CN101428209B - Nano-fibre supported titanium dioxide photocatalyst and preparation method thereof - Google Patents
Nano-fibre supported titanium dioxide photocatalyst and preparation method thereof Download PDFInfo
- Publication number
- CN101428209B CN101428209B CN2007101769942A CN200710176994A CN101428209B CN 101428209 B CN101428209 B CN 101428209B CN 2007101769942 A CN2007101769942 A CN 2007101769942A CN 200710176994 A CN200710176994 A CN 200710176994A CN 101428209 B CN101428209 B CN 101428209B
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- nanofiber
- titanium
- spinning
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention provides a nanofiber load titanium dioxide photocatalyst and a preparation method thereof, which belong to the technical field of preparation of novel nanometer photocatalyst functional materials. The method comprises the following steps: preparing a homogeneous spinning solution with titanium precursor, a hydrolysis inhibitor, a polymer and an organic solvent; carrying out spinning according to a proper electrostatic spinning process to obtain a nanofiber felt/film; introducing hydroxyl groups into electrospun nanofiber, and immersing the electrospun nanofiber in an aqueous solution containing an ammoniation agent, so that hydrolysis and ammoniation reaction of titanium precursor occurs and produces titanium-ammino complex; and carrying out post treatment processes such as baking and the like to obtain the nanofiber load titanium dioxide photocatalyst. The catalyst has excellent photo-catalytic activity in response to ultraviolet light or visible light, and can effectively improve the bonding reliability of titanium dioxide with nanofiber with the help of the action of nitrogen bond.
Description
Technical field
The invention belongs to the preparing technical field of nano-photocatalyst (photocatalyst) functional material, relate to a kind of nano-fibre supported titanium dioxide photocatalyst and preparation method thereof, the catalyst of preparation can be applicable to mineralising and handles poisonous VOC (VOCs) in organic pollution in the water, the oxidative degradation room air, and bacterium and virus harmful in the life are killed in oxidation.
Background technology
Anatase titanium dioxide has excellent photocatalysis activity at ultraviolet region, both can be applied to handle the organic pollution in industrial and the sanitary wastewater and purify water, also can be applied to the pernicious gas in the photocatalytic oxidation degradation room air, even can also be a kind of photochemical catalyst therefore by the bacterium and the virus of strong oxide group (OH) kill harmful that optically catalytic TiO 2 produced with broad prospect of application.But have following two problems in actual applications and restricted the extensive use of titanium dioxide optical catalyst: the energy gap of (1) anatase titanium dioxide is 3.2eV, can only just can have excellent photocatalysis activity under less than the exciting of the ultraviolet light of 380nm at wavelength, yet the content of sunshine medium ultraviolet light only accounts for about 4%, thereby solar energy utilization rate is extremely low; (2) nano TiO 2 powder is in handling the process of liguid phase pollutant, exist adsorption capacity weak, easily reunite inactivation, easily run off and reclaim difficulty, easily precipitate and be difficult to obtain illumination, and because self dispersion causes secondary pollution problems.Therefore, titanium dioxide is carried out modification and load, thereby making it even have photocatalytic activity under the exciting of indoor light source at visible light (account for solar radiation 46%), and eliminate nano-powder and handle the problem that liguid phase pollutant faced, is the research focus of this area.
Aspect modification, at present report to have pair titanium dioxide to carry out nitrogen-doped modified, nitrogen will replace a spot of Lattice Oxygen in the titanium dioxide, N
pEnergy level and O
2pThe hydridization of energy level makes the band gap of titanium dioxide narrow down, thereby the titanium dioxide that nitrogen mixes not only has excellent photocatalysis activity under ultraviolet light, and under visible light, also have original photocatalytic activity (R.Asahi, T.Morikawa, a T.Ohwaki, K.Aoki, Y.Taga, Visible-light photocatalysis in nitrogen-doped titanium oxides, Science, 2001,293:269-271.).Aspect load technology, nano-fiber material is a kind of material with huge specific area and draw ratio, and the surface has and is in metastable surface atom in a large number, thereby can excellent suction-operated be arranged to organic pollution, play the effect of adsorption and enrichment organic pollution, therefore can be as the effective carrier of titanium dioxide optical catalyst nano particle.Method of electrostatic spinning is a kind of method of simple relatively, continuous nano-fibre that the preparation diameter is evenly distributed, and application method of electrostatic spinning, can directly prepare nano-fibre supported titanium dioxide photocatalyst (the Youliang Hong that titania nanoparticles is evenly distributed at fiber surface, Domgmei Li, Jian Zheng, Guangtian Zou, Sol-gel growthof titania from electrospun polyacrylonitrile nanofibres, Nanotechnology, 2006,17,1986-1993).But in the prepared photochemical catalyst, still physical bond between titania nanoparticles and the nanofiber, each other not satisfactory in conjunction with fixing, titanium dioxide splits away off easily, influences photocatalysis performance; Simultaneously, the titanium dioxide of load is subjected to the restriction of energy gap, only can be activated and can not be activated by visible light by ultraviolet light, and the wave-length coverage that is suitable for is narrower, influences photocatalysis efficiency.
Summary of the invention
The invention provides a kind of nano-fibre supported titanium dioxide photocatalyst and preparation method thereof, can will pass through nitrogen key used load on the surface of electro spinning nano fiber through nitrogen-doped modified titania nanoparticles, solve the fixing that combines of titanium dioxide and nanofiber, improve its photocatalytic activity under visible light simultaneously.
The preparation method of nano-fibre supported titanium dioxide photocatalyst provided by the invention is:
(a) titanium precursor body, hydrolysis inhibitor, polymer and organic solvent are made into the spinning solution of homogeneous, and carry out spinning, obtain electro spinning nano fiber felt/film according to suitable electrostatic spinning process;
(b) introduce oh group on electro spinning nano fiber felt/film, the Activity of Chemical Reaction group can take place in formation, be impregnated in again in the aqueous phase solution that contains aminating agent, and generation hydrolysis of titanium precursor body and aminating reaction, and generate the titanium ammino-complex;
(c) will be through nanofiber mats/film roasting in addition in protective gas atmosphere of hydrolysis and ammonification; hydrogen migration and dehydration condensation take place and change the titanium dioxide that nitrogen mixes in titanium ammino-complex each other; amino group on the while titanium ammino-complex and the oh group generation dehydration on the nanofiber; formation has pretends nitrogen key firmly, finally obtains nano-fibre supported titanium dioxide photocatalyst.
The method of on electro spinning nano fiber felt/film, introducing oh group of the present invention, determine according to different types of polymer, if promptly polymer raw material is a polyacrylonitrile, because it does not contain oh group, therefore the electro spinning nano fiber felt/film of gained need carry out permanent tension force or the hot drawing-off of constant strain and carry out pre-oxidation at 230～300 ℃ again at 120～160 ℃, thereby introduces oh group on strand; And if polymer raw material is the polymer that polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl butyral resin etc. have oh group, then do not need hot drawing-off and pre-oxidation treatment.
Titanium precursor body described in the preparation method of the present invention comprises one or more combinations of organic or inorganic titanium salts such as butyl titanate, isopropyl titanate, titanium tetrachloride, titanium sulfate, titanyl sulfate; Hydrolysis inhibitor comprises one or more combinations of anhydrous acetic acid, acrylic acid, catechol, acetoacetic acid allyl ester, acetylacetone,2,4-pentanedione and hydrochloric acid, sulfuric acid, phosphoric acid.
The polymer of the preparation nanofiber described in the preparation method of the present invention comprises a kind of or two kinds of combinations in polyacrylonitrile, polyvinyl alcohol, polyvinylpyrrolidone or the polyvinyl butyral resin; Corresponding organic solvent comprises one or more combinations in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), oxolane, the chloroform.
Aminating agent described in the preparation method of the present invention comprises one or more combinations of Ammonia derivatives such as ammoniacal liquor, methylamine, ethamine, aniline, urea, thiocarbamide, ammonium carbonate and ammonium nitrate and ammonium salt, the concentration of maceration extract is 0.1～5mol/L, and dip time is 1～10h.
Roasting process protective gas described in the preparation method of the present invention comprises one or more combinations in nitrogen, ammonia, argon gas and other inert gas.
Electrostatic spinning process parameter described in the preparation method of the present invention is: in the spinning solution, the concentration of polymer is 7～15wt%, the concentration of titanium precursor body and hydrolysis inhibitor thereof is 0.1～1mol/L, the syringe needle internal diameter is 0.6～2mm, the electrostatic potential that applies is 8～20kV, the spinning solution flow is 0.3～1.5mL/h, and receiving range is 10～30cm, adopts single needle head or the spinning of spininess head.
Titanium dioxide described in the preparation method of the present invention is Detitanium-ore-type, rutile-type or the mixing crystal formation of the two, corresponding sintering temperature is 300～800 ℃, programming rate is 1～5 ℃/min, and cooling rate is 2～20 ℃/min, and roasting time is 1～10 hour.
In the nano-fibre supported titanium dioxide photocatalyst of the present invention, the titania nanoparticles that nitrogen mixes passes through nitrogen key used load on the surface of electro spinning nano fiber felt/film.Wherein, the particle diameter of titanium dioxide is 10～100nm, the doping of nitrogen be in the titanium dioxide oxygen atom amount of substance 0.1～1%, the load capacity of titanium dioxide is 5～30wt% of nanofiber, and the diameter of nanofiber is 50～500nm.
((λ=540nm) methylene blue (MB) in the degradation water down tests sign to the photocatalytic activity of nano-fibre supported titanium dioxide photocatalyst of the present invention for λ=365nm) or visible light at ultraviolet light by it, concrete steps are: the described photochemical catalyst of 20mg is joined in the 10mL methylene blue solution (40mg/L), and stir, again solution is placed on high-pressure sodium lamp (λ=365nm) or hinelight (illumination in addition under the λ=540nm), and the maintenance system temperature is about 25 ℃, each hour measured solution absorbency and is converted into the concentration of methylene blue solution by absorbance-concentration relationship curve with ultraviolet-visible spectrophotometer then, thereby according to the concentration of methylene blue solution over time, judge the photocatalytic activity of photochemical catalyst under ultraviolet light and visible light respectively.
Effect of the present invention: adopt ammonification and roasting technique, in addition nitrogen-doped modified to titanium dioxide, obtain the titanium dioxide that nitrogen mixes; And on electro spinning nano fiber felt/film, introduce oh group, form the nitrogen key by amino group on the titanium ammino-complex and the dehydration between the oh group on the polymer nanofiber, the titania nanoparticles that final nitrogen mixes is carried on the surface of nanofiber by the nitrogen key.Prepared nano-fibre supported titanium dioxide photocatalyst not only all has good photocatalytic activity under ultraviolet light and visible light, and can improve the fixing that combines of titanium dioxide and nanofiber effectively.Method of the present invention is simple, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the SEM figure of embodiment 1 described nano-fibre supported nitrogen-doped titanium dioxide photocatalyst;
Fig. 2 is the XRD figure of embodiment 1 and embodiment 2 described nano-fibre supported nitrogen-doped titanium dioxide photocatalysts;
Fig. 3 is different photochemical catalysts degradation capability comparison diagrams to methylene blue under Different Light, wherein (a) and (b) be respectively embodiment 1 described nano-fibre supported nitrogen-doped titanium dioxide and Comparative Examples 1 described nano-fibre supported not titania-doped two kinds of photochemical catalysts at high-pressure sodium lamp (under the illumination of λ=365nm); (c) and (d) then be respectively embodiment 1 described nano-fibre supported nitrogen-doped titanium dioxide and Comparative Examples 1 described nano-fibre supported not titania-doped two kinds of photochemical catalysts at hinelight (under the illumination of λ=540nm).
The specific embodiment
The present invention will be described in detail below by embodiment and Comparative Examples:
Embodiment 1
The mixed solution of 6mL butyl titanate and 4mL acetate is joined in the dimethyl formamide solution (concentration is 10wt%) of 60mL polyacrylonitrile, under hyperacoustic stirring, be used for electrostatic spinning then until the solution that forms homogeneous.In the electrostatic spinning process, select No. 12 injection needles (internal diameter is 1.1mm) for use, the electrostatic potential that applies is 10kV, the spinning solution flow is 0.4mL/h, receiving range between metal roller and the syringe needle is 20cm, cylinder external diameter linear velocity is 8m/s, obtains the nanofiber mats/film of certain thickness partial parallel orientation through the spinning of 5h.Electro spinning nano fiber felt/the film of gained is carried out the hot drawing-off 10min of constant strain under 135 ℃, under 250 ℃, carry out constant strain pre-oxidation 1h again.At last; with nanofiber mats/film immersion of introducing oh group in the ammonia spirit of 25vol% behind the 2h; place carbide furnace roasting 2h under the protection of 600 ℃ and high pure nitrogen; programming rate is 3 ℃/min; cooling rate cooling taking-up with 5 ℃/min then can obtain nano-fibre supported nitrogen-doped titanium dioxide photocatalyst (effect is seen Fig. 1); wherein the particle diameter of titanium dioxide is about 35nm; the nitrogen doping is about 0.2%; crystalline phase is Detitanium-ore-type and rutile-type mixing crystal formation; both ratios are 3: 1, approach the crystalline phase ratio (effect is seen Fig. 2) of Degussa P25 type titanium dioxide.Titanium dioxide is about 15wt% in the lip-deep load capacity of nanofiber, and the diameter of nanofiber is 200～300nm.Prepared nano-fibre supported nitrogen-doped titanium dioxide photocatalyst all has original photocatalytic Degradation (effect is seen Fig. 3) to methylene blue under ultraviolet light and visible light.
Comparative Examples 1
The mixed solution of 6mL butyl titanate and 4mL acetate is joined in the dimethyl formamide solution (concentration is 10wt%) of 60mL polyacrylonitrile, under hyperacoustic stirring, be used for electrostatic spinning then until the solution that forms homogeneous.In the electrostatic spinning process, select No. 12 injection needles (internal diameter is 1.1mm) for use, the electrostatic potential that applies is 10kV, the spinning solution flow is 0.4mL/h, receiving range between metal roller and the syringe needle is 20cm, cylinder external diameter linear velocity is 8m/s, obtains the nanofiber mats/film of certain thickness partial parallel orientation through the spinning of 5h.Electro spinning nano fiber felt/the film of gained is carried out the hot drawing-off 10min of constant strain under 135 ℃, under 250 ℃, carry out constant strain pre-oxidation 1h again.At last; with nanofiber mats/film immersion of introducing oh group in deionized water behind the 2h; place carbide furnace roasting 2h under the protection of 600 ℃ and high pure nitrogen; programming rate is 3 ℃/min; cooling rate cooling taking-up with 5 ℃/min then can obtain nano-fibre supported not doped titanium dioxide photocatalyst; it has good photocatalytic activity to methylene blue under ultraviolet light, but the photocatalytic activity under visible light weak (effect is seen Fig. 3).
Embodiment 2
The mixed solution of 6mL butyl titanate and 4mL acetate is joined in the dimethyl formamide solution (concentration is 10wt%) of 60mL polyacrylonitrile, under hyperacoustic stirring, be used for electrostatic spinning then until the solution that forms homogeneous.In the electrostatic spinning process, select No. 12 injection needles (internal diameter is 1.1mm) for use, the electrostatic potential that applies is 10kV, the spinning solution flow is 0.4mL/h, receiving range between metal roller and the syringe needle is 20cm, cylinder external diameter linear velocity is 8m/s, obtains the nanofiber mats/film of certain thickness partial parallel orientation through the spinning of 5h.Electro spinning nano fiber felt/the film of gained is carried out the hot drawing-off 10min of constant strain under 135 ℃, under 250 ℃, carry out constant strain pre-oxidation 1h again.At last; with nanofiber mats/film immersion of introducing oh group in the ammonia spirit of 25vol% behind the 2h; place carbide furnace roasting 2h under the protection of 500 ℃ and high pure nitrogen; programming rate is 3 ℃/min; cooling rate cooling taking-up with 5 ℃/min then can obtain nano-fibre supported nitrogen-doped titanium dioxide photocatalyst; wherein the particle diameter of titanium dioxide is about 30nm; the nitrogen doping is about 0.2%; crystalline phase almost all is a Detitanium-ore-type (effect is seen Fig. 2); and titanium dioxide is about 15wt% in the lip-deep load capacity of nanofiber, and the diameter of nanofiber is 250～350nm.
Embodiment 3
The mixed solution of 6mL butyl titanate and 4mL acetate is joined in the dimethyl sulphoxide solution (concentration is 10wt%) of 60mL polyacrylonitrile, under hyperacoustic stirring, be used for electrostatic spinning then until the solution that forms homogeneous.In the electrostatic spinning process, select No. 9 injection needles (internal diameter is 0.9mm) for use, the electrostatic potential that applies is 15kV, the spinning solution flow is 0.3mL/h, receiving range between metal roller and the syringe needle is 25cm, cylinder external diameter linear velocity is 8m/s, obtains the nanofiber mats/film of certain thickness partial parallel orientation through the spinning of 5h.Electro spinning nano fiber felt/the film of gained is carried out the hot drawing-off 10min of constant strain under 135 ℃, under 250 ℃, carry out constant strain pre-oxidation 1h again.At last; with nanofiber mats/film immersion of introducing oh group in the ammonia spirit of 25vol% behind the 2h; place carbide furnace roasting 2h under the protection of 600 ℃ and high pure nitrogen; programming rate is 3 ℃/min, takes out with the cooling rate cooling of 5 ℃/min and then can obtain nano-fibre supported nitrogen-doped titanium dioxide photocatalyst.
Embodiment 4
6g titanium sulfate and 4mL sulfuric acid are joined in the dimethyl sulphoxide solution (concentration is 10wt%) of 60mL polyacrylonitrile successively, under hyperacoustic stirring, be used for electrostatic spinning then until the solution that forms homogeneous.In the electrostatic spinning process, select No. 12 injection needles (internal diameter is 1.1mm) for use, the electrostatic potential that applies is 10kV, the spinning solution flow is 0.4mL/h, receiving range between metal roller and the syringe needle is 20cm, cylinder external diameter linear velocity is 8m/s, obtains the nanofiber mats/film of certain thickness partial parallel orientation through the spinning of 5h.Electro spinning nano fiber felt/the film of gained is carried out the hot drawing-off 10min of constant strain under 135 ℃, under 250 ℃, carry out constant strain pre-oxidation 1h again.At last; with nanofiber mats/film immersion of introducing oh group in the ammonia spirit of 25vol% behind the 2h; place carbide furnace roasting 2h under the protection of 600 ℃ and high pure nitrogen; programming rate is 3 ℃/min, takes out with the cooling rate cooling of 5 ℃/min and then can obtain nano-fibre supported nitrogen-doped titanium dioxide photocatalyst.
Embodiment 5
The mixed solution of 6mL butyl titanate and 4mL acetate is joined in the dimethyl sulphoxide solution (concentration is 10wt%) of 60mL polyvinylpyrrolidone, under hyperacoustic stirring, be used for electrostatic spinning then until the solution that forms homogeneous.In the electrostatic spinning process, select No. 12 injection needles (internal diameter is 1.1mm) for use, the electrostatic potential that applies is 10kV, the spinning solution flow is 0.4mL/h, receiving range between metal roller and the syringe needle is 20cm, cylinder external diameter linear velocity is 8m/s, obtains the nanofiber mats/film of certain thickness partial parallel orientation through the spinning of 5h.With the electro spinning nano fiber felt/film immersion of gained in the aqueous solution of urea of 1mol/L behind the 2h; be placed in the carbide furnace roasting 2h under the protection of 600 ℃ and high pure nitrogen again; programming rate is 3 ℃/min, takes out with the cooling rate cooling of 5 ℃/min and then can obtain nano-fibre supported nitrogen-doped titanium dioxide photocatalyst.
Embodiment 6
The mixed solution of 6mL butyl titanate and 4mL acetate is joined in the dimethyl sulphoxide solution (concentration is 10wt%) of 60mL polyvinylpyrrolidone, under hyperacoustic stirring, be used for electrostatic spinning then until the solution that forms homogeneous.In the electrostatic spinning process, select No. 12 injection needles (internal diameter is 1.1mm) for use, the electrostatic potential that applies is 10kV, the spinning solution flow is 0.4mL/h, receiving range between metal roller and the syringe needle is 20cm, cylinder external diameter linear velocity is 8m/s, obtains the nanofiber mats/film of certain thickness partial parallel orientation through the spinning of 5h.With the electro spinning nano fiber felt/film immersion of gained in the aqueous solution of urea of 1mol/L behind 2 h, be placed in the carbide furnace roasting 1h under the atmosphere of 600 ℃ and high pure nitrogen and ammonia gas mixture body (1: 1) again, programming rate is 2 ℃/min, takes out with the cooling rate cooling of 10 ℃/min and then can obtain nano-fibre supported nitrogen-doped titanium dioxide photocatalyst.
Claims (4)
1. the preparation method of a nano-fibre supported titanium dioxide photocatalyst, comprise: with the titanium precursor body, hydrolysis inhibitor, polymer and organic solvent are made into the spinning solution of homogeneous, and prepare nanofiber mats/film with method of electrostatic spinning, it is characterized in that: on electro spinning nano fiber felt/film, introduce oh group, be impregnated in again in the aqueous phase solution that contains aminating agent, generation hydrolysis of titanium precursor body and aminating reaction, and generation titanium ammino-complex, roasting in addition in protective gas atmosphere then, obtain nano-fibre supported titanium dioxide photocatalyst, wherein said polymer is a polyacrylonitrile, polyvinyl alcohol, polyvinylpyrrolidone, a kind of or two kinds of combinations in the polyvinyl butyral resin; Corresponding organic solvent is one or more combinations in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), oxolane, the chloroform; The electrostatic spinning process parameter is: in the spinning solution, the concentration of polymer is 7～15wt%, the concentration of titanium precursor body and hydrolysis inhibitor thereof is 0.1～1mol/L, the syringe needle internal diameter is 0.6～2mm, the electrostatic potential that applies is 8～20KV, the spinning solution flow is 0.3～1.5mL/h, and receiving range is 10～30cm, adopts single needle or the spinning of spininess head; Described aminating agent comprises one or more combinations in ammoniacal liquor, methylamine, ethamine, aniline, urea, thiocarbamide, ammonium carbonate and the ammonium nitrate, and the concentration of maceration extract is 0.1～5mol/L, and dip time is 1～10h; In the described nano-fibre supported titanium dioxide photocatalyst, the titanium dioxide that nitrogen mixes passes through nitrogen key used load on the surface of electro spinning nano fiber felt/film, wherein, the particle diameter of titanium dioxide is 10～100nm, the doping of nitrogen be in the titanium dioxide oxygen atom amount of substance 0.1～1%, the load capacity of titanium dioxide is 5～30wt% of nanofiber, and the diameter of nanofiber is 50～500nm.
2. according to the preparation method of claim 1, it is characterized in that: described titanium precursor body comprises one or more combinations of butyl titanate, isopropyl titanate, titanium tetrachloride, titanium sulfate, titanyl sulfate; Corresponding hydrolysis inhibitor comprises one or more combinations of anhydrous acetic acid, acrylic acid, catechol, acetoacetic acid allyl ester, acetylacetone,2,4-pentanedione and hydrochloric acid, sulfuric acid, phosphoric acid.
3. according to the preparation method of claim 1, it is characterized in that: select the polymer of polyacrylonitrile for use as the preparation nanofiber, because polyacrylonitrile does not contain oh group, therefore the electro spinning nano fiber felt/film of gained need carry out permanent tension force or the hot drawing-off of constant strain and carry out pre-oxidation at 230～300 ℃ again at 120～160 ℃, thereby introduces oh group on strand.
4. according to the preparation method of claim 1, it is characterized in that described titanium dioxide is Detitanium-ore-type, rutile-type or the mixing crystal formation of the two, corresponding sintering temperature is 300～800 ℃, programming rate is 1～5 ℃/min, and cooling rate is 2～20 ℃/min, and roasting time is 1～10 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101769942A CN101428209B (en) | 2007-11-08 | 2007-11-08 | Nano-fibre supported titanium dioxide photocatalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101769942A CN101428209B (en) | 2007-11-08 | 2007-11-08 | Nano-fibre supported titanium dioxide photocatalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101428209A CN101428209A (en) | 2009-05-13 |
| CN101428209B true CN101428209B (en) | 2010-12-01 |
Family
ID=40643972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101769942A Expired - Fee Related CN101428209B (en) | 2007-11-08 | 2007-11-08 | Nano-fibre supported titanium dioxide photocatalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101428209B (en) |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4949909B2 (en) * | 2007-03-29 | 2012-06-13 | 保土谷化学工業株式会社 | Dispersant for carbon fiber, carbon fiber dispersion obtained by dispersion, conductive composite material derived from carbon fiber dispersion, conductive paint, coating method, and article coated by the method |
| EP2492391A1 (en) * | 2011-02-26 | 2012-08-29 | Clariant International Ltd. | Optimized layer-by-layer assemblies for indoor photo-catalytical pollutants removal |
| JP6141836B2 (en) | 2011-06-30 | 2017-06-07 | スリーエム イノベイティブ プロパティズ カンパニー | Non-woven electret fiber web and method for producing the same |
| CN103120934A (en) * | 2011-11-11 | 2013-05-29 | 奥克化学扬州有限公司 | Method for preparing TiO2/SiO2 catalyst for exchanging and synthesizing diphenyl carbonate by dimethyl carbonate and phenol ester |
| CN103215748A (en) * | 2013-04-01 | 2013-07-24 | 复旦大学 | Functional fiber felt covered by transition metal oxide nanomaterials and preparation method thereof |
| CN103721705B (en) * | 2014-01-14 | 2015-12-02 | 武汉理工大学 | A kind of porous TiO 2fiber-loaded noble metal formaldehyde room-temperature oxidation Catalysts and its preparation method |
| CN103880071B (en) * | 2014-03-17 | 2015-08-12 | 兰州大学 | A kind of preparation method of spumescence titanium dioxide |
| CN104264265B (en) * | 2014-09-16 | 2016-03-30 | 北京化工大学 | A kind of preparation method of hybrid nanofiber |
| CN105803560A (en) * | 2014-12-30 | 2016-07-27 | 上海水星家用纺织品股份有限公司 | Electrostatic spinning porous light catalytic fiber preparation method and use |
| CN104746179A (en) * | 2015-03-20 | 2015-07-01 | 济南大学 | Preparation method of TiO2 nano fibers with adjustable crystal phase |
| CN104772160B (en) * | 2015-04-17 | 2017-03-15 | 北京师范大学 | A kind of carbonitride photocatalytic activity nano fibrous membrane and preparation method thereof |
| CN105170181A (en) * | 2015-09-25 | 2015-12-23 | 天津工业大学 | Method for optimizing catalytic performance of carbon/titanium dioxide composite fiber membrane |
| CN107020077A (en) * | 2016-02-01 | 2017-08-08 | 中国科学院上海高等研究院 | A kind of methanol aoxidizes nano-fiber catalyst of methyl formate processed and preparation method thereof |
| CN108160121B (en) * | 2016-04-25 | 2021-02-12 | 项敬来 | Composite visible light photocatalyst Ag2CO3/TiO2/UIO-66-(COOH)2And application of organic matter degradation |
| CN105951194B (en) * | 2016-06-16 | 2018-12-14 | 浙江理工大学 | A kind of centrifugal spinning preparation method of titanium dioxide/polyacrylonitrile micro/nano-fibre film |
| CN106245158A (en) * | 2016-08-15 | 2016-12-21 | 江苏师范大学 | The preparation method of nitrogen-doped carbon/dioxide composite nanofiber carrier |
| CN106311205A (en) * | 2016-08-16 | 2017-01-11 | 曹健 | Preparation method of carbon-doped TiO2 nano-fibers |
| CN106319762B (en) * | 2016-08-26 | 2018-03-16 | 中原工学院 | A kind of TiN/C nanofibers with cable type structure of graphene doping and preparation method and application |
| CN107785565B (en) * | 2017-10-31 | 2021-01-22 | 湘潭大学 | Sn-TiO2Electrostatic spinning preparation method of-C nanofibers |
| CN108914250B (en) * | 2018-08-16 | 2020-07-17 | 山东大学 | Preparation method of polyacetylacetonato titanium precursor sol spinning solution, titanium oxide continuous fiber and nano fiber |
| CN109097869A (en) * | 2018-08-17 | 2018-12-28 | 绩溪袁稻农业产业科技有限公司 | A kind of preparation method of thin base functionality Electrospun nano-fibers |
| CN108992701A (en) * | 2018-08-17 | 2018-12-14 | 佛山市森昂生物科技有限公司 | A kind of preparation method of nasal packing hemostatic material |
| CN109174133B (en) * | 2018-09-18 | 2020-10-27 | 南京大学 | Molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet and preparation method thereof |
| CN109833856B (en) * | 2019-03-18 | 2022-07-26 | 耐酷时科技有限责任公司 | Photocatalytic fiber material and preparation method thereof |
| CN109775757B (en) * | 2019-03-19 | 2021-09-28 | 广州大学 | Preparation method of three-dimensional titanium dioxide material |
| CN110038451A (en) * | 2019-04-23 | 2019-07-23 | 东南大学 | Ceramic nanofibers base compound purifying film and its preparation method and application |
| CN113668232B (en) * | 2021-03-19 | 2023-05-16 | 浙江旭亿新材料科技股份有限公司 | Preparation method of polyacrylonitrile fiber with titanium dioxide thorn structure on surface |
| CN113337900B (en) * | 2021-06-02 | 2023-05-26 | 西安交通大学 | Photocatalytic fabric and preparation method and application thereof |
| CN115520942A (en) * | 2021-06-25 | 2022-12-27 | 清华大学 | Biological neural network-shaped electro-catalytic membrane and preparation method and application thereof |
| CN114481623A (en) * | 2022-02-09 | 2022-05-13 | 孙秋宁 | Anti-mosquito fabric and preparation method thereof |
| CN115287903B (en) * | 2022-07-29 | 2023-06-27 | 东莞市日东智能装备有限公司 | Seamless curtain with adhesive decorative connecting piece and preparation process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772373A (en) * | 2005-10-31 | 2006-05-17 | 山东大学 | Prepn of photocatalytic titania fiber material |
| CN1846850A (en) * | 2005-12-23 | 2006-10-18 | 北京纳诺天地科技有限公司 | Fibrous nanometer catalyst material excited with natural light and its prepn process |
| EP1813701A1 (en) * | 2004-11-19 | 2007-08-01 | Bridgestone Corporation | Carbon fiber, porous support-carbon fiber composite, process for producing them, catalyst structure, electrode for solid polymer fuel cell and solid polymer fuel cell |
-
2007
- 2007-11-08 CN CN2007101769942A patent/CN101428209B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1813701A1 (en) * | 2004-11-19 | 2007-08-01 | Bridgestone Corporation | Carbon fiber, porous support-carbon fiber composite, process for producing them, catalyst structure, electrode for solid polymer fuel cell and solid polymer fuel cell |
| CN1772373A (en) * | 2005-10-31 | 2006-05-17 | 山东大学 | Prepn of photocatalytic titania fiber material |
| CN1846850A (en) * | 2005-12-23 | 2006-10-18 | 北京纳诺天地科技有限公司 | Fibrous nanometer catalyst material excited with natural light and its prepn process |
Non-Patent Citations (2)
| Title |
|---|
| 沈翔等.聚丙烯腈/二氧化钛杂化纳米活性碳纤维制备与结构变化规律.化工进展26 7.2007,26(7),974-979. |
| 沈翔等.聚丙烯腈/二氧化钛杂化纳米活性碳纤维制备与结构变化规律.化工进展26 7.2007,26(7),974-979. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101428209A (en) | 2009-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101428209B (en) | Nano-fibre supported titanium dioxide photocatalyst and preparation method thereof | |
| CN108842304B (en) | Porous supported electrostatic spinning nano photocatalytic fiber membrane and preparation method thereof | |
| CN107456987B (en) | Method for preparing carbon nitride/titanium dioxide heterojunction photocatalyst by electrostatic spinning one-step method | |
| CN103451773B (en) | Bismuth ferrite nano fiber material and preparation method thereof | |
| Yao et al. | Electrospun Bi-decorated BixTiyOz/TiO2 flexible carbon nanofibers and their applications on degradating of organic pollutants under solar radiation | |
| CN109759114B (en) | g-C3N4/TiO2RGO three-dimensional Z-shaped photocatalyst and in-situ electrospinning preparation method thereof | |
| CN103623803A (en) | Visible light photocatalyst and preparation method therefor | |
| CN103074704B (en) | Electrospinning preparation method of BiVO4 (bismuth vanadium oxide) fibers | |
| CN108914250B (en) | Preparation method of polyacetylacetonato titanium precursor sol spinning solution, titanium oxide continuous fiber and nano fiber | |
| KR101172037B1 (en) | Manufacturing method of titanium dioxide fiber added silver | |
| CN111705419B (en) | Metal-loaded carbon nitride-doped graphene-based flexible non-woven fabric and preparation method and application thereof | |
| CN102086045B (en) | TiO2 secondary nanorod array and preparation method and application thereof | |
| CN104826622A (en) | Nano titanium dioxide material supported by porous carbon nano fiber and doped with samarium, preparation method and application thereof | |
| CN102489289A (en) | SnO2/TiO2 composite nanofiber photocatalyst and preparation method thereof | |
| KR20190041570A (en) | Nanocomposite material and method thereof | |
| KR100865737B1 (en) | Photocatalyst filter using metal oxide nanofiber, method for fabricating the same and air cleaner using the same | |
| CN107376905B (en) | Preparation method of Ag/ZnO composite material capable of degrading formaldehyde | |
| Nor et al. | A review study of nanofibers in photocatalytic process for wastewater treatment | |
| CN113546625B (en) | Electrostatic spinning defect TiO 2 /Fe 3 O 4 Composite nanofiber material and preparation method thereof | |
| Zhou et al. | The preparation of continuous CeO 2/CuO/Al 2 O 3 ultrafine fibers by electro-blowing spinning (EBS) and its photocatalytic activity | |
| CN106669660A (en) | Hierarchical-structure MnOx/TiO2 nanofiber catalyst for acetone oxidation and preparation method of hierarchical-structure MnOx/TiO2 nanofiber catalyst | |
| CN108525662B (en) | Truncated cube Ag2O modified TiO2Preparation and application of hollow nanofiber photocatalyst | |
| CN107497427B (en) | Preparation method of silver/graphene/zinc oxide composite material capable of degrading formaldehyde | |
| CN108103766A (en) | A kind of molybdenum disulfide composite fibre photochemical catalyst and preparation method for sewage disposal | |
| CN100404126C (en) | Fibrous nanometer catalyst material excited with natural light and its prepn process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101201 Termination date: 20201108 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |