CN1618516A - Composite nano-photo-catalyst used for purifying air - Google Patents
Composite nano-photo-catalyst used for purifying air Download PDFInfo
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- CN1618516A CN1618516A CN 200410080246 CN200410080246A CN1618516A CN 1618516 A CN1618516 A CN 1618516A CN 200410080246 CN200410080246 CN 200410080246 CN 200410080246 A CN200410080246 A CN 200410080246A CN 1618516 A CN1618516 A CN 1618516A
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Abstract
A composite nano-photocatalyst for cleaning air is composed of anatase-type TiO2, and the (15-25)-nm Fe2O3 and V2O5. It can effectively decompose the formaldehyde, benzene and ammonia in air under irradiation of light.
Description
Technical Field
The invention relates to a nano composite photocatalyst, in particular to a nano composite photocatalyst for purifying air and a preparation method thereof. Belongs to the technical field of nano catalysis.
Background
Most materials for decoration, such as artificial boards, foamed plastics, wall paper and wall cloth, carpet and floor, paint and coating, can directly or indirectly release harmful gases (such as formaldehyde, benzene series, hydrogen sulfide, ammonia and the like); many domestic exhaust gases, such as food deterioration exhaust gases, cooking fumes, cigarette combustion gases, automobile exhaust gases, etc., also contain these harmful gases; these intangible killers pose a significant threat to the health of people, and researchers in various countries are seeking effective air purification techniques to solve these problems in a variety of ways. The traditional technologies of filtering, adsorbing, negative oxygen ion, ozone and the like are difficult to continuously purify pollutants, the technologies of disinfector, ultraviolet lamp and the like have toxic and side effects on human bodies, and the photocatalytic purification technology has become one of the most promising air purification technologies due to the excellent characteristics of high efficiency, durability, convenience, safety and the like.
The photocatalyst is generally composed of a semiconductor material with certain defects, the energy band structure of the semiconductor particles is composed of a low-energy valence band and a high-energy conduction band, a forbidden band exists between the valence band and the conduction band, and the width of the forbidden band is generally below 3 electron volts. When light with energy larger than or equal to forbidden band width (h upsilon is larger than or equal to 3ev) irradiates a semiconductor, the semiconductor particles absorb the energy of light quantum to generate electron-hole pairs, the valence band hole is a good oxidant, the conduction band electron is a good reducing agent, and if the electron-hole pairs are effectively separated and localized on an effective carrying site on the surface of a catalyst, the electron-hole pairs can oxidize or reduce harmful substance molecules adsorbed on the surface of the catalyst and convert the harmful substance molecules into harmless simple molecules. The mechanism of the photocatalytic reaction of, for example, formaldehyde is:
most of the currently used photocatalysts are limited to conventional titanium dioxide powder, the photocatalysts can only absorb ultraviolet light with the wavelength less than 385nm, generated electron-hole pairs are easy to recombine during migration, and if proper bearing sites are not available for capturing the electron-hole pairs, energy is consumed within a few nanoseconds. Therefore, the method improves the absorption of the catalyst to visible light by means of doping or compounding and the like, and properly increases the carrying position to reduce the recombination probability of photo-generated electron-hole pairs, thereby being an effective way for preparing the photocatalyst with wide light area and high activity.
Chinese patent 00129180.7 discloses a photocatalyst for purifying air, which isIn TiO2The powder is loaded with metal platinum and metal oxides of magnesium, lithium, manganese and the like to prepare a powder catalyst, and the catalyst has activity only under ultraviolet light and has no obvious removal effect on benzene series and ammonia. Chinese patent 02150913.1 discloses a method for preparing a novel composite photocatalyst, which is a method for preparing a composite photocatalyst of nano-scale titanium dioxide and alumina by using metatitanic acid as an intermediate for producing titanium white by a sulfuric acid method as a raw material, wherein the activity of the catalyst is mainly reflected in an ultraviolet region. Chinese patent 02801197 discloses a "photocatalyst having catalytic activity even in the visible light range", which is a composite photocatalyst composed of two semiconductor oxides having different junction surfaces, and the activity of the photocatalyst is low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-efficiency broad-spectrum nano composite photocatalyst and a preparation method thereof. In order to achieve the purpose, the invention firstly discovers the following preparation characteristics through a large number of experiments:
1. through modification treatment such as compounding or doping, the recombination probability of photogenerated electron-hole pairs in the conventional nano titanium dioxide can be changed, so that the service life of the electron-hole pairs is changed, and the activity of the photocatalyst is changed;
2. under the same preparation process conditions, different oxides are compounded or different metals or metal ions are doped in the titanium dioxide powder, so that the activity of the photocatalyst is greatly changed;
3. photocatalysts with different activities can also be obtained by using the same composite or doped substance through different preparation processes.
On the basis, through repeated screening and evaluation, the nano-scale composite oxide catalyst prepared by using butyl titanate, ammonium metavanadate and ammonium ferric sulfate as main raw materials through a sol-gel technology and a special processing technology has good material decomposition capacity, and the specific preparation method comprises the following steps: (1) dissolving butyl titanate in methanol, adding a proper amount of acetic acid and distilled water to prepare sol with the concentration of the butyl titanate of 0.35-0.55 mol/L(ii) a (2) Dispersing ammonium metavanadate and ammonium ferric sulfate in methanol, addingAddingcitric acid to adjust the pH value to be 0.5-0.8, and stirring for 30 minutes at 20-30 ℃ to form gel, wherein the atomic ratio of Fe to V is 100: 24-38. Adding a proper amount of methanol to disperse the gel, adding the dispersed gel into the sol in the step (1) under the condition of stirring, and stirring for 30 minutes at the temperature of 20-30 ℃ to form the gel again, wherein the atomic ratio of Ti to Fe is 100: 12-28; (3) and (3) aging the gel formed again in the step (2) at about 40 ℃ for 20 hours, drying at 100-110 ℃, cooling to room temperature, grinding, and roasting at 400-450 ℃ for 1 hour to obtain the composite photocatalyst with the average particle size of 15-25 nm. In which TiO is2Of anatase type structure, Fe2O3And V2O5It has amorphous or microcrystalline structure.
The photocatalyst of the invention has the following remarkable characteristics:
1. the preparation process is simple, the raw material cost is low, and the repeatability is good;
2. can be conveniently used in materials such as paint, film and the like, and has long service life;
3. the nano-silver has extremely high activity in an ultraviolet region and also has obvious activity even in a visible region;
4. has high decomposition activity on formaldehyde, benzene series, ammonia, sulfur dioxide, hydrogen sulfide, bacteria and the like in the air.
Detailed Description
The first embodiment is as follows: dissolving 100ml of tetrabutyl titanate in 600ml of methanol, adding 40ml of acetic acid and 20ml of distilled water, and preparing sol with the concentration of 0.385mol/L of tetrabutyl titanate for later use; in addition, 2 g of ammonium metavanadate and 25 g of iron ammonium alum were dispersed in 50ml of methanol, 10ml of a mixed solution of citric acid and acetic acid was added in a molar ratio of 1: 2, the pH was adjusted to 0.8 with concentrated nitric acid, and the mixture was stirred at room temperature for 30 minutes to form a gel. And dispersing the gel by using 30ml of methanol, adding the dispersed gel into the sol under the condition of stirring, continuously stirring for 30 minutes to form the gel again, aging the gel for 20 hours at about 40 ℃, drying the gel at 100-110 ℃, cooling the gel to room temperature, grinding the gel, and roasting the gel for 1 hour at 400-450 ℃ to obtain the composite photocatalyst with the average particle size of 15-25 nm.
Example two: dissolving tetrabutyl titanate, acetic acid and distilled water which are used as raw materials in methanol to prepare titanium sol, wherein the concentrations of the tetrabutyl titanate, the acetic acid and the distilled water are respectively 0.35, 1.0 and 1.5 mol/L. Mixing ammonium metavanadate, ammonium ferroalum and other raw materials according to the molar ratio of metal ions to organic mixed acid to methanol of 1: 3: 28, wherein the atomic ratio of Fe to V is 4: 1, and the molar ratio of citric acid to acetic acid in the organic mixed acid is 1: 2. Regulating pH value to 0.6 with concentrated nitric acid, and stirring at normal temperature to form gel. The gel was dispersed with methanol at a molar ratio of methanol to metal ions of 8: 1. Dripping the solution into titanium sol, keeping the atomic ratio of Ti to Fe at 100: 28, continuously stirring to form gel again, aging the gel for 20 hours at about 40 ℃, drying at 100-110 ℃, grinding, and roasting at 400 ℃ for 2 hours to obtain the composite photocatalyst with the average particle size of 15-25 nm.
Example three: dissolving tetrabutyl titanate, acetic acid and distilled water which are used as raw materials in methanol to prepare titanium sol, wherein the concentrations of the tetrabutyl titanate, the acetic acid and the distilled water are respectively 0.4, 1.2 and 1.5 mol/L. Mixing ammonium metavanadate, ammonium ferroalum and other raw materials according to the molar ratio of metal ions to organic mixed acid to methanol of 1: 3: 28, wherein the atomic ratio of Fe to V is 100: 30, and the molar ratio of citric acid to acetic acid in the organic mixed acid is 1: 2. Regulating pH value to 0.6 with concentrated nitric acid, and stirring at normal temperature to form gel. The gel was dispersed with methanol at a molar ratio of methanol to metal ions of 8: 1. Dripping the solution into titanium sol, keeping the atomic ratio of Ti to Fe at 100: 25, continuously stirring to form gel again, aging the gel for 20 hours at about 40 ℃, drying at 100-110 ℃, grinding, and roasting at 400 ℃ for 2 hours to obtain the composite photocatalyst with the average particle size of 15-25 nm.
Example four: dissolving tetrabutyl titanate, acetic acid and distilled water which are used as raw materials in methanol to prepare titanium sol, wherein the concentrations of the tetrabutyl titanate, the acetic acid and the distilled water are respectively 0.42, 1.0 and 1.8 mol/L. Mixing ammonium metavanadate, ammonium ferroalum and other raw materials according to the molar ratio of metal ions to organic mixed acid to methanol of 1: 3: 28, wherein the atomic ratio of Fe to V is 100: 35, and the molar ratio of citric acid to acetic acid in the organic mixed acid is 1: 2. Regulating pH value to 0.6 with concentrated nitric acid, and stirring at normal temperature to form gel. The gel was dispersed with methanol at a molar ratio of methanol to metal ions of 8: 1. Dripping the solution into titanium sol, keeping the atomic ratio of Ti to Fe at 100: 20, continuously stirring to form gel again, aging the gel for 20 hours at about 40 ℃, drying at 100-110 ℃, grinding, and roasting at 400 ℃ for 2 hours to obtain the composite photocatalyst with the average particle size of 15-25 nm.
Example five: dissolving tetrabutyl titanate, acetic acid and distilled water which are used as raw materials in methanol to prepare titanium sol, wherein the concentrations of the tetrabutyl titanate, the acetic acid and the distilled water are respectively 0.45 mol/L, 1.5mol/L and 2.5 mol/L. Mixing ammonium metavanadate, ammonium ferroalum and other raw materials according to the molar ratio of metal ions to organic mixed acid to methanol of 1: 3: 28, wherein the atomic ratio of Fe to V is 100: 38, and the molar ratio of citric acid to acetic acid in the organic mixed acid is 1: 2. Regulating pH value to 0.6 with concentrated nitric acid, and stirring at normal temperature to form gel. The gel was dispersed with methanol at a molar ratio of methanol to metal ions of 8: 1. Dripping the solution into titanium sol, keeping the atomic ratio of Ti to Fe at 100: 15, continuously stirring to form gel again, aging the gel for 20 hours at about 40 ℃, drying at 100-110 ℃, grinding, and roasting at 400 ℃ for 2 hours to obtain the composite photocatalyst with the average particle size of 15-25 nm.
Claims (3)
1. A nano-class composite photocatalyst for purifying air is prepared from TiO2(anatase type), Fe2O3And V2O5The composition comprises Ti and Fe at an atomic ratio of 100: 12-28, Fe and V at an atomic ratio of 100: 24-38, and Fe2O3And V2O5Exist in an amorphous or microcrystalline state and have an average particle size of 15 to 25 nm.
2. The nano composite photocatalyst as claimed in claim 1, wherein the catalyst can effectively decompose harmful gases in air such as formaldehyde, benzene series, hydrogen sulfide and ammonia under the condition of illumination, and has good photocatalytic performance even in the visible light region.
3. The nanocomposite photocatalyst of claim 1, wherein the preparation method comprises the following characteristics:
dissolving tetrabutyl titanate in methanol, and adding a proper amount of acetic acid and distilled water to prepare a sol of tetrabutyl titanate; dispersing ammonium metavanadate and ammonium ferric sulfate in methanol, adding citric acid to adjust the pH value to be 0.5-0.8, and stirring for 30 minutes at 20-30 ℃ to form gel, wherein the atomic ratio of Fe to V is 100: 24-38. Adding a proper amount of methanol to disperse the gel, adding the dispersed gel into the sol under the condition of stirring, and stirring for 30 minutes at the temperature of 20-30 ℃ to form the gel again, wherein the atomic ratio of Ti to Fe is 100: 12-28; and (3) aging the gel formed again at about 40 ℃ for 20 hours, drying at 100-110 ℃, cooling to room temperature, grinding for 30 minutes, and roasting at 400-450 ℃ for 1 hour to obtain the composite photocatalyst with the average particle size of 15-25 nm.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031722A (en) * | 2010-10-25 | 2011-04-27 | 华南理工大学 | Zeolite-loaded and vanadium ion-doped titanium dioxide antibacterial paper and preparation method thereof |
| CN101480624B (en) * | 2008-01-08 | 2011-09-14 | 财团法人工业技术研究院 | Production method of photocatalyst filter medium |
| CN102205247A (en) * | 2011-03-24 | 2011-10-05 | 桂林理工大学 | Composite oxide photocatalyst LiCuNb3-xTaxO9 with visible light response and preparation method thereof |
| CN101612575B (en) * | 2009-07-10 | 2011-11-09 | 天津大学 | Fe2O3 and V2O5 dual-active component catalyst for diesel engine and preparation method thereof |
| CN101518732B (en) * | 2008-11-27 | 2012-03-28 | 北京联合大学生物化学工程学院 | Nano catalytic material for decomposing nitrogen oxides |
| CN102039137B (en) * | 2009-10-21 | 2012-09-12 | 中国石油化工股份有限公司 | Honeycomb catalyst for catalytically incinerating sulfur recovery tail gases and preparation method |
| CN104894691A (en) * | 2015-06-29 | 2015-09-09 | 吉首大学 | Method for preparing Fe2O3/V2O5 composite fibers with electrostatic spinning method |
| CN105903307A (en) * | 2016-04-06 | 2016-08-31 | 山东宝梵环保科技有限公司 | Air purifying composition and preparation method and application method thereof, and formation method for elliptical granules of air purifying composition |
| CN110455977A (en) * | 2019-06-30 | 2019-11-15 | 北京联合大学 | A kind of low-temperature catalyzed luminous sensitive material of formaldehyde and ammonia |
| CN110658186A (en) * | 2019-10-22 | 2020-01-07 | 北京联合大学 | Sensitive material for simultaneously measuring formaldehyde, benzene and carbon monoxide |
| CN111167464A (en) * | 2020-02-14 | 2020-05-19 | 辽宁大学 | Preparation of double Z-type V based on in-situ synthesis method2O5/FeVO4/Fe2O3Method for preparing photocatalyst and its application |
| CN113161522A (en) * | 2021-03-12 | 2021-07-23 | 广东工业大学 | Amorphous vanadium oxide/carbon composite material and preparation method and application thereof |
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2004
- 2004-09-28 CN CN 200410080246 patent/CN1269568C/en not_active Expired - Fee Related
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101480624B (en) * | 2008-01-08 | 2011-09-14 | 财团法人工业技术研究院 | Production method of photocatalyst filter medium |
| CN101518732B (en) * | 2008-11-27 | 2012-03-28 | 北京联合大学生物化学工程学院 | Nano catalytic material for decomposing nitrogen oxides |
| CN101612575B (en) * | 2009-07-10 | 2011-11-09 | 天津大学 | Fe2O3 and V2O5 dual-active component catalyst for diesel engine and preparation method thereof |
| CN102039137B (en) * | 2009-10-21 | 2012-09-12 | 中国石油化工股份有限公司 | Honeycomb catalyst for catalytically incinerating sulfur recovery tail gases and preparation method |
| CN102031722A (en) * | 2010-10-25 | 2011-04-27 | 华南理工大学 | Zeolite-loaded and vanadium ion-doped titanium dioxide antibacterial paper and preparation method thereof |
| CN102031722B (en) * | 2010-10-25 | 2012-05-09 | 华南理工大学 | Zeolite-loaded and vanadium ion-doped titanium dioxide antibacterial paper and preparation method thereof |
| CN102205247A (en) * | 2011-03-24 | 2011-10-05 | 桂林理工大学 | Composite oxide photocatalyst LiCuNb3-xTaxO9 with visible light response and preparation method thereof |
| CN102205247B (en) * | 2011-03-24 | 2012-09-05 | 桂林理工大学 | Composite oxide photocatalyst LiCuNb3-xTaxO9 with visible light response and preparation method thereof |
| CN104894691A (en) * | 2015-06-29 | 2015-09-09 | 吉首大学 | Method for preparing Fe2O3/V2O5 composite fibers with electrostatic spinning method |
| CN104894691B (en) * | 2015-06-29 | 2016-05-11 | 吉首大学 | A kind of method of electrostatic spinning is prepared Fe2O3/V2O5The method of composite fibre |
| CN105903307A (en) * | 2016-04-06 | 2016-08-31 | 山东宝梵环保科技有限公司 | Air purifying composition and preparation method and application method thereof, and formation method for elliptical granules of air purifying composition |
| CN110455977A (en) * | 2019-06-30 | 2019-11-15 | 北京联合大学 | A kind of low-temperature catalyzed luminous sensitive material of formaldehyde and ammonia |
| CN110455977B (en) * | 2019-06-30 | 2021-06-08 | 北京联合大学 | Low-temperature catalytic luminescence sensitive material of formaldehyde and ammonia |
| CN110658186A (en) * | 2019-10-22 | 2020-01-07 | 北京联合大学 | Sensitive material for simultaneously measuring formaldehyde, benzene and carbon monoxide |
| CN110658186B (en) * | 2019-10-22 | 2021-08-13 | 北京联合大学 | Sensitive material for simultaneously measuring formaldehyde, benzene and carbon monoxide |
| CN111167464A (en) * | 2020-02-14 | 2020-05-19 | 辽宁大学 | Preparation of double Z-type V based on in-situ synthesis method2O5/FeVO4/Fe2O3Method for preparing photocatalyst and its application |
| CN111167464B (en) * | 2020-02-14 | 2021-11-26 | 辽宁大学 | Preparation of double Z-type V based on in-situ synthesis method2O5/FeVO4/Fe2O3Method for preparing photocatalyst and its application |
| CN113161522A (en) * | 2021-03-12 | 2021-07-23 | 广东工业大学 | Amorphous vanadium oxide/carbon composite material and preparation method and application thereof |
| CN113161522B (en) * | 2021-03-12 | 2022-07-19 | 广东工业大学 | Amorphous vanadium oxide/carbon composite material and preparation method and application thereof |
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| CN1269568C (en) | 2006-08-16 |
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