CN1702202A - Active carbon fiber containing nano titanium dioxide particles and its preparation method and uses - Google Patents
Active carbon fiber containing nano titanium dioxide particles and its preparation method and uses Download PDFInfo
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- CN1702202A CN1702202A CN 200510035311 CN200510035311A CN1702202A CN 1702202 A CN1702202 A CN 1702202A CN 200510035311 CN200510035311 CN 200510035311 CN 200510035311 A CN200510035311 A CN 200510035311A CN 1702202 A CN1702202 A CN 1702202A
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- activated carbon
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002245 particle Substances 0.000 title claims abstract description 57
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims description 39
- 238000002360 preparation method Methods 0.000 title claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 title description 7
- 239000004917 carbon fiber Substances 0.000 title description 6
- 239000000835 fiber Substances 0.000 claims abstract description 16
- 239000002657 fibrous material Substances 0.000 claims abstract description 12
- 238000003980 solgel method Methods 0.000 claims abstract description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000005416 organic matter Substances 0.000 claims description 11
- 230000001699 photocatalysis Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000007146 photocatalysis Methods 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 244000198134 Agave sisalana Species 0.000 claims description 3
- 229920000297 Rayon Polymers 0.000 claims description 3
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 229960002380 dibutyl phthalate Drugs 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 48
- 239000000356 contaminant Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract 2
- 238000002835 absorbance Methods 0.000 abstract 1
- 238000000137 annealing Methods 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 150000003609 titanium compounds Chemical class 0.000 abstract 1
- 230000001131 transforming effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 239000004408 titanium dioxide Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- -1 titanium dioxide activated carbon fiber Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002156 adsorbate Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Abstract
This invention relates to a method for preparing an activated carbon fiber of Titania particle having nanometer and its usage. The fiber is formed from the activated carbon fiber material loaded with the Titania particles, wherein the mass ratio of the Titania particles is 5~25%. The preparing method uses the sol-gel processing: a) hydrolyzing organic titanium compounds of the TiO2 to the TiO2 collosol, and depositing on the activated carbon fiber, b) drying the colloslo and getting the jel, c) annealing, and transforming to nanometer TiO2 particles compounded in the surface of the fiber, then getting the fiber. The fiber not only maintains the poriness but also enhances the optical catalytic activity of the Titania particle, and can be used for removing the volatile organic contaminant with low concentration, wherein its absorbance can reach to 500mg/g and its optical catalytic dissolution rate can reach to 36%.
Description
Technical field
The present invention relates to a kind of activated carbon fiber that contains nano titanium dioxide particles and preparation method thereof, and this activated carbon fiber that contains nano titanium dioxide particles is used for the purposes of purifying volatile organic pollution.
Background technology
Activated carbon fiber has abundant microporous and high specific area, and its adsorption capacity is higher than other porous adsorbing materials such as polymeric adsorbent, zeolite, silica gel etc. far away; Also more much better than its like product activated carbon.Activated carbon fiber is bigger several times even tens times than granular activated charcoal to the adsorbance of organic steam; And because activated carbon fiber and the strong active force of adsorbate, its micropore directly contacts with adsorbate, has reduced the distance of diffusion.The absorption of activated carbon fiber and gas can reach balance in tens of seconds to several minutes; Activated carbon fiber has very strong interaction force to organic matter, can adsorb the organic pollution of removing ppm, ppb level and even lower concentration.At present, this class material has been applied to the purified treatment to volatile organic matter (VOC).But, the complexity of technological design and the complexity of use have been increased owing to after the saturated absorption of activated carbon fiber, must carry out desorption and regeneration and could continue to use.By the structural change to sorbing material, the realization original position is regenerated in real time, is to improve material to the processing of VOC and the effective way of transformation efficiency.
TiO
2Photochemical catalyst has such as the advantage that photoetch does not take place after the illumination, resistance to acids and bases is good, chemical property is stable, the source is abundant, is current a kind of photochemical catalyst that application potential is arranged most.Find n-type semiconductor TiO first from Fujishima in 1972 etc.
2Electrode has had since the photoelectrocatalysis effect, and its range of application expands to the environmental protection field by the exploitation (as solar cell) and the energy storage (as the photodissociation of water) of new forms of energy.Because TiO
2The photochemical catalytic oxidation organic pollution aspect the processing of low-concentration organic waste water and organic exhaust gas, has wide practical use effectively.Photocatalysis technology based on titanium dioxide semiconductor also exists some critical technical problems to fail to solve at present, makes it be subjected to very big restriction in commercial Application.For example, suspended state TiO
2There is easily shortcoming such as cohesion and difficult recovery, brought certain difficulty etc. to practical application, and had secondary pollution problem.
Summary of the invention
The object of the present invention is to provide a kind of activated carbon fiber that contains nano titanium dioxide particles, the preparation of loaded with nano fine particulate titanium dioxide contains the method for the activated carbon fiber of nano titanium dioxide particles on activated carbon fiber material, and this activated carbon fiber that contains nano titanium dioxide particles is used for the purposes of purifying volatile organic pollution.
The activated carbon fiber that contains nano titanium dioxide particles of the present invention had both kept the porous of activated carbon fiber, strengthened the titanium dioxide fine particles photocatalytic activity again, can be used for the removal of light-concentration volatile organic pollution, be particularly useful for the absorption and the decomposition of volatile organic contaminant in the little space.
The activated carbon fiber that the present invention contains nano titanium dioxide particles is to be formed by nano titanium dioxide particles in the activated carbon fiber material load, and wherein nano titanium dioxide particles accounts for 5～25% of gross mass.
Described activated carbon fiber material can be to be formed through the high temperature cabonization activation by sisal fiber, pitch fibers, viscose, PVA fiber or PAN fiber.
The contained nano titanium dioxide particles of activated carbon fiber that contains nano titanium dioxide particles of the present invention can prepare by sol-gel process, and loads on the activated carbon fiber material.
The activated carbon fiber that the present invention contains nano titanium dioxide particles can prepare by the following method:
Activated carbon fiber material be impregnated in butyl titanate and the normal propyl alcohol mixed solution, and sonic oscillation or fully stirring make the abundant and solution impregnation of activated carbon fiber material, add entry then and make the butyl titanate hydrolysis produce TiO
2Sol deposition is on activated carbon fiber; Wherein, Butyl Phthalate: water: normal propyl alcohol: carbon fiber=1: (0.2～10): (2～10): (0.05～5) mass ratio; Reacted product removes through evaporation or 90～100 ℃ of oven dry and anhydrates and organic solvent, makes the TiO on activated carbon fiber surface
2The colloidal sol polycondensation becomes gel, then with the deposition of gained TiO
2The activated carbon fiber of gel is removed remaining organic matter and is made TiO at 450～850 ℃ of sintering temperatures
2Crystalline form changes, and obtains the required activated carbon fiber that contains nano titanium dioxide particles.
The present invention utilizes the high-specific surface area and the abundant nano-pore structure of activated carbon fiber, by sol-gel process (sol-gel) technology, with TiO
2The presoma organic titanic compound generate TiO through hydrolysis
2 Colloidal solAnd be deposited on the carrier active carbon fiber, further polycondensation obtains TiO
2Gel makes TiO through heat treatment (sintering) then
2 GelBe converted into nano-TiO
2Particulate is compounded in the surface of activated carbon fiber, and the nano titanium dioxide particles that makes load on the activated carbon fiber is with Detitanium-ore-type TiO
2Be main, prepare ACF-TiO
2Composite---contain the activated carbon fiber of nano titanium dioxide particles.This composite had both kept the porous of activated carbon fiber, had strengthened the titanium dioxide fine particles photocatalytic activity again, and the excellent adsorption capacity that can utilize activated carbon fiber is utilized TiO then with the VOC enrichment
2With its photodegradative synergy, maximize favourable factors and minimize unfavourable ones, overcome TiO
2The recombination rate in the light induced electron-hole of catalysis material, expansion TiO
2Semi-conductive sunshine utilizes scope, solves suspended state TiO
2Easily cohesion, the difficult shortcoming that reclaims.
Evidence, the activated carbon fiber that contains nano titanium dioxide particles of the present invention can reach more than the 500mg/g the adsorption capacity of volatile organic contaminant, can reach 36% to the photocatalysis Decomposition rate of volatile organic contaminant.
Therefore, the activated carbon fiber that contains nano titanium dioxide particles of the present invention can be used for the material as the airborne low concentration volatile organic matter of photocatalysis Decomposition.
When activated carbon fiber of the present invention is used to adsorb the decomposing volatile organic pollution, be that the gas that will contain volatile organic matter (VOC) contains the annular fixed bed of the activated carbon fiber of nano titanium dioxide particles by the above, and under ultra violet lamp, the gas that contains VOC is fully contacted with the activated carbon fiber of load nano-titanium dioxide particulate, can be with the VOC catalytic decomposition.
The activated carbon fiber that contains nano titanium dioxide particles of the present invention is carried out under dynamic condition the adsorption capacity of volatile organic contaminant and the mensuration of photocatalysis Decomposition efficient.The gas that contains volatile organic matter that makes certain humidity according to exit concentration, is estimated adsorption capacity or the decomposition efficiency of activated carbon fiber to volatile organic matter by the above-mentioned activated carbon fiber fixed bed that contains nano titanium dioxide particles.
Description of drawings
Fig. 1 is the sem photograph that contains the activated carbon fiber sample of nano titanium dioxide particles, shows the nano titania sized particles of activated carbon fiber surface dense distribution, and particle is ball-shaped, and diameter is about 10nm.
Fig. 2 is the transmission electron microscope picture of sample, shows the nano titania size crystal grain of activated carbon fiber surface dense distribution, and size is about about 10nm.
Fig. 3 is the x-ray diffraction pattern of powder that contains the activated carbon fiber of nano titanium dioxide particles.Titanium dioxide on its diffraction pattern announcement activated carbon fiber is based on the anatase titanium dioxide crystal formation.
The specific embodiment
Embodiment 1
Butyl titanate is mixed by 1: 3 mass ratio with normal propyl alcohol, after fully mixing, the sisal based activated carbon fiber that adds 0.5 part of quality behind the dipping 0.5h, adds the water of 10 parts of quality, after the hydrolysis fully solvent and water evaporation are removed, take out fiber, in 90 ℃ of oven dry, with after 500 ℃ of sintering, obtain the carried titanium dioxide activated carbon fiber, wherein nano titanium dioxide particles accounts for 5% of gross mass.Product is through scanning electron microscope analysis, and its surperficial carbon-coating is inlayed uniform spherical particle thing, about particle particle diameter 10nm.This particle proves the anatase titanium dioxide crystal through the X-ray diffraction analysis.
Embodiment 2
Butyl titanate is mixed by 1: 6: 0.1 mass ratio with normal propyl alcohol and viscose-based active carbon fiber, after fully mixing, the water that adds 10 parts of quality makes the butyl titanate hydrolysis, under the low pressure solvent and water evaporation are removed then, take out fiber, in 90 ℃ of oven dry, with after 850 ℃ of sintering, obtain the carried titanium dioxide activated carbon fiber, wherein nano titanium dioxide particles accounts for 25% of gross mass.Product is through scanning electron microscope analysis, and its surperficial carbon-coating is inlayed intensive particle, about particle particle diameter 200nm.This particle proves the anatase titanium dioxide crystal through the X-ray diffraction analysis.
Embodiment 3
Butyl titanate is mixed by 1: 7: 0.1 mass ratio with normal propyl alcohol and asphalt based active carbon fiber, after sonic oscillation mixes, the water that adds 2 parts of quality makes the butyl titanate hydrolysis, fiber is in 100 ℃ of oven dry, with after 500 ℃ of sintering, obtain the carried titanium dioxide activated carbon fiber, wherein nano titanium dioxide particles accounts for 20% of gross mass.Product is through scanning electron microscope analysis, and its surperficial carbon-coating is inlayed intensive particle, about particle particle diameter 10nm.This particle proves the anatase titanium dioxide crystal through the X-ray diffraction analysis.Without the activated carbon fiber of carried titanium dioxide and through TiO
2The pore structure of the activated carbon fiber of load comparison shows that, specific area, total pore volume and micropore average diameter after activated carbon fiber-loaded are all than slightly reducing before the load.
Embodiment 4
Butyl titanate is mixed by 1: 10: 0.1 mass ratio with normal propyl alcohol and PAN based active carbon fiber, after sonic oscillation mixes, the water that adds 2 parts of quality makes the butyl titanate hydrolysis, fiber is in 100 ℃ of oven dry, with after 500 ℃ of sintering, obtain the carried titanium dioxide activated carbon fiber, wherein nano titanium dioxide particles accounts for 15% of gross mass.Product is through scanning electron microscope analysis, and its surperficial carbon-coating is inlayed intensive particle.This particle proves the anatase titanium dioxide crystal through the X-ray diffraction analysis.X-ray analysis and transmission electron microscope analysis show that all crystal grain diameter is about 20nm.
Embodiment 5
The gas that will contain the volatile organic gas toluene vapor is the fixed bed of the activated carbon fiber of the activated carbon fiber by carried titanium dioxide not and load anatase titanium dioxide nano particle respectively.Gas flow rate is 400mL/min, and the inlet toluene concentration is 2.0mg/L, relative humidity 55%.Absorption is carried out at ambient temperature, and being adsorbed on does not have under the light conditions, and the activated carbon fiber of carried titanium dioxide does not penetrate when 1500min, and activated carbon fiber is 500mg/g to the adsorption capacity of toluene; The activated carbon fibrous composite of load anatase titanium dioxide nano particle penetrates when 450min, and composite is 500mg/g to the adsorption capacity of toluene.
Embodiment 6
To contain the fixed bed of the gas of volatile organic gas toluene vapor by the activated carbon fiber of load anatase titanium dioxide nano particle.Gas flow rate is 400mL/min, and the inlet toluene concentration is 1.5mg/L, relative humidity 55%.Absorption is carried out at ambient temperature.Do not having under the light conditions, the outlet toluene concentration is 4 μ g/L; Under the UV-irradiation situation, the outlet toluene concentration is 0.4 μ g/L.Show that this material has strong catalytic decomposition ability to toluene, the photocatalysis Decomposition rate of toluene is 90% under this condition.
Embodiment 7
To contain the fixed bed of the gas of volatile organic gas toluene vapor by the activated carbon fiber of load 20wt% titania nanoparticles.Gas flow rate is 250mL/min, and the inlet toluene concentration is 3.0mg/L, relative humidity 55%.Absorption is carried out at ambient temperature.By containing the gas of toluene, absorption is reached capacity continuously, exit concentration equals entrance concentration.Open then at UV-irradiation and cause photocatalysis, recording the outlet toluene concentration is 1.8mg/L.The photocatalysis Decomposition rate of toluene is 10% under this condition.
Claims (6)
1. an activated carbon fiber that contains nano titanium dioxide particles is characterized in that this activated carbon fiber is to be formed by nano titanium dioxide particles in the activated carbon fiber material load, and wherein nano titanium dioxide particles accounts for 5～25% of gross mass.
2. an activated carbon fiber as claimed in claim 1 is characterized in that described activated carbon fiber material is to be formed through the high temperature cabonization activation by sisal fiber, pitch fibers, viscose, PVA fiber or PAN fiber.
3. an activated carbon fiber that contains nano titanium dioxide particles as claimed in claim 1 or 2 is characterized in that described nano titanium dioxide particles is through the sol-gel process preparation, and loads on the activated carbon fiber material.
4. the described preparation method who contains the activated carbon fiber of nano titanium dioxide particles of one of claim 1～3, activated carbon fiber material be impregnated in butyl titanate and the normal propyl alcohol mixed solution, sonic oscillation or fully stirring, make the abundant and solution impregnation of activated carbon fiber material, add entry then and make the butyl titanate hydrolysis produce TiO
2Sol deposition is on activated carbon fiber; Wherein, Butyl Phthalate: water: normal propyl alcohol: activated carbon fiber=1: (0.2～10): (2～10): (0.05～5) mass ratio; Reacted product removes through evaporation or 90～100 ℃ of oven dry and anhydrates and organic solvent, makes the TiO on activated carbon fiber surface
2The colloidal sol polycondensation becomes gel, then with the deposition of gained TiO
2Activated carbon fiber remove remaining organic matter and make TiO at 450～850 ℃ of sintering temperatures
2Crystalline form changes, and obtains the required activated carbon fiber that contains nano titanium dioxide particles.
5. the described activated carbon fiber of nano titanium dioxide particles that contains of one of claim 1～3 is as the application that is used for the material of the airborne low concentration volatile organic matter of photocatalysis Decomposition.
6. according to the described application of claim 5, it is characterized in that to contain the gas of volatile organic matter by the described activated carbon fiber fixed bed that contains nano titanium dioxide particles, and under ultra violet lamp, the gas that contains volatile organic matter is fully contacted with the activated carbon fiber of load nano-titanium dioxide particulate, can be with the VOC catalytic decomposition.
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| CNB2005100353112A CN1303267C (en) | 2005-06-22 | 2005-06-22 | Active carbon fiber containing nano titanium dioxide particles and its preparation method and uses |
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|---|---|---|---|
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| CN1303267C CN1303267C (en) | 2007-03-07 |
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| CN1317069C (en) * | 2005-01-07 | 2007-05-23 | 武汉理工大学 | Prepn process of multilayer porous active compound TiO2 photocatalyst |
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