CN104818525B - A kind of cross structure fluotitanic acid - Google Patents
A kind of cross structure fluotitanic acid Download PDFInfo
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- CN104818525B CN104818525B CN201510078965.7A CN201510078965A CN104818525B CN 104818525 B CN104818525 B CN 104818525B CN 201510078965 A CN201510078965 A CN 201510078965A CN 104818525 B CN104818525 B CN 104818525B
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Abstract
The invention discloses cross structure fluotitanic acid (HTiOF3) crystal, it mainly utilizes the chitosan/polyvinyl alcohol composite fibre absorption Ti rich in hydroxyl and amino4+Afterwards, the vapor with hydrofluoric acid under gas phase hydrothermal condition reacts.This method preparation process is simple, and does not need complicated last handling process.In addition, the preparation technology reaction time is short, reaction condition is easily controllable, and scientific basis is provided to study the regulation and control of crystal morphology.
Description
Technical field
The invention belongs to fluotitanic acid field, more particularly to a kind of cross structure fluotitanic acid.
Background technology
The regulation and control of crystal shape are a great challenge in many fields, and classical aeolotropic crystal growth theory is as brilliant
Self limitation of body and Wulff are constructed and received.Growth of the interface of crystal and surrounding medium to crystal is one critically important
Factor.It is to add suitable end-capping reagent to regulate and control the most frequently used method of crystal growth behavior in liquid-phase system, such as organic surface
Activating agent or inorganic ions.These end-capping reagents can be preferentially adsorbed on specific crystal face to stop or delay its growth to produce
Anisotropic shape evolution.
TiO2Because it is especially changed in environment and energy related field in solar energy, solar fuel cell and light are urged
Change etc. important application and be widely studied.TiO2The performance not only size with it, shape, pattern, state of aggregation, surface
Property, crystalline phase are relevant, and inseparable with crystal face.Generally, the diconical Anatase TiO of top rake2Monocrystalline can be in hydrogen fluorine
It is synthesized in the presence of acid, it has already been proven that the surface energy that surface fluorination effect can effectively reduce { 001 } crystal face is less than its value
{ 101 } crystal face.In most of reports before, Anatase TiO2Monocrystalline pattern rule, two { 001 } crystal faces, which are exposed to, to be cut
On the upper and lower surfaces of angle bipyramid, { 101 } crystal face is formed on other eight isosceles trapezoid faces.In these reports, { 001 } is brilliant
The Anatase TiO of face exposure2Monocrystalline synthesizes typically by liquid phase hydro-thermal method, and the reaction time is longer, and { 001 } of exposure is brilliant
Face ratio is not high enough.There is document report recently, the ultra-thin TiO of { 001 } crystal face exposure has been obtained by a kind of gas phase hydro-thermal method2It is single
Brilliant nanometer sheet, unlike liquid phase hydro-thermal method, occurs a kind of new intermediate fluotitanic acid during this crystalline transformation
(HTiOF3) six prisms.But reaction system is all in the presence of hydrofluoric acid, with titanium or tetrafluoride in almost all of report
Titanium is titanium source to synthesize the Anatase TiO of { 001 } crystal face exposure2Monocrystalline, organic media is not added in system.
In the liquid phase hydrothermal system of routine, main reactant is all in reaction solution, and the master in gas phase hydrothermal system
Reactant is wanted to be placed directly on base material, so its synthetic product is all directly to be grown on base material.Although gas
It is identical that phase hydro-thermal issues raw chemical reaction with liquid phase hydrothermal condition, but their reaction environment difference is huge.In liquid phase
Reaction under hydrothermal condition occurs in bulk solution, and structure growth must be after bulk solution be by structure growth product saturation
It can realize.Under gas phase hydrothermal condition, all reactions occur to be condensed by return volatile reactants in gas phase and vapor in substrate
In the liquid lamella formed, and reacting is triggered by return volatile reactants.Under this special reaction environment, volatility is anti-
High speed mass transfer of the thing in liquid lamella is answered to trigger and keep fast reaction so that liquid lamella is satisfied rapidly by structure growth product
With cause the fast-growth of structure.In addition, mass transfer of the structure growth product along substrate surface of generation be severely limited to it is very thin
Liquid layer thickness so that product can only growth in situ.Therefore, liquid phase hydro-thermal method is different from, gas phase hydro-thermal method has original because of it
Bit architecture conversion ability and can be used in controlledly synthesis.
The problem to be solved in the present invention is regulation and control growth of the functional group of introducing organic media to cross structure.
The content of the invention
To solve the technical problem of the present invention, used technical scheme is with the chitosan rich in amino and hydroxyl/poly-
Vinyl alcohol polymer composite fiber is substrate, first adsorbs titanium ion, and growth is then regulated and controled under conditions of gas phase hydro-thermal.
Using macromolecular fibre as substrate, gas phase hydro-thermal method prepares cross structure fluotitanic acid (HTiOF3), this method has
The advantages that simple to operate, the reaction time is short, and product structure size is controllable.This method provides science for the regulation and control of crystal morphology
Foundation.
A kind of cross structure fluotitanic acid, it is characterised in that preparation method is:
（1）With 3mol or so HCl, hydrolyzing chitosan 2h or so under conditions of 105 DEG C or so, reaction finishes, centrifugation,
After washing, products therefrom is freeze-dried；
（2）By chitosan dried powder obtained by step (1) be made into 50ml or so mass fraction be 0.02% or so it is molten
Liquid, the poly-vinyl alcohol solution for being then 0.02% or so with 50ml or so mass fraction is sufficiently mixed, in -50 DEG C or so of cold hydrazine
In it is quick-frozen after be placed on freeze drier and be freeze-dried, obtain the chitosan/polyvinyl alcohol composite fibre of white；
（3）The chitosan/polyvinyl alcohol composite fibre of gained white is annealed in air atmosphere under the conditions of 250 DEG C or so
1h or so；Fiber after annealing is immersed in the mixed aqueous solution of 50ml or so titanium tetrafluorides and glucose, taken after 1h or so
Go out, be freeze-dried, be then placed on polytetrafluoroethylene (PTFE) support, this branch is placed in ptfe autoclave inner bag,
20ml or so 2% or so hydrofluoric acid aqueous solution is added in inner bag, then reactor is placed in baking oven, 200 DEG C or so reaction 3h are left
It is right；Question response finishes, and immediately takes out reactor, makes its natural cooling at room temperature, takes out the sample on support, obtains cross
The fiber of structure fluotitanic acid load, you can.
A kind of described cross structure fluotitanic acid, it is characterised in that in the mixed aqueous solution of titanium tetrafluoride and glucose,
The quality of both titanium tetrafluoride and glucose is 1g or so.
A kind of described cross structure fluotitanic acid, it is characterised in that：
The heating rate of annealing process is 1 DEG C/min or so.
Gas phase hydro-thermal method prepares cross structure fluotitanic acid (HTiOF3) technical scheme：
3mol HCl, the hydrolyzing chitosan under the conditions of 105 DEG C are used first（Aladdin reagent）2h, reaction finish, centrifugation, water
After washing, products therefrom is freeze-dried.Gained chitosan dried powder is made into the solution that 50ml mass fractions are 0.02%, so
It is sufficiently mixed afterwards with 50ml mass fractions for 0.02% poly-vinyl alcohol solution, it is dry that freezing is placed in after quick-frozen in -50 DEG C of cold hydrazine
It is freeze-dried on dry machine, obtains the chitosan/polyvinyl alcohol composite fibre of white.It is to improve the mechanical strength of fiber, this is fine
The 1h that annealed in air atmosphere under the conditions of 250 DEG C is tieed up, heating rate is 1 DEG C/min.Fiber after annealing is immersed in 50ml tetra-
Titanium fluoride/glucose（Both quality are 1g）Mixed aqueous solution in, taken out after 1h, be freeze-dried.Then it is placed on poly-
On tetrafluoroethene support, this branch is placed in ptfe autoclave inner bag, it is water-soluble that the hydrofluoric acid of 20ml 2% is added in inner bag
Liquid, then reactor is placed in baking oven, 200 DEG C of reaction 3h.Question response finishes, and immediately takes out reactor, makes it in room temperature
Lower natural cooling.The sample on support is taken out, produces cross structure fluotitanic acid (HTiOF3) load fiber.
Beneficial effect relative to existing crystal morphology control technique is：First, this gas phase hydro-thermal method preparation process
Simply, the reaction time greatly shortens relative to the liquid phase hydro-thermal method of routine, and reaction product is without complicated subsequent treatment（Such as from
The heart）；Second, crystal can be directly grown in macromolecular fibre substrate by the preparation method, and crystal morphology then with base contained by
Organo-functional group is closely related, and this is that conventional liquid phase hydro-thermal method can not accomplish.
The invention discloses cross structure fluotitanic acid (HTiOF3) crystal and preparation method thereof, it mainly utilizes and is rich in
The chitosan/polyvinyl alcohol composite fibre of hydroxyl and amino adsorbs Ti4+Afterwards, the vapor under gas phase hydrothermal condition with hydrofluoric acid
Reaction.This method preparation process is simple, and does not need complicated last handling process.In addition, the preparation technology reaction time is short,
Reaction condition is easily controllable, and scientific basis is provided to study the regulation and control of crystal morphology.
Brief description of the drawings
Fig. 1 a are the atomic force microscope images of products therefrom after hydrochloric acid hydrolyzing chitosan, and display product is about for size
50nm spheric granules；Fig. 1 b are the scanning electron microscopic picture of chitosan/polyvinyl alcohol composite fibre, it can be seen that fiber is in hollow
Tubulose, diameter are about 1 to 3 μm；Fig. 1 c are the thermogravimetric song of chitosan, polyvinyl alcohol and chitosan/polyvinyl alcohol composite fibre
The first derivative of line, according to the weightless peak of three kinds of samples, 250 DEG C are chosen as annealing temperature；Fig. 1 d answer for chitosan/polyvinyl alcohol
The scanning electron microscopic picture of condensating fiber sample obtained by 250 DEG C of annealing 1h in air atmosphere, it can be seen that fiber remains in that hollow
Tubular structure, diameter slightly shrink.
Fig. 2 a are cross structure fluotitanic acid (HTiOF3) carrying fiber scanning electron microscopic picture, it can be seen that cross
Sample is evenly distributed on fiber, and the size of cross is about 4 μm；Fig. 2 b are the XRD spectrum of cross carrying fiber, itself and fluorine
Metatitanic acid (HTiOF3) standard diagram it is corresponding.
Fig. 3 a-g and h-j are respectively electron beam edge<001>With<010>The transmission electron microscope and high score of cross sample during direction
Distinguish transmission electron microscope picture and SEAD pattern, it can be seen that branch is isometric wide and structure is complete by four of cross
It is complete the same, crystal structure and the fluotitanic acid (HTiOF of whole cross3) completely the same.
Embodiment
3mol HCl, the hydrolyzing chitosan under the conditions of 105 DEG C are used first（Aladdin reagent）2h, reaction finish, centrifugation, water
After washing, products therefrom is freeze-dried.Gained chitosan dried powder is made into the solution that 50ml mass fractions are 0.02%, so
It is sufficiently mixed afterwards with 50ml mass fractions for 0.02% poly-vinyl alcohol solution, it is dry that freezing is placed in after quick-frozen in -50 DEG C of cold hydrazine
It is freeze-dried on dry machine, obtains the chitosan/polyvinyl alcohol composite fibre of white.It is to improve the mechanical strength of fiber, this is fine
The 1h that annealed in air atmosphere under the conditions of 250 DEG C is tieed up, heating rate is 1 DEG C/min.Fiber after annealing is immersed in 50ml tetra-
Titanium fluoride/glucose（Both quality are 1g）Mixed aqueous solution in, taken out after 1h, be freeze-dried.Then it is placed on poly-
On tetrafluoroethene support, this branch is placed in ptfe autoclave inner bag, it is water-soluble that the hydrofluoric acid of 20ml 2% is added in inner bag
Liquid, then reactor is placed in baking oven, 200 DEG C of reaction 3h.Question response finishes, and immediately takes out reactor, makes it in room temperature
Lower natural cooling.The sample on support is taken out, produces cross structure fluotitanic acid (HTiOF3) load fiber.
Fig. 1 a are the atomic force microscope images of products therefrom after hydrochloric acid hydrolyzing chitosan, and display product is about for size
50nm spheric granules；Fig. 1 b are the scanning electron microscopic picture of chitosan/polyvinyl alcohol composite fibre, it can be seen that fiber is in hollow
Tubulose, diameter are about 1 to 3 μm；Fig. 1 c are the thermogravimetric song of chitosan, polyvinyl alcohol and chitosan/polyvinyl alcohol composite fibre
The first derivative of line, according to the weightless peak of three kinds of samples, 250 DEG C are chosen as annealing temperature；Fig. 1 d answer for chitosan/polyvinyl alcohol
The scanning electron microscopic picture of condensating fiber sample obtained by 250 DEG C of annealing 1h in air atmosphere, it can be seen that fiber remains in that hollow
Tubular structure, diameter slightly shrink.
Fig. 2 a are cross structure fluotitanic acid (HTiOF3) carrying fiber scanning electron microscopic picture, it can be seen that cross
Sample is evenly distributed on fiber, and the size of cross is about 4 μm；Fig. 2 b are the XRD spectrum of cross carrying fiber, itself and fluorine
Metatitanic acid (HTiOF3) standard diagram it is corresponding.
Fig. 3 a-g and h-j are respectively electron beam edge<001>With<010>The transmission electron microscope and high score of cross sample during direction
Distinguish transmission electron microscope picture and SEAD pattern, it can be seen that branch is isometric wide and structure is complete by four of cross
It is complete the same, crystal structure and the fluotitanic acid (HTiOF of whole cross3) completely the same.
Claims (1)
1. a kind of cross structure fluotitanic acid, it is characterised in that preparation method is:
（1）With 3mol HCl, under conditions of 105 DEG C hydrolyzing chitosan 2h, reaction finish, after centrifuging, washing, gained is produced
Thing is freeze-dried；
（2）By step（1）Gained chitosan dried powder be made into 50ml mass fraction be 0.02% solution, then with 50ml
The poly-vinyl alcohol solution that mass fraction is 0.02% is sufficiently mixed, and is placed in after quick-frozen in -50 DEG C of cold hydrazine cold on freeze drier
It is lyophilized dry, obtain the chitosan/polyvinyl alcohol composite fibre of white；
（3）The chitosan/polyvinyl alcohol composite fibre of gained white is annealed 1h in air atmosphere under the conditions of 250 DEG C；It will move back
Fiber after fire is immersed in the mixed aqueous solution of 50ml titanium tetrafluorides and glucose, is taken out after 1h, freeze-drying, then by it
It is placed on polytetrafluoroethylene (PTFE) support, this branch is placed in ptfe autoclave inner bag, 20ml2% hydrogen fluorine is added in inner bag
Aqueous acid, then reactor is placed in baking oven, 200 DEG C of reaction 3h；Question response finishes, and immediately takes out reactor, makes it
Natural cooling at room temperature, the sample on support is taken out, obtains the fiber of cross structure fluotitanic acid load, you can；
In the mixed aqueous solution of titanium tetrafluoride and glucose, the quality of both titanium tetrafluoride and glucose is 1g, annealing process
Heating rate be 1 DEG C/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101148779B (en) * | 2007-07-24 | 2011-07-27 | 山东大学 | Preparation method for potassium titanate crystal whisker |
| CN101660203B (en) * | 2009-09-09 | 2011-07-27 | 中国科学院电工研究所 | Preparation method of anatase single crystal TiO2 with large active surface |
| CN101892512B (en) * | 2010-07-14 | 2012-08-08 | 中国科学院电工研究所 | Large-area (001) anatase TiO2 monocrystal preparation method |
| CN102839413B (en) * | 2012-09-18 | 2015-04-08 | 武汉理工大学 | Method for preparing ultrathin layered K2Ti4O9 crystal whiskers |
| CN103290427B (en) * | 2013-06-14 | 2015-09-09 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method preparing potassium fluotitanate |
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