CN105148953B - A kind of bundle-shaped TiOF2Low temperature preparation method - Google Patents
A kind of bundle-shaped TiOF2Low temperature preparation method Download PDFInfo
- Publication number
- CN105148953B CN105148953B CN201510541139.1A CN201510541139A CN105148953B CN 105148953 B CN105148953 B CN 105148953B CN 201510541139 A CN201510541139 A CN 201510541139A CN 105148953 B CN105148953 B CN 105148953B
- Authority
- CN
- China
- Prior art keywords
- tiof
- solution
- bundle
- shaped
- ratio
- 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
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of bundle-shaped TiOF2Low temperature preparation method, it is utilized using tetra-n-butyl titanate as presoma, and bundle-shaped TiOF is made under the conditions of low-temperature atmosphere-pressure using improved sol-gal process2, bundle-shaped TiOF2Specific surface area is big, and crystal grain is tiny, good to the degradation property of rhodamine B (RhB), it is relatively low in 380~780nm visible wavelength range internal reflection rate, respond, and the preparation method of the present invention is simple, reaction condition is gentle, no coupling product, has good application prospect.
Description
Technical field
The invention belongs to photochemical catalyst study on the synthesis technical field, more particularly to a kind of bundle-shaped TiOF2Low temperature preparation
Method.
Background technology
At present, H.Li etc. (Nanoscale, 2014；6:897-902) research finds Emission in Cubic TiOF2Can be a kind of
Good visible light catalyst, and good degradation property is shown to rhodamine B (RhB) and 4- chlorophenols l (4-CP), but this is vertical
Cube TiOF2Preparation using hydro-thermal method, as H.Li, Pengyu Dong (Materials Letters, 2015,143
(15):20‐23)、S.Z.Qiao(Chem Commun,47(2011):6138–6140)、Hongsen Li
(Electrochimica Acta, Volume 62,15February 2012, Pages 408-415) etc. uses TiF4For forerunner
(the Journal of such as body, Kangle Lv (.Appl.Mater.Interfaces 2013,5,8663-8669), Jiaguo Yu
Alloys and Compounds,2011,509(13):4557-4562) it is presoma with Butyl Phthalate (TBT), Seung-
Taek Myung etc. (Journal of Power Sources, Volume 288,15August 2015, Pages 376-383)
It is presoma with TiO2, has prepared cube or cube combines flower-shaped Emission in Cubic TiOF2.But hydro-thermal method needs
High temperature and high pressure environment, complex process and compares power consumption, simpler, more energy efficient if it can prepare at low temperature.
The content of the invention
In order to overcome the shortcomings of present in above-mentioned technology, the invention provides a kind of mild condition, energy consumption are low and prepared
Product is in the bundle-shaped TiOF of bundle-shaped2Low temperature preparation method.
Technical scheme is realized by following steps used by the present invention realizes above-mentioned purpose：
(1) it is 1 according to butyl titanate and absolute ethyl alcohol volume ratio：1~1.2：1 ratio measures absolute ethyl alcohol and adds metatitanic acid
In butyl ester, mix, obtain solution A；
(2) measure absolute ethyl alcohol and HF, add in deionized water, make deionized water and absolute ethyl alcohol, the HF volume ratio be
1:0.1：0.1~1：0.2:0.2, obtain B solution；
(3) it is 1 according to the mol ratio of deionized water in the butyl titanate in solution A and B solution：90~1：105 ratio
Solution A and B solution are measured, is mixed dropwise, drips speed control in per second 2~3 drops, 55~60 DEG C, 500~800r/min constant temperature magnetic force
Stirring 1~3 hour, obtains TiOF2Gel, it is placed in 1~3d of ageing at room temperature；
(4) by the TiOF of ageing2Gel moves to 80~100 DEG C of constant temperature dryings in baking oven, is washed repeatedly with distilled water, ethanol
Wash, dried in 80~100 DEG C of air dry ovens, TiOF is obtained after grinding2Powder；
(5) by TiOF obtained by step (4)2It is 5mol/L's that the ratio that powder is 2g/100mL according to solid-to-liquid ratio, which adds concentration,
In NaOH solution, magnetic agitation 1~1.5 hour, after being cleaned, centrifuging with distilled water, 80~100 DEG C of drums in air dry oven are put into
Constant temperature drying in wind drying box, obtain bundle-shaped TiOF2。
Above-mentioned steps (5) are by TiOF obtained by step (4)2It is 5mol/L's that powder adds concentration according to 2g/100mL ratio
In NaOH solution, 500~800r/min magnetic agitations 1 hour, after being cleaned, centrifuging with distilled water, it is put into 100 in air dry oven
Constant temperature drying in DEG C air dry oven, obtains bundle-shaped TiOF2。
The bundle-shaped TiOF of the present invention2Low temperature preparation method be using tetra-n-butyl titanate as presoma, use is improved
Sol-gel process obtained TiOF under the conditions of low-temperature atmosphere-pressure2In bundle-shaped, specific surface area is big, and crystal grain is tiny, to Luo Dan
The degradation property of bright B (RhB) is good, relatively low in 380~780nm visible wavelength range internal reflection rate, responds, and this hair
Bright preparation method is simple, reaction condition is gentle, no coupling product, has good application prospect.
Brief description of the drawings
Fig. 1 is that the SEM of the products therefrom of comparative example 1 schemes.
Fig. 2 is the gained bundle-shaped TiOF of embodiment 12SEM figure.
Fig. 3 is bundle-shaped TiOF2XRD.
Fig. 4 is that different naoh concentrations prepare sample and P25 UV-vis DRS comparison diagram.
Embodiment
Technical scheme is further described in conjunction with embodiment and experiment, accompanying drawing, but the present invention is not
It is only limitted to following implementation situations.
Embodiment 1
The present embodiment prepares bundle-shaped TiOF2Method comprise the steps of：
(1) 30.4mL absolute ethyl alcohols are measured, are 1.15 according to butyl titanate and absolute ethyl alcohol volume ratio:1 ratio adds
In 35.2mL butyl titanates, mix, obtain solution A；
(2) 30.4mL absolute ethyl alcohols are measured to add in 180mL deionized waters, while add 20.2mL HF, make deionized water
Volume ratio with absolute ethyl alcohol, HF is 1:0.169：0.112, obtain B solution；
(3) B solution is added dropwise to solution A, makes the butyl titanate in A mixed liquors and deionized water in B mixed liquors
Mol ratio is 1：100, speed control is dripped in per second 3 drops, 60 DEG C, 650r/min temperature constant magnetic stirrings 2 hours, obtains TiOF2It is solidifying
Glue, it is placed in and is aged 2d at room temperature；
(4) by the TiOF of ageing2Gel moves to 100 DEG C of constant temperature dryings in air dry oven, is handed over repeatedly with distilled water, ethanol
For washing each 3 times, dried in 100 DEG C of air dry ovens, TiOF is obtained after grinding2Powder；
(5) by TiOF obtained by step (4)2It is 5mol/L's that the ratio that powder is 2g/100mL according to solid-to-liquid ratio, which adds concentration,
In NaOH solution, 650r/min magnetic agitations 1 hour, after conventionally being cleaned, centrifuging with distilled water, forced air drying is put into
Constant temperature drying in 100 DEG C of air dry ovens, obtains bundle-shaped TiOF in case2。
Embodiment 2
The present embodiment prepares bundle-shaped TiOF2Method comprise the steps of：
(1) absolute ethyl alcohol is measured, is 1 according to butyl titanate and absolute ethyl alcohol volume ratio:1 ratio adds butyl titanate
In, mix, obtain solution A；
(2) measure absolute ethyl alcohol and HF, add in deionized water, make deionized water and absolute ethyl alcohol, the HF volume ratio be
1:0.1：0.1, obtain B solution；
(3) B solution is added dropwise to solution A, makes the butyl titanate in A mixed liquors and deionized water in B mixed liquors
Mol ratio is 1：90, speed control is dripped in per second 2 drops, 55 DEG C, 500r/min temperature constant magnetic stirrings 3 hours, obtains TiOF2Gel,
It is placed in and is aged 1d at room temperature；
(4) by the TiOF of ageing2Gel moves to 80 DEG C of constant temperature dryings in air dry oven, is handed over repeatedly with distilled water, ethanol
For washing each 3 times, dried in 80 DEG C of air dry ovens, TiOF is obtained after grinding2Powder；
(5) by TiOF obtained by step (4)2It is 5mol/L's that the ratio that powder is 2g/100mL according to solid-to-liquid ratio, which adds concentration,
In NaOH solution, 500r/min magnetic agitations 1.5 hours, after conventionally being cleaned, centrifuging with distilled water, it is put into air blast and does
Constant temperature drying in 80 DEG C of air dry ovens, obtains bundle-shaped TiOF in dry case2。
Embodiment 3
The present embodiment prepares bundle-shaped TiOF2Method comprise the steps of：
(1) absolute ethyl alcohol is measured, is 1.2 according to butyl titanate and absolute ethyl alcohol volume ratio:1 ratio adds butyl titanate
In, mix, obtain solution A；
(2) measure absolute ethyl alcohol and HF, add in deionized water, make deionized water and absolute ethyl alcohol, the HF volume ratio be
1：0.2:0.2, obtain B solution；
(3) solution A is added dropwise to B solution, makes the butyl titanate in A mixed liquors and deionized water in B mixed liquors
Mol ratio is 1：105, speed control is dripped in per second 3 drops, 58 DEG C, 800r/min temperature constant magnetic stirrings 1 hour, obtains TiOF2Gel,
It is placed in and is aged 3d at room temperature；
(4) by the TiOF of ageing2Gel moves to 90 DEG C of constant temperature dryings in air dry oven, is handed over repeatedly with distilled water, ethanol
For washing each 3 times, dried in 100 DEG C of air dry ovens, TiOF is obtained after grinding2Powder；
(5) by TiOF obtained by step (4)2It is 5mol/L's that the ratio that powder is 2g/100mL according to solid-to-liquid ratio, which adds concentration,
In NaOH solution, 800r/min magnetic agitations 1.2 hours, after conventionally being cleaned, centrifuging with distilled water, it is put into air blast and does
Constant temperature drying in 80 DEG C of air dry ovens, obtains bundle-shaped TiOF in dry case2。
Embodiment 4
The present embodiment prepares bundle-shaped TiOF2Method comprise the steps of：
(1) absolute ethyl alcohol is measured, is 1.1 according to butyl titanate and absolute ethyl alcohol volume ratio:1 ratio adds butyl titanate
In, mix, obtain solution A；
(2) measure absolute ethyl alcohol and HF, add in deionized water, make deionized water and absolute ethyl alcohol, the HF volume ratio be
1:0.15：0.12, obtain B solution；
(3) solution A is added dropwise to B solution, makes the butyl titanate in A mixed liquors and deionized water in B mixed liquors
Mol ratio is 1：95, speed control is dripped in per second 3 drops, 60 DEG C, 700r/min temperature constant magnetic stirrings 2 hours, obtains TiOF2Gel,
It is placed in and is aged 2d at room temperature；
(4) by the TiOF of ageing2Gel moves to 95 DEG C of constant temperature dryings in air dry oven, is handed over repeatedly with distilled water, ethanol
For washing each 3 times, dried in 95 DEG C of air dry ovens, TiOF is obtained after grinding2Powder；
(5) by TiOF obtained by step (4)2It is 5mol/L's that the ratio that powder is 2g/100mL according to solid-to-liquid ratio, which adds concentration,
In NaOH solution, 700r/min magnetic agitations 1.2 hours, after conventionally being cleaned, centrifuging with distilled water, it is put into air blast and does
Constant temperature drying in 90 DEG C of air dry ovens, obtains bundle-shaped TiOF in dry case2。
In order to verify beneficial effects of the present invention, inventor is analyzed by largely testing, specific as follows：
(1) sem analysis
According to the product obtained by the method for (1) the step of the embodiment of the present invention 1~(4) as a comparison case 1, model is used
TiOF of the JSM-5800 SEM (SEM) to the embodiment of the present invention 12Pattern (Fig. 2) characterized, accelerate electricity
Press as 15kV, and contrasted with the product morphology (Fig. 1) of comparative example 1, as a result as depicted in figs. 1 and 2.
Contrasted from Fig. 1 and Fig. 2, the TiOF of comparative example 12The pattern of products therefrom when powder does not react with NaOH solution
Cluster, similar cauliflower-shaped structure, and products therefrom is in bundle-shaped after being reacted under the conditions of constant temperature stirring at low speed with NaOH, elongated knot
Structure, the diameter of pipe is in 10nm or so, but its length even can reach tens microns from 200nm.
(2) XRD analysis
It is respectively obtained by 1mol, 2mol, 5mol, 15mol NaOH solution processing to concentration according to the operation of embodiment 1
TiOF2Through XRD analysis, as a result as shown in figure 3,
Shown by Fig. 3 results, 2mol, 5mol NaOH treated TiOF2Occurs corresponding Emission in Cubic at 2 θ=23
(JPDS 08‐0060)TiOF2100 faces, it is possible thereby to illustrate the TiOF that Emission in Cubic crystal grain can be prepared under low temperature2, and
Peak width is larger, shows that catalyst crystal grain is tiny.
(3) UV-vis DRS contrasts
TiOF prepared by different naoh concentrations2TU-1901 dual-beam of the sample with commercially available P25 with general analysis
The UV-vis DRS light absorpting ability of the integrating sphere functional test sample of ultra-violet and visible spectrophotometer, as a result such as Fig. 4
It is shown.
As seen from contrast in Figure 4, the wave-length coverage of visible ray is about 380nm~780nm in solar irradiation, of the invention
TiOF2It is lower slightly relative to reflectivity of the commercially available P25 in the wave-length coverage of the visible above light of 700nm, in other ripples of visible ray
It is roughly the same in long scope, i.e. TiOF of the invention2Response compared with commercially available P25 under the wave-length coverage of visible ray is more preferable.
The product of other embodiment 2~4 is also accordingly detected according to above-mentioned experimental method, its experimental result with it is upper
The experiment results stated approach, moreover, the present invention is not limited only to above-mentioned implementation situation.
Claims (1)
- A kind of 1. bundle-shaped TiOF2Low temperature preparation method, it is characterised in that comprise the steps of：(1) it is 1.15 according to butyl titanate and absolute ethyl alcohol volume ratio:1 ratio measures absolute ethyl alcohol and added in butyl titanate, Mix, obtain solution A；(2) absolute ethyl alcohol and HF are measured, is added in deionized water, the volume ratio for making deionized water and absolute ethyl alcohol, HF is 1: 0.169：0.112, obtain B solution；(3) it is 1 according to the mol ratio of deionized water in the butyl titanate in solution A and B solution：100 ratio measure solution A and B solution, mix dropwise, drip speed control in per second 3 drops, 60 DEG C, 650r/min temperature constant magnetic stirrings 2 hours, obtain TiOF2It is solidifying Glue, it is placed in and is aged 2d at room temperature；(4) by the TiOF of ageing2Gel moves to 100 DEG C of constant temperature dryings in baking oven, is washed repeatedly with distilled water, ethanol, at 100 DEG C Dried in air dry oven, TiOF is obtained after grinding2Powder；(5) by TiOF obtained by step (4)2The ratio that powder is 2g/100mL according to solid-to-liquid ratio adds the NaOH that concentration is 5mol/L In solution, 650r/min magnetic agitations 1 hour, after being cleaned, centrifuging with distilled water, it is put into air dry oven, 100 DEG C of constant temperature dry It is dry, obtain bundle-shaped TiOF2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510541139.1A CN105148953B (en) | 2015-08-28 | 2015-08-28 | A kind of bundle-shaped TiOF2Low temperature preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510541139.1A CN105148953B (en) | 2015-08-28 | 2015-08-28 | A kind of bundle-shaped TiOF2Low temperature preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105148953A CN105148953A (en) | 2015-12-16 |
| CN105148953B true CN105148953B (en) | 2018-01-16 |
Family
ID=54790167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510541139.1A Expired - Fee Related CN105148953B (en) | 2015-08-28 | 2015-08-28 | A kind of bundle-shaped TiOF2Low temperature preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105148953B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106927500B (en) * | 2017-02-09 | 2018-08-28 | 西安科技大学 | The three-dimensional graduation difluoro oxygen titanium micron ball and its preparation method and application that multi-stage nano piece is constructed |
| CN111054402B (en) * | 2020-02-18 | 2022-11-11 | 浙江工业大学 | TiOF 2 Catalyst, preparation method and application thereof |
| CN113117703B (en) * | 2021-04-22 | 2023-05-26 | 国中创业(北京)环保科技有限公司 | Coral TiOF 2 Photocatalyst, preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102294253B (en) * | 2011-06-10 | 2013-04-17 | 上海师范大学 | Low temperature preparation method for TiOF2 photocatalyst film, and application thereof |
| CN103736508B (en) * | 2013-12-26 | 2015-08-19 | 大连大学 | A kind of atmospheric pressure plasma prepares F doped Ti O 2method |
| CN104275170B (en) * | 2014-09-12 | 2016-06-15 | 西安科技大学 | A kind of { 001} face anatase TiO2The normal temperature preparation method of monocrystalline |
-
2015
- 2015-08-28 CN CN201510541139.1A patent/CN105148953B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105148953A (en) | 2015-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106268734B (en) | A kind of preparation method of water dispersible ternary mixed crystal nano titanium dioxide photocatalyst | |
| CN105148953B (en) | A kind of bundle-shaped TiOF2Low temperature preparation method | |
| CN107162047B (en) | A kind of preparation method of titanium dioxide hollow ball | |
| CN103657623B (en) | Microballoon-type titanium dioxide photocatalyst and preparation method thereof | |
| CN109482241B (en) | TiO2/MOF-5 photocatalyst and preparation method thereof | |
| CN108190949A (en) | A kind of method of quick preparation small particle anatase-type nanometer titanium dioxide | |
| CN104923230A (en) | Titanium dioxide/ferroferric oxide nanocomposite and preparation method therefor | |
| CN104003406A (en) | Preparation method and applications of super-hydrophobic SiO2 aerogel powder | |
| CN108529692A (en) | The preparation method of hollow ball shape nickel oxide | |
| CN101220128B (en) | Polymethyl methacrylate composite microsphere, preparation method and application thereof | |
| CN109879312A (en) | A kind of preparation method of photocatalyst of titanium dioxide nano-powder | |
| CN105665018A (en) | Preparation method and application of composite solid superacid catalyst | |
| CN102936028A (en) | Method for preparing platy lanthanum hydroxide nanocrystalline through microwave-ultrasonic method | |
| CN103388273A (en) | Method for preparing nanometer hydrophobic paper by utilizing corrugated paper/nanometer titanium dioxide | |
| CN105289457B (en) | A kind of hollow structure TiO2The preparation method and applications of nano material | |
| CN106571240B (en) | A kind of preparation method and its usage of hollow silica/titanium dioxide microballoon sphere of original position carbon doped layer time structure | |
| CN103435097A (en) | Preparation method and application of nano zirconia | |
| CN103803633B (en) | Preparation method of zinc oxide/titanium dioxide nanometer composite material | |
| CN101837296B (en) | Solid super acid for esterification of rosin esterification and preparation method thereof | |
| CN103787408B (en) | A kind of preparation method of trifluoro oxygen titanium acid ammonium | |
| CN105565375A (en) | Preparing method for nanoscale porous titanium dioxide hollow spheres | |
| CN109516490A (en) | A kind of preparation method of the cerium oxide nanoparicles of structure-controllable | |
| CN107899562A (en) | A kind of preparation method of flower-shaped hierarchy titanium dioxide gas-phase photocatalysis material | |
| CN102295307A (en) | Method for preparing nano ZnO | |
| CN105107532B (en) | A kind of WO3/TiOF2The preparation method of composite visible light catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180116 Termination date: 20180828 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |