CN109682846A - A kind of method of comprehensive detection carbon material - Google Patents
A kind of method of comprehensive detection carbon material Download PDFInfo
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- CN109682846A CN109682846A CN201811574050.5A CN201811574050A CN109682846A CN 109682846 A CN109682846 A CN 109682846A CN 201811574050 A CN201811574050 A CN 201811574050A CN 109682846 A CN109682846 A CN 109682846A
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- 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
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- G01N23/227—Measuring photoelectric effect, e.g. photoelectron emission microscopy [PEEM]
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Abstract
The present invention provides a kind of methods of comprehensive detection carbon material.The method may include step: separating the first, second sample from carbon material, carries out X-ray diffraction test to the first sample, obtain X ray diffracting spectrum, carries out ftir analysis test to the second sample, obtain infrared spectrogram；Determine whether the lamella of carbon material is peeling-off according to X ray diffracting spectrum, determine whether carbon material has oxygen-containing functional group according to infrared spectrogram, if judging result be carbon material piece interlayer it is peeling-off and have oxygen-containing functional group, then the carbon material is graphene oxide, when determining carbon material for graphene oxide, the type and quantity of functional group and the specific number of plies of carbon material on carbon material are determined.Beneficial effects of the present invention can include: method is easy and effective, and comprehensive identification can be efficiently and accurately carried out to carbon material.
Description
Technical field
The present invention relates to measuring for materials fields, particularly, are related to the simple and feasible comprehensive detection carbon material of one kind
Method.
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.
Generally, it is considered that the only number of plies in 10 layers of graphite below just can be regarded as two-dimensional structure, titled with the title of graphene
Meaning.According to the difference of the graphene oxide number of plies, significant changes can occur for electronic structure, to influence its electric conductivity, this is in lithium
The application field of ion battery is very crucial.In addition, some researches show that, the thermal conductivity of single-layer graphene oxide, translucency is more preferable,
Multilayer graphene oxide is higher to the disposal efficiency of organic dyestuff.Therefore, to the research of graphene oxide number of plies measurement method
Facilitate the deep relationship understood between graphene oxide performance and microstructure.
In order to which it plays bigger effect in the related art, people go to understand graphene oxide with furtheing investigate in recent years
Structural property (such as number of plies), and the structural property of graphene oxide and the type and quantity of its functional group are closely related, because
This, the identification to graphene oxide, especially the identification of functional group's type and quantity and the number of plies is highly important thereon.
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, one of the objects of the present invention is to provide a kind of methods of simple and feasible comprehensive detection carbon material.
To achieve the goals above, the present invention provides a kind of methods of comprehensive detection carbon material.The method may include
Following steps: separating the first sample, the second sample from carbon material, 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；It is penetrated according to the X
Ray diffraction diagram spectrum judges whether the lamella of carbon material is peeling-off, judges whether carbon material has according to the infrared spectrogram and contains
Oxygen functional group, if it is determined that result be carbon material piece interlayer it is peeling-off and have oxygen-containing functional group, then the carbon material be oxygen
Graphite alkene, in the case where determining the carbon material for graphene oxide, determine on the carbon material type of functional group and
The number of plies of quantity and carbon material, wherein the whether peeling-off step of the lamella for determining carbon material includes: according to institute
X ray diffracting spectrum is stated, the crystal parameter of the first sample is obtained, and then obtains the interplanar distance of the first sample, if the first sample
Interplanar distance be greater than the interplanar distance of graphite, and compared with the X ray diffracting spectrum of graphite, on the X ray diffracting spectrum
There is new diffraction maximum, then conclude that the piece interlayer of carbon material is peeling-off, otherwise not can determine that the piece interlayer of carbon material is shelled
From；It includes: to search middle infrared in the infrared spectrogram that whether the judgement carbon material, which has the step of oxygen-containing functional group,
Determine whether the carbon material has oxygen-containing functional group according to the absorption peak on the middle infrared；On the determining carbon material
The step of type and quantity of functional group includes: to separate third sample from carbon material, carries out x-ray photoelectron energy to third sample
Spectrum analysis test, obtains the x-ray photoelectron spectroscopy figure of carbon material, determines carbon according to the infrared spectrogram and the energy spectrum diagram
The type and quantity of functional group on material.The step of determining carbon material number of plies includes: to separate the 4th sample from carbon material, right
4th sample carries out Raman spectrum test, obtains Raman spectrogram, calculates I according to Raman spectrogramG/I2D, work as IG/I2DIt is less than
When 1.0, tentatively judge carbon material for single or double layer structure；Work as IG/I2DWhen being 1.0~1.5, tentatively judge carbon material for 3 layers
Or 4 layers of structure；Work as IG/I2DWhen greater than 1.5, tentatively judge carbon material for 5 layers or more structures, wherein the IGIndicate G peak intensity
Degree, the I2DIndicate 2D peak intensity.
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.The graphite can wrap
Include crystalline flake 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, on the determining carbon material the step of functional group's type can include:
Wave number corresponding to absorption peak on the middle infrared is compared with ir data library, determines carbon material Shangguan
The type that can be rolled into a ball.
On the determining carbon material the step of number of functional groups can include: judge the energy spectrum diagram according to the size in conjunction with energy
The above corresponding element in each peak, is modified by peak intensity of the sensitivity factor to peak corresponding to each element, by each after amendment
Ratio between peak peak intensity corresponding to element obtains the relative amount ratio of each element, according to the relative amount ratio, determine described in
The quantity of functional group on carbon material.
In an exemplary embodiment of the present invention, the functional group's type, quantity on the determining carbon material the step of
Later, the method may also include that the functional group's type and number of functional groups according to the determination, obtain each on the carbon material
The quantity of functional group.
In an exemplary embodiment of the present invention, the wavelength of the middle infrared is 2.5~25 μm.It is infrared in described
Area may include characteristic frequency area and fingerprint region.The wavelength in the characteristic frequency area can be 2.5~7.7 μm, the wave of the fingerprint region
It is long to be greater than 7.7 μm, not larger than 25 μm.
Described the step of obtaining the corresponding wave number of absorption peak on the middle infrared can include: can be in the characteristic frequency area
The corresponding wave number of upper acquisition absorption peak obtains the corresponding wave number of absorption peak on the fingerprint region.
In an exemplary embodiment of the present invention, if element corresponds to multiple peaks in the energy spectrum diagram, with described
The peak intensity of highest peak is as the modified object in multiple peaks.
In an exemplary embodiment of the present invention, the area or intensity for choosing highest peak are as the base quantitatively calculated
Plinth, and intensity is modified using sensitivity factor.
An exemplary embodiment according to the present invention, the ftir analysis is surveyed and X-ray photoelectricity
Requirement of the sub- energy spectrum analysis test to graphene oxide is: graphene oxide powder is carried out tabletting by the powder of tabletting.
An exemplary embodiment according to the present invention is tentatively judging the carbon material for the feelings of single or double layer structure
Under condition, the 5th sample is separated from the carbon material, the 5th sample is tested using atomic force microscope, described in determination
Carbon material is single or double layer structure；In the case where judging the carbon material tentatively for 3 layers or 4 layers of structure, the drawing is calculated
The Lorentz force peak number of the peak the 2D fitting of graceful test result Raman spectrogram, differentiating carbon material is 3 layers or 4 layers of structure；Preliminary
In the case where judging the carbon material for 5 layers or more structures, the 6th sample is separated from the carbon material, it is saturating by high-resolution
Radio mirror obtains the electron micrograph image of the 6th sample, and observation determines the specific number of plies of carbon material.
An exemplary embodiment according to the present invention, it is described that the 5th sample is tested using atomic force microscope
Step can include: obtain the three-dimensional image of the 5th sample using atomic force microscope, and by the three-dimensional image
The thickness of display and the graphene oxide thickness of single layer compare, so that it is determined that the carbon material number of plies is single or double layer.
An exemplary embodiment according to the present invention, the halfwidth at the peak 2D are 28cm-1~32cm-1And IG/I2D
In the case that the intensity ratio at peak is less than 0.7, tentatively judge carbon material for single layer structure；Halfwidth at the peak 2D is
48cm-1~52cm-1And IG/I2DThe intensity ratio at peak be more than or equal to 0.7 less than 1.0 in the case where, tentatively judge that carbon material is
Double-layer structure.
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 graphene oxide and the specific number of plies of graphene oxide and the type and quantity of functional group.
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.
Fig. 4 shows the xps energy spectrum figure of carbon material in example；
Fig. 5 shows the Raman spectrogram of crystalline flake graphite in example；
Fig. 6 shows the Raman spectrogram of carbon material in example；
Fig. 7 shows the high resolution TEM figure of carbon material in example.
Specific embodiment
Hereinafter, the side of comprehensive detection carbon material of the invention will be described in detail in conjunction with attached drawing and exemplary embodiment
Method.
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 spectroscopic analysis (X-ray photoelectron spectroscopy, XPS) is gone with X-ray
Radiation sample comes out the inner electron of atom or molecule or valence electron stimulated emission.It is known as by the electronics that photon excitation comes out
Photoelectron can measure photoelectronic energy, and using photoelectronic kinetic energy as abscissa, relative intensity (pulse/s) is that ordinate can
Make photoelectron spectroscopy figure.It can analyze reaction of atomic according to photoelectron the intensity of spectral line in energy spectrum diagram (area of Photoelectron peak)
Content or relative concentration.
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.To graphene oxide into
When row characterization, the features such as shape, position and intensity of wave crest formed in Raman map all can be with graphene oxide layer
Several increases and corresponding change occurs.
Atomic force microscope (AFM) is observed and is analyzed using interaction force generally existing between sample and scanning needle point
Object surface appearance feature.It has a nanoscale probe, and being fixed on can be on the micron order elastic cantilever of sensitive manipulation.When
When probe is very close to sample, the atom and the interatomic active force of sample surfaces on top can make cantilever bending, deviate original flat
Weighing apparatus position.3-D image is rebuild according to the spatial offset amount or vibration frequency of probe, pattern, the atom of sample surfaces can be obtained
Ingredient, mechanical property or other properties.
Transmission electron microscope (TEM) can directly observe sample structure feature, such as the number of plies by the full resolution pricture of sample
And size.
Therefore, the reasonable combination of X-ray diffraction analysis (XRD) and ftir analysis (FTIR) can be used
To judge whether carbon material is graphene oxide；After determining that carbon material is graphene oxide, Fourier transform infrared spectroscopy
The vibration of chemical bond and functional group in graphene oxide, XPS energy can also be reflected by analyzing each peak in the infrared spectroscopy of (FTIR)
Compose the relative amount that each peak is able to reflect element in graphene oxide.High resolution transmission electron microscope (HRTEM), Raman light
Spectrum (Raman), atomic force microscope (AFM) combines to identify the number of plies of graphene oxide.By
This, the present invention is by reasonably combining the type for making above-mentioned test analysis come comprehensive detection carbon material.Carbon material can for by
According to product obtained from graphene oxide preparation method, or to be produced according to obtained from redox graphene preparation method
Object.
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 step of whether carbon material is graphene oxide judged can include:
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 (alternatively referred to as oxygen-containing functional group), if the piece interlayer that judging result is carbon material occurs
It removes and there is 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 includes: infrared in searching in the infrared spectrogram that whether the judgement carbon material, which has the step of oxygen-containing group,
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 (i.e. oxygen-containing functional group) on graphene oxide.
(2) in the case where judging the carbon material for graphene oxide, the type of functional group on the carbon material is determined
And quantity.The graphene oxide functional group that the present invention is analyzed by the way that FTIR and XPS test is applied in combination.
Specifically, the step of detecting carbon material functional group type and quantity can include:
In the case where determining the carbon material for graphene oxide, third sample is separated from carbon material, to third sample
X-ray photoelectron spectroscopic analysis test is carried out, the x-ray photoelectron spectroscopy figure of carbon material is obtained.
The type and quantity of functional group on carbon material are determined according to the infrared spectrogram and the energy spectrum diagram.Wherein, may be used
Wave number corresponding to absorption peak on the middle infrared of the infrared spectrogram is compared with ir data library, determines institute
State the type of functional group on carbon material.Can according in conjunction with can size judge the corresponding element in each peak in the energy spectrum diagram, it is logical
It crosses sensitivity factor to be modified the peak intensity at peak corresponding to each element, by between peak peak intensity corresponding to each element after amendment
Ratio obtains the relative amount ratio of each element, according to the relative amount ratio, determines the quantity of functional group on carbon material.
(3) after determining that the carbon material is graphene oxide, the number of plies of the carbon material is detected.
Method of the invention can be by high resolution transmission electron microscope (HRTEM), Raman spectrum (Raman), atom
Force microscope (AFM) combines, i.e., the number of plies of graphene oxide is first primarily determined with Raman spectrum, if the number of plies exists
1~2 layer, then its number of plies is further determined using atomic force microscope；If the number of plies is at 3~4 layers, quasi- by the peak Raman spectrum 2D
The Lorentz force peak number closed out determines；Its number of plies is intuitively obtained using high resolution TEM if 5 layers or more if the number of plies,
It is capable of the number of plies of the determination graphene oxide of system perfecting.
Determine the specific steps of the number of plies can include:
1) the graphene oxide number of plies is primarily determined by Raman spectrum.The present invention mainly utilizes Raman scattering i.e. Stokes
Scattering primarily determines the graphene oxide number of plies.When inelastic scattering has energy exchange, wavelength shift is changed, and most of frequency is not
It changes, only fraction shifts, and this scattering is known as Raman scattering.When energy is reduced, wave number displacement becomes smaller, and generates
Stockes line；When energy increases, wave number displacement becomes larger, and generates anti-stockes line, they are symmetrically dispersed in Rayleigh scattering
The two sides of line are respectively corresponding to obtain or lose the energy of 1 vibration quantum.When being characterized to graphene oxide,
The features such as shape, position and the intensity of wave crest formed in Raman map can all occur with the increase of the graphene oxide number of plies
Corresponding change.According to these variations, then preliminary judgement can be carried out to the graphene oxide number of plies.
Firstly, separating the sample of test from carbon material, Raman spectrum test is carried out to the sample, obtains graphite oxide
The Raman spectrogram of alkene (i.e. carbon material).It generally will form 3 main peak types on the Raman spectrogram of graphene oxide, be respectively
The peak D, the peak G and the peak 2D (frequency multiplication peak).Wherein, the peak D represents the sp of aromatic rings in graphene oxide structure2The symmetrical of carbon atom stretches
Vibration (radial breathing), is generally used to measure the order degree of sample structure.The peak G is normally at 1580cm-1Position, peak shape is very
Sharply.That the peak G represents is sp in graphene oxide2The in plane vibration mode of hydbridized carbon atoms.The position at the peak G is to graphene oxide
The number of plies is very sensitive, through the position at the peak G, it can be determined that the number of plies of specific graphene oxide sample.With the increase of the number of plies, G
Peak is mobile towards lower wave number direction, that is, mobile towards low energy direction, shows the weakening of the bond energy between graphene oxide layer.Due to
The peak position of graphene oxide will receive temperature, doping and very faint stress influence, so, when need using Raman into
When the row graphene oxide number of plies calculates, extreme care is answered in operation.The peak 2D represents the vibration mode of two photonic crystal lattices, is the peak D
Frequency multiplication peak.In graphene oxide raman spectrum, even if the peak D is not present, the peak 2D is also always very strong, nor represents defect.
For single-layer graphene oxide sample, the peak 2D is an individual symmetrical peak, halfwidth about 30cm-1.It is right with the increase of the number of plies
Title property reduces, and the peak 2D splits into the peak of multiple overlappings.This apparent peak shape change can effectively distinguish graphene oxide layer number.
Due to the limitation of itself Raman figure, it is only applicable to graphene oxide measurement of the number of plies less than 5 layers.To sum up, it can use IG/I2DPeak
Intensity ratio can primarily determine the number of plies of graphene oxide.IGIndicate G peak intensity, the I2DIndicate 2D peak intensity.
As I in graphene oxide spectrogramG/I2DWhen the intensity ratio at peak is less than 1.0, can tentatively it judge in graphene oxide
There are single layer structure or double-layer structure, if need to determine in graphene oxide is single layer or double-layer structure, needs aobvious with atomic force
Micro mirror does further measurement；Work as IG/I2DIntensity ratio be 1.0~1.5 when, then judge graphene oxide be 3 layers or 4 layers knot
Structure, wherein the peak 2D of 3 layers of graphene oxide can be judged with six Lorentz peaks to be fitted.Work as IG/I2DIntensity > 1.5
When, the Raman spectrum of graphene oxide and the Raman spectrum of graphite are similar, it is difficult to measure the graphene oxide number of plies, need to use at this time
High resolution TEM does further measurement.
2) the system measurement graphene oxide number of plies.
It can use atomic force microscope for the graphene oxide that Preliminary Determination is single or double layer to carry out its number of plies
It is further to determine.After Raman spectrum primarily determines in sample and has single or double layer graphene oxide, atomic force microscope energy
The three-dimensional image for directly obtaining graphene oxide is single layer or the double-deck graphite oxide by the measurement determination to thickness
Alkene.It is described to determine that graphene oxide is single layer or double-layer structure includes the graphene oxide thickness and list that measured by thickness
The graphene oxide thickness of layer compares, and determines the graphene oxide number of plies.For example, for the oxygen being attached in the substrates such as mica sheet
Graphite alkene overburden will increase the about extra play of 0.35nm, so observing the thickness one of single-layer graphene oxide at AFM
As about 0.7~1.2nm.This thickness can be identified into single-layer graphene oxide compared with thickness of sample in afm image, utilize height
Line of writing music, which carries out statistical disposition, can identify the double-deck graphene oxide.
For Preliminary Determination is 3 layers or 4 layers of graphene oxide, it can be fitted by the peak Raman spectrum 2D
Lorentz force peak number determines.For example, can be judged by six Lorentz peaks to be fitted.
The graphene oxide for being 5 layers or more for Preliminary Determination, can use high resolution TEM and does to its number of plies
It is further to determine.It can be by the full resolution pricture at graphene oxide edge or fold come straight using transmission electron microscope (TEM)
The number of plies and size for connecing observation graphene oxide, can directly read the number of plies of graphene oxide directly from image.But
In the less apparent situation of contrast, especially for single layer and the double-deck graphene oxide, high resolution transmission electron microscope
It can not accurately judge the number of plies of graphene oxide.
In the present embodiment, the detection of carbon material functional group type and quantity, the detection of the carbon material number of plies can be in no particular order
Sequentially.
In the present embodiment, the step of detecting carbon material functional group type and quantity may also include that according to the determination
Functional group's type and number of functional groups obtain the quantity of carbon material Shang Ge functional group.Wherein, it needs to combine FTIR carry out official
The differentiation of type can be rolled into a ball.
In the present embodiment, during determining the carbon material number of plies, can use the peak 2D in Raman spectrogram half is high
Wide and IG/I2DThe intensity ratio at peak primarily determines that graphene oxide is single or double layer structure.When the halfwidth at the peak 2D is 28cm-1
~32cm-1And IG/I2DWhen the intensity ratio at peak is less than 0.7, tentatively judge graphene oxide for single layer structure；Half when the peak 2D is high
Width is 48cm-1~52cm-1And IG/I2DWhen the intensity ratio at peak is more than or equal to 0.7 less than 1.0, tentatively judge that graphene oxide is
Double-layer structure.
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 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, when Infrared irradiation when carbon material by frequency consecutive variations, molecule can absorb certain
The radiation of frequency, and the net change of dipole moment is caused by its vibration or rotational motion, molecular vibration and rotational energy level are generated from base
State weakens the transmitted intensity corresponding to these absorption regions to the transition of excitation state.Record the percentage transmittance of infrared light
With wave number or wavelength plot, infrared spectroscopy is just obtained.Infrared spectrogram leads to common wavelengths (λ) or wave number (σ) is abscissa,
The position for indicating absorption peak is ordinate with light transmittance (T%) or absorbance (A), indicates absorption intensity.In organic molecule
In, the atom of constitutional chemistry key or functional group is in the state constantly vibrated, the vibration frequency phase of vibration frequency and infrared light
When.Therefore, when with Infrared irradiation organic molecule, absorption of vibrations can occur for chemical bond or functional group in molecule, no
Same chemical bond or functional group's absorption frequency is different, and different location will be on infrared spectroscopy, be contained in molecule to can get
There is the information of which kind of chemical bond or functional group.
The step of determining functional group's type on graphene oxide can include:
Infrared spectroscopy is divided into three regions: near infrared region (0.75~2.5 μm), middle infrared (2.5~25 μm) and remote
Infrared region (25~300 μm).It is, in general, that near infrared spectrum is generated by the frequency multiplication of molecule, sum of fundamental frequencies；Middle infrared spectrum belongs to
The fundamental vibration spectrum of molecule；Far-infrared spectrum then belongs to the rotation spectrum of molecule and the vibrational spectrum of certain groups.
By the source of absorption peak, mid-infrared light spectrogram (2.5~25 μm) is generally divided into (2.5~7.7 μm of characteristic frequency
That is 4000~1330cm-1) and fingerprint region (7.7~16.7 μm, i.e. 1330~400cm-1) two regions.Wherein characteristic frequency
Absorption peak in area is substantially to be generated by the stretching vibration of group；Fingerprint region is mainly by some singly-bound C-O, C-N and C-X (halogen
Plain atom) etc. stretching vibration and the hydric groups such as C-H, O-H bending vibration and C-C skeletal vibration generate.
Therefore, for the analyzing step of obtained carbon material infrared spectrogram can include: the first step finds graphene oxide
Middle infrared (2.5~25 μm).Second step finds characteristic frequency area (2.5~7.7 μm, i.e. 4000-1330cm-1) and fingerprint
Area (7.7~16.7 μm, i.e. 1330~400cm-1).Step 3: red according to the corresponding wave number comparison of characteristic peak in infrared spectrogram
Outer spectrum library determines what functional group the group is.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, 1078cm-1It is epoxy group C-
The stretching vibration of O-C.
In the present embodiment, the step of determining carbon material number of functional groups can include: since the spectral peak of XPS often compares
Width cannot determine intensity according only to peak heights, generally using the area under spectral peak as intensity, be substantially equal to peak height and multiply half-peak
It is wide.The area or intensity for choosing highest peak mostly use sensitivity factor method as the basis quantitatively calculated, because each element generates
Intensity and content when photoelectron is not necessarily directly proportional, to be modified using sensitivity factor to intensity, way are as follows: with
Peak side, background the point of intersection of tangents subject to background correction, peak area or peak intensity are calculated, then respectively divided by the sensitivity of respective element
The factor, so that it may obtain the relative amount of each element, then obtain each element relative amount ratio.Or using formula ni/nj=
(Ii/Si)/(Ij/Sj) directly seek the relative amount ratios of two elements, wherein ni、njIt may respectively be the atomic concentration of different elements,
Ii、IjIt may respectively be the intensity of spectral line of different elements, Si、SjIt may respectively be the sensitivity factor of different elements.
Quantity according to element relative amount than functional group can be calculated.Such as: when C/O=2:1, oxidation stone can be calculated
The quantity of oxygen-containing functional group in ink.Different elements have fixed combination energy numerical value in corresponding functional group, by tabling look-up
Perhaps it compares with other work or combines FTIR it is determined which kind of functional group, then have stoichiometric relationship, it can be from member
The content of element obtains the content of corresponding functional group.
In the present embodiment, the method may further comprise the step of: the functional group's type and functional group number according to the determination
Amount, obtains the quantity of carbon material Shang Ge functional group.Wherein, the differentiation for needing that FTIR is combined to carry out functional group's type.
In the present embodiment, when carrying out FTIR and XPS test, for graphene oxide, it is desirable that be by carbon material
Powder tabletting.
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).Infrared spectrogram shown in Fig. 3 shows there is oxygen-containing group on carbon material, combines as a result,
The analysis of XRD can determine whether that carbon material is graphene oxide.
It can be observed that the position of the absorption peak of part functional group, thus can determine whether there is carbonyl in graphene oxide from Fig. 3
Base, carboxyl, hydroxyl, epoxy group, the functional groups such as carbon-carbon double bond.Wherein 3397cm-1The wider absorption peak in left and right is stretching for hydroxyl O-H
Contracting vibration；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.
(3) XPS analysis test is carried out to carbon material, obtains the xps energy spectrum figure of carbon material as shown in Figure 4.It is considerable from Fig. 4
The intensity that C1s and O1s corresponds to peak is observed, C:O=2:1 is calculated according to sensitivity factor method.It can be calculated according to carbon-to-oxygen ratio
The quantity of oxygen-containing functional group, other elements all calculate its number of functional groups, such as sulfur-bearing or halogen using sensitivity factor method
The number of functional groups of element etc..
(4) are carried out by Raman spectrum test, and obtains corresponding Raman spectrogram for crystalline flake graphite, carbon material.Wherein, Fig. 5
The Raman spectrogram of crystalline flake graphite is shown, Fig. 6 shows the Raman spectrogram of carbon material.
The present invention is carried out into one using the comparative analysis of crystalline flake graphite and the Raman map (i.e. Fig. 5 and Fig. 6) of carbon material
The explanation of step.As shown in figure 5, crystalline flake graphite is in 1360cm-1Place has a faint absorption peak (peak D), in 1580cm-1It deposits at place
In a point and strong absorption peak (peak G) corresponding to the first-order Raman scattering of E2g optical mode illustrates that the structure of graphite is unconventional
It is whole.After graphite is oxidized, the peak G of graphite oxide has broadened, and moves to 1590cm-1Place, and also in 1360cm-1Locate
An existing stronger peak D, after showing that graphite is oxidized, a part of sp in structure2Hydbridized carbon atoms are converted to sp3Hybrid structure, i.e.,
C=C double bond in graphite linings is destroyed.
As shown in fig. 6, graphene oxide is in 1590cm-1There is a stronger absorption peak (peak G) in place, compared to scale
The peak G of graphite occurs illustrating that graphene oxide is reduced compared with the crystalline flake graphite number of plies to the movement of high wave number direction.In 2700cm-1Place
There is the wider peak 2D in a peak (frequency multiplication peak), this is by two in the carbon atom phonon double resonance transition with reversed momentum
Caused by, the movement of this characteristic peak and shape then have close be associated with the graphene oxide number of plies.And IG/I2D> 1.5, it says
The multilayered structure that this bright graphene oxide is 5 layers or more, cannot be further analyzed using Raman spectrum, therefore, I
Sample is measured using high magnification transmission electron microscope.
Transmission electron microscope analysis is done to one region of carbon material and obtains high resolution TEM (HRTEM) figure (Fig. 7 a institute
Show), the stacked graph of graphene oxide can be intuitively obtained, the number of plies that this graphene oxide sample can be obtained after statistical counting is 7
Layer.In addition it takes another region of carbon material to do transmission electron microscope analysis and obtains Fig. 7 b, can obviously observe two panels multilayer oxygen fossil in Fig. 7 b
Black alkene lamination is staggered, and the lamination being located above is of five storeys graphene oxide, underlying to have 7 layers.
In conclusion the advantages of comprehensive detection carbon material method of the invention can include: method is easy and effective, Neng Gouyou
Machine various test is applied in combination, can efficiently and accurately judge different material and method production product whether
For the type and quantity and the specific number of plies of functional group on graphene oxide and identification 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 (10)
1. a kind of method of comprehensive detection carbon material, which is characterized in that the described method comprises the following steps:
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 functional group, if it is determined that result be carbon material piece interlayer it is peeling-off and have oxygen-containing functional group,
Then the carbon material is graphene oxide, in the case where determining the carbon material for graphene oxide, determines the carbon material
The type and quantity of upper functional group and the number of plies of carbon material, wherein
The 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: infrared in searching in the infrared spectrogram that whether the judgement carbon material, which has the step of oxygen-containing functional group,
Area, determines whether the carbon material has oxygen-containing functional group according to the absorption peak on the middle infrared；
The step of type and quantity of functional group includes: to separate third sample from carbon material on the determining carbon material, to third
Sample carries out X-ray photoelectron spectroscopic analysis test, the x-ray photoelectron spectroscopy figure of carbon material is obtained, according to the infrared light
Spectrogram and the energy spectrum diagram determine the type and quantity of functional group on carbon material.
The step of determining carbon material number of plies includes: to separate the 4th sample from carbon material, carries out Raman spectrum to the 4th sample
Test obtains Raman spectrogram, calculates I according to Raman spectrogramG/I2D, work as IG/I2DWhen less than 1.0, tentatively judge that carbon material is
Single or double layer structure；Work as IG/I2DWhen being 1.0~1.5, tentatively judge carbon material for 3 layers or 4 layers of structure；Work as IG/I2DIt is greater than
When 1.5, tentatively judge carbon material for 5 layers or more structures, wherein the IGIndicate G peak intensity, the I2DIndicate 2D peak intensity.
2. the method for comprehensive detection carbon material according to claim 1, which is characterized in that function on the determining carbon material
The step of group's type includes: that wave number corresponding to absorption peak on the middle infrared is compared with ir data library,
Determine the type of functional group on the carbon material；
On the determining carbon material the step of number of functional groups include: according in conjunction with can size judge it is each in the energy spectrum diagram
The corresponding element in peak is modified by peak intensity of the sensitivity factor to peak corresponding to each element, passes through each element institute after amendment
Ratio between corresponding peak peak intensity obtains the relative amount ratio of each element, according to the relative amount ratio, determines the carbon material
The quantity of upper functional group.
3. the method for comprehensive detection carbon material according to claim 1, which is characterized in that tentatively judging the carbon material
In the case where for single or double layer structure, the 5th sample is separated from the carbon material, using atomic force microscope to the 5th sample
Product are tested, using the determination carbon material as single or double layer structure；
In the case where judging the carbon material tentatively for 3 layers or 4 layers of structure, the Raman test result Raman spectrogram is calculated
The peak 2D fitting Lorentz force peak number, differentiate carbon material be 3 layers or 4 layers of structure；
In the case where judging the carbon material tentatively for 5 layers or more structures, the 6th sample is separated from the carbon material, is passed through
High resolution TEM obtains the electron micrograph image of the 6th sample, and observation determines the specific number of plies of carbon material.
4. the method for comprehensive detection carbon material according to claim 1, which is characterized in that the preliminary judgement carbon material is
The step of single or double layer structure can include: when the halfwidth at the peak 2D is 28cm-1~32cm-1And IG/I2DThe intensity at peak it
When than less than 0.7, tentatively judge carbon material for single layer structure；When the halfwidth at the peak 2D is 48cm-1~52cm-1And IG/I2D
When the intensity ratio at peak is more than or equal to 0.7 less than 1.0, tentatively judge carbon material for double-layer structure.
5. the method for comprehensive detection carbon material according to claim 1, which is characterized in that the carbon material is according to oxidation
Product obtained from graphene preparation method, or for according to product obtained from redox graphene preparation method.
6. the method for comprehensive detection carbon material according to claim 3, which is characterized in that the graphite-phase should be the oxygen
The raw material of graphite alkene 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.
7. the method for comprehensive detection carbon material according to claim 1, which is characterized in that the crystal parameter includes crystal face
Index or the angle of diffraction.
8. the method for comprehensive detection carbon material according to claim 7, which is characterized in that the crystal parameter be diffraction
In the case where angle, described the step of obtaining interplanar distance includes: to obtain interplanar distance, the formula 1 by 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.
9. the method for comprehensive detection carbon material according to claim 1, which is characterized in that in the determining carbon material function
After the step of group's type, quantity, the method also includes: according to the functional group's type and number of functional groups of the determination, obtain
To the quantity of carbon material Shang Ge functional group.
10. the method for comprehensive detection carbon material according to claim 2, which is characterized in that if element is in the energy spectrum diagram
The upper multiple peaks of correspondence, then using the peak intensity of highest peak in the multiple peak as the modified object.
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