CN108911692A - The preparation method of the modified adjustable photocatalysis aerosil fibre of hydrophilic and hydrophobic of graphene oxide - Google Patents
The preparation method of the modified adjustable photocatalysis aerosil fibre of hydrophilic and hydrophobic of graphene oxide Download PDFInfo
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Abstract
The present invention relates to the preparation methods of the modified adjustable photocatalysis aerosil fibre of hydrophilic and hydrophobic of graphene oxide, include the following steps：1, silicon source, alcohol, water and acid catalyst are mixed；2, deionized water and base catalyst is added into silicon dioxide gel obtained in 1；Modification sol A is obtained after stirring；3, titanium dioxide is added into modification sol A and the mixed sols of graphene oxide obtains modification sol B；4, fibre is immersed in modification sol B, obtains gel by standing；5, hydrophobically modified is carried out to the modified photocatalysis aerosil fibre semi-finished product of graphene oxide and is dried to obtain finished product.The additive amount that the present invention passes through change graphene oxide and titanium dioxide, conveniently adjusted finished product hydrophilicity and hydrophobicity, and the mode of gel is repeatedly carried out to fibre by using different modification sols, it is made while having aerosil/fibre of hydrophilicity and hydrophobicity.
Description
Technical field
The present invention relates to aerosil composite article fields, and in particular to a kind of modified close and distant of graphene oxide
The preparation method of aqueous adjustable photocatalysis aerosil fibre.
Background technique
Due to a kind of hydrophobic type aerosil heat insulation composite material of the prior art such as CN104556965A, mainly by
Aerosil and inorfil composition, and doped with fire retardant and infrared barrier agent in aerosil, because
This is with good heat insulation and flame retardant property, but it is hydrophobic type, and applicable situation is limited, while mechanical property is general,
Without photocatalysis effect.
Summary of the invention
The present invention in view of the above problems, urge by the adjustable light of hydrophilic and hydrophobic for proposing a kind of graphene oxide modification
The preparation method for changing aerosil fibre, effectively increases the performance of aerosil.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
The preparation method of the modified adjustable photocatalysis aerosil fibre of hydrophilic and hydrophobic of graphene oxide,
It is characterized by comprising the following steps：
Step 1 mixes silicon source, alcohol, water and acid catalyst, controls the pH value of mixed solution between 2-6；After stirring
Obtain silicon dioxide gel；
Deionized water and base catalyst are added into step 1 for step 2 in silicon dioxide gel obtained, control mixing is molten
The pH value of liquid obtains modification sol A between 7-11, after stirring；
Step 3, into modification sol A, the mixed sols of addition titanium dioxide and graphene oxide obtains modification sol B；
Fibre is completely immersed in modification sol B by step 4, and gel is obtained after standing after a period of time；
Step 5 carries out aging process to the gel in S4 using silicon source/alcohol mixed solution, reuses displacement solvent pair
Gel carries out solvent displacement, obtains the modified photocatalysis aerosil fibre semi-finished product of graphene oxide；
Step 6 carries out hydrophobic change to the modified photocatalysis aerosil fibre semi-finished product of graphene oxide
Property and drying, obtain the modified photocatalysis aerosil fibre of graphene oxide.
Further, in step 3, further include the steps that dispersing modification sol B using ultrasonic wave, ultrasonic power
Between 10-200W, ultrasonic time is between 0-20min, and ultrasonic temperature is between 25-80 DEG C；
Further, when the quality of graphene oxide in the mixed sols of titanium dioxide and graphene oxide in step 3
No more than in silicon source the 0.12% of element silicon quality and the quality of titanium dioxide is equivalent to the 4.5%- of element silicon quality in silicon source
When 45%, the modified photocatalysis aerosil fibre of graphene oxide obtained is hydrophobic type.
Further, when the quality of graphene oxide in the mixed sols of titanium dioxide and graphene oxide in step 3
When being equivalent to the 0.12%-0.25% of element silicon quality in silicon source and the quality of titanium dioxide is not more than element silicon quality in silicon source
4.5% when, the modified photocatalysis aerosil fibre of graphene oxide obtained is hydrophilic.
Further, the step 3 is specially：Sol A is divided into two parts, into a Sol A be added titanium dioxide and
The mixed sols of graphene oxide obtains the first modification sol B, and wherein the quality of graphene oxide is equivalent to silicon in mixed sols
4.5% of the quality of the 0.12%-0.25% and titanium dioxide of element silicon quality no more than element silicon quality in silicon source in source；To
Titanium dioxide is added in another Sol A and the mixed sols of graphene oxide obtains the second modification sol B；Wherein mixed sols
The quality of middle graphene oxide is no more than in silicon source the 0.12% of element silicon quality and the quality of titanium dioxide is equivalent in silicon source
The 4.5%-45% of element silicon quality；
The step 4 is specially：A part of fibre is immersed in the first modification sol B, through quiet after a period of time
It postpones to obtain the first gel, the exposed fibre outside the first gel be immersed in the second modification sol B, through after a period of time
The mixed gel that two sides have different hydrophilicity and hydrophobicities is obtained after standing.
Further, in the step 4, by changing fibre in the first modification sol B and the second modification sol B
Immersion volume, different hydrophilic gel-organophilic gel volume ratio aerosil/fibre can be made.
Further, in the step 3, Sol A is divided into more parts, and configures the increase of graphene oxide concentration gradient and two
The mixed sols that titanium oxide concentration gradient reduces, and the graphene oxide and dioxy of various concentration is added in more parts of Sol As respectively
Change titanium mixed sols, gradient concentration graphene oxide-titania gel is made, in the step 4, fibre is successively soaked
Enter in graphene oxide concentration-titanium dioxide concentration modification sol of various concentration, by control accurate colloidal sol height, uses
It immerses, the mode that gel is alternately implemented step by step, realizes thickness direction graphene oxide-titanium dioxide concentration segmentation diffusion, obtain
Graded oxidation graphene-content of titanium dioxide silica dioxide gel is obtained, silica dioxide gel replaces through aging, solvent, is hydrophobic
The modified photocatalysis aerosil/fibre of gradient concentration graphene oxide can be made in processing and drying.
Further, the silicon source and the molar ratio of alcohol are 1:The molar ratio of (1-50), the silicon source and water is 1:(1-
20)。
Further, the fiber is inorganic or organic fiber, can be basalt fibre, alumina fibre, glass fibers
One of dimension, ceramic fibre, alumina silicate fibre, aramid fiber, polytetrafluoroethylene fibre, ultra high molecular weight polyethylene fiber or
A variety of, fibre can be one of fiber itself, fibre fabric, knitted fabric or non-woven cloth or a variety of.
Beneficial effects of the present invention are：Graphene oxide is the derivative of graphene, it not only has fabulous mechanical property
Energy, great specific surface area, and a large amount of oxygen-containing functional group in surface makes it have higher activity, thus use graphite oxide
Alkene modification can enhance aerosil/fibre mechanical property, improve the hydrophily of fibre, improve fiber
The absorption property of product.
Titanium dioxide is common catalysis material, it is active it is high, stability is good, the harmless, duration
The characteristics of growing, can working at normal temperatures and pressures.Therefore it is high well will to assign aerosil/fibre for its addition
Imitate lasting photocatalysis performance.
The additive amount that the present invention passes through change graphene oxide and titanium dioxide, it may be convenient to adjust silica airsetting
Glue/fibre hydrophilicity and hydrophobicity, and by using different modification sols repeatedly to the side of fibre progress gel
Formula is made while having aerosil/fibre of hydrophilicity and hydrophobicity.It can also be by changing oxygen in modification sol
The concentration of graphite alkene and titanium dioxide obtains the modification sol of various concentration graphene oxide and titanium dioxide, dense using difference
The modification sol of graphene oxide and titanium dioxide is spent to repeatedly gel is carried out to fibre, can obtain gradient concentration oxidation
The modified photocatalysis aerosil/fibre of graphene, use scope are expanded.The gradient of graphene oxide
The connection of aeroge between various concentration can be enhanced in concentration, improves that its is blockiness, and it is good to obtain aeroge skeleton structure, low
The fibre of density, high porosity improves its mechanical property in addition, gradient concentration can effectively reduce fibre internal stress
Energy；Improve the rate of adsorption of fibre；It is effectively reduced heat transfer temperature gradient, improves its heat-proof quality.
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
A kind of preparation for the adjustable photocatalysis aerosil fibre of hydrophilic and hydrophobic that graphene oxide is modified
Method is mainly made by titanium dioxide, graphene oxide, aerosil and fibre.Wherein silica airsetting
Glue is the silica dioxide gel obtained using two step of soda acid, sol-gal process, via exchange of solvent etc. one using silicon source as presoma
It is dry after serial procedures to be made；Titanium dioxide is as tetrabutyl titanate through Nano sol made from sol-gal process；Fiber can be with
Be short fine or long filament, can be inorganic or organic fiber, fibre can be fiber itself, fibre fabric, knitted fabric or
One of non-woven cloth is a variety of.The specific steps are：
S1. silicon source, alcohol, water and acid catalyst are mixed in a certain proportion stirring 0-24h and prepare silicon dioxide gel, wherein
Silicon source can be waterglass, methyl orthosilicate, ethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane etc.；
Alcohol can be methanol, ethyl alcohol etc.；Water can be deionized water, distilled water etc.；Acid catalyst can be hydrochloric acid, acetic acid, hydrogen
Fluoric acid, oxalic acid etc.；The molar ratio of silicon source and alcohol can be 1:Between (1-50), and according to the difference of silicon source, preferably compare
Example is also different；The molar ratio of silicon source and water can be 1:Between (1-20), and according to the difference of silicon source, preferred proportion is not yet
Together；The amount of acid catalyst is determined that pH value is between 2-6 at this time for control by the pH value of the mixed solution after addition acid catalyst,
Preferable ph is between 3-5；
Further, drying control chemical additive (DCCA) can be added by silicon dioxide gel into S1, wherein drying
Control chemical addition agent can be n,N-Dimethylformamide, n,N-dimethylacetamide, glycerol, oxalic acid, tetramethyl hydroxide
Ammonium etc.；The additive amount of dry chemistry control additive is that dry chemistry control additive/silicon source volume ratio is 0-10%；
S2. deionized water and base catalyst is added in silicon dioxide gel obtained into S1, wherein base catalyst can be with
It is ammonium hydroxide, sodium hydroxide, ammonium fluoride etc..Deionized water and base catalyst are while being added, and show as the water-soluble of base catalyst
Liquid, this base catalyst instillation for being primarily due to excessive concentrations can make silicon dioxide gel local base concentration excessive and coagulate rapidly
Glue generates cotton-shaped or blocky white precipitate, therefore the present invention controls base catalyst concentration of aqueous solution in 0.01mol/l-1mol/l
Between, preferably base catalyst concentration of aqueous solution is between 0.05-0.25mol/l.The amount of base catalyst is according to addition base catalysis
The pH value of the mixed solution determines after agent, and pH value is between 7-11 at this time for control, and preferable ph is between 8-10；
S3. the mixed sols that titanium dioxide and graphene oxide are added into the colloidal sol of S2 (aoxidizes in control mixed sols
The quality of graphene is equivalent to the 0-0.25% of element silicon quality and the quality of titanium dioxide in silicon source and is equivalent to silicon member in silicon source
The 0-45% of quality amount), it should be noted that since graphene oxide is easily reunited, titanium dioxide and oxidation stone is added
It needs to disperse modification sol using ultrasonic wave after the mixed sols of black alkene, ultrasonic power is between 10-200W, when ultrasonic
Between between 0-20min, ultrasonic temperature is between 25-80 DEG C；
S4. fibre is completely immersed in S3 in colloidal sol, becomes gel after standing after a period of time.Wherein fiber system
Product can be fiber itself, can also be any fibre as made from short fine or long filament, for example, can be by it is a series of such as
Non-woven cloth made from the processes such as the later process such as the preceding working procedures such as shredding, combing, lapping or needle thorn, spun lacing, fibre fabric,
One of knitted fabric is a variety of；
Fiber can be inorganic or organic fiber, such as basalt fibre, alumina fibre, glass fibre, ceramic fibre, silicon
Sour aluminum fiber, aramid fiber, polytetrafluoroethylene fibre, ultra high molecular weight polyethylene fiber etc..
S5. using the mixed solution of a certain proportion of silicon source/alcohol is carried out to the gelatinous fibre product in S4 certain time
Aging is reused displacement solvent and carries out solvent displacement to gelatinous fibre product, then mixed using hydrophobic modifier/displacement solvent
Solution carries out hydrophobically modified to gelatinous fibre product, and it is molten to the gelatinous fibre product progress after hydrophobically modified to reuse displacement solvent
Agent displacement.Wherein silicon source and the volume ratio of alcohol can be (0%-100%):(100%-0%), ageing time can be 0-72h.
It is different according to the difference of drying mode to replace solvent.According to supercritical drying, replacement media can be methanol, ethyl alcohol, two
Carbonoxide, perflexane etc.；According to constant pressure and dry, replacement media can be pentane, isopentane, n-hexane, normal heptane,
Normal octane, methanol, ethyl alcohol etc..The time of solvent displacement can be 0-72h, and displacement number can be 1-5 times；Hydrophobic modifier
It can be methyltrimethoxysilane, methyltriethoxysilane, trim,ethylchlorosilane, hexamethyldisilazane, three second of phenyl
Oxysilane etc.；The amount of hydrophobic modifier is 0%-20% by hydrophobic modifier/displacement solvent volume ratio；Hydrophobically modified
Time can be 0-72h；
S6. supercritical drying or constant pressure and dry are carried out to fibre in S5, overcritical or constant pressure and dry titanium dioxide is made
Aerosil/fibre that titanium and graphene oxide are modified jointly.Fibre carries out supercritical drying in S5
When dry, drying condition is determined according to the super critical point parameter of replacement media.Such as the super critical point parameter of ethyl alcohol is：Stagnation temperature
243.0 DEG C of degree, critical pressure 6.38MPa；The supercritical parameter of carbon dioxide is：31.0 DEG C of critical-temperature, critical pressure
7.37MPa；Fibre carries out constant pressure and dry in S5, and drying temperature is 40-100 DEG C, drying time 0-72h, is made
Modified aerosil/the fibre of constant pressure and dry graphene oxide.
Embodiment 1
A kind of hydrophobic type graphene oxide improved silica aeroge/fibre preparation with photocatalysis effect
Method is mainly made by titanium dioxide, graphene oxide, aerosil and fibre.Wherein silica airsetting
Glue is the silica dioxide gel obtained using two step of soda acid, sol-gal process, via exchange of solvent etc. one using silicon source as presoma
It is dry after serial procedures to be made；Titanium dioxide is as tetrabutyl titanate through Nano sol made from sol-gal process；Fiber can be with
Be short fine or long filament, can be inorganic or organic fiber, fibre can be fiber itself, fibre fabric, knitted fabric or
One of non-woven cloth is a variety of.The specific steps are：
S1. ethyl orthosilicate is chosen：Ethyl alcohol：The molar ratio of water is 1:8:7, and n,N-Dimethylformamide is added and (is positive
The 5% of silester volume), it is mixed stirring 1h and prepares silicon dioxide gel, add certain hydrochloric acid solution, control mixing
The pH value of solution is between 3-5；
S2. the ammonia spirit of 0.1mol/l, the mixing after control addition is added in silicon dioxide gel obtained into S1
Solution ph is between 8-10.
S3. the mixed sols of titanium dioxide and graphene oxide is added into the colloidal sol of S2, is wherein aoxidized in mixed sols
The quality of graphene is relative in silicon source the 0.06% of element silicon quality and the quality of titanium dioxide is equivalent to element silicon in silicon source
The 9% of quality, it should be noted that since graphene oxide is easily reunited, be added graphene oxide solution after need using
Ultrasonic wave disperses modification sol；Between ultrasonic power 40W, ultrasonic time 10min, ultrasonic temperature is at 40 DEG C；
S4. fiberglass products are completely immersed in S3 in colloidal sol, become gel after standing after a period of time.
It S5. the use of volume ratio is 1:1 silicon source/dehydrated alcohol mixed solution carries out the old of 48h to the gel in S4
Change, reuses n-hexane and gel is carried out 3 times, 8h/ solvent displacement；And using hydrophobic modifier trim,ethylchlorosilane to solidifying
Glue carries out hydrophobically modified, and wherein trim,ethylchlorosilane/n-hexane volume ratio is 10%, hydrophobically modified 3 times, 8h/ times, reuses just
Hexane carries out gel 3 times, 8h/ solvent displacement；
S6. constant pressure and dry is carried out to gel in S5, the dry 6h at 40 DEG C, then the dry 2h at 100 DEG C, is made low close
The titanium dioxide and the common improved silica aeroge/fiberglass products of graphene oxide of degree and high porosity, it is super thin
Water, and there are excellent absorption property, good photocatalysis performance and high frequency sound absorption qualities, and the heat at 800 DEG C is steady
It is qualitative.
Embodiment 2
A kind of hydrophilic graphene oxide improved silica aeroge/fibre preparation with photocatalysis effect
Method includes the following steps：
S1. ethyl orthosilicate is chosen：Ethyl alcohol：The molar ratio of water is 1:8:7, and n,N-Dimethylformamide is added and (is positive
The 5% of silester volume), it is mixed stirring 1h and prepares silicon dioxide gel, add certain hydrochloric acid solution, control mixing
The pH value of solution is between 3-5；
S2. the ammonia spirit of 0.1mol/l, the mixing after control addition is added in silicon dioxide gel obtained into S1
Solution ph is between 8-10.
S3. the mixed sols of titanium dioxide and graphene oxide is added into the colloidal sol of S2, is wherein aoxidized in mixed sols
The quality of graphene is relative in silicon source the 0.2% of element silicon quality and the quality of titanium dioxide is equivalent to element silicon matter in silicon source
Amount 3.6%, it should be noted that since graphene oxide is easily reunited, be added graphene oxide solution after need using
Ultrasonic wave disperses modification sol；Between ultrasonic power 40W, ultrasonic time 10min, ultrasonic temperature is at 40 DEG C；
S4. fiberglass products are completely immersed in S3 in colloidal sol, become gel after standing after a period of time.
It S5. the use of volume ratio is 1:1 silicon source/dehydrated alcohol mixed solution carries out the old of 48h to the gel in S4
Change, reuses n-hexane and gel is carried out 3 times, 8h/ solvent displacement；And using hydrophobic modifier trim,ethylchlorosilane to solidifying
Glue carries out hydrophobically modified, and wherein trim,ethylchlorosilane/n-hexane volume ratio is 10%, hydrophobically modified 3 times, 8h/ times, reuses just
Hexane carries out gel 3 times, 8h/ solvent displacement；
S6. constant pressure and dry is carried out to gel in S5, the dry 6h at 40 DEG C, then the dry 2h at 100 DEG C, is made low
The common improved silica aeroge/fiberglass products of the titanium dioxide and graphene oxide of density and high porosity, it is complete
It is complete hydrophilic, and there are excellent absorption property, good photocatalysis performance and high frequency sound absorption qualities, and at 800 DEG C
Thermal stability.
Embodiment 3
It is a kind of while there is the hydrophilic and hydrophobic performance graphene oxide improved silica gas with photocatalysis effect
Gel/fibre preparation method, includes the following steps：
S1. ethyl orthosilicate is chosen：Ethyl alcohol：The molar ratio of water is 1:8:7, and n,N-Dimethylformamide is added and (is positive
The 5% of silester volume), it is mixed stirring 1h and prepares silicon dioxide gel, add certain hydrochloric acid solution, control mixing
The pH value of solution is between 3-5；
S2. the ammonia spirit of 0.1mol/l, the mixing after control addition is added in silicon dioxide gel obtained into S1
Solution ph is between 8-10.
S3. the colloidal sol of S2 is divided into 2 parts, 2 kinds of different titanium dioxide and graphene oxide volume ratio is added thereto respectively
Mixed sols (control a copy of it mixed sols in graphene oxide quality relative to element silicon quality in silicon source
0.2% and the quality of titanium dioxide be equivalent to 3.6% of element silicon quality in silicon source, obtain the first modification sol B, another
The quality of graphene oxide is suitable relative to the quality of 0.06% and titanium dioxide of element silicon quality in silicon source in mixed sols
The 9% of element silicon quality in silicon source obtains the second modification sol B, it should be noted that since graphene oxide is easily rolled into a ball
It is poly-, therefore need to disperse modification sol using ultrasonic wave after graphene oxide solution is added；Ultrasonic power 40W, ultrasound
Between time 10min, ultrasonic temperature is at 40 DEG C；
It further, can be by changing immersion of the fibre in the first modification sol B and the second modification sol B
Different hydrophilic gel-organophilic gel volume ratio aerosil/fibre can be made in volume.
S4. basalt fibre product part is immersed into the quality of graphene oxide relative to element silicon quality in silicon source
0.2% and the quality of titanium dioxide be equivalent in silicon source in the mixed sols of element silicon quality 3.6%, stood after a period of time
After become gel；The non-gel section of basalt fibre is immersed to the quality for the graphene oxide being added again relative to silicon member in silicon source
The 0.06% of quality amount and the quality of titanium dioxide be equivalent in silicon source in 9% mixed sols of element silicon quality, by one
The section time becomes gel after standing, and obtains having 2 kinds of graphene oxide-titanium dioxide concentration basalt fibre products.
It S5. the use of volume ratio is 1:1 silicon source/dehydrated alcohol mixed solution carries out the old of 48h to the gel in S4
Change, reuses n-hexane and gel is carried out 3 times, 8h/ solvent displacement；And using hydrophobic modifier trim,ethylchlorosilane to solidifying
Glue carries out hydrophobically modified, and wherein trim,ethylchlorosilane/n-hexane volume ratio is 10%, hydrophobically modified 3 times, 8h/ times, reuses just
Hexane carries out gel 3 times, 8h/ solvent displacement；
S6. constant pressure and dry is carried out to gel in S5, the dry 6h at 40 DEG C, then the dry 2h at 100 DEG C, is made low
The common improved silica aeroge/basalt fibre product of the titanium dioxide and graphene oxide of density and high porosity, it
Two sides have different hydrophilicity and hydrophobicities, and have excellent absorption property, good photocatalysis performance and high frequency sound absorption properties
Can, and the thermal stability at 800 DEG C.
The graphene oxide improved silica aeroge/fibre side with photocatalysis effect of the present embodiment
Hydrophilic, the other side is hydrophobic, applied widely and easy to use.
Further, in the step 3, Sol A is divided into more parts, and configures the increase of graphene oxide concentration gradient and two
The mixed sols that titanium oxide concentration gradient reduces, and the graphene oxide and dioxy of various concentration is added in more parts of Sol As respectively
Change titanium mixed sols, gradient concentration graphene oxide-titania gel is made, in the step 4, fibre is successively soaked
Enter in graphene oxide concentration-titanium dioxide concentration modification sol of various concentration, by control accurate colloidal sol height, uses
The mode alternately implemented step by step with gel is immersed, thickness direction graphene oxide-titanium dioxide concentration segmentation diffusion is realized, obtains
Graded oxidation graphene-content of titanium dioxide silica dioxide gel is obtained, silica dioxide gel replaces through aging, solvent, is hydrophobic
The modified photocatalysis aerosil/fibre of gradient concentration graphene oxide can be made in processing and drying.
The addition of gradient concentration graphene oxide-titanium dioxide can obtain gradient hydrophobe aerosil/fibre
Fiber products, use scope are expanded.Gas between various concentration can be enhanced in graphene oxide-titanium dioxide of gradient concentration
The connection of gel, improves that its is blockiness, obtains that aeroge skeleton structure is good, the fibre of low-density, high porosity.This
Outside, gradient concentration can effectively reduce the internal stress of fibre, improve the mechanical property of fibre；Improve fibre
The rate of adsorption；Assign its different photocatalysis efficiency.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. the preparation method of the modified adjustable photocatalysis aerosil fibre of hydrophilic and hydrophobic of graphene oxide,
It is characterized in that, includes the following steps：
Step 1 mixes silicon source, alcohol, water and acid catalyst, controls the pH value of mixed solution between 2 and 6；Two are obtained after stirring
Silica sol；
Deionized water and base catalyst are added into step 1 for step 2 in silicon dioxide gel obtained, control mixed solution
PH value obtains modification sol A between 7-11, after stirring；
Step 3, into modification sol A, the mixed sols of addition titanium dioxide and graphene oxide obtains modification sol B；
Fibre is completely immersed in modification sol B by step 4, and gel is obtained after standing after a period of time；
Step 5 carries out aging process to the gel in step 4 using silicon source/alcohol mixed solution, reuses displacement solvent to solidifying
Glue carries out solvent displacement, obtains the modified photocatalysis aerosil fibre semi-finished product of graphene oxide；
Step 6, the photocatalysis aerosil fibre semi-finished product modified to graphene oxide carry out hydrophobically modified and
It is dry, obtain the modified photocatalysis aerosil fibre of graphene oxide.
2. the adjustable photocatalysis aerosil of the modified hydrophilic and hydrophobic of graphene oxide according to claim 1 is fine
The preparation method of fiber products, which is characterized in that further include the step dispersed using ultrasonic wave to modification sol B in step 3
Suddenly, ultrasonic power is between 10-200W, and ultrasonic time is between 0-20min, and ultrasonic temperature is between 25-80 DEG C.
3. the adjustable photocatalysis aerosil of the modified hydrophilic and hydrophobic of graphene oxide according to claim 1 is fine
The preparation method of fiber products, which is characterized in that when aoxidizing stone in the mixed sols of titanium dioxide and graphene oxide in step 3
The quality of black alkene is no more than in silicon source the 0.12% of element silicon quality and the quality of titanium dioxide is equivalent to element silicon matter in silicon source
When the 4.5%-45% of amount, the modified photocatalysis aerosil fibre of graphene oxide obtained is hydrophobic type.
4. the adjustable photocatalysis aerosil of the modified hydrophilic and hydrophobic of graphene oxide according to claim 1 is fine
The preparation method of fiber products, which is characterized in that when aoxidizing stone in the mixed sols of titanium dioxide and graphene oxide in step 3
When the quality of black alkene is equivalent to the 0.12%-0.25% of element silicon quality in silicon source and the quality of titanium dioxide is not more than in silicon source
Element silicon quality 4.5% when, the modified photocatalysis aerosil fibre of graphene oxide obtained is hydrophilic
Type.
5. the adjustable photocatalysis aerosil of the modified hydrophilic and hydrophobic of graphene oxide according to claim 1 is fine
The preparation method of fiber products, which is characterized in that the step 3 is specially：Sol A is divided into two parts, is added into a Sol A
The mixed sols of titanium dioxide and graphene oxide obtains the first modification sol B, wherein in mixed sols graphene oxide matter
Amount is equivalent to the quality of the 0.12%-0.25% and titanium dioxide of element silicon quality in silicon source no more than element silicon quality in silicon source
4.5%；Titanium dioxide is added into another Sol A and the mixed sols of graphene oxide obtains the second modification sol B；Its
Quality phase of the quality of graphene oxide no more than 0.12% and titanium dioxide of element silicon quality in silicon source in middle mixed sols
As the 4.5%-45% of the element silicon quality in silicon source；
The step 4 is specially：A part of fibre is immersed in the first modification sol B, after standing after a period of time
The first gel is obtained, the exposed fibre outside the first gel is immersed in the second modification sol B, is stood after a period of time
The mixed gel that two sides have different hydrophilicity and hydrophobicities is obtained afterwards.
6. the adjustable photocatalysis aerosil of the modified hydrophilic and hydrophobic of graphene oxide according to claim 5 is fine
The preparation method of fiber products, which is characterized in that in the step 4, by changing fibre in the first modification sol B and second
Different hydrophilic gel-organophilic gel volume ratio aerosil/fiber can be made in immersion volume in modification sol B
Product.
7. the modified photocatalysis aerosil of the adjustable graphene oxide of hydrophilic and hydrophobic according to claim 5/
The preparation method of fibre, which is characterized in that in the step 3, Sol A is divided into more parts, and it is dense to configure graphene oxide
The mixed sols that gradient increases and titanium dioxide concentration gradient reduces is spent, and the oxygen of various concentration is added in more parts of Sol As respectively
Gradient concentration graphene oxide-titania gel is made in graphite alkene and titanium dioxide mixed sols, will in the step 4
Fibre successively immerses in graphene oxide concentration-titanium dioxide concentration modification sol of various concentration, passes through control accurate
Colloidal sol height realizes thickness direction graphene oxide-titanium dioxide concentration in such a way that immersion and gel are alternately implemented step by step
Segmentation diffusion, obtain graded oxidation graphene-content of titanium dioxide silica dioxide gel, silica dioxide gel through aging,
The modified photocatalysis aerosil/fibre of gradient concentration graphene oxide can be made in solvent displacement, hydrophobic treatment and drying
Fiber products.
8. the adjustable photocatalysis aerosil of the modified hydrophilic and hydrophobic of graphene oxide according to claim 1 is fine
The preparation method of fiber products, which is characterized in that the silicon source and the molar ratio of alcohol are 1:(1-50), mole of the silicon source and water
Than being 1:(1-20).
9. the adjustable photocatalysis aerosil of the modified hydrophilic and hydrophobic of graphene oxide according to claim 1 is fine
The preparation method of fiber products, which is characterized in that the fiber is inorganic or organic fiber, and the fiber is basalt fibre, oxygen
Change aluminum fiber, glass fibre, ceramic fibre, alumina silicate fibre, aramid fiber, polytetrafluoroethylene fibre, superhigh molecular weight polyethylene
One of alkene fiber is a variety of, and the fibre is one in fiber itself, fibre fabric, knitted fabric or non-woven cloth
Kind is a variety of.
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