CN102266786A - SiO2 supported s-doped TiO2 visible light catalyst and preparation method thereof - Google Patents

SiO2 supported s-doped TiO2 visible light catalyst and preparation method thereof Download PDF

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CN102266786A
CN102266786A CN2011101587461A CN201110158746A CN102266786A CN 102266786 A CN102266786 A CN 102266786A CN 2011101587461 A CN2011101587461 A CN 2011101587461A CN 201110158746 A CN201110158746 A CN 201110158746A CN 102266786 A CN102266786 A CN 102266786A
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visible light
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catalyst
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CN102266786B (en
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陈孝云
陈星�
游惠娟
林丰收
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Fujian Agriculture and Forestry University
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Abstract

The invention relates to an SiO2 supported s-doped TiO2 visible light catalyst and a preparation method thereof. Through organic combination of nonmetallic ion doping and porous carrier suppoting, the preparation method employs a liquid phase hydrolysis method to coat SiO2 microballoons with a titanium predecessor, and then conducts modification by nonmetallic S doping, so that an S-doped TiSxOy/SiO2 visible light catalyst with good dispersity and a crystal grain size of 8-30nm can be obtained By doping S on the surface of TiO2 to form a new energy level structure, the catalyst absorption bathochromic-shift is changed to 450-550nm. A proper amount of S doping not only can realize the visible light catalytic activity of TiO2/SiO2, but also improves the ultraviolet light catalytic activity substantially. Besides, SiO2 supporting can improve TiO2 particle conglomeration and the separating property of the TiO2 catalyst, thus being convenient for the post processing of the catalyst.

Description

SiO＜sub〉2＜/sub〉load S doped Ti O＜sub〉2＜/sub〉visible light catalyst and preparation method thereof
Technical field
The invention belongs to catalyst field, more specifically relate to a kind of SiO 2Load S doped Ti O 2Visible light catalyst and preparation method thereof.
Background technology
Nano-TiO 2Combine processing with heliotechnics, purifying waste water is considered to the green environmental protection technique of tool application prospect of 21 century, nano-TiO 2Be used for environmental pollution improvement as photochemical catalyst and have good stability and non-secondary pollution and advantage such as applied widely.But also there is restriction TiO 2The technical bottleneck of photocatalysis technology practicability.
At first, because TiO 2In use there is separation difficulty in photocatalyst powder, is difficult for the shortcoming of recovery.In order to overcome this shortcoming, scholars have carried out TiO 2The powder load Study on Technology is about to TiO 2Powder load is in adsorbent class carriers such as active carbon, silica, zeolite, glass microballoons, and it is bigger as porous material, strong adhesion, specific area that the advantage of such carrier is this, is the catalyst carrier of using always.
Secondly, because TiO 2Energy gap be 3.2eV, can only absorbing wavelength less than the ultraviolet light of 387nm, and sunshine medium ultraviolet light energy only accounts for 4%, and is low to solar energy utilization rate.In order to improve TiO 2Visible light catalysis activity, people have carried out metal ion mixing, nonmetal (C, N, F and S etc.) mix, study on the modification such as noble metal loading and dye photoactivation.Discover that nonmetal (C, N, F and S etc.) are entrained in and improve TiO 2The visible light activity aspect has good effect.
Summary of the invention
In order better to improve TiO 2Visible light catalysis activity and improve TiO 2The separating property of photochemical catalyst, the present invention organically combines nonmetallic ion-doped and porous carrier load, prepares a kind of S doped Ti S of easily separated, good dispersion x O y / SiO 2Visible light catalyst, this catalyst has not only been realized TiO 2/ SiO 2Visible light catalysis activity, and the ultraviolet catalytic activity also is significantly improved.
The present invention implements by following technical solution:
A kind of SiO 2Load S doped Ti O 2Visible light catalyst is the TiS with visible light catalysis activity x O y / SiO 2, its crystallite dimension is 8-30nm.
Described 0＜x＜1,0＜y＜2.
A kind of SiO 2Load S doped Ti O 2The preparation method of visible light catalyst is to be mixed solvent, SiO with ionic liquid/water 2For carrier, titanium tetrachloride are that Ti source, thiocarbamide are the S source, adopt liquid-phase hydrolysis-precipitation method preparation.
The mixed solvent of described ionic liquid/water, the volume ratio of ionic liquid and water is: 5:1 ~ 1:2.
Described ionic liquid comprises 1-butyl-3-methyl imidazolium tetrafluoroborate.
Described preparation method's concrete steps are:
1) takes by weighing the SiO of 1.0 ~ 8.0g 2Join in the there-necked flask; Ionic liquid/the water mixed solvent that adds 100-500mL again, and the pH to 3-5 of dripping hydrochloric acid regulator solution form mixed solution;
2) TiCl of Dropwise 5-30mL 4In the mixed solution of step 1), reaction 20-40min;
3) with step 2) solution that obtains is warming up to 70 ~ 90 ℃, and uses NH 3.HO 2The pH value of regulator solution is reacted 30-60min to neutral, obtains containing the solution of solid product;
4) solution that contains solid product that step 3) is obtained ageing 8-15h under room temperature washs solid product with distilled water then, is washed till no Cl -, wash 2-4 time with ethanol again; Get solid product SiO 2/ TiO 2
5) add thiocarbamide and ethanol in the solid product that step 4) obtains, making the Ti and the ratio of the mole of thiocarbamide is 1:0.30 ~ 1:3.00, and the addition of ethanol is 80-120mL, under agitation react 1-3 h, ageing 8-12 h under the room temperature, 70-90 ℃ of vacuum drying, grind, get material;
6) material after will grinding is put in the Muffle furnace, and the speed with 10-20 ℃/min in air atmosphere is warming up to 400-800 ℃, and constant temperature calcining 1-5 h, naturally cools to room temperature, makes described SiO 2Load S doped Ti O 2Visible light catalyst.
Advantage of the present invention is: the present invention by doping S at TiO 2The surface forms new level structure, makes catalyst absorb red shift to 450-550 nm, and an amount of S mixes not only can realize TiO 2/ SiO 2Visible light catalysis activity, and the ultraviolet catalytic activity also is significantly increased; And, pass through SiO 2Load can improve TiO 2Particle aggregation improves TiO 2The separating property of catalyst makes things convenient for the post-processed of this catalyst.This catalyst has bigger using value aspect actual waste water processing and the air cleaning.
Simultaneously, do not see as yet both at home and abroad at present, relevant is synthetic SiO in the mixed solvent at green ionic liquid/water 2Load S doped Ti O 2The relevant report of visible light responsive photocatalyst.
Description of drawings
Fig. 1 mixes the TiO of S amount for difference under the ultraviolet light x S y / SiO 2Pyrogentisinic Acid's degraded situation;
Fig. 2 mixes the TiO of S amount for difference under the visible light x S y / SiO 2Pyrogentisinic Acid's degraded situation;
Fig. 3 is the different TiO that mix the S amount x S y / SiO 2The DRS figure of catalyst;
Fig. 4 is the different TiO that mix the S amount x S y / SiO 2The first derivative figure of the DRS figure of catalyst.
The specific embodiment
1) takes by weighing the SiO of 1.0 ~ 8.0g 2Join in the there-necked flask; (volume ratio is: 5:1 ~ 1:2), and the pH to 3 of dripping hydrochloric acid regulator solution form mixed solution to add ionic liquid/water mixed solvent of 100-500mL again;
2) TiCl of Dropwise 5 mL 4In the mixed solution of step 1), reaction 20min;
3) with step 2) solution that obtains is warming up to 70 ℃, and uses NH 3.HO 2The pH value of regulator solution is reacted 30min to neutral, obtains containing the solution of solid product;
4) solution that contains solid product that step 3) is obtained ageing 8h under room temperature washs solid product with distilled water then, is washed till no Cl -, wash 2 times with ethanol again; Get solid product SiO 2/ TiO 2
5) add thiocarbamide and ethanol in the solid product that step 4) obtains, making the Ti and the ratio of the mole of thiocarbamide is 1:0.30, and the addition of ethanol is 8mL, under agitation reacts 1 h, ageing 8h under the room temperature, and 70 ℃ of vacuum drying are ground, and get material;
6) material after will grinding is put in the Muffle furnace, and the speed with 10 ℃/min in air atmosphere is warming up to 400 ℃, and constant temperature calcining 1 h, naturally cools to room temperature, makes described SiO 2Load S doped Ti O 2Visible light catalyst.
Embodiment 1
1) takes by weighing the SiO of 1.0g 2Join in the there-necked flask; (volume ratio is: 5:1), and the pH to 3 of dripping hydrochloric acid regulator solution, form mixed solution to add 1-butyl-3-methyl imidazolium tetrafluoroborate/water mixed solvent of 100mL again;
2) TiCl of Dropwise 5 mL 4In the mixed solution of step 1), reaction 20min;
3) with step 2) solution that obtains is warming up to 70 ℃, and uses NH 3.HO 2The pH value of regulator solution is reacted 30min to neutral, obtains containing the solution of solid product;
4) solution that contains solid product that step 3) is obtained ageing 8h under room temperature washs solid product with distilled water then, is washed till no Cl -, wash 2 times with ethanol again; Get solid product SiO 2/ TiO 2
5) add thiocarbamide and ethanol in the solid product that step 4) obtains, making the Ti and the ratio of the mole of thiocarbamide is 1:0.30, and the addition of ethanol is 80mL, under agitation reacts 1h, ageing 8 h under the room temperature, and 70 ℃ of vacuum drying are ground, and get material;
6) material after will grinding is put in the Muffle furnace, and the speed with 10 ℃/min in air atmosphere is warming up to 400 ℃, and constant temperature calcining 1h, naturally cools to room temperature, makes described SiO 2Load S doped Ti O 2Visible light catalyst.
Embodiment 2
1) takes by weighing the SiO of 8.0g 2Join in the there-necked flask; (volume ratio is: 4:1), and the pH to 5 of dripping hydrochloric acid regulator solution, form mixed solution to add 1-butyl-3-methylimidazole salt/water mixed solvent of 500mL again;
2) TiCl of dropping 30mL 4In the mixed solution of step 1), reaction 40min;
3) with step 2) solution that obtains is warming up to 90 ℃, and uses NH 3.HO 2The pH value of regulator solution is reacted 60min to neutral, obtains containing the solution of solid product;
4) solution that contains solid product that step 3) is obtained ageing 15h under room temperature washs solid product with distilled water then, is washed till no Cl -, wash 4 times with ethanol again; Get solid product SiO 2/ TiO 2
5) add thiocarbamide and ethanol in the solid product that step 4) obtains, making the Ti and the ratio of the mole of thiocarbamide is 1:3.00, and the addition of ethanol is 120mL, under agitation reacts 3 h, ageing 12 h under the room temperature, and 90 ℃ of vacuum drying are ground, and get material;
6) material after will grinding is put in the Muffle furnace, and the speed with 20 ℃/min in air atmosphere is warming up to 800 ℃, and constant temperature calcining 5 h, naturally cools to room temperature, makes described SiO 2Load S doped Ti O 2Visible light catalyst.
Embodiment 3
1) takes by weighing the SiO of 4.0g 2Join in the there-necked flask; (volume ratio is: 1:2), and the pH to 4 of dripping hydrochloric acid regulator solution, form mixed solution to add 1-butyl-3-methyl imidazolium tetrafluoroborate/water mixed solvent of 300mL again;
2) TiCl of dropping 25mL 4In the mixed solution of step 1), reaction 30min;
3) with step 2) solution that obtains is warming up to 80 ℃, and uses NH 3.HO 2The pH value of regulator solution is reacted 50min to neutral, obtains containing the solution of solid product;
4) solution that contains solid product that step 3) is obtained ageing 10h under room temperature washs solid product with distilled water then, is washed till no Cl -, wash 3 times with ethanol again; Get solid product SiO 2/ TiO 2
5) add thiocarbamide and ethanol in the solid product that step 4) obtains, making the Ti and the ratio of the mole of thiocarbamide is 1:2.00, and the addition of ethanol is 100mL, under agitation reacts 2h, ageing 10 h under the room temperature, and 80 ℃ of vacuum drying are ground, and get material;
6) material after will grinding is put in the Muffle furnace, and the speed with 15 ℃/min in air atmosphere is warming up to 500 ℃, and constant temperature calcining 4 h, naturally cools to room temperature, makes described SiO 2Load S doped Ti O 2Visible light catalyst.
The above only is preferred embodiment of the present invention, and all equalizations of being done according to the present patent application claim change and modify, and all should belong to covering scope of the present invention.
  

Claims (5)

1. SiO 2Load S doped Ti O 2Visible light catalyst is characterized in that: the crystallite dimension of described catalyst is 8-30nm.
2. SiO as claimed in claim 1 2Load S doped Ti O 2The preparation method of visible light catalyst is characterized in that: described preparation method is to be mixed solvent, SiO with ionic liquid/water 2For carrier, titanium tetrachloride are that Ti source, thiocarbamide are the S source, adopt liquid-phase hydrolysis-precipitation method preparation.
3. a kind of SiO according to claim 2 2Load S doped Ti O 2The preparation method of visible light catalyst is characterized in that: the mixed solvent of described ionic liquid/water, the volume ratio of ionic liquid and water is: 5:1 ~ 1:2.
4. according to claim 2 or 3 described a kind of SiO 2Load S doped Ti O 2The preparation method of visible light catalyst is characterized in that: described ionic liquid comprises 1-butyl-3-methyl imidazolium tetrafluoroborate.
5. a kind of SiO according to claim 2 2Load S doped Ti O 2The preparation method of visible light catalyst is characterized in that: described preparation method's concrete steps are:
1) takes by weighing the SiO of 1.0 ~ 8.0g 2Join in the there-necked flask; Ionic liquid/the water mixed solvent that adds 100-500mL again, and the pH to 3-5 of dripping hydrochloric acid regulator solution form mixed solution;
2) TiCl of Dropwise 5-30mL 4In the mixed solution of step 1), reaction 20-40min;
3) with step 2) solution that obtains is warming up to 70 ~ 90 ℃, and uses NH 3.HO 2The pH value of regulator solution is reacted 30-60min to neutral, obtains containing the solution of solid product;
4) solution that contains solid product that step 3) is obtained ageing 8-15h under room temperature washs solid product with distilled water then, is washed till no Cl -, wash 2-4 time with ethanol again; Get solid product SiO 2/ TiO 2
5) add thiocarbamide and ethanol in the solid product that step 4) obtains, making the Ti and the ratio of the mole of thiocarbamide is 1:0.30 ~ 1:3.00, and the addition of ethanol is 80-120mL, under agitation react 1-3 h, ageing 8-12 h under the room temperature, 70-90 ℃ of vacuum drying, grind, get material;
6) material after will grinding is put in the Muffle furnace, and the speed with 10-20 ℃/min in air atmosphere is warming up to 400-800 ℃, and constant temperature calcining 1-5 h, naturally cools to room temperature, makes described SiO 2Load S doped Ti O 2Visible light catalyst.
CN2011101587461A 2011-06-14 2011-06-14 SiO2 supported s-doped TiO2 visible light catalyst and preparation method thereof Expired - Fee Related CN102266786B (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102531099A (en) * 2012-03-02 2012-07-04 山东轻工业学院 Application of nitrogen-doped TiO2-SiO2 compound photochemical catalyst in sewage degradation treatment
CN104549191A (en) * 2015-01-28 2015-04-29 国药集团化学试剂有限公司 Method for preparing titanium oxide photocatalyst
CN105032471A (en) * 2015-06-17 2015-11-11 中国矿业大学(北京) Preparation of nanometer TiO2/zeolite composite material capable of responding to visible light
CN106166495A (en) * 2016-07-06 2016-11-30 陕西科技大学 A kind of sulfur doping oxygen-starved TiO2the preparation method of photocatalyst
CN106241818A (en) * 2016-08-10 2016-12-21 渤海大学 SiO2irregular nanocrystal network structure and preparation method thereof
CN111420685A (en) * 2019-01-10 2020-07-17 欧阳峰 FSBi-doped TiO for efficiently degrading acrylonitrile wastewater by sunlight catalysis2/SiO2Preparation and use of the catalyst

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CN101862647A (en) * 2010-06-18 2010-10-20 长安大学 Preparation method for preparing titanium dioxide photochemical catalyst by ionic liquid
CN102079542A (en) * 2011-01-11 2011-06-01 福建农林大学 Method for synthesizing meso-porous TiO2 by cellulose template in ionic liquid / water medium

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CN1634654A (en) * 2004-12-02 2005-07-06 上海大学 Preparation method of nitrogen doped composite semiconductor photocatalyst
CN101862647A (en) * 2010-06-18 2010-10-20 长安大学 Preparation method for preparing titanium dioxide photochemical catalyst by ionic liquid
CN102079542A (en) * 2011-01-11 2011-06-01 福建农林大学 Method for synthesizing meso-porous TiO2 by cellulose template in ionic liquid / water medium

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102531099A (en) * 2012-03-02 2012-07-04 山东轻工业学院 Application of nitrogen-doped TiO2-SiO2 compound photochemical catalyst in sewage degradation treatment
CN104549191A (en) * 2015-01-28 2015-04-29 国药集团化学试剂有限公司 Method for preparing titanium oxide photocatalyst
CN105032471A (en) * 2015-06-17 2015-11-11 中国矿业大学(北京) Preparation of nanometer TiO2/zeolite composite material capable of responding to visible light
CN106166495A (en) * 2016-07-06 2016-11-30 陕西科技大学 A kind of sulfur doping oxygen-starved TiO2the preparation method of photocatalyst
CN106166495B (en) * 2016-07-06 2018-08-28 陕西科技大学 A kind of sulfur doping oxygen-starved TiO2The preparation method of photochemical catalyst
CN106241818A (en) * 2016-08-10 2016-12-21 渤海大学 SiO2irregular nanocrystal network structure and preparation method thereof
CN111420685A (en) * 2019-01-10 2020-07-17 欧阳峰 FSBi-doped TiO for efficiently degrading acrylonitrile wastewater by sunlight catalysis2/SiO2Preparation and use of the catalyst

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