CN106082201A - Graphene composite nano material of ultra-thin TiOx nano sheet load and preparation method thereof - Google Patents

Graphene composite nano material of ultra-thin TiOx nano sheet load and preparation method thereof Download PDF

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CN106082201A
CN106082201A CN201610469377.0A CN201610469377A CN106082201A CN 106082201 A CN106082201 A CN 106082201A CN 201610469377 A CN201610469377 A CN 201610469377A CN 106082201 A CN106082201 A CN 106082201A
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graphene
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CN106082201B (en
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张海娇
顾岚冰
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University of Shanghai for Science and Technology
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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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases

Abstract

The present invention relates to graphene composite nano material of a kind of ultra-thin TiOx nano sheet load and preparation method thereof.The present invention with graphene oxide and butyl titanate (TBOT) as raw material, pure water is solvent, and TPAOH (TPAOH) is alkali source, and 3 aminopropyl triethoxysilanes (APTES) are as crystallization promoting agent, use simple hydrothermal synthesis method, obtain lamellar TiO that pattern is homogeneous2/ graphene composite nano material.Within this material, the ultra-thin TiOx nano sheet homoepitaxial of anatase phase, in graphenic surface, forms the nanostructured of a kind of uniqueness.Resulting materials has potential application prospect in the field such as environmental improvement and new forms of energy.

Description

Graphene composite nano material of ultra-thin TiOx nano sheet load and preparation method thereof
Technical field
The present invention relates to graphene composite nano material of a kind of ultra-thin TiOx nano sheet load and preparation method thereof.
Background technology
Become in global range along with the fast development of modern science and technology, environmental pollution and energy shortage and merited attention most Hot issue.Photocatalitic Technique of Semiconductor with the solar energy of abundant cleaning as the energy, because of its feature such as green and energy-conservation, inhales Draw extensive concern.In these metal oxide semiconductor materials, titanium dioxide is the most potential important materials of one One of, owing to it has the plurality of advantages such as low cost, high activity and stability be good, be widely used in solaode, photocatalysis, The fields such as lithium ion battery, gas sensor and medicine transmission.But, in actual applications, titanium dioxide itself is relatively poor Charge transport properties and wide forbidden band (3.2 eV) limit it and further develop.Therefore, in order to improve its property Can, a lot of effort are made, as reduced grain size, and the titanium oxide of synthesis nanostructured, or construct some composite constructions, As metal nanoparticle adulterates, semiconductor heterostructure and carbon composite etc..Especially, with being combined of carbon nanomaterial, quilt It is considered current very effective mode.And the unique two-dimensional structure of Graphene, bigger specific surface area, excellent electric conductivity and Fabulous chemical stability also becomes prepares the carrier that composite is ideal, can improve composite wood largely The performance of material.
Although the preparation of titanium dioxide/graphene composite material and application are all achieved with certain progress, but still have Railway Project has had a strong impact on its performance: 1) phenomenon that in building-up process, titanium dioxide is easily reunited greatly reduces the ratio of material Surface area, and add the transmission range of particle in the course of reaction such as photon, electronics, cause performance to reduce；2) titanium dioxide is not Evitable random growth can cause Graphene avtive spot under-utilized, causes both to weaken by synergism；3) some synthesis Process is complex, even also needs to the chemical reagent etc. of substantial amounts of costliness, causes high production cost.Therefore, the most simply The titanium dioxide equally loaded graphene composite nano material effectively preparing specific morphology has very important research meaning Justice.
Summary of the invention
An object of the present invention is the graphene composite nano material providing a kind of ultra-thin TiOx nano sheet to load.
The two of the purpose of the present invention are to provide the preparation method of this composite nano materials.
For achieving the above object, the present invention is by the following technical solutions:
A kind of graphene composite nano material of ultra-thin TiOx nano sheet load, it is characterised in that: this material is by ultra-thin TiO2Nanometer sheet homoepitaxial, on Graphene, forms the nanostructured of a kind of uniqueness, described ultra-thin TiO2The thickness of nanometer sheet Degree is: 6 nm.
A kind of method of graphene composite nano material preparing above-mentioned ultra-thin TiOx nano sheet load, its feature exists Concretely comprising the following steps in the method:
A. by graphene oxide, join in deionized water, be configured to the mixed solution that concentration is 0.0625 mol/L；Add 3- Aminopropyl triethoxysilane (APTES), stirs 1～3 h；Again butyl titanate (TBOT) is dropwise instilled above-mentioned solution, continue Continuous stirring 0.5～1 h；Add TPAOH (TPAOH) and continue stirring 0.5～1 h；Described reduction-oxidation graphite Alkene, 3-aminopropyl triethoxysilane, butyl titanate, the mol ratio of TPAOH be: 1:0.076 ~ 0.304: 0.11~0.19 : 0.03~0.06；
B. step a gained mixed solution is reacted under the conditions of 140～180 DEG C 12～24 h；After having reacted, by centrifugation, wash Wash, dry, obtain black powder product；
C. by step b gained black powder product in an inert atmosphere, calcine 2～4 h under the conditions of 650～850 DEG C, obtain two Titanium oxide/graphene composite nano material.
The present invention with the graphene oxide of butyl titanate (TBOT) and pyrolysis reduction as primary raw material, at 3-aminopropyl three Under the common effect of Ethoxysilane and TPAOH, prepare the TiO with uniform morphology2/ graphene is combined Nano material.The advantages such as the inventive method has simple to operate, and reaction condition is controlled.The composite nano materials prepared by this method There is ultra-thin TiOx nano sheet be evenly distributed and the feature of well-crystallized.During present invention process, by 3-aminopropyl three Graphene amination is modified by Ethoxysilane, the alkaline Water Under that butyl titanate provides at TPAOH subsequently Solution grows into ultra-thin TiOx nano sheet, finally by homoepitaxial vertical with under the mutual electrostatic interaction of amidized Graphene In the surface of graphene oxide of reduction, form a kind of composite with unique nanostructured.
Compared with prior art, the technology of the present invention has following remarkable advantage: technique is simple, mild condition；Prepare answers Close that appearance of nano material is homogeneous and favorable dispersibility, before the fields such as the pollution control of environment and new forms of energy have certain application Scape.
Accompanying drawing explanation
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.
Detailed description of the invention
All embodiments are all operated by the operating procedure of technique scheme.Graphene oxide used in the present invention Preparation method refer toJ. Am. Chem. Soc., 2008, 130, 5856-5857.Specific as follows: first by existing Know that technology produces Graphene: first graphite powder is dissolved in concentrated sulphuric acid, then with potassium peroxydisulfate (K2S2O8) and phosphorus pentoxide (P2O5) Deng material, it is carried out pre-oxidation treatment.Again by a certain amount of potassium permanganate (KMnO4) grind fully under condition of ice bath to stone Ink carries out fully oxidized.Finally with dilute hydrochloric acid solution carry out pickling processes and repeatedly washing process after i.e. can get Graphene oxygen Compound.The graphene oxide of above-mentioned preparation can prepare redox graphene nanometer sheet by high temperature pyrolysis.
Embodiment 1
A. the graphene oxide weighing 30 mg pyrolysis reduction joins ultrasonic 2 h in 40 mL deionized waters so that it is be uniformly dispersed；
B. in above-mentioned a solution, add 176 μ L 3-aminopropyl triethoxysilane (APTES) solution, continue stirring 1 h；
C. pipette 265 μ L butyl titanates with liquid-transfering gun and be added dropwise over above-mentioned solution, continue stirring 1h under room temperature, add 123 μ L TPAOH in above-mentioned solution, continuously stirred 1h；
D. reacted mixed solution is poured in band teflon-lined autoclave, react under the conditions of 180 DEG C 24 h；
E., after having reacted, product is taken out from reactor, with deionized water and ethanol cyclic washing, centrifugal after, at 60 DEG C Lower drying and in nitrogen atmosphere 750 DEG C calcining 2 h, obtain TiO prepared by the present invention2/ graphene composite nano materials.
Obtained sample is carried out physical property sign, and its partial results is as shown in drawings.From result, gained titanium oxide Nanometer sheet is anatase phase, and a large amount of ultra-thin titanium dioxide nanosheet homoepitaxial is on redox graphene, defines A kind of network nano structure of uniqueness.
Embodiment 2
Preparation process and the step of the present embodiment are substantially the same manner as Example 1, are except for the difference that b step:
In above-mentioned a solution, add 88 μ L 3-aminopropyl triethoxysilane (APTES) solution, continue stirring 1 h.
Acquired results and embodiment 1 basic simlarity, difference is that the ultra-thin titanium dioxide nanosheet obtained can not be good It is supported on graphenic surface, and has and be in free state on a small quantity.
Embodiment 3
Preparation process and the step of the present embodiment are substantially the same manner as Example 1, are except for the difference that step c:
Pipette 331 μ L butyl titanates with liquid-transfering gun dropwise to instill and under above-mentioned solution, room temperature, stir 1 h, add 123 μ L TPAOH, in above-mentioned solution, stirs.
In gained composite, TiOx nano sheet packing phenomenon ratio is more serious, and can not be supported on completely on Graphene.
Comparative example 1
Preparation process and the step of the present embodiment are substantially the same manner as Example 1, are except for the difference that b step:
Do not add 3-aminopropyl triethoxysilane.
Acquired results and embodiment 1 difference are relatively big, and what difference was to obtain is, and that titanium dioxide is reunited is serious, and pattern is uneven One, and titanium dioxide is free on outside Graphene in a large number.
Comparative example 2
Preparation process and the step of the present embodiment are substantially the same manner as Example 1, are except for the difference that step c:
Pipette 265 μ L tetra-n-butyl titanates with liquid-transfering gun and dropwise instill above-mentioned solution, continue stirring 1 h under room temperature, do not add four Propyl group ammonium hydroxide is in above-mentioned solution.
Acquired results and embodiment 1 difference are relatively big, and difference is that the titanium dioxide nanoplate agglomeration obtained is serious.
Seeing accompanying drawing, Fig. 1 is the embodiment of the present invention 1 gained TiO2The XRD spectra of/graphene composite nano materials.XRD Analyze: carry out on Japan's RigaKu D/max-2550 type X-ray diffractometer；Use CuK α diffraction.Knowable to Fig. 1, calcining After TiO2/ graphene sample diffraction peak to go out peak position consistent with standard spectrogram (JCPDF No:21-1272), corresponding TiO2Anatase.Compared with not calcining, in the sample after burning, the degree of crystallinity of titanium oxide significantly improves.Additionally, 2q= About the 22 ° small peaks occurred may belong to caused by the small amounts silicon that APTES hydrolysis generates.
Seeing accompanying drawing, Fig. 2 is the embodiment of the present invention 1 gained TiO2The scanning electron microscope of/graphene composite nano materials (SEM) picture.Sem analysis: use NEC company JSM-6700F type to launch sem observation material morphology. Knowable to SEM result, material morphology is homogeneous, and substantial amounts of ultra-thin TiOx nano sheet homoepitaxial, in graphenic surface, forms one Plant unique network nano structure.
Seeing accompanying drawing, Fig. 3 is the embodiment of the present invention 1 gained TiO2The transmission electron microscope of/graphene composite nano materials (TEM) picture.Tem analysis: use Jeol Ltd. JEOL-200CX type transmission electron microscope observation material morphology And structure.The part different from the TEM picture depth is it can be seen that nano titania thin slice homoepitaxial, and at edge of materials It can clearly be seen that the existence of Graphene, show that titanium oxide is successfully combined with each other with Graphene, consistent with SEM result.

Claims (2)

1. the graphene composite nano material of a ultra-thin TiOx nano sheet load, it is characterised in that: this material is by ultra-thin TiO2Nanometer sheet homoepitaxial, on Graphene, forms unique nanostructured, described ultra-thin TiO2The thickness of nanometer sheet is about It is 6 nm.
2. the side of the graphene composite nano material preparing ultra-thin TiOx nano sheet according to claim 1 load Method, it is characterised in that concretely comprising the following steps of the method:
By graphene oxide, join in deionized water, be configured to the mixed solution that concentration is 0.0625 mol/L；Add 3-ammonia Propyl-triethoxysilicane (APTES), stirs 1～3 h；Again butyl titanate (TBOT) is dropwise instilled above-mentioned solution, continue Stirring 0.5～1 h；Add TPAOH (TPAOH) and continue stirring 0.5～1 h；Described redox graphene, 3-aminopropyl triethoxysilane, butyl titanate, the mol ratio of TPAOH be: 1:0.076 ~ 0.304:0.11 ~0.19 : 0.03~0.06；
Step a gained mixed solution is reacted under the conditions of 140～180 DEG C 12～24 h；After having reacted, by centrifugation, wash Wash, dry, obtain black powder product；
By step b gained black powder product in an inert atmosphere, calcine 2～4 h under the conditions of 650～850 DEG C, obtain dioxy Change titanium/graphene composite nano material.
CN201610469377.0A 2016-06-25 2016-06-25 The graphene composite nano material and preparation method thereof of ultra-thin TiOx nano piece load Active CN106082201B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109574069A (en) * 2018-11-21 2019-04-05 上海大学 The titanium dioxide classification nanostructure and preparation method thereof of carbon quantum dot induction
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
CN115895764A (en) * 2022-12-30 2023-04-04 陕西煤业化工技术研究院有限责任公司 Preparation method of graphene oxide lubricating oil anti-wear additive

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102569761A (en) * 2010-12-08 2012-07-11 中国科学院金属研究所 Titanium dioxide/graphene nanocomposite material and preparation method and application thereof
CN104600271A (en) * 2015-02-03 2015-05-06 辽宁工程技术大学 Preparation method of sodium titanate/graphene composite cathode material of sodium ion battery
CN105289566A (en) * 2015-09-24 2016-02-03 上海大学 Synthetic method of glucosamine-assisted-crystallized TiO2@graphene composite nanomaterial

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102569761A (en) * 2010-12-08 2012-07-11 中国科学院金属研究所 Titanium dioxide/graphene nanocomposite material and preparation method and application thereof
CN104600271A (en) * 2015-02-03 2015-05-06 辽宁工程技术大学 Preparation method of sodium titanate/graphene composite cathode material of sodium ion battery
CN105289566A (en) * 2015-09-24 2016-02-03 上海大学 Synthetic method of glucosamine-assisted-crystallized TiO2@graphene composite nanomaterial

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HAIJIAO ZHANG ET AL.: "A Facile One-Step Synthesis of TiO2/Graphene Composites for Photodegradation of Methyl Orange", 《NANO RESEARCH》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN109574069A (en) * 2018-11-21 2019-04-05 上海大学 The titanium dioxide classification nanostructure and preparation method thereof of carbon quantum dot induction
CN109574069B (en) * 2018-11-21 2021-10-12 上海大学 Carbon quantum dot induced titanium dioxide hierarchical nanostructure and preparation method thereof
CN115895764A (en) * 2022-12-30 2023-04-04 陕西煤业化工技术研究院有限责任公司 Preparation method of graphene oxide lubricating oil anti-wear additive
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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