CN105817250B - A kind of carbon-based material and preparation method thereof - Google Patents
A kind of carbon-based material and preparation method thereof Download PDFInfo
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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Abstract
The invention discloses a kind of carbon-based materials, and on the basis of the total weight of the carbon-based material, which contains the oxygen element of the carbon of 70-99.75 weight %, the nitrogen of 0.05-10 weight % and 0.2-20 weight %.The present invention also provides a kind of methods for preparing above-mentioned carbon-based material, and this method comprises the following steps: (1) mixing solid carbon source, presoma and aqueous hydrogen peroxide solution, obtain mixed material；Wherein, the presoma contains organic alkali source；(2) the mixed material for obtaining step (1) carries out hydro-thermal process, the material after obtaining hydro-thermal process；And the solid in the material after hydro-thermal process is separated and is dried, the material after being dried；(3) material after drying that step (2) obtains is roasted.The present invention also provides purposes of the carbon-based material as described above in catalysis oxidation reactions of hydrocarbons.The present invention can improve the selectivity and conversion ratio that hydrocarbon oxidation prepares alkene simultaneously.
Description
Technical field
Technical field of material chemistry of the present invention, and in particular, to a kind of carbon-based material, a kind of method for preparing carbon-based material and should
The purposes of carbon-based material.
Background technique
Carbon-based material includes carbon nanotube, graphene, fullerene, carbon nano-fiber and Nano diamond etc..Carbon substrate
Material can be used as the catalysis material of oxidizing hydrocarbons especially alkane, such as: there are document (Applied Catalysis, 29 (1987)
311-326) reporting becomes styrene for oxidative dehydrogenation of ethylbenzene for catalyst using active carbon, and there are also document (ACTA
PHYSICA POLONIC A, Vol.118, (2010), 459-464) to report using active carbon be that catalyst converts normal butane
For butylene and butadiene.
Studies have shown that miscellaneous if modifying oxygen-containing, nitrogen etc. on nano-carbon material (such as carbon nanotubes and graphene) surface
The saturation of atom and unsaturation functional group, thus it is possible to vary the catalytic activity of nano-carbon material, it such as can be by nano-carbon material
It carries out oxidation processes realization and introduces oxygen atom in nano-carbon material, to increase containing for oxygen-containing functional group in nano-carbon material
Amount.For example, can be by nano-carbon material in strong acid (such as HNO3、H2SO4) and/or strong oxidizing solution (such as H2O2、KMnO4) in into
Row back flow reaction can also assist carrying out microwave heating or sonic oscillation while back flow reaction, to enhance oxidation reaction
Effect.
It may skeleton knot to nano-carbon material but carry out back flow reaction in strong acid and/or strong oxidizing solution
Structure has an adverse effect, or even destroys the skeleton structure of nano-carbon material.Such as: nano-carbon material is aoxidized with nitric acid,
Although a large amount of oxygen-containing functional groups can be introduced on nano-carbon material surface, easily cause nano-carbon material be cut off and/or
The defects of graphite network structure position is obviously increased, so as to reduce the performance of nano-carbon material, such as thermal stability.In addition,
By carrying out back flow reaction in strong acid and/or strong oxidizing solution, when introducing oxygen atom, the introduction volume of oxygen atom is to reaction
The dependence of operating condition is high, and fluctuation range is wider, is not easy accurately to control.
Alkene especially alkadienes and aromatic olefin are important industrial chemicals, such as butadiene is production synthetic rubber
The primary raw material of (such as butadiene-styrene rubber, butadiene rubber, nitrile rubber, neoprene).It is raw using styrene and butadiene copolymer
It produces the extensive resin of various uses (such as ABS resin, SBS resin, BS resin and MBS resin), makes butadiene in production of resins
Gradually occupy an important position.In addition, butadiene can also be used to produce ethylidene norbornene (EP rubbers Third monomer), Isosorbide-5-Nitrae-fourth
Glycol, adiponitrile (nylon66 fiber monomer), sulfolane, anthraquinone and tetrahydrofuran etc., therefore butadiene is also important basic chemical industry
Raw material.In addition, styrene is also important the monomer of synthetic rubber and plastics, can be used to produce butadiene-styrene rubber, polystyrene
With foamed polystyrene etc.；It is also used for being copolymerized the engineering plastics for manufacturing a variety of different purposes from other monomers.Such as with acrylonitrile, fourth
Diene, which is copolymerized, is made ABS resin, is widely used in various household electrical appliance and industrial；It is with SAN resin made from acrylonitrile compolymer
Impact resistance, bright in color resin；It is a kind of thermoplastic elastomer with SBS obtained by butadiene copolymer, is widely used as polychlorostyrene second
Alkene, polyacrylic modifying agent etc..Styrene is handed over mainly for the production of styrene series resin and butadiene-styrene rubber, and production ion
One of the raw material of resin and pharmaceuticals is changed, in addition, styrene can also be used in the industries such as pharmacy, dyestuff, pesticide and ore dressing.
Hydrocarbon oxidative dehydrogenation is to prepare the important method of alkene, such as butane oxidation dehydrogenation can be generated 1- butylene, 1- fourth
Alkene oxidative dehydrogenation can generate 1,3- butadiene in turn；Vinylbenzene oxidative dehydrogenation can also be generated into styrene.Hydrocarbon oxidative dehydrogenation
When preparing alkene, there is selectivity and conversion ratio to be difficult to the problem of improving simultaneously.
Summary of the invention
The purpose of the present invention is in the presence of overcoming hydrocarbon oxidative dehydrogenation to prepare alkene selectivity and conversion ratio be generally difficult to
The problem of improving simultaneously, provide it is a kind of can catalytic hydrocarbon oxidative dehydrogenation prepare alkene and obtain simultaneously highly selective and conversion ratio
The purposes of carbon-based material, the preparation method of the carbon-based material and the carbon-based material.
It was found by the inventors of the present invention that using presoma and aqueous hydrogen peroxide solution containing organic amine and/or quaternary ammonium base
Hydro-thermal process is carried out to carbon source material, by the solid separation in the material after hydro-thermal process and after drying and roasting, is capable of forming
The activity of alkene is prepared with catalytic hydrocarbon oxidation and obtains highly selective and conversion ratio carbon-based material simultaneously, results in this
Invention.
On the one hand, the present invention provides a kind of carbon-based materials, on the basis of the total weight of the carbon-based material, the carbon-based material
The oxygen element of carbon containing 70-99.75 weight %, the nitrogen of 0.05-10 weight % and 0.2-20 weight %；Wherein,
In the x-ray photoelectron spectroscopy of the carbon-based material, the amount and 531.8- of the oxygen element that the peak within the scope of 533.1-533.5eV determines
The ratio of the amount for the oxygen element that peak within the scope of 532.2eV determines is in the range of 0.2-5.
On the other hand, the present invention also provides a kind of method for preparing carbon-based material, this method comprises the following steps: (1)
Solid carbon source, presoma and aqueous hydrogen peroxide solution are mixed, mixed material is obtained；Wherein, the presoma contains and has
Machine alkali source, organic alkali source include machine amine and/or quaternary ammonium base；(2) the mixed material for obtaining step (1) carries out water
Heat treatment, the material after obtaining hydro-thermal process；And separate the solid in the material after hydro-thermal process；(3) step (2) is obtained
Hydro-thermal process after material in solid roasted.
On the other hand, the present invention also provides the carbon-based materials that method as described above is prepared.
In another aspect, the present invention also provides the carbon that carbon-based material as described above and method as described above are prepared
Purposes of the sill in catalysis oxidation reactions of hydrocarbons.
Through the above technical solutions, the present invention can improve the selectivity and conversion ratio that hydrocarbon oxidation prepares alkene simultaneously.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of carbon-based materials, and on the basis of the total weight of the carbon-based material, which contains 70-
The oxygen element of the carbon of 99.75 weight %, the nitrogen of 0.05-10 weight % and 0.2-20 weight %；Wherein, the carbon substrate
In the x-ray photoelectron spectroscopy of material, the amount and 531.8-532.2eV of the oxygen element that the peak within the scope of 533.1-533.5eV determines
The ratio of the amount for the oxygen element that peak in range determines is in the range of 0.2-5.
Wherein it is preferred to which the peak within the scope of 533.1-533.5eV determines in the x-ray photoelectron spectroscopy of the carbon-based material
Oxygen element amount and 531.8-532.2eV within the scope of peak determine oxygen element amount ratio in the range of 0.5-2.Into
Preferably, in the x-ray photoelectron spectroscopy in the carbon-based material, the oxygen that the peak within the scope of 533.1-533.5eV determines is first for one step
The ratio of the amount for the oxygen element that the amount of element and the peak within the scope of 531.8-532.2eV determine is in the range of 0.6-1.8.It is penetrated by X
The area of O1s spectral peak in photoelectron spectra can determine the total amount of O element in carbon-based material.Wherein, 533.1-533.5eV
The amount for the oxygen element that peak in range determines can indicate the Relative mole content of C-O group in carbon-based material, 531.8-
The amount for the oxygen element that peak within the scope of 532.2eV determines can indicate the Relative mole content of C=O group in carbon-based material.
In the present invention, in carbon-based material the content of each element be by carbon-based material 300 DEG C at a temperature of in helium atmosphere
After middle processing 3h, the numerical value measured using X-ray photoelectron spectroscopy, measuring method for known to those skilled in the art, this
Place does not repeat.
In the present invention, x-ray photoelectron spectroscopy map refers to that XPS map, XPS map can be normal according to instrument analysis field
The method of rule measures to obtain, and the calculating of the amount for the element that peak in x-ray photoelectron spectroscopy in particular range determines can be according to
The method of instrument analysis field routine is calculated, such as can be measured according to the specification of x-ray photoelectron spectroscopy
And quantitative calculating is carried out using the data software that x-ray photoelectron spectroscopy carries, the present invention does not have particular/special requirement to this.This hair
In bright, x-ray photoelectron spectroscopy data be sample 300 DEG C at a temperature of handle 3h in helium atmosphere after measure.Its
In, when the content value of measurement is lower than 0.1 weight %, the content of the element is denoted as 0.
In the present invention, from the point of view of the catalytic capability for further increasing the carbon-based material, it is preferable that carbon-based with this
On the basis of the total weight of material, the carbon-based material contain the carbon of 80-97 weight %, 0.2-8 weight % nitrogen and
The oxygen element of 0.5-15 weight %.In order to further improve the catalytic capability of the carbon-based material, it is highly preferred that the carbon substrate
Expect the carbon containing 85-95 weight %, the nitrogen of 0.5-5 weight % and the oxygen element of 2-10 weight %.
Carbon-based material according to the present invention, in the x-ray photoelectron spectroscopy of the carbon-based material, 398.0-400.5eV range
The ratio of the amount for the nitrogen that the amount for the nitrogen that interior peak determines and the peak within the scope of 395.0-405.0eV determine is in 0.5-1
In the range of；More preferably in the range of 0.6-0.9.Carbon can be determined by the area of the N1s spectral peak in x-ray photoelectron spectroscopy
The total amount of N element in sill, generally, the amount for the nitrogen that the peak within the scope of 395.0-405.0eV determines can refer to substantially
Show the Relative mole content of nitrogen contained by whole nitrogen-containing groups in carbon-based material.Wherein, the peak within the scope of 398.0-400.5eV is true
The amount of fixed nitrogen can indicate (such as pyrroles, pyridine, amide and the surface amino groups of nitrogen contained by NH group in carbon-based material substantially
In nitrogen) Relative mole content.
Carbon-based material according to the present invention, in the x-ray photoelectron spectroscopy of the carbon-based material, 400.6-401.5eV range
The ratio of the amount for the nitrogen that the amount for the nitrogen that interior peak determines and the peak within the scope of 395.0-405.0eV determine is in 0-0.5
In the range of；More preferably in the range of 0.1-0.4.Wherein, the amount for the nitrogen that the peak within the scope of 400.6-401.5eV determines
Substantially the Relative mole content of contained graphite mould nitrogen in carbon-based material can be indicated, the peak within the scope of 395.0-405.0eV determines
The amount of nitrogen can indicate the Relative mole content of nitrogen contained by whole nitrogen-containing groups of carbon-based material substantially.
Carbon-based material according to the present invention, in the x-ray photoelectron spectroscopy of the carbon-based material, 283.8-284.2eV range
The ratio of the amount for the carbon that the amount for the carbon that interior peak determines and the peak within the scope of 280.0-294.0eV determine is in 0.6-1
In the range of；More preferably in the range of 0.7-0.9.Carbon can be determined by the area of the C1s spectral peak in x-ray photoelectron spectroscopy
The total amount of C element in sill, generally, the amount for the carbon that the peak within the scope of 280.0-294.0eV determines can refer to substantially
Show the Relative mole content of carbon contained by whole carbon-containing groups of carbon-based material.Wherein, the peak within the scope of 283.8-284.2eV is true
The amount of fixed carbon can indicate the Relative mole content of contained graphitic carbon in carbon-based material substantially.
Carbon-based material according to the present invention, in the x-ray photoelectron spectroscopy of the carbon-based material, 286.2-286.6eV range
The sum of amount of carbon that the amount for the carbon that interior peak determines and the peak within the scope of 288.6-289.0eV determine and 280.0-
The ratio of the amount for the carbon that peak within the scope of 294.0eV determines is in the range of 0.02-0.2；More preferably 0.05-0.15's
In range.The total amount of C element in carbon-based material can be determined by the area of the C1s spectral peak in x-ray photoelectron spectroscopy, generally
The amount on ground, the carbon that the peak within the scope of 280.0-294.0eV determines can indicate whole carbon-containing groups of carbon-based material substantially
The Relative mole content of contained carbon.Wherein, the amount for the carbon that the peak within the scope of 286.2-286.6eV determines can refer to substantially
Show the Relative mole content of carbon contained by C-O group in carbon-based material (carbon in such as carboxyl, acid anhydride and ester), 288.6-289.0eV
The amount for the carbon that peak in range determines can indicate that carbon contained by C=O group is (in such as hydroxyl and ether in carbon-based material substantially
Carbon) Relative mole content.
Carbon-based material according to the present invention, in the x-ray photoelectron spectroscopy of the carbon-based material, 286.2-286.6eV range
The ratio of the amount for the carbon that the amount for the carbon that interior peak determines and the peak within the scope of 288.6-289.0eV determine is in 0.3-2
In the range of；More preferably in the range of 0.6-1.7.
In the present invention, position combination as corresponding to the summit at the peak at above-mentioned each peak be can determine that, by mentioned earlier range
Determining peak refer to combination corresponding to summit can peak within that range, in the range may include a peak, can also
To include more than two peaks.Such as: the peak within the scope of 288.6-289.0eV refers to that combination corresponding to summit can be in
Whole peaks in the range of 288.6-289.0eV.
Carbon-based material according to the present invention, wherein the W of the carbon-based material500/W800It can be in the range of 0.02-0.5
It is interior；The W of the preferably described carbon-based material500/W800In the range of 0.05-0.25.Under the preferable case, the carbon-based material
Better catalytic effect can be obtained when being used as catalyst, when being especially used as the catalyst of hydrocarbons dehydrogenation reaction, energy
Obtain higher feed stock conversion and selectivity of product.Wherein, W800Refer to air atmosphere and 25 DEG C of initial temperature and 10
DEG C/Elevated Temperature Conditions of min under, slip of the carbon-based material in the weight at 800 DEG C relative to the weight at 400 DEG C, i.e.,
(carbon-based material is in the weight and weight difference of the carbon-based material at 800 DEG C at 400 DEG C)/carbon-based material exists
Weight at 400 DEG C, W500Under the Elevated Temperature Conditions for referring to air atmosphere and 25 DEG C of initial temperature and 10 DEG C/min, the carbon
Slip of the sill in the weight at 500 DEG C relative to the weight at 400 DEG C, i.e. (weight of the carbon-based material at 400 DEG C
Amount is with the carbon-based material in the weight difference at 500 DEG C) the weight of/carbon-based material at 400 DEG C.
Carbon-based material according to the present invention, it is preferable that the distribution uniform of nitrogen therein and oxygen element.Such as passing through
When X-ray microregion element is analyzed, in the identical different X-ray microcells of the area on the surface of the carbon-based material, nitrogen and oxygen element
The coefficient of variation of content is 20% hereinafter, more preferably 15% hereinafter, particularly preferably 10% hereinafter, particularly preferably 5%
Below.Wherein, X-ray microcell refers to the observation area selected when carrying out the analysis of X-ray microregion element.Wherein, the coefficient of variation
Concept refers to the standard deviation of multiple measured values and the percentage of their average, i.e. (standard deviation SD/ is average by coefficient of variation CV=
Value MN) × 100%.Wherein, the method for carrying out the analysis of X-ray microregion element can be measured according to the method for instrument analysis field routine
It obtains, such as specific test method may include: the carbon-based material with energy depressive spectroscopy along length in the range of 25-250nm
Such as the length direction of carbon nanotube is scanned, and is determined concentration on the length direction of nitrogen-atoms and oxygen atom respectively or is contained
Amount (5 concentration of measurement or content), is made five effective samples by same nano-carbon material and is scanned Electronic Speculum-power spectrum point respectively
Analysis, each sample take 5 different carbon nanotubes to be scanned, and nitrogen-atoms and oxygen atom respectively obtain 25 concentration or content number
According to calculating the coefficient of variation of corresponding nitrogen-atoms and oxygen atom.Herein the coefficient of variation refer to 25 measured values standard deviation and they
Average percentage, i.e. coefficient of variation CV=(standard deviation SD/ average value MN) × 100%.In order to preferably reflect carbon
The distributing homogeneity of nitrogen and oxygen element in sill, the surface of selected carbon-based material in the analysis of X-ray microregion element
Area can be 10-250nm2, preferably 20-200nm2。
Wherein, the structural form of the carbon-based material may include carbon nanotube, graphene, fullerene, nano carbon particle,
Active carbon, thin layer graphite, carbon nano-fiber and Nano diamond at least one of structural form structure.
Wherein, the carbon-based material can for carbon nanotube, graphene, fullerene, nano carbon particle, active carbon,
One of carbon-based material of thin layer graphite, carbon nano-fiber and nano diamond structure or a variety of mixtures.Wherein, described
Carbon-based material, which has, is selected from carbon nanotube, graphene, fullerene, nano carbon particle, active carbon, thin layer graphite, carbon nano-fiber
With the structure of Nano diamond.
The present invention also provides a kind of methods for preparing carbon-based material, and this method comprises the following steps: (1) by solid carbon
Source, presoma and aqueous hydrogen peroxide solution mixing, obtain mixed material；Wherein, the presoma contains organic alkali source, institute
Stating organic alkali source includes machine amine and/or quaternary ammonium base；(2) the mixed material for obtaining step (1) carries out hydro-thermal process, obtains
Material after to hydro-thermal process；And separate the solid in the material after hydro-thermal process；(3) at the hydro-thermal for obtaining step (2)
The solid in material after reason is roasted.
According to the method for the present invention, wherein the mixed time and temperature does not have particular/special requirement, can become in a big way
Change, such as the mixed time can be 0.5-72h, mixed temperature can be 20-80 DEG C.
According to the method for the present invention, wherein the nitrogen in carbon and organic alkali source in the solid carbon source
Molar ratio can be 1:(0.002-50), preferably 1:(0.005-20), more preferably 1:(0.01-10).
According to the method for the present invention, wherein in the carbon and the aqueous hydrogen peroxide solution in the solid carbon source
The molar ratio of hydrogen peroxide can be 1:(0.01-10), preferably 1:(0.04-5), more preferably 1:(0.1-2).
Wherein, the content of hydrogen peroxide can select in the larger context in the aqueous hydrogen peroxide solution, the mistake
The concentration for aoxidizing aqueous solution of hydrogen can be the normal concentration of this field, such as can be 0.5-80 weight %.Concentration meets above-mentioned
It is required that hydrogen peroxide aqueous solution can using conventional method prepare, also be commercially available, such as: be commercially available
The hydrogen peroxide of the hydrogen peroxide of 28-32 weight %, the hydrogen peroxide of 48-52 weight % or 68-72 weight %.In order to obtain better effect
Fruit, the concentration of the aqueous solution of hydrogen peroxide are preferably 1-30 weight %.
According to the method for the present invention, wherein hydro-thermal refers to be kept under air-proof condition at autogenous pressures at 100 DEG C or more
Part water maintains the reaction condition of liquid, and hydro-thermal can heat water so that part water spontaneous vaporization is pressurized under air-proof condition
It arrives；Preferably, the temperature for carrying out hydro-thermal process is 105-200 DEG C；More preferably 120-180 DEG C.Wherein, the time of hydro-thermal process
It can be 0.5-96h, preferably 2-72h.
Wherein, the operation of the solid in material after separating hydro-thermal process can be by being centrifuged and/or filtering etc. conventional point
It is carried out from mode.
Wherein, after the solid in material after separating hydro-thermal process, solid can be dried, condition is dried
It can change in a big way, the condition of the drying is not particularly limited in the present invention, can be conventional selection, preferably
Ground, the temperature being dried are 80-180 DEG C, time 0.5-24h.The drying can carry out under normal pressure, can also subtract
It is carried out under pressure (i.e. negative pressure).
Wherein, the roasting can carry out in inert atmosphere, can also carry out in oxygen-containing atmosphere, can also be successively
It is carried out in inert atmosphere and oxygen-containing atmosphere, wherein the inert atmosphere refers to the atmosphere formed by non-active gas, institute
State non-active gas such as group 0 element gas (such as argon gas) and/or nitrogen.Preferably, the roasting is in the gas containing oxygen
Middle progress, on the basis of the total volume of the gas containing oxygen, the content of the oxygen in the gas containing oxygen is 2-25 body
Product %.In order to more convenient and implement the present invention at low cost, under preferable case, the roasting can carry out in air.
Wherein, the condition roasted can change in a big way, such as the temperature of roasting is 200-500 DEG C, excellent
It is selected as 300-450 DEG C, the time of roasting is 0.5-48h, preferably 2-24h.The strategy of temperature programming can be used by carrying out roasting
Heated, for example, roasting temperature be 200-450 DEG C when, 1-12h is roasted at 200-300 DEG C first, is then existed
1-12h is roasted at 310-450 DEG C；Such as the temperature of roasting be 300-450 DEG C when, roast 1-12h at 300-350 DEG C first,
Then 1-12h is roasted at 380-450 DEG C.Wherein, room temperature can be cooled to natural cooling after roasting.
According to the method for the present invention, wherein selecting for the solid carbon source can be the selection of carbon catalytic field routine, only
The catalysis aoxidized after the solid carbon source hydrothermal treatment with catalytic hydrocarbon, such as the solid carbon source is wanted to can wrap
Include carbon nanotube, graphene, fullerene, nano carbon particle, active carbon, thin layer graphite, carbon nano-fiber and Nano diamond etc.
At least one of.Preferably, the solid carbon source includes at least one of carbon nanotube, Nano diamond and graphene.
Wherein, the carbon nanotube may include single-walled carbon nanotube and/or multi-walled carbon nanotube.The carbon nanotube
Specific surface area can change in a big way, for example, 20-1000m2/ g, preferably 30-500m2/g.The carbon nanotube can
It can also be prepared according to literature method with being commercially available, this is does not repeat known to those skilled in the art herein.
In the case of with the method for the invention it is preferred to, when the solid carbon source is multi-walled carbon nanotube, the multi wall carbon
The W of nanotube500/W800It can be in the range of 0.02-0.5；The W of the more preferably described multi-walled carbon nanotube500/W800?
In the range of 0.05-0.25.Under the preferable case, the carbon-based material that method of the invention obtains can when being used as catalyst
Better catalytic effect is obtained, when being especially used as the catalyst of hydrocarbons dehydrogenation reaction, higher raw material conversion can be obtained
Rate and selectivity of product.Wherein, W800Under the Elevated Temperature Conditions for referring to air atmosphere and 25 DEG C of initial temperature and 10 DEG C/min,
Slip of the solid carbon source in the weight at 800 DEG C relative to the weight at 400 DEG C, i.e., (solid carbon source is at 400 DEG C
Under weight and the solid carbon source in the weight difference at 800 DEG C) the weight of/solid carbon source at 400 DEG C, W500Refer to
Under the Elevated Temperature Conditions of air atmosphere and 25 DEG C of initial temperature and 10 DEG C/min, weight of the solid carbon source at 500 DEG C
Relative to the slip of the weight at 400 DEG C, i.e., (weight of the solid carbon source at 400 DEG C and the solid carbon source are 500
Weight difference at DEG C) the weight of/solid carbon source at 400 DEG C.
In a kind of more preferably embodiment of the invention, the solid carbon source is multi-walled carbon nanotube, described more
The specific surface area of wall carbon nano tube is 50-500m2/ g, preferably 100-400m2/g；The W of the multi-walled carbon nanotube500/W800It can
In the range of 0.02-0.5；The W of the more preferably described multi-walled carbon nanotube500/W800In the range of 0.05-0.25.
Wherein, the solid carbon source can also contain oxygen element, nitrogen and remaining nonmetalloid according to source difference
(such as phosphorus atoms and sulphur atom), can also be without containing oxygen element, nitrogen and remaining nonmetalloid (such as phosphorus atoms and sulphur original
Son).
According to the method for the present invention, when the solid carbon source contains oxygen element, wherein the content of oxygen element is generally not high
In 2 weight %, preferably not higher than 0.5 weight %, it is further preferably not higher than 0.2 weight %.
According to the method for the present invention, when the solid carbon source contains nitrogen, wherein the content of nitrogen is generally not high
In 0.5 weight %, preferably not higher than 0.2 weight %, it is further preferably not higher than 0.1 weight %.
According to the method for the present invention, when the solid carbon source contains remaining nonmetalloid (such as phosphorus atoms and sulphur atom),
Wherein in the solid carbon source oxygen atom and remaining nonmetallic heteroatoms (such as phosphorus atoms and sulphur atom) outside nitrogen-atoms it is total
(based on the element) is measured generally not higher than 0.5 weight %, preferably not higher than 0.2 weight %, is further preferably not higher than 0.1
Weight %.
According to the method for the present invention, the organic amine may include aliphatic amine, hydramine, amide, aliphatic cyclic amine and aromatic amine
One of or it is a variety of.
In the present invention, the quaternary ammonium base can be various organic level Four ammonium alkali；The aliphatic amine can be NH3In extremely
The various compounds that few hydrogen is formed after being replaced by aliphatic alkyl (preferably alkyl)；The hydramine can be NH3In
The various compounds that at least one hydrogen is formed after being replaced by the aliphatic alkyl (preferably alkyl) of hydroxyl；The amide can be with
The compound formed after being replaced for the hydroxyl in carboxylic acid by amino (or amido)；The aliphatic cyclic amine can be NH3In at least one
The various compounds that a hydrogen is formed after being replaced by cycloalkyl group；The aromatic amine can be NH3In at least one hydrogen it is fragrant
The various compounds that alkyl is formed after replacing.
Specifically, the quaternary ammonium base can be quaternary ammonium base shown in formula I, what the aliphatic amine can indicate for Formula II
Aliphatic amine, the hydramine can be the hydramine such as formula III expression:
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, C1-C4Alkyl include C1-C4Straight chained alkyl and C3-C4
Branched alkyl, such as: R1、R2、R3And R4It can be respectively methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, different
Butyl or tert-butyl.
R5(NH2)n(Formula II)
In Formula II, n is an integer of 1 or 2.When n is 1, R5For C1-C6Alkyl, including C1-C6Straight chained alkyl and C3-C6
Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, new penta
Base, isopentyl, tertiary pentyl or n-hexyl.When n is 2, R5For C1-C6Alkylidene, including C1-C6Straight-chain alkyl-sub and C3-C6
Branched alkylidene, such as methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.More preferably fat
Race's amine compounds are one of ethamine, n-butylamine, butanediamine and hexamethylene diamine or a variety of.
(HOR6)mNH(3-m)(formula III)
In formula III, m R6It is identical or different, respectively C1-C4Alkylidene, including C1-C4Straight-chain alkyl-sub and C3-
C4Branched alkylidene, such as methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is 1,2 or 3.It is highly preferred that the hydramine
Compound is one of monoethanolamine, diethanol amine and triethanolamine or a variety of.
Wherein, the specific example of the aliphatic amine can include but is not limited to ethamine, n-propylamine, n-butylamine, two positive third
At least one of amine, butanediamine and hexamethylene diamine.The specific example of the fatty alcohol amine can include but is not limited to monoethanolamine,
At least one of diethanol amine and triethanolamine；The specific example of the quaternary ammonium base can include but is not limited to tetramethyl hydrogen-oxygen
Change at least one of ammonium, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.The amide it is specific
Example can include but is not limited to formamide, acetamide, propionamide, butyramide, isobutyramide, acrylamide, polyacrylamide,
At least one of caprolactam, dimethylformamide and dimethyl acetamide.The specific example of the aliphatic cyclic amine may include
But it is not limited to triethylenediamine, diethylenetriamines, hexa, hexamethylene imine, triethylenediamine, ring second
At least one of alkene imines, morpholine, piperazine and cyclohexylamine.The specific example of the aromatic amine can include but is not limited to benzene
Amine, diphenylamines, benzidine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, o-toluidine, m-toluidine, open-chain crown ether,
23 dimethyl aniline, 2,4- dimethylaniline, 2,5- dimethylaniline, 2,6- dimethylaniline, 3,4- dimethylaniline, 3,
At least one in 5- dimethylaniline, 2,4,6- trimethylaniline, o ethyl aniline, N- butylaniline and 2,6- diethylaniline
Kind.
On the other hand, the present invention also provides the carbon-based materials that method as described above is prepared.
Wherein, the carbon-based material that this method obtains can the carbon containing 70-99.75 weight %, 0.05-10 weight %
Nitrogen and 0.2-20 weight % oxygen element, preferably comprise the nitrogen member of the carbon of 80-97 weight %, 0.2-8 weight %
Element and 0.5-15 weight % oxygen element, further preferably the carbon of 85-95 weight %, 0.5-5 weight % nitrogen and
The oxygen element of 2-10 weight %.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that this method obtains, the peak within the scope of 533.1-533.5eV
Range of the ratio of the amount for the oxygen element that the amount of determining oxygen element and the peak within the scope of 531.8-532.2eV determine in 0.2-5
It is interior.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that this method obtains, the peak within the scope of 398.0-400.5eV
Range of the ratio of the amount for the nitrogen that the amount of determining nitrogen and the peak within the scope of 395.0-405.0eV determine in 0.5-1
It is interior.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that this method obtains, the peak within the scope of 400.6-401.5eV
Range of the ratio of the amount for the nitrogen that the amount of determining nitrogen and the peak within the scope of 395.0-405.0eV determine in 0-0.5
It is interior.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that this method obtains, the peak within the scope of 283.8-284.2eV
Range of the ratio of the amount for the carbon that the amount of determining carbon and the peak within the scope of 280.0-294.0eV determine in 0.6-1
It is interior.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that this method obtains, the peak within the scope of 286.2-286.6eV
The sum of amount of carbon that the amount of determining carbon and the peak within the scope of 288.6-289.0eV determine and 280.0-294.0eV
The ratio of the amount for the carbon that peak in range determines is in the range of 0.02-0.2.
Wherein, in the x-ray photoelectron spectroscopy for the carbon-based material that this method obtains, the peak within the scope of 286.2-286.6eV
Range of the ratio of the amount for the carbon that the amount of determining carbon and the peak within the scope of 288.6-289.0eV determine in 0.3-2
It is interior.
The carbon-based material obtained according to the method for the present invention, mistake of the carbon-based material in 400-800 DEG C of temperature range
Rate is W again800, the weight-loss ratio in 400-500 DEG C of temperature range is W500, W500/W800It is preferred that in the range of 0.02-0.5,
More preferably in the range of 0.05-0.25.Better catalytic effect can be obtained in this way, and it is anti-to be especially used as hydrocarbons dehydrogenation
When the catalyst answered, higher feed stock conversion and selectivity of product can be obtained.In the present invention, the weight-loss ratio is in air atmosphere
Middle measurement, initial temperature are 25 DEG C, and heating rate is 10 DEG C/min.
The carbon-based material obtained according to the method for the present invention, the distribution uniform of nitrogen therein and oxygen element.Such as logical
When crossing the analysis of X-ray microregion element, in the identical different X-ray microcells of the area on the surface of the carbon-based material, nitrogen and oxygen element
Content the coefficient of variation below 20%.Wherein, X-ray microcell refers to the sight selected when carrying out the analysis of X-ray microregion element
Survey region.Wherein, the concept of the coefficient of variation refers to the standard deviation of multiple measured values and the percentage of their average, that is, makes a variation
Coefficient CV=(standard deviation SD/ average value MN) × 100%.Wherein, the method for carrying out the analysis of X-ray microregion element can be according to instrument
It may include: along length with energy depressive spectroscopy in 25- that the method for analysis field routine, which measures to obtain for example specific test method,
The length direction of carbon-based material such as carbon nanotube in the range of 250nm is scanned, and determines nitrogen-atoms and oxygen atom respectively
Five effectively examinations are made by same nano-carbon material in concentration or content (5 concentration of measurement or content) on the length direction
Sample is scanned Electronic Speculum-energy spectrum analysis respectively, and each sample takes 5 different carbon nanotubes to be scanned, nitrogen-atoms and oxygen atom
25 concentration or content data respectively are obtained, calculates the coefficient of variation of corresponding nitrogen-atoms and oxygen atom.The coefficient of variation refers to herein
The percentage of the standard deviation of 25 measured values and their average, i.e. coefficient of variation CV=(standard deviation SD/ average value MN) ×
100%.In order to preferably reflect the distributing homogeneity of nitrogen and oxygen element in carbon-based material, the analysis of X-ray microregion element
In the area on surface of selected carbon-based material can be 10-250nm2, preferably 20-200nm2。
Wherein, it includes this hair that method of the invention, which obtains having the possible cause of the carbon-based material of above-mentioned pathognomonic feature parameter,
It is that the treatment processes such as hydro-thermal and roasting are combined under specific material variety and material proportion in bright method.
The structural form of the carbon-based material obtained according to the method for the present invention may include carbon nanotube, graphene, fullerene,
At least one of nano carbon particle, active carbon, thin layer graphite, carbon nano-fiber and structural form of Nano diamond.
In another aspect, the present invention also provides the carbon-based materials that carbon-based material as described above and method as above are prepared
Purposes in catalysis oxidation reactions of hydrocarbons.
Wherein, the carbon atom number of the hydrocarbon can be 2-15, and the hydrocarbon includes alkane, alkene and the aromatic hydrocarbon containing alkyl
At least one of；The alkyl contains at least two carbon atoms.Preferably, the hydrocarbon includes butane, 1- butylene, ethylbenzene, third
At least one of alkane, ethane and pentane.
Wherein, carbon-based material as described above can use in oxidation reactions of hydrocarbons as catalyst, and have higher
Hydrocarbon catalyticing oxidation performance.
Wherein, the condition of oxidation reactions of hydrocarbons can be the process conditions of low-carbon alkanes catalytic oxidation routine, such as react
Temperature can be 200-650 DEG C, preferably 300-600 DEG C, more preferably 350-550 DEG C are still more preferably 400-450
DEG C, it can be 0.05-80MPa, preferably 0.1-40MPa, more preferably 0.1-20MPa that the pressure of reaction, which can be pressure, more
Further preferably 0.1-5MPa, the concentration of hydrocarbon can be the preferred 1-10 volume % of 1-30 volume %, the molar ratio of hydrocarbon and oxygen
Can be (0.1-10): 1, preferably (0.2-5): 1, in raw material in addition to containing hydrocarbon and oxygen, it can also contain other with carrier gas
The balanced gas that form introduces, wherein carrier gas can contain nitrogen, group 0 element gas (such as argon gas), CO2With in vapor etc.
At least one.The duration of the reaction can be selected according to the temperature of contact, can use the body of the gas of charging
Air speed is accumulated to indicate the duration of reaction.Generally, the volume space velocity of the gas of charging can be 0.1-10000h-1, preferably
For 1-6000h-1, more preferably 5-5000h-1, further preferably 10-4000h-1。
Present invention be described in more detail by the following examples.In following embodiment and comparative example, if not otherwise specified,
Used reagent is commercially available analytical reagents.Wherein, the phosphorus content without containing oxygen element carbon nanotube is greater than 96 weights
% is measured, ash content is less than 1.5 weight %, specific surface area 168m2/ g is purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences,
Phosphorus content containing oxygen element carbon nanotube is greater than 95 weight %, and oxygen element content is 1.1 weight %, and ash content is less than 1.2 weights
Measure %, specific surface area 211m2/ g is purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.The phosphorus content of graphene is greater than
99 weight %, ash content is less than 0.8 weight %, specific surface area 627m2/ g is purchased from the limited public affairs of Chinese Academy of Sciences Chengdu organic chemistry
Department.
In following embodiment and comparative example, X-ray photoelectron spectroscopic analysis is in Thermo Scientific company
It is carried out on ESCALab250 type x-ray photoelectron spectroscopy.Excitaton source be monochromatization Al K α X-ray, energy 1486.6eV,
Power is 150W.Penetrating used in narrow scan can be 30eV.Base vacuum when analysis test is 6.5 × 10-10mbar.Electronics knot
Closing can be corrected with the peak C1s (284.0eV) of simple substance carbon.The Thermo that Correlation method for data processing is carried in x-ray photoelectron spectroscopy
It carries out on Avantage software, version number V5.926, is carried out in analysis module using sensitivity factor method known to industry
It is quantitative to wait analysis.
In following embodiment and comparative example, thermogravimetric analysis carries out on TA5000 thermal analyzer, and test condition is air gas
Atmosphere, heating rate are 10 DEG C/min, and temperature range is room temperature (25 DEG C) to 1000 DEG C.
In following embodiment and comparative example, using the ASAP2000 type N of Micromertrics company, the U.S.2Physical absorption
Instrument measurement the specific area.
In following embodiment and comparative example, using the scanning electron microscope equipped with energy depressive spectroscopy (component), (Dutch PHILIPS is public
Take charge of XL 30ESEM type scanning electron microscope) measure nano-carbon material (by taking carbon nanotube as an example) surface nitrogen atom and oxygen atom
Distributing homogeneity, specific test method are as follows: carbon nanotube with energy depressive spectroscopy along length in the range of 25-250nm
Length direction is scanned, and the concentration (5 concentration of measurement) of nitrogen-atoms and oxygen atom on the length direction is determined respectively, by same
One nano-carbon material is made five effective samples and is scanned Electronic Speculum-energy spectrum analysis respectively, and each sample takes 5 different carbon nanometers
Pipe is scanned, and nitrogen-atoms and oxygen atom respectively obtain 25 concentration datas, calculates the variation lines of corresponding nitrogen-atoms and oxygen atom
Number.The coefficient of variation refers to the standard deviation of 25 measured values and the percentage of their average, i.e. coefficient of variation CV=(mark herein
Quasi- difference SD/ average value MN) × 100%.
Embodiment 1
At room temperature, by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetrapropylammonium hydroxide) and mistake
Oxidation aqueous solution of hydrogen (content of hydrogen peroxide is 2 weight %) is stirred 2h, obtains mixed material, wherein the solid
The molar ratio of the nitrogen in carbon and the presoma in carbon source is 1:0.1, the solid carbon source and aquae hydrogenii dioxidi
The molar ratio of hydrogen peroxide in solution is 1:0.5, and mixed material obtained above is placed in in polytetrafluoroethylene (PTFE)
In the sealing autoclave of lining, in 140 DEG C at autogenous pressures hydro-thermal process for 24 hours, by consolidating in the material after hydro-thermal process
Body is separated by filtration and is dried, and dry temperature is 120 DEG C, until the solid being separated by filtration is kept substantially constant weight
(dry time be 6h), the material after being dried, the then maturing temperature by the material after obtained drying at 330 DEG C
Under, 2h is roasted in air, then under 430 DEG C of maturing temperature, roasts 2h in air, obtains the carbon substrate of the present embodiment
Material.
Embodiment 2
At room temperature, by solid carbon source (carbon nanotube without containing oxygen element), presoma (caprolactam) and hydrogen peroxide
Aqueous solution (content of hydrogen peroxide is 5 weight %) is stirred 1h, obtains mixed material, wherein in the solid carbon source
Carbon and the presoma in the molar ratio of nitrogen be 1:0.05, in the solid carbon source and aqueous hydrogen peroxide solution
Hydrogen peroxide molar ratio be 1:0.2, mixed material obtained above is placed in the close of polytetrafluoroethyllining lining
Seal autoclave in, in 180 DEG C at autogenous pressures hydro-thermal process for 24 hours, by the material after hydro-thermal process solid filter
It separates and is dried, dry temperature is 120 DEG C, until the solid being separated by filtration is kept substantially constant weight and (dries
Time is 6h), the material after being dried, then by the material after obtained drying under 300 DEG C of maturing temperature, in air
Middle roasting 2h roasts 2h then under 400 DEG C of maturing temperature in air, obtains the carbon-based material of the present embodiment.
Embodiment 3
At room temperature, by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetraethyl ammonium hydroxide) and mistake
Oxidation aqueous solution of hydrogen (content of hydrogen peroxide is 30 weight %) is stirred 3h, obtains mixed material, wherein the solid
The molar ratio of the nitrogen in carbon and the presoma in carbon source is 1:5, and the solid carbon source and hydrogen peroxide are water-soluble
The molar ratio of hydrogen peroxide in liquid is 1:0.1, and mixed material obtained above is placed in polytetrafluoroethyllining lining
Sealing autoclave in, in 120 DEG C of hydro-thermal process 48h at autogenous pressures, by the solid in the material after hydro-thermal process
It is separated by filtration and is dried, dry temperature is 120 DEG C, until the solid being separated by filtration is kept substantially constant weight and (does
The dry time is 6h), the material after being dried, then by the material after obtained drying under 350 DEG C of maturing temperature,
2h is roasted in air, then under 450 DEG C of maturing temperature, roasts 2h in air, obtains the carbon-based material of the present embodiment.
Embodiment 4
At room temperature, by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetrapropylammonium hydroxide) and mistake
Oxidation aqueous solution of hydrogen (content of hydrogen peroxide is 40 weight %) is stirred 5h, obtains mixed material, wherein the solid
The molar ratio of the nitrogen in carbon and the presoma in carbon source is 1:0.008, the solid carbon source and hydrogen peroxide
The molar ratio of hydrogen peroxide in aqueous solution is 1:4, and mixed material obtained above is placed in in polytetrafluoroethylene (PTFE)
In the sealing autoclave of lining, in 160 DEG C of hydro-thermal process 12h at autogenous pressures, by consolidating in the material after hydro-thermal process
Body is separated by filtration and is dried, and dry temperature is 120 DEG C, until the solid being separated by filtration is kept substantially constant weight
(dry time be 6h), the material after being dried, the then maturing temperature by the material after obtained drying at 330 DEG C
Under, 2h is roasted in air, then under 380 DEG C of maturing temperature, roasts 2h in air, obtains the carbon substrate of the present embodiment
Material.
Embodiment 5
At room temperature, by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetrapropylammonium hydroxide) and mistake
Oxidation aqueous solution of hydrogen (content of hydrogen peroxide is 0.5 weight %) is stirred 6h, obtains mixed material, wherein described solid
The molar ratio of the nitrogen in carbon and the presoma in body carbon source is 1:15, the solid carbon source and aquae hydrogenii dioxidi
The molar ratio of hydrogen peroxide in solution is 1:0.04, and mixed material obtained above is placed in in polytetrafluoroethylene (PTFE)
In the sealing autoclave of lining, in 150 DEG C at autogenous pressures hydro-thermal process for 24 hours, by consolidating in the material after hydro-thermal process
Body is separated by filtration and is dried, and dry temperature is 120 DEG C, until the solid being separated by filtration is kept substantially constant weight
(dry time be 6h), the material after being dried, the then maturing temperature by the material after obtained drying at 350 DEG C
Under, 2h is roasted in air, then under 450 DEG C of maturing temperature, roasts 2h in air, obtains the carbon substrate of the present embodiment
Material.
Embodiment 6
Carbon-based material is prepared using the method with embodiment 1, unlike, the temperature of hydro-thermal process is 195 DEG C.
Embodiment 7
Carbon-based material is prepared using the method with embodiment 1, unlike, the temperature of hydro-thermal process is 105 DEG C.
Embodiment 8
Carbon-based material is prepared using the method with embodiment 1, unlike, tetrapropylammonium hydroxide is replaced with into hexamethylene diamine
With the equal weight mixtures of n-butylamine.
Embodiment 9
Carbon-based material is prepared using the method with embodiment 1, unlike, tetrapropylammonium hydroxide is replaced with into diethanol
The equal weight mixtures of amine and aniline.
Embodiment 10
Carbon-based material is prepared using the method with embodiment 1, unlike carbon nanotube is replaced with etc. to the graphite of weight
Alkene.
Embodiment 11
Carbon-based material is prepared using the method with embodiment 1, unlike, the material after obtained drying is at 330 DEG C
Under maturing temperature, 4h is roasted in air.
Embodiment 12
Carbon-based material is prepared using the method with embodiment 1, unlike, the material after obtained drying is at 430 DEG C
Under maturing temperature, 4h is roasted in air.
Embodiment 13
Carbon-based material is prepared using the method with embodiment 1, unlike, the material after obtained drying is at 500 DEG C
Under maturing temperature, 1h is roasted in air.
Embodiment 14
Carbon-based material is prepared using the method with embodiment 1, unlike, the material after obtained drying is at 210 DEG C
Under maturing temperature, 4h is roasted in air.
Embodiment 15
Carbon-based material is prepared using the method with embodiment 1, unlike, solid carbon source is the carbon nanometer containing oxygen element
Pipe, roasting carry out in argon gas.
Embodiment 16
Carbon-based material is prepared using the method with embodiment 1, unlike, solid carbon source is the carbon nanometer containing oxygen element
Pipe, roasting carry out in air.
Embodiment 17
Carbon-based material is prepared using the method with embodiment 1, unlike, roasting carries out in nitrogen.
Comparative example 1
At room temperature, by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetrapropylammonium hydroxide) and mistake
Oxidation aqueous solution of hydrogen (content of hydrogen peroxide is 2 weight %) is stirred 6h, obtains mixed material, wherein the solid
The molar ratio of the nitrogen in carbon and the presoma in carbon source is 1:0.1, the solid carbon source and aquae hydrogenii dioxidi
The molar ratio of hydrogen peroxide in solution is 1:0.5, mixed material obtained above is dried, dry temperature is
120 DEG C, until the solid being separated by filtration is kept substantially constant weight (the dry time is 6h), the material after being dried,
Then by the material after obtained drying under 330 DEG C of maturing temperature, 2h is roasted in air, then in 430 DEG C of roasting
At a temperature of, 2h is roasted in air, using the material after roasting as the carbon-based material of this comparative example.
Comparative example 2
At room temperature, by solid carbon source (carbon nanotube without containing oxygen element), presoma (tetrapropylammonium hydroxide) and mistake
Oxidation aqueous solution of hydrogen (content of hydrogen peroxide is 2 weight %) is stirred 6h, obtains mixed material, wherein the solid
The molar ratio of the nitrogen in carbon and the presoma in carbon source is 1:0.1, the solid carbon source and aquae hydrogenii dioxidi
The molar ratio of hydrogen peroxide in solution is 1:0.5, and mixed material obtained above is placed in in polytetrafluoroethylene (PTFE)
It, will be in the material after hydro-thermal process in 140 DEG C of hydro-thermal process 24 hours at autogenous pressures in the sealing autoclave of lining
Solid is separated by filtration and is dried, and dry temperature is 120 DEG C, until the solid being separated by filtration is kept substantially constant weight
(the dry time is 6h), the material after being dried, then using the material after obtained drying as the carbon-based of this comparative example
Material.
Testing example 1
The side of method or reference in reference literature (Jian Zhang et al., Science 322 (2008), 73-77)
Method, buy to the obtained carbon-based material of embodiment 1-17 and comparative example 1-2 and as described above containing/receive without containing oxygen element carbon
Mitron carries out elemental analysis and XPS atlas analysis.Wherein, be in x-ray photoelectron spectroscopy 300 DEG C at a temperature of in helium
It is measured after processing 3h in atmosphere.The results are shown in Table 1.
In table 1, the O of XPS map column indicates the amount and 531.8- for the oxygen element that the peak within the scope of 533.1-533.5eV determines
The ratio of the amount for the oxygen element that peak within the scope of 532.2eV determines；The C1 of XPS map column is indicated within the scope of 283.8-284.2eV
Peak determine carbon amount and 280.0-294.0eV within the scope of peak determination carbon amount ratio × 100 (percentage
Ratio)；The amount and the peak within the scope of 288.6-289.0eV that C2 indicates the carbon that the peak within the scope of 286.2-286.6eV determines
Amount × 100 (percent value) for the carbon that the sum of determining amount of carbon is determined with the peak within the scope of 280.0-294.0eV；
C3 refers to the amount for the carbon that the peak within the scope of 286.2-286.6eV determines and the carbon that the peak within the scope of 288.6-289.0eV determines
The ratio of the amount of element.The N1 of XPS map column refers to the amount and 395.0- for the nitrogen that the peak within the scope of 398.0-400.5eV determines
Ratio × 100 (percent value) of the amount for the nitrogen that peak within the scope of 405.0eV determines；N2 refers to 400.6-401.5eV range
Ratio × 100 (hundred of the amount for the nitrogen that the amount for the nitrogen that interior peak determines and the peak within the scope of 395.0-405.0eV determine
Divide ratio).W indicates W500/W800× 100 (percent values).C, N and the O of element group in column respectively indicate the element of carbon, nitrogen and oxygen
Composition.When CV indicated the analysis of X-ray microregion element, in the identical different X-ray microcells of the area on the surface of the carbon-based material, nitrogen member
The coefficient of variation of the content of element and oxygen element.
Table 1
According to the analysis test data of embodiment 1-17 in table 1 and comparative example 1-2 can be seen that may be due to joined before
It drives body and hydrogen peroxide and has carried out hydro-thermal and roasting, so that in the XPS map of carbon-based material, within the scope of 533.1-533.5eV
Peak determine oxygen element amount and 531.8-532.2eV within the scope of peak determine oxygen element amount ratio 0.2-5's
In range；What the amount for the nitrogen that the peak within the scope of 398.0-400.5eV determines and the peak within the scope of 395.0-405.0eV determined
The ratio of the amount of nitrogen is in the range of 0.5-1；The amount for the nitrogen that peak within the scope of 400.6-401.5eV determines with
The ratio of the amount for the nitrogen that peak within the scope of 395.0-405.0eV determines is in the range of 0-0.5；283.8-284.2eV model
The ratio of the amount for the carbon that the amount for the carbon that peak in enclosing determines and the peak within the scope of 280.0-294.0eV determine is in 0.6-
In the range of 1；The amount for the carbon that peak within the scope of 286.2-286.6eV determines and the peak within the scope of 288.6-289.0eV are true
The ratio of the amount for the carbon that the sum of fixed amount of carbon is determined with the peak within the scope of 280.0-294.0eV is 0.02-0.2's
In range；What the amount for the carbon that the peak within the scope of 286.2-286.6eV determines and the peak within the scope of 288.6-289.0eV determined
The ratio of the amount of carbon is in the range of 0.3-2；W500/W800For 0.05-0.25；In the identical different X-ray microcells of area, N
The coefficient of variation of the content of element and O element is below 20%.
Testing example 2
That buys respectively by the obtained carbon-based material of the embodiment 1-17 of 0.25g and comparative example 1-2 and as described above contains
Oxygen element carbon nanotube and without containing oxygen element carbon nanotube as catalyst, be loaded into universal fixed bed miniature quartz pipe
In reactor, two end seal of miniature quartz pipe reactor has quartz sand, under the conditions of normal pressure and 420 DEG C, by the material (volume of butane
Concentration is 1.98%, and butane and oxygen molar ratio 2:3, Balance Air is nitrogen) total volume air speed be 1000h-1Under reacted,
According to the method in document (322 (2008) 73-77 of Jian Zhang et al., Science) after reaction 8h, measures butane and turn
Rate, butadiene selective and total olefin selectivity, the results are shown in Table 2.
Table 2
According to the data of table 2, it is found that the carbon-based material that the present invention obtains can improve hydrocarbon oxygen as catalyst simultaneously
Fluidized dehydrogenation prepares the selectivity and conversion ratio of alkene.Contain the carbon of 85-95 weight %, 0.5-5 in the preferably carbon-based material
The nitrogen of weight % and the oxygen element of 2-10 weight %, in the x-ray photoelectron spectroscopy in the carbon-based material, 533.1-
The amount for the oxygen element that the amount for the oxygen element that peak within the scope of 533.5eV determines and the peak within the scope of 531.8-532.2eV determine
In the case that ratio is in the range of 0.6-1.8, can further simultaneously improve hydrocarbon oxidative dehydrogenation prepare alkene selectivity and
Conversion ratio.Also, it, can in the case where the temperature of preferred hydro-thermal process is 120-180 DEG C and maturing temperature is 300-450 DEG C
Selectivity and conversion ratio that oxidative dehydrogenation prepares alkene are further improved simultaneously.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (21)
1. a kind of carbon-based material, it is characterised in that: on the basis of the total weight of the carbon-based material, which contains 70-
The oxygen element of the carbon of 99.75 weight %, the nitrogen of 0.05-10 weight % and 0.2-20 weight %；Wherein, the carbon substrate
In the x-ray photoelectron spectroscopy of material, the amount and 531.8-532.2eV of the oxygen element that the peak within the scope of 533.1-533.5eV determines
The ratio of the amount for the oxygen element that peak in range determines in the range of 0.2-5, what the peak within the scope of 398.0-400.5eV determined
The ratio of the amount for the nitrogen that the amount of nitrogen and the peak within the scope of 395.0-405.0eV determine is in the range of 0.5-1.
2. carbon-based material according to claim 1, wherein on the basis of the total weight of the carbon-based material, the carbon-based material
The oxygen element of carbon containing 80-97 weight %, the nitrogen of 0.2-8 weight % and 0.5-15 weight %, the carbon-based material
X-ray photoelectron spectroscopy in, the amount and 531.8-532.2eV model of the oxygen element that peak within the scope of 533.1-533.5eV determines
The ratio of the amount for the oxygen element that peak in enclosing determines is in the range of 0.5-2.
3. carbon-based material according to claim 2, wherein on the basis of the total weight of the carbon-based material, the carbon-based material
The oxygen element of carbon containing 85-95 weight %, the nitrogen of 0.5-5 weight % and 2-10 weight %, in the carbon-based material
X-ray photoelectron spectroscopy in, the amount and 531.8-532.2eV model of the oxygen element that peak within the scope of 533.1-533.5eV determines
The ratio of the amount for the oxygen element that peak in enclosing determines is in the range of 0.6-1.8.
4. carbon-based material described in any one of -3 according to claim 1, wherein the x-ray photoelectron of the carbon-based material
In power spectrum, what the amount for the nitrogen that the peak within the scope of 400.6-401.5eV determines was determined with the peak within the scope of 395.0-405.0eV
The ratio of the amount of nitrogen is in the range of 0-0.5.
5. carbon-based material described in any one of -3 according to claim 1, wherein the x-ray photoelectron energy of the carbon-based material
In spectrum, the amount for the carbon that the peak within the scope of 283.8-284.2eV the determines carbon determining with the peak within the scope of 280.0-294.0eV
The ratio of the amount of element is in the range of 0.6-1；
The carbon that the amount for the carbon that peak within the scope of 286.2-286.6eV determines and the peak within the scope of 288.6-289.0eV determine
Range of the ratio of the amount for the carbon that the sum of amount of element is determined with the peak within the scope of 280.0-294.0eV in 0.02-0.2
It is interior；
The carbon that the amount for the carbon that peak within the scope of 286.2-286.6eV determines and the peak within the scope of 288.6-289.0eV determine
The ratio of the amount of element is in the range of 0.3-2.
6. carbon-based material described in any one of -3 according to claim 1, wherein the area phase on the surface of the carbon-based material
In same different X-ray microcells, the coefficient of variation of the content of nitrogen and oxygen element each comfortable 20% or less.
7. carbon-based material described in any one of -3 according to claim 1, wherein the W of the carbon-based material500/W800?
In the range of 0.02-0.5；Wherein, W800Refer to the Elevated Temperature Conditions of air atmosphere and 25 DEG C of initial temperature and 10 DEG C/min
Under, slip of the carbon-based material in the weight at 800 DEG C relative to the weight at 400 DEG C, W500Refer to air atmosphere and 25
DEG C initial temperature and 10 DEG C/min Elevated Temperature Conditions under, the carbon-based material is in the weight at 500 DEG C relative at 400 DEG C
Weight slip.
8. carbon-based material described in any one of -3 according to claim 1, wherein the structural form of the carbon-based material includes carbon
The structure of nanotube, graphene, fullerene, nano carbon particle, active carbon, thin layer graphite, carbon nano-fiber and Nano diamond
At least one of form.
9. a kind of method for preparing carbon-based material described in any one of claim 1-8, it is characterised in that: this method includes
Following steps:
(1) solid carbon source, presoma and aqueous hydrogen peroxide solution are mixed, obtains mixed material；Wherein, the presoma
Containing organic alkali source, organic alkali source includes machine amine and/or quaternary ammonium base；
(2) the mixed material for obtaining step (1) carries out hydro-thermal process, the material after obtaining hydro-thermal process；And it separates
The solid in material after hydro-thermal process；
(3) solid in the material after hydro-thermal process that step (2) obtains is roasted.
10. according to the method described in claim 9, wherein, in the carbon and organic alkali source in the solid carbon source
The molar ratio of nitrogen is 1:(0.002-50)；The mistake in carbon and the aqueous hydrogen peroxide solution in the solid carbon source
The molar ratio of hydrogen oxide is 1:(0.01-10).
11. method according to claim 9 or 10, wherein in the carbon and organic alkali source in the solid carbon source
Nitrogen molar ratio be 1:(0.01-10)；In carbon and the aqueous hydrogen peroxide solution in the solid carbon source
The molar ratio of hydrogen peroxide is 1:(0.1-2).
12. according to the method described in claim 9, wherein, the concentration of the aqueous hydrogen peroxide solution is 0.5-80 weight %.
13. according to the method described in claim 9, wherein, the temperature for carrying out hydro-thermal process is 105-200 DEG C；It carries out at hydro-thermal
The time of reason is 0.5-96h；The temperature of roasting is 200-500 DEG C, and the time of roasting is 0.5-48h.
14. according to the method for claim 13, wherein the temperature for carrying out hydro-thermal process is 120-180 DEG C；The temperature of roasting
It is 300-450 DEG C.
15. according to the method described in claim 9, wherein, roasting carries out in the gas containing oxygen, with the gas containing oxygen
On the basis of the total volume of body, the content of the oxygen in the gas containing oxygen is 2-25 volume %.
16. according to the method described in claim 9, wherein, the carbon source is selected from carbon nanotube, graphene, fullerene, nano-sized carbon
At least one of particle, thin layer graphite, active carbon, carbon nano-fiber and Nano diamond.
17. according to the method described in claim 9, wherein, the organic amine include aliphatic amine, hydramine, amide, aliphatic cyclic amine and
At least one of aromatic amine；The aliphatic amine is selected from ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine and hexamethylene diamine
At least one of；The hydramine is selected from least one of monoethanolamine, diethanol amine and triethanolamine；The quaternary ammonium base choosing
From at least one of tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide；Institute
State amide be selected from formamide, acetamide, propionamide, butyramide, isobutyramide, acrylamide, polyacrylamide, caprolactam,
At least one of dimethylformamide and dimethyl acetamide；The aliphatic cyclic amine is selected from triethylenediamine, diethylidene three
In amine, hexa, hexamethylene imine, triethylenediamine, cyclic ethylene imines, morpholine, piperazine and cyclohexylamine extremely
Few one kind；The aromatic amine is selected from aniline, diphenylamines, benzidine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, o-methyl-benzene
Amine, m-toluidine, open-chain crown ether, 23 dimethyl aniline, 2,4- dimethylaniline, 2,5- dimethylaniline, 2,6- bis-
Methylaniline, 3,4- dimethylaniline, 3,5- dimethylaniline, 2,4,6- trimethylaniline, o ethyl aniline, N- butylaniline
At least one of with 2,6- diethylaniline.
18. the carbon-based material that method described in any one of claim 9-17 is prepared.
19. purposes of the carbon-based material described in any one of claim 1-8 and 18 in catalysis oxidation reactions of hydrocarbons.
20. purposes according to claim 19, wherein the carbon atom number of the hydrocarbon is 2-15, and the hydrocarbon includes alkane, alkene
At least one of hydrocarbon and the aromatic hydrocarbon containing alkyl；The alkyl contains at least two carbon atoms.
21. purposes according to claim 20, wherein the hydrocarbon includes butane, 1- butylene, ethylbenzene, propane, ethane and penta
At least one of alkane.
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