CN109613030A - A method of determining whether carbon material is doping graphene oxide - Google Patents
A method of determining whether carbon material is doping graphene oxide Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 46
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Classifications
-
- 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
-
- 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
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
-
- 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
Abstract
It whether is the method for adulterating graphene oxide the present invention provides a kind of judgement carbon material.The method, which can comprise the following steps that from carbon material, separates the first sample, the second sample, carries out X-ray diffraction test to the first sample, obtains X ray diffracting spectrum, carries out ftir analysis test to the second sample, obtains infrared spectrogram；Determine whether the lamella of carbon material is peeling-off according to the X ray diffracting spectrum, determine whether carbon material has oxygen-containing group according to the infrared spectrogram, if it is determined that result be carbon material piece interlayer it is peeling-off and have oxygen-containing group, then the carbon material is graphene oxide, then determines whether the carbon material is the classification for adulterating graphene oxide and identification doping.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 a kind of simple and feasible judgement carbon material whether be
The method for adulterating graphene oxide.
Background technique
Graphene (Graphene) is by sp2Plane hexagonal lattice knot made of the single layer of carbon atom close-packed arrays of hydridization
Structure, 4 electronics of C outermost layer carry out sp with the C atom of surrounding wherein 3 electronics participate in the bonding of graphene2Hydridization forms C-C
Key, remaining one electronically form can in graphene planes the free-moving big pi bond of delocalization.Graphene is logical in 2004 earliest
The lamellar graphite alkene that the method for crossing adhesive tape removing obtains, hereafter causes extensive research interest.Research finds that graphene has
Many excellent performances, as high-termal conductivity (5000W/mK), high carrier migrate (200000cm2V-1s-1), high-specific surface area
(2630m2/ g), room-temperature quantum Hall effect etc..
Compared with graphene, the element of graphene oxide is formed and is not fixed, and there are hydroxyls (- OH), ring for graphene oxide
The oxygen-containing functional groups such as oxygroup [- C (O) C-], carbonyl (- C=O), carboxyl (- COOH), ester group (- COO-).Due to these oxygen-containing officials
The thickness of the presence that can be rolled into a ball, graphene oxide is much higher than graphene, makes its Partial Physical Property, such as electric conductivity, mechanical property etc.
It is greatly reduced.But these oxygen-containing functional groups make graphene oxide have good dispersibility and reactivity, graphene oxide
In oxygen-containing functional group etc. be easy to occur with the compound containing amino, carboxyl, isocyanate group etc. with reproducibility group it is anti-
It answers, various doping is carried out to graphene oxide to realize.
The doping for carrying out N, P, S etc. to graphene oxide can effectively adjust its band structure and physical and chemical performance.
Graphene oxide current density, methanol tolerance and good cyclical stability with higher are adulterated, and is mixed containing nitrogen, phosphorus atoms
Miscellaneous graphene oxide can be used as efficient flame-retarding agent, and crucial effect is played to graphene oxide fire-retardant film.
And different characterization methods is utilized to realize the identification to doping graphene oxide to the controllable of doping graphene oxide
Metaplasia, which produces, can play crucial directive function, and obtained characterization result is combined the knot analyzed, obtained with basic theory
There is important value and significance by for exploring doping graphene oxide physicochemical characteristics.Accordingly, we have proposed one kind
The identification method of simple and feasible doping 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, whether being doping oxygen one of the objects of the present invention is to provide a kind of simple and feasible judgement carbon material
The method of graphite alkene.
It to achieve the goals above, whether is the side for adulterating graphene oxide the present invention provides a kind of judgement carbon material
Method.The method, which can comprise the following steps that from carbon material, separates the first sample, the second sample, carries out X-ray to the first sample and spreads out
Test is penetrated, X ray diffracting spectrum is obtained, ftir analysis test is carried out to the second sample, obtains infrared light
Spectrogram；Judge whether the lamella of carbon material is peeling-off according to the X ray diffracting spectrum, is judged according to the infrared spectrogram
Whether carbon material has oxygen-containing group, if it is determined that result be carbon material piece interlayer it is peeling-off and there is oxygen-containing group, then institute
Stating carbon material is graphene oxide, in the case where the carbon material is graphene oxide, determines whether the carbon material is to mix
Miscellaneous graphene oxide, wherein the whether peeling-off step of the lamella for determining carbon material includes: to be spread out according to the X-ray
Map is penetrated, the crystal parameter of the first sample is obtained, and then obtains the interplanar distance of the first sample, if the interplanar distance of the first sample
Occur new spread out greater than the interplanar distance of graphite, and compared with the X ray diffracting spectrum of graphite, on the X ray diffracting spectrum
Peak is penetrated, 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；The judgement
It includes: to search middle infrared in the infrared spectrogram that whether carbon material, which has the step of oxygen-containing group, according to red in described
Absorption peak on outskirt determines whether the carbon material has oxygen-containing group；Whether the judgement carbon material is doping oxidation stone
The step of black alkene includes: that third sample is separated from the carbon material, carries out X-ray photoelectron spectroscopic analysis survey to third sample
Examination, obtains x-ray photoelectron spectroscopy figure, if there is new peak in addition to the peak C1S and the peak OlS on the x-ray photoelectron spectroscopy figure,
Determine whether graphene oxide is doping graphene oxide according to the corresponding combination energy size of the new peak.
In an exemplary embodiment of the present invention, described after determining the carbon material for doping graphene oxide
Method may further comprise the step of:
Utilize the new peak and the corresponding knot of new peak occurred in addition to the peak C1S and the peak OlS on the x-ray photoelectron spectroscopy figure
Conjunction can determine that doped chemical type, and the doping side of doping graphene oxide is determined according to the corresponding combination energy size of the new peak
Formula is impurity or absorption doping.
In an exemplary embodiment of the present invention, described after determining the carbon material for doping graphene oxide
Method may further comprise the step of: separates the 4th sample from the carbon material, carries out Raman spectrum test to the 4th sample, is drawn
Graceful spectrogram,
If the peak G blue shift and the red shift of the peak G' in the Raman spectrogram, determine that the doping way of the carbon material is mixed for N-shaped
It is miscellaneous；If the peak G blue shift and the peak G' blue shift, determine that adulterating the doping way of graphene oxide is p-type doping；
Alternatively, with to the 4th sample Koln anomalous effect weaken, if in the Raman spectrogram peak G be displaced to high wave number and
The peak G' is displaced to lower wave number, then determines the doping way of the carbon material for n-type doping；If in the Raman spectrogram peak G to
High wave number is displaced and the peak G' is displaced to high wave number, then determines that adulterating the doping way of graphene oxide is p-type doping.
In an exemplary embodiment of the present invention, the method may further comprise the step of: according to the x-ray photoelectron
The area ratio of new peak determines the content of doped chemical in energy spectrum diagram.
In an exemplary embodiment of the present invention, the method may further comprise the step of: to the x-ray photoelectron energy
New peak carries out swarming fitting on spectrogram, determines doped chemical chemical bond configuration type.
In an exemplary embodiment of the present invention, the method may further comprise the step of: according to the x-ray photoelectron
New peak carries out the corresponding area ratio in sub- peak after swarming fitting in energy spectrum diagram, determines that the percentage of doped chemical chemical bond configuration contains
Whether amount and determining doped chemical exist in the form of compound state.
In an exemplary embodiment of the present invention, it is described doping graphene oxide doped chemical include nitrogen, phosphorus and
At least one of sulphur.
In an exemplary embodiment of the present invention, the graphite-phase should be the raw material for preparing the carbon material, described
The interplanar distance of graphite can be prepared by the following: being carried out X-ray diffraction test to the graphite, obtained the crystal ginseng of graphite
Number, 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, the wavelength of the middle infrared is 2.5~25 μm.
In an exemplary embodiment of the present invention, the middle infrared includes characteristic frequency area and fingerprint region, described
The wavelength in characteristic frequency area is 2.5~7.7 μm, and the wavelength of the fingerprint region is greater than 7.7 μm, is less than or equal to 25 μm.
In an exemplary embodiment of the present invention, after determining that the carbon material has the step of oxygen-containing group,
The method, which may further comprise the step of:, searches middle infrared in the infrared spectrogram, reads absorption peak on the middle infrared
Corresponding wave number；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 whether carbon material is doping graphene oxide, and is the type for adulterating graphene oxide.
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 in example；
Fig. 2 shows the XRD spectras of carbon material in example；
Fig. 3 shows the FTIR abosrption spectrogram of carbon material in example.
Specific embodiment
Hereinafter, it will describe whether judgement carbon material of the invention is to mix in detail in conjunction with attached drawing and exemplary embodiment
The method of miscellaneous 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.
Ftir analysis test is a kind of according to the interatomic Relative Vibration of intramolecule and molecule turn
The information such as dynamic determine material molecular structure and identify the analysis method of compound.Molecular motion has translation, rotation, vibration and electricity
Four kinds of son movement, wherein latter three kinds are quantum motion.Molecule absorbs the photon that an energy is hv from lower energy level E1, can
To transit to higher energy level E2, entire motion process meets law of conservation of energy E2-E1=hv.Differ smaller between energy level,
The frequency for the light that molecule is absorbed is lower, and wavelength is longer.Infrared absorption spectrum be as caused by molecular vibration and rotational transition,
Constitutional chemistry key or the atom of functional group are in the state of constantly vibration (or rotation), the vibration frequency of vibration frequency and infrared light
Rate is suitable.So absorption of vibrations, different changes can occur for chemical bond or functional group in molecule when with Infrared irradiation molecule
It learns key or functional group's absorption frequency is different, different location will be on infrared spectroscopy, to can get in molecule which kind of contains
The information of chemical bond or functional group.The rotational energy level difference of molecule is smaller, and the light frequency absorbed is low, and wavelength is very long, so point
The pure rotational spectrum of son appears in far-infrared band (25~300 μm).Vibrational energy is differential more much bigger than rotational energy level difference, molecule vibration
The light frequency that kinetic energy order transition is absorbed wants higher, and the pure vibrational spectrum of molecule is generally present in middle infrared (2.5~25 μ
m).Only when vibration, when the dipole moment of molecule changes, which just has infrared active；If when vibration, molecule
Polarizability changes, then the vibration has Raman active.
X-ray photoelectron spectroscopy (X-ray photoelectron spectroscopy, XPS) can provide the element of sample
Composition, chemical valence state and related electronic structure important information are a technologies for analyzing substance surface chemical property, are one
Kind is based on photoelectric electron spectrum, it is the inner electron that material surface atom is inspired using x-ray photon, by right
These electronics carry out energy spectrometer and a kind of power spectrum for obtaining.The surface of solids is excited with beam of x-rays, while measuring analyzed material
Launch the kinetic energy of electronics in material 1~10nm of surface, and obtains XPS spectrum.Photoelectron spectrum record is more than the electronics of certain kinetic energy, light
The spectral peak occurred in electron Spectrum is the transmitting of certain characteristic energy electronics in atom, and the energy and intensity of photoelectron spectral peak can be used for
Qualitative and quantitative analysis all surface element.
Raman spectrum be the characterization material crystal structure of quick nondestructive a kind of, electronic band structure, phonon energy dispersion and
The important technological means of Electron-phonon coupling, the fault of construction (peak D) of graphene, sp2The in plane vibration (peak G) of carbon atom
Good embodiment has been obtained in Raman spectrum with information such as the interlayer way of stacking (peak G') of carbon atom.
In an exemplary embodiment of the present invention, the test method can comprise the following steps that
(1) judge whether the carbon material is graphene oxide.Whether the present invention mainly sends out from piece interlayer relative to graphite
Whether raw removing there is oxygen-containing group to identify whether carbon material is graphene oxide.For this purpose, the present invention mainly passes through reasonable group
The X-ray diffraction analysis (XRD) used and ftir analysis (FTIR) are closed to judge whether carbon material is oxygen
Graphite alkene.
The first sample, the second sample are separated from carbon material, X-ray diffraction test is carried out to the first sample, X-ray is obtained and spreads out
Map is penetrated, ftir analysis test is carried out to the second sample, obtains infrared spectrogram.As object to be determined
Carbon material can be for by treated the graphite type material of the oxidation operation in graphene processing technology.
Judge whether the lamella of carbon material is peeling-off according to the X ray diffracting spectrum, according to the infrared spectrogram
Judge whether carbon material has oxygen-containing group, if judging result be carbon material piece interlayer it is peeling-off and have oxygen-containing group,
Then the carbon material is graphene oxide.
The whether peeling-off step of the lamella for judging carbon material can include: according to the X ray diffracting spectrum, obtain
The crystal parameter of the first sample is obtained, and then obtains the interplanar distance of the first sample, if the interplanar distance of the first sample is greater than graphite
Interplanar distance, and occur new diffraction maximum compared with the X ray diffracting spectrum of graphite, on X ray diffracting spectrum, then conclude carbon
The piece interlayer of material is peeling-off, otherwise not can determine that the piece interlayer of carbon material is peeling-off.Wherein, crystal parameter may include crystalline substance
2 θ of facial index or the angle of diffraction.The interplanar distance of carbon material is obtained according to crystal parameter.The case where crystal parameter is 2 θ of the angle of diffraction
Under, interplanar distance, formula 1 can be obtained by formula 1 are as follows: 2dsin θ=n λ, in formula, d is interplanar distance, and λ is the wave of X-ray
Long, n is diffraction progression.Wherein, the interplanar distance of graphite can be known data, can also obtain by the same method.It is described
New diffraction maximum may include (100) crystallographic plane diffraction peak on carbon material diffracting spectrum.
It is described judge carbon material whether have the step of oxygen-containing group include: in the infrared spectrogram search in it is infrared
Area judges that the carbon material has oxygen-containing group according to the absorption peak on the middle infrared.If carbon material is graphite oxide
Different absorption peaks can be obtained since chemical bond or group different on graphene oxide are to the difference of infrared Absorption frequency in alkene
The infrared absorption spectrum of position, can be obtained the group or chemical bond classification of corresponding absorption peak after carrying out swarming fitting to it, by
This can quickly and easily determine the presence of oxygen-containing group on graphene oxide.
(2) determine whether carbon material is doping graphene oxide.
Sample is separated from carbon material, and X-ray photoelectron spectroscopic analysis test is carried out to the sample, obtains X-ray light
Electronic energy spectrum.If there is new peak in addition to the peak C1S and the peak OlS on the x-ray photoelectron spectroscopy figure, according to the new peak pair
The combination energy position (combining energy size) answered determines whether graphene oxide is doping graphene oxide.
(3) in the case where determining carbon material to adulterate graphene oxide, determine the classification of doping graphene oxide.This hair
It is bright that the classification of doping graphene oxide is just carried out by X-ray photoelectron spectroscopic analysis test, Raman spectrum analysis test
Determine.
Specifically, determine that doping graphene oxide classification can comprise the following steps that
1) the XPS Momentum profiles figure of graphene oxide to be measured, of x-ray photoelectron spectroscopy figure (XPS map peak) are analyzed
Several and position, can accurately provide the chemical bond present in graphene oxide, it is possible thereby to analyze graphene oxide doped
Element species and doping type.Specifically, graphene oxide only occur at 284.6eV and 531.8eV C1S and
The peak OlS, and in doping graphene oxide, it removes except combination can be for corresponding peak at 284.6eV and 531.8eV, can also
There is new peak.It can be determined that the doped chemical kind in doping graphene oxide according to the new peak of appearance and the corresponding combination of new peak
Class.Also, according to new peak to combination energy position can also determine adulterate graphene oxide doping way be impurity
Or absorption doping.For example, can intuitively can determine to adulterate graphene oxide according to the position of the corresponding combination energy of new peak
It whether is absorption doping.
2) sample is separated from carbon material again, and Raman spectrum analysis test is carried out to the sample, obtains Raman spectrogram.
P-type or n-type doping will affect the Electron-phonon coupling of graphene, so as to cause Raman shift.In Raman spectrum
Scheme in (Raman spectrogram), in the case where the peak G blue shift and the red shift of the peak G', it is possible to determine that adulterate the doping side of graphene oxide
Formula is n-type doping.In the case where the peak G blue shift and the peak G' blue shift, it is possible to determine that the doping way for adulterating graphene oxide is p
Type doping.
Alternatively, the Raman G summit of the graphene oxide after doping is with its Koln for the graphene oxide after doping
Anomalous effect (Kohn anomaly) weakens and is displaced to high wave number, and the peak G' is displaced in n-type doping to lower wave number, and p-type is mixed
Miscellaneous Shi Xianggao wave number position, it is possible thereby to determine that the doping graphene oxide adulterates for n-type doping or p-type.
It in the present embodiment, can also be according to the X-ray photoelectricity during determining to adulterate graphene oxide classification
The area ratio of new peak determines the content of doped chemical in sub- energy spectrum diagram.
In the present embodiment, during determining to adulterate graphene oxide classification, also to the x-ray photoelectron spectroscopy
New peak carries out swarming fitting on figure, determines doped chemical chemical bond configuration type.And the son after being fitted according to new peak swarming
Whether the corresponding area ratio in peak determines the percentage composition of doped chemical chemical bond configuration and determines doped chemical with compound state
Form exists.Gauss swarming method can be used in the method for the swarming fitting.
It in the present embodiment, can also be according to the corresponding combination energy of the new peak described on the x-ray photoelectron spectroscopy figure
Whether the doping method that graphene oxide is adulterated described in location determination is absorption doping.
In the present embodiment, the object carbon material that the present invention identifies may include the doubtful carbon materials for doping graphene oxide
Material.Carbon material may include the substance according to product obtained from graphene oxide preparation method, or after being doped to the product；
Carbon material may also include according to product obtained from redox graphene preparation method, or the object after being doped to the product
Matter.I.e. the present invention can be prepared carbon material whether be doping graphene oxide or doping redox graphene reflect
It is fixed.
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 graphite can be obtained by above-mentioned method, i.e., carry out X-ray to graphite and spread out
Test is penetrated, the crystal parameter of graphite is obtained, and then obtains the interplanar distance of graphite.The crystal face interlamellar spacing of the graphite can be 0.3
~0.4nm.
In the present embodiment, the wavelength of the middle infrared is 2.5~25 μm.The middle infrared includes characteristic frequency area
And fingerprint region, the wavelength in the characteristic frequency area are 2.5~7.7 μm, 7.7 μm of the wavelength > of the fingerprint region and≤25 μm.
In the present embodiment, after determining that the carbon material has the step of oxygen-containing group, the method may also include
Step: searching middle infrared in the infrared spectrogram, reads the corresponding wave number of absorption peak on the middle infrared；It will be described
Wave number is compared with ir data library, determines the type of oxygen-containing group on the carbon material.
Specifically, the step of determining oxygen-containing group type 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 the type that the group is according to the corresponding wave number comparison infrared spectrum database of characteristic peak.Example
Such as: 1725cm-1It is the stretching vibration of carbonyl C==O on carboxyl；1615cm-1It is the stretching vibration of carbon-carbon double bond C==C；
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) are carried out by X-ray diffraction test, and obtains corresponding XRD spectra for crystalline flake graphite, carbon material.
Fig. 1 shows the XRD spectra of crystalline flake graphite, and Fig. 2 shows the XRD spectras of carbon material.
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.
(2) ftir analysis test is carried out to carbon material, obtains the FTIR of carbon material as shown in Figure 3
Absorption spectrum (i.e. infrared spectrogram) shows there is oxygen-containing group on carbon material.As shown in figure 3, fitting result shows
3198cm-1Nearby there is an absorption band ,-OH the stretching vibration of hydroxyl should be belonged to.2926,2854cm in spectrogram-1Locate peak difference
Belong to CH2Antisymmetry, symmetrical stretching vibration；1733cm-1Neighbouring peak belongs to carbon material lamella edge carboxyl, in carbonyl
C=O stretching vibration；1630cm-1Neighbouring peak belongs to the-OH bending vibration of hydrone；1400cm-1Neighbouring peak ownership
The OH bending vibration of hydroxyl in structure；1247cm-1Neighbouring peak belongs to the C-O stretching vibration in carboxyl；1122cm-1It is attached
Close 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 a small amount of CO due to adsorbing in graphite oxide sample2The asymmetric stretching vibration of molecule,
In face caused by (outer) bending vibration.The presence of these oxygen-containing groups illustrates that graphite has been oxidized, and these polar groups
Especially surface hydroxyl makes graphene oxide be easy to form hydrogen bond with hydrone, this is also that graphene oxide has good hydrophilic
The reason of property.The results of FT-IR shows: carbon graphite carbon generates on the carbon atom in big pi bond a variety of containing oxygen key, such as C after oxidation
=O and C-O etc. makes part sp2Hybridized orbit is changed into sp3Hybridized orbit.
(3) X-ray photoelectron spectroscopic analysis test is carried out to carbon material, obtains x-ray photoelectron spectroscopy figure.The X-ray
Two peaks new peak P2p and P2s can occur in position at except 284.6eV and 531.8eV on photoelectron spectroscopy figure.According to the new of appearance
Peak and the corresponding combination energy size of new peak can be determined that the non-P doping graphene oxide of graphene oxide.
The ratio between peak area by calculating new peak can obtain doping graphene oxide doped content.In two new peaks occurred
The peak P2p occurs widthization and is in mal-distribution, shows that at least two kinds of chemical bond configurations exist.Gauss swarming method can be used P2p
Peak is divided into two different sub- peak positions, and You Gezi peak area ratio can calculate the percentage composition of each chemical bond configuration, obtains doping member
Element is present in graphite linings grid in the form of compound state, thus can also be accredited as impurity.Also, according to doped chemical
Binding site can also identify whether doping graphene oxide belongs to absorption doping.
In conclusion the advantages of whether judgement carbon material of the invention is doping graphene oxide method can include: method
It is easy and effective, a variety of detection methods can be reasonably combined, different material can efficiently and be accurately determined and method is raw
Whether the product of production is doping graphene oxide；Meanwhile the present invention can also the doping to graphene oxide accurately divided
Analysis, such as analytical element type, doped chemical content, chemical bond configuration, chemical bond configuration percentage etc..
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 (10)
- Determine whether carbon material is the method for adulterating graphene oxide 1. a kind of, which is characterized in that the method includes following steps It is rapid:The first sample, the second sample are separated from carbon material, X-ray diffraction test is carried out to the first sample, obtains X-ray diffractogram Spectrum carries out ftir analysis test to the second sample, obtains infrared spectrogram；Judge whether the lamella of carbon material is peeling-off according to the X ray diffracting spectrum, is judged according to the infrared spectrogram Whether carbon material has oxygen-containing group, if it is determined that result be carbon material piece interlayer it is peeling-off and there is oxygen-containing group, then institute Stating carbon material is graphene oxide, in the case where the carbon material is graphene oxide, determines whether the carbon material is to mix Miscellaneous graphene oxide, whereinThe whether peeling-off step of the lamella for determining carbon material includes: to obtain first according to the X ray diffracting spectrum The crystal parameter of sample, and then the interplanar distance of the first sample is obtained, if the interplanar distance of the first sample is greater than the crystal face of graphite Spacing, and compared with the X ray diffracting spectrum of graphite, occur new diffraction maximum on the X ray diffracting spectrum, then concludes carbon materials The piece interlayer of material is peeling-off, otherwise not can determine that the piece interlayer of carbon material is peeling-off；It includes: to search middle infrared in the infrared spectrogram that whether the judgement carbon material, which has the step of oxygen-containing group, Determine whether the carbon material has oxygen-containing group according to the absorption peak on the middle infrared；The step of whether the judgement carbon material is doping graphene oxide includes: that third sample is separated from the carbon material, X-ray photoelectron spectroscopic analysis test is carried out to third sample, x-ray photoelectron spectroscopy figure is obtained, if the x-ray photoelectron There is new peak in addition to the peak C1S and the peak OlS in energy spectrum diagram, graphene oxide is determined according to the corresponding combination energy size of the new peak It whether is doping graphene oxide.
- Determine whether carbon material is the method for adulterating graphene oxide 2. according to claim 1, which is characterized in that true The fixed carbon material is after adulterating graphene oxide, and the method also includes steps:Utilize the corresponding combination energy of new peak and new peak occurred in addition to the peak C1S and the peak OlS on the x-ray photoelectron spectroscopy figure It determines doped chemical type, and is according to the doping way of the corresponding combination energy location determination doping graphene oxide of the new peak Impurity or absorption doping.
- Determine whether carbon material is the method for adulterating graphene oxide 3. according to claim 1, which is characterized in that true The fixed carbon material is after adulterating graphene oxide, and the method also includes steps: the 4th sample is separated from the carbon material, Raman spectrum test is carried out to the 4th sample, obtains Raman spectrogram,If the peak G blue shift and the red shift of the peak G' in the Raman spectrogram, determine the doping way of the carbon material for n-type doping； If the peak G blue shift and the peak G' blue shift, determine that adulterating the doping way of graphene oxide is p-type doping；Alternatively, weakening with the 4th sample Koln anomalous effect, if the peak G is displaced and G' to high wave number in the Raman spectrogram Peak is displaced to lower wave number, then determines the doping way of the carbon material for n-type doping；If the peak G is to height in the Raman spectrogram Wave number is displaced and the peak G' is displaced to high wave number, then determines that adulterating the doping way of graphene oxide is p-type doping.
- Determine whether carbon material is the method for adulterating graphene oxide 4. according to claim 1, which is characterized in that described Method further comprises the steps of: the content that doped chemical is determined according to the area ratio of new peak on the x-ray photoelectron spectroscopy figure.
- Determine whether carbon material is the method for adulterating graphene oxide 5. according to claim 4, which is characterized in that described Graphite-phase should be the raw material for preparing the carbon material, and the interplanar distance of the graphite is prepared by the following: to the graphite X-ray diffraction test is carried out, obtains the crystal parameter of graphite, and then obtain the interplanar distance of graphite.
- Determine whether carbon material is the method for adulterating graphene oxide 6. according to claim 1, which is characterized in that described Crystal parameter includes the indices of crystallographic plane or the angle of diffraction.
- Determine whether carbon material is the method for adulterating graphene oxide 7. according to claim 6, which is characterized in that in institute In the case where crystal parameter is stated as the angle of diffraction, described the step of obtaining interplanar distance includes: to obtain interplanar distance by formula 1, The 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.
- Determine whether carbon material is the method for adulterating graphene oxide 8. according to claim 1, which is characterized in that described New diffraction maximum includes (100) crystallographic plane diffraction peak on X ray diffracting spectrum.
- Determine whether carbon material is the method for adulterating graphene oxide 9. according to claim 1, which is characterized in that described The wavelength of middle infrared is 2.5~25 μm.
- Determine whether carbon material is the method for adulterating graphene oxide 10. according to claim 1, which is characterized in that After determining that the carbon material has the step of oxygen-containing group, the method also includes steps: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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