CN110124724A - A kind of preparation method of functionalization graphene quantum dot/composite titania material - Google Patents
A kind of preparation method of functionalization graphene quantum dot/composite titania material Download PDFInfo
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- CN110124724A CN110124724A CN201910554049.4A CN201910554049A CN110124724A CN 110124724 A CN110124724 A CN 110124724A CN 201910554049 A CN201910554049 A CN 201910554049A CN 110124724 A CN110124724 A CN 110124724A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000002096 quantum dot Substances 0.000 title claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 16
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 39
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 16
- 239000012498 ultrapure water Substances 0.000 claims abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 238000000502 dialysis Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 150000004040 pyrrolidinones Chemical class 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 239000011812 mixed powder Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000011056 performance test Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000004809 Teflon Substances 0.000 description 7
- 229920006362 Teflon® Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The present invention provides a kind of preparation methods of functionalization graphene quantum dot/composite titania material, it is first with isopropyl titanate (IV) for titanium source, using polyvinylpyrrolidone as dispersing agent, under acidic environment, it disperses titanium tetraisopropylate (IV) in ethylene glycol, obtained titanium solution；Again titanium solution is subjected to solvent thermal reaction at 160 ~ 165 DEG C and obtains the flower-shaped titanium dioxide of yellow；Yellow titanium dioxide obtains flower-shaped titanium dioxide by calcining；Then flower-shaped titanium dioxide and N doped graphene quantum dot ultrasonic disperse are placed in autoclave in ultrapure water and carry out hydro-thermal reaction, obtain titanium dioxide/graphene quantum dot composite material.Photocatalysis performance test result shows that the quantum dot composite material has higher photocatalytic activity, significantly improves to the degradation capability of organic pollutant.
Description
Technical field
The present invention relates to a kind of preparation method of composite titania material more particularly to a kind of functionalization graphene quantum
The preparation of point/composite titania material belongs to material mainly as photochemical catalyst for the organic pollutant in degrading waste water
Preparation field and with photocatalytic applications field.
Background technique
Water and the mankind, the energy, food safety and environmental pollution etc. are classified as one of ten big problems together.Especially in development
Country, due to not can be carried out the infrastructure of effective and extensive purified water and disinfection, the propagation such as disease are rapid.From this meaning
Upper theory, photocatalytic applications can provide huge applications prospect in the purification of water and waste water to solve urgent water environmental problems.Such as
Light degradation or conversion organic pollutant, the toxicity for removing heavy metal ion etc..Titanium dioxide (TiO2) base optic catalytic due to its easily
Industrialization, stability is good, rich reserves, non-toxic, high photolytic activity and cause great concern.Graphene quantum dot is as one
The novel zero dimension carbon nanomaterial of kind, different with micron-sized zero band gap material graphene, its size is often at 10 nanometers
Hereinafter, enabling it to band because exciton is had quantum confined effect by beam and being opened the semiconductor material to be formed with BREATHABLE BANDWIDTH
Material, is widely used in fluorescence imaging, electrochemical sensing, drug delivery, dye cell, photocatalysis etc..
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of functionalization graphene quantum dot/composite titania material；
The present invention can be carried out research to functionalization graphene quantum dot/composite titania material photocatalytic of preparation simultaneously.
One, functionalization graphene quantum dot/composite titania material preparation
(1) preparation of flower-shaped titanium dioxide
It is that dispersing agent disperses ethylene glycol for titanium tetraisopropylate (IV) under acidic environment with polyvinylpyrrolidone (PVP)
In, it is sufficiently stirred, obtains titanium solution；Titanium solution is placed in stainless steel autoclave, 12 ~ 13h is reacted at 160 ~ 165 DEG C；It is cold
But to after room temperature, filtering reacting liquid, for several times, dry 12 ~ 12.5 h, are obtained at 60 ~ 65 DEG C for product distilled water and ethanol washing
The yellow powder titanium dioxide arrived；Then yellow powder titanium dioxide is placed in vacuum tube furnace, in air atmosphere,
Anneal 1.5 ~ 2 h at 550 ~ 600 DEG C, obtains the flower-shaped titanium dioxide of white, is labeled as FT.
Polyethylene of dispersing agent pyrrolidones is added in the form of 5 ~ 6mg of concentration/mL aqueous solution；Polyvinylpyrrolidone water
The volume ratio of solution and titanium tetraisopropylate is 1:30 ~ 1:35.
(2) preparation of N doped graphene quantum dot
By citric acid and urea by the quality of 1:1 ~ 1:1.2 than 20 ~ 25min of mixed grinding after, be heated to 175 ~ 180 DEG C, mixing
Powder melts and slowly turns yellow solution by white；1.5 ~ 2 h of ultrapure water ultrasound is added after solution is cooled to room temperature, then
Supernatant is collected in centrifugation, finally by supernatant bag filter 40 ~ 48 h of dialysis, is dialysed freeze-dried, is obtained brown powder
N doped graphene quantum dot is labeled as N-GQDs.
Centrifugal speed is 12000 ~ 13000 rpm；
Bag filter uses the bag filter of 3000 ~ 8000Da；
(3) preparation of titanium dioxide/graphene quantum dot composite material
The flower-shaped titanium dioxide (FT) of white and N doped graphene quantum dot (N-GQDs) compare ultrasonic disperse with the quality of 1:5 ~ 1:50
It in ultrapure water, is subsequently placed in autoclave, in 119 ~ 120 DEG C of 5.5 ~ 6 h of holding, after being cooled to room temperature, filters, use is ultrapure
Water and ethanol washing are for several times, dry, obtain titanium dioxide/graphene quantum dot composite material, are labeled as FT/N-GQDs.
Two, the structure and performance of titanium dioxide/graphene quantum dot composite material
Fig. 1 is present invention preparation NGQDs, the X-ray diffraction (XRD) figure of FT, FT-NGQDs.2 θ in FT-NGQDs figure=
27.4 °, 36.1 °, 41.2 °, 54.3 °, 56.7 °, 69.0 ° correspond to (110), (101), (111), (211), (220),
(301), show that prepared that come out is Rutile Type TiO for we2.Diffraction maximum positioned at 2 θ=26.2 ° is graphite (002)
Crystal face characteristic diffraction peak, diffraction maximum of the NGQDs in 2 θ=11.3 ° show that the NGQDs that we prepare has many oxygen-containing groups.
Fig. 2 is the Raman spectrogram of titanium dioxide/graphene quantum dot composite material prepared by the present invention.FT in figure and
FT-NGQDs has Rutile Type TiO2Characteristic peak 138cm-1, 226 cm-1, 441 cm-1, 606 cm-1, the drawing of FT-NGQDs
Graceful figure has the feature D(1350cm of graphene-1) band and G(1599cm-1) band, illustrate that NGQDs is present in FT-NGQDs sample
Surface.
Fig. 3 is the ultraviolet spectrogram of titanium dioxide/graphene quantum dot composite material prepared by the present invention.It can by Fig. 3
To find out, titanium dioxide/graphene quantum dot composite material compares pure titinium dioxide and inhales at visible region (400-800 nm)
Luminosity is remarkably reinforced, and shows that composite material is obviously improved visible light absorption capacity, therefore its releasable photocatalytic activity
It is significantly improved compared with pure titinium dioxide.
Fig. 4 is the photocatalytic degradation figure of titanium dioxide/graphene quantum dot composite material prepared by the present invention.Pass through Fig. 4
As can be seen that titanium dioxide/graphene quantum dot composite material compares pure titinium dioxide in terms of photocatalytic degradation rhodamine B
It can obtain to beat and greatly promote.Ordinate indicates that degradation concentration accounts for the percent value of former total concentration in figure, and linear gradient is bigger, represents
Its photocatalytic activity is higher, and degradation of contaminant ability is stronger.
In conclusion the present invention has the advantage that compared with the prior art
1, the present invention flower-shaped titanium dioxide and graphene quantum dot are carried out in a high pressure reaction kettle it is compound, obtain titanium dioxide at
Function load graphene quantum dot so that composite material have more highlight catalytic active, therefore can be used for photocatalytic water, energy storage material,
The preparation of environment conscious material etc., to make being more widely applied for composite titania material；
2, when nitrogen is introduced into the carbon skeleton of graphene quantum dot by the present invention, the electronics of its adjustable quantum dot
Characteristic simultaneously forms active site on the surface of graphene quantum dot, obtains more excellent electric property and optical property, works as nitrogen
When doped graphene quantum dot is applied to photocatalysis, the spy with good carrier transport ability and sensitized semiconductor
Property, the absorbing properties of photochemical catalyst are improved, charge migration is greatly facilitated and answering for photo-generate electron-hole can be inhibited
It closes, extends charge life with this and promote light-catalyzed reaction process；Two can be effectively promoted by compound N doped graphene quantum dot
The photocatalytic activity of titanium oxide, degradable organic pollutant time greatly shorten, and reach that 60 min are i.e. degradable to be finished.
Detailed description of the invention
Fig. 1 is the XRD of functionalization graphene quantum dot/composite titania material prepared by the present invention.
Fig. 2 is the Raman spectrogram of titanium dioxide/graphene quantum dot composite material prepared by the present invention.
Fig. 3 is the ultraviolet spectrogram of titanium dioxide/graphene quantum dot composite material prepared by the present invention.
Fig. 4 is the photocatalysis figure of functionalization graphene quantum dot/composite titania material prepared by the present invention.
Specific embodiment
Below by specific example to the preparation of polyphenylene sulfide prepared by the present invention/graphene quantum dot composite material, property
Energy etc. is described further.
Embodiment 1
(1) preparation of flower-shaped titanium dioxide: 0.5mL isopropyl titanate (IV) is slowly dropped into the dense HCl of 6mL, and is stirred at room temperature
Mix 1 h.Then be added slowly with stirring 15mL PVP(6mg/mL) aqueous solution, stirring 2 hours after, by 45mL ethylene glycol with
Above-mentioned solution is mixed and stirred for 2 hours.Mixture is placed in the stainless steel autoclave of 100mL teflon lined, in drum
12h is kept at 160 DEG C in wind drying box, after being cooled to room temperature.By the solution filtering after reaction, with distilled water and ethanol washing
For several times, dry 12h at 60 DEG C；Obtained yellow powder is put into porcelain boat, is placed in vacuum tube furnace, then in air gas
It anneals 2 hours under atmosphere in 550 DEG C, to remove PVP residue, product is flower-shaped TiO2(FT)；
(2) preparation of N doped graphene quantum dot: 2.1g citric acid and 2.4g urea are mixed, and grind 20min, will be ground
Powder be added in round-bottomed flask, heated at 180 DEG C, powder melts during heating and slowly turned yellow by white molten
Liquid, after 30 minutes, acquired solution is cooled to room temperature, and 50mL ultrapure water is added, and ultrasonic 2h is collected for 20 minutes with 13000rpm centrifugation
Dialyzate is finally freeze-dried then with bag filter (3000Da) dialysis 48h, obtains N-GQDs brown ceramic powder by supernatant；
(3) preparation of titanium dioxide/graphene quantum dot: by 0.1g FT and 0.5mg NGQDs ultrasonic disperse in 50mL ultrapure water
In 30 minutes, mixture is placed in the stainless steel autoclave of 100mL Teflon teflon lined, 120 DEG C keep
6h, after being cooled to room temperature, filtering for several times with ultrapure water and ethanol washing is dried overnight at 60 DEG C, obtains FT/N-GQDs.
Sample is labeled as FT-NGQDs-0.5.
The composite material promotes the degradation property comparison pure titinium dioxide of organic pollutant, pure as can see from Figure 4
Titanium dioxide degradable rate is 60%, and composite material comparison pure material performance about promotes 25%~40%, and best doping is small one
When degradation time under, can whole degradable organic pollutants.
Embodiment 2
(1) preparation of flower-shaped titanium dioxide: with embodiment 1；
(2) preparation of N doped graphene quantum dot: with embodiment 1；
(3) preparation of titanium dioxide/graphene quantum dot: by 0.1g FT and 1mg NGQDs ultrasonic disperse in 50mL ultrapure water
30 minutes, mixture is placed in the stainless steel autoclave of 100mL Teflon lining, autoclave is then by polytetrafluoroethylene (PTFE)
The stainless steel autoclave of lining is in 120 DEG C of holding 6h, after being cooled to room temperature, filtering, for several times with ultrapure water and ethanol washing,
It is dried overnight at 60 DEG C, obtains FT/N-GQDs.Sample is labeled as FT-NGQDs-1.
The composite material has promotion to the degradation property comparison FT-NGQDs-0.5 of organic pollutant, promotes about 5%.
Embodiment 3
(1) preparation of flower-shaped titanium dioxide: with embodiment 1；
(2) preparation of N doped graphene quantum dot: with embodiment 1；
(3) preparation of titanium dioxide/graphene quantum dot: by 0.1g FT and 3mg NGQDs ultrasonic disperse in 50mL ultrapure water
30 minutes, mixture is placed in the stainless steel autoclave of 100mL Teflon lining, autoclave is then by polytetrafluoroethylene (PTFE)
The stainless steel autoclave of lining is in 120 DEG C of holding 6h, after being cooled to room temperature, filtering, for several times with ultrapure water and ethanol washing,
It is dried overnight at 60 DEG C, obtains FT/N-GQDs.Sample is labeled as FT-NGQDs-3.
The composite material has promotion to the degradation property comparison FT-NGQDs-1 of organic pollutant, promotes degradation capability 10%.
Embodiment 4
(1) preparation of flower-shaped titanium dioxide: with embodiment 1；
(2) preparation of N doped graphene quantum dot: with embodiment 1；
(3) preparation of titanium dioxide/graphene quantum dot: by 0.1g FT and 5mg NGQDs ultrasonic disperse in 50mL ultrapure water
30 minutes, mixture is placed in the stainless steel autoclave of 100mL Teflon teflon lined, in 120 DEG C of holding 6h,
After being cooled to room temperature, filtering for several times with ultrapure water and ethanol washing is dried overnight at 60 DEG C, obtains FT/N-GQDs.Sample
Labeled as FT-NGQDs-5
The composite material has reduction to the degradation property comparison FT-NGQDs-3 of organic pollutant, about reduces by 10%；But this is compound
Material promotes the degradation property comparison pure titinium dioxide of organic pollutant, about promotes 30%.
Claims (7)
1. a kind of preparation method of functionalization graphene quantum dot/composite titania material, comprises the following steps that:
(1) preparation of flower-shaped titanium dioxide: using polyvinylpyrrolidone as dispersing agent, under acidic environment, by titanium tetraisopropylate
(IV) it is scattered in ethylene glycol, is sufficiently stirred, obtain titanium solution；Titanium solution is placed in stainless steel autoclave, at 160 ~ 165 DEG C
12 ~ 13h of lower reaction；After being cooled to room temperature, filtering, product distilled water and ethanol washing for several times, dry 12 at 60 ~ 65 DEG C ~
12.5 h, obtained yellow powder titanium dioxide；Then yellow powder titanium dioxide is placed in vacuum tube furnace, in sky
Under gas atmosphere, anneal 1.5 ~ 2 h at 550 ~ 600 DEG C, obtains the flower-shaped titanium dioxide of white；
(2) after 20 ~ 25min of citric acid and urea mixed grinding, 175 ~ 180 the preparation of N doped graphene quantum dot: are heated to
DEG C, mixed-powder melts and slowly turns yellow solution by white；Ultrapure water ultrasound 1.5 ~ 2 is added after solution is cooled to room temperature
H is then centrifuged for, and collects supernatant, finally by supernatant bag filter 40 ~ 48 h of dialysis, is dialysed freeze-dried, is obtained brown
Powdered N doped graphene quantum dot；
(3) preparation of titanium dioxide/graphene quantum dot composite material: the flower-shaped titanium dioxide of white and N doped graphene quantum
Point ultrasonic disperse is subsequently placed in autoclave in ultrapure water, in 115 ~ 120 DEG C of 5.5 ~ 6 h of holding, after being cooled to room temperature, and mistake
Filter, it is for several times with ultrapure water and ethanol washing, dry, titanium dioxide/graphene quantum dot composite material is obtained, FT/N- is labeled as
GQDs。
2. a kind of preparation method of functionalization graphene quantum dot/composite titania material as described in claim 1, feature
Be: in step (1), polyethylene of dispersing agent pyrrolidones is added with 5 ~ 6mg of concentration/mL aqueous solution；Polyvinylpyrrolidone
The volume ratio of aqueous solution and titanium tetraisopropylate is 1:30 ~ 1:35.
3. a kind of preparation method of functionalization graphene quantum dot/composite titania material as described in claim 1, feature
Be: in step (2), the mass ratio of citric acid and urea is 1:1 ~ 1:1.2.
4. a kind of preparation method of functionalization graphene quantum dot/composite titania material as described in claim 1, feature
Be: in step (2), centrifugal speed is 12000 ~ 13000 rpm.
5. a kind of preparation method of functionalization graphene quantum dot/composite titania material as described in claim 1, feature
Be: in step (2), bag filter uses the bag filter of 3000 ~ 8000Da.
6. a kind of preparation method of functionalization graphene quantum dot/composite titania material as described in claim 1, feature
Be: in step (3), the mass ratio of the flower-shaped titanium dioxide of white and N doped graphene quantum dot is 1:5 ~ 1:50.
7. a kind of preparation method of functionalization graphene quantum dot/composite titania material as described in claim 1, feature
Be: the mass ratio of hydrogenation grey titania powder and N doped graphene quantum dot is 1:5 ~ 1:50.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110624532A (en) * | 2019-09-19 | 2019-12-31 | 华南理工大学 | TiO 22-BiVO4-graphene ternary composite photocatalytic material and preparation method thereof |
| CN110801857A (en) * | 2019-12-02 | 2020-02-18 | 山东建筑大学 | Method for preparing titanium dioxide-nitrogen doped graphene composite photocatalytic material |
| CN111097481A (en) * | 2019-12-30 | 2020-05-05 | 山东泰和水处理科技股份有限公司 | Preparation method of titanium and nitrogen-containing doped graphene quantum dot molecular sieve |
| CN111945138A (en) * | 2020-08-17 | 2020-11-17 | 南京信息工程大学 | Graphene quantum dot-based functionalized titanium dioxide/chlorella nanocomposite and preparation method and application thereof |
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| CN114031112A (en) * | 2021-09-15 | 2022-02-11 | 中国科学技术大学 | Titanium oxide photo-thermal material, preparation method thereof and application thereof in photo-thermal tumor treatment under second biological infrared window |
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