CN105921142A - Preparation method of titanium dioxide based graphene /La3+ carbon fibers - Google Patents
Preparation method of titanium dioxide based graphene /La3+ carbon fibers Download PDFInfo
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- CN105921142A CN105921142A CN201610333209.9A CN201610333209A CN105921142A CN 105921142 A CN105921142 A CN 105921142A CN 201610333209 A CN201610333209 A CN 201610333209A CN 105921142 A CN105921142 A CN 105921142A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 54
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 22
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000004408 titanium dioxide Substances 0.000 title abstract description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 16
- 238000009987 spinning Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229960000583 acetic acid Drugs 0.000 claims abstract description 11
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 11
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 9
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 241000338670 Clossiana titania Species 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 27
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 description 21
- 239000002121 nanofiber Substances 0.000 description 13
- 239000010936 titanium Substances 0.000 description 13
- 239000000523 sample Substances 0.000 description 8
- 241000588724 Escherichia coli Species 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000003385 bacteriostatic effect Effects 0.000 description 5
- 230000001408 fungistatic effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000000845 anti-microbial effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- -1 rare earth ion Chemical class 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 206010034960 Photophobia Diseases 0.000 description 1
- 241000292525 Titanio Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003905 indoor air pollution Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004899 motility Effects 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- Pest Control & Pesticides (AREA)
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Abstract
The invention discloses a preparation method of titanium dioxide based graphene /La3+ carbon fibers. The preparation method includes the following steps that 1, graphene and polyacrylonitrile are dissolved in a DMF solution to prepare a graphene/polyacrylonitrile/DMF mixed solution, wherein the graphene concentration is 0.0007-0.0056 g/mL, and the polyacrylonitrile concentration is 0.08 g/mL; 2, lanthanum nitrate is added to a glacial acetic acid and tetra-n-butyl titanate mixed solution to form an La3+ doped TiO (OAc)2 solution; 3, the solution formed in the step 2 is slowly added to the graphene/polyacrylonitrile/DMF mixed solution in the step 1 under the action of mixing, and vacuum mixing is performed to obtain a spinning solution after adding is performed dropwise; 4, the spinning solution in the step 3 performs electrostatic spinning to obtain a product. The preparation method has the advantages of high strength, simple production equipment, easy and convenient operation and a good antibacterial effect.
Description
Technical field
The present invention relates to functional fiber technical field, particularly relate to a kind of titania-based Graphene/La3+Carbon
The preparation method of fiber.
Background technology
Since 20th century, along with the development of society and improving constantly of people's living standard, environmental pollution more comes
More being paid close attention to by people, Indoor Air Pollution with outdoor Air Pollution, soil pollution, water pollution etc. have influence on people's day by day
Healthy.Anti-biotic material has become cross-centennial environmental protection and the health-oriented products that countries in the world are generally acknowledged at present.Along with China
Expanding economy and the raising of living standards of the people, the application of anti-biotic material is the most increasingly.
Extensively utilize Heterogenous photocatalytic oxidation technology for semiconductors to carry out anti-microbial property research and become section of various countries in recent years
Grind the study hotspot of worker, conductor photocatalysis material have high efficiency, low power consuming, degraded completely, nothing
Secondary pollution, the advantage such as reuse capable of circulation, demonstrate huge application prospect.
TiO2Spectrochemical property is stable, and to biological non-toxicity, bandgap center position mates, can produce photoproduction after illumination
Hole and electronics have the strongest reducing power, can be the precipitation adsorption surface at catalyst by bacterial reduction.
But TiO2In actual utilization, there is also some science and technology difficult problems as catalysis material, main
Concentrate on two aspects: 1) TiO2As catalysis material light absorption wavelength scope, there is limitation, to can
See that light utilization efficiency is the highest；2) quantum yield is low.
Summary of the invention
The present invention provides that a kind of intensity is high, production equipment is simple, easy and simple to handle, the titanium dioxide of good anti-bacterial effect
Titanio Graphene/La3+The preparation method of carbon fiber.
The present invention removes to realize above-mentioned technique effect by techniques below means: a kind of titania-based Graphene/
La3+The preparation method of carbon fiber, comprises the steps:
(1) Graphene, polyacrylonitrile are dissolved in DMF solution prepared Graphene/polyacrylonitrile/DMF and mix
Close liquid；Wherein the concentration of Graphene is 0.0007-0.0049g/mL, and the concentration of polyacrylonitrile is 0.08g/mL；
(2) Lanthanum (III) nitrate is joined in glacial acetic acid, tetra-n-butyl titanate mixed solution, form La3+Doping
TiO(OAc)2Solution；Wherein Lanthanum (III) nitrate be concentration be 0.0069g/mL, glacial acetic acid, tetra-n-butyl titanate
Volume ratio be 4:5；
(3) step (2) is formed solution and be slowly added into the graphite in step (1) under the effect of stirring
In alkene/polyacrylonitrile/DMF mixed liquor, described Graphene/polyacrylonitrile/DMF mixed liquor and step (2) shape
The volume ratio becoming solution is 50:9；After dropping, vacuum stirring, obtain spinning liquid；
(4) spinning liquid of step (3) is carried out electrostatic spinning, and drawing-off, pre-oxidize, calcine after must produce
Product.
Preferably, described Graphene is Graphene prepared by Hummers method.
Preferably, it is placed in vacuum drying oven before polyacrylonitrile is dissolved in DMF to be dried.
Preferably, in described step (1), the concentration of Graphene is 0.0014g/mL.
Preferably, in described step (1), the concentration of Graphene is 0.0028g/mL.
Preferably, in described step (1), the concentration of Graphene is 0.0042g/mL.
Preferably, the time of the vacuum stirring of described step (3) is 10h.
Preferably, pre-oxidation pre-oxidizes 1h at 200 DEG C.
Preferably, calcining specifically comprises the processes of: the speed with 100 DEG C/h heats up in tube furnace, and
500 DEG C of insulation calcining 2h.
It is an advantage of the current invention that: the present invention utilizes rare earth ion La3+There is undersaturated electron configuration,
Titanium dioxide can make its lattice be distorted after rare earth ion doped, produces substantial amounts of oxygen defect, trapping
More electronics, reaches to improve the purpose of catalytic efficiency；Rare earth ion can also absorb infrared light simultaneously,
Then converting thereof into visible ray, this also substantially increases TiO2The light spectrality that visible ray is utilized.Use tool
There is specific surface area big and the Graphene (GO) of good adsorption properties be as the carrier of catalysis material, it is also possible to
Change TiO2Surface property, thus it is effectively reduced the probability that photo-generate electron-hole combines, improve quick to light
Sensitivity.It addition, electrostatic spinning technique have workable, technique is adjustable, equipment simply possess operation letter
The advantage such as just.Use titania-based Graphene/La that the inventive method is made3+Carbon fiber have intensity high,
Production equipment is simple, easy and simple to handle, the advantage of good anti-bacterial effect.
Accompanying drawing explanation
Fig. 1 is TiO2The SEM figure of nanofiber.
Fig. 2 is the titania-based Graphene/La of the embodiment of the present invention 13+The SEM figure of carbon fiber.
Fig. 3 is the titania-based Graphene/La of the embodiment of the present invention 23+The SEM figure of carbon fiber.
Fig. 4 is the titania-based Graphene/La of the embodiment of the present invention 33+The SEM figure of carbon fiber.
Fig. 5 is the titania-based Graphene/La of the embodiment of the present invention 43+The SEM figure of carbon fiber.
Fig. 6 is the titania-based Graphene/La of the embodiment of the present invention 53+The SEM figure of carbon fiber.
Fig. 7 is titania-based Graphene/La in the present invention3+Carbon fiber physical property with GO doping change and
The graph of a relation of change.
Detailed description of the invention
The TiO of the present invention2The preparation method of nanofiber uses " polyacrylonitrile/titania hybrid nano active
Carbon fiber preparation and structure Changing Pattern " chemical industry progress, the method described in 2007,26 (7): 974-979
Preparation.
Embodiment one
1, get the raw materials ready: weigh 2g polyacrylonitrile (PAN) respectively, measure 25ml DMF, 2ml glacial acetic acid
With 2.5ml tetra-n-butyl titanate (Ti (OC4H9)4) mixed solution.
2, use: Hummers method prepares Graphene, carries out supersound process under the conditions of room temperature 25 DEG C.Stone
Ink alkene (GO) doping is 0.05 with the mass ratio of Ti.
3, GO/DMF mixed solution is added gradually in PAN/DMF, vacuum stirring, and ultrasonic 10h,
Finally obtain 25ml GO/PAN spinning liquid；In GO/DMF Yu PAN/DMF, the volume ratio of DMF is 1:
1。
4, then the Lanthanum (III) nitrate of 0.031g is joined containing 2ml glacial acetic acid and 2.5ml tetra-n-butyl titanate
(Ti(OC4H9)4) in mixed solution, form La3+The TiO (OAc) of doping2Solution, then stirs at magnetic force
Mix down and be slowly added in above-mentioned GO/PAN mixed solution, after dropping, continue magnetic agitation 10h,
Finally give spinning solution and carry out spinning.
The spinning liquid configured is placed in self-control electrostatic spinning apparatus needle tubing in, spinning head with receive device it
Between distance be 15cm, be 1.0mL/h, ring in DC voltage 15kV, spinning solution spouting velocity
Border temperature be set to 25 DEG C, relative humidity under conditions of 65%, carry out electrostatic spinning, after spinning 10h,
Obtain GO and different rare earth La3+The TiO of content2Nanofiber.Then by prepared TiO2Nanofiber two
End graphite flake is fixed, and two ends distance is maintained at 10cm, is placed on 120 DEG C by clamp and carries out
Drawing-off, and carry out pre-oxidizing 1h in 200 DEG C.The black sample GO/La finally pre-oxidation obtained3+It is co-doped with
Miscellaneous TiO2It is placed in tube furnace and heats up with the speed of 100 DEG C/h, and at 500 DEG C of insulation calcining 2h,
Obtain GO/La eventually3+The TiO of codope2(GLCT) nanofiber.
5, antibacterial tests:
With colibacillus for test antibacterial, use the mode test sample cultivating bacteria growing inhibiting
Bactericidal property.Choosing escherichia coli (E.coli ATCC8739) is that anti-microbial property tests strain, and choosing is by this reality
The fiber executing example is cut into the billet of diameter 1.0cm, and test organisms suspension is uniformly applied to the fiber of antimicrobial treatment,
It is put in detection bacterium plate, puts cultivation 24h in 37 DEG C of incubators, observe antibacterial circle diameter.Will not in experiment
Make the fiber of antimicrobial treatment as control sample.
According to judgement to bacteriostasis in " disinfection technology standard 2006 ": antibacterial circle diameter is more than 20mm table
Showing have strong fungistatic effect, inhibition zone is moderate antibacterial at 10mm～20mm, and inhibition zone is weak less than 10mm
Antibacterial, judge that nano-complex has preferable fungistatic effect.Sample is compared by the size comparing antibacterial circle diameter
The power of bactericidal property, bacteriostatic diameter is 14mm, GO/La3+The TiO of codope2(GLCT) Nanowire
Dimension belongs to moderate antibacterial to escherichia coli.
Embodiment two
1, get the raw materials ready: weigh 2g polyacrylonitrile (PAN) respectively, measure 25ml DMF, 2ml glacial acetic acid
With 2.5ml tetra-n-butyl titanate (Ti (OC4H9)4) mixed solution, GO doping with the mass ratio of Ti is
0.10。
2, step 2,3,4,5 repetition examples one.
3, antibacterial tests: such as embodiment 1
Compared the power of sample bactericidal property by the size comparing antibacterial circle diameter, bacteriostatic diameter is 19mm,
GO/La3+The TiO of codope2(GLCT) nanofiber is preferable to escherichia coli fungistatic effect.
Embodiment three
1, get the raw materials ready: weigh 2g polyacrylonitrile (PAN) respectively, measure 25ml DMF, 2ml glacial acetic acid
With 2.5ml tetra-n-butyl titanate (Ti (OC4H9) 4) mixed solution, GO doping with the mass ratio of Ti is
0.2。
2, step 2,3,4,5 repetition examples one.
Compared the power of sample bactericidal property by the size comparing antibacterial circle diameter, bacteriostatic diameter is 22mm,
GO/La3+The TiO of codope2(GLCT) nanofiber is good to escherichia coli fungistatic effect.
Embodiment four
1, get the raw materials ready: weigh 2g polyacrylonitrile (PAN) respectively, measure 25ml DMF, 2ml glacial acetic acid
With 2.5ml tetra-n-butyl titanate (Ti (OC4H9)4) mixed solution, GO doping with the mass ratio of Ti is
0.3。
2, step 2,3,4,5 repetition examples one.
Compared the power of sample bactericidal property by the size comparing antibacterial circle diameter, bacteriostatic diameter is 10mm,
GO/La3+The TiO of codope2(GLCT) nanofiber belongs to moderate antibacterial to escherichia coli are antibacterial.
Embodiment five
1, get the raw materials ready: weigh 2g polyacrylonitrile (PAN) respectively, measure 25ml DMF, 2ml glacial acetic acid
With 2.5ml tetra-n-butyl titanate (Ti (OC4H9)4) mixed solution, GO doping with the mass ratio of Ti is
0.35。
2, step 2,3,4,5 repetition examples one.
Compared the power of sample bactericidal property by the size comparing antibacterial circle diameter, bacteriostatic diameter be antibacterial directly
Footpath is 8mm, GO/La3+The TiO of codope2(GLCT) nanofiber is poor to escherichia coli fungistatic effect.
From above each example: by converting the percentage composition of GO, having of different performance can be obtained aobvious
Writing the fiber of antibacterial functions, the fiber utilizing the present invention to make can be widely applied to clothing, socks, home textile product
The field such as product, medical product, production process is green, environment friendly and pollution-free.
Under normal circumstances, the concentration of GO to control one reasonably in the range of, on the one hand because metatitanic acid four just
Butyl ester and PAN have certain tolerance degree to GO, and along with the raising of GO content, fiber by
Gradual change is thick, is unfavorable for light-catalysed carrying out, and is also easier to block electrostatic spinning jet.On the other hand,
When the content of GO is too low, it is unfavorable for TiO2The raising of surface area, and be fully exposed under visible ray,
Hinder to a certain extent from light source or the absorption of suspended particles scattered photon；Content mistake as GO
Gao Shi, GO will be coated on TiO2Surface, be unfavorable for GO at titanium dioxide surface graft growth, meanwhile,
A large amount of GO impacts reunited hinder photo-generated carrier within the limited life-span to TiO2Surface migration, not only
It is unable to reach the purpose improving catalytic performance, reduces its antibacterial effect to a certain extent.Therefore carrying out
During the configuration of electrostatic spinning liquid, need rational allocation GO proportioning.
The light that the fiber taken off from electrostatic spinning machine also needs to through high-temperature calcination just can obtain needing is urged
Agent, and calcination process can produce certain impact to GO.Organic group such as surface may be by part oxygen
Changing, the skeleton of GO may be by breakage etc..From Fig. 1-6, each sample be one-dimensional, randomly take
To nanofibrous structures.Wherein TiO2Nanofiber diameter after calcining wants thin compared with the diameter of other samples
Some, probably at about 200nm, and the diameter of other fiber samples is probably at about 400-500nm.Such as figure
Shown in 1, amplify pure TiO after calcining2The fiber surface of nanofiber is relatively smooth, and the surface of other samples is slightly
Micro-have projection to be coated with wherein by fiber due to Graphene, so can't see the existence of Graphene in SEM figure.
GO is laminated structure, and size is at 400nm, close with fibre diameter, therefore we it can be inferred that, the own warp of GO
It is distributed in nanofiber as display in stereoscan photograph.And along with graphene oxide addition
Be continuously increased, pearl joint phenomenon is obvious all the more, especially when the mass ratio of GO doping Yu Ti is 0.35, fibre
Having occurred and that adhesion between dimension, this is possibly due to the addition of graphene oxide, have impact on PAN macromole original
Seriality, the reunion of Graphene simultaneously also can produce pearl joint, and what too much pearl joint was serious have impact on Static Spinning
The seriality of silk.Meanwhile, from this figure it can be seen that along with the increase of Graphene content, fibre diameter phase
Ratio is compared before not adding Graphene, and fiber is tapered, and it is uneven that diameter becomes thickness.
It can be seen from figure 7 that along with the increase (method with above-mentioned enforcement of GO doping Yu the mass ratio of Ti
Prepare fiber, wherein the mass ratio of GO doping and Ti be respectively 0.05,0.1,0.15,0.2,0.25,0.3,
0.35), the hot strength of fiber, percentage elongation are gradually increased, when the mass ratio of GO doping Yu Ti is 0.2,
Hot strength, percentage elongation are maximum, and this has higher Young's modulus and hardness, good mainly due to GO
Motility, when adding appropriate, the addition of graphene oxide enhances the switching performance between PAN macromolecular chain
Fiber strength is made to increase.Wherein, hot strength be up to 19.8%, 57.2MPa.Matter when GO doping Yu Ti
The increase of amount ratio continues to increase, and the hot strength of fiber, percentage elongation are the most on a declining curve, produce this phenomenon
Reason be mainly when the too high levels of GO, in nanofiber produce pearl joint, low-fiber mechanical property drops.
This embodiment is only the preferred embodiment of the invention, not in order to limit the invention,
Any amendment, equivalent and the improvement etc. made within all spirit in the invention and principle, all should
Within being included in the protection domain of the invention.
Claims (9)
1. titania-based Graphene/La3+The preparation method of carbon fiber, it is characterised in that include as
Lower step:
(1) Graphene, polyacrylonitrile are dissolved in DMF solution prepared Graphene/polyacrylonitrile/DMF and mix
Close liquid；Wherein the concentration of Graphene is 0.0007-0.0049g/mL, and the concentration of polyacrylonitrile is 0.08g/mL；
(2) Lanthanum (III) nitrate is joined in glacial acetic acid, tetra-n-butyl titanate mixed solution, form La3+Doping
TiO(OAc)2Solution；Wherein Lanthanum (III) nitrate be concentration be 0.0069g/mL, glacial acetic acid, tetra-n-butyl titanate
Volume ratio be 4:5；
(3) step (2) is formed solution and be slowly added into the graphite in step (1) under the effect of stirring
In alkene/polyacrylonitrile/DMF mixed liquor, described Graphene/polyacrylonitrile/DMF mixed liquor and step (2) shape
The volume ratio becoming solution is 50:9；After dropping, vacuum stirring, obtain spinning liquid；
(4) spinning liquid of step (3) is carried out electrostatic spinning, and drawing-off, pre-oxidize, calcine after must produce
Product.
Titania-based Graphene/the La of one the most according to claim 13+The preparation method of carbon fiber,
It is characterized in that, described Graphene is Graphene prepared by Hummers method.
Titania-based Graphene/the La of one the most according to claim 13+The preparation method of carbon fiber,
It is characterized in that, polyacrylonitrile is placed in vacuum drying oven before being dissolved in DMF and is dried.
Titania-based Graphene/the La of one the most according to claim 13+The preparation method of carbon fiber,
It is characterized in that, in described step (1), the concentration of Graphene is 0.0014g/mL.
Titania-based Graphene/the La of one the most according to claim 13+The preparation method of carbon fiber,
It is characterized in that, in described step (1), the concentration of Graphene is 0.0028g/mL.
Titania-based Graphene/the La of one the most according to claim 13+The preparation method of carbon fiber,
It is characterized in that, in described step (1), the concentration of Graphene is 0.0042g/mL.
Titania-based Graphene/the La of one the most according to claim 13+The preparation method of carbon fiber,
It is characterized in that, the time of the vacuum stirring of described step (3) is 10h.
Titania-based Graphene/the La of one the most according to claim 13+The preparation method of carbon fiber,
It is characterized in that, pre-oxidation pre-oxidizes 1h at 200 DEG C.
Titania-based Graphene/the La of one the most according to claim 13+The preparation method of carbon fiber,
It is characterized in that, calcining specifically comprises the processes of: in tube furnace, the speed with 100 DEG C/h heats up, and
500 DEG C of insulation calcining 2h.
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| CN107413325A (en) * | 2017-08-08 | 2017-12-01 | 东华大学 | A kind of rare earth/carbon co-doped flexible TiO2Nano fibrous membrane and preparation method thereof |
| CN109589996A (en) * | 2018-11-30 | 2019-04-09 | 清华大学 | A kind of TiO2Base/two-dimensional material nano composite photocatalytic tunica fibrosa and preparation method thereof |
| CN115036151A (en) * | 2022-07-08 | 2022-09-09 | 嘉兴学院 | Preparation method of conductive high polymer-based composite electrode material |
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| HYOUNG-IL KIM ET AL: ""Graphene oxide embedded into TiO2 nanofiber: Effective hybrid photocatalyst for solar conversion"", 《JOURNAL OF CATALYSIS》 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107326534A (en) * | 2017-06-29 | 2017-11-07 | 合肥银派科技有限公司 | A kind of graphene micron filamentary silver composite antibacterial non-woven fabrics and preparation method thereof |
| CN107413325A (en) * | 2017-08-08 | 2017-12-01 | 东华大学 | A kind of rare earth/carbon co-doped flexible TiO2Nano fibrous membrane and preparation method thereof |
| CN107413325B (en) * | 2017-08-08 | 2019-10-29 | 东华大学 | A kind of rare earth/carbon co-doped flexibility TiO2Nano fibrous membrane and preparation method thereof |
| CN109589996A (en) * | 2018-11-30 | 2019-04-09 | 清华大学 | A kind of TiO2Base/two-dimensional material nano composite photocatalytic tunica fibrosa and preparation method thereof |
| CN109589996B (en) * | 2018-11-30 | 2023-04-07 | 清华大学 | TiO 2 2 Base/two-dimensional material nano composite photocatalytic fiber membrane and preparation method thereof |
| CN115036151A (en) * | 2022-07-08 | 2022-09-09 | 嘉兴学院 | Preparation method of conductive high polymer-based composite electrode material |
| CN115036151B (en) * | 2022-07-08 | 2023-11-24 | 嘉兴学院 | Preparation method of conductive polymer-based composite electrode material |
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Application publication date: 20160907 |