CN106082201B - The graphene composite nano material and preparation method thereof of ultra-thin TiOx nano piece load - Google Patents
The graphene composite nano material and preparation method thereof of ultra-thin TiOx nano piece load Download PDFInfo
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- CN106082201B CN106082201B CN201610469377.0A CN201610469377A CN106082201B CN 106082201 B CN106082201 B CN 106082201B CN 201610469377 A CN201610469377 A CN 201610469377A CN 106082201 B CN106082201 B CN 106082201B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/45—Aggregated particles or particles with an intergrown morphology
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The present invention relates to a kind of graphene composite nano materials and preparation method thereof of ultra-thin TiOx nano piece load.The present invention is with graphene oxide and butyl titanate (TBOT) for raw material, pure water is solvent, and tetrapropylammonium hydroxide (TPAOH) is alkali source, and 3- aminopropyl triethoxysilane (APTES) is used as crystallization promoting agent, using simple hydrothermal synthesis method, the uniform sheet TiO of pattern is obtained2/ graphene composite nano material.Within this material, the ultra-thin TiOx nano piece homoepitaxial of anatase phase forms a kind of unique nanostructure in graphene surface.Resulting materials have potential application prospect in the fields such as environmental improvement and new energy.
Description
Technical field
The present invention relates to a kind of graphene composite nano materials and preparation method thereof of ultra-thin TiOx nano piece load.
Background technique
Along with the fast development of modern science and technology, environmental pollution and energy shortage have become in global range and most merit attention
Hot issue.To enrich clean solar energy as the Photocatalitic Technique of Semiconductor of the energy, because of the features such as it is green and energy conservation, inhale
Extensive concern is drawn.In these metal oxide semiconductor materials, titanium dioxide is a kind of very potential important materials
One of, due to its have low cost, high activity and stability is good many advantages, such as, be widely used in solar battery, photocatalysis,
The fields such as lithium ion battery, gas sensor and drug delivery.However, in practical applications, titanium dioxide itself is relatively poor
Charge transport properties and wide forbidden band (~3.2 eV) limit its and further develop.Therefore, in order to improve its property
Can, it is many to make great efforts to be made, particle size is such as reduced, synthesizes the titanium oxide of nanostructure, or construct some composite constructions,
If metal nanoparticle adulterates, semiconductor heterostructure and carbon composite etc..Particularly, compound with carbon nanomaterial, quilt
It is considered current very effective mode.And the unique two-dimensional structure of graphene, biggish specific surface area, excellent electric conductivity and
Fabulous chemical stability, which also becomes, prepares the ideal carrier of composite material, can largely improve composite wood
The performance of material.
Although the preparation and application of titanium dioxide/graphene composite material have all made some progress, still have
Railway Project has seriously affected its performance: 1) titanium dioxide phenomenon easy to reunite greatly reduces the ratio of material in synthesis process
Surface area, and the transmission range of particle in the reaction process such as photon, electronics is increased, lead to reduced performance；2) titanium dioxide is not
Evitable random growth will cause graphene active site underutilization, and the two synergistic effect is caused to weaken；3) some are synthesized
Process is complex, or even also needs the chemical reagent etc. of a large amount of valuableness, leads to high production cost.Therefore, how simply
The graphene composite nano material for be effectivelying prepared the titanium dioxide uniform load of specific morphology is anticipated with very important research
Justice.
Summary of the invention
One of the objects of the present invention is to provide a kind of graphene composite nano materials of ultra-thin TiOx nano piece load.
The second object of the present invention is to provide the preparation method of the composite nano materials.
To achieve the above object, the invention adopts the following technical scheme:
A kind of graphene composite nano material of ultra-thin TiOx nano piece load, it is characterised in that: the material is by ultra-thin
TiO2Nanometer sheet homoepitaxial is on graphene, forming a kind of unique nanostructure, the ultra-thin TiO2Nanometer sheet
Thickness are as follows: 6 nm.
A method of the graphene composite nano material of above-mentioned ultra-thin TiOx nano piece load being prepared, feature exists
In the specific steps of this method are as follows:
A. it by graphene oxide, is add to deionized water, is configured to the mixed solution that concentration is 0.0625 mol/L；Add
Enter 3- aminopropyl triethoxysilane (APTES), stirs 1~3 h；Butyl titanate (TBOT) is instilled dropwise again above-mentioned molten
Liquid continues 0.5~1 h of stirring；Tetrapropylammonium hydroxide (TPAOH) is added and continues 0.5~1 h of stirring；The reduction-oxidation
Graphene, 3- aminopropyl triethoxysilane, butyl titanate, tetrapropylammonium hydroxide molar ratio are as follows: 1:0.076 ~
0.304: 0.11~0.19 : 0.03~0.06；
B. mixed solution obtained by step a is reacted into 12~24 h under the conditions of 140~180 DEG C；After the reaction was completed, through from
The heart, washing, drying obtain black powder product；
C. in an inert atmosphere by black powder product obtained by step b, 2~4 h are calcined under the conditions of 650~850 DEG C, i.e.,
Obtain titanium dioxide/graphene composite nano materials.
The present invention is using the graphene oxide of butyl titanate (TBOT) and pyrolysis reduction as primary raw material, in 3- aminopropyl three
Under the collective effect of Ethoxysilane and tetrapropylammonium hydroxide, the TiO with uniform morphology is prepared2/ graphene is compound
Nano material.The method of the present invention has many advantages, such as easy to operate, and reaction condition is controllable.The composite nano materials prepared by this method
Have the characteristics that ultra-thin TiOx nano piece is evenly distributed and well-crystallized.During present invention process, pass through 3- aminopropyl three
Ethoxysilane modifies graphene amination, and subsequent butyl titanate is lauched in the alkaline condition that tetrapropylammonium hydroxide provides
Solution grows into ultra-thin TiOx nano piece, finally by vertical homoepitaxial under the mutual electrostatic interaction with amidized graphene
In the surface of graphene oxide of reduction, a kind of composite material with unique nanostructure is formed.
Compared with prior art, the technology of the present invention has following remarkable advantage: simple process, mild condition；It is obtained multiple
Close that appearance of nano material is uniform and favorable dispersibility, before there is certain application in the fields such as the pollution control of environment and new energy
Scape.
Detailed description of the invention
Fig. 1 is gained TiO in the embodiment of the present invention 12The XRD spectra of/graphene composite nano materials.
Fig. 2 is gained TiO in the embodiment of the present invention 12The SEM picture of/graphene composite nano materials.
Fig. 3 is gained TiO in the embodiment of the present invention 12The TEM picture of/graphene composite nano materials.
Specific embodiment
The operating procedure of all embodiments according to the above technical scheme is operated.Graphene oxide used in the present invention
Preparation method refer toJ. Am. Chem. Soc., 2008, 130, 5856-5857.It is specific as follows: first by it is existing
Know that technology produces graphene: graphite powder being first dissolved in the concentrated sulfuric acid, then with potassium peroxydisulfate (K2S2O8) and phosphorus pentoxide (P2O5)
Equal materials carry out pre-oxidation treatment to it.Again by a certain amount of potassium permanganate (KMnO4) grind sufficiently under condition of ice bath to stone
Ink carries out fully oxidized.Graphene oxygen can be obtained after finally carrying out pickling processes and multiple washing process with dilute hydrochloric acid solution
Compound.The graphene oxide of above-mentioned preparation can prepare redox graphene nanometer sheet by high temperature pyrolysis.
Embodiment 1
A. the graphene oxide for weighing 30 mg pyrolysis reductions is added to 2 h of ultrasound in 40 mL deionized waters, makes its dispersion
Uniformly；
B. 176 μ L 3- aminopropyl triethoxysilane (APTES) solution are added into above-mentioned a solution, continue stirring 1
h；
C. 265 μ L butyl titanates are pipetted with liquid-transfering gun and above-mentioned solution are added dropwise, continue under room temperature stir 1 h, then plus
Enter 123 μ L tetrapropylammonium hydroxide in above-mentioned solution, persistently stirs 1h；
D. the mixed solution after reaction is poured into the autoclave with polytetrafluoroethyllining lining, under the conditions of 180 DEG C
React 24 h；
E. after the reaction was completed, product is taken out from reaction kettle, after being washed, be centrifuged repeatedly with deionized water and ethyl alcohol,
At 60 DEG C drying and in nitrogen atmosphere 750 DEG C of 2 h of calcining to get TiO prepared by the present invention2/ graphene composite Nano
Material.
Obtained sample is subjected to physical property characterization, partial results are as shown in the picture.As can be seen from the results, gained titanium oxide
Nanometer sheet is anatase phase, and a large amount of ultra-thin titanium dioxide nanosheet homoepitaxials are formd on redox graphene
A kind of unique network nano structure.
Embodiment 2
The preparation process and step of the present embodiment are substantially the same manner as Example 1, the difference is that being b step:
88 μ L 3- aminopropyl triethoxysilane (APTES) solution are added into above-mentioned a solution, continue to stir 1 h.
Acquired results are substantially similar to embodiment 1, and the ultra-thin titanium dioxide nanosheet that difference is cannot be good
In load on the surface of graphene, and have on a small quantity in free state.
Embodiment 3
The preparation process and step of the present embodiment are substantially the same manner as Example 1, the difference is that being step c:
331 μ L butyl titanates are pipetted with liquid-transfering gun and instill above-mentioned solution dropwise, and 1 h is stirred under room temperature, adds 123
μ L tetrapropylammonium hydroxide stirs evenly in above-mentioned solution.
In gained composite material, TiOx nano piece packing phenomenon cannot be supported on graphene completely than more serious.
Comparative example 1
The preparation process and step of the present embodiment are substantially the same manner as Example 1, the difference is that being b step:
3- aminopropyl triethoxysilane is not added.
Acquired results and 1 difference of embodiment are larger, and what difference was is that titanium dioxide is reunited seriously, and pattern is uneven
One, and titanium dioxide is largely free on outside graphene.
Comparative example 2
The preparation process and step of the present embodiment are substantially the same manner as Example 1, the difference is that being step c:
Pipette 265 μ L tetra-n-butyl titanates with liquid-transfering gun and instill above-mentioned solution dropwise, continue under room temperature stir 1 h, not plus
Enter tetrapropylammonium hydroxide in above-mentioned solution.
Acquired results and 1 difference of embodiment are larger, and the titanium dioxide nanoplate agglomeration that difference is is serious.
Referring to attached drawing, Fig. 1 is 1 gained TiO of the embodiment of the present invention2The XRD spectra of/graphene composite nano materials.XRD
Analysis: it is carried out on Japanese RigaKu D/max-2550 type X-ray diffractometer；Using CuK α diffraction.From Fig. 1 it is found that calcining
TiO afterwards2The peak position out at/graphene sample diffraction peak is consistent with standard spectrogram (JCPDF No:21-1272), corresponding
TiO2Anatase.Compared with not calcining, the crystallinity of titanium oxide is significantly improved in the sample after burning.In addition, 2q=
The small peak of 22 ° or so appearance may belong to caused by the small amounts silicon that APTES hydrolysis generates.
Referring to attached drawing, Fig. 2 is 1 gained TiO of the embodiment of the present invention2The scanning electron microscope of/graphene composite nano materials
(SEM) picture.Sem analysis: material morphology is observed using Japan Electronics Corporation JSM-6700F type transmitting scanning electron microscope.
From SEM result it is found that material morphology is uniform, a large amount of ultra-thin TiOx nano piece homoepitaxial forms one in graphene surface
The unique network nano structure of kind.
Referring to attached drawing, Fig. 3 is 1 gained TiO of the embodiment of the present invention2The transmission electron microscope of/graphene composite nano materials
(TEM) picture.Tem analysis: Jeol Ltd. JEOL-200CX type transmission electron microscope observation material morphology is used
And structure.The parts different from the TEM picture depth can be seen that nano titania thin slice homoepitaxial, and at edge of materials
It can clearly be seen that the presence of graphene, shows that titanium oxide is successfully combined with each other with graphene, it is consistent with SEM result.
Claims (2)
1. a kind of graphene composite nano material of ultra-thin TiOx nano piece load, it is characterised in that: the material is by ultra-thin
TiO2Nanometer sheet homoepitaxial is on graphene, foring network nano structure, the ultra-thin TiO2Nanometer sheet with a thickness of
6nm, TiO2Nanometer sheet is anatase phase, is modified by 3- aminopropyl triethoxysilane graphene amination, subsequent titanium
Sour four butyl esters grow into ultra-thin TiOx nano piece in the hydrolyzed under basic conditions that tetrapropylammonium hydroxide provides, finally by with
Vertical homoepitaxial forms ultra-thin oxygen in the surface of graphene oxide of reduction under the mutual electrostatic interaction of amidized graphene
Change the graphene composite nano material structure of titanium nanometer sheet load.
2. a kind of side for the graphene composite nano material for preparing ultra-thin TiOx nano piece load according to claim 1
Method, it is characterised in that the specific steps of this method are as follows:
A. it by the graphene oxide of reduction, is add to deionized water, is configured to the mixed solution that concentration is 0.0625mol/L；
It is added 3- aminopropyl triethoxysilane (APTES), stirs 1~3h；Butyl titanate (TBOT) is instilled dropwise again above-mentioned molten
Liquid continues 0.5~1h of stirring；Tetrapropylammonium hydroxide (TPAOH) is added and continues 0.5~1h of stirring；The graphene oxide of reduction,
3- aminopropyl triethoxysilane, butyl titanate, tetrapropylammonium hydroxide molar ratio are as follows: 1:0.076~0.304:0.11
~0.19:0.03~0.06；
B. mixed solution obtained by step a is reacted 12 under the conditions of 140~180 DEG C~for 24 hours；After the reaction was completed, it is centrifuged, washed
It washs, dry, obtain black powder product；
C. in an inert atmosphere by black powder product obtained by step b, 2~4h is calcined under the conditions of 650~850 DEG C to get dioxy
Change titanium/graphene composite nano material.
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| RU2787441C1 (en) * | 2021-12-15 | 2023-01-09 | Общество с ограниченной ответственностью "Наноструктурные добавки" | Method for producing a suspension based on a titanium dioxide nanocomposite on graphene flakes |
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| CN109809428A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of composite material and preparation method of inorganic carrier area load carbon-coating |
| CN109574069B (en) * | 2018-11-21 | 2021-10-12 | 上海大学 | Carbon quantum dot induced titanium dioxide hierarchical nanostructure and preparation method thereof |
| CN115895764B (en) * | 2022-12-30 | 2024-04-05 | 陕西煤业化工技术研究院有限责任公司 | Preparation method of graphene oxide lubricating oil antiwear additive |
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| CN105289566B (en) * | 2015-09-24 | 2019-04-02 | 上海大学 | The TiO of Glucosamine crystallization in motion2The synthetic method of@graphene composite nano material |
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| RU2787441C1 (en) * | 2021-12-15 | 2023-01-09 | Общество с ограниченной ответственностью "Наноструктурные добавки" | Method for producing a suspension based on a titanium dioxide nanocomposite on graphene flakes |
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