CN108298542A - A kind of method and its application growing graphene in silicon carbide - Google Patents
A kind of method and its application growing graphene in silicon carbide Download PDFInfo
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- CN108298542A CN108298542A CN201710021554.3A CN201710021554A CN108298542A CN 108298542 A CN108298542 A CN 108298542A CN 201710021554 A CN201710021554 A CN 201710021554A CN 108298542 A CN108298542 A CN 108298542A
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The present invention provides a kind of method growing graphene in silicon carbide, includes the following steps：1）Under reducing atmosphere by SiC powder, it is pre-processed at 600 1200 DEG C；2）Again by step 1）In SiC after pretreatment under an inert atmosphere, after 1,100 1800 DEG C are kept the temperature, obtain needed for surface growth graphene SiC.Invention further provides a kind of graphenes made from the above method and silicon carbide composite catalyst and its application.A kind of method and its application growing graphene in silicon carbide provided by the invention, high-quality graphene/silicon carbide composite can be prepared, as catalyst, its performance is greatly improved, and the photodegradation, carbon dioxide by photoelectric catalytic reduction, electro-catalysis that can be used for carbon dioxide restore in carbon dioxide, electrolysis water.
Description
Technical field
The invention belongs to technical field of material chemistry, are related to a kind of method and its application growing graphene in silicon carbide,
More particularly to one kind in silicon carbide extending and growing graphene, prepare graphene and silicon carbide composite catalyst method and
It is applied.
Background technology
Silicon carbide is widely studied due to a series of excellent physicochemical properties, for example, silicon carbide have it is excellent
Chemical stability and thermal stability, higher breakdown electric field add suitable energy gap, be it is a kind of very having application before
The catalysis material of scape.But silicon carbide is in the photocatalytic process, the electronics for moving to particle surface easily occurs with hole again
It is compound and cause quantum efficiency low.How to improve the electronics for moving to particle surface and reduce electronics and hole meet then at
In order to improve the key of reaction efficiency.
Graphene has excellent electric conductivity, high carrier mobility, can reinforce the export of light induced electron, and then subtract
Electrons and holes is compound less.In addition, graphene has high specific surface area, it can enhance and reaction species etc. are adsorbed, are activated
Ability.
How commodity SiC powder particle surface growth mass is high, graphene that the number of plies is as few as possible, be improve,
The key of modified SiC catalytic performances.It is existing at present using the adulterating of graphene, be modified and improve complex catalyst photocatalysis performance
Case study (Oliveira A G D, Martelli P B.Electrochemical synthesis of TiO 2/
Graphene oxide composite films for photocatalytic applications[J].Journal of
Alloys&Compounds,2016,654:514–522.).The method for introducing graphene in the catalyst at present mainly has：It is compound
Method (Hidayah N M S, Liu W W, Chin W L, et al.Effect on Variation of KMnO4Amount
for Production of Graphene Oxide(GO)[J].Advanced Materials Research,2016,1133
(6):1237–1244.)；Epitaxy (Hirooka A, Habuka H, Kato T.Etching Rate Behavior of 4H-
Silicon Carbide Epitaxial Film Using Chlorine Trifluoride Gas[C]//Materials
Science Forum.2016:715-718.) etc..
But existing commercialization silicon carbide, although purity has been up to 99.9wt%, SiC particulate surface is contained micro
Carbon impurity.The study found that these carbon impurities have more detrimental effect to epitaxial growth method, directly with the silicon carbide of commercialization
Powder is raw material, almost can not generate the graphene of high quality.
Invention content
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide one kind growing stone in silicon carbide
The method and its application of black alkene solve the problems, such as that commercialization silicon carbide carbon impurity influences, hinders graphene growth,
The quality that graphene is made in epitaxy is improved, the complex catalyst catalytic performance obtained is greatly improved.
In order to achieve the above objects and other related objects, first aspect present invention provides a kind of in silicon carbide growth stone
The method of black alkene, includes the following steps：
1) it under reducing atmosphere by SiC powder, is pre-processed at 600-1200 DEG C；
2) again by SiC after pretreatment in step 1) under an inert atmosphere, after 1100-1800 DEG C is kept the temperature, obtain
The SiC of required surface growth graphene.
Preferably, in step 1), the SiC powder is the grain size total distributed range of commercialization 100nm-1100nm's
Silicon carbide powder.The SiC powder is the cheap commercialization SiC of high-purity, containing impurity such as C, Si, O, commodity used
Change SiC is the SiC with certain grain size distribution range.
It is highly preferred that the SiC powder is selected from carborundum powder of the grain size total distributed range in 100nm-300nm of commercialization
End, the grain size total distributed range being commercialized exist in the silicon carbide powder of 300nm-600nm, the grain size total distributed range of commercialization
One kind in the silicon carbide powder of 700nm-1100nm.
Preferably, in step 1), the reducing atmosphere is hydrogen atmosphere.
It is highly preferred that further include inert gas in the hydrogen atmosphere, the volume of hydrogen and inert gas in hydrogen atmosphere
The ratio between be 5:95-100:0.
It is further preferred that one kind in nitrogen, argon gas, helium, neon, Krypton, xenon of the inert gas or
It is a variety of.Most preferably, the inert gas is argon gas.
It is further preferred that it is 50 that the hydrogen atmosphere, which is selected from the ratio between volume of hydrogen and inert gas,:50 hydrogen gas
The ratio between volume of atmosphere or hydrogen and inert gas is 100:One kind in 0 hydrogen atmosphere.
Preferably, in step 1), the pretreatment is started to warm up from room temperature.
Preferably, in step 1), the pretreated heating rate is 5-60 DEG C/min.
It is highly preferred that the pretreated heating rate is 20-50 DEG C/min.
Preferably, in step 1), the pretreated temperature is 800-1100 DEG C.
It is highly preferred that the pretreated temperature is 1000-1100 DEG C.
Preferably, in step 1), the pretreated time is 0.5-6h.
It is highly preferred that the pretreated time is 0.5-5h.
Preferably, in step 1), room temperature is required cool to after the pretreatment.
Preferably, in step 2), the inert atmosphere in nitrogen, argon gas, helium, neon, Krypton, xenon one
Kind or multiple atmosphere.
It is highly preferred that the inert atmosphere is argon gas atmosphere.
Preferably, in step 2), the heat preservation is started to warm up from room temperature.
Preferably, in step 2), the heating rate of the heat preservation is 2-50 DEG C/min.
It is highly preferred that the heating rate of the heat preservation is 2-30 DEG C/min.Most preferably, the heating rate of the heat preservation is
5-30℃/min。
Preferably, in step 2), the temperature of the heat preservation is 1200-1700 DEG C.
It is highly preferred that the temperature of the heat preservation is 1500 DEG C.
Preferably, in step 2), the time of the heat preservation is 5s-2h.
It is highly preferred that the time of the heat preservation is 1h.
Preferably, in step 2), room temperature is required cool to after the heat preservation.
Preferably, in step 1) or/and 2), the room temperature is 15-35 DEG C.
Second aspect of the present invention provides a kind of graphene and silicon carbide composite catalyst, by above-mentioned in silicon carbide
The method for growing graphene is made.
Third aspect present invention provides a kind of purposes of graphene and silicon carbide composite catalyst, is used for carbon dioxide
Photovoltaic reaction, electrolysis water.
Preferably, the purposes of a kind of graphene and silicon carbide composite catalyst is used for carbon dioxide photovoltaic reaction.
It is highly preferred that the carbon dioxide photovoltaic reaction is selected from the photodegradation of carbon dioxide, photoelectrocatalysis restores titanium dioxide
It is one or more in carbon, electro-catalysis reduction carbon dioxide.
Preferably, the reaction condition of the catalyst is to take out catalyst obtained after ultrasonic disperse in ethyl alcohol and bear
It is loaded on carbon paper, after vacuum drying oven dries 3-5h, is fitted into reaction unit, reaction temperature is 10-30 DEG C, and reaction pressure is normal
Pressure, gas flow rate 10-200ml/min, electrolyte KHCO3Aqueous solution, bias are -0.4-0V, and light source used is xenon lamp
Source.
It is highly preferred that the vacuum drying oven drying time is 4h.
It is highly preferred that the reaction unit, which is three electrodes, seals quartz reactor.
It is highly preferred that the normal pressure is 100KPa.
It is highly preferred that the gas is CO2。
It is highly preferred that the KHCO3A concentration of 0.4-0.6M of aqueous solution.It is further preferred that the KHCO3Aqueous solution
A concentration of 0.5M.
It is highly preferred that the bias is -0.2V.
It is highly preferred that the xenon source is middle religion gold source CEL-HXF300, AM1.5 optical filters.
As described above, a kind of method and its application growing graphene in silicon carbide provided by the invention, to commodity
The SiC powder of change is modified, and using silicon carbide after purification as raw material, successfully passes the high quality graphite that epitaxy has been prepared
Alkene/silicon carbide composite (see the Raman spectrograms of Fig. 1 SiC extending and growing graphenes), has well solved commercialization silicon carbide
The carbon impurity on surface hinders the problem of graphene growth, improves the quality that graphene is made in epitaxy, has potential economical
Value and social value.In addition, using the purifying silicon carbide with different-grain diameter size, additionally it is possible to control out the graphite generated
The number of plies of alkene film.The SiC of the graphene coated obtained, graphene number of plies is few and uniform, and catalyst performance has obtained greatly
It improves, light degradation, carbon dioxide by photoelectric catalytic reduction, the electro-catalysis that can be used for carbon dioxide restore carbon dioxide, electrolysis water
In the oxidation of methane.Especially in the present invention catalyst for preparing have in carbon dioxide photovoltaic reaction it is reproducible, urge
The advantages that agent activity is high；Such as on the catalyst of the present invention, CO2It can be converted into ethyl alcohol and methanol etc., the catalyst
Long lifespan, performance is good, the catalytic performance of far superior to conventional SiC catalyst.
A kind of method growing graphene in silicon carbide in the present invention simplifies technique compared with prior art
Flow need not use chemical reagent during preparation, reduce the discharge of waste liquid, saved cost, reduce pollution,
With potential economic value and social value.
Description of the drawings
Fig. 1 is shown as the Raman spectrograms of SiC extending and growing graphenes in the embodiment of the present invention 1.
Fig. 2 is shown as the Raman spectrograms of the SiC of not pretreated extending and growing graphene in the embodiment of the present invention 1.
Fig. 3 is shown as the XRD spectra of the SiC of extending and growing graphene in the embodiment of the present invention 4.
Fig. 4 is shown as the transmission electron microscope photo of the SiC of extending and growing graphene in the embodiment of the present invention 4.
Specific implementation mode
With reference to specific embodiment, the present invention is further explained, it should be appreciated that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
Illustrate that embodiments of the present invention, those skilled in the art can be by this specification below by way of specific specific example
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
It should be clear that in the following example not specifically dated process equipment or device be all made of conventional equipment in the art or
Device；All pressure values and range all refer to relative pressure, and the reagent used is conventional reagent in the art.
In addition, it should also be understood that, one or more method and step mentioned in the present invention does not repel before and after the combination step
It can also be inserted into other methods step there may also be other methods step or between these explicitly mentioned steps, unless separately
It is described；It should also be understood that the combination connection relation between one or more equipment/device mentioned in the present invention is not repelled
The front and back two equipment/devices specifically mentioned there may also be other equipment/device or at these of the unit equipment/device it
Between can also be inserted into other equipment/device, unless otherwise indicated.Moreover, unless otherwise indicated, the number of various method steps is only
Differentiate the convenient tool of various method steps, rather than to limit the ordering of various method steps or limiting the enforceable model of the present invention
It encloses, relativeness is altered or modified, and without material changes in technical content, when being also considered as, the present invention is enforceable
Scope.
Embodiment 1
The commercialization SiC powder raw material that 100mg particle size ranges are 100nm-300nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1000 DEG C of constant heat preservation 2h are warming up to from room temperature with 20 DEG C/min, is obtained by pretreatment
SiC.Meanwhile the commercialization SiC powder raw material that 100mg particle size ranges are 100nm-300nm is weighed, without pretreatment.
Embodiment 2
The commercialization SiC powder raw material that 100mg particle size ranges are 100nm-300nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1000 DEG C of constant heat preservation 2h are warming up to from room temperature with 30 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 10 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 1h to 1500 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is the SiC of graphene coated.
Raman characterizations are carried out to above-mentioned SiC, concrete outcome is shown in Fig. 1.
Meanwhile it is the commercialization SiC powder raw material of 100nm-300nm to take 100mg particle size ranges, without pre-processing,
In argon gas atmosphere, since room temperature, it is rapidly heated to 1500 DEG C with the speed of 10 DEG C/min, and keep the temperature 1h, after natural cooling
The SiC of graphene is grown to surface, which is the SiC of graphene coated.Raman characterizations, concrete outcome are carried out to above-mentioned SiC
See Fig. 2.
Since graphene has corresponding Raman spectrum, shape, width and the position of Raman spectrums related to its number of plies.By scheming
The characterization result of the Raman of SiC extending and growing graphenes is understood after pretreatment in 1, it can be seen that the SiC is typical graphite
Alkene structure, with most important three characteristic peaks of graphene：The peaks D, the peaks G and the peaks 2D have preferable graphene-structured.By scheming
Without the characterization result of Raman after pretreatment SiC extending and growing graphenes it is found that compared to Figure 1 in 2, the Raman of the SiC
Collection of illustrative plates does not have the characteristic peak of graphene, it is meant that does not generate apparent graphene-structured.
Embodiment 3
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1000 DEG C of constant heat preservation 2h are warming up to from room temperature with 20 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 30 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 30min to 1700 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 4
The commercialization SiC powder raw material that 100mg particle size ranges are 700nm-1100nm is weighed, is laid on corundum crucible,
So that SiC is sufficiently exposed in hydrogen atmosphere, is warming up to 1000 DEG C of constant heat preservation 2h from room temperature with 50 DEG C/min, obtains by locating in advance
The SiC of reason.It will be quick with the speed of 10 DEG C/min since room temperature in argon gas atmosphere after pretreated SiC coolings
1500 DEG C are warming up to, and keeps the temperature 1h, the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC.XRD analysis is carried out to above-mentioned SiC, shoots TEM Electronic Speculum, concrete outcome is shown in Fig. 3,4.It can by the characterization result of the XRD in Fig. 3
To know, the 2 θ values at each peak are 35.66 ° respectively in pattern, 41.48 °, 60.06 °, 71.80 °, 75.56 °, correspond to (111) respectively,
(103), (220), (311) and (222) diffraction surfaces.Peak position and peak intensity and standard powder diffraction data card (JCPDS,
NO.65-0360,) coincide substantially, therefore the SiC is typical SiC structures.It can by the TEM electromicroscopic photographs in Fig. 4
Know, SiC particulate edge is coated by multi-layer graphene.
Embodiment 5
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, without pretreatment, in argon gas
In atmosphere, directly since room temperature, 1500 DEG C is warming up to the speed of 10 DEG C/min, and keep the temperature 1h, stone is obtained after natural cooling
The SiC of black alkene cladding.
Embodiment 6
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1100 DEG C of constant heat preservation 5h are warming up to from room temperature with 35 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will be rapidly heated with the speed of 5 DEG C/min after pretreated SiC coolings
To 1500 DEG C, and 30min is kept the temperature, the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 7
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1100 DEG C of constant heat preservation 5h are warming up to from room temperature with 35 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 10 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 30min to 1500 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 8
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1100 DEG C of constant heat preservation 5h are warming up to from room temperature with 35 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 20 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 30min to 1500 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 9
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1100 DEG C of constant heat preservation 5h are warming up to from room temperature with 35 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 25 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 30min to 1500 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 10
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1100 DEG C of constant heat preservation 5h are warming up to from room temperature with 45 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 10 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 1h to 1500 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is the SiC of graphene coated,
With preferable graphene-structured.
Embodiment 11
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1100 DEG C of constant heat preservation 5h are warming up to from room temperature with 45 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 30 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 5min to 1500 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 12
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1100 DEG C of constant heat preservation 5h are warming up to from room temperature with 40 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 30 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 10min to 1500 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 13
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1100 DEG C of constant heat preservation 5h are warming up to from room temperature with 40 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 30 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 15min to 1500 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 14
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1100 DEG C of constant heat preservation 5h are warming up to from room temperature with 40 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 30 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 20min to 1500 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 15
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1100 DEG C of constant heat preservation 5h are warming up to from room temperature with 30 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 30 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 25min to 1500 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 16
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1000 DEG C of constant heat preservation 2h are warming up to from room temperature with 30 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 30 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 35min to 1500 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 17
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1000 DEG C of constant heat preservation 2h are warming up to from room temperature with 30 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 30 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 40min to 1500 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 18
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1000 DEG C of constant heat preservation 2h are warming up to from room temperature with 30 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 30 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 45min to 1500 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 19
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1000 DEG C of constant heat preservation 2h are warming up to from room temperature with 50 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 30 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 50min to 1500 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 20
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1000 DEG C of constant heat preservation 2h are warming up to from room temperature with 50 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 30 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 55min to 1500 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 21
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1000 DEG C of constant heat preservation 2h are warming up to from room temperature with 50 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 30 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 60min to 1500 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 22
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1000 DEG C of constant heat preservation 2h are warming up to from room temperature with 20 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 30 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 30min to 1400 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 23
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1000 DEG C of constant heat preservation 2h are warming up to from room temperature with 20 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 30 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 30min to 1450 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 24
The commercialization SiC powder raw material that 100mg particle size ranges are 300nm-600nm is weighed, is laid on corundum crucible, makes
SiC is sufficiently exposed in hydrogen atmosphere, and 1000 DEG C of constant heat preservation 2h are warming up to from room temperature with 20 DEG C/min, is obtained by pretreatment
SiC.It in argon gas atmosphere, since room temperature, will quickly be risen with the speed of 30 DEG C/min after pretreated SiC coolings
Temperature keeps the temperature 30min to 1550 DEG C, and the SiC of surface growth graphene is obtained after natural cooling, which is graphene coated
SiC has preferable graphene-structured.
Embodiment 25
By the 700nm-1100nm SiC catalyst of gained graphene coated in embodiment 4, in ethyl alcohol after ultrasonic disperse,
Take 1mg catalyst to be supported on carbon paper, in the photo electrocatalysis reactor of three electrode band quartz windows, reaction temperature be 20 DEG C,
Reaction pressure is normal pressure, CO2Flow velocity is 50ml/min, electrolyte is 0.5M KHCO3 aqueous solutions, bias used be -0.2V, institute
It is xenon source (middle religion gold source CEL-HXF300, AM1.5 optical filters) with light source.It the results are shown in Table 1.
Comparative example
It is catalyst by commercially available 700nm-1100nmSiC, in ethyl alcohol after ultrasonic disperse, 1mg catalyst is taken to load
On carbon paper, in the photo electrocatalysis reactor of three electrode band quartz windows, reaction temperature is 20 DEG C, reaction pressure be normal pressure,
CO2The KHCO that flow velocity is 50ml/min, electrolyte is 0.5M3Aqueous solution, bias used are -0.2V, light source used is xenon source
(middle religion gold source CEL-HXF300, AM1.5 optical filters).It the results are shown in Table 1.
1 embodiment 25 of table is with catalyst in comparative example in photoelectric reduction CO2Gas-phase product on-line chromatograph analysis in reaction
Correction data table
| Embodiment 25 | Comparative example | |
| Total CH4Yield/umolg -1h -1 | 7.0 | 5.1 |
| Total CO yield/umolg -1h -1 | 66.9 | 26.5 |
Note：The data that sampling analysis obtains when each selective data in table 1 is reaction time 5h.
As shown in Table 1, compared with comparative example, photoelectric reduction is participated in by the catalyst of gained in embodiment 4 in embodiment 25
CO2After reaction, the gas-phase product total output obtained increases, and illustrates that photoelectric reduction reaction efficiency gets a promotion.
So the present invention effectively overcomes various shortcoming in the prior art and has high industrial utilization.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should by the present invention claim be covered.
Claims (13)
1. a kind of method growing graphene in silicon carbide, includes the following steps：
1) it under reducing atmosphere by SiC powder, is pre-processed at 600-1200 DEG C；
2) again by SiC after pretreatment in step 1) under an inert atmosphere, after 1100-1800 DEG C is kept the temperature, obtain institute
Need the SiC of surface growth graphene.
2. a kind of method growing graphene in silicon carbide according to claim 1, which is characterized in that in step 1)
In, the SiC powder is silicon carbide powder of the grain size total distributed range in 100nm-1100nm of commercialization.
3. a kind of method growing graphene in silicon carbide according to claim 1, which is characterized in that in step 1)
In, the reducing atmosphere is hydrogen atmosphere.
4. a kind of method growing graphene in silicon carbide according to claim 3, which is characterized in that the hydrogen
Further include inert gas in atmosphere, the ratio between volume of hydrogen and inert gas is 5 in hydrogen atmosphere:95-100:0.
5. a kind of method growing graphene in silicon carbide according to claim 4, which is characterized in that the inertia
Gas is one or more in nitrogen, argon gas, helium, neon, Krypton, xenon.
6. a kind of method growing graphene in silicon carbide according to claim 1, which is characterized in that in step 1)
In, the pretreatment is started to warm up from room temperature；The pretreated heating rate is 5-60 DEG C/min.
7. a kind of method growing graphene in silicon carbide according to claim 1, which is characterized in that in step 1)
In, the pretreatment time is 0.5-6h.
8. a kind of method growing graphene in silicon carbide according to claim 1, which is characterized in that in step 2)
In, one or more atmosphere of the inert atmosphere in nitrogen, argon gas, helium, neon, Krypton, xenon.
9. a kind of method growing graphene in silicon carbide according to claim 1, which is characterized in that in step 2)
In, the heat preservation is started to warm up from room temperature；The heating rate of the heat preservation is 2-50 DEG C/min.
10. a kind of method growing graphene in silicon carbide according to claim 1, which is characterized in that in step
2) in, the time of the heat preservation is 5s-2h.
11. a kind of graphene and silicon carbide composite catalyst, by any described one kind of claim 1-10 in silicon carbide table
Look unfamiliar long graphene method be made.
12. a kind of graphene according to claim 11 and silicon carbide composite catalyst carbon dioxide photovoltaic reaction,
Purposes in electrolysis water.
13. purposes according to claim 12, which is characterized in that the reaction condition of the catalyst is to be urged obtained
Agent is taken out after ultrasonic disperse in ethyl alcohol and is supported on carbon paper, after vacuum drying oven dries 3-5h, is fitted into reaction unit, reacts
Temperature is 10-30 DEG C, and reaction pressure is normal pressure, gas flow rate 10-200ml/min, electrolyte KHCO3Aqueous solution, bias
For -0.4-0V, light source used is xenon source.
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