CN1846850A - Fibrous nanometer catalyst material excited with natural light and its prepn process - Google Patents
Fibrous nanometer catalyst material excited with natural light and its prepn process Download PDFInfo
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- CN1846850A CN1846850A CN 200510132083 CN200510132083A CN1846850A CN 1846850 A CN1846850 A CN 1846850A CN 200510132083 CN200510132083 CN 200510132083 CN 200510132083 A CN200510132083 A CN 200510132083A CN 1846850 A CN1846850 A CN 1846850A
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Abstract
The fibrous nanometer catalyst material excited with natural light and its preparation process belongs to the field of environment purifying material technology. The nanometer photocatalytic particle and polymer carrier solution are high voltage electrostatic spun to form nanometer fiber with nanometer TiO2 particle. The preparation process includes sol-gel process to prepare chemically doped nanometer TiO2; modifying with conjugated organic matter; adding the prepared nanometer TiO2 particle into polymer solution and spinning in high voltage electric field to obtain fibrous nanometer catalyst. The fibrous nanometer catalyst material needs no ultraviolet ray excitation, and may be excited with natural light to degrade organic pollutant. The present invention may be used in purifying air and water.
Description
Technical field
The invention belongs to the surrounding purifying material field, specially refer to a kind of preparation method who utilizes the light activated fibrous nanometer catalysis material of nature and its door.
Technical background
Along with developing rapidly of modern industrial technology, the mankind are faced with numerous environmental problems, the organic pollution of, bio-refractory big for toxicity be treated as a difficult problem, this type of material is difficult to remove with biological method, thereby environment is produced very big harm.Photocatalytic method is as a kind of high-level oxidation technology, and it is to utilize the photoproduction strong oxidizer that the organic pollution exhaustive oxidation is little molecules such as H2O, CO2, so be a kind of environmentally friendly green water technology.Carey in 1976 etc. have carried out ground-breaking work aspect the photocatalytic degradation water pollutant, opened up application prospect (the Carey JH of photocatalysis technology in the environmental protection field, Lawrence HM.BullEnviron Contam toxicol, 1994,28 (5): 786).Though light-catalysed principle is not fully aware of, utilize the research of light-catalyzed reaction very active, pollutant is removed in photocatalysis at present becomes a wherein most active research direction, uses photocatalysis technology and has developed a series of products.Be used for light-catalysed photochemical catalyst CdS, SnO are arranged
2, TiO
2, ZnO, ZnS, PbS, MoO
3, SrTiO
3, V
2O
5, WO
3And MoSi
2Deng, TiO in these semiconductors
2, CdS and ZnO catalytic activity the highest, but CdS and ZnO instability when illumination is penetrated, TiO
2Be currently to think that a kind of photochemical catalyst of application potential is arranged most, because nano TiO 2 not only has very high photocatalytic activity, and have advantages such as acid-alkali-corrosive-resisting, resistance to chemical attack, cost be low, nontoxic, it becomes maximum, the most widely used a kind of photochemical catalysts of current research.But, because TiO
2Forbidden band own is wide, and the electron-hole pair of generation is not only very easily compound but also the life-span is shorter, and the photoresponse scope is narrower, makes photocatalytic activity be subjected to certain restriction, and the spectral region of utilizing also is subjected to certain restriction.Influence TiO
2The factor of photocatalytic activity is a lot, for example TiO
2The crystal formation of particle, particle diameter, configuration of surface etc., experiment shows, dichloride in anatase type TiO
2Than rutile type nano TiO
2Has higher catalytic efficiency.In order to improve TiO
2Photocatalytic activity improves photocatalysis efficiency, thereby relevant TiO
2The preparation method of particulate and doped metal ion, be doped with organic dye, catalyst carrier, carried noble metal, surface treatment, the research of introducing aspects such as intermediate level, different atmosphere processing in the forbidden band is TiO always
2The research focus of photochemical catalyst.The nano-TiO that has photocatalytic activity in the low-light district
2Prepare (referring to Chinese patent application publication number CN1448214A).The photocatalysis development starting stage is with decentralized photo TiO
2Particle is suspended in the aqueous solution as photochemical catalyst, penetrates down in illumination organic matter is carried out the photocatalytic degradation reaction, and this system is called the suspended phase system.But TiO
2Photocatalyst powder is superfine little, is easy to cohesion in the aqueous solution, is difficult to separate reclaim.In addition, suspended particles stop the degree of depth that has influenced light radiation to the absorption of light, and these shortcomings are used this technology and are restricted.Therefore the development of photocatalysis technology will be depended on the load of catalyst and the development of novel reactor with application.At present, photochemical catalyst TiO
2Carrying method have a lot, as powder sintering method, sol-gel processing, sputtering method, solution immersion, chemical vapour deposition technique, liquid phase deposition, electrodeposition process, plasma chemistry sedimentation and binder method etc., the people is arranged with nano-TiO
2Load on the carriers such as glass, metal, active carbon, also the someone has prepared TiO
2Nanofiber (Fabrication of Titania Nanofibersby Electrospinning, Nano letters, 2003,3 (4): 555), TiO
2Nanotube.Nanotube TiO
2Appearance structure and physicochemical characteristics [J]. Science Bulletin 2000,45:1104) etc.,, all can not adopt high polymer material as carrier because said method all needs high-temperature process.But also the someone adopts high polymer to make carrier loaded nano-TiO
2, as Dhananjeyan etc. with nano-TiO
2(P-25) load to modified poly ethylene film (Dhananjeyan M R, Mielczarski E, Thampi K R, et al, J Phys Chem.B 2001,105:12046) Naskar etc. loads on the organic dyestuff in the degradation water solution on the foamed polyethylene film (Naskar S, Pillay S A, Chanda M with the method for nano TiO 2 particles by hot pressing, JPhotochem Photobiol, A:Chemistry, 1998,113:257).Said method does not need the processing through high temperature, but is exposed to outer nano-TiO on the unit are
2Still less.At above deficiency, our company is long-pending to research and develop experience for many years, develops a kind of new product, by to nano-TiO
2Carry out semiconductor and organically-modified, prepare the nano-TiO that has photocatalysis performance in the low-light district
2, the diameter of nano particle is between 20nm ~ 100nm.Then with the nano-TiO for preparing
2Be dispersed in the high polymeric solution, prepare by high-voltage electrostatic spinning and contain nano-TiO
2The nanofiber of particle, the diameter of nanofiber between 20nm ~ 5 μ m, therefore when nanofiber diameter during in the 100nm left and right sides, more nano-TiO
2Be exposed to the surface of nanofiber, nano TiO 2 that this method improves greatly and extraneous contact area, thereby also improved nano-TiO
2Utilization rate, this neomorph nanocatalyst is easy to use, both can be used in to purify air, and also nanocatalyst of the present invention can be used for the purification of liquid.
Summary of the invention
The skill that the present invention need solve is stated problem, in prior art, and photochemical catalyst TiO
2The carrying method majority need high-temperature process, do not need high-temperature process though perhaps have, be exposed to outer nano-TiO on the unit are
2Still less, can't satisfy requirement to purifying, to research and develop a kind of neomorph natural daylight excitation nano catalyst again for this reason, the purpose of this invention is to provide a kind of fiber attitude sodium rice catalyst material and manufacture method thereof of utilizing natural daylight to intensify.The present invention realizes that by the following technical solutions a kind of fiber attitude sodium rice catalyst material that utilizes natural daylight to intensify comprises the photocatalytic nanometer particle, it is characterized in that, also comprises high polymer base carrier solution, by high-voltage electrostatic spinning, makes nano-TiO
2The nanofiber of particle.The diameter of described photocatalytic nanometer particle is between 20nm ~ 100 μ m.Described nano-TiO
2The nanofiber of particle, its fibre diameter is between 20nm ~ 5 μ m.A kind of manufacture method of utilizing the fiber attitude sodium rice catalyst material that natural daylight intensifies is characterized in that, according to the following steps operation, a. at first goes out the nano-TiO of chemical doping by Prepared by Sol Gel Method
2, b. adopts the conjugated system organic matter to its modification, prepares the nano-TiO that has photocatalysis performance under visible light
2, c. is with the nano-TiO that makes
2Add in the certain density high polymeric solution, by ultrasonic and mechanical agitation, it is uniformly dispersed, d. is with the TiO of gained
2/ PVP suspension joins in the syringe, and spinning under high voltage electric field has promptly obtained light activated naturally fibrous nanometer catalyst.
Because the beneficial effect that has adopted technique scheme, the present invention to have is as follows: 1) select the nano TiO 2 that has photocatalysis performance under the visible light among the present invention for use, the neomorph natural daylight excitation nano catalyst of preparation just has photocatalysis performance under visible light.2) nano TiO 2 particles is uniformly dispersed in matrix in the neomorph natural daylight excitation nano catalyst of the present invention, this neomorph natural daylight excitation nano catalyst has very big specific area, and a large amount of nano TiO 2 particles is exposed to fiber surface, has very high photocatalysis efficiency.3) this method preparation section is simple, and is with low cost, and this product has a wide range of applications, and can be used for air and water purification.
The benefit of described material reduces, 1 reaction condition gentleness, and the visible light or the low light level just can react down; 2 catalyst activity height in the short period of time, can be removed airborne formaldehyde, sulfur dioxide and oxynitrides etc.; 3 environmental protection generate without any pernicious gas in the course of reaction, and simultaneously, catalyst is easy to separate and reclaims, and can not cause environmental pollution.Prove that by experiment the neomorph natural daylight excitation nano catalyst that we are prepared under the prerequisite that guarantees above condition, has shown high photocatalytic degradation efficient, the degradation rate of radiation of visible light 120min PARA FORMALDEHYDE PRILLS(91,95) reaches 20.3%.The invention provides modified Nano TiO
2Branch bulk storage method in high polymeric solution and neomorph natural daylight excitation nano Preparation of catalysts method.Neomorph natural daylight excitation nano catalyst of the present invention, diameter adopt the method preparation of high-voltage electrostatic spinning in the 20nm-5mm scope.This method provides a kind of material for air purification that has photocatalysis performance under visible light, and described neomorph catalyst does not need ultraviolet source to excite, just can degradable organic pollutant under the effect of natural daylight.
Description of drawings
Fig. 1 is the TEM image of the light activated fibrous nanometer catalyst of nature;
Fig. 2 is the curve of degradation of formaldehyde under the light activated fibrous nanometer catalyst visible light of nature;
Fig. 3 is the manufacture method flow chart of the light activated fibrous nanometer catalyst material of nature.
The specific embodiment
With reference to Fig. 1, expression utilizes the TEM image of the light activated fibrous nanometer catalyst material of nature, with reference to Fig. 2, is the curve map of above-mentioned material degradation of formaldehyde under visible light.With reference to Fig. 3, shown the process chart of making above-mentioned material, it is as follows to provide specific embodiment in conjunction with this figure:
Embodiment:
Step 1: nano-TiO
2Preparation and modification at room temperature 19g (0.15mol) zinc nitrate is dissolved in the NH4OH aqueous solution of 1000ml5%.Adopt refrigerated bath then, with 0.6mol technical grade titanium tetrachloride slowly be added drop-wise to should whose solution in, under at the uniform velocity stirring, evenly produce white precipitate.Under agitation add 0.15mol hydrochloric acid then, make the white precipitate dissolving, obtain transparent liquid.Heat this liquid down at 95 ℃ and make its evaporation 2h, remove redundant moisture, obtain collosol and gel.Filter the gained sol-gel and use 500ml water washing 4 times, making its pH is 7.With the dry 3h under 20 ℃ and 10mmHg of the collosol and gel after the washing, obtain white micro mist, i.e. the metastable state TiO 2 precursor.Should in Muffle furnace, calcine 1h down by the white micro mist in 860 ℃, obtain Zinc oxide doped nano TiO 2 matrix, matrix is ground, be distributed in 200ml50 ℃ the pure water, add the 0.2g neopelex, fully mixing and at 100 ℃ of dry 10h of following ageing is grinding, and obtains the nano TiO 2 of modification.
Step 2: the preparation of nano TiO 2/PVP suspension system is 1: 1 ethanol and water as solvent with mass ratio, configuration 10g concentration is 28% PVP (K30, mean molecule quantity is 30000) solution, taking by weighing the above-mentioned nano TiO 2 of 0.6g adds in the PVP solution that configures, ultrasonic processing 1h, tool stirs 20min (5000rad/min), obtains finely dispersed nano TiO 2/PVP suspension system.Step 3: neomorph natural daylight excitation nano Preparation of catalysts joins spinning in the device for spinning of nanometer ultrapurification material production equipment with the nano TiO 2/PVP suspension system of preparation in the step 2, spinning is apart from 15cm, spinning voltage is respectively 20KV, has just obtained neomorph natural daylight excitation nano catalyst on the negative electrode receiver sheet.The test of photocatalysis performance test light catalytic performance is carried out in homemade photo catalysis reactor, photo catalysis reactor is that diameter is 50mm, length is the transparent glass tube of 200mm, lie in a horizontal plane on the experimental bench, light source is the xenon lamp of 500W, be placed on about 40cm place, reactor top, at first utilize gas flow controller in reactor, to feed formaldehyde and oxygen by a certain percentage, mixed gas in the reactor flows in the atmosphere by blast pipe simultaneously, about 10min that ventilates, gas concentration substantially constant in the reactor is closed the exhaust valve at reactor two ends, placed 10 minutes, after the question response device concentration stabilize, open uviol lamp, every 6min gets gas sample one time, measure the concentration of formaldehyde gas in the reactor, the concentration of formaldehyde gas is to measure by gas-chromatography.
Claims (4)
1. a fibrous nanometer catalyst material that utilizes natural daylight to intensify comprises the photocatalytic nanometer particle, it is characterized in that, also comprises high polymer base carrier solution, by high-voltage electrostatic spinning, makes nano-TiO
2The nanofiber of particle.
2. fibrous nanometer catalyst material according to claim 1 is characterized in that, the diameter of described photocatalytic nanometer particle is between 20nm ~ 100 μ m.
3. fibrous nanometer catalyst material according to claim 1 is characterized in that, described nano-TiO
2The nanofiber of particle, its fibre diameter is between 20nm ~ 5 μ m.
4. a manufacture method of utilizing the fibrous nanometer catalyst material that natural daylight intensifies is characterized in that, according to the following steps operation, a. at first goes out the nano-TiO of chemical doping by Prepared by Sol Gel Method
2, b. adopts the conjugated system organic matter to its modification, prepares the nano-TiO that has photocatalysis performance under visible light
2, c. is with the nano-TiO that makes
2Add in the certain density high polymeric solution, by ultrasonic and mechanical agitation, it is uniformly dispersed, d. is with the TiO of gained
2/ PVP suspension joins in the syringe, and spinning under high voltage electric field has promptly obtained light activated naturally fibrous nanometer catalyst.
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Cited By (5)
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CN101428209B (en) * | 2007-11-08 | 2010-12-01 | 北京化工大学 | Nano-fibre supported titanium dioxide photocatalyst and preparation method thereof |
CN101612565B (en) * | 2009-07-21 | 2011-08-31 | 中国科学院上海硅酸盐研究所 | Bi2WO6 nano-fiber cloth and preparation method and application thereof |
CN103007966A (en) * | 2012-12-11 | 2013-04-03 | 湖南大学 | Photocatalyst as well as preparation method and application method thereof |
CN103643363A (en) * | 2013-11-20 | 2014-03-19 | 苏州工业园区友顺制衣厂 | Manufacturing process for no-clean self-cleaning environment-friendly cloth |
CN114917961A (en) * | 2022-06-10 | 2022-08-19 | 东南大学 | Preparation of metal semiconductor heterostructure photocatalytic filter screen based on super-wetting surface |
Family Cites Families (6)
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CN1176743C (en) * | 2002-03-29 | 2004-11-24 | 徐瑞芬 | Nano titanium dioxide photocatalyst,prep. and use thereof |
CN1467314A (en) * | 2003-06-12 | 2004-01-14 | 东南大学 | Antibiotic nanometer fibrous material and method for preparing the same |
WO2005026398A2 (en) * | 2003-09-05 | 2005-03-24 | Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College | Nanofibers, and apparatus and methods for fabricating nanofibers by reactive electrospinning |
CN1226471C (en) * | 2003-12-04 | 2005-11-09 | 东南大学 | Twisted ultra-fine nanometer fiber film material and preparing method thereof |
JP4328899B2 (en) * | 2004-03-19 | 2009-09-09 | 学校法人慶應義塾 | Nanofiber sheet having photocatalytic function and method for producing the same |
CN1296417C (en) * | 2004-09-01 | 2007-01-24 | 武汉大学 | Cellulose and nanometer titania composite material, preparation and use thereof |
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2005
- 2005-12-23 CN CNB2005101320830A patent/CN100404126C/en not_active Expired - Fee Related
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101428209B (en) * | 2007-11-08 | 2010-12-01 | 北京化工大学 | Nano-fibre supported titanium dioxide photocatalyst and preparation method thereof |
CN101612565B (en) * | 2009-07-21 | 2011-08-31 | 中国科学院上海硅酸盐研究所 | Bi2WO6 nano-fiber cloth and preparation method and application thereof |
CN103007966A (en) * | 2012-12-11 | 2013-04-03 | 湖南大学 | Photocatalyst as well as preparation method and application method thereof |
CN103007966B (en) * | 2012-12-11 | 2014-06-11 | 湖南大学 | Photocatalyst as well as preparation method and application method thereof |
CN103643363A (en) * | 2013-11-20 | 2014-03-19 | 苏州工业园区友顺制衣厂 | Manufacturing process for no-clean self-cleaning environment-friendly cloth |
CN114917961A (en) * | 2022-06-10 | 2022-08-19 | 东南大学 | Preparation of metal semiconductor heterostructure photocatalytic filter screen based on super-wetting surface |
CN114917961B (en) * | 2022-06-10 | 2023-07-21 | 东南大学 | Preparation of metal semiconductor heterostructure photocatalytic filter screen based on super-wetting surface |
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