CN102380403A - Method for preparing visible photo-catalyst of titanium dioxide doped with sulphur - Google Patents
Method for preparing visible photo-catalyst of titanium dioxide doped with sulphur Download PDFInfo
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- CN102380403A CN102380403A CN2011102904632A CN201110290463A CN102380403A CN 102380403 A CN102380403 A CN 102380403A CN 2011102904632 A CN2011102904632 A CN 2011102904632A CN 201110290463 A CN201110290463 A CN 201110290463A CN 102380403 A CN102380403 A CN 102380403A
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Abstract
The invention relates to a method for preparing visible photo-catalyst of titanium dioxide doped with sulphur. The invention is characterized in that photo-catalyst of titanium dioxide which has solid super acidic property and is doped with S is prepared by one-step solvothermal method. The catalyst has strong absorption in visible areas and can degrade organic compounds, for example, rhodamine B and phenol. Compared with the photo-catalyst of the pure titanium dioxide, the invention has exceptive visible photo-catalytic activity. When the mole rate of best titanium to persulfate Ti : S2O8(2-) is equal to 0.5, 20 mg.L(-1) of the rhodamine B can be degraded under the visible light for 5 h, and the degradation rate reaches 97%; and 20 mg.L(-1) of the phenol can be degraded for 10 h, and the degradation rate reaches 87%. The method is environmental friendly, can be simple operated, has low cost and short period, and can be produced in bathes.
Description
Technical field
The present invention relates to a kind of preparation method of sulfur doping titanium dioxide visible light catalyst, belong to the photocatalysis technology field.
Background technology
Problem of environmental pollution day by day seriously reaches the outburst of energy crisis, has caused the attention of countries in the world.Photocatalysis technology is expected in solving environmental pollution and energy crisis, bring into play key effect, at present to attract increasing researcher to put among the correlative study.
TiO
2As a kind of efficient, nontoxic photochemical catalyst, the application in wastewater treatment, air cleaning, environmental protection field such as antibiotic receives much concern TiO
2Photochemical catalyst is described as " environmental catalysts " at present.Yet, TiO
2Its practicalization of some drawbacks limit, like energy gap broad (3.2eV), can only absorbing ultraviolet light could produce actively, can not effectively utilize sunshine; In addition, light induced electron and hole compound causes low photo-quantum efficiency.Therefore, improve TiO through modification
2Visible light catalytic efficient, become the focus of people research.In recent years, people attempt with mode such as nonmetallic ion-doped, metal-doped, noble metal loading, dye sensitization, semiconductor be compound TiO
2Carry out modification, improve TiO
2To absorption of visible light and the photocatalysis efficiency under visible light.Nonmetallic ion-dopedly prove a kind of TiO that improves effectively
2The method of visible absorption, it is wherein a kind of that S mixes.But traditional method mainly adopts high-temperature roasting to contain the presoma of Ti and S, is prone to be gathered into bulky grain under the catalyst high temperature, and specific area reduces, and photocatalytic activity reduces, and traditional preparation process method complicated operation, and the cycle is long, and energy consumption is higher.
At present, existing many researchers have reported that the titanium dioxide optical catalyst that S mixes can improve TiO effectively
2Visible light catalysis activity.Asahi etc. think that S mixes also to produce with the N similar band gap of mixing and narrow down, but because S
2-Ionic radius bigger, so replace the O difficulty (R.Asahi, T.Morikawa et al, Science.2001,293,269) relatively in the lattice.Research shows, sulfur doping TiO
2Middle sulphur atom existence form is not single, maybe be with S
4+Or S
6+Replace Ti
4+And be present in TiO
2, also maybe be with S
2-Replace oxygen atom and exist.Umebayashi etc. adopt oxidizing annealing TiS
2Method prepared S doped Ti O
2They think that residual S occupies TiO
2The position of O in the lattice forms the Ti-S key, and S mixes and makes TiO
2ABSORPTION EDGE move (T.Umebayashi, T.Yamaki et al, Phys.Lett.2002,81,454) to the visible light direction.Ohno etc. are that presoma has successively synthesized the S that replaces the Ti atom with sol-gal process with isopropyl titanate and thiocarbamide
6+And S
4+Ion.S-TiO
2(S
6+) catalyst has good visible light degrading activity (T.Ohno, T.Mitsui et al, Chem.Lett.2003,32,364) to methylene blue.S-TiO
2(S
4+) isopropyl alcohol there is good degradation (T.Ohno, Water Sci.Technol.2004,49,159) under the catalyst visible light.But most thiocarbamides that use are prone to introduce C, N element as the sulphur source in report before.Among the present invention, we adopt persulfate is the sulphur source, does not also appear in the newspapers at present.
The active group of titanium dioxide surface absorption has very big influence to photocatalytic activity.The surface sulfate radical has good raising effect to activity, and employing supercritical methanol technologies such as Li prepare SO
4 2-/ TiO
2, its Pyrogentisinic Acid under UV-irradiation has degrading activity (H.Li, G.Li et al, J.Mol.Catal.A:Chem.2005,269,93) preferably.SO
4 2-/ TiO
2Photocatalytic activity is preferably arranged, but all be based on UV-irradiation, be unfavorable for the utilization of visible light.Doping vario-property and surperficial SO with titanium dioxide
4 2-Hyper acidic combines, and can improve TiO greatly
2Visible light catalysis activity, but also do not have at present the report of this respect.
Summary of the invention
The present invention adopts the low-temperature solvent heat method to prepare the SO that S mixes through being the sulphur source with the persulfate
4 2-/ TiO
2Catalyst is applied to improve TiO with S doping vario-property and solid superacid property first simultaneously
2Visible light catalyst is active.This method environmental friendliness, raw material is easy to get, and energy resource consumption is few, and the cycle is short, and synthetic product has high visible light photocatalysis active, and operates fairly simplely, is convenient to large-scale production.
The visible light catalyst specific area of the method for the invention preparation is at 150～200m
2G
-1Between, pore volume is at 0.2～0.4cm
3G
-1Between, average pore size is between 3.5～7.0nm.
The preparation method of sulfur doping titanium dioxide photochemical catalyst of the present invention specifically may further comprise the steps:
(1) under the room temperature with a certain amount of butyl titanate mix with 25ml ethanol solution A; With 2ml acid mix with 25ml ethanol solution B.
(2) solution B is added drop-wise in the solution A, stirs, add a certain amount of persulfate, stirring at room 40min.
(3) above-mentioned mixed liquor changes in the autoclave of 100ml, uniform temperature reaction certain hour.
(4) filter, washing, drying, the titanium dioxide optical catalyst (abbreviating SST as) of sulfur doping.
Advantage of the present invention is embodied in:
1) synthetic operation is simple, and the time is shorter;
2) synthetic raw materials usedly cheaply be easy to get;
3) synthetic whole technology does not need high-temperature roasting, and process is controlled easily, is easy to expanding application;
4) catalyst of preparation has very high visible light photocatalysis active and stability.
Description of drawings
Fig. 1 is the wide-angle x-ray diffraction pattern that embodiment 1-5 obtains 5 SST samples.
Fig. 2 is the nitrogen adsorption isotherm figure that embodiment 2 obtains SST, and the little figure of the inside is a graph of pore diameter distribution.
Fig. 3 is the ultraviolet-visible spectrogram that diffuses that embodiment 1, example 2 obtain SST and commercialization titanium dioxide P25.
Fig. 4 is that embodiment 1, example 2 obtain SST and the P25 20mgL that under visible light, degrades respectively
-1The activity figure of phenol.
Photocatalytic activity evaluation method provided by the invention
Estimate the photocatalytic activity of prepared sample through the photocatalytic degradation of phenol.Selecting phenol is because it is a kind of typical aromatic pollution.Its maximum absorption wavelength is 269nm.Get the 0.060g sample at every turn and put into the quartz test tube that diameter is 2cm, adding 60ml concentration again is 20mgL
-1Phenol solution and ultrasonic dispersion.At first, dark attitude stirs 30min, makes the absorption of phenol on sample reach balance.With the halogen lamp irradiation of 1000W, the light of wavelength X＜420nm filters with optical filter then.The distance of light source and quartz test tube is 10cm.Behind every illumination 2h,,, calculate the degradation rate behind its illumination 10h according to the relation curve of concentration and absorbance with the absorption intensity of Cary 100 measurement of ultraviolet-visible spectrophotometer solution at the 269nm place.
The specific embodiment
Below in conjunction with instance the present invention is further detailed.
Embodiment 1:
(1) under the room temperature 5ml butyl titanate is mixed stirring 10min with 25ml ethanol and get solution A; 2ml hydrochloric acid (0.1M) is mixed stirring 10min get solution B with 25ml ethanol.
(2) solution B is added drop-wise in the solution A stirring at room 40min.
(3) above-mentioned mixed liquor changes in the autoclave of 100ml, 120 ℃ of hydro-thermal 12h.
(4) after reaction was accomplished, cooling naturally was filtered, washing, and 40 ℃ of vacuum drying get unadulterated titanium dioxide optical catalyst.
Embodiment 2:
(1) under the room temperature 5ml butyl titanate is mixed stirring 10min with 25ml ethanol and get solution A; 2ml hydrochloric acid (0.1M) is mixed stirring 10min get solution B with 25ml ethanol.
(2) solution B is added drop-wise in the solution A, stirs 20min, add the 2.0g potassium peroxydisulfate, stirring at room 40min.
(3) above-mentioned mixed liquor changes in the autoclave of 100ml, 120 ℃ of hydro-thermal 12h.
(4) after reaction was accomplished, cooling naturally was filtered, washing, and 60 ℃ of vacuum drying get the titanium dioxide optical catalyst of sulfur doping.
Embodiment 3:
(1) under the room temperature 5ml butyl titanate is mixed stirring 10min with 25ml ethanol and get solution A; 2ml hydrochloric acid (0.1M) is mixed stirring 10min get solution B with 25ml ethanol.
(2) solution B is added drop-wise in the solution A, stirs 20min, add the 4.0g potassium peroxydisulfate, stirring at room 40min.
(3) above-mentioned mixed liquor changes in the autoclave of 100ml, 120 ℃ of hydro-thermal 12h.
(4) after reaction was accomplished, cooling naturally was filtered, washing, and 60 ℃ of vacuum drying get the titanium dioxide optical catalyst of sulfur doping.
Embodiment 4:
(1) under the room temperature 5ml butyl titanate is mixed stirring 10min with 25ml ethanol and get solution A; 2ml hydrochloric acid (0.1M) is mixed stirring 10min get solution B with 25ml ethanol.
(2) solution B is added drop-wise in the solution A, stirs 20min, add the 1.75g sodium peroxydisulfate, stirring at room 40min.
(3) above-mentioned mixed liquor changes in the autoclave of 100ml, 120 ℃ of hydro-thermal 20h.
(4) after reaction was accomplished, cooling naturally was filtered, washing, and 80 ℃ of vacuum drying get the titanium dioxide optical catalyst of sulfur doping.
Embodiment 5:
(1) under the room temperature 5ml butyl titanate is mixed stirring 10min with 25ml ethanol and get solution A; 2ml hydrochloric acid (0.1M) is mixed stirring 10min get solution B with 25ml ethanol.
(2) solution B is added drop-wise in the solution A, stirs 20min, add the 3.5g sodium peroxydisulfate, stirring at room 40min.
(3) above-mentioned mixed liquor changes in the autoclave of 100ml, 120 ℃ of hydro-thermal 20h.
(4) after reaction was accomplished, cooling naturally was filtered, washing, and 80 ℃ of vacuum drying get the titanium dioxide optical catalyst of sulfur doping.
Claims (6)
1. the preparation method of a sulfur doping titanium dioxide visible light catalyst is characterized in that, this method may further comprise the steps:
(1) under the room temperature with a certain amount of butyl titanate mix with 25ml ethanol solution A; With 2ml acid mix with 25ml ethanol solution B.
(2) solution B is added drop-wise in the solution A, stirs, add a certain amount of persulfate, stirring at room 40min.
(3) above-mentioned mixed liquor changes in the autoclave of 100ml, uniform temperature reaction certain hour.
(4) filter, washing, drying, the titanium dioxide optical catalyst of sulfur doping.
2. the preparation method of sulfur doping titanium dioxide photochemical catalyst according to claim 1 is characterized in that, the mol ratio of said butyl titanate and ethanol is 1: 3～1: 6 in the step (1).Used acid is hydrochloric acid, and its acidity is 0.01M～0.2M.
3. the preparation method of sulfur doping titanium dioxide photochemical catalyst according to claim 1 is characterized in that, said persulfate in the step (2) can be selected sodium peroxydisulfate or potassium peroxydisulfate for use, and its consumption is that titanium and persulfate mol ratio are 0.25: 1～5: 1.
4. the preparation method of sulfur doping titanium dioxide photochemical catalyst according to claim 1 is characterized in that, the required solvent thermal temperature of said preparation is 100～150 ℃ in the step (3), and the reaction time is 10～20h.
5. the preparation method of sulfur doping titanium dioxide photochemical catalyst according to claim 1 is characterized in that, said Preparation of catalysts needs vacuum drying in the step (4), and temperature is 40～80 ℃.
6. according to the sulfur doping titanium dioxide visible light catalyst of the said method preparation of claim 1, it is characterized in that part S mixes TiO
2Intracell, part S is with SO
4 2-Form is present in catalyst surface, and the two synergy has good visible light photocatalytic degradation ability to organic compounds such as degraded rhodamine B, phenol.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105931851A (en) * | 2016-07-11 | 2016-09-07 | 王瑞明 | Method for preparing nanometre titanium dioxide film photo-anode |
| CN108855139A (en) * | 2018-07-13 | 2018-11-23 | 吉林大学 | A kind of titanium sheet, the preparation method and applications of surface modification sulfur doping titanium dioxide nanometer sheet |
| CN110193371A (en) * | 2019-05-31 | 2019-09-03 | 云南大学 | A kind of S6+/S4+The controllable sulfur doping TiO of ratio, pattern, crystal form2The preparation method of visible light catalyst |
| CN111589042A (en) * | 2020-05-26 | 2020-08-28 | 常熟理工学院 | Dry dechlorination process for waste incineration fly ash |
| CN113385192A (en) * | 2021-05-31 | 2021-09-14 | 中国十七冶集团有限公司 | Sulfur-doped TiO for water purification system of construction site2Method for producing thin film |
| CN114377723A (en) * | 2022-01-22 | 2022-04-22 | 海南大学 | Titanium dioxide and visible light catalysis hydrogen production thereof |
| CN115818706A (en) * | 2022-09-30 | 2023-03-21 | 浙江大学 | Preparation method of mixed crystal titanium dioxide nanoflower array with long and thin petals |
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| CN101053839A (en) * | 2007-05-18 | 2007-10-17 | 浙江大学 | Sulfur doped titanium dioxide photocatalyst with anatase structure water-heating preparation method |
| CN101898139A (en) * | 2010-06-25 | 2010-12-01 | 张麒 | Formula of titanium dioxide photochemical catalyst doped with tungstic oxide and preparation method |
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| CN101053839A (en) * | 2007-05-18 | 2007-10-17 | 浙江大学 | Sulfur doped titanium dioxide photocatalyst with anatase structure water-heating preparation method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105931851A (en) * | 2016-07-11 | 2016-09-07 | 王瑞明 | Method for preparing nanometre titanium dioxide film photo-anode |
| CN105931851B (en) * | 2016-07-11 | 2018-07-31 | 泉州台商投资区华奥电子科技有限公司 | The preparation method of nano-titanium dioxide film light anode |
| CN108855139A (en) * | 2018-07-13 | 2018-11-23 | 吉林大学 | A kind of titanium sheet, the preparation method and applications of surface modification sulfur doping titanium dioxide nanometer sheet |
| CN108855139B (en) * | 2018-07-13 | 2021-02-09 | 吉林大学 | Titanium sheet with surface modified sulfur-doped titanium dioxide nanosheet, preparation method and application thereof |
| CN110193371A (en) * | 2019-05-31 | 2019-09-03 | 云南大学 | A kind of S6+/S4+The controllable sulfur doping TiO of ratio, pattern, crystal form2The preparation method of visible light catalyst |
| CN111589042A (en) * | 2020-05-26 | 2020-08-28 | 常熟理工学院 | Dry dechlorination process for waste incineration fly ash |
| CN111589042B (en) * | 2020-05-26 | 2021-04-27 | 常熟理工学院 | Dry dechlorination process for waste incineration fly ash |
| CN113385192A (en) * | 2021-05-31 | 2021-09-14 | 中国十七冶集团有限公司 | Sulfur-doped TiO for water purification system of construction site2Method for producing thin film |
| CN114377723A (en) * | 2022-01-22 | 2022-04-22 | 海南大学 | Titanium dioxide and visible light catalysis hydrogen production thereof |
| CN114377723B (en) * | 2022-01-22 | 2022-12-13 | 海南大学 | Titanium dioxide and visible light catalysis hydrogen production thereof |
| CN115818706A (en) * | 2022-09-30 | 2023-03-21 | 浙江大学 | Preparation method of mixed crystal titanium dioxide nanoflower array with long and thin petals |
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Application publication date: 20120321 |