CN102125861B - F-doped wide optical domain response TiO2 photocatalyst and preparation method thereof - Google Patents

F-doped wide optical domain response TiO2 photocatalyst and preparation method thereof Download PDF

Info

Publication number
CN102125861B
CN102125861B CN 201110023736 CN201110023736A CN102125861B CN 102125861 B CN102125861 B CN 102125861B CN 201110023736 CN201110023736 CN 201110023736 CN 201110023736 A CN201110023736 A CN 201110023736A CN 102125861 B CN102125861 B CN 102125861B
Authority
CN
China
Prior art keywords
ionic liquid
domain response
mixes
photochemical catalyst
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN 201110023736
Other languages
Chinese (zh)
Other versions
CN102125861A (en
Inventor
陈孝云
陈星�
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujian Agriculture and Forestry University
Original Assignee
Fujian Agriculture and Forestry University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujian Agriculture and Forestry University filed Critical Fujian Agriculture and Forestry University
Priority to CN 201110023736 priority Critical patent/CN102125861B/en
Publication of CN102125861A publication Critical patent/CN102125861A/en
Application granted granted Critical
Publication of CN102125861B publication Critical patent/CN102125861B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Catalysts (AREA)

Abstract

The invention relates to an F-doped wide optical domain response TiO2 photocatalyst and a preparation method thereof. In the photocatalyst, ionic liquid/water is used as a mixed solvent, ammonium fluoride is used as an F source, and titanium tetrachloride is used as a Ti source; and the F-doped wide optical domain response TiO2 photocatalyst is prepared by adopting a liquid hydrolysis-precipitation method. The results show that: the TiO2 doped by a proper amount of F has high activity in an ultraviolet light area, a visible light area and sunlight; and the TiO2 particles are dispersed uniformly, the phase transition temperature is improved, and the phase transition velocity is retarded. The successful research of the method provides certain theoretical direction effect for developing a visible light catalyst in environmentally-friendly solvent ionic liquid.

Description

A kind of F wide smooth domain response TiO that mixes 2Photochemical catalyst and preparation method thereof
Technical field
The present invention is specifically related to a kind of F wide smooth domain response TiO that mixes 2Photochemical catalyst and preparation method thereof.
Background technology
Utilize photocatalysis oxidation technique to solve research and development very fast of problem of environmental pollutions such as serious day by day water, air, soil in recent years.But see from application point, also have following problem at present: photochemical catalyst spectral response range＜380nm is low to solar energy utilization ratio; With its electricity-light conversion efficiency of electrically driven (operated) ultraviolet source low (＜25 %), most of electric energy is converted into heat energy, migrates out reaction system and is not utilized, and reaction system gross energy utilization rate is low; Conventional TiO 2The quantum efficiency of photochemical catalyst is low etc.Therefore, development sunshine responsive photocatalyst expand its spectral response range (＞380nm), improve the photocatalysis quantum efficiency and become worldwide research focus.Methods such as doped transition metal ions, noble metal loading, semiconductor are compound, dye sensitization all can improve TiO to some extent 2Visible light catalysis activity.But the ultraviolet region of catalyst is active, stability, efficiency of light absorption, service life etc. still are difficult to guarantee.
Nonmetallic ion (N, S, C, F) mixes to improving TiO 2Visible light-responded ability has effect preferably.But major part all concentrates on development and preparation visible light catalyst in the traditional chemical solvent at present, perhaps adopts the traditional chemical method that it is carried out doping vario-property and prepares visible light catalyst, and these method effects are all also not satisfactory.Therefore seek the method for the visible light catalyst of a kind of environmental friendliness technology, synthesized high-performance, become the focus of numerous scholar's research.
Summary of the invention
The invention reside in provides a kind of F the wide smooth domain response TiO that mixes 2Photochemical catalyst and preparation method thereof, the preparation method is simple, the TiO that prepared F mixes 2Under ultraviolet region, visible region and sunshine, all show higher activity.
The present invention implements through following technical scheme:
A kind of F wide smooth domain response TiO that mixes 2Photochemical catalyst is to be mixed solvent with ionic liquid/water, and ammonium fluoride is the F source, and titanium tetrachloride is the Ti source, the F that adopts liquid-phase hydrolysis-precipitation method the to make wide smooth domain response TiO that mixes 2Photochemical catalyst.
The mixed solvent of described ionic liquid/water, the volume ratio of ionic liquid and water is: 3:1 ~ 10:1.
Described ionic liquid comprises 1-butyl-3-methylimidazole hexafluorophosphate.
Said preparation method's concrete steps are:
1) in ionic liquid/water blending agent of 100 ~ 300mL, dripping hydrochloric acid, pH to 3 ~ 5 of adjusting blending agent;
2) TiCl of Dropwise 5 ~ 15mL 4In the blending agent of step 1), reaction 20 ~ 40min;
3) with step 2) solution that obtains is warming up to 70 ~ 90 ℃, and uses NH 4The pH value of OH regulator solution is reacted 30 ~ 60min to neutral, obtains containing the solution of solid product;
4) solution that the contains solid product ageing 8 ~ 15h under room temperature that step 3) is obtained washs solid product with distilled water then, is washed till no Cl -, wash 2 ~ 4 times with ethanol again, transfer in the ceramic crucible;
5) in porcelain crucible, add ammonium fluoride and ethanol again, making the Ti and the ratio of the mole of fluorine is 1:0.10 ~ 1:2.00, and the addition of ethanol is 80 ~ 120mL, under agitation reacts 1 ~ 3 h, ageing 8 ~ 12 h under the room temperature, and 70 ~ 90 ℃ of vacuum drying are ground, and 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 ~ 900 ℃, and constant temperature calcining 1 ~ 3 h, naturally cools to room temperature, makes the described F wide smooth domain response TiO that mixes 2Photochemical catalyst.
The mixed solvent of the ionic liquid/water of said step 1), the volume ratio of ionic liquid and water is: 3:1 ~ 10:1.
The ionic liquid of said step 1) comprises 1-butyl-3-methylimidazole hexafluorophosphate.
Material after will grinding in the said step 6) is put in the Muffle furnace, in air atmosphere, is warming up to 550 ~ 750 ℃ and constant temperature calcining 1 ~ 3h with the speed of 10 ~ 20 ℃/min, naturally cools to room temperature, makes the described F wide smooth domain response TiO that mixes 2Photochemical catalyst.
Advantage of the present invention is: preparation method of the present invention is simple, is mixed solvent with green ionic liquid/water, and ammonium fluoride is the F source, and titanium tetrachloride is the Ti source, adopts liquid-phase hydrolysis-precipitation method to make the F wide smooth domain response TiO that mixes 2Photochemical catalyst all shows higher activity under ultraviolet region, visible region and sunshine.And TiO 2Particle is uniformly dispersed, and phase transition temperature improves, and phase transition rate slows down.The successful development of this method is for exploitation visible light catalyst in the environmentally friendly solvent ionic liquid provides the certain theoretical guidance effect.
Description of drawings
Fig. 1 is that 600 ℃ of activation make different F doping F-TiO 2The diffuse reflection spectrum of photochemical catalyst;
Fig. 2 is different heat treatment temperature F-TiO 2XRD spectrum;
Fig. 3 is different heat treatment temperature T iO 2XRD spectrum;
Fig. 4 is different F doping F-TiO under the visible light 2Photocatalytic activity (600 ℃ of roastings);
Fig. 5 is different F doping F-TiO under the ultraviolet light 2Photocatalytic activity (600 ℃ of roastings);
Fig. 6 is different F doping F-TiO under the sunshine 2Photocatalytic activity (600 ℃ of roastings).
The specific embodiment
A kind of F wide smooth domain response TiO that mixes 2The preparation method's of photochemical catalyst concrete steps are:
1) in ionic liquid/water blending agent of 100-300mL, dripping hydrochloric acid, pH to 3 ~ 5 of adjusting blending agent;
2) TiCl of Dropwise 5-15mL 4In the blending agent of step 1), reaction 20 ~ 40min;
3) with step 2) solution that obtains is warming up to 70 ~ 90 ℃, and with the pH value of NH4OH regulator solution to neutral, reaction 30 ~ 60min obtains containing the solution of solid product;
4) solution that the contains solid product ageing 8 ~ 15h under room temperature that step 3) is obtained washs solid product with distilled water then, is washed till no Cl -, drip AgNO 3Solution does not have white precipitate and produces, and washes 2-4 time with ethanol again, transfers in the ceramic crucible;
5) in porcelain crucible, add ammonium fluoride and ethanol again, making the Ti and the ratio of the mole of fluorine is 1:0.10 ~ 1:2.00, and the addition of ethanol is 80 ~ 120mL, under agitation reacts 1 ~ 3 h, ageing 8 ~ 12 h under the room temperature, and 70 ~ 90 ℃ of vacuum drying are ground, and 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 ~ 900 ℃, and constant temperature calcining 1 ~ 3 h, naturally cools to room temperature, makes the described F wide smooth domain response TiO that mixes 2Photochemical catalyst.
Said ionic liquid comprises 1-butyl-3-methylimidazole hexafluorophosphate.
Described ionic liquid/water blending agent, the volume ratio of ionic liquid and water is: 3:1 ~ 10:1.
Embodiment 1
A kind of F wide smooth domain response TiO that mixes 2The preparation method's of photochemical catalyst concrete steps are:
1) in ionic liquid/water blending agent of 100mL, dripping hydrochloric acid, the pH to 3 of adjusting blending agent;
2) TiCl of Dropwise 5 mL 4In the blending agent of step 1), reaction 20min;
3) with step 2) solution that obtains is warming up to 70 ℃, and with the pH value of NH4OH regulator solution to neutral, reaction 30min obtains containing the solution of solid product;
4) solution that the contains solid product ageing 8h under room temperature that step 3) is obtained washs solid product with distilled water then, is washed till no Cl -, drip AgNO 3Solution does not have white precipitate and produces, and washes 2 times with ethanol again, transfers in the ceramic crucible;
5) in porcelain crucible, add ammonium fluoride and ethanol again, making the Ti and the ratio of the mole of fluorine is 1:0.10, 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 1 h, naturally cools to room temperature, makes the described F wide smooth domain response TiO that mixes 2Photochemical catalyst.
Said ionic liquid comprises 1-butyl-3-methylimidazole hexafluorophosphate.
Described ionic liquid/water blending agent, the volume ratio of ionic liquid and water is: 3:1.
Embodiment 2
A kind of F wide smooth domain response TiO that mixes 2The preparation method's of photochemical catalyst concrete steps are:
1) in ionic liquid/water blending agent of 300mL, dripping hydrochloric acid, the pH to 5 of adjusting blending agent;
2) TiCl of dropping 15mL 4In the blending agent of step 1), reaction 40min;
3) with step 2) solution that obtains is warming up to 90 ℃, and with the pH value of NH4OH regulator solution to neutral, reaction 60min obtains containing the solution of solid product;
4) solution that the contains solid product ageing 15h under room temperature that step 3) is obtained washs solid product with distilled water then, is washed till no Cl -, wash 4 times with ethanol again, transfer in the ceramic crucible;
5) in porcelain crucible, add ammonium fluoride and ethanol again, making the Ti and the ratio of the mole of fluorine is 1:2.00, 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 900 ℃, and constant temperature calcining 3 h, naturally cools to room temperature, makes the described F wide smooth domain response TiO that mixes 2Photochemical catalyst.
Said ionic liquid is 1-hexyl-3 methyl imidazolium tetrafluoroborate.
Described ionic liquid/water blending agent, the volume ratio of ionic liquid and water is: 10:1.
Embodiment 3
A kind of F wide smooth domain response TiO that mixes 2The preparation method's of photochemical catalyst concrete steps are:
1) in ionic liquid/water blending agent of 200mL, dripping hydrochloric acid, the pH to 4 of adjusting blending agent;
2) TiCl of dropping 10mL 4In the blending agent of step 1), reaction 30min;
3) with step 2) solution that obtains is warming up to 80 ℃, and with the pH value of NH4OH regulator solution to neutral, reaction 40min obtains containing the solution of solid product;
4) solution that the contains solid product ageing 10h under room temperature that step 3) is obtained washs solid product with distilled water then, is washed till no Cl -, wash 3 times with ethanol again, transfer in the ceramic crucible;
5) in porcelain crucible, add ammonium fluoride and ethanol again, making the Ti and the ratio of the mole of fluorine is 1:0.6, and the addition of ethanol is 100mL, under agitation reacts 2 h, 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 650 ℃, and constant temperature calcining 2 h, naturally cools to room temperature, makes the described F wide smooth domain response TiO that mixes 2Photochemical catalyst.
Said ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate.
Described ionic liquid/water blending agent, the volume ratio of ionic liquid and water is: 7:1.
The above is merely preferred embodiment of the present invention, and all equalizations of doing according to claim of the present invention change and modify, and all should belong to covering scope of the present invention.

Claims (2)

1. a F wide smooth domain response TiO that mixes 2The preparation method of photochemical catalyst is characterized in that: said TiO 2Photochemical catalyst is to be mixed solvent with ionic liquid/water, and ammonium fluoride is the F source, and titanium tetrachloride is the Ti source, the F that adopts liquid-phase hydrolysis-precipitation method the to make wide smooth domain response TiO that mixes 2Photochemical catalyst; The mixed solvent of described ionic liquid/water, the volume ratio of ionic liquid and water is: 3:1 ~ 10:1; Described ionic liquid is 1-butyl-3-methylimidazole hexafluorophosphate;
Said preparation method's concrete steps are:
1) in ionic liquid/water blending agent of 100 ~ 300mL, dripping hydrochloric acid, pH to 3 ~ 5 of adjusting blending agent;
2) TiCl of Dropwise 5 ~ 15mL 4In the blending agent of step 1), reaction 20 ~ 40min;
3) with step 2) solution that obtains is warming up to 70 ~ 90 ℃, and uses NH 4The pH value of OH regulator solution is reacted 30 ~ 60min to neutral, obtains containing the solution of solid product;
4) solution that the contains solid product ageing 8 ~ 15h under room temperature that step 3) is obtained washs solid product with distilled water then, is washed till no Cl -, wash 2 ~ 4 times with ethanol again, transfer in the ceramic crucible;
5) in porcelain crucible, add ammonium fluoride and ethanol again, making the Ti and the ratio of the mole of fluorine is 1:0.10 ~ 1:2.00, and the addition of ethanol is 80 ~ 120mL, under agitation reacts 1 ~ 3 h, ageing 8 ~ 12 h under the room temperature, and 70 ~ 90 ℃ of vacuum drying are ground, and 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 ~ 900 ℃, and constant temperature calcining 1 ~ 3 h, naturally cools to room temperature, makes the described F wide smooth domain response TiO that mixes 2Photochemical catalyst.
2. the F according to claim 1 wide smooth domain response TiO that mixes 2The preparation method of photochemical catalyst; It is characterized in that: the material after will grinding in the said step 6), to put in the Muffle furnace, the speed with 10 ~ 20 ℃/min in air atmosphere is warming up to 550 ~ 750 ℃ and constant temperature calcining 1 ~ 3h; Naturally cool to room temperature, make the described F wide smooth domain response TiO that mixes 2Photochemical catalyst.
CN 201110023736 2011-01-21 2011-01-21 F-doped wide optical domain response TiO2 photocatalyst and preparation method thereof Expired - Fee Related CN102125861B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201110023736 CN102125861B (en) 2011-01-21 2011-01-21 F-doped wide optical domain response TiO2 photocatalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201110023736 CN102125861B (en) 2011-01-21 2011-01-21 F-doped wide optical domain response TiO2 photocatalyst and preparation method thereof

Publications (2)

Publication Number Publication Date
CN102125861A CN102125861A (en) 2011-07-20
CN102125861B true CN102125861B (en) 2012-12-05

Family

ID=44264286

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201110023736 Expired - Fee Related CN102125861B (en) 2011-01-21 2011-01-21 F-doped wide optical domain response TiO2 photocatalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN102125861B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104607215B (en) * 2015-01-11 2017-02-22 北京工业大学 Preparation method of fluorine-modified low-temperature plasma catalyst
CN105510401B (en) * 2015-12-01 2017-12-01 中国科学院新疆理化技术研究所 Utilize the method for titanium dioxide nanoplate base gas sensor array identification explosive
CN112090296A (en) * 2020-08-31 2020-12-18 济南大学 Based on F-TiO2/Fe-g-C3N4Self-cleaning flat plate type PVDF ultrafiltration membrane and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6576589B1 (en) * 1999-09-20 2003-06-10 Lg Electronics Inc. Method for making anatase type titanium dioxide photocatalyst
CN101293669A (en) * 2008-06-20 2008-10-29 南开大学 Method for preparing nano-titanium dioxide powder with controllable phase ratio of anatase and rutile
CN101444724A (en) * 2008-12-24 2009-06-03 南开大学 Method for preparing high activity non-metallic ion co-doped titanium dioxide photochemical catalyst
CN101862647A (en) * 2010-06-18 2010-10-20 长安大学 Preparation method for preparing titanium dioxide photochemical catalyst by ionic liquid

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6576589B1 (en) * 1999-09-20 2003-06-10 Lg Electronics Inc. Method for making anatase type titanium dioxide photocatalyst
CN101293669A (en) * 2008-06-20 2008-10-29 南开大学 Method for preparing nano-titanium dioxide powder with controllable phase ratio of anatase and rutile
CN101444724A (en) * 2008-12-24 2009-06-03 南开大学 Method for preparing high activity non-metallic ion co-doped titanium dioxide photochemical catalyst
CN101862647A (en) * 2010-06-18 2010-10-20 长安大学 Preparation method for preparing titanium dioxide photochemical catalyst by ionic liquid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李晓辉等.N、F共掺杂TiO2可见光响应光催化剂的酸催化水解法制备及表征.《物理化学学报》.2008,第24卷(第11期),第2019-2024页. *

Also Published As

Publication number Publication date
CN102125861A (en) 2011-07-20

Similar Documents

Publication Publication Date Title
CN103212392B (en) Method for preparing TiO2/kieselguhr composite photocatalytic material by using sol-gel method
Li et al. Enhanced photocatalytic activity of Fe2O3 decorated Bi2O3
CN104475079A (en) Preparation method of supported photocatalytic composite material
CN102285686B (en) Method for preparing iron-nitrogen codoped mesoporous nano titanium dioxide by fast sol-gel method
CN106000431B (en) Sheet CdS/BiOCl composite nano materials and preparation method thereof
CN101444724A (en) Method for preparing high activity non-metallic ion co-doped titanium dioxide photochemical catalyst
CN102211033A (en) Method for preparing platinum and nitrogen codoped active carbon supported titanium dioxide photocatalyst
CN103240073B (en) Zn<2+>-doped BiVO4 visible-light-driven photocatalyst and preparation method thereof
CN102335602A (en) Bismuth tungstate composite photocatalyst, preparation method thereof, and application thereof
CN104258837B (en) The preparation method of carbon-silicon coblended nano TiO 2
CN104525182B (en) Cerium niobium antimony base composite particles photochemical catalyst, preparation and the application of porous nanometer structure
CN105536839A (en) Method for preparing WO3/g-C3N4 composite photocatalysis material
CN102125861B (en) F-doped wide optical domain response TiO2 photocatalyst and preparation method thereof
CN1311900C (en) Water heating preparation of phthalocyanin sennsitized nano cobalt dioxide powder
CN102633302A (en) Method for synthesizing meso pore TiO2 in ionic liquid/water media by cellulose templates
CN103349985B (en) Nano titanium dioxide photocatalyst of silver load and preparation method thereof
Liu et al. Boosting photocatalytic hydrogen evolution via triplet–triplet annihilation upconversion
CN102266786B (en) SiO2 supported s-doped TiO2 visible light catalyst and preparation method thereof
CN103721699A (en) NaInO2 photocatalyst and preparation method thereof
CN103769073B (en) A kind of preparation method of potassium doped nanometer titanium dioxide photocatalyst
CN104096555A (en) Preparation method for rare earth doped silicon dioxide-titanium dioxide photocatalytic material
Chang et al. SiO2@ TiO2: Eu3+ and its derivatives: Design, synthesis, and properties
CN101890343B (en) Low temperature surface modification method for titanium dioxide nanocrystal
CN105797739A (en) Preparation method and application of iron hydroxide/bismuth vanadate composite photocatalyst
CN105664992B (en) A kind of preparation method of nitrogen-doped titanium dioxide nanosheet photocatalyst

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20121205

Termination date: 20160121

EXPY Termination of patent right or utility model