CN101791545A - Method for preparing (001) surface-exposed micrometer laminar titanium dioxide photocatalyst - Google Patents

Method for preparing (001) surface-exposed micrometer laminar titanium dioxide photocatalyst Download PDF

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Publication number
CN101791545A
CN101791545A CN201010116456A CN201010116456A CN101791545A CN 101791545 A CN101791545 A CN 101791545A CN 201010116456 A CN201010116456 A CN 201010116456A CN 201010116456 A CN201010116456 A CN 201010116456A CN 101791545 A CN101791545 A CN 101791545A
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China
Prior art keywords
titanium dioxide
micrometer
exposed
laminar
dioxide photocatalyst
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CN201010116456A
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Chinese (zh)
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朱建
王金果
卞振锋
曹锋雷
李和兴
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Shanghai Normal University
University of Shanghai for Science and Technology
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Shanghai Normal University
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Abstract

The invention discloses a method for preparing a photocatalyst, in particular a method for preparing a (001) surface-exposed micrometer laminar titanium dioxide photocatalyst, which belongs to the technical field of photocatalysts. In the method, the micrometer laminar anatase titanium dioxide photocatalyst with a (001) surface exposure rate of over 90 percent is prepared by using a simple solvothermal method and by changing the components of raw material liquid, the solvothermal time and the solvothermal temperature. Concretely, the method comprises the following process steps: firstly, preparing the raw material liquid at normal temperature; secondly, transferring the raw material liquid to a polytetrafluoroethylene kettle (the solution accounts for 80 percent of the volume of the kettle) and controlling reaction temperature and time to obtain a white precipitate; and thirdly, centrifugally separating the precipitate to obtain the (001) surface-exposed micrometer laminar titanium dioxide photocatalyst. The prepared photocatalyst has a higher catalytic activity than common commercial TiOw (Degussa, P-25) for the selective photocatalytic oxidation reaction of methylbenzene for preparing benzaldehyde.

Description

A kind of { preparation method of 001} surface-exposed micrometer laminar titanium dioxide photocatalyst
Technical field
The present invention relates to a kind of preparation method of photochemical catalyst, be specially that a kind of { preparation method of 001} surface-exposed micrometer laminar titanium dioxide photocatalyst belongs to the photochemical catalyst field.
Background technology
In recent years, utilize conductor photocatalysis to prepare new forms of energy and processing environment pollution having caused world's extensive concern.TiO2 is nontoxic with it, catalytic activity is high, chemical stability good, cheap and easy to get and can directly utilize advantages such as sunshine to be subject to people's attention, and become typical photochemical catalyst.The photocatalysis performance of titanium dioxide depends primarily on the crystal face of crystalline phase, degree of crystallinity, specific surface, structure and exposure.Up to the present, for crystalline phase, degree of crystallinity and specific surface the optically catalytic TiO 2 Effect on Performance is had more deep research.Theoretical calculating shows that the height of the average surface energy of each crystal face of anatase titania crystal is smoothly: 0.90Jm-2{001}>0.53Jm-2{100}>0.44Jm-2{101}.Therefore, in the anatase titania crystal, { reactivity of 001} high energy crystal face will be higher than { 101} crystal face, but mainly still { the 001} crystal face exposes as the master at present synthetic titanium dioxide, and about { it is also less that 001} high energy crystal face exposes the relevant report of titanium dioxide with low-energy.2008, Yang Huagui seminar synthesized by hydro-thermal method that { 001} face exposure is 47% monocrystalline anatase titania; Also the someone has reported that { 001} face exposure reaches 89% platy-monocrystal titanium dioxide subsequently.Yet existing report all is to utilize hydrofluoric acid to synthesize the { single crystal titanium dioxide that the 001} face exposes, and synthetic sample topography is single, size is non-adjustable, simple in structure and exposure is all less than 90% as the pattern controlling agent under hydrothermal condition.
Adopt solvent thermal process,, impel that special { formation of 001} surface-exposed micrometer laminar titanium dioxide through centrifugal treating, can obtain that { 001} face exposure is greater than 90% micrometer laminar anatase titania by high temperature and high pressure environment.It is this that { 001} surface-exposed micrometer laminar anatase titania has potential using value at aspects such as organic synthesis, environmental improvement, DSSC, photoelectric materials.
Summary of the invention
The objective of the invention is for a kind of simple and efficient, preparation { new method of 001} surface-exposed micrometer laminar titanium dioxide photocatalyst that controllability is strong is provided.
Purpose of the present invention can be achieved through the following technical solutions.
A kind of the preparation method of 001} surface-exposed micrometer laminar titanium dioxide photocatalyst, concrete steps are as follows:
1) under the normal temperature, the titanium tetrafluoride of 0.1-1.5g is joined in the 40-200ml phenmethylol, vigorous stirring to titanium tetrachloride dissolves fully and forms transparent solution;
2) transparent solution is transferred in the 50-500ml polytetrafluoroethylene (PTFE) water heating kettle, kept naturally cooling to room temperature behind the 6-72h, promptly make micron film stratiform anatase single crystal titanium dioxide after centrifugal at 140-200 ℃.
The loading of the mixed solution of described titanium tetrafluoride and phenmethylol be whole kettle long-pending 80%.
The ratio of described titanium tetrafluoride and phenmethylol was 1: 500 to 1: 200 (be meant the volume (milliliter) of the quality (gram) of titanium tetrafluoride divided by phenmethylol, unit was g/ml).
Step 2) in, be 24h preferred natural cool time.
The present invention is by simple solvent thermal process, can prepare by changing material liquid component, hot time of solvent and temperature that { 001} face exposure is greater than 90% micrometer laminar anatase titania photochemical catalyst.Concrete technology follows these steps to carry out: at first, and at normal temperature configuration material liquid.Then material liquid is transferred in the polytetrafluoroethylkettle kettle (solution accounts for kettle long-pending 80%), control reaction temperature and time, can be obtained white precipitate.Precipitation obtains { 001} surface-exposed micrometer laminar titanium dioxide photocatalyst after centrifugation.Prepared photochemical catalyst demonstrates in the methylbenzene selective photochemical catalytic oxidation prepares the reaction of benzaldehyde and is higher than common commercial TiO 2(Degussa, catalytic activity P-25).
Description of drawings
Fig. 1 is the x-ray crystallogram of the embodiment of the invention 2.
Fig. 2 is the scanning electron microscope diagram (a) and the transmission electron microscope figure (b) of the embodiment of the invention 2.
Fig. 3 is the scanning electron microscope diagram of prepared micrometer laminar titanium dioxide of differential responses time of the present invention: (a) embodiment 1, and (b) embodiment 2, and (c) embodiment 3.
The specific embodiment
Further set forth technical characterstic of the present invention below in conjunction with accompanying drawing and specific embodiment.
Embodiment 1
Under the normal temperature, the titanium tetrafluoride of 0.10g is joined in the 40ml phenmethylol, vigorous stirring to titanium tetrachloride dissolves the formation clear solution fully, solution is transferred in the 50ml polytetrafluoroethylkettle kettle then, keep naturally cooling to room temperature behind the 12h at 160 ℃, promptly make micron film stratiform anatase single crystal titanium dioxide after centrifugal.
Embodiment 2
Under the normal temperature, the titanium tetrafluoride of 0.10g is joined in the 40ml phenmethylol, vigorous stirring to titanium tetrachloride dissolves fully and forms transparent solution, then solution is transferred in the 50ml polytetrafluoroethylene (PTFE) water heating kettle, keep naturally cooling to room temperature behind the 24h at 160 ℃, promptly make micron film stratiform anatase single crystal titanium dioxide after centrifugal.
Embodiment 3
Under the normal temperature, the titanium tetrafluoride of 0.10g is joined in the 40ml phenmethylol, vigorous stirring to titanium tetrachloride dissolves fully and forms transparent solution, then solution is transferred in the 50ml polytetrafluoroethylene (PTFE) water heating kettle, keep naturally cooling to room temperature behind the 72h at 200 ℃, promptly make micron film stratiform anatase single crystal titanium dioxide after centrifugal.
Embodiment 4
Under the normal temperature, the titanium tetrafluoride of 0.10g is joined in the 40ml phenmethylol, vigorous stirring to titanium tetrachloride dissolves fully and forms transparent solution, then solution is transferred in the 50ml polytetrafluoroethylene (PTFE) water heating kettle, keep naturally cooling to room temperature behind the 24h at 140 ℃, promptly make micron film stratiform anatase single crystal titanium dioxide after centrifugal.
Embodiment 5
Under the normal temperature, the titanium tetrafluoride of 0.20g is joined in the 80ml phenmethylol, vigorous stirring to titanium tetrachloride dissolves fully and forms transparent solution, then solution is transferred in the 100ml polytetrafluoroethylene (PTFE) water heating kettle, keep naturally cooling to room temperature behind the 24h at 200 ℃, promptly make micron film stratiform anatase single crystal titanium dioxide after centrifugal.
Embodiment 6
Under the normal temperature, the titanium tetrafluoride of 1.5g is joined in the 400ml phenmethylol, vigorous stirring to titanium tetrachloride dissolves fully and forms transparent solution, then solution is transferred in the 500ml polytetrafluoroethylene (PTFE) water heating kettle, keep naturally cooling to room temperature behind the 24h at 180 ℃, promptly make micron film stratiform anatase single crystal titanium dioxide after centrifugal.
Embodiment 7
Under the normal temperature, the titanium tetrafluoride of 0.60g is joined in the 120ml phenmethylol, vigorous stirring to titanium tetrachloride dissolves fully and forms transparent solution, then solution is transferred in the 150ml polytetrafluoroethylene (PTFE) water heating kettle, keep naturally cooling to room temperature behind the 48h at 160 ℃, promptly make micron film stratiform anatase single crystal titanium dioxide after centrifugal.
Embodiment 8
Under the normal temperature, the titanium tetrafluoride of 0.45g is joined in the 200ml phenmethylol, vigorous stirring to titanium tetrachloride dissolves fully and forms transparent solution, then solution is transferred in the 250ml polytetrafluoroethylene (PTFE) water heating kettle, keep naturally cooling to room temperature behind the 72h at 200 ℃, promptly make micron film stratiform anatase single crystal titanium dioxide after centrifugal.
Embodiment 9
Under the normal temperature, the titanium tetrafluoride of 0.13g is joined in the 40mL phenmethylol, vigorous stirring to titanium tetrachloride dissolves fully and forms transparent solution, then solution is transferred in the 50mL polytetrafluoroethylene (PTFE) water heating kettle, keep naturally cooling to room temperature behind the 6h at 180 ℃, promptly make micron film stratiform anatase single crystal titanium dioxide after centrifugal.
The x-ray crystallogram of the foregoing description products obtained therefrom as shown in Figure 1, illustrate preparation { micrometer laminar titanium dioxide that the 001} face exposes has good degree of crystallinity, and its crystalline phase is pure anatase phase, does not contain rutile and brockite mutually.The scanning electron microscope diagram of products obtained therefrom illustrates that the titanium dioxide for preparing is the structure that is similar to the bouquet shape that is assembled by regular micron lamella as shown in Figure 2; The crystal face of transmission electron microscope figure explanation its exposure for single micron lamella be have high reaction activity the 001} face, its lattice fingerprint size is 0.189nm, the angle of (200) and (020) direction is 90 to spend.
Fig. 3 is the pattern of the catalyst that different time synthesizes under the uniform temp, the gap comes into existence between the prolongation lamella of explanation along with the reaction time, all can not form regular micron lamella when while overlong time or deficiency, only the lamella that forms when 24h is comparatively regular.
Table 1 is the structural parameters that differential responses time and temperature make micrometer laminar anatase titania photochemical catalyst
Embodiment Specific area (m 2/g) { 001} face exposure %
??1 ??14 ??90
??2 ??16 ??95
??3 ??13 ??91
??4 ??23 ??92
??5 ??14 ??93
??6 ??15 ??89
??7 ??13 ??86
??8 ??17 ??90
??9 ??14 ??88
The reaction of photochemical catalytic oxidation toluene producing benzaldehyde:
Under 20 ℃, the uviol lamp that is 310nm with six 6W wavelength is a light source, adds 10mL distilled water, 10uL toluene and 0.10g catalyst in the 150mL quartz reactor, and the distance of light source and quartz ampoule is 8cm, and mixing speed is 1000rpm.Turn on light gas chromatography analysis for sampling reaction raw materials and product behind the illumination reaction 2h.Response data is listed in table 2.
Table 2 is embodiment 2 and commercial TiO 2(Degussa, photochemical catalytic oxidation toluene producing benzaldehyde activity P-25).
Sample Conversion ratio (%) Selectivity (%) Productive rate (%)
Embodiment 2 ??25 ??91 ??23
Commercial TiO 2 ??8.5 ??83 ??7.1
The above results shows that the activity of embodiment 2 is commercial TiO 23 times.

Claims (4)

1. one kind the preparation method of 001} surface-exposed micrometer laminar titanium dioxide photocatalyst is characterized in that: concrete steps are as follows:
1) under the normal temperature, the titanium tetrafluoride of 0.1-1.5g is joined in the 40-200ml phenmethylol, vigorous stirring to titanium tetrachloride dissolves fully and forms transparent solution;
2) transparent solution is transferred in the 50-500ml polytetrafluoroethylene (PTFE) water heating kettle, kept naturally cooling to room temperature behind the 6-72h, promptly make micron film stratiform anatase single crystal titanium dioxide after centrifugal at 140-200 ℃.
2. according to claim 1 a kind of the preparation method of 001} surface-exposed micrometer laminar titanium dioxide photocatalyst is characterized in that: the loading of the mixed solution of described titanium tetrafluoride and phenmethylol be whole kettle long-pending 80%.
It is 3. according to claim 1 that a kind of { preparation method of 001} surface-exposed micrometer laminar titanium dioxide photocatalyst is characterized in that: the ratio of described titanium tetrafluoride and phenmethylol was at 1: 500 to 1: 200.
4. according to claim 1 a kind of the preparation method of 001} surface-exposed micrometer laminar titanium dioxide photocatalyst is characterized in that: step 2) in, nature is 24h cool time.
CN201010116456A 2010-03-02 2010-03-02 Method for preparing (001) surface-exposed micrometer laminar titanium dioxide photocatalyst Pending CN101791545A (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101935066A (en) * 2010-09-21 2011-01-05 浙江大学 Method for preparing titanium dioxide three-dimensional ordered nano structure
CN102659178A (en) * 2012-05-11 2012-09-12 上海师范大学 Synthesis technology for visible light titanium dioxide nanosheet with exposed {001} face and oxygen defects
CN102942218A (en) * 2012-11-09 2013-02-27 南京工业大学 Method for preparing organic acid and base collaboratively supporting layered titanium dioxide
CN103086424A (en) * 2013-02-28 2013-05-08 天津工业大学 One-step synthesis method of mixed-phase titanium dioxide with exposed high-activity surfaces
CN104275170A (en) * 2014-09-12 2015-01-14 西安科技大学 Normal-temperature preparation method of {001} surface anatase TiO2 monocrystals
CN105148902A (en) * 2015-07-23 2015-12-16 上海师范大学 Cavity core-shell structured TiO2/WO3 composite photocatalyst and preparation method therefor and application thereof
CN106513019A (en) * 2016-09-19 2017-03-22 长沙学院 Process for preparing TiO2 two-dimensional flake-like composite photocatalytic material with MoS2 / exposed (001) surface
CN109179499A (en) * 2018-10-23 2019-01-11 亚士漆(上海)有限公司 A kind of anatase-type nanometer titanium dioxide, and its preparation method and application
CN110156073A (en) * 2018-01-31 2019-08-23 安徽大学 Steam hot solution evaporation preparation TiO2Method
CN111036210A (en) * 2019-12-25 2020-04-21 青岛理工大学 (001) Surface exposed-three-dimensional laminated structure TiO2Preparation method of/nano-iron composite catalyst
CN111268725A (en) * 2020-02-09 2020-06-12 中国矿业大学 Preparation method and application of {001} crystal face exposed porous titanium dioxide nanosheet

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101935066B (en) * 2010-09-21 2012-08-15 浙江大学 Method for preparing titanium dioxide three-dimensional ordered nano structure
CN101935066A (en) * 2010-09-21 2011-01-05 浙江大学 Method for preparing titanium dioxide three-dimensional ordered nano structure
CN102659178A (en) * 2012-05-11 2012-09-12 上海师范大学 Synthesis technology for visible light titanium dioxide nanosheet with exposed {001} face and oxygen defects
CN102942218A (en) * 2012-11-09 2013-02-27 南京工业大学 Method for preparing organic acid and base collaboratively supporting layered titanium dioxide
CN102942218B (en) * 2012-11-09 2014-06-25 南京工业大学 Method for preparing organic acid and base collaboratively supporting layered titanium dioxide
CN103086424B (en) * 2013-02-28 2015-12-09 天津工业大学 The method of one-step synthesis mixed phase and exposure high reactivity face titanium dioxide
CN103086424A (en) * 2013-02-28 2013-05-08 天津工业大学 One-step synthesis method of mixed-phase titanium dioxide with exposed high-activity surfaces
CN104275170A (en) * 2014-09-12 2015-01-14 西安科技大学 Normal-temperature preparation method of {001} surface anatase TiO2 monocrystals
CN105148902A (en) * 2015-07-23 2015-12-16 上海师范大学 Cavity core-shell structured TiO2/WO3 composite photocatalyst and preparation method therefor and application thereof
CN105148902B (en) * 2015-07-23 2018-01-19 上海师范大学 Cavity core shell structure TiO2/WO3Composite photo-catalyst and its preparation and application
CN106513019A (en) * 2016-09-19 2017-03-22 长沙学院 Process for preparing TiO2 two-dimensional flake-like composite photocatalytic material with MoS2 / exposed (001) surface
CN110156073A (en) * 2018-01-31 2019-08-23 安徽大学 Steam hot solution evaporation preparation TiO2Method
CN109179499A (en) * 2018-10-23 2019-01-11 亚士漆(上海)有限公司 A kind of anatase-type nanometer titanium dioxide, and its preparation method and application
CN111036210A (en) * 2019-12-25 2020-04-21 青岛理工大学 (001) Surface exposed-three-dimensional laminated structure TiO2Preparation method of/nano-iron composite catalyst
CN111268725A (en) * 2020-02-09 2020-06-12 中国矿业大学 Preparation method and application of {001} crystal face exposed porous titanium dioxide nanosheet

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