CN109342471A - A method of determining carbon material attribute - Google Patents
A method of determining carbon material attribute Download PDFInfo
- Publication number
- CN109342471A CN109342471A CN201811574085.9A CN201811574085A CN109342471A CN 109342471 A CN109342471 A CN 109342471A CN 201811574085 A CN201811574085 A CN 201811574085A CN 109342471 A CN109342471 A CN 109342471A
- Authority
- CN
- China
- Prior art keywords
- carbon material
- functional group
- sample
- peak
- determining
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 99
- 125000000524 functional group Chemical group 0.000 claims abstract description 63
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 58
- 238000001228 spectrum Methods 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000012360 testing method Methods 0.000 claims abstract description 22
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 18
- 238000004458 analytical method Methods 0.000 claims abstract description 13
- 238000010586 diagram Methods 0.000 claims abstract description 12
- 239000011229 interlayer Substances 0.000 claims abstract description 10
- 241000446313 Lamella Species 0.000 claims abstract description 7
- 238000004611 spectroscopical analysis Methods 0.000 claims abstract description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 40
- 239000010439 graphite Substances 0.000 claims description 40
- 239000013078 crystal Substances 0.000 claims description 33
- 238000010521 absorption reaction Methods 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 10
- 230000035945 sensitivity Effects 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 3
- -1 graphite alkene Chemical class 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 9
- 238000004566 IR spectroscopy Methods 0.000 description 5
- 230000033001 locomotion Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001845 vibrational spectrum Methods 0.000 description 3
- 229910014033 C-OH Inorganic materials 0.000 description 2
- 229910014570 C—OH Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000003705 background correction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001686 rotational spectrum Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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
- G01N23/207—Diffractometry using detectors, e.g. using a probe in a central position and one or more displaceable detectors in circumferential positions
-
- 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
- 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
- G01N23/22—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 measuring secondary emission from the material
- G01N23/227—Measuring photoelectric effect, e.g. photoelectron emission microscopy [PEEM]
- G01N23/2273—Measuring photoelectron spectrum, e.g. electron spectroscopy for chemical analysis [ESCA] or X-ray photoelectron spectroscopy [XPS]
Abstract
The present invention provides a kind of methods for determining carbon material attribute.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, third sample is separated from carbon material, X-ray photoelectron spectroscopic analysis test is carried out to third sample, obtains energy spectrum diagram；The type and quantity of functional group on carbon material are determined according to infrared spectrogram and energy spectrum diagram.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, are related to the simple and feasible judgement carbon material attribute 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.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 judgement carbon material attribute.
To achieve the goals above, the present invention provides a kind of methods for determining carbon material attribute.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
Quantity, wherein the whether peeling-off step of the lamella for determining carbon material includes: to be obtained according to the X ray diffracting spectrum
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 occur new diffraction maximum on the X ray diffracting spectrum, then break and compared with the X ray diffracting spectrum of graphite
The piece interlayer for determining carbon material is peeling-off, otherwise not can determine that the piece interlayer of carbon material is peeling-off；The judgement carbon material is
No to have the step of oxygen-containing functional group include: to search middle infrared in the infrared spectrogram, according on the middle infrared
Absorption peak determine whether the carbon material has oxygen-containing functional group；The type and quantity of functional group on the determining carbon material
The step of include: to separate third sample from carbon material, to third sample carry out X-ray photoelectron spectroscopic analysis test, obtain carbon
The x-ray photoelectron spectroscopy figure of material；The kind of functional group on carbon material is determined according to the infrared spectrogram and the energy spectrum diagram
Class and quantity.
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.
Compared with prior art, beneficial effects of the present invention can include: method is easy and effective, can be efficiently and accurately
Identify carbon material whether be graphene oxide and graphene oxide functional group type and quantity.
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.
Specific embodiment
Hereinafter, the side of judgement carbon material attribute 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.
Therefore, organic cooperation 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.As a result, the present invention by be reasonably applied in combination XRD,
FTIR and XPS test analysis determines the type of carbon material.Carbon material can be to obtain according to graphene oxide preparation method
Product, or for according to product obtained from redox graphene preparation method.
In an exemplary embodiment of the present invention, the test method can comprise the following steps that
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.
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；According to the infrared spectrogram
The type and quantity of functional group on carbon material are determined with the energy spectrum diagram.It wherein, can be by the middle infrared of the infrared spectrogram
Wave number corresponding to upper absorption peak is compared with ir data library, determines the type of functional group on the carbon material.It can
According in conjunction with can size judge the corresponding element in each peak in the energy spectrum diagram, by sensitivity factor to corresponding to each element
The peak intensity at peak is modified, and obtains the relative amount of each element by the ratio between peak peak intensity corresponding to each element after amendment
Than determining the quantity of functional group on carbon material according to the relative amount ratio.
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 is specific 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, since the spectral peak of XPS is often wider, intensity cannot be determined according only to peak heights, generally
Area under using spectral peak is substantially equal to peak height and multiplies half-peak breadth as intensity.The area or intensity for choosing highest peak are as quantitative scoring
The basis of calculation, mostly uses sensitivity factor method, because the intensity and content when each element generation photoelectron are not necessarily directly proportional, from
And intensity is modified using sensitivity factor, way are as follows: be subject to peak side, background point of intersection of tangents background correction, meter
Peak area or peak intensity are calculated, then respectively divided by the sensitivity factor of respective element, 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) the opposite of two elements is directly asked to contain
Measure ratio, 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、Sj
It 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..
In conclusion the advantages of whether judgement carbon material of the invention is graphene oxide method can include: method is easy
And it is effective, can efficiently and accurately judge whether the product of different material and method production is graphene oxide, Yi Jijian
Determine the type and quantity of functional group on graphene oxide.
In conclusion the advantages of judgement carbon material attribution method of the invention can include: method is easy and effective, Ke Yigao
Whether the product for imitating and accurately judging different material and method production is on graphene oxide and identification graphene oxide
The type and quantity of oxygen-containing functional group.
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 for determining carbon material attribute, 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, 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.
2. the method according to claim 1 for determining carbon material attribute, which is characterized in that
On the determining carbon material the step of functional group's type include: by wave number corresponding to absorption peak on the middle infrared with
Ir data library is compared, and determines 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 according to claim 1 for determining carbon material attribute, 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.
4. the method according to claim 3 for determining carbon material attribute, 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.
5. the method according to claim 4 for determining carbon material attribute, which is characterized in that the graphite includes scale stone
Ink.
6. the method according to claim 1 for determining carbon material attribute, which is characterized in that the crystal parameter includes crystal face
Index or the angle of diffraction.
7. it is according to claim 5 determine carbon material attribute method, 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.
8. the method according to claim 1 for determining carbon material attribute, which is characterized in that the new diffraction maximum includes
(100) crystallographic plane diffraction peak.
9. the method according to claim 1 for determining carbon material attribute, 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 according to claim 1 for determining carbon material attribute, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811574085.9A CN109342471A (en) | 2018-12-21 | 2018-12-21 | A method of determining carbon material attribute |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811574085.9A CN109342471A (en) | 2018-12-21 | 2018-12-21 | A method of determining carbon material attribute |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109342471A true CN109342471A (en) | 2019-02-15 |
Family
ID=65303216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811574085.9A Pending CN109342471A (en) | 2018-12-21 | 2018-12-21 | A method of determining carbon material attribute |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109342471A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554009A (en) * | 2015-09-24 | 2017-04-05 | 天津工业大学 | A kind of preparation method of nitrogen-doped graphene load gold nano particle |
| CN106938842A (en) * | 2016-01-04 | 2017-07-11 | 天津工业大学 | It is a kind of to be pyrolyzed the method that citric acid prepares graphene quantum dot |
-
2018
- 2018-12-21 CN CN201811574085.9A patent/CN109342471A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554009A (en) * | 2015-09-24 | 2017-04-05 | 天津工业大学 | A kind of preparation method of nitrogen-doped graphene load gold nano particle |
| CN106938842A (en) * | 2016-01-04 | 2017-07-11 | 天津工业大学 | It is a kind of to be pyrolyzed the method that citric acid prepares graphene quantum dot |
Non-Patent Citations (3)
| Title |
|---|
| 常铁军等: "《材料近代分析测试方法》", 31 August 2005 * |
| 王新伟等: "《石墨烯的化学方法合成及其表征》", 《中国科技论文在线》 * |
| 王露: "《氧化石墨烯的表面改性及其与环氧树脂的复合研究》", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ye et al. | An overview of advanced methods for the characterization of oxygen vacancies in materials | |
| Zhang et al. | Characterization of semiconductor photocatalysts | |
| Lazzarini et al. | Graphitization of activated carbons: a molecular-level investigation by INS, DRIFT, XRD and Raman techniques | |
| Abello et al. | Structural characterization of nanocrystalline SnO2by X-ray and Raman spectroscopy | |
| Cançado et al. | Quantifying defects in graphene via Raman spectroscopy at different excitation energies | |
| Wen et al. | In-plane anisotropic Raman spectroscopy of van der Waals α-MoO3 | |
| Simonenko et al. | Formation of One-Dimensional Hierarchical MoO 3 Nanostructures under Hydrothermal Conditions | |
| Yoon et al. | Raman spectroscopy for characterization of graphene | |
| Tang et al. | Giant Narrow-Band Optical Absorption and Distinctive Excitonic Structures of Monolayer C 3 N and C 3 B | |
| Xiao et al. | Compressed few-layer black phosphorus nanosheets from semiconducting to metallic transition with the highest symmetry | |
| Pfaff et al. | Comparative microstructural analysis of nongraphitic carbons by wide-angle X-ray and neutron scattering | |
| Bousige et al. | Lattice dynamics of a rotor-stator molecular crystal: Fullerene-cubane C 60⋅ C 8 H 8 | |
| Gupta et al. | MXene and their integrated composite-based acetone sensors for monitoring of diabetes | |
| Bizarro et al. | Physicochemical characterization of photocatalytic materials | |
| Carboni et al. | Introducing Ti-GERS: Raman Scattering Enhancement in Graphene-Mesoporous Titania Films | |
| CN109342471A (en) | A method of determining carbon material attribute | |
| CN109682846A (en) | A kind of method of comprehensive detection carbon material | |
| Pei et al. | Raman observation of the “volcano curve” in the formation of carbonized metal–organic frameworks | |
| CN109540941A (en) | A method of detection carbon material type | |
| Yadav et al. | Local structural investigations of graphitic ZnO and reduced graphene oxide composite | |
| Romero Millán et al. | Iron nanoparticles to catalyze graphitization of cellulose for energy storage applications | |
| CN109580676A (en) | A method of determining whether carbon material is graphene oxide | |
| Cavallari et al. | Neutron scattering study of nickel decorated thermally exfoliated graphite oxide | |
| CN109682670A (en) | A method of judging whether carbon material is graphene oxide | |
| Gupta et al. | Novel nanocarbon hybrids of single-walled carbon nanotubes and dispersed nanodiamond: Structure and hierarchical defects evolution irradiated with gamma rays |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190215 |