CN104401980B - Fe2o3-SnO2the hydrothermal preparing process of/Graphene tri compound nano material - Google Patents
Fe2o3-SnO2the hydrothermal preparing process of/Graphene tri compound nano material Download PDFInfo
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Abstract
The present invention relates to a kind of Fe2O3-SnO2The hydrothermal preparing process of/Graphene tri compound nano material.The present invention, with Graphene, iron chloride and stannous chloride as raw material, prepares constitutionally stable Graphene tri compound nano material by simple one step hydro thermal method.Can be seen that from TEM photo, the composite nano materials prepared is self assembly by the way of the graphene nanometer sheet of flake ferric oxide nano particle with two dimension is combined with blade, and this combination can improve the structural stability of Graphene metal oxide composite nano materials to a certain extent.The more important thing is, graphene composite nano material prepared by this method has potential application prospect in the field such as environment, the energy.
Description
Technical field
The present invention relates to a kind of Sn2+The Fe guided2O3-SnO2The hydro-thermal preparation side of/Graphene tri compound nano material
Method.
Background technology
Graphene is sp2The two dimensional crystal material that the carbon atom of hydridization is interconnected to form, because it has bigger ratio table
Area, cellular void structure, good heat conductivility, superpower electric conductivity, high mechanical strength, the carrier mobility of superelevation
The excellent specific property such as rate, light transmission, has just got more and more people's extensive concerning since within 2004, finding first.Additionally, receive as one
The two-dimensional material of meter level, Graphene or well composite material carrier.Finder professor Geim of Graphene the most once pointed out, stone
Ink alkene the most direct application in future is exactly graphene composite material.In these composites, with metal oxide
Compound research is the most extensive.It is primarily due to this type of composite keeping while Graphene part excellent properties own, also
Achieve the effective efficiency of Graphene, impart the new character of material and function, expanded it and further applied.
At present, along with graphene composite material research is deepened continuously, about Graphene as base load metal oxygen
The report of compound nano material also grows with each passing day.People can realize receiving at Graphene by different physico-chemical processes
Different metal oxide nano-materials is loaded (such as Fe on rice sheet2O3、SnO2、Fe3O4、Co3O4、ZnO2、MnO2、TiO2Deng).This
Plant the metal oxide that binary graphene composite material can be good at playing Graphene and being supported on graphene nanometer sheet
Both respective performances, and can realize multi-field application by cooperative effect between the two, such as battery, are catalyzed, store up
Energy, biological medicine etc., illustrate potential application prospect.Wherein, iron oxide nano material is with low cost by it, environment is friendly
The advantages such as good and resistance to corrosion is strong, show one's talent in numerous metal oxide materials, and are widely used in multiple fields.
Summary of the invention
It is an object of the invention to provide a kind of Fe2O3-SnO2The hydro-thermal preparation side of/Graphene tri compound nano material
Method, it is characterised in that this composite nano materials achieves Graphene and is combined with the blade of composite: be with sheet Graphene
Substrate, similar rectangle sheet Fe of load above2O3Nano particle, SnO2Nano particle is dispersed in the form of fine particle
Fe2O3Around nano particle, thus form constitutionally stable Fe2O3-SnO2/ Graphene tri compound nano material.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that
A. redox graphene is dissolved in deionized water, is configured to the suspension of 0.20 ~ 0.30 wt%；
B. by ferric chloride solution that concentration is 0.12 mol/L and stannous chloride solution that concentration is 0.07 mol/L successively
Join in 28 ~ 42 mL step a gained suspensions, ultrasonically treated 20 min, obtain mixed solution；Wherein graphite in mixed liquor
The mass ratio of alkene, iron chloride and stannous chloride is 1:0.16 ~ 0.35:0.1 ~ 0.26；
C. by step b gained mixed solution at 180 DEG C of Water Under thermal response 1 ~ 24 h；Product is taken out, through routine
Be centrifuged, wash, the step such as drying, obtain Fe2O3-SnO2/ Graphene tri compound nano material.
In the technical process of the present invention, a small amount of Sn2+Addition can induce sheet Fe2O3The formation of nano particle, from
And effectively can be combined by the way of blade is combined with the Graphene of two dimension.Compared with other, this mode is the most firm, more
Be conducive to improving composite resistance to overturning in performance test.Additionally, Sn2+Not only act as Fe2O3Nano particle
Pattern guide effect, and unnecessary Sn2+Can adsorb at graphenic surface and be received by the hydrothermal Graphene that is finally supported on
Rice sheet surface, such that it is able to successfully realize one-step method to prepare Fe2O3-SnO2/ Graphene tri compound nano material.
Compared with prior art, the technology of the present invention has a following remarkable advantage:
The inventive method has easy and simple to handle, and reaction condition is gentle, and abundant raw material is easy to get, and it is excellent that with low cost, productivity is high etc.
Point.The Graphene trielement composite material prepared by this method, pattern is homogeneous, Stability Analysis of Structures, can play in composite simultaneously
The excellent specific property of each component, has broad application prospects in the field such as lithium ion battery, organic pollutant removal.
Accompanying drawing explanation
Fig. 1 is gained Fe in the embodiment of the present invention 12O3-SnO2The TEM picture of/Graphene tri compound nano material.
Fig. 2 is gained Fe in the embodiment of the present invention 12O3-SnO2The XRD spectra of/Graphene tri compound nano material.
Fig. 3 is gained Fe in the embodiment of the present invention 12O3-SnO2The Raman spectrogram of/Graphene tri compound nano material.
Fig. 4 is gained Fe in the embodiment of the present invention 42O3The TEM picture of/Graphene binary composite nano material.
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 to J. Am. Chem.Soc., 2008,130,5856-5857.
Embodiment 1
First Graphene is produced by existing known technology: first with potassium peroxydisulfate (K2S2O8) and phosphorus pentoxide (P2O5)
Deng material, Graphene carried out in the concentrated sulfuric acid pre-oxidation treatment.The most in concentrated sulfuric acid with potassium permanganate (KMnO4)
Graphite is carried out fully oxidized.Finally carry out post-processing with dilute hydrochloric acid solution and i.e. can get graphene oxide (GO).With above-mentioned
The graphene oxide of preparation is presoma, can prepare single-layer graphene nanometer sheet (rGO) by pyrolysis reduction method；
B. accurately weigh 0.05 g rGO with electronic balance to be dissolved in 35 g deionized waters, ultrasonic 2 h, with preparation all
One stable rGO suspension；
The most accurately pipette 600 l ferric chloride solution (FeCl3·6H2O, 0.12 mol/L) and 450 l stannous chlorides molten
Liquid (SnCl2·2H2O, 0.07 mol/L) join above-mentioned rGO suspension, after stirring a period of time, ultrasonically treated 20 min；
D. above-mentioned mixed solution is poured in band teflon-lined 150 ml autoclave, at 180 DEG C of bars
24 h are reacted under part；
E., after having reacted, product is taken out from reactor, with deionized water and ethanol cyclic washing, centrifugal after, will
Dry at product 60 DEG C, obtain Fe prepared by the present invention2O3-SnO2/ Graphene tri compound nano material.
The sample of gained is carried out physical property sign, and its partial results is as shown in drawings.Gained composite is accordion
The graphene nanometer sheet area load Fe of tile2O3Nano particle (250 nm × 95 about nm)；Additionally, its surface is also
It is attached to the extra small SnO of about 5 ~ 10 nm2Nano particle.
Embodiment 2: preparation process and the step of the present embodiment are substantially the same manner as Example 1, difference is step C:
Accurately pipette 2 ml ferric chloride solution (FeCl3·6H2O, 0.12 mol/L) and 1.5 ml stannous chloride solutions
(SnCl2·2H2O, 0.07 mol/L) join above-mentioned rGO suspension.
Acquired results is different with embodiment 1, when increasing the consumption of source of iron and Xi Yuan by a certain percentage, and Graphene table
The Fe of face load2O3The pattern of nano particle has bigger change, starts Fe strip occur2O3Nano particle, and due to this
Kind of structure can not well be combined with graphene film, reduces the stability of composite, ultrasonically treated after have part Fe2O3Receive
Rice corpuscles obscission.
Embodiment 3: preparation process and the step of the present embodiment are substantially the same manner as Example 1, difference is step C:
Accurately pipette 600 l ferric chloride solution (FeCl3·6H2O, 0.12 mol/L) and 1.5 ml stannous chloride solutions
(SnCl2·2H2O, 0.07 mol/L) join above-mentioned rGO suspension.
Acquired results and embodiment 1 have bigger difference.In the Graphene trielement composite material prepared, graphenic surface loads
Fe2O3Nano particle is gradually long, and the SnO of load on graphenic surface2Nano particle also showed increased.
Comparative example
The preparation process of the present embodiment is identical with embodiment 1 with step, and difference is step C:
Accurately pipette 600 l ferric chloride solution (FeCl3·6H2O, 0.12 mol/L) join above-mentioned rGO suspension, do not have
There is any Xi Yuan of interpolation.
Acquired results is significantly different with embodiment 1.In the Graphene trielement composite material prepared, graphenic surface load
Fe2O3Nano particle does not has the pattern of stable homogeneous, but occurs that larger particles shape stacks, the graphite after ultrasonically treated
Alkene composite, the Fe of its graphenic surface2O3Nano particle has partial exfoliation, and the Fe of the irregular pattern of graininess is described2O3Receive
Rice corpuscles is combined instability with graphene nanometer sheet, illustrates a small amount of Sn simultaneously2+Existence, uniform sheet can be induced
Fe2O3The generation of nano particle.
Seeing accompanying drawing, Fig. 1 is the embodiment of the present invention 1 gained Fe2O3-SnO2The transmission of/Graphene tri compound nano material
Electronic Speculum (TEM) picture.Tem analysis: use Jeol Ltd. JEOL-200CX type transmission electron microscope observation material
Pattern.From TEM picture it can be seen that the Graphene tri compound nano material for preparing of the present invention, maintain complete Graphene
Lamellar structure, the surface of Graphene is uniform-distribution with rectangular pieces stratiform Fe2O3Nano particle, and the most equally distributed
Extra small nano particle is SnO2。
Seeing accompanying drawing, Fig. 2 is the embodiment of the present invention 1 gained Fe2O3-SnO2The XRD of/Graphene tri compound nano material
Spectrogram.XRD analysis: carry out on Japan's RigaKu D/max-2550 type X-ray diffractometer；Use CuK α diffraction.From figure
Understand, Fe2O3The position of diffraction maximum and hematite-type Fe in standard spectrum2O3Standard card (JCPDS No.33-0664) can be very
Good coupling, it was demonstrated that the hematite-type Fe of well-crystallized2O3Successfully load on graphene nanometer sheet.
Seeing accompanying drawing, Fig. 3 is the embodiment of the present invention 1 gained Fe2O3-SnO2The Raman of/Graphene tri compound nano material
Spectrum (Raman) spectrogram.Raman analyzes: use the Invia Raman spectrometer of Reinshaw (Renishaw) company of Britain, and it swashs
Sending out wavelength is 514.5 nm, and sweep limits is 1000-1800 cm-1.From Raman spectrogram it can be seen that be positioned at 1349 cm-1With
1591 cm-1There are characteristic peak D peak and the G peak of the strongest absworption peak, respectively graphene carbon material.Compared with pure Graphene, stone
The I of ink alkene trielement composite materialD/IGChanging, this illustrates after the metal oxide nanoparticles introducing load, Graphene
Disordering degree change, mainly by materials grain boundaries, carbon atom space, interstitial carbon and disordered carbon arrangement etc.
Defect cause.
Seeing accompanying drawing, Fig. 4 is gained Fe in comparative example of the present invention2O3The TEM picture of/Graphene binary composite nano material.
It can be seen that, fashionable when not having any Xi Yuan to add, the Fe of load on graphene nanometer sheet2O3Nano particle pattern heterogeneity, presents
Blocky-shaped particle pile up, material is carried out ultrasonically treated after, the Fe of load2O3Nano particle has obscission, and Fe is described2O3Nanometer
Particle and the combination of graphene film are the most insecure, and the structural stability of material is the best.
Claims (1)
1. a Fe2O3-SnO2The hydrothermal preparing process of/Graphene tri compound nano material, it is characterised in that the tool of the method
Body step is:
A. redox graphene is dissolved in deionized water, is configured to the suspension of 0.20 ~ 0.30 wt%；
B. ferric chloride solution and the stannous chloride solution that concentration is 0.07 mol/L that concentration is 0.12 mol/L are sequentially added into
In 28 ~ 42 mL step a gained suspensions, ultrasonically treated 20 min, obtain mixed solution；Wherein Graphene, chlorine in mixed liquor
The mass ratio changing iron and stannous chloride is 1:0.16 ~ 0.35:0.1 ~ 0.26；
C. by step b gained mixed solution at 180 DEG C of Water Under thermal response 1 ~ 24 h；Product is taken out, through conventional from
The heart, the step washed, dry, obtain Fe2O3-SnO2/ Graphene tri compound nano material.
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| CN105529441B (en) * | 2015-09-17 | 2018-06-01 | 上海大学 | SnO2-TiO2@graphene tri compound nano materials and preparation method thereof |
| CN105950109B (en) * | 2016-04-29 | 2018-09-28 | 安徽理工大学 | Redox graphene, stannic oxide and ferric oxide composite material |
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| CN107381652B (en) * | 2017-07-13 | 2019-11-12 | 济南大学 | A kind of Sn with alcohol sensible effect2O3Nanometer sheet/α-Fe2O3Nanocube heterojunction material |
| CN108034407A (en) * | 2017-12-07 | 2018-05-15 | 上海电机学院 | A kind of preparation method of absorbing material |
| CN108598403B (en) * | 2018-04-16 | 2020-07-24 | 江西师范大学 | Method for forming binary transition metal oxide cathode material of lithium ion battery |
| CN109273675B (en) * | 2018-08-03 | 2020-10-23 | 深圳市山木新能源科技股份有限公司 | Graphene composite material, preparation method thereof and lithium ion battery cathode |
| CN110586100A (en) * | 2019-10-08 | 2019-12-20 | 扬州大学 | Fe2O3/FeO heterostructure and preparation method and application thereof |
| CN112964758B (en) * | 2021-01-29 | 2022-01-25 | 浙江大学 | Manganese dioxide nanosheet/titanium dioxide nanowire array composite resistance type sensor and preparation method and application thereof |
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