CN104043470A - Preparation method of nano titanium dioxide photocatalyst capable of degradation of high-concentration benzene - Google Patents
Preparation method of nano titanium dioxide photocatalyst capable of degradation of high-concentration benzene Download PDFInfo
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- CN104043470A CN104043470A CN201410230962.6A CN201410230962A CN104043470A CN 104043470 A CN104043470 A CN 104043470A CN 201410230962 A CN201410230962 A CN 201410230962A CN 104043470 A CN104043470 A CN 104043470A
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Abstract
The invention relates to a preparation method of a nano titanium dioxide photocatalyst capable of high-efficiency degradation of high-concentration benzene. The photocatalyst is obtained by in NH3 and H2 atmospheres, carrying out annealing treatment on titanium dioxide prepared by a hydrothermal method; the photocatalyst is represented by N-H-TiO2. The used atmospheres are NH3 and H2, the flow quantities are all 200-400 ml/min in a gas introducing process, the heat treatment temperature is 550-650 DEG C, the temperature rising rate is 5-10 DEG C/min, heat preservation is carried out in the two atmospheres, a furnace gate is directly opened when the heat preservation time is reached, and natural cooling to the room temperature is carried out. The N-H-TiO2 nano photocatalyst is pale yellow in color, has evenly dispersed particles, has the advantages of low cost, simple process and high-efficiency and stable performance, and can quickly completely degrade the toxic volatile organic compound benzene under visible light. The preparation method can control the temperature, time and heat treatment atmospheres, and has the advantages of simpleness, controllability, low energy consumption, high efficiency, and no pollution.
Description
Technical field
The invention belongs to material science and technology and field of Environment Protection, specifically, be a kind of under visible ray the thorough preparation method of the nano titanium dioxide photocatalyst of degrading high concentration benzene (>150ppm).
Background technology
Titanium dioxide (TiO
2) there is good chemical stability, nontoxicity, anti-photoetch, the advantage such as cheap, be widely used in the aspects such as photocatalysis, solar cell, air and water purification.Titanium dioxide, as a kind of catalyst, can be decomposed into carbon dioxide and water by the organic pollutions such as benzene (indoor polluted gas).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 can only absorb 3%～5% the ultraviolet light that only accounts for sunshine, greatly limited 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 dwindle band gap, the separative efficiency etc. of widening photoresponse scope and increasing electron-hole pair can carry out light-catalyzed reaction efficiently, researchers have adopted a lot of methods, comprise doping metals or nonmetallic ion and narrow gap semiconductor coupling, auto-dope, heat treatment etc.Wherein, in reducing atmosphere to TiO
2the nano titanium dioxide photocatalyst of heat-treating to prepare containing defects such as aerobic rooms has 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 be by regulating the parameter optimization techniques such as temperature and time in experimentation, produce the defects such as oxygen room of debita spissitudo, and can combine and give play to the synergy of defect and doped chemical with doping, be more conducive to the carrying out of light-catalyzed reaction and the raising of efficiency.
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 people healthy.So, remove up hill and dale as far as possible fast benzene and seem particularly important.But, the existing photochemical catalyst benzene of often can only partly degrading under visible ray, 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 exist a lot of problems, and such as complex process, condition is harsh, manufacturing cycle is long, energy resource consumption is high.In addition, the effect of the factors such as the defect producing in the preparation process of photochemical catalyst being played lacks the problems such as thorough understanding and ability of regulation and control and also seriously hinders the follow-up study of 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 be under visible ray the thorough preparation method of the nano titanium dioxide photocatalyst of degrading high concentration benzene, utilize the prepared catalyst of the method to there is stronger light absorpting ability and efficient photocatalysis efficiency, and degradation speed is fast, finally can be by the degraded up hill and dale fast of this poisonous volatile organic matter of benzene, 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:
The 1st step is by TiO
2nanometer powder is put into tube furnace and is sealed, after pass into ammonia (concentration is 99.999%) by the Bas Discharged remaining in quartz ampoule;
After the 2nd step Bas Discharged, tube furnace is warming up to 550-650 ℃ after insulation, heating rate is 5-10 ℃/min, 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;
After the 3rd step temperature retention time arrives, open the fire door of tube furnace, make it continue to pass into H
2situation under be quickly cooled to room temperature, obtain described titanium dioxide optical catalyst N-H-TiO
2.
As the improvement of technique scheme, in tube furnace, pass 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 and latter half time equate.
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 obtaining after heat treatment
2visible absorption ability strengthens, and photocatalytic activity is significantly improved, and degradation speed is fast, thereby this poisonous volatile organic matter of benzene is thoroughly degraded, environment purification, pollution abatement.
The present invention utilizes common tube furnace to realize effective control of temperature, time and atmosphere to heat treatment process, the pure TiO making with hydro-thermal method
2for raw material is prepared a kind of photochemical catalyst N-H-TiO of efficient stable
2, it can be by the thoroughly degraded fast of this volatile organic contaminant of the benzene of high concentration.Preparation method of the present invention can accurately 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
A in Fig. 1, b, c is respectively N-H-TiO
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 of-650 these four kinds of nano materials (XRD);
Fig. 3 is N-H-TiO of the present invention
2the performance test results with other sample photocatalytic degradation benzene of the same type.Wherein, (3a) C/C
0the degradation rate that represents benzene, (3b) C-C
0the amount of the product C O2 that expression generates (unit: ppm), C
0for initial concentration, C is the material concentration in degradation process.
The specific embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described further.At this, it should be noted that, for the explanation of these embodiments, be used for helping to understand the present invention, but do not form limitation of the invention.In addition,, in each embodiment of described the present invention, involved technical characterictic just can not combine mutually as long as do not form each other conflict.
The inventive method is prepared can efficient degradation high concentration benzene nano titanium dioxide photocatalyst N-H-TiO
2the pure TiO that hydro-thermal reaction 12h at 150-200 ℃ is made
2in ammonia and these two kinds of atmosphere of hydrogen, after heat treatment, obtain.N-H-TiO
2degree of crystallinity Gao Bingneng effectively absorb visible ray, photocatalytic activity strengthens, degradation speed is fast, finally can be by the degraded up hill and dale fast of this organic pollution of benzene under visible ray.
In such scheme, nano titanium dioxide photocatalyst N-H-TiO
2particle size be about 33.55nm.To N-H-TiO
2while carrying out photocatalysis performance test, the initial concentration of degraded object benzene is about 150ppm, and the benzene of thoroughly the degrading time used is 3h.
The method of preparing above-mentioned nano titanium dioxide photocatalyst, the method has 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: according to above-mentioned hydro-thermal method, make pure TiO
2after, heat treatment that it is annealed in tube furnace, 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 are sealed with stainless steel sealing flange, then pass into the ammonia of high-purity (concentration is 99.999%) by the Bas Discharged remaining in quartz ampoule, duration of ventilation is 20-30min.
(2) after exhaust completes, open the power switch of tube furnace, carry out process of thermal treatment flow process.The initial temperature of tube furnace is set as to 20 ℃, and annealing temperature is 550-650 ℃, and heating rate is 5-10 ℃/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, open the fire door of tube furnace, make it in the situation that continuing to pass into protective atmosphere, be quickly cooled to room temperature, finally obtain the high efficiency photocatalyst N-H-TiO described in the present invention
2.
In tube furnace, pass in the process of gas NH
3and H
2gas flow all remain on 200-400ml/min.
In said method, the model of tube furnace used is: 1200 ℃ of open tubular furnace-OTF-1200X, peak power is 2.5KW.
Embodiment 1:
The present embodiment be in the present invention, mention by pure TiO
2in ammonia and two kinds of atmosphere of hydrogen, heat-treat and obtain nano titanium dioxide photocatalyst N-H-TiO
2, the benzene of then degrading up hill and dale fast under visible ray.Its preparation method and photocatalysis performance test are carried out according to following steps:
1, prepare pure TiO
2
The hydro-thermal reaction 12h at 160 ℃ by distilled water and butyl titanate, after then washing, drying, obtains white TiO
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, sealing with stainless steel sealing flange in the quartz ampoule of ceramic boat immigration tube furnace and at two ends, then passes into highly purified ammonia by the Bas Discharged remaining in quartz ampoule.In this process, ammonia flow is 200ml/min, and duration of ventilation is 30min.
3, heat treatment
After exhaust completes, open the power switch of tube furnace, carry out process of thermal treatment flow process.The initial temperature of tube furnace is set as to 20 ℃, and annealing temperature is 600 ℃, and heating rate is 5 ℃/min, continues to pass into NH
3and H
2these two kinds of gases are also incubated 4h after intensification completes in annealing atmosphere.After temperature retention time arrives, open the fire door of tube furnace, make it in the situation that continuing to pass into protective atmosphere, be quickly cooled to room temperature, finally obtain the high efficiency photocatalyst N-H-TiO described in the present invention
2-600.
4, photocatalysis performance test
By N-H-TiO of the present invention
2under radiation of visible light, utilize gas chromatograph to detect the product C O in Photocatalytic Degradation Process
2growing amount and the concentration of the benzene test result that obtains Fig. 2.This test result is under radiation of visible light, to utilize gas chromatograph to detect the product C O in Photocatalytic Degradation Process
2growing amount and the concentration of benzene obtain.Wherein blank is the blank experiment that benzene usings as this test of degrading in catalyst-free situation, TiO
2refer to pure TiO prepared by hydro-thermal method
2, H-TiO
2by TiO in hydrogen atmosphere
2at 600 ℃, be incubated the 2h sample that heat treatment obtains of annealing, N-TiO
2in ammonia atmosphere by TiO
2at 600 ℃, be incubated the 2h sample that heat treatment obtains of annealing, N-H-TiO
2-550, N-H-TiO
2-500 and N-H-TiO
2-650 is respectively by TiO
2in ammonia and these two kinds of atmosphere of hydrogen at 550 ℃, the sample that the heat treatment of annealing at 600 ℃ and 650 ℃ obtains.
Example 2 and 3:
Example 2 and 3 is 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 (first, then pass into NH3 and H2) under the atmosphere of different order, to material property, brings large change; N-H-TiO2 has excellent performance at degraded benzene fermentation, and the efficiency of its degraded is apparently higher than most catalysis materials of current existence.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 disclosed content of this embodiment and accompanying drawing.So every, do not depart from the equivalence completing under spirit disclosed in this invention or revise, all falling into the scope of protection of the invention.
Claims (4)
1. a preparation method for nano titanium dioxide photocatalyst, the method comprises the steps:
The 1st step is by TiO
2nanometer powder is put into tube furnace and is sealed, after pass into ammonia by the Bas Discharged remaining in quartz ampoule;
After the 2nd step Bas Discharged, tube furnace is warming up to 550-650 ℃ after insulation, heating rate is 5-10 ℃/min, 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;
After the 3rd step temperature retention time arrives, open the fire door of tube furnace, make it in the situation that continuing to pass into hydrogen, be quickly cooled to room temperature, obtain described titanium dioxide optical catalyst N-H-TiO
2.
2. the preparation method of a kind of nano titanium dioxide photocatalyst according to claim 1, is characterized in that, passes in the process of gas in tube furnace, and the gas flow of ammonia and hydrogen all remains on 200-400ml/min.
3. the preparation method of a kind of nano titanium dioxide photocatalyst according to claim 1, is characterized in that, temperature retention time is 4-8h, and the first half of temperature retention time and latter half time equate.
4. according to the preparation method of a kind of nano titanium dioxide photocatalyst described in claim 1,2 or 3, it is characterized in that described TiO
2nanometer powder is the pure TiO that hydro-thermal method prepares
2nanometer powder.
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Cited By (2)
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| CN106732568A (en) * | 2016-12-07 | 2017-05-31 | 南京大学 | A kind of preparation method and application of parachloronitrobenzene selective hydrogenation parachloroanilinum catalyst |
| 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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Cited By (3)
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| CN106732568A (en) * | 2016-12-07 | 2017-05-31 | 南京大学 | A kind of preparation method and application of parachloronitrobenzene selective hydrogenation parachloroanilinum catalyst |
| CN106732568B (en) * | 2016-12-07 | 2019-07-30 | 南京大学 | A kind of preparation method and application of parachloronitrobenzene selective hydrogenation parachloroanilinum catalyst |
| 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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