cost, pollution-free, and the modes of emplacement by changing reaction condition and supporter can be to carbon
Pattern, the growth position of nanotube realize control.Prepared catalytic membrane can be widely applied to gas pollutant administer and purification,
The fields such as catalyst carrier, have a good application prospect.
Detailed description of the invention
Fig. 1 is the electron microscope of the carbon nano-tube film of different-shape in embodiment 1-3；(a) carbon nano-tube film aligned
(b) the spiral helicine carbon nano-tube film of the carbon nano-tube film (c) of netted intertexture.
Fig. 2 is carbon nano-tube film in embodiment 1 for the retention datagram of PM2.5.
Specific embodiment
The present invention is done below with reference to embodiment and is further explained.The following example is merely to illustrate the present invention, but
It is not used to limit practical range of the invention.
Embodiment 1
It is cleaned by ultrasonic 10 min with 100 W power for being put into dehydrated alcohol with a thickness of the silicon carbide supporter of 3 mm, then exists
1 h is dried at 80 DEG C；100 ml of ferrocene ethanol solution of 0.05 mol/L is prepared, keeps it mixed with 100 30 min of W power ultrasound
It closes uniform；Reactor is placed on by reactor radial cross-section is parallel to graphite gasket sealing before and after treated silicon carbide
In, using tetrafluoro washer as sealing ring, the flange of reactor inlet, outlet is tightened, argon gas is passed through；Argon gas gas velocity is 7.5 cm/s,
It is kept the temperature after rising to 800 DEG C with 5 DEG C/min；Change argon gas gas velocity is 0.9 cm/s, and syringe draws above-mentioned prepared 40 mL
Reaction solution is that 0.5 mm/min is injected into reactor with fltting speed, stops heat preservation after 2 h of isothermal reaction；It is naturally cooling to room
Temperature closes argon gas and tube furnace power supply, takes out the silicon carbide for growing the carbon nanotube aligned；It puts it into flask,
Be added mass fraction be 10% dilute nitric acid solution, be cleaned by ultrasonic 20 min, then in deionized water rinse after be put into baking oven
80 DEG C of 2 h of baking, then by treated, carbon nanotube/silicon carbide film is placed in apparatus for atomic layer deposition, deposits 60 at 200 DEG C
Catalytic membrane can be obtained in secondary carried metal palladium (carbon nanotube is to align).Through scanning electron microscope, Raman spectrum, thermogravimetric characterization
, the carbon nanotube of the growing oriented arrangement of silicon carbide, distribution is more uniform, and it is intensive or local local anomaly do not occur
Non-growing phenomenon forms 10 μm of carbon nanotube pipe range；Raman spectrum is in 1580 cm-1With 1355 cm-1Locate the strong peak occurred
The carbon nanotube for showing preparation is multi-walled carbon nanotube, and by the test of air flux and aperture, discovery growth carbon nanometer
Guan Qian, about 30 μm of the average pore size of silicon carbide ceramics supporter, air flux is 800 m3/m2HKPa grows rear supports
Aperture be about 11 μm, air flux be 450 m3/m2HKPa, catalytic membrane have PM2.5 the rejection of 95 % or more,
The catalytic effect of PARA FORMALDEHYDE PRILLS(91,95) at room temperature is up to 60 %, and toluene catalytically effect is up to 50 %.
Embodiment 2
It is cleaned by ultrasonic 10 min with 200 W power for being put into dehydrated alcohol with a thickness of the sheet-shaped silicon carbide supporter of 4 mm, then
1.5 h are dried at a temperature of 70 DEG C；80 ml of ferrocene ethanol solution of 0.06 mol/L is prepared, with 200 W power ultrasounds 20
Min is uniformly mixed it；Treated supporter is put in the reactor perpendicular to reactor radial cross-section, with tetrafluoro
Washer is sealing ring, tightens the flange of reactor inlet, outlet, is passed through high pure nitrogen；Nitrogen gas velocity be 9 cm/s, with 6 DEG C/
Min speed is kept the temperature after being warming up to 850 DEG C；Change nitrogen gas velocity is 4.5 cm/s, and above-mentioned prepared 50 mL reaction solution is even
In speed injection reactor, fltting speed is 1.5 mm/min, stops heat preservation after 3 h of isothermal reaction；Cooled to room temperature is closed
Nitrogen and tube furnace power supply, the silicon carbide film after taking out reaction；It puts it into flask, dilute nitre that mass fraction is 10 % is added
Acid solution is cleaned by ultrasonic 30 min, dries 2.5 h after then being rinsed with deionized water at 75 DEG C again, then will treated silicon carbide
Film is placed in apparatus for atomic layer deposition, and 50 loaded metal platinums are deposited at 280 DEG C, and catalytic membrane can be obtained, and (carbon nanotube is
Netted intertexture).It is characterized through scanning electron microscope, Raman spectrum, thermogravimetric, silicon carbide ceramics supporting body surface grows the carbon of netted intertexture
Nanotube also has in duct the carbon nanotube of curling to occur, and Raman spectrum is in 1580 cm-1With 1355 cm-1Locate the strong peak occurred
The carbon nanotube for showing preparation is multi-walled carbon nanotube, and by the test of air flux and aperture, discovery growth carbon nanometer
Guan Qian, about 26 μm of the average pore size of silicon carbide supporter, air flux is 680 m3/m2HKPa, reaction back aperture is about 7 μ
M, air flux are 250 m3/m2HKPa, catalytic membrane have PM2.5 the rejection of 98 % or more, and PARA FORMALDEHYDE PRILLS(91,95) is at room temperature
Catalytic effect up to 55 % or more, toluene catalytically effect is up to 60 %.
Embodiment 3
It is cleaned by ultrasonic 10 min with 300 W power for being put into dehydrated alcohol with a thickness of the tabular alumina supporter of 3 mm, then
1 h is dried with 90 DEG C of baking ovens；60 ml of ferrocene ethanol solution of 0.09 mol/L is prepared, with 100 30 min of W power ultrasound
It is uniformly mixed it；0.1 g ferrocene powder coating is weighed again in oxidation aluminium surface, and it is flat that a graphite gasket is put before aluminium oxide
Row is put in the reactor in reactor radial cross-section, using tetrafluoro washer as sealing ring, tightens the method for reactor inlet, outlet
Orchid is passed through high pure nitrogen, and nitrogen gas velocity is 6 cm/s, keeps the temperature after being warming up to 900 DEG C with 6 DEG C/min speed；Change nitrogen gas
Speed is 15 cm/s, and syringe is drawn 50 mL mixed solutions and at the uniform velocity injected in reactor, and fltting speed is 2.0 mm/min, every note
15 s that pause, circulation injection are penetrated after 2 s；Stop heating after 4 h of isothermal reaction；Cooled to room temperature closes nitrogen and tubular type
Furnace power supply takes out the pellumina of growth carbon nanotube after reaction；It puts it into flask, it is 10.5 %'s that mass fraction, which is added,
Dilute nitric acid solution is cleaned by ultrasonic 40 min, dries 2 h after then being rinsed with ionized water in 90 DEG C of baking ovens, then pellumina is placed on
In apparatus for atomic layer deposition, 60 carried metal Ag are deposited at 250 DEG C to get to catalytic membrane (carbon nanotube is helical form).
It is characterized through scanning electron microscope, Raman spectrum, thermogravimetric, alumina ceramic supporting body surface grows spiral helicine carbon nanotube, hole
The carbon nanotube of intertexture is grown in road, Raman spectrum is in 1580 cm-1With 1355 cm-1The Qiang Fengjun that place occurs shows preparation
Carbon nanotube be multi-walled carbon nanotube, and by air flux and aperture test, discovery growth carbon nanotube before, aluminium oxide
About 15 μm of the average pore size of ceramic supporting body, air flux is 300 m3/m2HKPa, the aperture for growing rear supports is about 4
μm, air flux is 90 m3/m2HKPa, catalytic membrane have PM2.5 the rejection of 99 % or more, and PARA FORMALDEHYDE PRILLS(91,95) is at room temperature
Catalytic effect up to 55 % or more, toluene catalytically effect is up to 46 %.
Embodiment 4
It is cleaned by ultrasonic 20 min with 100 W power for being put into dehydrated alcohol with a thickness of the tabular alumina supporter of 3 mm, then
1 h is dried with 85 DEG C of baking ovens；50 ml of ferrocene ethanol solution of 0.1 mol/L is prepared, is made with 100 30 min of W power ultrasound
It is uniformly mixed and reaction solution is made；Aluminium oxide is put in the reactor perpendicular to reactor radial cross-section, is close with tetrafluoro washer
The flange of reactor inlet, outlet is tightened in seal, is passed through high pure nitrogen, nitrogen gas velocity is 9 cm/s, with 8 DEG C/min speed liter
Temperature is to keeping the temperature after 850 DEG C；Change nitrogen gas velocity is 4.5 cm/s, and syringe draws 50 mL mixed solutions and at the uniform velocity injects reactor
Interior, fltting speed is 2.0 mm/min；Stop heating after 3 h of isothermal reaction；Cooled to room temperature closes nitrogen and tube furnace
Power supply takes out the pellumina of growth carbon nanotube after reaction；It puts it into flask, dilute nitre that mass fraction is 10 % is added
Acid solution is cleaned by ultrasonic 30 min, dries 2 h after then being rinsed with ionized water in 90 DEG C of baking ovens, then pellumina is placed on atom
In layer precipitation equipment, 60 load nickel oxide are deposited at 200 DEG C to get catalytic membrane is arrived (carbon nanotube is netted intertexture).Through
Scanning electron microscope, Raman spectrum, thermogravimetric characterize, and alumina ceramic supporting body surface grows spiral helicine carbon nanotube, duct
In grow the carbon nanotube of intertexture, Raman spectrum is in 1580 cm-1With 1355 cm-1The Qiang Fengjun that place occurs shows preparation
Carbon nanotube is multi-walled carbon nanotube, and by the test of air flux and aperture, before discovery grows carbon nanotube, aluminium oxide pottery
About 12 μm of the average pore size of porcelain supporter, air flux is 280 m3/m2HKPa, the aperture for growing rear supports is about 3 μ
M, air flux are 90 m3/m2HKPa, catalytic membrane have PM2.5 the rejection of 99 % or more, and PARA FORMALDEHYDE PRILLS(91,95) is at room temperature
Catalytic effect up to 30 % or more, toluene catalytically effect is up to 28 %.
Embodiment 5
It is cleaned by ultrasonic 10 min with 100 W power for being put into dehydrated alcohol with a thickness of the sheet-shaped silicon carbide supporter of 3 mm, so
2 h are dried at 80 DEG C afterwards；40 ml of ferrocene ethanol solution of 0.12 mol/L is prepared, is made with 100 30 min of W power ultrasound
It is uniformly mixed and reaction solution is made；It is radial horizontal by reactor is parallel to graphite gasket sealing before and after treated silicon carbide
Section is put in the reactor, using tetrafluoro washer as sealing ring, is tightened the flange of reactor inlet, outlet, is passed through argon gas；Argon gas gas
Speed is 7.5 cm/s, is kept the temperature after rising to 800 DEG C with 5 DEG C/min；Change argon gas gas velocity is 0.9 cm/s, will be above-mentioned prepared
40 mL reaction solutions are 0.5 mm/min injection such as in reactor with fltting speed, stop heat preservation after 2 h of isothermal reaction；Naturally it drops
It warms to room temperature, closes argon gas and tube furnace power supply, take out the silicon carbide for growing the carbon nanotube aligned；Put it into burning
Bottle in, be added mass fraction be 15 % dilute nitric acid solution, be cleaned by ultrasonic 30 min, then in deionized water rinse after be put into
70 DEG C of 3 h of baking in baking oven, then carbon nanotube/silicon carbide film is placed in apparatus for atomic layer deposition by treated, at 220 DEG C
It deposits 60 load manganese dioxide, catalytic membrane can be obtained (carbon nanotube is to align).Through scanning electron microscope, Raman spectrum,
Thermogravimetric characterizes, the carbon nanotube of the growing oriented arrangement of silicon carbide, and distribution is more uniform, and it is intensive local anomaly do not occur
Or the non-growing phenomenon in part, form 10 μm of carbon nanotube pipe range；Raman spectrum is in 1580 cm-1With 1355 cm-1Locate
Existing Qiang Fengjun shows that the carbon nanotube of preparation is multi-walled carbon nanotube, and by the test of air flux and aperture, discovery life
Before long carbon nanotube, about 30 μm of the average pore size of silicon carbide ceramics supporter, air flux is 800 m3/m2HKPa, growth
The aperture of rear supports is about 11 μm, and air flux is 450 m3/m2HKPa, catalytic membrane have 95 % or more for PM2.5
Rejection, the catalytic effect of PARA FORMALDEHYDE PRILLS(91,95) at room temperature is up to 20 %, and toluene catalytically effect is up to 20 %.
Claims (8)
1. a kind of preparation method of the carbon nanotube base gas catalysis film of morphology controllable, which comprises the steps of:
(1) pretreatment of supporter: supporter being put into ethyl alcohol and is cleaned by ultrasonic 10-20min, is removed supporter sintering and was prepared
Impurity in journey, in an oven with 70-90 DEG C of baking 1-2h；
(2) ferrocene ethanol solution is prepared, ultrasonic mixing is formed uniformly reaction solution；
(3) step (1) treated supporter is selected suitable modes of emplacement: supporter is parallel to reactor radial cross-section and puts
In the reactor or supporter is placed in the reactor perpendicular to reactor radial cross-section, and inlet and outlet washer sealing leads to
Enter protective gas, is kept the temperature after being warming up to 800-900 DEG C of reaction temperature with the speed of 5-8 DEG C/min；
(4) prepared reaction solution in appropriate step (2) is drawn with syringe, be fixed on syringe propeller, setting promotes
Speed, it is ensured that reaction solution at the uniform velocity injects in the reactor in tube furnace；
(5) it is reacted under the protective atmosphere of certain gas velocity: maintaining isothermal reaction 2-4 h, naturally cool to after reaction
Room temperature takes out the supporter of growth carbon nanotube；
(6) supporter of step (5) is put into beaker, is that 10-15 % dust technology is cleaned by ultrasonic 20-40 with mass fraction
Min, then with cleaning in deionized water to drying after neutrality；
(7) carbon nano-tube film of step (6) is placed in apparatus for atomic layer deposition, depositing catalytic is living at 200-280 DEG C
Property component, deposition 40-60 time recycle.
2. a kind of preparation method of the carbon nanotube base gas catalysis film of morphology controllable according to claim 1, feature
It is, in step (1), the support body is sheet-like porous material, such as alumina ceramic plate, silicon carbide ceramics diaphragm, porous gold
Belong to piece etc., the aperture of supporter is 10-50 μm.
3. a kind of preparation method of the carbon nanotube base gas catalysis film of morphology controllable according to claim 1, feature
It is, in step (2), the ferrocene ethanol solution concentration is 0.05-0.12 mol/L；Ultrasonic power is 100-300 W,
Ultrasonic time is 10-20 min.
4. a kind of preparation method of the carbon nanotube base gas catalysis film of morphology controllable according to claim 1, feature
It is, in step (3), the protective gas is high-purity argon gas or high pure nitrogen, and gas velocity is 6-9 cm/s.
5. a kind of preparation method of the carbon nanotube base gas catalysis film of morphology controllable according to claim 1, feature
It is, in step (4), the load responsive fluid that syringe is drawn is 40-50 mL, and fltting speed is 0.5-2.0 mm/min；Continuous note
Penetrate or 2 s of every injection after pause 15 s circulation injection.
6. a kind of preparation method of the carbon nanotube base gas catalysis film of morphology controllable according to claim 1, feature
It is, in step (5), the protective gas gas velocity selection follows following principle: preparing the carbon nano-tube film aligned, gas
Speed is 0.9-1.5 cm/s, guarantees directed flow of the carbon source under gas effect, carbon source generation and deposition velocity close to balance；System
The carbon nano-tube film of standby netted intertexture, gas velocity are 1.5-9 cm/s, guarantee flowing velocity of the carbon source under gas effect at one
In lower range, the high yield of deposition is realized；Spiral helicine carbon nano-tube film is prepared, gas velocity is 9-15 cm/s, guarantees carbon source gas
Flow process in, carbon source generate be higher than deposition velocity.
7. a kind of preparation method of the carbon nanotube base gas catalysis film of morphology controllable according to claim 1, feature
It is, drying temperature is 70-90 DEG C in step (6), dries 2-3h.
8. a kind of preparation method of the carbon nanotube base gas catalysis film of morphology controllable according to claim 1, feature
It is, in step (7), catalytic active component is precious metals pt, Pd, Ag or nickel oxide, manganese dioxide metal oxide.
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