CN108046224A - A kind of control synthetic method of the class graphene carbonitride two-dimensional nano piece with pyramid array structure - Google Patents
A kind of control synthetic method of the class graphene carbonitride two-dimensional nano piece with pyramid array structure Download PDFInfo
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- CN108046224A CN108046224A CN201810034685.XA CN201810034685A CN108046224A CN 108046224 A CN108046224 A CN 108046224A CN 201810034685 A CN201810034685 A CN 201810034685A CN 108046224 A CN108046224 A CN 108046224A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
Abstract
The present invention provides a kind of control synthetic method of the class graphene azotized carbon nano piece with pyramid array structure, and preparation process includes：Using melamine as raw material, using carbon fiber as microwave absorption, crucible is put into togerther to be placed in microwave cavity, it is heated after vacuumizing in microwave irradiation, in microwave radiation heating process, duty cycle and pulse period are adjusted, so as to obtain the class graphene azotized carbon nano piece with pyramid array structure；Using above-mentioned technical proposal, simple and fast efficient class graphene azotized carbon nano piece of the preparation with pyramid array structure feature can be applied to photocatalytic degradation organic matter, photodissociation hydrogen manufacturing, catalyst carrier and sensor etc..
Description
Technical field
The invention belongs to the technology of preparing scopes of graphite phase carbon nitride, and in particular to one kind has pyramid array structure spy
The control synthesis of the class graphene azotized carbon nano piece of sign.
Background technology
Graphite phase carbon nitride (g-C3N4) it is a kind of typical polymer without metal, with class graphite laminate structure half
Conductor has very strong thermal stability and chemical stability and suitable energy gap, unique electronic band structure, quilt
The fields such as photocatalysis, sensor, catalyst carrier and photoelectricity are widely used in, are a kind of extremely potential semiconductor materials
Material.Since graphene is born, in view of this two-dimensional ultrathin new structure and its unusual functional characteristic showed, make
The synthesis and function for obtaining two-dimensional nano functional material are explored, and are become the new hot spot of people's research and application, are attract people competitively
Various methods are developed and utilized, are formed with realizing as the new of other ingredients such as carborundum, boron nitride, carbonitride, tungsten disulfide
The target control synthesis of two-dimensional nano functional material.The results show that similar to the relation of graphene and graphite, mutually tied compared to body
The graphite phase carbon nitride of structure, with class graphene carbonitride (Graphene-like g-C existing for two-dimensional nano sheet form3N4) really
Show more excellent comprehensive function characteristic in fact.
At present, for composition for carbonitride functional material preparation method, mainly have thermal polycondensation synthetic method, solvent-thermal method,
Electrochemical deposition method etc..A series of thermal polycondensation synthetic reaction is occurred by the presoma of thermal induction carbon source and nitrogen source, can be formed
Graphite phase carbon nitride has the characteristics that reaction process is direct, easy, of low cost, but the graphite phase carbon nitride crystallization synthesized
Property is poor, and the reaction time is long.Solvent-thermal method has the characteristics that reaction system uniformity is good and process is manageable, passes through solvent-thermal method
The special constructions such as graphite phase carbon nitride nanometer rods/nanobelt can be prepared, but generally to be used in solvent-thermal method preparation process
Toxic organic solvent, is unfavorable for environmental protection.Electrochemical deposition method consersion unit is simple, is easy to industrialization, commonly used to make
Standby graphite phase carbon nitride film or coating, but be not suitable for the preparation of graphite phase carbon nitride powder.It is prepared with upper type generally existing
Cycle length, complex process, the features such as cost is higher, crystallinity is poor.It is further preferred that the product that the above method obtains is past
Toward the carbonitride for being all body phase, i.e. graphite phase carbon nitride, it is difficult to acquire the azotized carbon nano piece of class graphene-structured
(Graphene-like g-C3N4)。
In order to further enhance the photoelectric properties of graphite phase carbon nitride, graphite phase carbon nitride is changed there has been proposed many
The method of property.General modification includes with metal, nonmetallic doping or with the compound of other semiconductors and preparing porous
Graphite phase carbon nitride etc..But these are modified there is also shortcoming, such as：Excessively high synthesis temperature, synthesis cycle are long, metal
The use of salt and the azotized carbon nano piece that is prepared into class graphene-structured etc..It is well known that the performance of pattern and substance ceases
Manner of breathing closes, and orderly array can generate fabulous electronics seepage channel to the conversion of electrons, improve absorption to light and
Propagation efficiency, so as to improve the photoelectric properties of substance.At present, someone has prepared three-dimensional graphite phase carbon nitride array junctions
Structure, if Huang Xuning of Fudan University et al. is using pulse laser sediment method (CN107352518A), in smooth substrates material table
Face deposits nickel film, then using plasma sputtering deposition method, using glow discharge device, will cover the substrate of nickel film
It is transferred in arc chamber, methane/nitrogen hydrogen gas mixture is passed through arc chamber, starts glow discharge, by adjusting discharge current
With discharge voltage, graphite phase carbon nitride nano-cone array is prepared.But its synthesis technology is complicated, and equipment requirement is high, is not suitable for industry
Metaplasia is produced, and product still shows as the two-dimensional nano sheet material of three-dimensional bulk structure rather than class graphene-structured.
Compared to traditional preparation method, microwave rule has many advantages, and raw material is simple, of low cost, without locating in advance
Reason；And without using the various costlinesses such as catalyst, organic solvent in preparation process or to environment harmful reagent；And microwave method passes through
Unique body phase self-heating mode, substantially reduces the heat transfer in conventional heating or thermal convection current time so that preparation process letter
It is single, quick.
Applicant did substantial amounts of research work in the compound using microwave method synthesis class graphene-structured, applied
People is in the research process of early period, using graphite as microwave absorption, has been synthesized using High-Power Microwave heating with larger surface
Long-pending g-C3N4But the obtained g-C of this method (CN105752953A),3N4Still belong to graphite-phase g-C3N4, do not obtain
Graphene-like g-C3N4。
In follow-up study, it is found by the applicant that during microwave reaction, enhance energy exchange efficiency to improve the play of reaction
Strong degree is conducive to obtain the less two-dimensional nanostructure of the number of plies, on this basis, has more preferable electromagnetic response using to microwave
Carbon fiber substitution graphite be microwave absorption (CN106542509A), can Fast back-projection algorithm obtain class graphene-structured
Graphene-like g-C3N4, that is, it is rendered as the g-C of two-dimensional ultrathin nanometer sheet form3N4.But in this method due to the use of
Energy exchange efficiency higher carbon fiber as microwave absorption, improve prepare speed, realize rapidly and efficiently synthesize it is same
When, the unstable state that the raw material system at resonator is in height is also resulted in, reaction is difficult to control, and has finally obtained various shapes
The product of state.
It is existing the study found that the graphite phase carbon nitride two-dimensional nano piece with pyramid array structure feature, due to its table
The special pyramid shape array of protrusions in face while increasing specific surface area, also increases absorption or electron emission active site
Deng so as to show unique photoelectric properties, therefore in photocatalysis (such as photocatalysis hydrolytic hydrogen production/oxygen or hydrogen storage or organic dirt
Contaminate object light catalytic degradation), semiconductor (spinning electron or feds), medicine (bio-sensing/Biological imaging and molecule knowledge
Not, drug conveying etc.) etc. each field suffer from wide research and development space.And since class graphene carbonitride is compared with stone
Black phase carbon nitride has better catalytic performance, it is possible to imagine there is the class graphene nitrogen of pyramid array structure feature
Change carbon two-dimensional nano piece, there is more wide prospect of the application, therefore how to control synthesis is a kind of there is pyramid array structure
The class graphene carbonitride two-dimensional nano piece of feature, becomes a problem.
The content of the invention
Problem to be solved by this invention is：There is provided a kind of simple and fast efficient prepare has pyramid array structure spy
The method of the class graphene azotized carbon nano piece of sign, can be applied to photocatalytic degradation organic matter, photodissociation hydrogen manufacturing, catalyst carrier
With sensor etc..
To solve the above problems, the technical solution adopted by the present invention is：A kind of class graphite with pyramid array structure
The control synthetic method of alkene azotized carbon nano piece, preparation process include：Using melamine as raw material, inhaled by microwave of carbon fiber
Agent is received, crucible is put into togerther and is placed in microwave cavity, is heated after vacuumizing in microwave irradiation, microwave radiation is heated
Cheng Zhong adjusts duty cycle and pulse period, so as to obtain the class graphene azotized carbon nano with pyramid array structure
Piece.
Further, duty cycle when microwave irradiation is handled is 25~75%, and the pulse period is 6~10s.
Further, the vacuum pressure is 5~25kPa.
Further, the microwave irradiation power is 2~6kW.
Further, the microwave cavity temperature is 500~650 DEG C；Reaction time is 10~25min.
Further, the mass ratio of the melamine and carbon fiber is (10~30):1.
The present invention is converged using magnetron as high-power microwave source by the electromagnetic field density height superposition at resonator center
Collection, polarized using interfacial polarization, induced dipole etc., realize that raw material is added hot mode with body and is rapidly heated, while electromagnetic field is generated,
To special coupling intervention effect be generated to the chemical reaction with atomic nucleus outer-shell electron pairing bonding, that is, pass through microwave action
Non-thermal effect reduces reaction activity, so as to change response path and realize the quick preparation of graphite phase carbon nitride.Difference and biography
The processing modes such as conduction, the convection current of system, microwave radiation can also generate electromagnetic field while penetration body heat phase is realized, right
Special coupling intervention effect will be generated with the chemical reaction of atomic nucleus outer-shell electron pairing bonding or even reaction road can be changed
Footpath, so as to acquire the product or the target product of special construction form that conventional method is difficult to or even can not obtain.
It is worth noting that, during microwave complex functionality material, synthesis mechanism follows the " two-dimensional nucleation based on smooth interface
Layer growth mechanism ", i.e. product its surface after layer growth is carried out show the structure feature of continuous formation, are obtaining protrusion
It is more difficult in terms of the product of array special construction pattern.Gregory D professors H of such as Glasgow, United Kingdom university, into
Extremely smooth carborundum (SiC) crystal grain in obtained surface when row microwave single mode irradiates；Profit in the research of inventor early period
When carrying out the irradiation of multimode resonance with microwave, identical result has also been obtained：In the graphite phase carbon nitride using microwave synthesis
(CN105752953A) and during class graphene azotized carbon nano piece (CN106542509A), its surface is all continuous light
Sliding.
The present invention also serves as carbon by selecting and the use of strong corresponding carbon fiber can be generated with microwave being microwave absorption
Source.I.e. High-Power Microwave it is radiation-induced under, form excitation induced low temperature plasma in carbon fiber surface, realizing moment
While heating, and the atom on substance surface layer will be also activated.At the same time, melamine is in the electromagnetic heating of microwave irradiation
Under the conditions of, fast decoupled obtains the compound group or structure fragment containing carbonnitrogen bond.With the intermediate of these high activities or activation
Centered on atom, growth site is formed by quick forming core, and duty cycle during radiation treatment is coordinated to set, passes through microwave electricity
Pulse excitation disturbance under magnetic field environment, by destroying the continuous state in synthesis/growth course, has so as to help to realize
The class graphene azotized carbon nano piece of pyramid array special construction.
Using above-mentioned technical proposal, beneficial effects of the present invention are：
1) preparation process is simple, quick, easily operated, it is only necessary to pass through the setting of duty cycle and pulse period, you can real
The target control synthesis under microwave electromagnetic field environment is intervened in existing pulse excitation disturbance.
2) raw material is simple, of low cost, without pretreatment；It is and each without using catalyst, organic solvent etc. in preparation process
Kind is expensive or to environment harmful reagent.
3) non-environmental-pollution in preparation process, it is environmental friendly, except power consumption in preparation process, exhaust gas is not generated, is given up
Liquid, waste residue etc..
4) product property is homogeneous.Catalyst, template and substrate etc. are not introduced in synthesis, greatly reduces containing for impurity
Amount, advantageously reduces influence of the impurity component to target product structure, property, while also avoids product needs in traditional handicraft
The time of separating-purifying and cost consumption.
Description of the drawings
Fig. 1 is the scanning electron microscope image of 4 products therefrom of comparative example；
Fig. 2 is the images of transmissive electron microscope of 5 products therefrom of comparative example；
Fig. 3 is the X-ray diffracting spectrum of 1 products therefrom of embodiment；
Fig. 4 is the scanning electron microscope image of 1 products therefrom of embodiment；
Fig. 5 is the images of transmissive electron microscope of 1 products therefrom of embodiment.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail.
The conventional thermal polycondensation process of comparative example 1 prepares graphite phase carbon nitride
At present, there are many method that graphite type carbon nitride is prepared using thermal polycondensation process, such as patent CN103193785A (a kind of
Class graphene C3N4Material and its preparation method and application), this method (is also cyanamid dimerization, C using dicyanodiamine2H4N4) it is original
Material, in nitrogen (N2) under atmosphere calcining obtain graphite phase carbon nitride.Due to the use of inert gas in this preparation process, to equipment
It is required that it is higher, and cost is added, the time length (6~8h) of reaction is also the defects of one of them is very important.In addition, specially
A kind of sharp CN104492470A (preparation method of graphite type carbon nitride photocatalyst material) is with cyanamid dimerization (C2H4N4) and bar ratio
Appropriate acid (C4H4N2O3·2H2O it is) co-precursor, with lithium chloride (LiCl) and potassium chloride (KCl) for heat medium, in protective gas
N2Under the conditions of calcining prepare graphite phase carbon nitride.The material system that this method uses is excessively complicated, and is used in reaction process
Protective gas adds cost；In addition, the long reaction time long (12h) limits it and is widely applied.
2 solvent-thermal method of comparative example prepares graphite phase carbon nitride
Such as document《Solvent-thermal method prepares graphite type carbon nitride and its degradation of phenol research》(chemistry and bioengineering 2017,
34(09):19-23) select carbon tetrachloride (CCl4) it is raw material, plot ratio 50% will be reacted with the heating rate of 1 DEG C/min
Temperature rises to 250 DEG C, under the process conditions that 12h is kept the temperature in hydrothermal synthesis kettle, successfully obtains graphite phase carbon nitride.But to solvent
Calorimetry analysis is it can be found that this method has inevitably used virose solvent such as benzene and carbon tetrachloride, reaction time
More than ten hour is at least needed, and the collection of sample also takes very much.For another example (batch graphite mould nitrogenizes patent CN102153055A
The solvothermal preparation method of carbon) utilize Cyanuric Chloride (C3N3Cl3) and Sodamide (NaNH2) it is raw material, it is added to benzene (C6H6) etc.
In organic solvent and constant temperature 12h or so, then filtration and washing obtains graphite phase carbon nitride.The organic solvent and original that this method uses
Material is all harmful to environment and human body；In addition, the long reaction time reduces combined coefficient, and extraction, purifying and the receipts of sample
The subsequent processes such as collection are also complicated cumbersome.
3 electrochemical deposition method of comparative example prepares graphite phase carbon nitride
Document《Electrochemical deposition method prepares class graphite phase carbon nitride》(Science Bulletin, 2003,48 (9):905~908) it is same
Sample is with Si (100) substrate, with 1:1.5 Cyanuric Chloride (C3N3Cl3) and melamine (C3H6N6) saturation acetone (C2H6CO it is) molten
Liquid is deposition liquid, and at 25 DEG C, by the high pressure of 1200V, it is 0.8 that 8 hours of electrochemical deposition, which have obtained N/C, on a si substrate
Graphite phase carbon nitride crystal.Although graphite phase carbon nitride crystal, most of graphite-phases are obtained using electrochemical deposition method
Carbonitride is all that polycrystalline state coexists, and the purity of graphite phase carbon nitride is low；In addition, it must be used to acetonitrile and acetone in reaction process
Organic solvents is waited to be unfavorable for environmental protection as electrolyte.
For another example document《The electrochemical deposition of class graphitic nitralloy carbon》(artificial lens journal 2003,32 (3):252-256) use
1:1.5 Cyanuric Chloride (C3N3Cl3) and saturation acetonitrile (C2H3N) solution of melamine (C3H6N6) are deposition liquid, are applied
The high-tension current of 1200V, electrochemical deposition has obtained class graphite phase carbon nitride crystal under Si (100) substrate upper chamber normal temperature and pressure；
But it is that polycrystalline state coexists to synthesize carbonitride, and the graphite phase carbon nitride purity of preparation is very low.
Comparative example 4 efficiently synthesizes graphite phase carbon nitride crystal grain based on microwave
After just waiting, (Wang Jigang, remaining to always cherish the memory of, Zhang Hao, Zhou Qing, Zhang Anlei, Gu Yong climb a kind of preparations of graphite phase carbon nitride of to king
Method, granted patent number, ZL201610065411.8), using graphite or carborundum as microwave absorption, handled using microwave irradiation
Melamine, cyanamid dimerization, cyanamide, thiocarbamide and urea are when nitrogen-rich organics object, in the electromagnetic field of microwave irradiation, control pressure
Power be 5~35kPa, microwave irradiation 2~10kW of power, 50~00 DEG C/min of heating rate, 450~700 DEG C of insulation reactions 5~
30min quickly and efficiently obtains scale as 500~more than 800nm or even a few micrometers of graininess, lamellar, tubulose, ball
The graphite phase carbon nitride (please referring to Fig.1) of the forms such as shape.But since the size of product is larger, quantum confined effect etc. is difficult to play
Effect, and it is not belonging to the two-dimensional nanostructure product that current people competitively pursue, and surface continuous and derivable.
Comparative example 5 efficiently synthesizes the graphite phase carbon nitride nanometer sheet of continuous level structure based on microwave
King after just waiting, (Wang Jigang, remaining to always cherish the memory of, learn military affairs, Zhou Qing, Zhang Hao, and Gu Yong is climbed, Zhang Anlei, a kind of efficiently to prepare class by hook
The method of graphene carbonitride, publication number：CN 106542509A, application number：Etc. 2016109082650) one kind is disclosed to be based on
Microwave irradiation, the method for rapidly and efficiently preparing the graphite phase carbon nitride nanometer sheet of planar structure.In the method, by by trimerization
One kind in the organic compounds containing nitrogens such as cyanamide, cyanamid dimerization, cyanamide, thiocarbamide or urea is put after uniformly being mixed with carbon fiber
Enter in ceramic crucible.Then crucible is placed in High-Power Microwave stove resonator, class is prepared using High-Power Microwave irradiated heat technology
Graphene carbonitride.But what the invention was prepared is that the class graphene azotized carbon nano piece of plane continuous and derivable (refer to figure
2) apparent array of protrusions structure, can not be found under an electron microscope, therefore the surface area of array of protrusions can not be utilized to carry
High, activated adoption site or tip emission sites increase and further improve the properties such as photoelectric activity, photocatalysis or Flied emission.
Embodiment 1
By 10g melamines (C3H6N6) and 0.5g graphite fibres powder grinding, be uniformly mixed.Then mixture is put into
Industrial High-Power Microwave stove resonator center is placed in into ceramic crucible with cover.Micro-wave oven resonator, which is vacuumized, makes vacuum degree
For 15kPa, microwave is then turned on, microwave power 5kW starts to keep the temperature after temperature reaches 570 DEG C, and it is 25% to keep duty cycle,
Pulse period is 8s.Micro-wave oven is closed after 10min, reaction system is made to take out sample after cooling to room temperature with the furnace.
The powdered product obtained after microwave irradiation is tied using x-ray diffraction pattern, scanning electron microscope and transmission electron microscope etc.
Structure characterizes, it was demonstrated that product is the graphite phase carbon nitride with pyramid dot matrix shape, and products pure.Fig. 3 is the X- of products therefrom
X ray diffraction collection of illustrative plates, there is (100) diffraction maximum in 13.3 ° of right positions in figure, and corresponding is carbonitride in same plane
Seven piperazine ring structure structures of interior repetition, it is understood that repeat the distance in 5-triazine units between adjacent N holes, corresponding interplanar
Away from for 0.681nm.Occur apparent (002) diffraction maximum 27 ° of positions, be the interlayer stacking characteristic peak of aromatic substance, it is right
The interlamellar spacing answered is 0.325nm, it was demonstrated that product is the layer structure carbonitride with similar graphite, i.e. class graphene carbonitride.
Fig. 4 is the stereoscan photograph of products therefrom, and its surface that synthesis is can see in figure has well-regulated pyramid dot matrix shape
Arrangement and the direction of arrangement and order neat and consistent.Fig. 5 is the transmission electron microscope photo of products therefrom, can clearly be found in figure
Substantial amounts of bulge-structure belongs to the structure feature to form the pyramid array starting stage.
Embodiment 2
It is moved into after weighing two component raw materials in same embodiment 1 and being sufficiently mixed in ceramic crucible.Crucible is placed in
After industrial High-Power Microwave resonator.Micro-wave oven resonator is evacuated to vacuum degree as 5kPa, microwave is then turned on, sets microwave work(
Rate is 5kW, starts to keep the temperature after temperature reaches 550 DEG C, and it is 45% to keep duty cycle, pulse period 6s.It is closed after 15min micro-
Ripple stove makes reaction system take out sample after cooling to room temperature with the furnace.Using Scanning election microscope product morphology, golden word can be observed
Tower array protrusion is presented on class graphene azotized carbon nano piece surface.
Embodiment 3
It is moved into after weighing two component raw materials in same embodiment 1 and being sufficiently mixed in ceramic crucible.Crucible is placed in
After industrial High-Power Microwave resonator.Micro-wave oven resonator is evacuated to vacuum degree as 20kPa, microwave is then turned on, sets microwave
Power is 2kW, starts to keep the temperature after temperature reaches 650 DEG C, micro-wave oven is closed after 25min, reaction system is made to cool to room with the furnace
Sample is taken out after temperature.Since heating temperature is higher, deepened the color of the graphite phase carbon nitride of gained.Utilize scanning electron microscope
It checks product morphology, pyramid array protrusion can be observed and be presented on class graphene azotized carbon nano piece surface.
Embodiment 4
It is moved into after weighing two component raw materials in same embodiment 1 and being sufficiently mixed in ceramic crucible.Crucible is placed in
After industrial High-Power Microwave resonator.Micro-wave oven resonator is evacuated to vacuum degree as 10kPa, microwave is then turned on, sets microwave
Power is 2kW, starts to keep the temperature after temperature reaches 600 DEG C, and it is 75% to keep duty cycle, pulse period 10s.It is closed after 20min
Micro-wave oven is closed, reaction system is made to take out sample after cooling to room temperature with the furnace.Using Scanning election microscope product morphology, can be observed
Pyramid array protrusion is presented on class graphene azotized carbon nano piece surface.
Embodiment 5
It is moved into after weighing two component raw materials in same embodiment 1 and being sufficiently mixed in ceramic crucible.Crucible is placed in
After industrial High-Power Microwave resonator.Micro-wave oven resonator is evacuated to vacuum degree as 15kPa, microwave is then turned on, sets microwave
Power is 3.5kW, starts to keep the temperature after temperature reaches 520 DEG C, and it is 55% to keep duty cycle, pulse period 8s.It is closed after 20min
Micro-wave oven is closed, reaction system is made to take out sample after cooling to room temperature with the furnace.Using Scanning election microscope product morphology, can be observed
Pyramid array protrusion is presented on class graphene azotized carbon nano piece surface.
Embodiment 6
It is moved into after weighing two component raw materials in same embodiment 1 and being sufficiently mixed in ceramic crucible.Crucible is placed in
After industrial High-Power Microwave resonator.Micro-wave oven resonator is evacuated to vacuum degree as 10kPa, microwave is then turned on, sets microwave
Power is 3.5kW, starts to keep the temperature after temperature reaches 550 DEG C, and it is 50% to keep duty cycle, pulse period 6s.It is closed after 25min
Micro-wave oven is closed, reaction system is made to take out sample after cooling to room temperature with the furnace.Using Scanning election microscope product morphology, can be observed
Pyramid array protrusion pattern is presented on class graphene azotized carbon nano piece surface.
Embodiment 7
It is moved into after weighing two component raw materials in same embodiment 1 and being sufficiently mixed in ceramic crucible.Crucible is placed in
After industrial High-Power Microwave resonator.Micro-wave oven resonator is evacuated to vacuum degree as 25kPa, microwave is then turned on, sets microwave
Power is 6kW, starts to keep the temperature after temperature reaches 500 DEG C, micro-wave oven is closed after 10min, reaction system is made to cool to room with the furnace
Sample is taken out after temperature.Using Scanning election microscope product morphology, pyramid array bulge-structure can be observed and be presented on class graphite
Alkene azotized carbon nano piece surface.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of control synthetic method of the class graphene azotized carbon nano piece with pyramid array structure, preparation process bag
It includes：Using melamine as raw material, using carbon fiber as microwave absorption, it is put into togerther crucible and is placed in microwave cavity,
It is heated after vacuumizing in microwave irradiation, in microwave radiation heating process, duty cycle and pulse period is adjusted, so as to obtain the tool
There is the class graphene azotized carbon nano piece of pyramid array structure.
2. a kind of control of class graphene azotized carbon nano piece with pyramid array structure according to claim 1 is closed
Into method, it is characterised in that：Duty cycle during microwave irradiation processing is 25~75%, and the pulse period is 6~10s.
3. a kind of control of class graphene azotized carbon nano piece with pyramid array structure according to claim 1 is closed
Into method, it is characterised in that：The vacuum pressure is 5~25kPa.
4. a kind of control of class graphene azotized carbon nano piece with pyramid array structure according to claim 1 is closed
Into method, it is characterised in that：The microwave irradiation power is 2~6kW.
5. a kind of control of class graphene azotized carbon nano piece with pyramid array structure according to claim 1 is closed
Into method, it is characterised in that：The microwave cavity temperature is 500~650 DEG C.
6. a kind of control of class graphene azotized carbon nano piece with pyramid array structure according to claim 5 is closed
Into method, it is characterised in that：After temperature in microwave cavity reaches the temperature, 10~25min of insulation reaction.
7. a kind of control of class graphene azotized carbon nano piece with pyramid array structure according to claim 1 is closed
Into method, it is characterised in that：The mass ratio of the melamine and carbon fiber is (10~30):1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110455829A (en) * | 2019-08-19 | 2019-11-15 | 电子科技大学 | High-Power Microwave is to the non-thermal influencing mechanism extraction system of dielectric substance and method |
| CN111250140A (en) * | 2020-03-03 | 2020-06-09 | 武汉大学 | Carbon nitride nanorod array photocatalyst for photocatalytic nitrogen fixation and preparation method thereof |
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| CN106542509A (en) * | 2016-10-19 | 2017-03-29 | 张家港市东大工业技术研究院 | A kind of efficient method for preparing class Graphene carbonitride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110455829A (en) * | 2019-08-19 | 2019-11-15 | 电子科技大学 | High-Power Microwave is to the non-thermal influencing mechanism extraction system of dielectric substance and method |
| CN111250140A (en) * | 2020-03-03 | 2020-06-09 | 武汉大学 | Carbon nitride nanorod array photocatalyst for photocatalytic nitrogen fixation and preparation method thereof |
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