CN105883733B - Inflatable carbonitride and preparation method thereof, expansion method - Google Patents

Inflatable carbonitride and preparation method thereof, expansion method Download PDF

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CN105883733B
CN105883733B CN201610238831.1A CN201610238831A CN105883733B CN 105883733 B CN105883733 B CN 105883733B CN 201610238831 A CN201610238831 A CN 201610238831A CN 105883733 B CN105883733 B CN 105883733B
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carbonitride
inflatable
preparation
sulfuric acid
graphite
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CN105883733A (en
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王赪胤
滕镇远
吕红映
王罗娜
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Yangzhou University
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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
    • 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
    • C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
    • 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
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

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Abstract

Inflatable carbonitride and preparation method thereof, expansion method, it is related to environmental protection, field of fire-proof technology, pass through the method for liquid phase intercalation, it is prepared for inflatable carbonitride, the present invention has synthesized a kind of inflatable carbonitride through sulfuric acid intercalation processing, and the volume after high temperature puffing is handled is changed into original 100 times；The inflatable carbonitride that the present invention is synthesized has an excellent expansion character, great reference area, can further be made as high-performance flame-retardant material, catalysis material, and absorbing material, phase-changing energy storage material and pollutant sorbing material have expanded g C significantly3N4Application.

Description

Inflatable carbonitride and preparation method thereof, expansion method
Technical field
The present invention relates to environmental protection, field of fire-proof technology, and in particular to the preparation method and expansion method of inflatable carbonitride.
Background technology
Expansible graphite（EG）Obtained by natural flake graphite after chemical oxidization method or electrochemical oxidation process processing A kind of compound between graphite layers, for structure, EG is a kind of nanocomposite.Common H2SO4The obtained EG of oxidation by During to 200 DEG C of high temperature above, redox reaction occurs between sulfuric acid and graphite carbon atom, substantial amounts of SO is produced2, CO2 and water Steam, makes EG start expansion, and reaches maximum volume at 1100 DEG C, 280 when its final volume can reach initial times.Through Obtained ultra-large volume compound is referred to as expanded graphite or graphite worm after pyroreaction.
Graphite after expansible graphite and expansion has purposes widely.Expansible graphite can be used as a kind of Halogen Environmental protection fire retarding agent, its advantage has：
Poisonous and corrosive gas is not generated when the 1, being heated, and the flue gas of generation is seldom.
2nd, required addition is small.
3rd, without molten drop drip phenomenon.
4th, environmental suitability is strong, non-migratory phenomenon.
5th, UV stable and good light stability.
Therefore, EG is widely used in various fire-retardant fireproof materials, such as fire proof sealing strip, fire-proof plate, fireproof antistatic Coating, fire prevention bag, plasticity fire prevention calking, fire trapping ring and flame retardant plastics etc..EG fire retardant mechanism belongs to the fire-retardant machine of solidifying phase Reason, is fire-retardant by solid matter generation inflammable substance by delaying or interrupting.EG is heated can start to a certain extent it is swollen Swollen, graphite after expansion becomes density very low vermiform by original flakey, so as to form good heat insulation layer.After expansion Graphite flake be both charcoal source in intumescent system, be heat insulation layer again, can be effectively heat-insulated, delay and terminate the decomposition of polymer； Meanwhile, largely absorbed heat in expansion process, reduce system temperature；And in expansion process, the acid ion in release jacket coating promotees Enter dehydration carbonization.Expanded graphite may be used as efficient sealed material preparation, the absorption of water environment pollution thing, efficient medical bandage Preparation, the synthesis of high-energy battery material, the preparation of phase-change heat-storage material and the preparation of military absorbing material.
However, the effect of the big pi bond due to graphite layers, is a kind of excellent conductor, its characteristic without forbidden band from Its application in terms of photochemical catalysis and absorbing material is limited in theory.Furthermore, expansible graphite is mainly by own vol The burning for expanding the expansion heat insulation layer of formation to delay or suppress polymer, with not occurred between flame-retardant polymer or seldom being sent out Biochemical effect, causes；And the adhesive force of the expanded graphite formed after EG expansions to each other is weaker, in polymeric matrix burning Afterwards, expanded graphite can not form firm foamed char, in the presence of flame pressure or heat convection, the expansion stone on surface Layer of ink may be destroyed, and be formed " flying dust ", cause the forfeiture of adiabatic expansion layer, and then trigger unburned polymer by point Combustion, flame continues to propagate, and flame retarding efficiency is limited.
In recent years, many flame retardant materials mixed with expansible graphite are used, compound flame retardant, order resistance is made Combustion engine reason turns into the meteorological and fire-retardant progress simultaneously of condensed phase, greatly increases the fire resistance of matrix material.However, compounding resistance Although retardant composite material fire resistance is improved, fire retardant addition is still very big, and fire retardant and base material is compatible Property still have much room for improvement, cause the mechanical property of polymer matrix composite by serious influence, find a kind of few additive, Research that is efficient and being provided simultaneously with fire-retardant and the fire-retardant advantage of condensed phase the fire retardant of gas phase still needs to deep progress.
In recent years, due to class graphite phase carbon nitride（g-C3N4）With suitable photocatalysis band gap, excellent semiconductive Can, excellent stability, makes its of great interest at high temperature.At room temperature, g-C3N4It is by with 3-s- triazines Ring（- C6N7）The flat sheet structure being connected between the sweet primary amine of the long-chain molecule of composition with hydrogen bond, the N that each interannular passes through end Atom is connected, and forms the pi-conjugated plane wirelessly expanded.Because the hydrogen bond between sweet primary amine is present, substantial amounts of sweet primary amine is made to be formed Orderly lamella, these pi-conjugated planes are accumulated by way of class graphite, form the lamellar structure with certain defect. This structure imparts g-C3N4Excellent wearability, chemical heat endurance and heat endurance etc., in catalyst carrier, energy storage Material and fire proofing have very high application prospect.But, although g-C3N4With stable, high temperature resistant, with suitable energy The advantages of band structure, but be due to the block structure of its multiple-level stack, thus g-C3N4Surface area very little, seriously constrain Application in terms of its photocatalysis.If can be by the C with layer structure3N4It is prepared into g-C3N4Interbed compound, by high temperature After expanding treatment, its specific surface area will be substantially improved.The mechanism of intumescence of analogy expansible graphite, due to 3-s- triazine rings（- C6N7）On nitrogen-atoms on there are a pair of lone pair electrons, reproducibility is slightly larger compared with the carbon atom C in plumbago single slice layer, and every 3 3- S- triazine rings（- C6N7）Between there is nano aperture between larger atom, the hole can provide for the attack of oxidant Effective attack site, thus g-C3N4More difficulty can be produced in the puffing process of interbed compound and oxidant reaction Combustion gas body；Meanwhile, g-C3N4Formed after expanded by heating can the effective burning of starvation and matrix fine and close carbon-coating, because This in theory, g-C3N4Interbed compound will be provided simultaneously with fire-retardant and condensed phase the advantage of gas phase as fire retardant.
But, although g-C3N4Layer structure with class graphite, but its each layer is big by the long-chain of sweet primary amine Molecule is formed with Hydrogenbond, g-C3N4Each lamella in have different degrees of defect, cause use sulfuric acid, permanganic acid Potassium and the intercalation method of sodium nitrate oxidation can destroy its layer structure.Therefore, find and prepare a kind of inflatable g-C3N4Method G-C will effectively be expanded3N4Application, to prepare high-performance flame-retardant material of new generation, photochemical catalyst, absorbing material, phase The new visual angle of change energy-storage material offer and mentality of designing.
The content of the invention
The defect existed based on above prior art, present invention aims at propose a kind of inflatable carbonitride.
The structural formula of the inflatable carbonitride of the present invention is：
Wherein, n is 1,2 or 3.
The inflatable carbonitride that the present invention is synthesized, the volume after high temperature puffing is handled is changed into original 100 times；This hair The inflatable carbonitride of bright synthesis has excellent expansion character, and great reference area can further be made as high-performance resistance Combustible material, catalysis material, absorbing material, phase-changing energy storage material and pollutant sorbing material have expanded g-C significantly3N4Should Use scope.
Second purpose of the invention is the preparation method of inflatable carbonitride more than proposing.
The inventive method comprises the following steps：
1）Under the conditions of magnetic agitation, by the carbonitride of graphite-structure（g - C3N4）It is dissolved in the concentrated sulfuric acid, nitridation is made Carbon-concentrated sulfuric acid solution；
2）Carbonitride-concentrated sulfuric acid solution is cooled to 8~10 DEG C, the inflatable Carbon Nitride Crystal separated out is obtained；
3）Inflatable Carbon Nitride Crystal is subjected to decompression suction filtration, using being dried in vacuo again after absolute ethyl alcohol washing precipitation, obtained To inflatable carbonitride.
The method of first passage liquid phase intercalation of the present invention, is prepared for inflatable carbonitride.Step 3）In, using absolute ethyl alcohol Washing removes the unnecessary sulfuric acid solution for remaining in inflatable Carbon Nitride Crystal surface.
Further, step 1 of the present invention）The mixing ratio of the middle concentrated sulfuric acid and graphite phase carbon nitride is 10 mL: 3g.Should Amount ratio can ensure that graphite phase carbon nitride can be dissolved completely in the concentrated sulfuric acid, the concentrated sulfuric acid is fully filled with graphite phase carbon nitride Divide mixing, form saturated solution, when temperature is reduced, have white crystal precipitation.If if the content of carbonitride is a lot, May result in part graphite phase carbon nitride can not be dissolved in the concentrated sulfuric acid, if if graphite phase carbon nitride content is seldom, graphite Phase carbon nitride, which is dissolved in after the concentrated sulfuric acid, can not form saturated solution, not have white crystal precipitation when reduction temperature.
The step 1）Described in dissolving be carbonitride in graphite-structure（g - C3N4）Mixing temperature with the concentrated sulfuric acid is Carried out under conditions of 60~80 DEG C.At this temperature, graphite phase carbon nitride is gradually dissolved in the concentrated sulfuric acid, until all molten Solution, solution is into clear light yellow.
The step 2）Middle cooldown rate is 2~4 DEG C/h.With the slow reduction of temperature, solution starts precipitation white can Expand Carbon Nitride Crystal.The purpose for setting this cooling velocity is to grow with enabling graphite phase carbon nitride crystal stable and uniform Come, if cooling velocity is more than the value, it is impossible to separate out white crystal.If cooling velocity is too slow, smaller particle very big crystalline substance can be produced Body.
The step 3）Described in vacuum drying temperature conditionss be 40~60 DEG C, vacuum be 66.6~68.6 kPa, Time is 2~4 h.The purpose for setting the temperature and vacuum degree condition is the absolute ethyl alcohol and a small amount of moisture for removing plane of crystal, Crystal is allowed to keep drying.If temperature is too low, crystal is difficult drying, if the too high crystal structure that can talk nitridation of temperature becomes Change.Sample, can be completely dried by vacuum drying 2-4 hours in this period, take out stand-by.
Third object of the present invention is the expansion method of inflatable carbonitride more than proposing.
Inflatable carbonitride is placed in quartz container, 20~40s of heating in 550~600 DEG C of Muffle furnace is placed in, takes out Afterwards, through cooling, expansion carbonitride is obtained.
The invention has the advantages that：
First, inflatable carbonitride prepared by the present invention, with unique physical and chemical performance, its volume can be 550 More than 100 times of original volume are drastically expanded at~600 DEG C, specific surface area is greatly improved, make efficient photochemical catalyst matrix material Material, absorbing material, pollutant sorbing material, efficient medical bandage material and high-energy battery material are prepared into order to may.Should Method does not need poisonous and hazardous reagent, and all raw materials and solvent obtain convenient, cheap.
Second, inflatable carbonitride produced by the present invention during expansion, can release what can not largely be ignited Inert gas, possibility is provided to prepare efficient condensed phase in situ, gas phase synergistic fire retardant.
3rd, the method that the present invention prepares inflatable carbonitride is carried out at liquid-crystalization using sulfuric acid to graphite phase carbon nitride Reason, is precipitated by recrystallizing, the mode of ethanol washing, prepares inflatable carbonitride.Need not in the preparation process of this method Poisonous and hazardous reagent, all raw materials and solvent obtain convenient, cheap, there is very big industrial applications prospect.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of inflatable carbonitride produced by the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph after inflatable carbonitride produced by the present invention is handled through high temperature puffing.
Fig. 3 is the optical microscope of inflatable carbonitride produced by the present invention.
Embodiment
First, inflatable carbonitride is prepared：
1st, weigh a certain amount of melamine to be placed in tube furnace, keep the L/min of nitrogen flow rate 2.0~4.0, lead to nitrogen 10~15 min, 4~6h is calcined at 550~600 DEG C with 8~10 DEG C/min programming rate, and grinding obtains powdered faint yellow The carbonitride of graphite-structure（g - C3N4）.
2nd, 30~50mL concentrated sulfuric acids are added in flask（It is preferred that 10mL）, and add 10~12g（It is preferred that 3g）Graphite-structure Carbonitride（g - C3N4）.It is placed in the thermostat water bath with magnetic stirring apparatus, magnetic stirring apparatus is opened, by water-bath temperature Degree rises to 60~80 DEG C, and stirring obtains carbonitride-concentrated sulfuric acid solution to nitridation carbon dissolution.
3rd, carbonitride-concentrated sulfuric acid solution is put into low temperature cold bath, 8~10 DEG C is cooled to 2~4 DEG C/h speed, with The slow reduction of temperature, solution starts to separate out the inflatable Carbon Nitride Crystal of white, final to obtain the inflatable nitridation carbon crystal of white Body.
4th, the inflatable Carbon Nitride Crystal of white is transferred on sand core funnel, depressurizes suction filtration, take solid phase to reuse anhydrous second Alcohol washing precipitation 6~8 times, then is placed in vacuum drying chamber, and to set drying condition be 40~60 DEG C, vacuum is 66.6~68.6 KPa, is dried in vacuo 2~4 h, obtained white granular solid is inflatable carbonitride.
Its structural formula is as follows：
Wherein, n is 1,2 or 3.
Through analysis, the inflatable carbonitride obtained every time is all the mixture that n is 1,2 or 3 in above formula.
2nd, it may expand the expansion method of carbonitride：
1st, the inflatable g of carbonitride 0.5~1 is taken, is put into the quartzy measuring cups of 500 mL.
2nd, quartzy measuring cup being put into Muffle furnace, time control is warming up to 550 in 20~40s, by muffle furnace~ 600℃。
3rd, cooling, the carbonitride after being expanded are taken out.
3rd, the performance test results：
From Fig. 1 inflatable carbonitride ESEM it can be seen from the figure that：Structure of the sulfate radical molecule intercalation to carbonitride In, material is in big bulk, and surface is more smooth.
Fig. 2 is inflatable carbonitride scanning electron microscope (SEM) photograph after high-temperature expansion produced by the present invention, as can be seen from the figure There is the lamellar structure of hole after the shape of material is expanded, have many little particle lenticulars above.
Fig. 3 is the optical microscope of inflatable carbonitride produced by the present invention, and as can be seen from the figure material has one Determine the lenticular of regular morphology.
Experimental result is shown：Inflatable carbonitride prepared by the present invention, with unique physical and chemical performance, its volume can To be drastically expanded to more than 100 times of original volume at 550~600 DEG C, specific surface area is greatly improved, and makes efficient photochemical catalyst Matrix material, absorbing material, pollutant sorbing material, efficient medical bandage material and high-energy battery material are prepared into order to can Energy.This method carries out liquid-crystalization processing using sulfuric acid to graphite phase carbon nitride, is precipitated by recrystallizing, the mode of ethanol washing, Prepare inflatable carbonitride.Poisonous and hazardous reagent is not needed in the preparation process of this method, all raw materials and solvent are obtained It is convenient, it is cheap, there is very big industrial applications prospect.

Claims (7)

1. may expand carbonitride, its structural formula is：
Wherein, n is 1,2 or 3.
2. the preparation method of carbonitride is may expand as claimed in claim 1, it is characterised in that comprised the following steps：
1）Under the conditions of magnetic agitation, by the carbonitride of graphite-structure（g - C3N4）It is dissolved in the concentrated sulfuric acid, obtained carbonitride- Concentrated sulfuric acid solution；
2）Carbonitride-concentrated sulfuric acid solution is cooled to 8~10 DEG C, the inflatable Carbon Nitride Crystal separated out is obtained；
3）Inflatable Carbon Nitride Crystal is subjected to decompression suction filtration, using being dried in vacuo again after absolute ethyl alcohol washing precipitation, obtaining can Expand carbonitride.
3. the preparation method of carbonitride is may expand according to claim 2, it is characterised in that：The step 1）The middle concentrated sulfuric acid with The carbonitride of graphite-structure（g - C3N4）Mixing ratio be 10 mL: 3g.
4. the preparation method of carbonitride is may expand according to claim 2, it is characterised in that：The step 1）Described in dissolve It is the carbonitride in graphite-structure（g - C3N4）Mixing temperature with the concentrated sulfuric acid is progress under conditions of 60~80 DEG C.
5. the preparation method of carbonitride is may expand according to claim 2, it is characterised in that：The step 2）Middle cooldown rate For 2~4 DEG C/h.
6. the preparation method of carbonitride is may expand according to claim 2, it is characterised in that：The step 3）Described in vacuum Dry temperature conditionss are 40~60 DEG C, vacuum be 66.6~68.6 kPa, time be 2~4 h.
7. the expansion method of carbonitride is may expand as claimed in claim 1, it is characterised in that：Inflatable carbonitride is placed in quartz In container, 20~40s of heating in 550~600 DEG C of Muffle furnace is placed in, after taking-up, through cooling, expansion carbonitride is obtained.
CN201610238831.1A 2016-04-18 2016-04-18 Inflatable carbonitride and preparation method thereof, expansion method Active CN105883733B (en)

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CN101323437B (en) * 2008-07-25 2010-09-08 中北大学 Explosion impact synthetic method of beta-C3N4
CN102974377B (en) * 2012-09-27 2014-11-26 清华大学 Carbon-nitrogen alkene photocatalyst and preparation method thereof
CN104634836B (en) * 2015-01-21 2017-03-15 扬州大学 The application of the preparation method and its heavy metal ion detection of graphite oxide phase carbon nitride modified electrode

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