CN107649107A - A kind of quantum dot/TiO2The preparation method and applications of composite - Google Patents
A kind of quantum dot/TiO2The preparation method and applications of composite Download PDFInfo
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- CN107649107A CN107649107A CN201710875824.7A CN201710875824A CN107649107A CN 107649107 A CN107649107 A CN 107649107A CN 201710875824 A CN201710875824 A CN 201710875824A CN 107649107 A CN107649107 A CN 107649107A
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 136
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 3
- 238000000053 physical method Methods 0.000 abstract description 2
- 238000005498 polishing Methods 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 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 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010936 titanium Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 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
- 239000001301 oxygen Substances 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of carbon quantum dot/TiO2Composite and TiO2Quantum dot/TiO2The preparation method and application of composite.Preparation method is as follows：Titanium dioxide is put into mortar, carbon quantum dot or the grinding of titanium dioxide quantum dot is added, that is, obtains carbon quantum dot/TiO2Or TiO2Quantum dot/TiO2Composite.The composite is significantly improved relative to pure titanium dioxide, its photocatalysis performance.This physical method synthetic composite material of the polishing that the present invention uses has obvious advantage than reporting before with chemical method synthetic composite material, and the method is simple, efficiently, is produced on a large scale.
Description
Technical field
The invention belongs to TiO2A kind of technical field of composite materials, and in particular to quantum dot/TiO2The preparation side of composite
Method and its application.
Background technology
Quantum dot is due to some unique properties such as quantum size effect and quantum confined effect, in photocatalysis, solar energy
The field such as battery and biomedicine is with a wide range of applications.Because quantum dot-based composite is than single metal oxide
Outstanding performance can be shown, there are reports for the current composite about quantum dot and metal oxide, but this
A little reports are big to be all based on chemical method synthesis, such as hydrothermal synthesis method, solvent-thermal process etc., and these methods are required for using high temperature height greatly
Pressure, and surfactant etc..But the quantum dot of relevant Physical synthesis and metal oxide composite and formed effective
The report of heterojunction structure almost do not have.
The content of the invention
The technical problems to be solved by the invention be in the prior art the shortcomings that and to provide a kind of preparation process simple
Easily-controllable, easy to operate, time-consuming quantum dot/TiO short, cost is low2The preparation method of composite, prepared quantum dot/
TiO2Composite compares pure TiO2, its photocatalysis performance is significantly improved.
It is a further object of the present invention to provide quantum dot/TiO prepared by above-mentioned preparation method2Composite is as photocatalysis
The application of material.
A kind of quantum dot/TiO2The preparation method of composite, its technique are：By TiO2It is put into mortar, adds quantum
After point material grinding, it is put into baking oven and dries, obtained quantum dot/TiO2Composite.
The quanta point material is C quantum dots or TiO2Quantum dot.
The C quantum dots and TiO2Mass fraction ratio be 0.2-0.8 wt%.
The TiO2Quantum dot and TiO2Mass fraction ratio be 1-4 wt%.
Above-mentioned quantum dot/TiO2The preparation method of composite, specific method are as follows：Weigh TiO2It is put into agate alms bowl,
Add after quanta point material after grinding 2-10 mim, be put into 50-100 DEG C of dry 0.5-2 h in baking oven obtain quantum dot/
TiO2Composite.
Quantum dot/TiO prepared by above-mentioned preparation preparation method2Composite can be as the application of catalysis material.
The inventive method utilizes the skin effect of quantum dot, because quantum dot surface carries many functional groups, these functions
Strong chemical action or Van der Waals force interaction between group and material are particularly conducive to quantum dot and are adsorbed onto material surface, i.e.,
Because coordination deficiency, unsaturated bond and the dangling bond of quantum dot surface atom are enriched, make these surface atoms that there is high activity, pole
It is unstable, it is easy to be combined with other atoms, efficiently carbon quantum dot/TiO has been prepared by the way that physical grinding method is simple and quick2
Composite and TiO2Quantum dot/TiO2Composite, and this composite material exhibits go out than pure TiO2More excellent property
Energy.Preparation process of the present invention is simple and easy to control, easy to operate, and time-consuming short, cost is low, from C quantum dots and TiO2Quantum dot come with
Two-dimension nano materials TiO2It is compound, because C quantum dots and TiO2Quantum dot stability is good, nontoxic, cheap, and it is compound after
The performance of material is also greatly improved, and can be used as catalysis material..
Brief description of the drawings
Fig. 1 is the pure TiO of the embodiment of the present invention 42Transmission electron microscope picture；
Fig. 2 is the TiO of the embodiment of the present invention 42Quantum dot/TiO2The low power transmission electron microscope picture of composite；
Fig. 3 is the TiO of the embodiment of the present invention 42Quantum dot/TiO2The high power transmission electron microscope picture of composite；
Fig. 4 is the pure TiO under the conditions of different capturing agents of the embodiment of the present invention 42And TiO2Quantum dot/TiO2Composite
Photocatalytic activity；
Fig. 5 is the pure TiO of the embodiment of the present invention 72Transmission electron microscope picture；
Fig. 6 is C quantum dots/TiO of the embodiment of the present invention 72The low power transmission electron microscope picture TEM figures of composite；
Fig. 7 is C quantum dots/TiO of the embodiment of the present invention 72The high power transmission electron microscope picture TEM figures of composite；
Fig. 8 is C quantum dots/TiO of the embodiment of the present invention 72The XPS figures of composite：（a）C quantum dots/TiO2With it is pure
TiO2The full spectrograms of XPS；（b）C1s；（c）Ti2p；（d）O1s；
Fig. 9 is the composite C quantum dots of the embodiment of the present invention 7/TiO2Photocatalytic activity figure.
Embodiment
Embodiment 1
A kind of quantum dot TiO2/ TiO2The preparation method of composite, is comprised the following steps that：Weigh 100 mg TiO2It is put into agate
In Nao alms bowls, 0.1 mL quantum dot titania solutions are added（10 mg/ml）After grinding 2 min, 100 DEG C of dryings in baking oven are put into
0.5 h obtains mass fraction than the quantum dot TiO for 1 wt%2/ TiO2Composite, it is named as T-1.
Embodiment 2
A kind of quantum dot TiO2/ TiO2The preparation method of composite, is comprised the following steps that：Weigh 100 mg TiO2It is put into
In agate alms bowl, 0.2 mL quantum dot titania solutions are added（10 mg/ml）After grinding 4 min, 90 DEG C of dryings in baking oven are put into
1 h obtains mass fraction than the quantum dot TiO for 2 wt%2/ TiO2Composite, it is named as T-2.
Embodiment 3
A kind of quantum dot TiO2/ TiO2The preparation method of composite, is comprised the following steps that：Weigh 100 mg TiO2It is put into agate
In Nao alms bowls, 0.3 mL quantum dot titania solutions are added（10 mg/ml）After grinding 8 min, 70 DEG C of dryings in baking oven are put into
0.8 h obtains mass fraction than the quantum dot TiO for 3wt%2/ TiO2Composite, it is named as T-3.
Embodiment 4
A kind of quantum dot TiO2/ TiO2The preparation method of composite, is comprised the following steps that：Weigh 100 mg TiO2It is put into
In agate alms bowl, 0.4 mL quantum dot titania solutions are added（10 mg/ml）After grinding 2 min, be put into baking oven 100 DEG C it is dry
Dry 2h obtains mass fraction than the quantum dot TiO for 4 wt%2/ TiO2Composite, it is named as T-4, pure titanium dioxide life
Entitled T-0.
TiO prepared by above-mentioned preparation preparation method2Quantum dot/TiO2Composite can be as the application of catalysis material.
Fig. 1 is pure TiO2Transmission electron microscope picture, pure TiO as can be seen from FIG.2Surface is smooth, and Fig. 2 and Fig. 3 divide
Wei not TiO2Quantum dot/TiO2The low power and high power transmission electron microscope picture of composite.It is to be compounded in two that yellow arrows are signified in Fig. 2
Quantum dot titanium dioxide on titanium oxide, before transmission sample is prepared, ultrasonic 1h is carried out to sample, quantum dot still uniformly divides
On the titanium dioxide, this also illustrates compound very firm between quantum dot titanium dioxide and titanium dioxide cloth.
Fig. 4 a are TiO2Quantum dot/TiO2The activity experiment of composite and pure titanic oxide material rhodamine B degradation
Figure.It can be found that rhodamine B for 10 mg/L from figure, pure titanium dioxide only degrades 55% in 1h, and compound 2
Performance is greatly improved after wt% quantum dot titanium dioxide, it is only necessary to which half an hour can is degradable by rhodamine B
.From Fig. 4 b and 4c it can also be seen that pure titanium dioxide and TiO2Quantum dot/TiO2Composite is in different capturing agents
Degradation rate, for pure titanium dioxide, hole plays decisive role, if hole all captured, whole photocatalysis is anti-
It will not should carry out, and for TiO2Quantum dot/TiO2Composite hole and negative oxygen ion all play certain effect.This also says
Bright quantum dot TiO2The compound photocatalysis mechanism for changing pure titanium dioxide, the utilization of electron hole is improved, so as to carry
High photocatalysis performance.
Embodiment 5
A kind of C quantum dots/TiO2The preparation method of composite, is comprised the following steps that：Weigh 100 mg TiO2It is put into agate
In Nao alms bowls, 20 μ L carbon quantum dot solution is added（10 mg/ml）After grinding 4 min, 50 DEG C of 2 h of drying are put into baking oven i.e.
Mass fraction is obtained than C quantum dots/TiO for 0.2 wt%2Composite, it is named as T-1.
Embodiment 6
A kind of C quantum dots/TiO2The preparation method of composite, is comprised the following steps that：Weigh 100 mg TiO2It is put into agate
In alms bowl, 40 μ L carbon quantum dot solution is added（10 mg/ml）After grinding 2 min, 60 DEG C of 0.5 h of drying are put into baking oven i.e.
Mass fraction is obtained than C quantum dots/TiO for 0.4 wt%2Composite, it is named as T-2.
Embodiment 7
A kind of C quantum dots/TiO2The preparation method of composite, is comprised the following steps that：Weigh 100 mg TiO2It is put into agate
In Nao alms bowls, 80 μ L carbon quantum dot solution is added（10 mg/ml）After grinding 6 min, 100 DEG C of 1 h of drying are put into baking oven i.e.
Mass fraction is obtained than C quantum dots/TiO for 0.8 wt%2Composite, is named as T-4, and pure titanium dioxide is named as T-
0。
Carbon quantum dot/TiO prepared by above-mentioned preparation preparation method2Composite can be as the application of catalysis material.
Fig. 5 is pure TiO2Transmission electron microscope picture, pure TiO as can be seen from FIG.2Surface is smooth, and Fig. 6 and Fig. 7 divide
Wei not C quantum dots/TiO2The low power and high power transmission electron microscope picture of composite.It is to be compounded in dioxy that yellow arrows are signified in Fig. 6
Change the C quantum dots on titanium, before transmission sample is prepared, ultrasonic 1h is carried out to sample, quantum dot is still evenly distributed in dioxy
Change on titanium, this also illustrates compound very firm between C quantum dots and titanium dioxide.
Fig. 8 a are pure TiO2With C quantum dots/TiO2The full spectrograms of XPS of composite, can clearly be distinguished from figure
Go out C, Ti and O element（C in pure titinium dioxide is probably derived from the organic precursor in preparation process）.From Fig. 8 b, 8c and 8d
C quantum dots/TiO is can be seen that in middle C1s, Ti2p and O1s fine spectrum2The peak position of composite is compared to pure TiO2Somewhat send out
Skew is given birth to, this shows the Ti central transferences of the electronics of part from the functional group on carbon quantum dot surface into titanium dioxide.From
Transmission and XPS can be seen that this simple physical method can effectively synthesize C quantum dots/TiO by polishing2Hetero-junctions
Structure.
Fig. 9 is pure TiO2With C quantum dots/TiO2Composite 300W xenon lamp irradiation under be not added with filter plate when pair
The degradation rate figure of rhodamine B, as can be seen from Figure pure TiO2Rhodamine B there remains 40% after irradiation 120 minutes, and C quantum
Point/TiO2Composite material exhibits have gone out higher catalytic activity, wherein the performance of compound 0.4 wt% C quantum dots is best,
It is in 120 minutes that rhodamine B is degradable.Fig. 9 b are its corresponding kinetics fitted figures, from figure it can also be seen that compound
Degradation rate after 0.4 wt% C quantum dots is pure TiO2Nearly 5 times.Fig. 9 c are pure TiO after filter plate has been added2With
C quantum dots/TiO2The photocatalytic degradation figure of composite, as can be seen from FIG. pure TiO2Almost do not have under visible light conditions
Any degraded, and C quantum dots/TiO2Composite can absorb visible ray and rhodamine B degradation, and this also illustrates using grinding
C quantum dots/TiO prepared by mill method2Composite is effective, can greatly improve its performance.
Claims (6)
- A kind of 1. quantum dot/TiO2The preparation method of composite, it is characterised in that technique is：By TiO2It is put into mortar, then adds Enter quanta point material grinding, be put into baking oven and dry, obtain quantum dot/TiO2Composite.
- A kind of 2. quantum dot/TiO according to claim 12The preparation method of composite, it is characterised in that：The quantum Point material is C quantum dots or TiO2Quantum dot.
- A kind of 3. quantum dot/TiO according to claim 22The preparation method of composite, it is characterised in that：The C amounts Son point and TiO2Mass fraction ratio be 0.2-0.8 wt%.
- A kind of 4. quantum dot/TiO according to claim 22The preparation method of composite, it is characterised in that：The TiO2 Quantum dot and TiO2Mass fraction ratio be 1-4 wt%.
- A kind of 5. quantum dot/TiO according to any of the above-described claim2The preparation method of composite, it is characterised in that tool Body method is as follows：Weigh TiO2It is put into agate alms bowl, adds after quanta point material after grinding 2-10 mim, be put into baking oven 50-100 DEG C of dry 0.5-2 h obtains quantum dot/TiO2Composite.
- 6. quantum dot/TiO prepared by the method according to any of the above-described claim2The application of composite, its feature exist In：For catalysis material.
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| CN201710875824.7A CN107649107A (en) | 2017-09-25 | 2017-09-25 | A kind of quantum dot/TiO2The preparation method and applications of composite |
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| CN201710875824.7A CN107649107A (en) | 2017-09-25 | 2017-09-25 | A kind of quantum dot/TiO2The preparation method and applications of composite |
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| Publication Number | Publication Date |
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Cited By (2)
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| CN109158125A (en) * | 2018-10-15 | 2019-01-08 | 长沙理工大学 | A kind of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis material and preparation method thereof |
| CN110628418A (en) * | 2019-09-29 | 2019-12-31 | 中国石油大学(华东) | TiO2-quantum dot composite material, preparation method thereof and application thereof in endotoxin detection |
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