CN101376098B - Method for preparing visible light responding TiO2 mixed crystal using bergmeal as substrate - Google Patents
Method for preparing visible light responding TiO2 mixed crystal using bergmeal as substrate Download PDFInfo
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- CN101376098B CN101376098B CN2008101560503A CN200810156050A CN101376098B CN 101376098 B CN101376098 B CN 101376098B CN 2008101560503 A CN2008101560503 A CN 2008101560503A CN 200810156050 A CN200810156050 A CN 200810156050A CN 101376098 B CN101376098 B CN 101376098B
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Abstract
A preparation method for visible light responding TiO2 mixed crystal which utilizes diatomite as a basal body and relates to photocatalysis and material chemistry technical field. The method comprises the steps of: 1. preparing titanium dioxide mixed crystal; 2. activating diatomite; 3. loading the prepared titanium dioxide mixed crystal on the activated diatomite, and preparing titanium dioxide compound photocatalyst which has diatomite as the basal body and is visible light responding. The catalyst produced by adopting the preparation method of the invention has high specific surface area, and has fair degradation efficiency to organisms in practical agricultural chemicals and waste water under visible light irradiation as to Degussa P25 under ultraviolet light irradiation. Furthermore,the catalyst can be recycled and has high repeating using efficiency.
Description
Technical field
The present invention relates to photocatalysis and material chemistry technical field, refering in particular to a kind of is the visible light-responded TiO of matrix with diatomite
2The preparation method of mixed crystal.
Background technology
Along with competing of people's environmental consciousness, material or green product that exploitation can combine with the Nature resource, with the degree of reduction to environmental disruption, and the raising quality of the life has become a main trend.In this numerous material, photochemical catalyst is an important developing direction wherein.
Photocatalysis is a novel environmental improvement technology and a novel energy technology with broad prospect of application.It has outstanding advantages such as low energy consumption, easy to operate, non-secondary pollution.In these researchs,, become the center of gravity of research because titanium dioxide has powerful redox ability, high chemical stability and nontoxic characteristic.Yet TiO
2Be wide-band gap material, the solar energy utilization ratio is low, need excite with ultraviolet source usually, and this has limited the application of its reality.Highly active TiO under the preparation visible light
2Be to use TiO
2One of key subject of photocatalysis technology, appearing as of mixed crystal improves TiO
2Self visible light activity has been created may.At present, be that (the rutile-type mass fraction is 25% to active standard, and Detitanium-ore-type is 75%, and specific area is about 50m with DegussaP25 in the research both at home and abroad
2/ g), it is a kind of typical mixed crystal system.According to another reports such as He Jianbo, the mixed crystal photocatalytic activity when anatase and rutile are 7:3 is the highest, and its photocatalytic activity is 2～4 times of same particle size anatase.Yu etc. think that the mixed crystal of anatase and brockite can suppress the compound of light induced electron and hole, and suitable brockite content can improve TiO
2Photocatalytic activity.Up to the present, the visible light-responded TiO that reports in the prior art
2Photochemical catalyst will cause its complex process by doping vario-property to improve visible light activity usually, and cost improves.Up to the present, do not see that the simple titanium dioxide of undoped modification directly has the report of visible light activity.The present invention passes through to regulate preparation condition, and itself and diatomite are interacted, and has prepared the titanium dioxide mixed crystal that directly has visible light activity.
In addition, traditional TiO
2Photochemical catalyst is mainly used in powder dispersion suspension system, and the suspension system existence is difficult to separate and reclaim, shortcomings such as easy cohesion.Make poor reproducibility, running cost is higher, therefore also is only limited to laboratory research, is not applied to production practices.So TiO
2Immobilized and integrated reaction and separation become one of challenging problem in the photocatalysis field.The main effect of carrier of photocatalyst: (1) is TiO fixedly
2Prevent to run off convenient the recovery.The present invention is carried on the TiO 2 sol for preparing on the good diatomite of activation just at this shortcoming, solves the problem of catalyst recovery difficulty; (2) can increase TiO
2Specific area, thereby improve TiO
2Absorptivity; (3) carrier may same TiO
2Act synergistically, help the separation in electronics-hole, and be beneficial to the absorption of reactant, thereby improve TiO
2Photocatalytic activity.Just as its absorption band generation red shift behind the discovery catalyst cupports such as Do, red shift has taken place in we prepared catalyst too.
Summary of the invention
The purpose of this invention is to provide and a kind ofly have visible light activity without any doping vario-property and separate easily and the preparation method of the titanium dioxide mixed crystal that reclaims.
The concrete operations step is as follows: titanium tetrachloride is added drop-wise in the ice bath, and regulating its pH value with ammoniacal liquor after stirring is between 5～9, obtains white precipitate, filters, and washing precipitate is to there not being chlorion; The water-soluble back of white precipitate is added 30% (mass fraction) hydrogenperoxide steam generator, and the volume ratio of hydrogen peroxide and titanium tetrachloride is 1:1～2:1, is placed under 80 ℃～150 ℃ temperature conditions again and is incubated 4～12 hours; Diatomite after the taking-up that itself and activation is good mixes stirring, dries, and 400 ℃～600 ℃ roastings 2～8 hours, obtaining with diatomite is the titanium dioxide mixed crystal powder of matrix.The titanium dioxide that adopts preparation method of the present invention to obtain is that crystal formation is the mixed crystal system of anatase and brockite, and target product has photocatalytic activity under radiation of visible light, effectively degradable organic pollutant; And after the load, it is big to have specific area, active high characteristics.
Among the above-mentioned preparation method, the rate of addition of titanium tetrachloride is 20～50 droplets/minute, regulates its pH value with ammoniacal liquor with 2000 rev/mins speed stirring after 2～5 hours;
Among the above-mentioned preparation method, the water-soluble back of white precipitate is added hydrogenperoxide steam generator, stir again and add surfactant and tackifier after 3 hours, the addition of surfactant and tackifier is that one of percentage of titanium hydroxide (being white precipitate) quality arrives one thousandth, and surfactant is carboxylate or phosphate or polyethylene glycol; Tackifier are carboxymethyl cellulose or carboxyethyl cellulose or acrylic acid; Surfactant: tackifier (mass ratio) are 1:1;
Among the above-mentioned preparation method, the check of chlorion is that filtrate is splashed in the liquor argenti nitratis ophthalmicus, sees to have or not white precipitate;
Among the above-mentioned preparation method, diatomaceous activation method is: elder generation in 400 ℃～800 ℃ roastings 1～5 hour, soaks activation 1～10 hour, dry for standby with diatomite again in 2%～10% dilute hydrochloric acid solution.
The evaluation method of photocatalytic activity provided by the invention:
Get the actual agricultural chemicals waste water of Jiangsu Gengyun Chemical Co., Ltd., the titanium deoxide catalyst 0.1g that gets the present invention's preparation carries out the photocatalysis experiment in 100ml waste water, survey the situation of change of its COD value.Be reflected under the irradiation of iodine-tungsten lamp and carry out.Under the similarity condition, under the medium pressure mercury lamp irradiation, be the contrast experiment with Degussa P25.Under visible light irradiation, compound system can be suitable with the DegussaP25 degradation efficiency under the ultraviolet light irradiation to organic degradation efficiency in the actual agricultural chemicals waste water.
Description of drawings
Fig. 1 is the X ray spectrogram that is carried on the nano titanium oxide on the diatomite according to example one preparation
A is anatase 101 crystal faces, and B is brockite 121 crystal faces, and prepared as can be seen titanium dioxide is the mixed crystal of anatase and brockite.
Fig. 2, Fig. 3 are the stereoscan photograph that is carried on the nano titanium oxide on the diatomite according to example one preparation, and as seen from the figure, the titanium dioxide of preparation has been carried in the middle of the good diatomaceous duct of activation uniformly.
Fig. 4 is the uv drs spectrogram that is carried on the nano titanium oxide on the diatomite according to examples preparation, can find out clearly among the figure, the red shift of the absorption band of titanium dioxide is to visible region, for it provides theoretical foundation in the catalytic activity under the visible light.
The specific embodiment
The present invention will be further described below in conjunction with concrete embodiment.
Embodiment 1:
1, slowly be added drop-wise to the 10ml titanium tetrachloride in the ice bath, 40 droplets/minute of control rate of addition, speed with 2000 rev/mins after all dripping stirred 2 hours, regulate its pH value 7.0 with ammoniacal liquor, obtain white precipitate, continue to stir after 3 hours filter, washing precipitate is to there not being chlorion, water-soluble back is to wherein adding the 10ml hydrogen peroxide, stirred 2 hours, and be placed on 100 ℃ of insulation 6h in the reactor behind the carboxymethyl cellulose of adding 0.1g sodium phosphate and 0.1g, standby after taking out.
2, diatomite is poured in 5% watery hydrochloric acid again and stirs 5h through 450 ℃ of activation 2h, takes out the back oven dry.
3, the titanium dioxide with preparation mixes stirring with activation diatomite well, oven dry, and 550 ℃ of roast 5h, obtaining target is the mixed crystal type titania powder with visible light activity of matrix with diatomite.
Embodiment 2:
1, slowly be added drop-wise to the 10ml titanium tetrachloride in the ice bath, 20 droplets/minute of control rate of addition, speed with 2000 rev/mins after all dripping stirred 3 hours, regulate its pH value 5.0 with ammoniacal liquor, obtain white precipitate, continue to stir after 3 hours filter, washing precipitate is to there not being chlorion, water-soluble back is to wherein adding the 20ml hydrogen peroxide, stirred 2 hours, and be placed on 150 ℃ of insulation 4h in the reactor behind the carboxymethyl cellulose of adding 0.05g sodium phosphate and 0.05g, standby after taking out.
2, diatomite is poured in 1% watery hydrochloric acid again and stirs 10h through 600 ℃ of activation 5h, takes out the back oven dry.
3, the titanium dioxide with preparation mixes stirring with activation diatomite well, oven dry, and 450 ℃ of roast 8h, obtaining target is the mixed crystal type titania powder with visible light activity of matrix with diatomite.
Embodiment 3:
1, slowly be added drop-wise to the 10ml titanium tetrachloride in the ice bath, 50 droplets/minute of control rate of addition, speed with 2000 rev/mins after all dripping stirred 5 hours, regulate its pH value 9.0 with ammoniacal liquor, obtain white precipitate, continue to stir after 3 hours filter, washing precipitate is to there not being chlorion, water-soluble back is to wherein adding the 15ml hydrogen peroxide, stirred 2 hours, and be placed on 80 ℃ of insulation 12h in the reactor behind the carboxymethyl cellulose of adding 0.02g sodium phosphate and 0.02g, standby after taking out.
2, diatomite is poured in 10% watery hydrochloric acid again and stirs 2h through 800 ℃ of activation 1h, takes out the back oven dry.
3, the titanium dioxide with preparation mixes stirring with activation diatomite well, oven dry, and 600 ℃ of roast 2h, obtaining target is the mixed crystal type titania powder with visible light activity of matrix with diatomite.
Claims (5)
1. one kind is the visible light-responded TiO of matrix with diatomite
2The preparation method of mixed crystal is specially: titanium tetrachloride is added drop-wise in the ice bath, and regulating its pH value with ammoniacal liquor after stirring is between 5～9, obtains white precipitate, filters, and washing precipitate is to there not being chlorion; The water-soluble back of white precipitate is added 30% (mass fraction) hydrogenperoxide steam generator, and the volume ratio of hydrogen peroxide and titanium tetrachloride is 1: 1～2: 1, is placed under 80 ℃～150 ℃ temperature conditions again and is incubated 4～12 hours; Diatomite after the taking-up that itself and activation is good mixes stirring, dries, and 400 ℃～600 ℃ roastings 2～8 hours, obtaining with diatomite is the visible light-responded TiO of matrix
2Mixed crystal.
2. according to claim 1 a kind of be the visible light-responded TiO of matrix with diatomite
2The preparation method of mixed crystal is characterized in that: the rate of addition of titanium tetrachloride is 20～50 droplets/minute, regulates its pH value with ammoniacal liquor with 2000 rev/mins speed stirring after 2～5 hours.
3. according to claim 1 a kind of be the visible light-responded TiO of matrix with diatomite
2The preparation method of mixed crystal, it is characterized in that: the water-soluble back of white precipitate is added hydrogenperoxide steam generator, stir again and add surfactant and tackifier after 3 hours, the addition of surfactant and tackifier is that one of percentage of white precipitate quality arrives one thousandth, and surfactant is carboxylate or phosphate or polyethylene glycol; Tackifier are carboxymethyl cellulose or carboxyethyl cellulose or acrylic acid; Surfactant: tackifier (mass ratio) are 1: 1.
4. according to claim 1 a kind of be the visible light-responded TiO of matrix with diatomite
2The preparation method of mixed crystal is characterized in that: the check of chlorion is that filtrate is splashed in the liquor argenti nitratis ophthalmicus, sees to have or not white precipitate.
5. according to claim 1 a kind of be the visible light-responded TiO of matrix with diatomite
2The preparation method of mixed crystal is characterized in that: diatomaceous activation method is: elder generation in 400 ℃～800 ℃ roastings 1～5 hour, soaks activation 1～10 hour, dry for standby with diatomite again in 2%～10% dilute hydrochloric acid solution.
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| CN104549198A (en) * | 2014-11-05 | 2015-04-29 | 华文蔚 | Preparation method of TiO2 catalyst |
| CN104525171A (en) * | 2014-11-05 | 2015-04-22 | 华文蔚 | A preparation method for a visible light response TiO2 catalyst with hydromica clay as matrix |
| CN105251493A (en) * | 2015-10-28 | 2016-01-20 | 昆明理工大学 | Preparing method for photocatalytic material |
| CN105944661A (en) * | 2016-05-20 | 2016-09-21 | 佛山市聚成生化技术研发有限公司 | Method of treating bisphenol A in water through titanium dioxide modified diatomite |
| CN105994261A (en) * | 2016-06-06 | 2016-10-12 | 佛山市聚成生化技术研发有限公司 | Photodegradable organophosphorus pesticide insecticide preparation method and photodegradable organophosphorus pesticide insecticide prepared by method |
| CN106046913A (en) * | 2016-07-29 | 2016-10-26 | 上海宇昂水性新材料科技股份有限公司 | Nanometer titania modified loading method and application |
| CN108355609A (en) * | 2018-04-28 | 2018-08-03 | 南京工程学院 | A kind of supported copper, silver ion are attapulgite modified and preparation method thereof |
| CN108479739A (en) * | 2018-05-10 | 2018-09-04 | 苏州泰利三佳纳米科技有限公司 | It is a kind of to prepare the diatomaceous method of dioxide photocatalyst titanium |
| CN109046340B (en) * | 2018-08-21 | 2021-09-24 | 中科广化（重庆）新材料研究院有限公司 | Surface-modified visible light catalytic material and preparation method and application thereof |
| CN111514915A (en) * | 2020-04-26 | 2020-08-11 | 江苏优升泰环保科技有限公司 | Catalyst suitable for kitchen oil fume purification and preparation method thereof |
| CN116440899A (en) * | 2023-03-14 | 2023-07-18 | 北京理工大学 | Noble metal supported catalyst with low loss rate, preparation method and application thereof |
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