CN110465280A - A kind of graphene-titanic oxide nanorod array composite material and preparation method and application - Google Patents
A kind of graphene-titanic oxide nanorod array composite material and preparation method and application Download PDFInfo
- Publication number
- CN110465280A CN110465280A CN201910858440.3A CN201910858440A CN110465280A CN 110465280 A CN110465280 A CN 110465280A CN 201910858440 A CN201910858440 A CN 201910858440A CN 110465280 A CN110465280 A CN 110465280A
- Authority
- CN
- China
- Prior art keywords
- graphene
- titanic oxide
- oxide nanorod
- composite material
- nanorod array
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002073 nanorod Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 81
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 73
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- 238000005507 spraying Methods 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 21
- 229910052719 titanium Inorganic materials 0.000 claims description 21
- 238000007747 plating Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- -1 graphite Alkene Chemical class 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 229910003087 TiOx Inorganic materials 0.000 claims description 2
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003595 mist Substances 0.000 claims 1
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 abstract description 26
- 229960003405 ciprofloxacin Drugs 0.000 abstract description 13
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000011941 photocatalyst Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 37
- 239000011521 glass Substances 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 230000005355 Hall effect Effects 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010409 thin film Substances 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/39—
Abstract
The invention belongs to photocatalyst technology fields, and in particular to a kind of graphene-titanic oxide nanorod array composite material and preparation method and application.The present invention provides a kind of graphene-titanic oxide nanorod array composite materials, including graphene layer and titanic oxide nanorod array layer, the graphene layer is attached to the single side of titanic oxide nanorod array layer, and the mass ratio of graphene and titanium dioxide is 1:1.5~3.Embodiment the result shows that, graphene provided by the invention-titanic oxide nanorod array composite material for Ciprofloxacin degrade when, degradation rate reaches 85% or more.
Description
Technical field
The invention belongs to photocatalyst technology fields, and in particular to a kind of graphene-titanic oxide nanorod array is compound
Material and its preparation method and application.
Background technique
Graphene is a kind of novel two dimensional crystal carbon material, graphene elasticity modulus with higher, high electron mobility
Rate, high thermal conductivity coefficient, low-resistivity, big specific surface area, excellent translucency and integer quantum Hall effect of exception etc..
Titanium dioxide (TiO2) it is a kind of semiconductor material, possess preferable photoelectric conversion capacity, in photovoltaic solar electricity
The fields such as pond, light-catalyzed reaction have a wide range of applications, but its there are light induced electron and the recombination probabilities in hole high, electron transfer
The disadvantages such as free path is low, so researchers are in recent years to TiO2Photochemical catalyst has carried out extensive study on the modification.Utilize graphite
Alkene titanium dioxide is modified be Recent study hot spot, such as Chinese patent 201510354461.3 discloses titanium dioxide
Titanium/graphene nanocomposite material, but the material as photochemical catalyst in use, its catalytic performance is unsatisfactory.
Summary of the invention
The purpose of the present invention is to provide a kind of graphene-titanic oxide nanorod array composite material, the present invention is provided
Composite material have excellent photocatalysis performance.
To achieve the goals above, the invention provides the following technical scheme:
The present invention provides a kind of graphene-titanic oxide nanorod array composite materials, including graphene layer and dioxy
Change titanium nanometer stick array layer, the graphene layer is attached to the single side of titanic oxide nanorod array layer, graphene and titanium dioxide
The mass ratio of titanium is 1:1.5~3.
Preferably, the graphene layer with a thickness of 15~40 μm.
Preferably, in the titanic oxide nanorod array layer, the diameter of titanium dioxide nano-rod is 10~20nm, length
For 100~150nm.
Preferably, the graphene-titanic oxide nanorod array composite material is with a thickness of 20~36 μm.
The present invention provides the preparations of the graphene described in above-mentioned technical proposal-titanic oxide nanorod array composite material
Method, comprising the following steps:
Substrate is mixed with organic titanium source solution, hydrothermal synthesis and heat treatment is carried out, obtains carried titanium dioxide nanometer rods
The substrate of array；
Using the substrate of carried titanium dioxide nanometer stick array as receiving body, surpass on the whole in titanic oxide nanorod array
Sound is atomized spraying plating graphene dispersing solution, obtains graphene-titanic oxide nanorod array composite material after cooling.
Preferably, the temperature of the hydrothermal synthesis is 150~180 DEG C, and the time is 3~5h.
Preferably, the temperature of the heat treatment is 400~500 DEG C, and the time is 60~90min.
Preferably, the graphene dispersing solution the preparation method comprises the following steps: graphene and acetone are mixed, ultrasound is carried out after stirring
Dispersion, obtains graphene dispersing solution.
Preferably, when carrying out the ultrasonic atomizatio spraying plating, for receive graphene dispersing solution underlayer temperature be 300~
400℃；
Spray head is 40~50mm at a distance from substrate；
The spouting velocity of graphene dispersing solution is 10~18 μ L/s.
The present invention provides the graphene described in above-mentioned technical proposal-titanic oxide nanorod array composite materials or above-mentioned
The graphene that preparation method described in technical solution is prepared-titanic oxide nanorod array composite material is as photochemical catalyst
Using.
The present invention provides a kind of graphene-titanic oxide nanorod array composite materials, including graphene layer and dioxy
Change titanium nanometer stick array layer, the graphene layer is attached to the single side of titanic oxide nanorod array layer, graphene and titanium dioxide
The mass ratio of titanium is 1:1.5~3.The present invention is using titanic oxide nanorod array layer as carrier, by adhering to graphite on carrier
Alkene layer improves the electron mobility of titanium dioxide and the photoelectric conversion capacity of titanium dioxide, and then the light for improving composite material is urged
Change performance.Embodiment the result shows that, graphene provided by the invention-titanic oxide nanorod array composite material is husky for cyclopropyl
When star is degraded, degradation rate reaches 85% or more.
Specific embodiment
The present invention provides a kind of graphene-titanic oxide nanorod array composite materials, including graphene layer and dioxy
Change titanium nanometer stick array layer, the graphene layer is attached to the single side of titanic oxide nanorod array layer, graphene and titanium dioxide
The mass ratio of titanium is 1:1.5~3.
Graphene provided by the invention-titanic oxide nanorod array composite material includes graphene layer, the graphene
The thickness of layer is preferably 15~40 μm, and more preferably 18~39 μm, be further preferably 20~36 μm.
Graphene provided by the invention-titanic oxide nanorod array composite material includes titanic oxide nanorod array
Layer, wherein titanium dioxide is rutile titanium dioxide.In the present invention, the thickness of the titanic oxide nanorod array layer is excellent
It is selected as 100~120nm, more preferably 120~130nm, is further preferably 130~150nm；The wherein diameter of titanium dioxide nano-rod
Preferably 10~15nm, more preferably 15~20nm；Length is preferably 100~130nm, more preferably 130~150nm.
In graphene of the present invention-titanic oxide nanorod array composite material, graphene described in above-mentioned technical proposal
Layer is attached to the single side of titanic oxide nanorod array layer, can improve the electron mobility of titanium dioxide and the light of titanium dioxide
Electric transfer capability, and then improve the photocatalysis performance of composite material.
In the present invention, the graphene-titanic oxide nanorod array composite material thickness is preferably 20~36 μm,
More preferably 20~25 μm.
The present invention provides the preparations of the graphene described in above-mentioned technical proposal-titanic oxide nanorod array composite material
Method, comprising the following steps:
Substrate is mixed with organic titanium source solution, hydrothermal synthesis and heat treatment is carried out, obtains carried titanium dioxide nanometer rods
The substrate of array；
Using the substrate of carried titanium dioxide nanometer stick array as receiving body, surpass on the whole in titanic oxide nanorod array
Sound is atomized spraying plating graphene dispersing solution, obtains graphene-titanic oxide nanorod array composite material after cooling.
The present invention mixes substrate with organic titanium source solution, carries out hydrothermal synthesis and heat treatment, obtains carried titanium dioxide
The substrate of nanometer stick array.In the present invention, the substrate preferably includes electro-conductive glass (FTO) or titanium plate, the thickness of the substrate
Degree and size are using well known to those skilled in the art.Before mixing, the present invention preferably pre-processes substrate, described pre-
The mode of processing preferably includes to be immersed in substrate in mixing washing lotion, is cleaned by ultrasonic, is then dried for standby.
In the present invention, the mixing washing lotion preferably includes ethyl alcohol, acetone and water, the quality of the ethyl alcohol, acetone and water
Than being preferably 0.8~1.2:0.8~1.2:2, more preferably 1:1:2；The purity of the ethyl alcohol is preferably 99.5wt%, and described third
The purity of ketone is preferably 99.5wt%；The mixing washing lotion preferably mixes ethyl alcohol, acetone and water, obtains after stirring；It is described to stir
The speed mixed is preferably 100~200r/min, more preferably 150r/min；Mixing time is preferably 10~20min, more preferably
15min。
In the present invention, when carrying out the ultrasonic cleaning, preferably ultrasonic power is controlled in 200~400W, more preferably
250~350W is further preferably 300W.
In the present invention, the temperature of the drying is preferably 100~105 DEG C, and more preferably 105 DEG C, the time is preferably 30
~60min, more preferably 35~50min.
In the specific embodiment of the invention, unless otherwise specified, the stirring, ultrasound and drying are referred both in above-mentioned condition
Lower progress.
In the present invention, the organic titanium source solution preferably includes organic titanium source and dilute hydrochloric acid, and the organic titanium source is preferred
For butyl titanate, purity is preferably 99.5%；The concentration of the dilute hydrochloric acid is preferably 0.4~0.6mol/L, more preferably
0.5mol/L.In the present invention, in the organic titanium source solution, the volume ratio of organic titanium source and dilute hydrochloric acid be preferably 1:30~
60, more preferably 1:35~55.
In specific implementation process of the present invention, the organic titanium source solution is preferably prepared via a method which to obtain: stirring
Under the conditions of mixing, butyl titanate is added in dilute hydrochloric acid, then proceedes to stir.In the present invention, the addition of the organic titanium source
Rate is preferably 8~10mL/min, more preferably 5~8mL/min.
In the present invention, the temperature of the hydrothermal synthesis is preferably 150~180 DEG C, and more preferably 155~175 DEG C, then it is excellent
It is selected as 160~170 DEG C；The time of hydrothermal synthesis is preferably 3~5h, more preferably 3.5~4.5h, is further preferably 4h.The present invention
The hydrothermal synthesis carries out preferably in water heating kettle.In specific operation process, the present invention is that first substrate is placed in water heating kettle,
Then organic titanium source solution is added.When the substrate is electro-conductive glass, when placement, preferably by the conducting surface direction of electro-conductive glass
Lower section.
In the present invention, the temperature of the heat treatment is preferably 400~500 DEG C, and more preferably 410~490 DEG C, further preferably
It is 415~485 DEG C；The time of heat treatment is preferably 60~90min, more preferably 65~85min, is further preferably 70~80min.
The present invention carries out the heat treatment preferably in Muffle furnace, specifically carries out in air atmosphere.When carrying out the heat treatment,
It is preferred that temperature needed for temperature is warming up to heat treatment by the rate of 1~3 DEG C/min, more preferably 1.5~2.5 DEG C/min.
The present invention makes titanium ion be combined with oxonium ion generation titanium dioxide by hydrothermal synthesis, then by heat treatment, titanium dioxide is allowed to send out
Raw crystal transfer, generates rutile titanium dioxide, obtains the substrate of required carried titanium dioxide nanometer stick array.
After heat treatment, the substrate after heat treatment is preferably successively cooled down, washed and dried by the present invention, next to carry out
Step processing.In the present invention, the cooling is preferably furnace cooling, and cooling outlet temperature is preferably room temperature；The washing is used
Detergent is preferably distilled water；Washing times are preferably 3~6, and more preferably 4~5；The mode of the drying is preferably dried.
After obtaining the substrate of carried titanium dioxide nanometer stick array, the present invention is with the lining of carried titanium dioxide nanometer stick array
Bottom is receiving body, in titanic oxide nanorod array institute ultrasonic atomizatio spraying plating graphene dispersing solution on the whole, obtains stone after cooling
Black alkene-titanic oxide nanorod array composite material.In the present invention, the graphene dispersing solution preferably includes graphene and third
Ketone, the concentration of the graphene are preferably 5~10mg/L, more preferably 6~9mg/L, are further preferably 7~8mg/L.In the present invention
In, the purity of the graphene is preferably 99.9%, and carbon-coating number is preferably 1~6 in graphene；The purity of the acetone is preferably
99.5%.
In the present invention, the preparation method of the graphene dispersing solution preferably includes: graphene and acetone being mixed, stirring
After carry out ultrasonic disperse, obtain graphene dispersing solution.In the present invention, the parameter and above-mentioned technology of the stirring and ultrasonic disperse
Stirring used in substrate cleaning treatment process described in scheme is consistent with the parameter selection range of ultrasonic cleaning, no longer heavy herein
It is multiple.The present invention keeps graphene evenly dispersed in acetone, prepares uniform graphite to subsequent using stirring and ultrasonic disperse
Alkene layer is advantageous.
Ultrasonic atomizatio spraying plating of the present invention refers to that treating plating liquid using ultrasonic wave is atomized, after forming droplet, then into
The process of row spraying plating.Relative to traditional spraying plating, ultrasonic atomizatio spraying plating can improve the uniformity of deposited metal.In the present invention, into
When the row ultrasonic atomizatio spraying plating, the underlayer temperature for receiving graphene dispersing solution is preferably 300~400 DEG C, more preferably
310~390 DEG C, be further preferably 315~385 DEG C；
Spray head is preferably 40~50mm at a distance from substrate, more preferably 42~48mm, is further preferably 43~47mm；It is described
Distance refers to the vertical range of spray head and upper surface of substrate (face where titanic oxide nanorod array)；
The spouting velocity of graphene dispersing solution is preferably 10~18 μ L/s, more preferably 11~17 μ L/s, is further preferably 12
~16 μ L/s.
Before spraying plating, the present invention preferably carries out ultrasonic atomizatio to graphene dispersing solution, and the frequency when ultrasonic atomizatio is preferred
It is further preferably 30000Hz for 20000~35000Hz, more preferably 25000~35000Hz.
When spraying plating, the movement speed of the spray head is preferably 20~25mm/s, more preferably 20mm/s.
In the present invention, by graphene spraying plating to substrate, covering film-forming region is considered as 1 spraying plating, time of the spraying plating
Number preferably 5~10 times, more preferably 6~9 times.The time interval of adjacent spraying plating twice is preferably 50~70s, and more preferably 52
~65s is further preferably 60s.
After spraying plating, the substrate after spraying plating is preferably carried out natural cooling by the present invention, obtains graphene-titanium dioxide nano-rod
Array composite material.
The present invention also provides the graphene described in above-mentioned technical proposal-titanic oxide nanorod array composite material or on
Graphene-titanic oxide nanorod array composite material that preparation method described in technical solution is prepared is stated as photochemical catalyst
Application.In the present invention, the application is preferably included in the application in degradation Ciprofloxacin.In the present invention, by graphene-
Titanic oxide nanorod array composite material (referring to the thin-film material and substrate of attachment on substrate, hereinafter referred to as catalyst) is used
In degrade Ciprofloxacin when, be preferably carried out as follows degradation:
Under the conditions of being protected from light, catalyst and ciprofloxacin solution are mixed, adsorbed, then illumination.
In the present invention, the concentration of the ciprofloxacin solution is preferably 1~2mg/L, more preferably 1.5mg/L；It is described
Ciprofloxacin solution liquid level preferred distance 20~30mm of catalyst surface, more preferably 25~30mm；The catalyst surface refers to
Upper surface of substrate.The present invention does not have particular/special requirement to the hybrid mode of the catalyst and ciprofloxacin solution, using this field
Mode known to technical staff.
In the present invention, the absorption preferably carries out under agitation, and the time of the absorption is preferably 30~
50min, more preferably 30~40min.
In the present invention, when carrying out the illumination, optical power density is preferably 100~120mW/cm2, wave-length coverage is preferred
For 400~800nm, light application time is preferably 120~200min, more preferably 130~180min, most preferably 150min；Institute
The light source for stating illumination is preferably LED light.
In order to further illustrate the present invention, below with reference to embodiment to a kind of graphene-titanium dioxide provided by the invention
Nanometer stick array composite material and preparation method and application are described in detail, but they cannot be interpreted as to the present invention
The restriction of protection scope.
In following embodiment, the purity of acetone used is 99.9%, and the purity of graphene is 99.9%, carbon layers having thicknesses 1
~6 layers, the purity of ethyl alcohol is 99.5%, and the concentration of concentrated hydrochloric acid is 1mol/L, and butyl titanate purity is 99.5%, is stirred as magnetic force
Stirring, revolving speed 150r/min, ultrasonic disperse power are 300W, and electro-conductive glass is FTO electro-conductive glass, ultrasonic atomizatio coating apparatus
For the MSK-USP-04C type ultrasonic atomizatio plated film instrument of Shenyang Kejing Automatic Equipment Co., Ltd's production.
Embodiment 1
1, the preparation of graphene solution
Using acetone as solvent, compound concentration is the graphene solution of 5mg/L, stirs 30min, rear ultrasonic disperse 60min.
2, the pretreatment of electro-conductive glass
By ethyl alcohol: acetone: water quality ratio is that 1:1:2 prepares mixed solution, stirs 10min.Electro-conductive glass is dipped into mixed
Close solution in, be cleaned by ultrasonic 15min, after be dried for standby.
3, the preparation of butyl titanate solution
Water and concentrated hydrochloric acid mixed solution are prepared for 1:1 by volume, after stirring 5min, is added while stirring into mixed solution
Enter butyl titanate, the additional amount of butyl titanate is the 1/30 of water and concentrated hydrochloric acid mixed liquor volume, is then stirred for 10min.
4, the preparation of carried titanium dioxide nanometer stick array electro-conductive glass
The electro-conductive glass that will have been pre-processed in step 2, conduction is put into inner liner of reaction kettle wall down, then by step
Prepared butyl titanate solution is transferred in reaction kettle in 3, sealing.3h is reacted under conditions of 150 DEG C.Naturally cool to room
Wen Hou takes out after drying 30min at 3 times wash with distilled water, 105 DEG C after electro-conductive glass, is placed in Muffle furnace, air atmosphere
Under, 450 DEG C are warming up to according to the rate of 2 DEG C/min, heat preservation 60min is heat-treated, and is cooled to room temperature with the furnace, is obtained load two
The electro-conductive glass of TiOx nano stick array.
5, graphene-titanic oxide nanorod array composite material preparation
Step 4 gained carried titanium dioxide nanometer stick array electro-conductive glass is placed on to the platform of ultrasonic atomizatio coating apparatus
On, setting platform heating temperature is 300 DEG C, and spray head is set as 40mm at a distance from electro-conductive glass (upper surface of electro-conductive glass),
Graphene solution spouting velocity is 10 μ L/s, and X-axis, Y-axis movement speed are set as 20mm/s.The internal spraying number 6 times in film-forming region,
Each spray intervals 1min after natural cooling, obtains graphene-titanic oxide nanorod array composite material.
Embodiment 2
Graphene-titanic oxide nanorod array composite material is prepared in the way of embodiment 1, the difference is that:
In step 1, compound concentration is the graphene solution of 8mg/L, stirs 45min, rear ultrasonic disperse 90min；
In step 2, when preparing mixed solution, 10min is stirred, is cleaned by ultrasonic 30min；
In step 3, water and concentrated hydrochloric acid mixed solution are prepared, stirs 8min, the additional amount of butyl titanate is water and concentrated hydrochloric acid
The 1/45 of mixed liquor volume；
In step 4, the material in reaction kettle reacts 4h under conditions of 165 DEG C；After cooled to room temperature, take out conductive
5 times wash with distilled water after glass, 75min is heat-treated at 450 DEG C after drying；
In step 5, setting platform heating temperature is 350 DEG C, and spray head is 45mm away from electro-conductive glass distance from top, and graphene is molten
Liquid spouting velocity is 14 μ L/s, the internal spraying number 8 times in film-forming region.
Embodiment 3
Graphene-titanic oxide nanorod array composite material is prepared in the way of embodiment 1, the difference is that:
In step 1, compound concentration is the graphene solution of 10mg/L, stirs 60min, rear ultrasonic disperse 120min；
In step 2, mixed solution is prepared, stirs 20min；Electro-conductive glass is dipped into mixed solution, is cleaned by ultrasonic
30min；
In step 3,10min is stirred when preparing mixed solution, the additional amount of butyl titanate is the 1/60 of mixed liquor volume；
In step 4, the material in reaction kettle reacts 5h under conditions of 180 DEG C；It is clear with distilled water after taking-up electro-conductive glass
It washes 6 times, is heat-treated 90min at 450 DEG C after drying；
In step 5, the platform heating temperature of setting ultrasonic atomizatio coating apparatus is 300 DEG C, and spray head is away from the top of electro-conductive glass
Distance is 50mm, and graphene solution spouting velocity is 18 μ L/s, and X-axis, Y-axis movement speed are 20mm/s.In film-forming region
Spray timings 10 times.
Application examples 1
Ciprofloxacin solution (concentration 15mg/L) and 1 gained graphene of embodiment-titanic oxide nanorod array is multiple
Condensation material (catalyst) mixing, concrete mode are as follows: the distance controlling by catalyst surface and ciprofloxacin solution liquid level is 25mm,
30min is stirred at dark, and Ciprofloxacin molecule is made to reach suction on graphene-titanic oxide nanorod array composite material surface
Attached-desorption equilibrium, then illumination (uses LED white light, optical power density: 100mW/cm2, long range is 400~800nm), into
Row photocatalyst for degrading, the back zone 150min sampling, absorbance is measured at its maximum absorption wavelength 276nm, degradation is calculated
Rate, calculation formula are as follows:
In formula 1, D indicates degradation rate (%), A0Expression concentration is 15mgL-1The absorbance of Ciprofloxacin, AtFor warp
Absorbance after 150min photocatalytic degradation.
Application examples 2~3
In the way of application examples 1, the gained of testing example 2 and 3 graphene-titanic oxide nanorod array composite material
Photocatalytic Degradation Property.
Characterization of structure and properties result
Graphene-dioxy obtained by Dektak150 type step instrument measurement Examples 1 to 3 using the production of Veeco company, the U.S.
Change the thickness of titanium nanometer stick array composite material, each sample is surveyed 5 times, and measurement result is averaged, and is considered as graphene-titanium dioxide
Titanium nanometer stick array thickness of composite material；Test result is shown in Table 1.
The Lambda750 type ultraviolet-visible-infrared spectrophotometer produced using Perkins Elmer company, the U.S., with
Blank electro-conductive glass is reference, and the light transmittance at wavelength X=550nm is compound as graphene-titanic oxide nanorod array
The light transmittance of material；Test result is shown in Table 1.
In application examples 1~5, the experimental provision of photocatalysis performance is the production of Beijing Bo Feilai Science and Technology Ltd.
Labsolar-IIIAGA type photocatalytic activity evaluation system, absorbance is using the production of U.S. Perkins Elmer company
Lambda750 type ultraviolet-visible-infrared spectrophotometer measurement；Test result is shown in Table 2.
Graphene-titanic oxide nanorod array composite material characterization result obtained by 1 Examples 1 to 3 of table
As shown in Table 1, the good graphene-titanium dioxide nano-rod of translucency can be prepared in method provided by the invention
Array composite material.
2 application examples of table, 1~3 degradation rate test result
| Application examples | 1 | 2 | 3 |
| Degradation rate (%) | 88 | 90 | 85 |
As shown in Table 2, graphene provided by the invention-titanic oxide nanorod array composite material has Ciprofloxacin
Excellent degradation property.
As seen from the above embodiment, the present invention provides graphene-titanic oxide nanorod array composite material with excellent
Degradation property, light transmission and photocatalysis performance, be suitable for degradation Ciprofloxacin reagent use.
Preparation method provided by the invention, simply, easily controllable, favorable repeatability.
Although above-described embodiment is made that detailed description to the present invention, it is only a part of the embodiment of the present invention,
Rather than whole embodiments, people can also obtain other embodiments under the premise of without creativeness according to the present embodiment, these
Embodiment belongs to the scope of the present invention.
Claims (10)
1. a kind of graphene-titanic oxide nanorod array composite material, which is characterized in that including graphene layer and titanium dioxide
Nanometer stick array layer, the graphene layer are attached to the single side of titanic oxide nanorod array layer, graphene and titanium dioxide
Mass ratio is 1:1.5~3.
2. graphene as described in claim 1-titanic oxide nanorod array composite material, which is characterized in that the graphite
Alkene layer with a thickness of 15~40 μm.
3. graphene as claimed in claim 1 or 2-titanic oxide nanorod array composite material, which is characterized in that described two
In TiOx nano stick array layer, the diameter of titanium dioxide nano-rod is 10~20nm, and length is 100~150nm.
4. graphene as claimed in claim 1 or 2-titanic oxide nanorod array composite material, which is characterized in that the stone
Black alkene-titanic oxide nanorod array composite material is with a thickness of 20~36 μm.
5. the described in any item graphenes of Claims 1 to 4-titanic oxide nanorod array composite material preparation method, packet
Include following steps:
Substrate is mixed with organic titanium source solution, hydrothermal synthesis and heat treatment is carried out, obtains carried titanium dioxide nanometer stick array
Substrate；
Using the substrate of carried titanium dioxide nanometer stick array as receiving body, in titanic oxide nanorod array institute ultrasonic mist on the whole
Change spraying plating graphene dispersing solution, obtains graphene-titanic oxide nanorod array composite material after cooling.
6. preparation method as claimed in claim 5, which is characterized in that the temperature of the hydrothermal synthesis is 150~180 DEG C, when
Between be 3~5h.
7. such as preparation method described in claim 5 or 6, which is characterized in that the temperature of the heat treatment is 400~500 DEG C, when
Between be 60~90min.
8. preparation method as claimed in claim 5, which is characterized in that the graphene dispersing solution the preparation method comprises the following steps: by stone
Black alkene and acetone mixing, carry out ultrasonic disperse after stirring, obtain graphene dispersing solution.
9. the preparation method as described in claim 5 or 8, which is characterized in that when carrying out the ultrasonic atomizatio spraying plating, for receiving
The underlayer temperature of graphene dispersing solution is 300~400 DEG C；
Spray head is 40~50mm at a distance from substrate；
The spouting velocity of graphene dispersing solution is 10~18 μ L/s.
10. the described in any item graphenes of Claims 1 to 4-titanic oxide nanorod array composite material or claim 5~
Graphene-titanic oxide nanorod array composite material that any one of 9 preparation methods are prepared is as photochemical catalyst
Using.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910858440.3A CN110465280A (en) | 2019-09-11 | 2019-09-11 | A kind of graphene-titanic oxide nanorod array composite material and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910858440.3A CN110465280A (en) | 2019-09-11 | 2019-09-11 | A kind of graphene-titanic oxide nanorod array composite material and preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110465280A true CN110465280A (en) | 2019-11-19 |
Family
ID=68515511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910858440.3A Pending CN110465280A (en) | 2019-09-11 | 2019-09-11 | A kind of graphene-titanic oxide nanorod array composite material and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110465280A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659096A (en) * | 2012-04-27 | 2012-09-12 | 湖南大学 | Preparation methods of graphene dispersion solution and thin film of graphene |
| CN102750998A (en) * | 2012-07-09 | 2012-10-24 | 深圳市贝特瑞纳米科技有限公司 | Transparent graphene conductive thin film and preparation method thereof |
| KR20130044987A (en) * | 2011-10-25 | 2013-05-03 | 울산대학교 산학협력단 | Composition for air purification comprising photocatalysts of graphene oxide-tio2 |
| CN104084186A (en) * | 2014-07-23 | 2014-10-08 | 武汉理工大学 | Graphene/titanium dioxide photocatalysis composite material and preparation method thereof |
| CN105492126A (en) * | 2013-03-14 | 2016-04-13 | 纳米技术仪器公司 | Ultrasonic spray coating of conducting and transparent films from combined graphene and conductive nano filaments |
| CN106317976A (en) * | 2016-09-08 | 2017-01-11 | 上海理工大学 | Preparation method of graphene/titanium dioxide transparent anticorrosive coating |
| CN107159178A (en) * | 2016-12-19 | 2017-09-15 | 广东工业大学 | A kind of TiO of graphene modified2The preparation method of membranaceous compound and its application in photocatalysis degradation organic contaminant |
| CN109318564A (en) * | 2018-09-10 | 2019-02-12 | 成都紫苑华光新材料科技有限公司 | A kind of method that the spraying of self assembly ultrasound prepares graphene heat conducting film |
-
2019
- 2019-09-11 CN CN201910858440.3A patent/CN110465280A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130044987A (en) * | 2011-10-25 | 2013-05-03 | 울산대학교 산학협력단 | Composition for air purification comprising photocatalysts of graphene oxide-tio2 |
| CN102659096A (en) * | 2012-04-27 | 2012-09-12 | 湖南大学 | Preparation methods of graphene dispersion solution and thin film of graphene |
| CN102750998A (en) * | 2012-07-09 | 2012-10-24 | 深圳市贝特瑞纳米科技有限公司 | Transparent graphene conductive thin film and preparation method thereof |
| CN105492126A (en) * | 2013-03-14 | 2016-04-13 | 纳米技术仪器公司 | Ultrasonic spray coating of conducting and transparent films from combined graphene and conductive nano filaments |
| CN104084186A (en) * | 2014-07-23 | 2014-10-08 | 武汉理工大学 | Graphene/titanium dioxide photocatalysis composite material and preparation method thereof |
| CN106317976A (en) * | 2016-09-08 | 2017-01-11 | 上海理工大学 | Preparation method of graphene/titanium dioxide transparent anticorrosive coating |
| CN107159178A (en) * | 2016-12-19 | 2017-09-15 | 广东工业大学 | A kind of TiO of graphene modified2The preparation method of membranaceous compound and its application in photocatalysis degradation organic contaminant |
| CN109318564A (en) * | 2018-09-10 | 2019-02-12 | 成都紫苑华光新材料科技有限公司 | A kind of method that the spraying of self assembly ultrasound prepares graphene heat conducting film |
Non-Patent Citations (2)
| Title |
|---|
| 冯良桓等: "《中国太阳能光伏进展》", 31 October 2006, 西南交通大学出版社 * |
| 王月花等: "《薄膜的设计、制备及应用》", 30 September 2016, 中国矿业大学出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Amiri et al. | Bi 2 WO 6/Ag 3 PO 4–Ag Z-scheme heterojunction as a new plasmonic visible-light-driven photocatalyst: performance evaluation and mechanism study | |
| CN112169819A (en) | g-C3N4 (101)-(001)-TiO2Preparation method and application of composite material | |
| CN105502503B (en) | A kind of hexagonal crystal tungsten bronze nanometer stub particle and preparation method thereof | |
| Cheng et al. | Green synthesis of plasmonic Ag nanoparticles anchored TiO2 nanorod arrays using cold plasma for visible-light-driven photocatalytic reduction of CO2 | |
| CN106040216B (en) | A kind of bilayer ZnO hollow ball catalysis materials and preparation method thereof | |
| CN105879886B (en) | A kind of preparation method of GO/Sb BiOBr composite photo-catalysts | |
| CN106000474B (en) | A kind of porphyrin/titanium dioxide uniformly organizes the preparation method and applications of nanosphere altogether | |
| CN112007632B (en) | Flower-shaped SnO 2 /g-C 3 N 4 Preparation method of heterojunction photocatalyst | |
| CN108675345A (en) | A kind of titanium dioxide nano hollow ball and preparation method thereof | |
| Shangguan et al. | Physicochemical properties and photocatalytic hydrogen evolution of TiO2 films prepared by sol–gel processes | |
| CN102464499A (en) | Titaniferous composition, method for forming nano particle film on ceramic or glass surface from titaniferous composition and application of titaniferous composition | |
| CN104001494A (en) | Synthetic method of graphite-like modified nano-zinc stannate | |
| CN106674568A (en) | Self-cleaning acrylonitrile butadiene styrene (ABS) sheet with visible-light response and preparation method thereof | |
| CN108640149B (en) | Titanium dioxide nano hollow ball and preparation method thereof | |
| CN109486248A (en) | A kind of preparation method of graphene dopen Nano oxide coating liquid and film | |
| CN102199371A (en) | Method for preparing photoinduced ultra hydrophilic automatically cleaning paint | |
| CN110465280A (en) | A kind of graphene-titanic oxide nanorod array composite material and preparation method and application | |
| CN106622292B (en) | A kind of artificial gold-graphene oxide composite photo-catalyst and preparation method, application | |
| CN103332870B (en) | A kind of preparation method of nano-titanium dioxide film | |
| CN108940325A (en) | A kind of binary composite semiconductor light-catalyst materials A g2CrO4/ BiOI and its preparation and application | |
| CN108525651A (en) | A kind of reduction titanium dioxide process with highlight catalytic active | |
| CN100436644C (en) | Process of preparing single-layer nanometer TiO2 rod film in pure rutile structure | |
| Akhbari et al. | The effects of solvent and ultrasonic irradiation in synthesis of thallium (I) nano supramolecular polymers and use them as template for synthesis of thallium (III) oxide nanostructures with desirable morphology | |
| Miao et al. | Preparation and activity evaluation of the novel Cu/TiO2 nanometer photocatalytic materials | |
| CN107376951B (en) | Sunlight catalytic porous glass and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191119 |