CN105692573B - A kind of preparation method of nanostructure nitridation carbon - Google Patents
A kind of preparation method of nanostructure nitridation carbon Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 63
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 239000000706 filtrate Substances 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 230000001476 alcoholic Effects 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000000502 dialysis Methods 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 235000019441 ethanol Nutrition 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 239000002077 nanosphere Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- -1 nitrile amine Chemical class 0.000 description 7
- JMANVNJQNLATNU-UHFFFAOYSA-N Cyanogen Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 241000219112 Cucumis Species 0.000 description 5
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003287 optical Effects 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propanol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002194 synthesizing Effects 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N Melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N carbodiimide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 239000002060 nanoflake Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010192 crystallographic characterization Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001965 increased Effects 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002127 nanobelt Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000005429 turbidity Methods 0.000 description 2
- 241000437273 Auricularia cornea Species 0.000 description 1
- 206010022114 Injury Diseases 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 210000003491 Skin Anatomy 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000001458 anti-acid Effects 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 238000005039 chemical industry Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 230000003000 nontoxic Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000607 poisoning Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 229910052904 quartz Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
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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
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
-
- 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
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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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
A kind of preparation method of nanostructure nitridation carbon, includes the following steps：（1）Dicyanodiamine is ground, is sieved, is placed in heating device, is passed through nitrogen, 400~700 DEG C is then heated to, and keep the temperature 1~2h, cools to room temperature with the furnace, obtain faint yellow solid g C3N4；（2）It will（1）Obtained g C3N4It is ground, is sieved, then be added into the water or alcoholic solution of potassium hydroxide or sodium hydroxide, heat condensing reflux, and stir, it is cooled to room temperature, then by 10~60min of sample ultrasonic, filtering, filtrate and filter residue are obtained, filtrate of dialysing obtains nanostructure nitridation carbon aqueous solution；（3）Nanostructure nitridation carbon aqueous solution is freeze-dried to constant weight, nanostructure nitridation carbon is obtained.Different according to nanostructure nitridation carbon pattern obtained by the method for the present invention, splitting is fine, and specific surface area is up to 320m2g‑1, water solubility and stability are good；The method of the present invention is simple, and reaction condition is mild, with short production cycle, of low cost.
Description
Technical field
The present invention relates to the preparation methods that a kind of nanostructure nitrogenizes carbon.
Background technology
Nano material is a research hotspot in recent years, some special effects that it has, such as skin effect, small size
Effect, quantum size effect, macro quanta tunnel effect etc. so that nano material is in mechanical property, magnetic performance, calorifics
Energy, optical property, electric property and chemistry and catalytic performance etc. have the unrivaled characteristic of other materials.
Carbonitride is made of two kinds of elements of carbon and nitrogen, and element rich reserves derive from a wealth of sources, simple synthetic method, economy
Well and it is easily obtained.Graphite phase carbon nitride（g-C3N4）Belong to narrow gap semiconductor, band gap width is about 2.7 eV, nontoxic, no
Containing metal；Meanwhile g-C3N4There is certain absorption to visible light, the corrosion of antiacid, alkali, light, stability is good, and structure and performance are easy
In regulation and control, there is preferable photocatalysis performance；g-C3N4Also there is huge application potential in other multiple fields, thus, at
For one of the hot spot of photocatalysis field, modern material and chemical research.
The common preparation method of carbonitride mainly has high pressure pyrolysismethod, vapour deposition process, ion implantation, hydro-thermal or solvent
Thermal synthesis method and electrochemical deposition method etc..In recent years, one kind directly heating condensation polymerization cyanamide, cyanamid dimerization and melamine etc.
The method of organic matter precursor becomes the more preparation g-C of application3N4The method of crystal.But prepared by these methods
Block materials specific surface area is often below 10 m2/ g, practical ranges are limited.For this purpose, usually considering into body phase carbon nitride
Introduce the adjustable pore structure in aperture, or change carbonitride nanometer particle size and pattern and by the means of stripping prepare few layer or
Person's single layer increases its specific surface area, to enhance its application in every field.
In recent years, have many work to be dedicated to preparing the g-C of bigger serface3N4.For example, utilizing SiO2As hard template,
The g-C of porous structure can be synthesized3N4, surface area is up to 505m2g-1, but porous g-C3N4After synthesis, need to remove hard mold
Plate often requires to use the HF or NH of severe toxicity4HF2, larger to the injury of human body（Preparation and
characterization of well-ordered hexagonal mesoporous carbon nitride, Adv
Mater,2005,17:1648）.Other than porous structure, also method, hot stripping method, molten is smashed using space confinement method, synthesis
Agent stripping method etc. is prepared a series of nitridation carbon quantum dot of different-shapes, nano wire, nanotube, nanobelt, nanometer rods, receives
Rice grain, nanosphere, nano-cluster etc..For example, Yang et al. is presoma using melamine, respectively at 700 DEG C, 1000 DEG C two
Step handles to obtain the nano strip product of fiber morphology（Synthesis and characterization of nitrogen-
rich carbon nitride nanobelts by pyrolysis of melamine, Appl Phys A,2011,105:
161）, specific surface area is 60 m2g-1, but in the growth preparation method, need long period pyroreaction, and high growth temperature
Nanostructure is difficult to carry out two level assembling again, it is difficult to construct more advanced nanostructure；Li et al. people is using anodised aluminium as mould
Plate, nitrile amine are presoma, and the azotized carbon nano stick with high-crystallinity and photocatalysis performance is prepared by confinement thermal polycondensation
（Condensed graphitic carbon nitride nanorods by nanoconfinement: promotion of
crystallinity on photocatalytic conversion, Chem Mater,2011,23:4344）, but it compares table
Area only has 25 m2g-1, and difficult as the removal of hard template silica in this method；Original is rich et al. using sodium chloride as template, three
Poly cyanamid is that presoma prepares water-soluble azotized carbon nano band, and obtains different-shape by the self assembly effect of different alcohol
Carbonitride（CN104108688B/ Water-soluble ribbon-like graphitic carbon nitride (g-
C3N4): green synthesis, seLf-assembly and unique optical properties）, party's legal system
Standby sample specific surface area is up to 120 m2g-1.But participate in reaction, Na since more sodium chloride being added when the method operates+From
Sub- radius is smaller, is reacted into carbonitride intramolecule, it is difficult to remove, cause the azotized carbon nano band to lose original optical
Energy.
Due to g-C3N4Layer structure with class graphene, so can be by g-C3N4Make nano flake even single layer
Structure.Currently, g-C3N4There are mainly three types of methods, i.e. oxidation stripping, solvent stripping and intercalation stripping for the stripping of stratified material, but
It is that there is also the problems of many, such as ultrasound stripping to need stripping, and low yield for a long time；Oxidation stripping needs high pressure or super
It is critical, and hardly result in the g-C that can increase in application with the good water solubility of remaining reaction object contact area3N4.Therefore, how
Cheaply, quickly, green, in bulk produce good water solubility g-C3N4And the hot issues needed to be studied.
Invention content
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of method letter
Single, with short production cycle, of low cost, gained nanostructure nitrogenizes that carbon ratio surface area is big, nanostructure of good water solubility nitrogenizes carbon
Preparation method.
The technical solution adopted by the present invention to solve the technical problems is as follows：A kind of preparation side of nanostructure nitridation carbon
Method includes the following steps：
（1）Dicyanodiamine is ground, 400~600 mesh are crossed（It is preferred that 450~550 mesh）It is put into porcelain boat after sieve, is placed in heating
In device, it is passed through nitrogen（It is passed through nitrogen rate preferably 2~6 mL/min）, then with 1~30 DEG C/min（It is preferred that 5~20 DEG C/
Min, more preferable 8~15 DEG C/min）Rate be warming up to 400~700 DEG C（It is preferred that 500~600 DEG C）, and 1~2h is kept the temperature, with stove
It is cooled to room temperature, obtains faint yellow solid g-C3N4；
（2）By step（1）Gained faint yellow solid g-C3N4It is ground, crosses 400~600 mesh sieve, then be added into hydrogen-oxygen
Change a concentration of 0.1~12.0mol/L of potassium or sodium hydroxide（It is preferred that 0.2~6.0mol/L）Aqueous solution or alcoholic solution in, add
Hot condensing reflux, and stir 0.5~72.0h（It is preferred that 4~48h, further preferred 12~40h）, it is cooled to room temperature, then by sample
Product ultrasound, filtering obtain filtrate and filter residue, filtrate of dialysing, and obtain nanostructure nitridation carbon aqueous solution；
（3）By step（2）Gained nanostructure nitridation carbon aqueous solution is freeze-dried to constant weight, obtains nanostructure nitridation carbon.
Above-mentioned steps（1）In, the dicyanodiamine heating gained faint yellow solid g-C3N4Can be by grinding, it can mistake
450~550 mesh sieve, and obtain the more uniform carbonitride of grain size.
Further, step（2）In, the step of the addition（1）Gained g-C3N4With the aqueous solution or alcoholic solution of potassium hydroxide
Mass volume ratio be： 100mg:10~30mL.
Further, step（2）In, the temperature of the heating condensing reflux is 20~150 DEG C.The purpose of condensing reflux is to make
Solvent cooled back in condenser pipe in reaction bulb it is non-volatile walk, using different temperature and mixing time will obtain different yields and
The product of different sizes.
Further, step（2）The nylon leaching film that filtering is 0.45 μm using porosity is filtered by Buchner funnel decompression
To filtrate and filter residue.
Further, step（2）In, it is 500~3000 bag filter that the dialysis, which refers to molecular weight, and 1~4d of dialysis is extremely
It is neutral.The purpose dialysed is to remove the potassium hydroxide and alcohol in phegma, solution is made to be replaced to neutrality and by alcohol
Cheng Shui.Dialysis is that bag filter is put into the deionized water of mobile phase, according to the principle of gradient elution or infiltration, high solubility
It is walked toward low solubility, solvent or ion exchange occurs, water penetration of the dialysis with outside enters in dialysis band, the potassium hydroxide of the inside
Dialysis is out pulled away from the inside with alcohol.The time that the dialysis sample reacted using alcohol is needed is longer, so that alcohol dialysis is clean.
Further, by step（2）Gained filter residue adds 20 ~ 50mL of water, and in the case where condition is 180w power, 10 ~ 60min of ultrasound makes
Dispersion.After ultrasonic disperse, the bag filter for being 500~3000 with molecular weight, 1~4d is to neutrality for dialysis, then freezes and do to constant weight.
Dissolution degree of the sample obtained by the reaction in alcohol is limited, in water can be with the reaction was complete, but can continue in highly polar water
Dispersion well, so needing to add water ultrasonic disperse so that reaction yield is optimized.
Further, step（2）The condition of response sample ultrasonic disperse under the cooling, it is ultrasonic preferably under 180w power
30min makes reaction sample fully be removed and be obtained the more uniform product of particle size.
Further, step（3）In, the temperature of the freeze-drying is -40~-10 DEG C, and drying time is that 10~72h is extremely produced
Product constant weight.
Step（2）In, the common alkylol in alcohol optimization experiment room in the alcoholic solution, can be methanol, ethyl alcohol, propyl alcohol,
One or more of n-butanol, isopropanol, ethylene glycol or glycerine.
Room temperature described in the method for the present invention refers to indoor environment temperature, preferably 18 DEG C -25 DEG C, more preferable 20 DEG C.
Compared with prior art, the method for the present invention has the beneficial effect that：
（1）According to the method for the present invention, by adjusting response parameter, the nanostructure of gained carbonitride has nanometer thin respectively
Piece, nanometer rods, nanosphere etc., can be seen that from AFM and TEM, g-C3N4Remove very well, specific surface area may be up to 320 m2g-1；Water
Dissolubility is very good, can reach 5g/L；The aqueous solution of the nanostructure of carbonitride can not generate precipitation after standing 30 days, stablize
Property is good；
（2）By the present invention in that using different alkylols and water as solvent, different-shape and each pattern ratio are obtained not
Same water-soluble carbonitride, the different higher structures obtained increase its surface area so that it can fully connect with remaining reaction object
It touches, makes it have and be more widely applied.
（3）The method of the present invention is raw materials used to be derived from a wealth of sources, and easy to operate, reaction condition is mild, with short production cycle, at low cost
It is honest and clean, it can easily remove the alkali or alcohol of introducing.
The present invention provides a kind of new approaches for the preparation and application of carbonitride, is led in environmental protection, the energy, national defence and chemical industry
Domain has broad application prospects and important realistic meaning.
Description of the drawings
Fig. 1 is 1 gained g-C of the embodiment of the present invention3N4The scanning electron microscope (SEM) photograph of water -1；
Fig. 2 is 1 gained g-C of the embodiment of the present invention3N4The transmission electron microscope picture of water -1；
Fig. 3 is 1 gained g-C of the embodiment of the present invention3N4The atomic force microscopy diagram of water -1；
Fig. 4 is 1 gained g-C of the embodiment of the present invention3N4The Tyndall effect figure of water -1；
Fig. 5 is g-C obtained by 1-5 of the embodiment of the present invention3N4The pictorial diagram of the different time of water；
Fig. 6 is 9 gained g-C of the embodiment of the present invention3N4The scanning electron microscope (SEM) photograph of methanol -1；
Fig. 7 is 10 gained g-C of the embodiment of the present invention3N4The scanning electron microscope (SEM) photograph of ethyl alcohol -1；
Fig. 8 is 10 gained g-C of the embodiment of the present invention3N4The transmission electron microscope picture of ethyl alcohol -1.
Fig. 9 is 12 gained g-C of the embodiment of the present invention3N4The scanning electron microscope (SEM) photograph of isopropanol -1.
Specific implementation mode
With reference to embodiment and attached drawing, invention is further described in detail.
Chemical reagent used in the embodiment of the present invention is obtained by routine business approach unless otherwise specified.Each reality
It applies the example room temperature and refers to 20 DEG C.
Embodiment 1
（1）Dicyanodiamine is ground, porcelain boat is put into after crossing 500 mesh sieve, is placed in tube furnace, with the flow velocity of 5mL/min
It is passed through nitrogen, is then warming up to 550 DEG C with the rate of 10 DEG C/min, and keep the temperature 2h, cools to room temperature, faint yellow solid g- with the furnace
C3N4；
（2）By step（1）Gained faint yellow solid g-C3N4It is ground, crosses 500 mesh sieve, then the g- for taking 100mg to be sieved
C3N4It is added in the aqueous solution of 20mL concentration of potassium hydroxide 3mol/L, 80 DEG C of heating condensing refluxes, and stirs for 24 hours, be cooled to room
Temperature, then by sample ultrasonic 30min, then be 1500 by filtrate molecular weight bag filter, 3d is to neutrality for dialysis, obtains 20mL nitridations
Carbon nano flake aqueous solution；
（3）By step（2）For gained azotized carbon nano band aqueous solution at -25 DEG C, 72h is to constant weight for freeze-drying, must nitrogenize
Carbon nano flake is labeled as g-C3N4Water -1.
Azotized carbon nano thin slice g-C obtained by the present embodiment3N4The specific surface area of water -1 is 320 m2g-1, yield reaches
100wt%；Its surface sweeping Electronic Speculum（SEM）, transmission electron microscope（TEM）, atomic force microscope（AFM）It is as shown in Figure 1, 2, 3 respectively.By Fig. 1
As it can be seen that obtained nanometer sheet is high-visible, the nanometer sheet obtained after freeze-drying can independently be filled by its own hydrogen bond energy
With forming fold " cloud ear ".
By Fig. 2 and Fig. 3 it is found that g-C3N4After potassium hydroxide aqueous solution reaction for 24 hours, receiving for single or few layer thickness can be obtained
Rice piece, width is about 0.2~1.8 μm；Its thickness is about 0.52~0.9nm（Theoretical value is 0.34nm）, this is because hydroxyl
Intercalation and oxygen-containing functional group are connected to caused by azotized carbon nano thin slice.
Fig. 4 is g-C3N4-Tyndall effect figure of -1 aqueous solution of water after standing one month, it can be seen that g-C3N4Water -1
Aqueous solution is extremely stable, does not generate precipitation.This is because the intercalation of hydroxyl enables to obtain functional group and hydrone on Melon
Between form strong hydrogen bond action, stablize clear dispersion liquid so can be formed, for its application provide a kind of new thinking.
Embodiment 2
The present embodiment is differed only in embodiment 1：
Step（2）In, the time of return stirring is 18h；Final products therefrom is azotized carbon nano thin slice, is labeled as g-
C3N4Water -2.Remaining same embodiment 1.
After testing, azotized carbon nano piece specific surface area obtained by the present embodiment is 280 m2g-1, yield also reaches 100wt%.Energy
Obtain the nanometer sheet of few layer thickness, obtained nanometer sheet width is about 0.8~3.3 μm, lamella compared with embodiment 1 obtain will be very much not
Few, causing to obtain solution does not have the clarification of embodiment 1.g-C3N4After -2 aqueous solution of water stands one month, bottom of bottle portion generates minute quantity
Precipitation, stability be not so good as g-C3N4-Water -1.
Embodiment 3
The present embodiment is differed only in embodiment 1：
Step（2）In, the time of return stirring is 12h, is labeled as g-C3N4Water -3.Remaining same embodiment 1.After testing, originally
Azotized carbon nano piece specific surface area obtained by embodiment is 235 m2g-1, obtained nanometer sheet width is about 1.2~3.6 μm, yield
For 75 wt%.The aqueous solution that the present embodiment obtains is light oyster white, and the bottom of bottle portion after a week that stands generates a small amount of precipitation.
Embodiment 4
The present embodiment is differed only in embodiment 1：
Step（2）In, the time of return stirring is 8h, is labeled as g-C3N4Water -4.Remaining same embodiment 1.After testing, this reality
It is 160 m to apply azotized carbon nano piece specific surface area obtained by example2g-1, obtained nanometer sheet width is about 1.3~4 μm, yield 58
wt%.The aqueous solution that the present embodiment obtains is milky, and the bottom of bottle portion after a week that stands generates precipitation.
Embodiment 5
The present embodiment is differed only in embodiment 1：
Step（2）In, the time of return stirring is 4h, is labeled as g-C3N4Water -5.Remaining same embodiment 1.After testing, this reality
It is 98m to apply azotized carbon nano piece specific surface area obtained by example2g-1, obtained nanometer sheet width is about 1.5~4.5 μm, and yield is
46wt%.The aqueous solution that the present embodiment obtains is milky turbidity liquid, and the bottom of bottle portion after a week that stands generates more precipitation.
Embodiment 6
The present embodiment is differed only in embodiment 1：
Step（2）In, 20 DEG C of condensation temperature are heated to reflux, g-C is labeled as3N4Water -6.Remaining same embodiment 1.After testing,
Azotized carbon nano piece specific surface area obtained by the present embodiment is 63m2g-1, obtained nanometer sheet width is about 1.5~4.6 μm, yield
For 36wt%.The aqueous solution that the present embodiment obtains is milky turbidity liquid, and the bottom of bottle portion after a week that stands generates more precipitation.
Embodiment 7
The present embodiment is differed only in embodiment 1：
Step（2）In, the aqueous solution that reaction is concentration of potassium hydroxide 0.2mol/L is added, is labeled as g-C3N4Water -7.
Remaining same embodiment 1.After testing, azotized carbon nano piece specific surface area obtained by the present embodiment is 38m2g-1, obtained nanometer sheet width
About 0.5~2.2 μm, yield 94.2wt%.The aqueous solution that the present embodiment obtains is, after standing January, bottom of bottle portion generates few
The precipitation of amount.
Embodiment 8
The present embodiment is differed only in embodiment 1：
Step（2）In, the sodium hydroxide of concentration 3mol/L is added in reaction solution, is labeled as g-C3N4Water -8.Yu Tong
Embodiment 1.After testing, azotized carbon nano piece specific surface area obtained by the present embodiment is 52m2g-1, obtained nanometer sheet width is about
0.5~1.8 μm, yield 100wt%.The aqueous solution that the present embodiment obtains is to stablize clarification ground dispersion liquid, is not produced after standing January
Raw precipitation.
Parsing:g-C3N4It is as shown in Figure 1 with the reaction principle figure of alkali；Basic principle is：OH under reflux condition-It inserts
Enter g-C3N4Layer structure and attack g-C3N4The hydrogen bond N of its interlayer...C-NH-C keys in H-N and layer, in linear polymeric
Hydrogen bond between chain is by new hydrogen bond-O-H...N and H-O-...H-N keys replace, and lead to the melon chains of polymerization（g-C3N4）It is stripped
It comes to form melon chains；In addition, CN polymeric chains are in heating and OH-Under the action of intercalation, the C- between two 3-s- triazine rings
NH-C keys will further carry out local cracking, obtain various sizes of azotized carbon nano piece.As shown in figure 5, prolonging with the time
Long, reaction is more and more abundant, and it is to react that 100 wt% can be reached for 24 hours to reach；Wherein sample starts gelation in 2h or so, increases
Add the reaction time, degree of gelation is bigger, obtains one to the end and stablizes clarification ground dispersion liquid.After dialysis, due to the work of hydrogen bond
With the stability of sample in water is all fine.
In addition, with the increase of alkali soluble degree, reaction speed is also getting faster, but if the solubility of alkali is excessively big,
Melon chains will be made to form small molecule, destroy its original property；In addition to this, it is contemplated that Na+It can make g-C3N4" poisoning " is broken
Its bad original optical property, and reaction efficiency not as good as potassium hydroxide it is good, remaining example of this patent is all using potassium hydroxide as reaction base.
The raising of temperature is also beneficial to the progress of reaction, but in view of the boiling point of solvent and high temperature may be that melon chains form small molecule,
Too high temperature should not be used.
[embodiment 9-12 is the reaction embodiment in alcoholic solution].
Embodiment 9
The present embodiment and embodiment 1 difference lies in：Step（2）In, take the g-C of 100mg sievings3N4It is added to 20mL hydrogen
In the methanol solution for aoxidizing potassium concn 3mol/L, 80 DEG C of heating condensing refluxes, and stir for 24 hours, it is cooled to room temperature, then by sample
Ultrasonic 30min, it is 0.45 μm of nylon leaching film then to use porosity, is filtered by Buchner funnel decompression and obtains filtrate and filter
Slag；The bag filter for being again 1500 by filtrate molecular weight, 4d is to neutrality for dialysis, obtains azotized carbon nano thin slice and nanometer rods are water-soluble
Liquid；Labeled as g-C3N4Methanol -1, SEM figure is as shown in Figure 6.
After testing, azotized carbon nano piece and nanometer rods specific surface area obtained by the present embodiment filtrate are 208m2g-1, reaction stripping
The nanometer sheet of single or few layer thickness is obtained, obtained nanometer sheet width is about 1.2~2.5 μm；The width of nanometer rods be 50nm~
200nm, a height of 300nm~650nm；The yield of filtrate is 32wt%.
The present embodiment step（2）In obtained filter residue add water 50mL, in the case where condition is 180w power, 10 ~ 60min of ultrasound makes
Dispersion.It obtains azotized carbon nano block and disperses solution, be labeled as g-C3N4-Methanol -2, specific surface area 42m2g-1.Obtained nitrogen
Change carbon nanometer blocks compared with g-C3N4Crystallinity is more preferable, and layer structure is due to OH-Insertion action be also partially stripped, make it in water
Dispersibility it is more preferable.
Embodiment 10
The present embodiment and embodiment 9 difference lies in：Step（2）In, use 20mL concentration of potassium hydroxide 3mol/L
Ethanol solution, remaining same embodiment 9；Filtrate is labeled as g-C3N4Ethyl alcohol -1, filter residue are labeled as g-C3N4Ethyl alcohol -2.g-C3N4-
Ethyl alcohol -1 its SEM and TEM difference is as shown in FIG. 7 and 8.After testing, azotized carbon nano piece and nanosphere obtained by the present embodiment filtrate
Specific surface area is 272m2g-1, reaction stripping obtains the nanometer sheet of single or few layer thickness, and obtained nanometer sheet width is about 1.5~
3.0μm；The yield of a diameter of 150nm-500nm of nanosphere, filtrate are 58wt%.Obtained filter residue g-C3N4Ethyl alcohol -2, table
Area is 65 m2g-1。
Embodiment 11
The present embodiment and embodiment 9 difference lies in：Step（2）In, use 20mL concentration of potassium hydroxide 3mol/L
Propanol solution, remaining same embodiment 9；Filtrate is labeled as g-C3N4Propyl alcohol -1, filter residue are labeled as g-C3N4Propyl alcohol -2.After testing,
Azotized carbon nano piece and nanosphere specific surface area obtained by the present embodiment filtrate are 254m2g-1, reaction, which is removed, obtains single or few thickness
The nanometer sheet of degree, obtained nanometer sheet width are about 1.8~3.4 μm；A diameter of 135nm-425nm of nanosphere, the production of filtrate
Rate is 46wt%.Obtained filter residue g-C3N4Propyl alcohol -2, surface area 46m2g-1。
Embodiment 12
The present embodiment and embodiment 9 difference lies in：Step（2）In, use 20mL concentration of potassium hydroxide 3mol/L
Aqueous isopropanol, remaining same embodiment 9；Filtrate is labeled as g-C3N4Isopropanol -1, filter residue are labeled as g-C3N4Isopropanol -2.
g-C3N4The SEM of isopropanol -1 is as shown in Figure 9.After testing, azotized carbon nano piece and nanosphere obtained by the present embodiment filtrate compare table
Area is 298m2g-1, obtained nanometer sheet width is about 1.3~3.2 μm；A diameter of 105nm~365nm of nanosphere, filtrate
Yield be 32wt%.Obtained filter residue g-C3N4Isopropanol -2, surface area are 79 m2g-1。
Parsing：Studies have shown that g-C3N4Pattern different nano junction can be obtained under the action of different alcohol from the reaction of alkali
Structure carbonitride, this is because the collective effect -ol solution energy of the steric hindrance of the alkylol used and polarity difference and alcohol and alkali
Caused by power difference.With the increase of alkylol carbon number, steric hindrance is increasing, the azotized carbon nano piece ruler for making stripping obtain
Very little to become larger, the product specific surface area caused reduces compared with water sample；Since steric hindrance nanometer sheet starts self assembly, first is obtained
Alcohol-nanometer rods；Ethyl alcohol, propyl alcohol, isopropanol-nanosphere, although isopropanol is equal with propyl alcohol carbon number, its branch makes its position
Hinder bigger, the quantity of nanosphere increases with steric hindrance and is increased, and the amount of nanometer sheet reduces therewith, in addition, the size of nanosphere with
The increase of steric hindrance and reduce, these reasons make product specific surface area gradually increase.Further, since alcoholysis and the intercalation energy of different alcohol
Power is different, most strong, the obtained product yield maximum of ethyl alcohol.
Claims (17)
1. a kind of preparation method of nanostructure nitridation carbon, which is characterized in that include the following steps：
（1）Dicyanodiamine is ground, porcelain boat is put into after crossing 400~600 mesh sieve, is placed in heating device and is passed through nitrogen, then
400~700 DEG C are warming up to the rate of 1~30 DEG C/min, and keeps the temperature 1~4h, room temperature is cooled to the furnace, obtains faint yellow solid g-
C3N4；
（2）By step（1）Gained faint yellow solid g-C3N4It is ground, crosses 400~600 mesh sieve, then be added into potassium hydroxide
Or in the aqueous solution or alcoholic solution of a concentration of 0.2~6.0mol/L of sodium hydroxide, at 80~150 DEG C, condensing reflux, and stir
4~for 24 hours, it is cooled to room temperature, then disperses sample ultrasonic, filter, obtain filtrate and filter residue, dialysis filtrate obtains nanostructure nitridation
Carbon aqueous solution；The faint yellow solid g-C3N4With the mass volume ratio of the aqueous solution or alcoholic solution of potassium hydroxide or sodium hydroxide
For：50~100mg:10~60mL；
（3）By step（2）Gained nanostructure nitridation carbon aqueous solution is freeze-dried to constant weight, obtains nanostructure nitridation carbon.
2. the preparation method of nanostructure nitridation carbon according to claim 1, it is characterised in that：Step（2）In, the dialysis
Refer to using molecular weight for 500~3000 bag filter, 1~4d of dialysis to neutrality.
3. the preparation method of nanostructure nitridation carbon according to claim 1 or claim 2, it is characterised in that：Step（2）Filtering uses
The nylon leaching film that porosity is 0.45 μm is filtered by Buchner funnel decompression and obtains filtrate and filter residue；By step（2）Gained filter residue
After adding water ultrasonic disperse, the bag filter for being 500~3000 with molecular weight, 1~4d is to neutrality for dialysis, then is freeze-dried to constant weight.
4. the preparation method of nanostructure nitridation carbon according to claim 1 or claim 2, it is characterised in that：Step（2）In, it is described
The condition of ultrasonic disperse is 10~60min of ultrasound under 180w power.
5. the preparation method of nanostructure nitridation carbon according to claim 3, it is characterised in that：Step（2）In, the ultrasound
The condition of dispersion is 10~60min of ultrasound under 180w power.
6. the preparation method of nanostructure nitridation carbon according to claim 1 or claim 2, it is characterised in that：Step（3）In, it is described
The temperature of freeze-drying is -40~-10 DEG C, and the time is 10~72h.
7. the preparation method of nanostructure nitridation carbon according to claim 3, it is characterised in that：Step（3）In, the freezing
Dry temperature is -40~-10 DEG C, and the time is 10~72h.
8. the preparation method of nanostructure nitridation carbon according to claim 4, it is characterised in that：Step（3）In, the freezing
Dry temperature is -40~-10 DEG C, and the time is 10~72h.
9. the preparation method of nanostructure nitridation carbon according to claim 1 or claim 2, it is characterised in that：Step（1）In, it is described
The flow velocity for being passed through nitrogen is 1~10mL/min.
10. the preparation method of nanostructure nitridation carbon according to claim 3, it is characterised in that：Step（1）In, it is described logical
The flow velocity for entering nitrogen is 1~10mL/min.
11. the preparation method of nanostructure nitridation carbon according to claim 4, it is characterised in that：Step（1）In, it is described logical
The flow velocity for entering nitrogen is 1~10mL/min.
12. the preparation method of nanostructure nitridation carbon according to claim 6, it is characterised in that：Step（1）In, it is described logical
The flow velocity for entering nitrogen is 1~10mL/min.
13. the preparation method of nanostructure nitridation carbon according to claim 1 or claim 2, it is characterised in that：Step（1）In, with 5
The rate of~20 DEG C/min is warming up to 500~600 DEG C.
14. the preparation method of nanostructure nitridation carbon according to claim 3, it is characterised in that：Step（1）In, with 5~20
DEG C/rate of min is warming up to 500~600 DEG C.
15. the preparation method of nanostructure nitridation carbon according to claim 4, it is characterised in that：Step（1）In, with 5~20
DEG C/rate of min is warming up to 500~600 DEG C.
16. the preparation method of nanostructure nitridation carbon according to claim 6, it is characterised in that：Step（1）In, with 5~20
DEG C/rate of min is warming up to 500~600 DEG C.
17. the preparation method of nanostructure nitridation carbon according to claim 9, it is characterised in that：Step（1）In, with 5~20
DEG C/rate of min is warming up to 500~600 DEG C.
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