CN107572491A - A kind of quick method for preparing large-area ultrathin nitrogen carbide nanometer sheet - Google Patents
A kind of quick method for preparing large-area ultrathin nitrogen carbide nanometer sheet Download PDFInfo
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- CN107572491A CN107572491A CN201710752475.XA CN201710752475A CN107572491A CN 107572491 A CN107572491 A CN 107572491A CN 201710752475 A CN201710752475 A CN 201710752475A CN 107572491 A CN107572491 A CN 107572491A
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- nanometer sheet
- dicyanodiamine
- presoma
- nitrogen carbide
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Abstract
The present invention relates to field of new materials, particularly a kind of quick method for preparing large-area ultrathin nitrogen carbide nanometer sheet, described method is：Dicyanodiamine presoma is obtained after dicyanodiamine is dissolved after refrigerating, separate out, filter, dry, then the product after calcining is distributed in deionized water after dicyanodiamine presoma being calcined to a period of time under conditions of 520 DEG C 550 DEG C, separates and produces two-dimentional g C3N4Nanometer sheet.This method has the advantages of synthesis condition is gentle, preparation is quick, cost is low, lamellar structure is big, good water solubility.
Description
Technical field
The present invention relates to the preparing technical field of new material, more particularly to one kind quickly prepares large-area ultrathin nitrogen carbide and received
The method of rice piece.
Background technology
Class graphite phase carbon nitride (g-C3N4) it is the nonmetallic polymer semiconductor of typical Two-dimensional Inorganic, there is similar graphite
Layer structure.Sp is occurred by C, N atom2Hydridization, pass through pzLone pair electrons on track form one and are similar to benzene ring structure
The conjugated system of one height delocalization of big pi bond and composition, therefore the electronics that largely can move freely between layers be present.Together
When, g-C3N4Energy gap be 2.7eV, can efficiently separate light induced electron and hole pair, improve photocatalysis efficiency, therefore
It is widely used in fields such as photocatalysis, photovoltaic solar cell, environmental protection, heterogeneous catalysis, it is considered to be tradition can be replaced
The novel and multifunctional material of carbonaceous material.In recent years, due to g-C3N4Be free from the functional material of metal, have high photostability,
Anti-light bleaching, high quantum production rate, hypotoxicity and biocompatibility, it is set also to be able to fast development in detection field is analyzed.
g-C3N4The structure of material and specific surface area strong influence its performance.In general, g-C3N4Specific surface area get over
It is high, there is provided avtive spot it is more, catalytic performance is better, and application is wider.However, g-C3N4Typically had by nitrogenous and carbon
Machine presoma is prepared by high temperature thermopolymerization.The g-C prepared using this method3N4For bulk structure, specific surface area is small, forbidden band is wide
Spend big, visible light utilization efficiency is low, photo-generate electron-hole to compound serious etc., limit its large-scale popularization and application.Therefore,
People use the means such as composite modified synthesis optimizing, physics, chemical doping, surface modification, nano modification to its physicochemical property
It is adjusted, to improve the application of material.Wherein, by nano modification, g-C is obtained3N4Nanometer sheet, g- can be improved
C3N4Specific surface area, reduce energy gap and suppress photo-generate electron-hole pair it is compound, so as to improve catalytic activity.Except this it
Outside, its photoelectric properties can also be improved.
Recently, to the g-C of single sheet structure3N4Nanometer sheet is also studied.Research shows, with block g-C3N4Phase
Than ultra-thin two-dimension g-C3N4Nanometer sheet has a preferably dispersiveness, higher specific surface area and bigger band gap, high quantum production rate,
High stability, good biocompatibility and nontoxicity so that it has stronger application in catalytic field and analysis detection field.Closely
Nian Lai, there is substantial amounts of work to show with the prepared g-C with adjustable dimension and stratiform of various methods3N4Nanometer sheet, tool
There are excellent property and the potential application in the range of every field.However, when these methods need considerably long supersound process
Between (10-16 hours), relatively low (the 0.15-0.35mg mL of yield-1), and the g-C of gained3N4Nanometer sheet specific surface area is relatively low,
Limit guest molecule and g-C3N4Between interaction.Therefore, it is how simpler, synthesize quickly and economically specific surface area
Larger g-C3N4Nanometer sheet turns into a research emphasis.
The content of the invention
The shortcomings that it is an object of the invention to overcome prior art and deficiency, there is provided one kind quickly prepares large-area ultrathin carbon
Change the method for nitrogen nanometer sheet, solve to prepare g-C at present3N4Charge stripping efficiency existing for nanometer sheet is low, time-consuming, turbid liquid concentration too
The problems such as low, nanometer sheet low yield, toxic organic solvent use, are cumbersome.The technical solution adopted in the present invention is with letter
Dicyanodiamine that is single, being easy to get is presoma, using dissolubility of the dicyanodiamine in water, by the method for stirring, makes dicyan two
Amine solvent so that each component is well mixed in material；Dicyanodiamine solid is slowly separated out by Cord blood；Again as forerunner
Body heat polymerize to obtain g-C3N4；Obtained g-C3N4For big lamellar structure, it is that can obtain g-C that the short time is scattered in aqueous systems3N4
Nanometer sheet.The two-dimentional g-C of the present invention3N4The preparation method of nanometer sheet is simple and easy, production process is environmentally friendly, does not need complex and expensive
Equipment, it is time-consuming it is short, charge stripping efficiency is high, synthesis condition is gentle, cost is low, lamellar structure is big, good water solubility, has in every field
There is larger application potential.
For the apparent elaboration present invention, a kind of quick method for preparing large-area ultrathin nitrogen carbide nanometer sheet, institute
The method stated is：Dicyanodiamine presoma is obtained after dicyanodiamine is dissolved after refrigerating, separate out, filter, dry, then by two
After cyanogen diamines presoma calcines a period of time under conditions of 520 DEG C -550 DEG C, the product after calcining is distributed to deionized water
In, separate and produce g-C3N4Nanometer sheet.
In the above-mentioned method for quickly preparing ultra-thin nitrogen carbide nanometer sheet, specifically comprise the following steps：
Step 1：By dicyanodiamine dissolving in deionized water；
Step 2：Product Cord blood 2-8h after stirring, slowly separates out dicyanodiamine solid；
Step 3：Product filters after taking out refrigeration；
Step 4：Product is dried, obtains the dicyanodiamine presoma after processing；
Step 5：Dicyanodiamine presoma after processing is subjected to calcination processing, by temperature programming, at 520 DEG C -550 DEG C
Lower reaction 3h, synthesize g-C3N4Material；
Step 6：By the g-C of synthesis3N4Material mixes with deionized water to be disperseed to can obtain two-dimentional g-C3N4Nanometer sheet.Its
Middle jitter time is 30-120min
It is above-mentioned it is quick prepare the method for large-area ultrathin nitrogen carbide nanometer sheet, in step 1, dicyanodiamine and go from
The weight ratio of sub- water is 1:4-1:12.
It is above-mentioned it is quick prepare the method for large-area ultrathin nitrogen carbide nanometer sheet, the storage temperature in step 2 is 4-8
℃。
Beneficial effect：
(1) present invention, using the dissolubility of dicyanodiamine, is simply pre-processed, so as to make using water as solvent to raw material
It is standby go out two-dimentional g-C3N4Nanometer sheet, obtained nanoscale twins material have the features such as big specific surface area, lamella is big and thin.
(2) solvent environment that the present invention uses is friendly, and the nanometer sheet turbid liquid concentration of preparation is high, and nanometer sheet yield is high, keeps away
Exempt from the use of toxic organic solvents.
(3) whole technical process of the invention is simple and easy to control, and energy consumption is low, it is not necessary to the equipment of complex and expensive, takes
It is short, charge stripping efficiency is high, synthesis condition is gentle, cost is low, and lamellar structure is big, good water solubility, every field have it is larger should
Use potentiality.
Brief description of the drawings
Fig. 1 is g-C prepared by the embodiment of the present invention 13N4The FT-IR figures of nanometer sheet；
Fig. 2 is g-C prepared by the embodiment of the present invention 13N4The UV-Vis figures of nanometer sheet；
Fig. 3 is g-C prepared by the embodiment of the present invention 13N4The TEM figures of nanometer sheet；
Fig. 4 is g-C prepared by the embodiment of the present invention 23N4The TEM figures of nanometer sheet；
Fig. 5 is g-C prepared by the embodiment of the present invention 33N4The TEM figures of nanometer sheet；
Fig. 6 is p-g-C prepared by the embodiment of the present invention 43N4The TEM figures of nanometer sheet；
Embodiment
With reference to embodiment, technical scheme is described in further detail, but not formed pair
Any restrictions of the present invention.
Embodiment 1
It is pretreatment dicyanodiamine presoma first, weighs 5g dicyanodiamines in 100mL round-bottomed flask, adds 40mL
Deionized water, stirring 4h make it dissolve and be well mixed；Product after stirring is preserved into 4h at 4 DEG C, slowly separates out dicyanodiamine；
Filtering gained solid is dried into 12h, the dicyanodiamine presoma after being handled at 80 DEG C.
Followed by prepare the large-area ultrathin g-C of the present invention3N4Nanometer sheet, gained dicyanodiamine presoma is placed in cover
Porcelain crucible in, calcine 3h at 530 DEG C, obtain flaxen g-C3N4.Then 100mg g-C are added in beaker3N4With
100mL deionized water rapid dispersions obtain suspension, centrifuge 5min under 5000rpm, take supernatant, you can obtain two-dimentional g-
C3N4Nanometer sheet.
The material characterize using IR, UV-Vis, TEM and determines its structure.Fig. 1 show the present invention and implements what is prepared
g-C3N4The FT-IR of nanometer sheet schemes, 811cm in figure-1And 1000-1800cm-1Section corresponds to breathing vibration and the virtue of piperazine ring respectively
The stretching vibration of fragrance CN heterocycles；3000-3600cm-1Exist mainly due to nano lamellar nitridation carbon surface caused by N-H,
Show the g-C prepared3N4Composition is consistent with document report, and the product of preparation is g-C3N4Material.Fig. 2 show of the invention real
Apply the g-C of preparation3N4The uv-visible absorption spectra of nanometer sheet, show the g-C prepared3N4The a length of 320nm of maximum absorption wave；Such as
Shown in Fig. 3, implement the g-C of preparation for the present invention3N4Transmission electron microscope (TEM) figure of nanometer sheet, show the g-C prepared3N4Material has
There is layer structure, and there is big lamella, width is 15-17 μm.
Embodiment 2
It is pretreatment dicyanodiamine presoma first, weighs 5g dicyanodiamines in 100mL round-bottomed flasks, adds 20mL and go
Ionized water, stirring 4h make dicyanodiamine dissolve and be well mixed；Product after stirring is placed in 6 DEG C of preservation 2h, slowly separates out dicyan
Diamines；The solid for filtering gained is dried into 12h, the dicyanodiamine presoma after being handled at 80 DEG C.
Followed by prepare the ultra-thin g-C of the present invention3N4Nanometer sheet, the dicyanodiamine presoma of gained is placed in porcelain with cover
In crucible, 3h is calcined in 520 DEG C, obtains flaxen g-C3N4.100mg g-C is added in beaker3N4With 100mL deionizations
Water rapid dispersion, obtains suspension, and 5min is centrifuged under 5000rpm, takes supernatant to can obtain two-dimentional g-C3N4Nanometer sheet.
As shown in figure 4, the g-C for implementing to prepare for the present invention3N4Transmission electron microscope (TEM) figure of nanometer sheet, show to use this side
Method can prepare the g-C of big lamellar structure3N4Nanometer sheet.
Embodiment 3
It is pretreatment dicyanodiamine presoma first, weighs 5g dicyanodiamine in 100mL round-bottomed flasks, adds 60mL
Deionized water, stirring 4h make dicyanodiamine dissolve and be well mixed；Product after stirring is preserved into 8h at 4 DEG C, slowly separates out two
Cyanogen diamines；The solid for filtering gained is dried into 12h, the dicyanodiamine presoma after being handled at 80 DEG C.
Followed by prepare the ultra-thin g-C of the present invention3N4Nanometer sheet, the dicyanodiamine presoma of gained is placed in porcelain with cover
In crucible, 3h is calcined in 550 DEG C, obtains flaxen g-C3N4.100mg g-C is added in beaker3N4With 100mL deionizations
Water rapid dispersion, obtains suspension, and 5min is centrifuged under 5000rpm, takes supernatant to can obtain two-dimentional g-C3N4Nanometer sheet.
As shown in figure 5, the g-C for implementing to prepare for the present invention3N4Transmission electron microscope (TEM) figure of nanometer sheet, show to use this side
Method can prepare the g-C of big lamellar structure3N4Nanometer sheet.
Embodiment 4
Large-area ultrathin p-g-C is prepared using the method for above-described embodiment 13N4Nanometer sheet.Take phytic acid 926 μ L and 4.1667g
Dicyanodiamine adds 40mL deionized water in 100ml round-bottomed flasks, and stirring 4h makes dicyanodiamine dissolve and be well mixed；
Product after stirring is placed in 4 DEG C of preservation 2h, slowly separates out dicyanodiamine；The solid of gained is dried into 12h at 80 DEG C, obtained everywhere
Dicyanodiamine presoma after reason.
The dicyanodiamine presoma of gained is placed in porcelain crucible with cover, 3h is calcined in 530 DEG C, obtains flaxen p-g-
C3N4.100mg p-g-C is added in beaker3N4With 100mL deionized water rapid dispersions, suspension is obtained, under 5000rpm
5min is centrifuged, takes supernatant to can obtain the p-g-C of two dimension3N4Nanometer sheet.
As shown in fig. 6, the p-g-C for implementing to prepare for the present invention3N4Transmission electron microscope (TEM) figure of nanometer sheet, shows to use this
Method can prepare the p-g-C of big lamellar structure3N4Nanometer sheet.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (5)
- A kind of 1. quick method for preparing large-area ultrathin nitrogen carbide nanometer sheet, it is characterised in that：Described method is：By dicyan Dicyanodiamine presoma is obtained after two amine solvents after refrigerating, separate out, filter, dry, then by dicyanodiamine presoma 520 The product after calcining is distributed in deionized water after calcining a period of time under conditions of DEG C -550 DEG C, separates and produces two-dimentional g- C3N4Nanometer sheet.
- 2. the quick method for preparing large-area ultrathin nitrogen carbide nanometer sheet according to claim 1, it is characterised in that：Specifically Comprise the following steps：Step 1：By dicyanodiamine dissolving in deionized water；Step 2：Product Cord blood 2-8h after dissolving, slowly separates out dicyanodiamine solid；Step 3：Product after the refrigeration of taking-up is filtered；Step 4：Product is dried, obtains the dicyanodiamine presoma after processing；Step 5：Dicyanodiamine presoma after processing is subjected to calcination processing, it is anti-at 520 DEG C -550 DEG C by temperature programming 3h is answered, synthesizes g-C3N4Material；Step 6：By the g-C of synthesis3N4Material mixes with deionized water to be disperseed to can obtain two-dimentional g-C3N4Nanometer sheet, wherein scattered Time is 30-120min.
- 3. the quick method for preparing large-area ultrathin nitrogen carbide nanometer sheet according to claim 2, it is characterised in that：Step In 1, dicyanodiamine dissolves in water, and the weight of dicyanodiamine and deionized water ratio is 1:4-1:12.
- 4. the quick method for preparing large-area ultrathin nitrogen carbide nanometer sheet according to claim 2, it is characterised in that：Step Storage temperature in 2 is 4-8 DEG C.
- 5. the quick method for preparing large-area ultrathin nitrogen carbide nanometer sheet according to claim 2, it is characterised in that：Step Drying temperature in 4 is 40-100 DEG C；Drying time is 3-15h.
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| CN108893723A (en) * | 2018-06-28 | 2018-11-27 | 武汉工程大学 | A method of quickly preparing ultra-thin ceramic piece |
| CN110304613A (en) * | 2018-03-20 | 2019-10-08 | 中国科学技术大学 | A kind of two-dimensional ultrathin metal nitride nanometer sheet and preparation method thereof |
| CN115069286A (en) * | 2022-06-29 | 2022-09-20 | 山东力合新材料科技有限公司 | Phosphorus-doped porous hierarchical structure carbon nitride photocatalyst and preparation method and application thereof |
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