CN104043470B - A kind of preparation method of nano titanium dioxide photocatalyst of energy degrading high concentration benzene - Google Patents
A kind of preparation method of nano titanium dioxide photocatalyst of energy degrading high concentration benzene Download PDFInfo
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- CN104043470B CN104043470B CN201410230962.6A CN201410230962A CN104043470B CN 104043470 B CN104043470 B CN 104043470B CN 201410230962 A CN201410230962 A CN 201410230962A CN 104043470 B CN104043470 B CN 104043470B
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Abstract
The present invention relates to a kind of can the nano titanium dioxide photocatalyst preparation method of efficient degradation high concentration benzene, this photochemical catalyst is at NH by titanium dioxide obtained for hydro-thermal method
3and H
2carry out annealing in process under atmosphere to obtain, be designated as N-H-TiO
2.The atmosphere used in the present invention is NH
3and H
2, in venting process, its flow is 200-400ml/min, and heat treatment temperature is 550-650 DEG C, and heating rate is 5-10 DEG C/min, the insulation under two kinds of atmosphere, directly opens fire door, naturally cool to room temperature after arrival temperature retention time.N-H-TiO of the present invention
2nano-photocatalyst is faint yellow, even particulate dispersion, and advantage is the cost of its cheapness and the performance of simple technique and efficient stable, this poisonous volatile organic matter of benzene of can thoroughly degrading fast under visible light.Preparation method of the present invention can realize the control to temperature, time and heat-treating atmosphere, have easy controlled, energy consumption is low, efficiency is high, free of contamination advantage.
Description
Technical field
The invention belongs to material science and technology and field of Environment Protection, specifically, is that one under visible light can the preparation method of the thorough nano titanium dioxide photocatalyst of degrading high concentration benzene (>150ppm).
Background technology
Titanium dioxide (TiO
2) there is the advantages such as good chemical stability, nontoxicity, anti-light burn into be cheap, be widely used in the aspects such as photocatalysis, solar cell, air and water purification.The organic pollutions such as benzene (indoor polluted gas), as a kind of catalyst, can be decomposed into carbon dioxide and water by titanium dioxide.Meanwhile, in transfer process, discharge negative oxygen ion, there is the effect of sterilizing.But, TiO
2broad-band gap (anatase is about 3.2eV, and rutile is about 3.0eV) cause it to absorb only accounting for the ultraviolet light of 3% ~ 5% of sunshine, significantly limit TiO
2the quantum yield of photochemical catalyst.So people are devoted to TiO
2photoresponse extend to visible-range, make it absorb more sunshine.In order to reduce band gap, the separative efficiency etc. of widening photoresponse scope and increasing electron-hole pair enables light-catalyzed reaction carry out efficiently, researchers have employed a lot of method, comprise doping metals or nonmetallic ion and narrow gap semiconductor coupling, auto-dope, heat treatment etc.Wherein, in reducing atmosphere to TiO
2heat-treat the nano titanium dioxide photocatalyst prepared containing defects such as Lacking oxygen and there is very large advantage, and heat treatment makes TiO
2preparation and the regulation and control of photocatalytic activity more simple and easy to do.People not only can by parameter optimization techniques such as the temperature and times in adjustment experimentation, produce the defects such as the Lacking oxygen of debita spissitudo, and can combine and given play to the synergy of defect and doped chemical, advantageously in the carrying out of light-catalyzed reaction and the raising of efficiency with doping.
Owing to having conjugatedπbond, this poisonous volatile organic contaminant of benzene is difficult to be degraded.When high concentration, benzene causes very large threat as indoor pollutant to the healthy of people.So, remove benzene as far as possible fast up hill and dale and seem particularly important.But existing photochemical catalyst often can only partly be degraded benzene under visible light, and efficiency is not high, degradation time is longer.The preparation method of titanium dioxide optical catalyst in the past, the Technology for Heating Processing of employing and equipment itself also exist a lot of problem, such as complex process, and condition is harsh, manufacturing cycle is long, energy resource consumption is high.In addition, the effect played factors such as the defects produced in the preparation process of photochemical catalyst lacks the problems such as thorough understanding and ability of regulation and control and also seriously hinders follow-up study to photocatalysis material of titanium dioxide and practical application.
Summary of the invention
The object of the invention is for above-mentioned background technology and existing problems, propose a kind of can the preparation method of the thorough nano titanium dioxide photocatalyst of degrading high concentration benzene under visible light, the catalyst prepared by the method is utilized to have stronger light absorpting ability and efficient photocatalysis efficiency, and degradation speed is fast, finally this poisonous volatile organic matter of benzene can be degraded fast up hill and dale, thus environment purification, pollution abatement.
For achieving the above object, a kind of preparation method of nano titanium dioxide photocatalyst, the method comprises the steps:
1st step is by TiO
2nanometer powder is put into tube furnace and is sealed, after pass into ammonia (concentration is 99.999%) air that remains in quartz ampoule discharged;
After 2nd step air is discharged, be incubated after tube furnace being warming up to 550-650 DEG C, heating rate is 5-10 DEG C/min, and the first half of temperature-rise period and temperature retention time continues to pass into NH
3, the latter half of insulation, stops passing into NH
3, and pass into H
2;
3rd step temperature retention time is opened the fire door of tube furnace, is made it continue to pass into H after arriving
2when be quickly cooled to room temperature, obtain described titanium dioxide optical catalyst N-H-TiO
2.
As the improvement of technique scheme, pass in tube furnace in the process of gas, NH
3and H
2gas flow all remain on 200-400ml/min.
As the further improvement of technique scheme, temperature retention time is 4-8h, and the first half of temperature retention time is equal with the latter half time.
As the further improvement of technique scheme, described TiO
2nanometer powder is the pure TiO that hydro-thermal method prepares
2nanometer powder.
Nano titanium dioxide photocatalyst N-H-TiO of the present invention
2there is good degree of crystallinity and stability, suitable particle size.The N-H-TiO obtained after heat treatment
2visible absorption ability strengthens, and photocatalytic activity is significantly improved, and degradation speed is fast, thus is thoroughly degraded by this poisonous volatile organic matter of benzene, environment purification, pollution abatement.
The present invention utilizes common tube furnace to achieve effective control of temperature to heat treatment process, time and atmosphere, with the pure TiO that hydro-thermal method is obtained
2for a kind of photochemical catalyst N-H-TiO of efficient stable prepared by raw material
2, this volatile organic contaminant of the benzene of high concentration can thoroughly be degraded by fast.Preparation method of the present invention accurately can control heat treated whole process, have that cost is low, efficiency is high, energy consumption is low, pollution-free and easy and simple to handle, be easy to the advantages such as popularization.
Accompanying drawing explanation
In Fig. 1, a, b, c are N-H-TiO respectively
2-550, N-H-TiO
2-600 and N-H-TiO
2the microscopic appearance of-650 these three kinds of nano materials;
Fig. 2 is TiO
2, N-H-TiO
2-550, N-H-TiO
2-600 and N-H-TiO
2the X-ray diffraction spectrum (XRD) of-650 these four kinds of nano materials;
Fig. 3 is N-H-TiO of the present invention
2with the performance test results of other sample photocatalytic degradation benzene of the same type.Wherein, (3a) C/C
0represent the degradation rate of benzene, (3b) C-C
0represent the amount (unit: ppm) of the product C O2 generated, C
0for initial concentration, C is the material concentration in degradation process.
Detailed description of the invention
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described further.It should be noted that at this, the explanation for these embodiments understands the present invention for helping, but does not form limitation of the invention.In addition, if below in described each embodiment of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
Prepared by the inventive method can the nano titanium dioxide photocatalyst N-H-TiO of efficient degradation high concentration benzene
2by the obtained pure TiO of hydro-thermal reaction 12h at 150-200 DEG C
2obtain after heat treatment in ammonia and these two kinds of atmosphere of hydrogen.N-H-TiO
2degree of crystallinity Gao Bingneng effectively absorb visible ray, photocatalytic activity strengthens, and degradation speed is fast, finally this organic pollution of benzene can be degraded fast up hill and dale under visible light.
In such scheme, nano titanium dioxide photocatalyst N-H-TiO
2particle size be about 33.55nm.To N-H-TiO
2when carrying out photocatalysis performance test, the initial concentration of degraded object benzene is about 150ppm, and thoroughly the degraded benzene time used is 3h.
Prepare the method for above-mentioned nano titanium dioxide photocatalyst, the method have that cost is low, efficiency is high, energy consumption is low, pollution-free and easy and simple to handle, be easy to the feature promoted.
Nano titanium dioxide photocatalyst N-H-TiO
2preparation method, it is characterized in that: obtain pure TiO according to above-mentioned hydro-thermal method
2after, it is carried out annealing heat treatment in tube furnace, and concrete steps are as follows:
(1) a certain amount of pure TiO2 nanometer powder is put into ceramic boat, then ceramic boat is put into the quartz ampoule of tube furnace and two ends stainless steel sealing flange is sealed, the air remained in quartz ampoule is discharged by the ammonia then passing into high-purity (concentration is 99.999%), and duration of ventilation is 20-30min.
(2) after being vented, open the power switch of tube furnace, perform process of thermal treatment flow process.The initial temperature of tube furnace is set as 20 DEG C, and annealing temperature is 550-650 DEG C, and heating rate is 5-10 DEG C/min, continues to pass into NH
3and H
2these two kinds of gases are also incubated 4h after intensification completes in annealing atmosphere.
(3), after temperature retention time arrives, opening the fire door of tube furnace, making it be quickly cooled to room temperature when continuing to pass into protective atmosphere, finally obtain the high efficiency photocatalyst N-H-TiO described in the present invention
2.
Pass in tube furnace in the process of gas, NH
3and H
2gas flow all remain on 200-400ml/min.
In the above-mentioned methods, the model of tube furnace used is: 1200 DEG C of open tubular furnace-OTF-1200X, and peak power is 2.5KW.
Embodiment 1:
The present embodiment be to mention in the present invention by pure TiO
2heat-treat in ammonia and hydrogen two kinds of atmosphere and obtain nano titanium dioxide photocatalyst N-H-TiO
2, benzene of then degrading up hill and dale fast under visible light.Its preparation method and photocatalysis performance test are carried out according to following steps:
1, pure TiO is prepared
2
The hydro-thermal reaction 12h at 160 DEG C by distilled water and butyl titanate, after then washing, drying, obtains the TiO of white
2powder sample;
2, pretreatment
By the pure TiO of preparation in above-mentioned steps 1
2nanometer powder uniform spreading, in the bottom of ceramic boat, then to move into ceramic boat in the quartz ampoule of tube furnace and at two ends with the sealing of stainless steel sealing flange, then to pass into highly purified ammonia and the air that remain in quartz ampoule discharged.Ammonia flow is 200ml/min in the process, and duration of ventilation is 30min.
3, heat treatment
After being vented, open the power switch of tube furnace, perform process of thermal treatment flow process.The initial temperature of tube furnace is set as 20 DEG C, and annealing temperature is 600 DEG C, and heating rate is 5 DEG C/min, continues to pass into NH
3and H
2these two kinds of gases are also incubated 4h after intensification completes in annealing atmosphere.Temperature retention time being opened the fire door of tube furnace, being made it be quickly cooled to room temperature when continuing to pass into protective atmosphere, finally obtain the high efficiency photocatalyst N-H-TiO described in the present invention after arriving
2-600.
4, photocatalysis performance test
By N-H-TiO of the present invention
2utilize the product C O in gas chromatograph detection Photocatalytic Degradation Process under visible light illumination
2growing amount and the concentration of benzene obtain the test result of Fig. 2.This test result utilizes the product C O in gas chromatograph detection Photocatalytic Degradation Process under visible light illumination
2growing amount and the concentration of benzene obtain.Wherein blank is that benzene of degrading in catalyst-free situation is tested using the blank as this test, TiO
2refer to pure TiO prepared by hydro-thermal method
2, H-TiO
2by TiO in hydrogen atmosphere
2at 600 DEG C, be incubated 2h carry out the sample that obtains of heat treatment of annealing, N-TiO
2by TiO in ammonia atmosphere
2at 600 DEG C, be incubated 2h carry out the sample that obtains of heat treatment of annealing, N-H-TiO
2-550, N-H-TiO
2-500 and N-H-TiO
2-650 is by TiO respectively
2at 550 DEG C in ammonia and these two kinds of atmosphere of hydrogen, at 600 DEG C and 650 DEG C, carry out the sample that annealing heat treatment obtains.
Example 2 and 3:
Example 2 and 3, according to the technological parameter in following table, adopts identical the carrying out flow process and can prepare nano titanium dioxide photocatalyst of example 1.
The present invention heat-treats under the atmosphere of different order (first, then pass into NH3 and H2), brings large change to material property; N-H-TiO2 has excellent performance at degraded benzene fermentation, and the efficiency of its degraded is apparently higher than the most catalysis materials existed at present.It is simple that the present invention has technique, and degradation efficiency is high, the advantage that the used time is short.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the content disclosed in this embodiment and accompanying drawing.The equivalence completed under not departing from spirit disclosed in this invention so every or amendment, all fall into the scope of protection of the invention.
Claims (1)
1. a preparation method for nano titanium dioxide photocatalyst, the method comprises the steps:
The pure TiO that 1st step will be prepared by hydro-thermal method
2nanometer powder is put into tube furnace and is sealed, after pass into ammonia the air that remains in quartz ampoule discharged;
After 2nd step air is discharged, be incubated after tube furnace being warming up to 550-650 DEG C, heating rate is 5-10 DEG C/min, and the first half of temperature-rise period and temperature retention time continues to pass into ammonia, the latter half of insulation, stops passing into ammonia, and passes into hydrogen; The gas flow of ammonia and hydrogen all remains on 200-400ml/min;
3rd step temperature retention time is 4-8h, the first half of temperature retention time is equal with the latter half time, and temperature retention time opens the fire door of tube furnace after arriving, making it be quickly cooled to room temperature when continuing to pass into hydrogen, obtaining described titanium dioxide optical catalyst N-H-TiO
2, this titanium dioxide optical catalyst N-H-TiO
2there is light absorpting ability and photocatalysis efficiency, and degradation speed is fast, finally this poisonous volatile organic matter of benzene can be degraded, fast up hill and dale with environment purification, pollution abatement.
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| CN116099530A (en) * | 2021-11-09 | 2023-05-12 | 中国科学院理化技术研究所 | Catalyst for preparing nitric acid by thermally-assisted photocatalytic nitrogen oxidation and preparation method and application thereof |
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| CN101327425A (en) * | 2007-06-21 | 2008-12-24 | 河南大学 | Method for preparing nitrogen-doped titanium dioxide photocatalyst |
| CN102343260A (en) * | 2011-06-28 | 2012-02-08 | 中国科学院金属研究所 | Method for preparing boron-doped titanium dioxide crystal containing specific crystal plane |
| WO2012052624A1 (en) * | 2010-10-21 | 2012-04-26 | Oulun Yliopisto | Photocatalytic material |
| CN103143341A (en) * | 2013-04-03 | 2013-06-12 | 福州大学 | Visible-light degradation tribenzene waste gas catalyst as well as preparation method and application thereof |
| CN103614759A (en) * | 2013-11-22 | 2014-03-05 | 西北师范大学 | Preparation method and application of N-doped titanium dioxide nano-composite structure |
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| CN101327425A (en) * | 2007-06-21 | 2008-12-24 | 河南大学 | Method for preparing nitrogen-doped titanium dioxide photocatalyst |
| WO2012052624A1 (en) * | 2010-10-21 | 2012-04-26 | Oulun Yliopisto | Photocatalytic material |
| CN102343260A (en) * | 2011-06-28 | 2012-02-08 | 中国科学院金属研究所 | Method for preparing boron-doped titanium dioxide crystal containing specific crystal plane |
| CN103143341A (en) * | 2013-04-03 | 2013-06-12 | 福州大学 | Visible-light degradation tribenzene waste gas catalyst as well as preparation method and application thereof |
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| Controlling the synergistic effect of oxygen vacancies and N dopants to enhance photocatalytic activity of N-doped TiO2 by H2 reduction;Zizhong Zhang，et al;《Applied Catalysis A: General》;20120311;第425卷;第118页第2.1节，第123页第4节 * |
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