CN109682670A - A method of judging whether carbon material is graphene oxide - Google Patents
A method of judging whether carbon material is graphene oxide Download PDFInfo
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- CN109682670A CN109682670A CN201811573889.7A CN201811573889A CN109682670A CN 109682670 A CN109682670 A CN 109682670A CN 201811573889 A CN201811573889 A CN 201811573889A CN 109682670 A CN109682670 A CN 109682670A
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
- G01N23/2055—Analysing diffraction patterns
Abstract
The present invention provides it is a kind of judge carbon material whether be graphene oxide method.The method includes the steps: the first, second, and third sample is separated from carbon material, the first, second sample is heat-treated in the first, second temperature, obtains the first, second heat treated sample；X-ray diffraction test is carried out to the first, second heat treated sample and third sample, obtains the first, second, and third ray test result, Raman spectrum test is carried out to the first and second heat treated samples, obtains the first and second Raman test results；Judge whether carbon material lamella is peeling-off according to third ray test result, judge whether carbon material has oxygen-containing group according to the first, second, and third ray test result and the first and second Raman test results, if judging, carbon material piece interlayer is peeling-off and has oxygen-containing group, and carbon material is graphene oxide.Beneficial effects of the present invention can include: method is easy and effective, can efficiently and accurately identify carbon material.
Description
Technical field
The present invention relates to measuring for materials fields, particularly, be related to it is a kind of it is simple and feasible judge carbon material whether be
The method of graphene oxide.
Background technique
Graphene is sp2The two-dimensional atomic crystal of the hexagonal honeycomb shape structure of the tightly packed formation of carbon atom, can be with heap
Pile forms three-dimensional graphite, curls into one-dimensional carbon nanotube, can also be wrapped to form the fullerene of zero dimension, is carbon material man
One nova of race.But until 2004, the Geim and Novoselov of Univ Manchester UK etc. removed skill using adhesive tape
Art just successfully prepares single-layer graphene for the first time, this discovery has also overthrown scientist about ideal two dimensional crystal material
It existing at room temperature cannot be foretold due to thermodynamic phase.As a kind of ideal two-dimensional atomic crystal, graphene
Conductivity and thermal conductivity, huge theoretical specific surface area with superelevation, high Young's modulus and tensile strength, it is expected to micro-
It is answered in the wide field of nanometer electronic device, Photoelectric Detection and transition material, structure and function enhancing composite material and energy storage etc.
With.
Currently, the preparation method of graphene is numerous, it is basically divided into two class method of Top-down and Bottom-up, wherein
Top-down method includes mechanical phonograph recorder separation and graphite oxide reduction method etc., and Bottom-up method includes chemical vapor deposition
(CVD) method, epitaxial growth method etc..The size that graphene is made in every kind of method is all different, and each method has respectively
Advantage and drawback.Most common is exactly to pass through intercalation, removing, oxidation stone using oxidation-reduction method (such as improvement Hummers method)
The obtained graphite oxide of ink, then graphene oxide solution is made by removing to graphite oxide suspension ultrasound, finally using various
Reducing agent, which restores graphene oxide, just can be obtained redox graphene, this method is meeting us to graphene product as far as possible
While matter requires, production technology is also simplified as far as possible.Based on this method, the technology of preparing of graphene oxide is gradually at this stage
Maturing, but still need to continue to explore, one of maximum bottleneck is just structure-controllable and the rule of the graphene oxide before reduction
Modelling preparation.And utilize different characterization method realizations to the identification of product graphene oxide to the controllable of the above graphene oxide
Metaplasia, which produces, can play crucial directive function, and obtained characterization result is combined the knot analyzed, obtained with basic theory
By for exploring graphene oxide physicochemical characteristics, improving its technology of preparing and further investigation mechanism has important value
And meaning.Accordingly, we have proposed a kind of identification methods of simple and feasible graphene oxide.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to solve above-mentioned one existing in the prior art
Or multiple problems.For example, simple and feasible judging whether carbon material is oxidation stone one of the objects of the present invention is to provide a kind of
The method of black alkene.
To achieve the goals above, the present invention provides it is a kind of judge carbon material whether be graphene oxide method.Institute
The method of stating, which can comprise the following steps that from carbon material, separates the first sample, the second sample and third sample, to the first sample first
Temperature is heat-treated, and the first heat treated sample is obtained, and is heat-treated to the second sample in second temperature, is obtained at the second heat
Manage sample, wherein the first temperature selects within the scope of 450~700 DEG C, and second temperature selects within the scope of 850~1150 DEG C；It is right
First heat treated sample, the second heat treated sample and third sample carry out X-ray diffraction test, accordingly obtain the test of the first ray
As a result, the second ray test result and third ray test result carry out the first heat treated sample and the second heat treated sample
Raman spectrum test, it is corresponding to obtain the first Raman test result and the second Raman test result；According to third ray test result
Judge whether the lamella of carbon material is peeling-off, is drawn according to the first, second, and third ray test result and first and second
Graceful test result judges whether carbon material has oxygen-containing group, if judging result be carbon material piece interlayer it is peeling-off and have
There is oxygen-containing group, then the carbon material is graphene oxide, wherein the whether peeling-off step of the lamella for judging carbon material
It suddenly include: that the crystal parameter of third sample is obtained, and then obtain the crystal face of third sample according to the third ray test result
Spacing, if the interplanar distance of third sample is greater than the interplanar distance of graphite, and compared with the X ray diffracting spectrum of graphite, third
Occur new diffraction maximum on the diffracting spectrum of ray test result, then concludes that the piece interlayer of carbon material is peeling-off, otherwise cannot
Determine that the piece interlayer of carbon material is peeling-off；If it is described judge carbon material whether have the step of oxygen-containing group include: respectively with
Third test result is compared, and diffraction peak width occurs in the diffracting spectrum of the first ray test result and the second ray test result
Change and peak position is deviated to wide-angle, the second ray test result is brighter than wideization of the first ray test result and offset
It is aobvious, moreover, the intensity ratio at the peak D and the peak G is greater than the first Raman test result in the Raman spectrogram of the second Raman test result,
Then concluding has oxygen-containing group in carbon material, otherwise not can determine that carbon material has oxygen-containing group.
In an exemplary embodiment of the present invention, the carbon material can be to obtain according to graphene oxide preparation method
The product arrived, or can be for according to product obtained from redox graphene preparation method.
In an exemplary embodiment of the present invention, the graphite-phase should be the graphene oxide preparation method or
The interplanar distance of the raw material of the redox graphene preparation method, the graphite can be prepared by the following: to described
Graphite carries out X-ray diffraction test, obtains the crystal parameter of graphite, and then obtain the interplanar distance of graphite.
In an exemplary embodiment of the present invention, the crystal parameter may include the indices of crystallographic plane or the angle of diffraction.
In an exemplary embodiment of the present invention, described to obtain in the case where the crystal parameter is the angle of diffraction
The step of interplanar distance can include: interplanar distance, the formula 1 are obtained by formula 1 are as follows: 2dsin θ=n λ, in formula, d is crystalline substance
Interplanar distance, λ are the wavelength of X-ray, and n is diffraction progression, and θ is the 1/2 of the angle of diffraction, i.e. 2 θ are the angle of diffraction.
In an exemplary embodiment of the present invention, diffraction maximum new on the X ray diffracting spectrum may include (100)
Crystallographic plane diffraction peak.
In an exemplary embodiment of the present invention, first temperature can select within the scope of 500~600 DEG C, institute
Stating second temperature can select within the scope of 900~1100 DEG C.
In an exemplary embodiment of the present invention, described to judge whether carbon material there is the step of oxygen-containing group also
Including in the verification step concluded after there is oxygen-containing group in carbon material, the verification step are as follows: from the carbon material
It separates the 4th sample and carries out ftir analysis test, obtain infrared spectrogram, looked on the infrared spectroscopy
Middle infrared is looked for, the carbon material is verified according to the absorption peak on the middle infrared with oxygen-containing group.
In an exemplary embodiment of the present invention, after determining that the carbon material has the step of oxygen-containing group,
The method also includes steps: separating the 5th sample from carbon material and carries out ftir analysis test, obtains red
External spectrum figure；Middle infrared is searched in the infrared spectrogram, reads the corresponding wave number of absorption peak on the middle infrared；It will
The wave number is compared with ir data library, determines the type of oxygen-containing group on the carbon material.
Compared with prior art, beneficial effects of the present invention can include: method is easy and effective, can be efficiently and accurately
Identify carbon material whether be graphene oxide and graphene oxide oxygen-containing group type.
Detailed description of the invention
By the description carried out with reference to the accompanying drawing, above and other purpose of the invention and feature will become more clear
Chu, in which:
Fig. 1 shows the XRD spectra of crystalline flake graphite；
Fig. 2 shows the XRD spectras for the carbon material not being heat-treated；
Fig. 3 shows the XRD spectra of carbon material after 550 degree of heat treatments；
Fig. 4 shows the XRD spectra of carbon material after 1000 degree of heat treatments；
Fig. 5 shows the Raman spectrogram of crystalline flake graphite；
Fig. 6 shows the Raman spectrogram for the carbon material not being heat-treated；
Fig. 7 shows the Raman spectrogram of carbon material after 550 degree of heat treatments；
Fig. 8 shows the Raman spectrogram of carbon material after 1000 degree of heat treatments；
Fig. 9 shows the FTIR spectrum figure for the carbon material not being heat-treated；
Figure 10 shows the FTIR spectrum figure of carbon material after 550 degree of heat treatments；
Figure 11 shows the FTIR spectrum figure of carbon material after 1000 degree of heat treatments.
Specific embodiment
Hereinafter, it will be described in detail in conjunction with attached drawing and exemplary embodiment and of the invention judge whether carbon material is oxygen
The method of graphite alkene.
Whether whether the present invention is mainly peeling-off relative to graphite from piece interlayer, there is oxygen-containing group to identify carbon material
It whether is graphene oxide.For this purpose, X-ray diffraction analysis (XRD) and Raman light that the present invention is mainly used by reasonable combination
Spectrum analysis (Raman) judges whether carbon material is graphene oxide.
When a branch of homogeneous X-ray is irradiated on crystal, the electricity of electronics in crystal around atom by X-ray mechanical periodicity
Field action and vibrate, thus make each electronics become emit spherical electromagnetic wave secondary wave source.The frequency of emitted spherical wave
It is consistent with incident X-ray.Periodicity based on crystal structure, the scattered wave of each atom (electronics on atom) in crystal
It can interfere and be superimposed, referred to as coherent scattering or diffraction.Diffraction phenomena of the X-ray in crystal, it is substantially a large amount of former
The result that sub- scattered wave interferes.Diffraction pattern caused by every kind of crystal all reflects the atom distribution rule of crystals
Rule.According to above-mentioned principle, the feature of the diffraction pattern of certain crystal is most importantly two: 1) distribution of the diffracted ray in space is advised
Rule；2) intensity of diffraction harness.Wherein, the regularity of distribution of diffracted ray is by unit cell dimension, shape, position to and interplanar distance determine,
Diffracted ray intensity then depends on the type, number and arrangement mode of atom in structure cell.Therefore, different crystal has different diffraction
Map.When meeting diffraction conditions, can apply bragg's formula: 2dsin θ=n λ is measured using the X-ray of known wavelength
The angle θ, to calculate interplanar distance d, this is for crystal structure analysis；The other is measuring θ using the crystal of known d
Angle to calculate the wavelength of characteristic X-ray, and then can find element contained in sample in existing data.
Raman spectrum is the effective tool for characterizing carbon nanomaterial structure feature and performance.It is imitated using Raman scattering
It answers, the scattering spectrum different from incident light frequency is analyzed to obtain molecular vibration, rotation aspect information, and be applied to divide
A kind of analysis method of minor structure research.So-called Raman scattering is a kind of inelastic scattering effect of the molecule to photon, when with
The exciting light sub-irradiation period of the day from 11 p.m. to 1 a.m of certain frequency, the frequency of a part scattering light and the frequency of incident light are equal.This scattering is point
A kind of elastic scattering of the son to photon.Collision only between molecule and photon is elastic collision, when not having energy exchange, can just be gone out
Existing this scattering, the scattering are known as Rayleigh scattering.The frequency of some scattering light and the frequency of exciting light differ, this to dissipate
Penetrating becomes Raman scattering (and being divided into stockes line and anti-stockes line).And the Raman scattering signal is received and drawn
The method of spectrum analysis can be described as Raman spectrum analysis, and common scattered signal is stockes line.Carbon nanomaterial Raman light
The peak G (1580cm in spectrum-1Near) represent sp2The E of carbon atom2gModel of vibration represents orderly sp2Bond structure, the peak D
(1350cm-1Near) defect and amorphous structure for being located at graphene edge are then represented, usually use the intensity ratio at the peak D and the peak G
ID/IGTo evaluate the degree of graphitization of nano-carbon material, ID/IGIt is worth smaller, shows that the order degree of graphite is higher, ratio is bigger,
Show that the unordered degree of graphite is bigger.
In an exemplary embodiment of the present invention, the test method can comprise the following steps that
The first sample, the second sample and third sample are separated from carbon material, hot place is carried out in the first temperature to the first sample
Reason, obtains the first heat treated sample, is heat-treated to the second sample in second temperature, obtains the second heat treated sample.Wherein,
First temperature can select within the scope of 450~700 DEG C, and second temperature can select within the scope of 850~1150 DEG C.As wait judge
The carbon material of object can be for by treated the graphite type material of the oxidation operation in graphene processing technology.
X-ray diffraction test is carried out to the first heat treated sample, the second heat treated sample and third sample, accordingly obtains the
One ray test result, the second ray test result and third ray test result, at the first heat treated sample and the second heat
It manages sample and carries out Raman spectrum test, it is corresponding to obtain the first Raman test result and the second Raman test result.Wherein, described
One ray test result, the second ray test result and third ray test result may include X-ray diffractogram, and the first Raman is surveyed
Test result and the second Raman test result may include Raman spectrogram.
Judge whether the lamella of carbon material is peeling-off according to third ray test result, according to first, second, and third
Ray test result and the first and second Raman test results judge whether carbon material has oxygen-containing group, if judging result is
The piece interlayer of carbon material is peeling-off and has oxygen-containing group, then the carbon material is graphene oxide.Wherein,
The third ray test result judges that the whether peeling-off step of the lamella of carbon material includes: according to described
Trilete rays test result, obtains the crystal parameter of third sample, and then obtains the interplanar distance of third sample, if third sample
Interplanar distance is greater than the interplanar distance of graphite, and compared with the X ray diffracting spectrum of graphite, the diffraction of third ray test result
Occur new diffraction maximum on map, then concludes that the piece interlayer of carbon material is peeling-off, otherwise not can determine that the piece interlayer of carbon material
It is peeling-off.Wherein, crystal parameter may include 2 θ of the indices of crystallographic plane or the angle of diffraction.The interplanar of carbon material is obtained according to crystal parameter
Away from.In the case where crystal parameter is 2 θ of the angle of diffraction, interplanar distance, formula 1 can be obtained by formula 1 are as follows: 2dsin θ=n λ, formula
In, d is interplanar distance, and λ is the wavelength of X-ray, and n is diffraction progression.Wherein, the interplanar distance of graphite can be known data,
It can also obtain by the same method.New diffraction maximum may include (100) crystallographic plane diffraction peak on the carbon material diffracting spectrum.
Described, if to judge whether carbon material has the step of oxygen-containing group include: respectively compared with third test result
There is diffraction peaks broadening in the diffracting spectrum of one ray test result and the second ray test result and peak position is inclined to wide-angle
It moves, the second ray test result becomes apparent from than wideization of the first ray test result and offset, moreover, the second Raman is tested
As a result in Raman spectrogram the intensity ratio at the peak D and the peak G be greater than the first Raman test result, then conclude in carbon material have contain
Otherwise oxygen groups not can determine that carbon material has oxygen-containing group.
In the present embodiment, the object carbon material that the present invention identifies may include the doubtful carbon material for graphene oxide.Carbon
Material can be for according to product obtained from graphene oxide preparation method；Carbon material can also be to prepare according to redox graphene
Product obtained from method.I.e. the present invention can be to being prepared whether carbon material is graphene oxide or redox graphene
It is identified.
In the present embodiment, graphite can prepare raw material for carbon material.Graphite may include crystalline flake graphite.
In the present embodiment, the crystal face interlamellar spacing of the graphite can be 0.3~0.4nm.
The crystal face interlamellar spacing of graphite can be obtained by above-mentioned method, i.e., carry out X-ray diffraction test to graphite, obtain stone
The crystal parameter of ink, and then obtain the interplanar distance of graphite.
In the present embodiment, ID/IGNumerical value can be used to indicate the degree of order.The method may further comprise the step of: in oxidation stone
In the qualification process of black alkene, in combination with the obtained Raman spectrum of test, by the strong and weak size at the peak comparative analysis G and the peak D and its
Ratio ID/IG, widthization degree can know lattice defect degree of the carbon material compared to graphite, the variation of structurally ordered degree respectively.
Wherein, the infrared spectrogram of graphite can be obtained by carrying out Raman spectrum test to graphite, with this and carbon material into
Row compares.
In the present embodiment, further, the first temperature and second temperature may respectively be 500~600 DEG C, 900~1100
℃。
For example, described by carbon material includes: the heating prompt drop with 5~10 DEG C/min the step of being heat-treated for 550 DEG C
By carbon material by heat to 550 DEG C, 1~180min, such as 100 ± 20min are kept the temperature, then cooled to room temperature.
Described by carbon material includes: with the heating prompt drop of 5~10 DEG C/min the step of being heat-treated for 1000 DEG C by carbon
Heat to 1000 DEG C, is kept the temperature 1~180min, such as 100 ± 20min, then cooled to room temperature by material.
It is in the present embodiment, described that judge whether carbon material has the step of oxygen-containing group further include concluding carbon materials described
With the verification step after oxygen-containing group in material, the verification step can are as follows: separates the 4th sample from the carbon material and carries out
Ftir analysis test, obtains infrared spectrogram, searches middle infrared on the infrared spectroscopy, according to institute
The absorption peak on middle infrared is stated to verify the carbon material with oxygen-containing group.
In the present embodiment, the method may further comprise the step of: red from reading in the infrared spectrogram of the carbon material
The wave number is compared with the database of infrared spectrogram, determines the carbon materials by wave number corresponding to the absorption peak of outskirt
The type of oxygen-containing group on material.
Specifically, the step of determining oxygen-containing group can include:
The first step finds the middle infrared (2.5~25 μm) in carbon material infrared spectrogram.
Second step finds characteristic frequency area (2.5~7.7 μm, i.e. 4000~1330cm-1) and fingerprint region (7.7~16.7 μ
M, i.e. 1330~400cm-1)。
Step 3: determining what function the group is according to the corresponding wave number comparison infrared spectrum database of characteristic peak
Group.Such as: 1725cm-1It is the stretching vibration of carbonyl C==O on carboxyl；1615cm-1It is the flexible vibration of carbon-carbon double bond C==C
It is dynamic；1373cm-1It is the stretching vibration of C-OH；And 1078cm-1It is the stretching vibration of epoxy group C-O-C.
The above exemplary embodiments for a better understanding of the present invention carry out further it below with reference to specific example
Explanation.
Crystalline flake graphite in example is the raw material for preparing graphene oxide, and carbon material is to prepare obtained from graphene oxide
Product.
(1) X-ray diffraction test is carried out to the carbon material after the heat treatment of crystalline flake graphite, carbon material and different temperatures, and obtained
To corresponding XRD spectra.
Fig. 1 shows the XRD spectra of crystalline flake graphite, and Fig. 2 shows the XRD spectra of carbon material, Fig. 3 and Fig. 4 show respectively
Gone out 550 DEG C, 1000 DEG C heat treatment after carbon material XRD spectra.
If Fig. 1 shows, crystalline flake graphite characteristic peak positions are in 2 θ=26.2 °, and corresponding crystal face is (002), in conjunction with Bragg equation
2dsin θ=n λ (d is crystal face interlamellar spacing, and θ is the angle of diffraction, and n is diffraction progression, and λ is the wavelength of X-ray) calculates to obtain interlamellar spacing d
=0.34nm.
What by Fig. 2, we were tested is not heat-treated the XRD spectra of meal material, observes its (001) crystallographic plane diffraction peak angle
Degree is 2 θ=10.4 °, is computed to obtain carbon material layer spacing d=0.85nm at this time, and interlamellar spacing obviously expands compared with crystalline flake graphite,
In addition in the appearance of its 43 ° neighbouring (100) crystallographic plane diffraction peak, illustrate that obvious removing has occurred in carbon material between layers.
After carrying out high-temperature heat treatment to carbon material, if it is graphene oxide, oxygen-containing group therein will be with carbon original
Son reacts, and causes the reduction of oxygen-containing group number and carbon-coating defect increases, the generation of its diffraction maximum is shown as in Fig. 3~Fig. 4
It is significantly broadened, and peak position is deviated to wide-angle direction, and with the raising of heat treatment temperature, the above variation is more obvious.More than
As a result illustrate in the carbon material sample of test piece interlamellar spacing significantly increase and may containing some oxygen-containing groups, after heat treatment with
Oxygen-containing group reduce, graphite flake layer spacing reduction causes crystallite dimension to reduce, while lattice defect increase, and crystal structure to
The transformation of class graphite can also specifically be confirmed in subsequent Raman characterization.
(2) Raman spectrum test is carried out to the carbon material after the heat treatment of crystalline flake graphite, carbon material and different temperatures, and obtained
Corresponding Raman spectrogram.
Fig. 5 shows the Raman spectrogram of crystalline flake graphite, and Fig. 6 shows the Raman spectrogram of carbon material, Fig. 3 and Fig. 4
Respectively illustrate 550 DEG C, 1000 DEG C heat treatment after carbon material Raman spectrogram.
Graphite raw material is 1360,1580cm in the Raman shift of first order Raman Spectrum area as can see from Figure 5-1There are two nearby
Apparent Raman peaks correspond respectively to D band and G band, and the peak D is usually by sp in carbocyclic ring2The mode of atom breathing vibration generates, and the peak G is then
By all sp in carbocyclic ring and long-chain2The extensional motion of atom pair generates, but is both by sp2Caused by chemical bond oscillations.?
It is not in the peak D in the Raman spectrum of complete graphite monocrystalline, and it is defective in graphite sample or disordered structure position is collected
When Raman scattering light, D bands of a spectrum can be just generated in Raman spectrum, as in Fig. 5 crystalline flake graphite in 1360cm-1The Raman nearby occurred
Peak, and no matter be the unordered of which kind of form in structure, D band can all occur, and be interpreted unordered induction Raman mould, by Graphite cloth
Caused by the double resonance Raman scattering processes that the phonon of the area Li Yuan K Near The Critical Point participates in.Second order Raman spectrum region in Fig. 5
2717cm-1Neighbouring stronger peak corresponds to D' band, be the peak D and frequency and frequency multiplication peak, the double resonance drawing participated in originating from biphonon
Graceful scattering, complete graphite crystal and it is defective in the presence of be Raman allow, therefore have stronger Raman signal.
The Raman spectrum (Fig. 5) of graphite is compared, the Raman spectrum of non-heat treated carbon material shows as G peak broadening, D in Fig. 6
Peak broadening and enhancing.The reason of generating this phenomenon may be interpreted as: graphite is after aoxidizing, carbon atom and oxygen-containing group in graphite flake layer
Group is bonded, the opposite disordered structure of carbon atom bonding in the form of sp3 hydridization, the symmetry of graphite lattice, long range order occurs
It is destroyed, this and the available confirmation of XRD spectra result before this.In Fig. 7~Fig. 8, with the raising of heat treatment temperature, the peak D
It gradually increases, R=ID/IGBe gradually increased, and due in the Raman characterization of nano-carbon material the peak G represent orderly sp2Bond
Structure, the peak D then represent the defect and amorphous structure positioned at graphene edge, and R value increase explanation is during heat treatment due to containing
The effect of oxygen groups and carbon causes defect in sheet of material to increase, and opposite disordered structure increases, after this conclusion and above-mentioned heat treatment
Resulting XRD spectra analysis result matches, and then can further verify us and obtain graphene oxide composite material.Heat treatment
Afterwards, R value increase explanation is during heat treatment since the effect of oxygen-containing group and carbon causes defect in sheet of material to increase, i.e., hot
Defect increases after processing, disordered structure increases.
(3) present invention can also further verify depositing for oxygen-containing group by ftir analysis test
?.Fig. 9 shows the FTIR spectrum figure (i.e. infrared spectrogram) of not thermally treated carbon material, and Figure 10 and Figure 11 are respectively illustrated
550 DEG C, 1000 DEG C heat treatment after carbon material infrared spectrogram.According to the infrared spectrogram of carbon material, we not only may be used
It, can be with the type of qualitative analysis wherein oxygen-containing group with the presence with verifying oxygen-containing group.
As shown in Figure 9, fitting result shows in 3198cm-1Nearby there is an absorption band, graphite oxide structure should be belonged to
- OH the stretching vibration of middle hydroxyl；2926,2854cm in Fig. 9-1Place peak is respectively belonging to CH2Antisymmetry, symmetrical stretching vibration；
1733cm-1Neighbouring peak belongs to carbon material lamella edge carboxyl, the C=O stretching vibration in carbonyl；1630cm-1Neighbouring peak
Belong to-OH the bending vibration of hydrone；1400cm-1Neighbouring peak belongs to the OH bending vibration of hydroxyl in structure；1247cm-1Neighbouring peak belongs to the C-O stretching vibration in carboxyl；1122cm-1Neighbouring peak belongs to the stretching vibration of C-O-C；
1054cm-1The stretching vibration that should belong to C-OH is returned at neighbouring peak；And 2345,617cm-1Absorption peak at two may be due to carbon
A small amount of CO of material absorption2In the asymmetric stretching vibration of molecule, face caused by (outer) bending vibration.These oxygen-containing groups are deposited
Illustrating that graphite has been oxidized, and these polar groups especially surface hydroxyl is easy to graphene oxide and hydrone
Hydrogen bond is formed, this is also that graphene oxide has the reason of excellent hydrophilic.
The results of FT-IR shows: graphitic carbon generates on the carbon atom in big pi bond a variety of containing oxygen key, such as C=O after oxidation
With C-O etc., make part sp2Hybridized orbit is changed into sp3Hybridized orbit, this and I in above-mentioned carbon material Raman spectrumD/IGIncrease
Big result matches.As shown in Figure 10 and Figure 11, oxygen-containing group tails off, this is because carrying out heat treatment process high temperature item
It reacts between oxygen-containing group and carbon atom under part, causes chemical bond rupture to generate gas molecule, lead to the reduction of oxygen-containing group,
This process also further increases the defect concentration of carbon material layer, matches with the Raman spectrogram after above-mentioned heat treatment.
In conclusion of the invention judges the advantages of whether carbon material is graphene oxide method can include: method is easy
And it is effective, can efficiently and accurately judge whether the product of different material and method production is graphene oxide, Yi Jijian
Determine the type of functional group on graphene oxide.
Although those skilled in the art should be clear above by combining exemplary embodiment to describe the present invention
Chu can carry out exemplary embodiment of the present invention each without departing from the spirit and scope defined by the claims
Kind modifications and changes.
Claims (9)
1. it is a kind of judge carbon material whether be graphene oxide method, which is characterized in that the described method comprises the following steps:
The first sample, the second sample and third sample are separated from carbon material, the first sample is heat-treated in the first temperature, is obtained
To the first heat treated sample, the second sample is heat-treated in second temperature, obtains the second heat treated sample, wherein first
Temperature selects within the scope of 450~700 DEG C, and second temperature selects within the scope of 850~1150 DEG C；
X-ray diffraction test is carried out to the first heat treated sample, the second heat treated sample and third sample, first is accordingly obtained and penetrates
Line test result, the second ray test result and third ray test result, to the first heat treated sample and the second heat treatment sample
Product carry out Raman spectrum test, corresponding to obtain the first Raman test result and the second Raman test result；
Judge whether the lamella of carbon material is peeling-off according to third ray test result, according to the first, second, and third ray
Test result and the first and second Raman test results judge whether carbon material has oxygen-containing group, if judging result is carbon materials
The piece interlayer of material is peeling-off and has oxygen-containing group, then the carbon material is graphene oxide, wherein
The whether peeling-off step of the lamella for judging carbon material includes: to be obtained according to the third ray test result
The crystal parameter of third sample, and then the interplanar distance of third sample is obtained, if the interplanar distance of third sample is greater than graphite
Interplanar distance, and compared with the X ray diffracting spectrum of graphite, there is new diffraction on the diffracting spectrum of third ray test result
Peak then concludes that the piece interlayer of carbon material is peeling-off, otherwise not can determine that the piece interlayer of carbon material is peeling-off；
Described, if to judge whether carbon material has the step of oxygen-containing group include: respectively compared with third test result, and first penetrates
There is diffraction peaks broadening in the diffracting spectrum of line test result and the second ray test result and peak position is deviated to wide-angle, the
Two ray test results become apparent from than wideization of the first ray test result and offset, moreover, the second Raman test result
Raman spectrogram in the intensity ratio at the peak D and the peak G be greater than the first Raman test result, then conclude in carbon material have oxygen-containing group
Otherwise group not can determine that carbon material has oxygen-containing group.
2. it is according to claim 1 judge carbon material whether be graphene oxide method, which is characterized in that the carbon materials
Material is according to product obtained from graphene oxide preparation method, or to obtain according to redox graphene preparation method
Product.
3. it is according to claim 2 judge carbon material whether be graphene oxide method, which is characterized in that the graphite
It mutually should be the raw material of the graphene oxide preparation method or the redox graphene preparation method,
The interplanar distance of the graphite is prepared by the following: being carried out X-ray diffraction test to the graphite, is obtained graphite
Crystal parameter, and then obtain the interplanar distance of graphite.
4. it is according to claim 1 judge carbon material whether be graphene oxide method, which is characterized in that the crystal
Parameter includes the indices of crystallographic plane or the angle of diffraction.
5. it is according to claim 4 judge carbon material whether be graphene oxide method, which is characterized in that in the crystalline substance
In the case that body parameter is the angle of diffraction, described the step of obtaining interplanar distance includes: that interplanar distance is obtained by formula 1, described
Formula 1 are as follows:
2dsin θ=n λ,
In formula, d is interplanar distance, and λ is the wavelength of X-ray, and n is diffraction progression, and θ is the 1/2 of the angle of diffraction.
6. it is according to claim 1 judge carbon material whether be graphene oxide method, which is characterized in that it is described new
Diffraction maximum includes (100) crystallographic plane diffraction peak.
7. it is according to claim 1 judge carbon material whether be graphene oxide method, which is characterized in that described first
Temperature selects within the scope of 500~600 DEG C, and the second temperature selects within the scope of 900~1100 DEG C.
8. it is according to claim 1 judge carbon material whether be graphene oxide method, which is characterized in that the judgement
It further includes in the verifying step concluded after having oxygen-containing group in carbon material that whether carbon material, which has the step of oxygen-containing group,
Suddenly, the verification step are as follows:
The 4th sample is separated from the carbon material and carries out ftir analysis test, obtains infrared spectrogram,
Middle infrared is searched on the infrared spectroscopy, the carbon material is verified according to the absorption peak on the middle infrared with oxygen-containing
Group.
9. it is according to claim 1 judge carbon material whether be graphene oxide method, which is characterized in that determining
After stating carbon material there is the step of oxygen-containing group, the method also includes:
The 5th sample is separated from carbon material and carries out ftir analysis test, obtains infrared spectrogram；
Middle infrared is searched in the infrared spectrogram, reads the corresponding wave number of absorption peak on the middle infrared；
The wave number is compared with ir data library, determines the type of oxygen-containing group on the carbon material.
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