CN105752953B - A kind of preparation method of graphite phase carbon nitride - Google Patents
A kind of preparation method of graphite phase carbon nitride Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of graphite phase carbon nitride, its preparation process includes：Using nitrogen-rich organic thing as raw material, using graphite or carborundum as microwave absorption, nitrogen-rich organic thing is well mixed with microwave absorption, in the electromagnetic field of microwave irradiation, control pressure is 5 35kPa, the power of microwave irradiation is 2 10kW, it is 50 500 DEG C/min to control heating rate, in 450 700 DEG C of 30min of insulation reaction 5, obtains graphite phase carbon nitride.This method is based on High-Power Microwave irradiation treatment method, can fast and efficiently obtain the graphite phase carbon nitride of layer structure；And this method has simply efficiently; cost is cheap, environment-friendly without using catalyst, organic solvent, protective gas etc. be various expensive or environmentally harmful reagent; the advantages that pretreatment of raw material need not be carried out, it is a kind of environment-friendly preparation method thereof for being advantageous to carry out large-scale commercial production.
Description
Technical field
The present invention relates to the preparing technical field of graphite phase carbon nitride, and in particular to one kind is based on High-Power Microwave irradiated heat
Technology, 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, be always scientific circles
One of most important tasks and missions.Wherein, semiconductor light-catalyst can be by pollution-free, nonhazardous and the nexhaustible sun
Chemical energy, or direct degradable organic pollutant can be converted into, is shown in solution energy crisis and environmental pollution etc. huge
Potentiality.Graphite phase carbon nitride is as a kind of novel semi-conductor optical function 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 are wide
It is general to apply in fields such as photocatalysis, sensor, bio-imaging, catalyst carrier and photoelectricity, it is considered to be most development potentiality
One of material.
At present, for the preparation of graphite phase carbon nitride, the preparation method of each tool technical characterstic has been had been developed for, has mainly been had
Solvent-thermal method, electrochemical deposition method, magnetron sputtering method, high temperature and high pressure method, chemical vapor deposition and thermal polycondensation process etc..Solvent-thermal method
Temperature conditionss are relatively mild, and nitrogen not easily runs off；And various templates can be added, control the pattern of product, for example, obtain micropore,
Mesoporous and large pore material.But the graphite phase carbon nitride crystallinity of solvent structure is poor, and generally to make in course of reaction
It is all harmful to environment and operating personnel with poisonous organic solvent.Electrochemical deposition method can be used to prepare carbon nitride films or
Coating, realize the uniform deposition on different labyrinths；But the carbon nitride films prepared are polycrystalline or amorphous state, and are not suitable for
Prepare the powder of graphite phase carbon nitride.Magnetron sputtering method is also quickly to prepare one of emerging technology of carbon nitride films, but to target
The purity requirement of material and reacting gas is high, and the film prepared is that polycrystalline state based on α or beta-phase carbon nitride coexists.High temperature is high
Platen press is one of basic skills of Nonequilibrium Materials such as synthesizing superhard carbonitride, but the carbonitride nitrogen content synthesized at present is than relatively low,
Product is based on diamond nanocrystalline；And graphite phase carbon nitride is as most stable of nitridation potassium fluotanta-late, is a kind of soft phase,
Therefore high temperature and high pressure method and be unsuitable for prepare graphite phase carbon nitride.Chemical vapour deposition technique is by being introduced in reaction system
N, C atom or ion of high activity, then obtain carbon nitride films in deposition on substrate, and it is equal to can be good at control synthesis thickness
Even film；But the film that this method obtains is amorphous mostly, and reactant utilization rate is low.Thermal polycondensation process is to utilize pyrolysis
Nitrogen-rich organic thing, graphite phase carbon nitride is prepared by the polycondensation process of presoma itself, course of reaction is directly, easy, cost is low
With it is environmentally safe；But the specific surface area for the graphite phase carbon nitride that conventional pyrolysis nitrogen-rich organic thing obtains is small, and crystallinity is poor, instead
It is long low with photocatalysis performance between seasonable.
Above-mentioned several method generally existing cycle length, complex process, cost is high, and environment is not friendly enough, and product crystallization
The defects of poor performance, the quick obtaining and practical application of graphite phase carbon nitride are limited to a certain extent, therefore develop a kind of
Quickly, efficiently, environmental protection, and the preparation method of low-cost industrial, the technique of quick obtaining 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, electrochemical deposition
Method, chemical vapour deposition technique and conventional thermal polycondensation process, based on the method for microwave irradiation synthetic powder, have fast speed, efficiency high,
Low-carbon environment-friendly, it is easy to a series of advantages such as industrialization and a large amount of productions.Melamine, cyanamid dimerization, cyanamide, thiocarbamide and urea
Etc. nitrogen-rich organic thing under the conditions of the Electromagnetic Heating of microwave irradiation, decomposable asymmetric choice net obtains the compound group or structure piece containing carbonnitrogen bond
Section.The intermediate of these high activities will can obtain the graphite with graphite packed structures by follow-up nucleation and accumulated growth
Phase carbon nitride.
At present, someone prepares carbon nitride material using microwave method, but due to by microwave equipment, knowledge hierarchy and
The limitation of application field, application of the people to High-Power Microwave technology are universal not enough.Common microwave heating equipment is that family expenses are micro-
Ripple stove, power is universal relatively low (300-1000W), all not ideal enough in preparation efficiency, effect etc..University of Anhui Yuan Yu rocs etc.
(Yuan Yupeng, Qiu Lingguang, Xu Gengsheng, Peng Fumin, Xu Wentao, Ma Lin, microwave heating is quick to prepare graphite-like structure nitridation carbon materials to people
Material, application number：201310404491.1. publication number：CN104415786A) to be prepared for graphite phase carbon nitride using microwave method (micro-
Wave power is up to 1000W), but microwave absorption and raw material is separated so that the thermal efficiency significantly reduces, it is difficult to play micro-
The advantage that amplitude quickly heats according to body phase, has had a strong impact on preparation efficiency；And expensive various metal oxides must be utilized to make
For microwave absorption, cost is caused to improve.
The content of the invention
The problem to be solved in the present invention is：A kind of method that preparation graphite phase carbon nitride simply, easily and fast is provided；
And obtained graphite phase carbon nitride has preferable crystallinity and purity, it can be used for degradation of organic substances, photodissociation hydrogen manufacturing, catalyst
Carrier and biomedical sensor etc..
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of preparation method of graphite phase carbon nitride,
Its preparation process includes：
1) raw material mixes：Using nitrogen-rich organic thing as presoma, using graphite or carborundum as microwave absorption, after being well mixed
It is put into ceramic crucible；
Described nitrogen-rich organic thing is one kind in melamine, cyanamid dimerization, cyanamide, thiocarbamide and urea；
2) microwave irradiation heats：Ceramic crucible in step 1) is put into microwave resonance intracavitary center, is evacuated to
Microwave resonance cavity pressure is 5-35kPa, the power of microwave irradiation is 2-10kW, and raw material is heated into 450- using microwave irradiation
After 700 DEG C, insulation reaction 5-30min, graphite phase carbon nitride is obtained；
Described nitrogen-rich organic thing and the mass ratio of microwave absorption are 1-5:1.
Described resonator vacuumizes, and the vacuum in resonator is 5-30kPa.
Described regulation microwave irradiation power, microwave power 2-5kW.
In described microwave irradiation heating process, High-Power Microwave irradiation can reach purpose that is quick, uniformly heating up, and control rises
Warm speed is 50-500 DEG C/min.
Technical principle：When microwave penetrates medium, because certain interaction occurs for microwave energy and medium, when utilizing microwave
Carry out radiation treatment when, by the molecule for making medium it is per second produce surpass hundred million times vibration, medium it is intermolecular mutually produce friction, draw
Rise medium temperature rise, make dielectric material it is internal, it is outside almost simultaneously heat temperature raising, by uniqueness body phase self-heating mode,
Substantially reduce the heat transfer in conventional heating or thermal convection current time.While the present invention is using High-Power Microwave heating, it can also produce
Raw electromagnetic field, special coupling intervention effect will be produced to the chemical reaction that bonding is matched with atomic nucleus outer-shell electron, that is, passed through
The non-thermal effect of microwave action, reaction activity is reduced, so as to change response path, realizes the quick of graphite phase carbon nitride powder
Prepare.
Beneficial effect：
1) preparation process is simple, quick, easy to operate.
2) raw material is simple, cost is cheap, it is not necessary to pre-processes；And without using catalyst, organic solvent, guarantor in preparation process
Protect the various expensive or environmentally harmful reagents such as gas.
3) non-environmental-pollution in preparation process, it is environmental friendly, except power consumption in preparation process, waste gas is not produced, is given up
Liquid and waste residue etc..
4) structure of gained graphite phase carbon nitride product and property are controllable；By adjusting nitrogen-rich organic thing and microwave absorption
Ratio, can obtain the graphite phase carbon nitride of different-shape and property.
Brief description of the drawings
Fig. 1 is the X-ray diffracting spectrum of the products therefrom of embodiment 1；
Fig. 2 is the scanning electron microscope image of the products therefrom of embodiment 1；
Fig. 3 is the images of transmissive electron microscope of the products therefrom of embodiment 1；
Fig. 4 is the scanning electron microscope image of the products therefrom of embodiment 2；
Fig. 5 is the scanning electron microscope image of the products therefrom of embodiment 3；
Fig. 6 is the scanning electron microscope image of the products therefrom of embodiment 4；
Fig. 7 is the scanning electron microscope image of the products therefrom of embodiment 5；
Fig. 8 is the scanning electron microscope image of the products therefrom of embodiment 6；
Fig. 9 is the scanning electron microscope image of the products therefrom of embodiment 7；
Figure 10 is the scanning electron microscope image of the products therefrom of embodiment 8；
Figure 11 is the scanning electron microscope image of the products therefrom of embodiment 9；
Figure 12 is the scanning electron microscope image of the products therefrom of embodiment 10.
Embodiment
Below by specific embodiment, " a kind of preparation method of graphite phase carbon nitride " of the invention is made further detailed
Description.
Comparative example 1
Conventional thermal polycondensation process prepares graphite phase carbon nitride
At present, the method that graphite type carbon nitride is prepared using thermal polycondensation process is a lot, such as patent CN103193785A (a kind of
Class graphene C3N4Material and its production and use), 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 using 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, is heating medium with lithium chloride (LiCl) and potassium chloride (KCl), 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 course of reaction
Protective gas, add cost；In addition, the long reaction time (12h) limits it and is widely applied.
Comparative example 2
Solution thermal polycondensation process prepares graphite phase carbon nitride
Organic solvent is introduced on the basis of conventional pyrocondensation polymerizing preparation method, porous type graphite phase carbon nitride can be obtained.It is as usual
A kind of " synthetic method of the mesoporous graphite phase carbon nitride of low cost " (application number of state university research：CN201410500429.7；It is public
The number of opening：CN104326446A), by by mesopore silicon oxide (SBA-15) material be impregnated into dicyanodiamine (be also cyanamid dimerization,
C2H4N4) ethylenediamine (C2H8N2) in solution, in inert protective atmosphere (N after stirring2) under be calcined 4h, then utilize hydrogen fluorine
The modes such as sour (HF) immersion go silicon template, then by centrifugation, drying and other steps, will can obtain outward appearance as black powder
Mesoporous graphite phase carbon nitride material.But the graphite phase carbon nitride typically acquired is faint yellow or glassy yellow, and this method obtains
The product arrived is black, it is meant that more graphite or agraphitic carbon composition in product be present；This method roasts in long-time simultaneously
The inert protective gas used during burning, and acid and alkali corrosion removing mesopore silicon oxide hard mould agent, and wash, centrifuge, be dry
The subsequent treatment such as dry so that this method process is still more tediously long, to inert protective gas, organic solvent and acid and alkali corrosion solvent
Deng use, be also not suitable with the requirement of the quick obtaining graphite phase carbon nitride of environment-friendly and green.
Comparative example 3
Solvent-thermal method prepares graphite phase carbon nitride
Patent CN102153055A (solvothermal preparation method of batch graphite type carbon nitride) utilizes 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 filter
Flushing obtains graphite phase carbon nitride.The organic solvent and raw material that this method uses are all harmful to environment and human body；It is in addition, long
Reaction time reduces combined coefficient, and the subsequent process such as extraction, purifying and collection of sample is also complicated cumbersome.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, uses
Solvent-thermal method reacts 20 hours at 400 DEG C, also successfully obtains graphite phase carbon nitride.But to solvent-thermal method analysis it can be found that
This method has inevitably all used virose solvent such as benzene and carbon tetrachloride, and the reaction time at least needs small more than ten
When, and the collection of sample is also very time-consuming.
Comparative example 4
Electrochemical deposition method prepares graphite phase carbon nitride
Document《The electrochemical deposition of class graphitic nitralloy carbon》(artificial lens journal 2003,32 (3)：252-256) with 1:1.5
Cyanuric Chloride (C3N3Cl3) and melamine (C3H6N6) saturation acetonitrile (C2H3N) solution is deposition liquid, applies 1200V height
Current voltage, electrochemical deposition has obtained class graphite phase carbon nitride crystal under Si (100) substrate upper chamber normal temperature and pressure；But synthesis nitridation
Carbon is that polycrystalline state coexists, and the graphite phase carbon nitride purity of preparation is very low.For another example document《Electrochemical deposition method prepares class graphite-phase nitrogen
Change carbon》(Science Bulletin, 2003,48 (9)：905-908) equally with Si (100) substrate, with 1:1.5 Cyanuric Chloride (C3N3Cl3)
With melamine (C3H6N6) saturation acetone (C2H6CO) solution is deposition liquid, at 25 DEG C, by 1200V high pressure, in Si
8 hours of electrochemical deposition have obtained the graphite phase carbon nitride crystal that N/C is 0.8 on substrate.Although utilize electrochemical deposition method
Graphite phase carbon nitride crystal has been obtained, but has all been that polycrystalline state coexists, the purity of graphite phase carbon nitride is low；In addition, in course of reaction
Acetonitrile and acetone and other organic solvent must be used to be unfavorable for environmental protection as electrolyte.
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) with Cyanuric Chloride (C3N3Cl3) be before
Drive body, Lithium Azide (LiN3) it is nitrogen source, solid phase reaction is carried out in 300-380 DEG C of temperature range and obtains C/N mol ratios and is
0.752 amorphous graphite phase carbon nitride.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 selecting Sodamide (NaNH2) or sodium azide
(NaN3) or potassium (K) and Cyanuric Chloride at 220-380 DEG C, the kish phase carbon nitride of different C/N mol ratio can be obtained.
Although the preparation technology of solid reaction process is fairly simple, solid reaction process prepare graphite phase carbon nitride, be typically chosen containing
The nitrogen-rich organic thing of triazine structure, to reduce the growth of the reaction barrier of carbonnitrogen bond and promotion class graphite laminate crystal structure, because
The selection of this reaction raw materials is subject to certain restrictions；In addition, the azido compound such as Lithium Azide and potassium belong to the easy of high activity
Quick-fried dangerous material, it is necessary to which operation is handled under a shielding gas, adds the danger and difficulty of operation；In addition, solid reaction process is imitated
Rate 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 for preparing carbon nitride films, document《Magnetron sputtering method prepare CNx films and
Its structural characterization》(material engineering, 2006 (7)：11-13) with argon gas/nitrogen (Ar/N2) mixed gas is high as sputter gas
Pure graphite is target, and using identical graphite flake as substrate., it is necessary to which graphite substrate is immersed into acetone before reaction
(C2H6CO), ethanol (C2H5OH) in solution, and it is respectively washed using the cleaning of ultrasonic activation instrument, sputtering chamber is put into after drying.So
After vacuumize, be first passed through argon gas, then be passed through nitrogen, sputtering power 100W, graphite phase carbon nitride crystal obtained after reacting 2h.
Although magnetron sputtering method can be big by changing the particle of the process parameter control carbonitride such as sputtering power and time
Small, reaction rate is than very fast, efficiency high, but what is obtained is not pure graphite phase carbon nitride crystal, and polycrystalline state carbonitride coexists；It is and anti-
The argon gas and nitrogen used during answering improves preparation cost.
Embodiment 1
By 10g melamines (C3H6N6) and it is the grinding of 2g graphite composite powders, well mixed.Then mixture is put into ceramics
It is placed in crucible in industrial High-Power Microwave stove resonator.Micro-wave oven resonator is evacuated to 5kPa, microwave is then turned on, treats temperature
Degree starts to be incubated after reaching 450 DEG C, and microwave power now closes micro-wave oven after 2kW or so, 5min, makes reaction system with stove
Sample is taken out after being cooled to room temperature.It can be seen that substantial amounts of glassy yellow powder in crucible be present.
The glassy yellow powder obtained after microwave irradiation is entered using x-ray diffraction pattern, ESEM, and transmission electron microscope etc.
Row structural characterization, it was demonstrated that product is pure graphite phase carbon nitride, and products pure, yield are about 46wt%.
Fig. 1 is the X-ray diffracting spectrum of products therefrom, and (100) diffraction maximum occur in 13.3 ° of right positions in figure,
Corresponding is the 3-s- triazine structures that carbonitride repeats in the same plane, it is understood that to repeat adjacent N in 5-triazine units
Distance between hole, corresponding interplanar distance are 0.681nm.Occur obvious (002) diffraction maximum 27 ° of positions, be virtue
The interlayer stacking characteristic peak of perfumery, corresponding interlamellar spacing are 0.325nm, it was demonstrated that product is the layer structure nitrogen with similar graphite
Change carbon, i.e. graphite phase carbon nitride.
Fig. 2 is the stereoscan photograph of products therefrom, and the carbonitride that synthesis is can see in figure is lamellar packing structure.
Fig. 3 is the transmission electron microscope photo of products therefrom, can be it has furthermore been found that product has obvious graphite laminate structure in figure.
Embodiment 2
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, start to be evacuated to 5kPa.Microwave is then turned on, microwave irradiation power is set as 3kW, treats temperature
Start to be incubated after reaching 550 DEG C, micro-wave oven is closed after 10min, reaction system is taken out yellow sample after cooling to room temperature with the furnace.
Analysis is characterized etc. by the X-ray diffraction and ESEM that are used in embodiment 1, provable gained yellow product is graphite-phase
Carbonitride.Due to improving microwave power, cause heating-up temperature higher, the color of the graphite phase carbon nitride of gained has been deepened,
Yield is about 41wt%.
Product X-x ray diffraction collection of illustrative plates shows that (100) diffraction maximum occur in 13.3 ° of positions, and corresponding is carbonitride
The 3-s- triazine structures repeated in the same plane, it is understood that to repeat the distance in 5-triazine units between adjacent N holes.
There is obvious (002) diffraction maximum in 27.1 ° of positions, are the interlayer stacking characteristic peaks of aromatic substance, it was demonstrated that product is that have
The layer structure carbonitride of similar graphite, i.e. graphite phase carbon nitride.
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 materials in same embodiment 1 and be sufficiently mixed, then move into and work is placed in ceramic crucible
In industry High-Power Microwave stove resonator.Micro-wave oven resonator is evacuated to vacuum 10kPa.Open microwave, set microwave irradiation power as
3kW, start to be incubated after temperature reaches 550 DEG C, micro-wave oven is closed after 20min, reaction system is taken after cooling to room temperature with the furnace
Go out buff sample.It is deep yellow by the phenetic analysis such as the X-ray diffraction used in embodiment 1 and ESEM, provable gained
Color product is graphite phase carbon nitride.Due to further extending soaking time, the color of graphite phase carbon nitride is changed into buff, production
Rate is 39wt%.
Product X-x ray diffraction collection of illustrative plates shows that (100) diffraction maximum occur in 13 ° of positions, and corresponding is that carbonitride exists
The 3-s- triazine structures repeated in same plane, it is understood that to repeat the distance in 5-triazine units between adjacent N holes.
There is obvious (002) diffraction maximum in 27.3 ° of positions, are the interlayer stacking characteristic peaks of aromatic substance, it was demonstrated that product is that have
The layer structure carbonitride of similar graphite, i.e. graphite phase carbon nitride.
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 melamines (C3H6N6) and it is the grinding of 5g graphite composite powders, well mixed.Then mixture is put into ceramics
Resonator in industrial High-Power Microwave stove is placed in crucible, starts to be evacuated to 10kPa.Microwave is opened, sets microwave irradiation work(
Rate is 3.5kW, starts to be incubated after temperature reaches 700 DEG C, micro-wave oven is closed after 10min, reaction system is cooled to room with the furnace
Yellowish-brown sample is taken out after temperature.By phenetic analysis such as the X-ray diffraction used in embodiment 1 and ESEMs, provable institute
It is graphite phase carbon nitride to obtain yellowish-brown product.Due to too high heating-up temperature, some decomposition of graphite phase carbon nitride, yield is about
For 23wt%.
Product X-x ray diffraction collection of illustrative plates shows that (100) diffraction maximum occur in 13.5 ° of positions, and corresponding is carbonitride
The 3-s- triazine structures repeated in the same plane, it is understood that to repeat the distance in 5-triazine units between adjacent N holes.
There is obvious (002) diffraction maximum in 27.6 ° of positions, are the interlayer stacking characteristic peaks of aromatic substance, it was demonstrated that product is that have
The layer structure carbonitride of similar graphite, i.e. graphite phase carbon nitride.
From scanning electron microscopic picture (Fig. 6), it can be found that, sheet, tubulose and spherical graphite phase carbon nitride exist simultaneously.
Embodiment 5
By 10g melamines (C3H6N6) and it is the grinding of 3g carborundum (SiC) powder, well mixed.Then mixture is put into
It is placed in into ceramic crucible in industrial High-Power Microwave stove resonator, starts to be evacuated to 5kPa.Microwave is opened, sets microwave spoke
It is 3kW according to power, starts to be incubated after temperature reaches 500 DEG C, micro-wave oven is closed after 5min, reaction system is cooled to room with the furnace
Faint yellow sample is taken out after temperature.By phenetic analysis such as the X-ray diffraction used in embodiment 1 and ESEMs, provable institute
It is graphite phase carbon nitride to obtain faint yellow product.The graphite phase carbon nitride yield that this method obtains is about 45wt%.
Product X-x ray diffraction collection of illustrative plates shows that (100) diffraction maximum occur in 13 ° of positions, and corresponding is that carbonitride exists
The 3-s- triazine structures repeated in same plane, it is understood that to repeat the distance in 5-triazine units between adjacent N holes.
There is obvious (002) diffraction maximum in 27.3 ° of positions, are the interlayer stacking characteristic peaks of aromatic substance, it was demonstrated that product is that have
The layer structure carbonitride of similar graphite, i.e. graphite phase carbon nitride.
From scanning electron microscopic picture (Fig. 7) it can be seen that having obtained some various sizes of spherical carbonitrides, diameter exists
Between 500nm-1 μm.
Embodiment 6
By 10g melamines (C3H6N6) and it is the grinding of 5g carborundum (SiC) powder, well mixed.Then mixture is put into
It is placed in into ceramic crucible in industrial High-Power Microwave stove resonator, starts to be evacuated to 5kPa.Microwave is opened, sets microwave spoke
It is 4kW according to power, starts to be incubated after temperature reaches 650 DEG C, micro-wave oven is closed after 30min, cools to reaction system with the furnace
Yellowish-brown sample is taken out after room temperature.It is provable by phenetic analysis such as the X-ray diffraction used in embodiment 1 and ESEMs
Gained yellowish-brown product is graphite phase carbon nitride.Due to extending soaking time and high heating-up temperature, graphite phase carbon nitride
Color is changed into buff.The graphite phase carbon nitride yield that this method obtains is about 19wt%.
Product X-x ray diffraction collection of illustrative plates shows that (100) diffraction maximum occur in 13.3 ° of positions, and corresponding is carbonitride
The 3-s- triazine structures repeated in the same plane, it is understood that to repeat the distance in 5-triazine units between adjacent N holes.
There is obvious (002) diffraction maximum in 27.7 ° of positions, are the interlayer stacking characteristic peaks of aromatic substance, it was demonstrated that product is that have
The layer structure carbonitride of similar graphite, i.e. graphite phase carbon nitride.
Can clearly it be found from scanning electron microscopic picture (Fig. 8), the graphite phase carbon nitride of sheet is piled into a big block
Body, width is at 4 μm or so.
Embodiment 7
By 10g cyanamid dimerizations (C2H4N4) and it is the grinding of 4g graphite, well mixed.Then mixture is put into ceramic crucible
In be placed in industrial 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 600 DEG C, micro-wave oven is closed after 30min, reaction system is taken after cooling to room temperature with the furnace
Go out yellow sample.By phenetic analysis such as the X-ray diffraction used in embodiment 1 and ESEMs, provable gained yellow production
Thing is graphite phase carbon nitride.The graphite phase carbon nitride yield that this method obtains is about 23wt%.
Product X-x ray diffraction collection of illustrative plates shows that (100) diffraction maximum occur in 13.4 ° of positions, and corresponding is carbonitride
The 3-s- triazine structures repeated in the same plane, it is understood that to repeat the distance in 5-triazine units between adjacent N holes.
There is obvious (002) diffraction maximum in 27.5 ° of positions, are the interlayer stacking characteristic peaks of aromatic substance, it was demonstrated that product is that have
The layer structure carbonitride of similar graphite, i.e. graphite phase carbon nitride.
Can clearly it be found from scanning electron microscopic picture (Fig. 9), the graphite phase carbon nitride of sheet is piled into a big block
Body, surface topography are stepped.
Embodiment 8
By 10g cyanamides (CH2N2) and it is the grinding of 4g carborundum (SiC) powder, well mixed.Then mixture is put into
It is placed in ceramic crucible in industrial High-Power Microwave stove resonator, starts to be evacuated to 10kPa.Microwave is opened, sets microwave spoke
It is 5kW according to power, starts to be incubated after temperature reaches 700 DEG C, micro-wave oven is closed after 15min, cools to reaction system with the furnace
Yellowish-brown sample is taken out after room temperature.It is provable by phenetic analysis such as the X-ray diffraction used in embodiment 1 and ESEMs
Gained yellowish-brown product is graphite phase carbon nitride.The graphite phase carbon nitride yield that this method obtains is about 25wt%.
Product X-x ray diffraction collection of illustrative plates shows that (100) diffraction maximum occur in 13.4 ° of positions, and corresponding is carbonitride
The 3-s- triazine structures repeated in the same plane, it is understood that to repeat the distance in 5-triazine units between adjacent N holes.
There is obvious (002) diffraction maximum in 27.6 ° of positions, are the interlayer stacking characteristic peaks of aromatic substance, it was demonstrated that product is that have
The layer structure carbonitride of similar graphite, i.e. graphite phase carbon nitride.
From scanning electron microscopic picture (Figure 10) it can be seen that having obtained some various sizes of flake graphite phase carbon nitrides, lamella
Thickness be about 800nm.
Embodiment 9
By 5g thiocarbamides (CN2H4S) grind with 5g graphite, be well mixed.Then mixture is put into juxtaposition in ceramic crucible
In in industrial High-Power Microwave stove resonator, start to be evacuated to 30kPa.Microwave is opened, microwave irradiation power is set as 4kW, treats
Temperature starts to be incubated after reaching 650 DEG C, and micro-wave oven is closed after 20min, reaction system is taken out yellow after cooling to room temperature with the furnace
Sample.By phenetic analysis such as the X-ray diffraction used in embodiment 1 and ESEMs, provable gained yellow product is stone
Black phase carbon nitride.The graphite phase carbon nitride yield that this method obtains is about 22wt%.
Product X-x ray diffraction collection of illustrative plates shows that (100) diffraction maximum occur in 13.5 ° of positions, and corresponding is carbonitride
The 3-s- triazine structures repeated in the same plane, it is understood that to repeat the distance in 5-triazine units between adjacent N holes.
There is obvious (002) diffraction maximum in 27.2 ° of positions, are the interlayer stacking characteristic peaks of aromatic substance, it was demonstrated that product is that have
The layer structure carbonitride of similar graphite, i.e. graphite phase carbon nitride.
Mutually nitrogenized with the flake graphite of thickness from scanning electron microscopic picture (Figure 11) it can be seen that having obtained some different sizes
Carbon.
Embodiment 10
By 5g urea (CO (NH2)2) and it is the grinding of 1g graphite, well mixed.Then mixture is put into ceramic crucible simultaneously
It is placed in industrial High-Power Microwave stove resonator, starts to be evacuated to 5kPa.Microwave is opened, microwave irradiation power is set as 5kW, treats
Temperature starts to be incubated after reaching 550 DEG C, and micro-wave oven is closed after 30min, reaction system is taken out yellow after cooling to room temperature with the furnace
Sample.By phenetic analysis such as the X-ray diffraction used in embodiment 1 and ESEMs, provable gained yellow product is stone
Black phase carbon nitride.The graphite phase carbon nitride yield that this method obtains is about 15wt%.
Product X-x ray diffraction collection of illustrative plates shows that (100) diffraction maximum occur in 13.2 ° of positions, and corresponding is carbonitride
The 3-s- triazine structures repeated in the same plane, it is understood that to repeat the distance in 5-triazine units between adjacent N holes.
There is obvious (002) diffraction maximum in 27.5 ° of positions, are the interlayer stacking characteristic peaks of aromatic substance, it was demonstrated that product is that have
The layer structure carbonitride of similar graphite, i.e. graphite phase carbon nitride.
It can be found that, many sizes are adhered to above big block graphite phase carbon nitride in 2 μ from scanning electron microscopic picture (Figure 12)
Below m graphite phase carbon nitride particle.
Claims (4)
1. a kind of preparation method of graphite phase carbon nitride, its preparation process include：Using nitrogen-rich organic thing as raw material, with graphite or carbon
SiClx is microwave absorption, and nitrogen-rich organic thing is well mixed with microwave absorption, in the electromagnetic field of microwave irradiation, control pressure
Power is 5-35kPa, the power of microwave irradiation is 2-10kW, and it is 50-500 DEG C/min to control heating rate, in 450-700 DEG C of insulation
5-30min is reacted, obtains graphite phase carbon nitride；
Described nitrogen-rich organic thing is one kind in melamine, cyanamid dimerization, cyanamide, thiocarbamide and urea.
A kind of 2. preparation method of graphite phase carbon nitride according to claim 1, it is characterised in that：Described nitrogen-rich organic
The mass ratio of thing and microwave absorption is 1-5:1.
A kind of 3. preparation method of graphite phase carbon nitride according to claim 1, it is characterised in that：Described control pressure
For 5-30kPa.
A kind of 4. preparation method of graphite phase carbon nitride according to claim 1, it is characterised in that：Described microwave irradiation
Power be 2-5kW.
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| CN110142055B (en) * | 2018-02-11 | 2022-04-12 | 天津理工大学 | Microwave irradiation method for enhancing photocatalytic performance of graphite-phase carbon nitride |
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| CN108706559B (en) * | 2018-05-30 | 2020-04-07 | 安徽大学 | Preparation method of graphite phase carbon nitride material |
| CN109622012B (en) * | 2018-12-07 | 2020-10-09 | 陕西科技大学 | Composite photocatalyst with exposed (010) crystal face BiOCl/graphite-like phase carbon nitride and preparation method and application thereof |
| CN109399588B (en) * | 2018-12-20 | 2020-06-02 | 山东大学 | g-C constructed on substrate3N4Continuous film and preparation method |
| CN109650358A (en) * | 2019-01-25 | 2019-04-19 | 张家港市东大工业技术研究院 | A method of quickly graphite phase carbon nitride nanometer rods are prepared without template |
| CN109850858B (en) * | 2019-03-22 | 2020-08-11 | 张家港市东大工业技术研究院 | Synthetic method of hydrophilic graphite phase carbon nitride material |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1219604A (en) * | 1997-12-11 | 1999-06-16 | 中国科学院物理研究所 | Synthesis method of crystalline phase carbonitride film by microwave plasma chemical gas-phase deposition |
| CN104415786A (en) * | 2013-09-04 | 2015-03-18 | 安徽大学 | Method for quickly preparing quasi-graphite-structure carbon nitride material by adopting microwave heating |
| CN104772157A (en) * | 2015-01-13 | 2015-07-15 | 华东理工大学 | Method for growing TiO2 nanocrystals on surface of g-C3N4, and application of obtained material |
-
2016
- 2016-01-29 CN CN201610065411.8A patent/CN105752953B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1219604A (en) * | 1997-12-11 | 1999-06-16 | 中国科学院物理研究所 | Synthesis method of crystalline phase carbonitride film by microwave plasma chemical gas-phase deposition |
| CN104415786A (en) * | 2013-09-04 | 2015-03-18 | 安徽大学 | Method for quickly preparing quasi-graphite-structure carbon nitride material by adopting microwave heating |
| CN104772157A (en) * | 2015-01-13 | 2015-07-15 | 华东理工大学 | Method for growing TiO2 nanocrystals on surface of g-C3N4, and application of obtained material |
Non-Patent Citations (1)
| Title |
|---|
| 石墨相氮化碳基功能材料的制备及光催化、传感性能研究;陈海玉;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20151015(第10期);第56-57页 * |
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