CN105752953A - Preparation method of graphite phase carbonitride - Google Patents
Preparation method of graphite phase carbonitride Download PDFInfo
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- CN105752953A CN105752953A CN201610065411.8A CN201610065411A CN105752953A CN 105752953 A CN105752953 A CN 105752953A CN 201610065411 A CN201610065411 A CN 201610065411A CN 105752953 A CN105752953 A CN 105752953A
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- 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
Abstract
The invention discloses a preparation method of graphite phase carbonitride. A preparation process comprises the following steps of using nitrogen-rich organic matters are raw materials; graphite or silicon carbide is used as a microwave absorption agent; the nitrogen-rich organic matters and the microwave absorption agent are uniformly mixed; in a microwave radiation electromagnetic field, the pressure is controlled to be 5 to 35 kPa, the microwave radiation power is 2 to 10 kW, the temperature rise speed is controlled to be 50 to 500 DEG C/min, and the heat insulation reaction is performed for 5 to 30 min at 450 to 700 DEG C; the graphite phase carbonitride is obtained. The method is based on a high-energy microwave radiation treatment method; the graphite phase carbonitride in a layered structure can be fast and efficiently obtained; the method is simple and efficient; the cost is low; varies kinds of expansive or environment-harmful reagents such as catalysts, organic solvents and protection gas are not used. The method has the advantages that the environment-friendly effect is achieved; the raw material pretreatment is not needed, and the like. The method belongs to a green preparation method favorable for large-scale business production.
Description
Technical field
The present invention relates to the preparing technical field of graphite phase carbon nitride, be specifically related to a kind of based on High-Power Microwave spoke
According to heating technique, the preparation method of quick obtaining graphite phase carbon nitride.
Background technology
Find alternative new cleaning fuel and solve energy crisis and the environmental pollution of the world today, always
One of most important tasks and missions of scientific circles.Wherein, semiconductor light-catalyst can be by pollution-free, nontoxic
Evil and nexhaustible solar energy are converted into chemical energy, or directly degradable organic pollutant, are solving energy danger
The aspect such as machine and environmental pollution shows huge potentiality.Graphite phase carbon nitride is as a kind of novel semi-conductor light
Functional material, due to its low-density, heat endurance, suitable energy gap, excellent acid-fast alkali-proof characteristic,
Unique electronic band structure, optical property and excellent surface characteristic, is widely used in photocatalysis, biography
The fields such as sensor, bio-imaging, catalyst carrier and photoelectricity are it is considered to be have most the material of development potentiality
One of.
At present, for the preparation of graphite phase carbon nitride, have been developed for the preparation method of each tool technical characterstic,
Mainly have solvent-thermal method, electrochemical deposition method, magnetron sputtering method, high temperature and high pressure method, chemical gaseous phase deposition and
Thermal polycondensation process etc..Solvent-thermal method temperature conditions is relatively mild, and nitrogen not easily runs off；And various template can be added
Agent, controls the pattern of product, such as, obtains micropore, mesoporous and large pore material.But the stone of solvent structure
Ink phase carbon nitride crystallinity is poor, and generally to use poisonous organic solvent in course of reaction, to environment
The most harmful with operating personnel.Electrochemical deposition method can be used to prepare carbon nitride films or coating, it is achieved not
With uniform deposition on labyrinth；But the carbon nitride films of preparation is polycrystalline or amorphous state, and be not suitable for system
The powder of standby graphite phase carbon nitride.Magnetron sputtering method be also quickly prepare carbon nitride films emerging technology it
One, but the purity requirement to target and reacting gas is high, and the film of preparation is to be with α or beta-phase carbon nitride
Main polycrystalline state coexists.High temperature and high pressure method is one of basic skills of Nonequilibrium Materials such as synthesizing superhard carbonitride,
But the carbonitride nitrogen content ratio of synthesis is relatively low at present, and product is based on diamond nanocrystalline；And graphite-phase nitridation
Carbon, as most stable of carbonitride existence form, is a kind of soft phase, therefore high temperature and high pressure method being unsuitable for
Preparation graphite phase carbon nitride.Chemical vapour deposition technique is by introducing highly active N, C in reaction system
Atom or ion, then obtain carbon nitride films at deposition on substrate, it is possible to well controls synthesis thickness equal
Even film；But the film that the method obtains is amorphous mostly, and reactant utilization rate is low.Thermal polycondensation
Method is to utilize pyrolysis nitrogen-rich organic thing, prepares graphite phase carbon nitride by the polycondensation process of presoma self, instead
Answer process directly, easy, low cost and environmentally safe；But the stone that conventional pyrolysis nitrogen-rich organic thing obtains
The specific surface area of ink phase carbon nitride is little, and crystallinity is poor, and reaction time length and photocatalysis performance are low.
It is long generally to there is the cycle in above-mentioned several method, complex process, and cost is high, and environment is the most friendly, and
The defects such as product crystal property difference, limit quick obtaining and the reality of graphite phase carbon nitride to a certain extent
Application, therefore a kind of quick, efficient, environmental protection of exploitation, and the preparation method of low-cost industrial, quickly obtains
The technique taking graphite phase carbon nitride is particularly important.
Microwave technology is to prepare the new technology of powder functional material or compound.Relative to solvent-thermal method, electrification
Sedimentation, chemical vapour deposition technique and conventional thermal polycondensation process, method based on microwave irradiation synthetic powder,
Have that speed is fast, the high and low carbocyclic ring of efficiency is protected, it is easy to a series of advantages such as industrialization and a large amount of productions.Trimerization
The nitrogen-rich organic things such as cyanamide, cyanamid dimerization, cyanamide, thiocarbamide and urea are at the Electromagnetic Heating bar of microwave irradiation
Under part, decomposable asymmetric choice net obtains the compound group containing carbonnitrogen bond or structure fragment.These highly active intermediates lead to
Later continuous nucleation and accumulated growth, will can obtain the graphite phase carbon nitride with graphite packed structures.
At present, someone utilizes microwave method to prepare carbon nitride material, but owing to by microwave equipment, knowing
Knowledge system and the restriction of application, people are the most universal to the application of High-Power Microwave technology.Common is micro-
Wave heating equipment is household microwave oven, and power is the most on the low side (300-1000W), in preparation efficiency, effect
Etc. aspect the most not ideal enough.University of Anhui Yuan Yu roc et al. (Yuan Yupeng, Qiu Lingguang, Xu Gengsheng, Peng Fumin,
Xu Wentao, Ma Lin, heating using microwave quickly prepares graphite-like structure carbon nitride material, application number:
201310404491.1. publication number: CN104415786A) to utilize microwave method to be prepared for graphite phase carbon nitride (micro-
Wave power is up to 1000W), but microwave absorption and the separated of raw material make the thermal efficiency significantly reduce,
It is difficult to play the advantage that microwave irradiation body the most quickly heats, has had a strong impact on preparation efficiency；And must utilize high
Expensive various metal oxides, as microwave absorption, cause cost to improve.
Summary of the invention
The problem to be solved in the present invention is: provide a kind of preparation graphite phase carbon nitride simply, easily and fast
Method；And the graphite phase carbon nitride obtained has preferable crystallinity and purity, it is possible to be used for degrading organic
Thing, photodissociation hydrogen manufacturing, catalyst carrier and biomedical sensor etc..
For solving above-mentioned technical problem, the technical solution used in the present invention is: the system of a kind of graphite phase carbon nitride
Preparation Method, its preparation process includes:
1) raw material mixing: with nitrogen-rich organic thing as presoma, with graphite or carborundum as microwave absorption,
Put in ceramic crucible after mixing；
Described nitrogen-rich organic thing is the one in melamine, cyanamid dimerization, cyanamide, thiocarbamide and urea；
2) microwave irradiation heating: step 1) in ceramic crucible put into microwave cavity center,
Be evacuated to microwave resonance cavity pressure be 5-35kPa, the power of microwave irradiation be 2-10kW, utilize micro-
After amplitude is according to being heated to 450-700 DEG C by raw material, insulation reaction 5-30min, obtain graphite phase carbon nitride；
Described nitrogen-rich organic thing is 1-5:1 with the mass ratio of microwave absorption.
Described resonator vacuumizes, and the vacuum in resonator is 5-30kPa.
Described regulation microwave irradiation power, microwave power is 2-5kW.
In described microwave irradiation heating process, High-Power Microwave irradiation energy reaches the purpose of intensification quick, uniform,
Controlling heating rate is 50-500 DEG C/min.
Know-why: when microwave penetrates medium, owing to microwave energy occurs certain interaction with medium, when
When utilizing microwave to carry out radiation treatment, the vibration that generation per second for the molecule making medium is surpassed hundred million times, dividing of medium
Produce mutually friction between son, cause medium temperature to raise, make that dielectric material is internal, outside to be heated the most simultaneously
Heat up, by unique body phase self-heating mode, substantially reduce the heat transfer in conventional heating or thermal convection current
Time.While the present invention utilizes High-Power Microwave heating, also can produce electromagnetic field, to atomic nucleus outer layer electricity
The chemical reaction of son pairing bonding will produce special coupling intervention effect, i.e. by the non-thermal effect of microwave action
Should, reduce reaction activity, thus change response path, it is achieved the quick preparation of graphite phase carbon nitride powder.
Beneficial effect:
1) preparation process is simply, quickly, easily operate.
2) raw material is simple, with low cost, it is not necessary to pretreatment；And preparation process does not use catalyst,
The various expensive or environmentally harmful reagent such as organic solvent, protective gas.
3) non-environmental-pollution in preparation process, technique environmental protection, except power consumption in preparation process, do not produce
Raw waste gas, waste liquid and waste residue etc..
4) structure and the character of gained graphite phase carbon nitride product are controlled；By adjusting nitrogen-rich organic thing and micro-
The ratio of wave absorbent, available different-shape and the graphite phase carbon nitride of character.
Accompanying drawing explanation
Fig. 1 is the X-ray diffracting spectrum of embodiment 1 products therefrom；
Fig. 2 is the scanning electron microscope image of embodiment 1 products therefrom；
Fig. 3 is the images of transmissive electron microscope of embodiment 1 products therefrom；
Fig. 4 is the scanning electron microscope image of embodiment 2 products therefrom；
Fig. 5 is the scanning electron microscope image of embodiment 3 products therefrom；
Fig. 6 is the scanning electron microscope image of embodiment 4 products therefrom；
Fig. 7 is the scanning electron microscope image of embodiment 5 products therefrom；
Fig. 8 is the scanning electron microscope image of embodiment 6 products therefrom；
Fig. 9 is the scanning electron microscope image of embodiment 7 products therefrom；
Figure 10 is the scanning electron microscope image of embodiment 8 products therefrom；
Figure 11 is the scanning electron microscope image of embodiment 9 products therefrom；
Figure 12 is the scanning electron microscope image of embodiment 10 products therefrom.
Detailed description of the invention
Below by specific embodiment, the present invention " preparation method of a kind of graphite phase carbon nitride " is made into
The detailed description of one step.
Comparative example 1
Conventional thermal polycondensation process prepares graphite phase carbon nitride
At present, thermal polycondensation process is utilized to prepare the method for graphite type carbon nitride a lot, such as patent
A CN103193785A (kind Graphene C3N4Material and its production and use), the method utilizes
Dicyanodiamine (is also cyanamid dimerization, C2H4N4) it is raw material, at nitrogen (N2) under atmosphere calcining obtain stone
Ink phase carbon nitride.Owing to using inert gas in this preparation process, the requirement to equipment is higher, and increases
Cost, the time length (6-8h) of reaction is also one of them very important defect.Additionally, patent
CN104492470A (preparation method of a kind of graphite type carbon nitride photocatalyst material) is with cyanamid dimerization
(C2H4N4) and barbiturates (C4H4N2O3·2H2O) be co-precursor, with lithium chloride (LiCl) and
Potassium chloride (KCl) is for adding thermal medium, at protective gas N2Under the conditions of calcining preparation graphite phase carbon nitride.Should
The material system that method uses is the most complicated, and employs protective gas in course of reaction, adds cost；
It addition, the long reaction time (12h) limits it and is widely applied.
Comparative example 2
Solution thermal polycondensation process prepares graphite phase carbon nitride
On the basis of conventional thermal polycondensation preparation method, introduce organic solvent, the nitridation of porous type graphite-phase can be obtained
Carbon.As Changzhou university research " synthetic method of the mesoporous graphite phase carbon nitride of a kind of low cost " (application number:
CN201410500429.7；Publication number: CN104326446A), by by mesopore silicon oxide (SBA-15)
Material is impregnated into dicyanodiamine and (is also cyanamid dimerization, C2H4N4) ethylenediamine (C2H8N2) in solution,
At inert protective atmosphere (N after stirring2Roasting 4h under), then utilizes hydrofluoric acid (HF) immersion etc.
Mode goes silicon template, then through centrifugal, drying and other steps, is black powder by available outward appearance
Mesoporous graphite phase carbon nitride material.But the graphite phase carbon nitride typically acquired is faint yellow or glassy yellow,
And the product that the method obtains is black, it is meant that product exists more graphite or agraphitic carbon composition；
The inert protective gas that the method uses in long-time roasting process simultaneously, and acid and alkali corrosion removing is mesoporous
Silica hard mould agent, and washing, centrifugal, the subsequent treatment such as be dried so that the method process is the most more
Tediously long, to inert protective gas, organic solvent and acid and alkali corrosion solvent etc. use, is also not suitable with environmental protection green
The requirement of the quick obtaining graphite phase carbon nitride of look.
Comparative example 3
Solvent-thermal method prepares graphite phase carbon nitride
Patent CN102153055A (solvothermal preparation method of graphite type carbon nitride in batches) utilizes three polychlorostyrene
Cyanogen (C3N3Cl3) and Sodamide (NaNH2) it is raw material, join benzene (C6H6) etc. in organic solvent
And constant temperature about 12h, then filtration and washing obtains graphite phase carbon nitride.The method use organic solvent and
Raw material is the most harmful to environment and human body；It addition, the long reaction time reduces combined coefficient, and sample
Extract, purify and the subsequent process such as collection is the most complicated loaded down with trivial details.For another example document " Solvothermal preparation
of graphite-like C3N4nanocrystals》(Journal of crystal growth,2003,247(3):
505-508.) select carbon tetrachloride (CCl4) and ammonium chloride (NH4Cl) it is raw material, with solvent-thermal method at 400 DEG C
Lower reaction 20 hours, the most successfully obtains graphite phase carbon nitride.But to solvent-thermal method analysis it is found that be somebody's turn to do
Method has the most all used virose solvent such as benzene and carbon tetrachloride, and the reaction time at least needs
Ten several hours, and the collection of sample is the most time-consuming.
Comparative example 4
Electrochemical deposition method prepares graphite phase carbon nitride
Document " electrochemical deposition of class graphitic nitralloy carbon " (artificial lens journal 2003,32 (3): 252-256)
With the Cyanuric Chloride (C of 1:1.53N3Cl3) and melamine (C3H6N6) saturated acetonitrile (C2H3N)
Solution is deposition liquid, applies the high-tension current of 1200V, electrochemistry under room temperature normal pressure on Si (100) substrate
Deposition has obtained class graphite phase carbon nitride crystal；But synthesis carbonitride is that polycrystalline state coexists, the graphite-phase of preparation
Carbonitride purity is the lowest.For another example document " electrochemical deposition method prepares class graphite phase carbon nitride " (Science Bulletin,
2003,48 (9): 905-908) same with Si (100) substrate, with the Cyanuric Chloride (C of 1:1.53N3Cl3)
With melamine (C3H6N6) saturated acetone (C2H6CO) solution is deposition liquid, at 25 DEG C, logical
Crossing the high pressure of 1200V, electrochemical deposition has obtained the stone that N/C is 0.8 for 8 hours on a si substrate
Ink phase carbon nitride crystal.Although utilizing electrochemical deposition method to obtain graphite phase carbon nitride crystal, but it is all many
Crystalline state coexists, and the purity of graphite phase carbon nitride is low；It addition, course of reaction must use acetonitrile and acetone
Deng organic solvent as electrolyte, it is unfavorable for environmental protection.
Comparative example 5
Solid reaction process prepares graphite phase carbon nitride
Such as document " Powder synthesis and characterization of amorphous carbon nitride "
(Chemistry of materials, 2000,12 (11): 3264-3270) is with Cyanuric Chloride (C3N3Cl3) it is front
Drive body, Lithium Azide (LiN3) it is nitrogen source, in 300-380 DEG C of temperature range, carry out solid phase reaction obtain
C/N mol ratio is the amorphous graphite phase carbon nitride of 0.752.For another example document " Synthesis of carbon
nitrides with graphite-like or onion-like lamellar structures via a solvent-free route
At low temperatures " (Carbon, 2005,43 (7): 1386-1391) by select Sodamide (NaNH2)
Or sodium azide (NaN3) or potassium (K) and Cyanuric Chloride at 220-380 DEG C, it is possible to obtain different C/N
The kish phase carbon nitride of mol ratio.Although the preparation technology of solid reaction process is fairly simple, but solid phase
Reaction method, in preparation graphite phase carbon nitride, is typically chosen the nitrogen-rich organic thing containing triazine structure, to reduce carbon
The reaction barrier of nitrogen key and the growth of promotion class graphite laminate crystal structure, therefore the selection of reaction raw materials is subject to
Certain restriction；Additionally, the azido compounds such as Lithium Azide and potassium broadly fall into highly active explosive dangerous material,
Operation must process under a shielding gas, add danger and the difficulty of operation；It addition, solid reaction process
Efficiency is low and consumes energy.
Comparative example 6
Magnetron sputtering method prepares graphite phase carbon nitride
Magnetron sputtering method is a kind of common method preparing carbon nitride films, and " prepared by magnetron sputtering method for document
CNx film and structural characterization thereof " (material engineering, 2006 (7): 11-13) with argon gas/nitrogen (Ar/N2)
Mixed gas is as sputter gas, and high purity graphite is target, and using identical graphite flake as substrate.Instead
Before should, need to immerse graphite substrate acetone (C2H6CO), ethanol (C2H5OH) in solution, and
Utilize ultrasonic activation instrument to clean to be respectively washed, after drying, put into sputtering chamber.Then vacuumize, be first passed through argon
Gas, then it is passed through nitrogen, sputtering power is 100W, obtains graphite phase carbon nitride crystal after reaction 2h.
Although magnetron sputtering method can be by changing the process parameter control carbonitride such as sputtering power and time
Granular size, reaction rate is than very fast, and efficiency is high, but obtain is not pure graphite phase carbon nitride crystal, many
Crystalline state carbonitride coexists；And argon gas and the nitrogen used in course of reaction improves preparation cost.
Embodiment 1
By 10g melamine (C3H6N6) and 2g graphite composite powder grind, mix.Then will mixing
Thing is put into and is placed in ceramic crucible in industry High-Power Microwave stove resonator.Micro-wave oven resonator is vacuumized
To 5kPa, being then turned on microwave, start insulation after temperature reaches 450 DEG C, microwave power now is at 2kW
Left and right, closes micro-wave oven after 5min, make reaction system take out sample after cooling to room temperature with the furnace.Can see
Substantial amounts of glassy yellow powder is there is in crucible.
Utilize x-ray diffraction pattern, ESEM, and transmission electron microscope etc. is bright orange to obtain after microwave irradiation
Look powder carries out structural characterization, it was demonstrated that product is pure graphite phase carbon nitride, and products pure, and productivity is about
For 46wt%.
Fig. 1 is the X-ray diffracting spectrum of products therefrom, and in figure, 13.3 ° of right position occur in that one (100)
Diffraction maximum, corresponding is 3-s-triazine structure that carbonitride repeats in the same plane, it is understood that attach most importance to
Answering the distance between adjacent N hole in 5-triazine units, corresponding interplanar distance is 0.681nm.Go out 27 ° of positions
Show obvious (002) diffraction maximum, be the interlayer stacking characteristic peak of aromatic substance, corresponding interlamellar spacing
For 0.325nm, it was demonstrated that product is the layer structure carbonitride with similar graphite, i.e. graphite phase carbon nitride.
Fig. 2 is the stereoscan photograph of products therefrom, it can be seen that the carbonitride of synthesis is lamellar heap in figure
Build structure.Fig. 3 is the transmission electron microscope photo of products therefrom, can be it has furthermore been found that product has bright in figure
Aobvious graphite laminate structure.
Embodiment 2
Move in ceramic crucible after weighing two component raw material in same embodiment 1 and being sufficiently mixed.By earthenware
After crucible is placed in industry High-Power Microwave resonator, start to be evacuated to 5kPa.It is then turned on microwave, sets microwave spoke
It is 3kW according to power, after temperature reaches 550 DEG C, starts insulation, close micro-wave oven after 10min, make reaction
System takes out yellow sample after cooling to room temperature with the furnace.By in embodiment 1 use X-ray diffraction and
ESEM signs etc. are analyzed, and provable gained yellow product is graphite phase carbon nitride.Owing to improve microwave
Power, causes heating-up temperature higher, and the color of the graphite phase carbon nitride of gained has been deepened, and productivity is about
41wt%.
Product X-x ray diffraction collection of illustrative plates shows, 13.3 ° of positions occur in that (100) diffraction maximum, correspondence
It is the 3-s-triazine structure that repeats in the same plane of carbonitride, it is understood that for repeating phase in 5-triazine units
Distance between adjacent N hole.Occur in that obvious (002) diffraction maximum 27.1 ° of positions, be aromatic substance
Interlayer stacking characteristic peak, it was demonstrated that product is the layer structure carbonitride with similar graphite, i.e. graphite-phase nitrogen
Change carbon.
From the scanning electron microscopic picture (Fig. 4) of product it can be found that, laminated structure edge some curling.
Embodiment 3
Weigh two component raw material in same embodiment 1 and be sufficiently mixed, then moving in ceramic crucible also
It is placed in industry High-Power Microwave stove resonator.Micro-wave oven resonator is evacuated to vacuum 10kPa.Open microwave,
Set microwave irradiation power as 3kW, after temperature reaches 550 DEG C, start insulation, after 20min, close microwave
Stove, makes reaction system take out buff sample after cooling to room temperature with the furnace.By what embodiment 1 used
The phenetic analysis such as X-ray diffraction and ESEM, provable gained buff product is graphite phase carbon nitride.
Owing to extending temperature retention time further, the color of graphite phase carbon nitride becomes buff, and productivity is 39wt%.
Product X-x ray diffraction collection of illustrative plates shows, 13 ° of positions occur in that (100) diffraction maximum, correspondence
It is the 3-s-triazine structure that repeats in the same plane of carbonitride, it is understood that for repeating phase in 5-triazine units
Distance between adjacent N hole.Occur in that obvious (002) diffraction maximum 27.3 ° of positions, be aromatic substance
Interlayer stacking characteristic peak, it was demonstrated that product is the layer structure carbonitride with similar graphite, i.e. graphite-phase nitrogen
Change carbon.
From scanning electron microscopic picture (Fig. 5) it can be found that, sheet and tubular graphene phase carbon nitride exist simultaneously.
Embodiment 4
By 10g melamine (C3H6N6) and 5g graphite composite powder grind, mix.Then will mixing
Thing is put into and is placed in resonator in industry High-Power Microwave stove in ceramic crucible, starts to be evacuated to 10kPa.
Open microwave, sets microwave irradiation power as 3.5kW, start to be incubated after temperature reaches 700 DEG C, 10min
Rear cut out micro-wave oven, makes reaction system take out yellowish-brown sample after cooling to room temperature with the furnace.By embodiment 1
The phenetic analysis such as the X-ray diffraction of middle employing and ESEM, provable gained yellowish-brown product is graphite
Phase carbon nitride.Due to too high heating-up temperature, some decomposition of graphite phase carbon nitride, productivity is about
23wt%.
Product X-x ray diffraction collection of illustrative plates shows, 13.5 ° of positions occur in that (100) diffraction maximum, correspondence
It is the 3-s-triazine structure that repeats in the same plane of carbonitride, it is understood that for repeating phase in 5-triazine units
Distance between adjacent N hole.Occur in that obvious (002) diffraction maximum 27.6 ° of positions, be aromatic substance
Interlayer stacking characteristic peak, it was demonstrated that product is the layer structure carbonitride with similar graphite, i.e. graphite-phase nitrogen
Change carbon.
From scanning electron microscopic picture (Fig. 6) it can be found that, sheet, tubulose and spherical graphite phase carbon nitride with
Time exist.
Embodiment 5
By 10g melamine (C3H6N6) and 3g carborundum (SiC) powder grind, mix.So
After mixture is put into ceramic crucible is placed in industry High-Power Microwave stove resonator, start to be evacuated to
5kPa.Open microwave, set microwave irradiation power as 3kW, start to be incubated after temperature reaches 500 DEG C,
Close micro-wave oven after 5min, make reaction system take out faint yellow sample after cooling to room temperature with the furnace.By reality
Execute the phenetic analysis such as the X-ray diffraction used in example 1 and ESEM, the faint yellow product of provable gained
It it is graphite phase carbon nitride.The graphite phase carbon nitride productivity that the method obtains is about 45wt%.
Product X-x ray diffraction collection of illustrative plates shows, 13 ° of positions occur in that (100) diffraction maximum, correspondence
It is the 3-s-triazine structure that repeats in the same plane of carbonitride, it is understood that for repeating phase in 5-triazine units
Distance between adjacent N hole.Occur in that obvious (002) diffraction maximum 27.3 ° of positions, be aromatic substance
Interlayer stacking characteristic peak, it was demonstrated that product is the layer structure carbonitride with similar graphite, i.e. graphite-phase nitrogen
Change carbon.
From scanning electron microscopic picture (Fig. 7) it can be seen that obtained some various sizes of spherical carbonitrides, directly
Footpath is between 500nm-1 μm.
Embodiment 6
By 10g melamine (C3H6N6) and 5g carborundum (SiC) powder grind, mix.So
After mixture is put into ceramic crucible is placed in industry High-Power Microwave stove resonator, start to be evacuated to
5kPa.Open microwave, set microwave irradiation power as 4kW, start to be incubated after temperature reaches 650 DEG C,
Close micro-wave oven after 30min, make reaction system take out yellowish-brown sample after cooling to room temperature with the furnace.By reality
Execute the phenetic analysis such as the X-ray diffraction used in example 1 and ESEM, provable gained yellowish-brown product
It it is graphite phase carbon nitride.Owing to extending temperature retention time and high heating-up temperature, the color of graphite phase carbon nitride
Become buff.The graphite phase carbon nitride productivity that the method obtains is about 19wt%.
Product X-x ray diffraction collection of illustrative plates shows, 13.3 ° of positions occur in that (100) diffraction maximum, correspondence
It is the 3-s-triazine structure that repeats in the same plane of carbonitride, it is understood that for repeating phase in 5-triazine units
Distance between adjacent N hole.Occur in that obvious (002) diffraction maximum 27.7 ° of positions, be aromatic substance
Interlayer stacking characteristic peak, it was demonstrated that product is the layer structure carbonitride with similar graphite, i.e. graphite-phase nitrogen
Change carbon.
Can find clearly from scanning electron microscopic picture (Fig. 8), the graphite phase carbon nitride of sheet is piled into one
Individual big block, width is about 4 μm.
Embodiment 7
By 10g cyanamid dimerization (C2H4N4) and 4g graphite grind, mix.Then mixture is put
Enter to be placed in ceramic crucible, in industry High-Power Microwave stove resonator, to start to be evacuated to 5kPa.Open micro-
Ripple, sets microwave irradiation power as 4kW, starts insulation after temperature reaches 600 DEG C, closes after 30min
Micro-wave oven, makes reaction system take out yellow sample after cooling to room temperature with the furnace.By what embodiment 1 used
The phenetic analysis such as X-ray diffraction and ESEM, provable gained yellow product is graphite phase carbon nitride.Should
The graphite phase carbon nitride productivity that method obtains is about 23wt%.
Product X-x ray diffraction collection of illustrative plates shows, 13.4 ° of positions occur in that (100) diffraction maximum, correspondence
It is the 3-s-triazine structure that repeats in the same plane of carbonitride, it is understood that for repeating phase in 5-triazine units
Distance between adjacent N hole.Occur in that obvious (002) diffraction maximum 27.5 ° of positions, be aromatic substance
Interlayer stacking characteristic peak, it was demonstrated that product is the layer structure carbonitride with similar graphite, i.e. graphite-phase nitrogen
Change carbon.
Can find clearly from scanning electron microscopic picture (Fig. 9), the graphite phase carbon nitride of sheet is piled into one
Individual big block, surface topography is stepped.
Embodiment 8
By 10g cyanamide (CH2N2) and 4g carborundum (SiC) powder grind, mix.Then
Mixture is put in ceramic crucible and be placed in industry High-Power Microwave stove resonator, start to be evacuated to
10kPa.Open microwave, set microwave irradiation power as 5kW, start to be incubated after temperature reaches 700 DEG C,
Close micro-wave oven after 15min, make reaction system take out yellowish-brown sample after cooling to room temperature with the furnace.By reality
Execute the phenetic analysis such as the X-ray diffraction used in example 1 and ESEM, provable gained yellowish-brown product
It it is graphite phase carbon nitride.The graphite phase carbon nitride productivity that the method obtains is about 25wt%.
Product X-x ray diffraction collection of illustrative plates shows, 13.4 ° of positions occur in that (100) diffraction maximum, correspondence
It is the 3-s-triazine structure that repeats in the same plane of carbonitride, it is understood that for repeating phase in 5-triazine units
Distance between adjacent N hole.Occur in that obvious (002) diffraction maximum 27.6 ° of positions, be aromatic substance
Interlayer stacking characteristic peak, it was demonstrated that product is the layer structure carbonitride with similar graphite, i.e. graphite-phase nitrogen
Change carbon.
From scanning electron microscopic picture (Figure 10) it can be seen that obtained some various sizes of flake graphite phase nitrogen
Changing carbon, the thickness of lamella is about 800nm.
Embodiment 9
By 5g thiocarbamide (CN2H4S) grind with 5g graphite, mix.Then mixture is put into
Ceramic crucible is placed in industry High-Power Microwave stove resonator, starts to be evacuated to 30kPa.Open microwave,
Set microwave irradiation power as 4kW, after temperature reaches 650 DEG C, start insulation, after 20min, close microwave
Stove, makes reaction system take out yellow sample after cooling to room temperature with the furnace.By the X-used in embodiment 1
The phenetic analysis such as x ray diffraction and ESEM, provable gained yellow product is graphite phase carbon nitride.The party
The graphite phase carbon nitride productivity that method obtains is about 22wt%.
Product X-x ray diffraction collection of illustrative plates shows, 13.5 ° of positions occur in that (100) diffraction maximum, correspondence
It is the 3-s-triazine structure that repeats in the same plane of carbonitride, it is understood that for repeating phase in 5-triazine units
Distance between adjacent N hole.Occur in that obvious (002) diffraction maximum 27.2 ° of positions, be aromatic substance
Interlayer stacking characteristic peak, it was demonstrated that product is the layer structure carbonitride with similar graphite, i.e. graphite-phase nitrogen
Change carbon.
From scanning electron microscopic picture (Figure 11) it can be seen that obtained the sheet stone of some different sizes and thickness
Ink phase carbon nitride.
Embodiment 10
By 5g urea (CO (NH2)2) and 1g graphite grind, mix.Then mixture is put into
Ceramic crucible is placed in industry High-Power Microwave stove resonator, starts to be evacuated to 5kPa.Open microwave,
Set microwave irradiation power as 5kW, after temperature reaches 550 DEG C, start insulation, after 30min, close microwave
Stove, makes reaction system take out yellow sample after cooling to room temperature with the furnace.By the X-used in embodiment 1
The phenetic analysis such as x ray diffraction and ESEM, provable gained yellow product is graphite phase carbon nitride.The party
The graphite phase carbon nitride productivity that method obtains is about 15wt%.
Product X-x ray diffraction collection of illustrative plates shows, 13.2 ° of positions occur in that (100) diffraction maximum, correspondence
It is the 3-s-triazine structure that repeats in the same plane of carbonitride, it is understood that for repeating phase in 5-triazine units
Distance between adjacent N hole.Occur in that obvious (002) diffraction maximum 27.5 ° of positions, be aromatic substance
Interlayer stacking characteristic peak, it was demonstrated that product is the layer structure carbonitride with similar graphite, i.e. graphite-phase nitrogen
Change carbon.
From scanning electron microscopic picture (Figure 12) it can be found that, above big block graphite phase carbon nitride, attachment is a lot
Size graphite phase carbon nitride particle below 2 μm.
Claims (4)
1. a preparation method for graphite phase carbon nitride, its preparation process includes: with nitrogen-rich organic thing as raw material,
With graphite or carborundum as microwave absorption, nitrogen-rich organic thing is mixed with microwave absorption, at microwave
In the electromagnetic field of irradiation, control pressure is 5-35kPa, the power of microwave irradiation is 2-10kW, controls to rise
Temperature speed is 50-500 DEG C/min, 450-700 DEG C of insulation reaction 5-30min, obtains graphite phase carbon nitride；
Described nitrogen-rich organic thing is the one in melamine, cyanamid dimerization, cyanamide, thiocarbamide and urea.
The preparation method of a kind of graphite phase carbon nitride the most according to claim 1, it is characterised in that: institute
The nitrogen-rich organic thing stated is 1-5:1 with the mass ratio of microwave absorption.
The preparation method of a kind of graphite phase carbon nitride the most according to claim 1, it is characterised in that: institute
The control pressure stated is 5-30kPa.
The preparation method of a kind of graphite phase carbon nitride the most according to claim 1, it is characterised in that: institute
The power of the microwave irradiation stated is 2-5kW.
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| CN106477539A (en) * | 2016-09-22 | 2017-03-08 | 西安交通大学 | A kind of preparation method of ultra-thin graphite phase carbon nitride |
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| CN108408697A (en) * | 2018-02-14 | 2018-08-17 | 东华大学 | A kind of richness amino graphitic nitralloy carbon and preparation method thereof |
| CN108706559A (en) * | 2018-05-30 | 2018-10-26 | 安徽大学 | A kind of preparation method of graphite phase carbon nitride material |
| CN109399588A (en) * | 2018-12-20 | 2019-03-01 | 山东大学 | A kind of g-C constructed on substrate3N4Continuous film and preparation method |
| CN109622012A (en) * | 2018-12-07 | 2019-04-16 | 陕西科技大学 | A kind of exposure (010) crystal face BiOCl/ class graphite phase carbon nitride composite photo-catalyst and its preparation method and application |
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