CN104891460B - Method for preparing graphite-phase carbon nitride nanosheets by using solution phase - Google Patents
Method for preparing graphite-phase carbon nitride nanosheets by using solution phase Download PDFInfo
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Abstract
The invention provides a method for preparing graphite-phase carbon nitride nanosheets by using a solution phase and belongs to the technical field of preparation of nano materials. The method comprises the following steps: calcining dicyanodiamine into a ceramic crucible with a cover, thereby obtaining a g-C3N4 polymer material; adding the g-C3N4 polymer material into a tetrahydrofuran solution of an alkali metal lithium or sodium, performing ultrasonic dispersion, adding halogenated organic solvent, and sequentially washing a solid product obtained by reaction with toluene, ethanol and water, thereby obtaining the g-C3N4 nanosheets. The preparation method has the advantages of cheap raw materials, simple process, high preparation efficiency and the like; the obtained g-C3N4 nanosheets are greatly enlarged in specific surface area, have good dispersibility in an organic phase and a water phase, and have favorable photocatalytic performance.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, is related to a kind of solution and prepares graphite phase carbon nitride (g-C3N4)
The method of nanometer sheet.
Background technology
In five kinds of allotropes of carbonitride, graphite phase carbon nitride, i.e. g-C3N4It is most stable of one kind.In recent years,
g-C3N4Be easy to get because of its good chemical stability, unique semiconductor energy band structure, nontoxic and raw material, it is excellent without metal etc.
Characteristic gets more and more people's extensive concerning in fields such as photocatalysis contaminant degradation, photolysis water hydrogen, photocatalysis organic syntheses.So
And, as a kind of polymer semiconducting material, by g-C3N4There is also some problems as photochemical catalyst, such as specific surface area it is little (～
10m2/ g), that the exciton binding energy of photo-generated carrier is high, photo-generate electron-hole is combined serious, visible light utilization efficiency is low.For
These problems, people are from g-C3N4The optimum synthesis of photochemical catalyst, physics are composite modified, chemical doping is modified, modification by copolymerization, table
The aspects such as face modification, nano modification are adjusted to its physicochemical property, such as semiconductor energy band structure, optical absorption property, with
Phase improves g-C3N4Photocatalysis performance.
Compared with body phase material, through the g-C of nano modification3N4The increase of photochemical catalyst specific surface area, degree of crystallinity are improved,
Its photocatalysis performance is obviously improved.At present, people have been synthesized with template and non-template method and have obtained a series of with special form
The g-C of looks3N4Nano-photocatalyst, such as mesoporous g-C3N4、g-C3N4Nanometer rods, g-C3N4Nano particle etc., has effectively facilitated g-
C3N4The development of photocatalyst material.Due to g-C3N4With class graphite laminate structure, it is also possible to by g-C3N4Peel off into nanometer thin
Piece or single layer structure, the stripping means commonly used at present has hot stripping method or solvent stripping method.Hot stripping method is by g-C3N4In air
In be heat-treated, body phase material is gradually decomposed into nano flake (Niu P etc., Adv.Funct.Mater., 2012,22:
4763-4770), and the conventional solvent of solvent stripping method be water (Zhang X D etc., J.Am.Chem.Soc., 2013,135,18-
21) with isopropanol (Yang S etc., Adv.Mater., 2013,25:2452) g-C for obtaining, is peeled off3N4Lamellar structure is more complete
Whole, defect is few, with higher photocatalysis efficiency.However, hot stripping method and solvent stripping method still suffer from testing poor controllability, system
The standby g-C for obtaining3N4Lamella poor dispersion, thickness are big, the low key issue of yield is not yet solved.
The content of the invention
It is an object of the invention to provide one kind can solve to prepare g-C at present3N4Nanometer sheet efficiency is low, thickness big, dispersiveness
The solution of the problems such as difference prepares graphite phase carbon nitride (g-C3N4) nanometer sheet method.
For achieving the above object, the inventive method obtains g- first with dicyanodiamine as presoma by heat polymerization
C3N4Polymeric material, then in the presence of halogenated organic reagent, carries out g-C in the tetrahydrofuran solution of alkali metal and naphthalene3N4
It is prepared by the solution of nanometer sheet.
A kind of solution prepares graphite phase carbon nitride (g-C3N4) nanometer sheet method, comprise the following steps：
1) with dicyanodiamine as raw material, calcined, obtained the g-C of yellow3N4Polymeric material；
2) by step 1) gained g-C3N4Polymeric material is dispersed in tetrahydrofuran solution, is surpassed under nitrogen protective condition
Sound disperses, the g-C for obtaining3N4Dispersion liquid, in g-C3N4Alkali metal and naphthalene are sequentially added in dispersion liquid, is persistently stirred, be subsequently adding halogen
For organic reagent, react under nitrogen protective condition, after reaction terminates, gained solid product is used successively toluene, second alcohol and water
Washed, obtained graphite phase carbon nitride (g-C3N4) nanometer sheet；
Step 1) in, the calcining is calcined in Muffle furnace in ceramic crucible with cover, and the temperature of calcining can be
450～550 DEG C, the time of calcining can be 2～4h.
Step 2) in, the alkali metal can be lithium metal or metallic sodium.
Step 2) in, the g-C3N4Polymeric material and alkali-metal mol ratio (C3N4:Alkali metal) can be 1:7～
150, the mol ratio of alkali metal and naphthalene>1.
Step 2) in, the halogenated organic reagent can be brominated alkanes Br (CH2)nCH3(n is integer, 4≤n≤12) and iodine
For alkane I (CH2)nCH3(n is integer, the one kind in 4≤n≤12).
Step 2) in, the halo organic reagent is preferably 1: 1 with alkali-metal mol ratio.
Step 2) in, the time of the reaction can be 5～24h.
Step 2) in, the time persistently stirred can be 30～120min.
G-C is obtained prepared by the present invention3N4Nanometer sheet preparation efficiency is high, and by detection, specific surface area is up to 53m2/ g,
Good dispersion in water and conventional organic solvent, with good photocatalysis performance, AFM (AFM) shows,
g-C3N4The thickness of nano flake is about 1～2nm.
The advantage that the present invention possesses compared with prior art：
(1) the invention provides a kind of g-C3N4The solution preparation method of nanometer sheet, the method preparation efficiency is high, controllable
Property strong, the g-C for preparing3N4Nanometer sheet thickness and size are adjustable；
(2) g-C that the present invention is prepared3N4Nanometer sheet has good dispersiveness in water and common organic solvents；
(3) g-C that the present invention is prepared3N4Nanometer sheet specific surface area is big, is conducive to photo-generated carrier under illumination condition
Efficiently separate, improve photocatalysis performance；
(4) preparation method mild condition, it is not necessary to expensive equipment, the prospect with large-scale application.
Description of the drawings
Fig. 1 is g-C3N4Polymeric material and the present invention prepare g-C3N4The X-ray powder diffraction figure of nanometer sheet
(XRD)。
Fig. 2 prepares g-C for the present invention3N4The scanning electron microscope (SEM) photograph (SEM) of nanometer sheet.
Fig. 3 prepares g-C for the present invention3N4The atomic force microscopy diagram (AFM) of nanometer sheet.
Fig. 4 is g-C3N4Polymeric material and the present invention prepare g-C3N4The UV Diffuse Reflectance Spectroscopy figure of nanometer sheet.
Fig. 5 is change curve of the 2- hydroxyterephthalic acids fluorescence intensity with light application time.
Specific embodiment
Embodiment 1
A kind of solution prepares graphite phase carbon nitride (g-C3N4) nanometer sheet method, comprise the following steps：
10g dicyanodiamines are added in the ceramic crucible with cover of 50mL, crucible is placed in Muffle furnace, with 2.5 DEG C/min
Speed be increased to 550 DEG C from room temperature, two hours of constant temperature.Calcining is cooled to room temperature after terminating, by sample in agate mortar
Grinding obtains yellow powder, i.e. g-C3N4Polymeric material.Under nitrogen protective condition, 108mg g-C are weighed3N4Polymeric material
Material is added in the tetrahydrofuran solution that 120mL fresh drieds are crossed, ultrasonic 5min, and 0.55g metals are then added in the dispersion liquid
Lithium and 5.08g naphthalenes, solution be changed into it is blackish green after persistently stir a hour, then with automatic injector with the speed of 10mL/h upwards
State and add Dodecyl Bromide in solution until solution green disappearance, continues to react 12h under nitrogen protection.After reaction terminates,
Add ethanol to remove unreacted lithium metal in above-mentioned reactant, 5min, gained solid are centrifuged with the rotating speed of 8000rpm/min
Product uses successively toluene, ethanol, water washing, finally obtains g-C3N4Nanometer sheet.
The result of embodiment 1 shows：Prepare g-C3N4G-C of the nanometer sheet than phase homogenous quantities3N4Polymeric material is more fluffy
Pine, gas absorption measuring g-C3N4The specific surface area of nanometer sheet is up to 53m2/g.Compare g-C3N4Polymeric material, g-C3N4
Dispersiveness of the nanometer sheet in different solvents (such as dichloromethane, chloroform, DMF) significantly improves.Fig. 1 is g-C3N4Polymer
Material and g-C3N4The XRD of nanometer sheet, it can be found that g-C3N4The XRD diffraction peak intensities of nanometer sheet are obviously reduced, and illustrate body phase
g-C3N4Polymeric material is successfully peeled off into nanometer sheet.Fig. 2 prepares g-C for the present invention3N4The SEM figures of nanometer sheet,
It can be seen that its obvious flaky texture.The AFM figures of Fig. 3 show, the g-C for preparing3N4Nanometer sheet thickness is about 1～
2nm.Fig. 4 is g-C3N4Polymeric material and g-C3N4The solid uv drses abosrption spectrogram of nanometer sheet, from fig. 4, it can be seen that this
The g-C that invention is prepared3N4Nanometer sheet is significantly improved in the absorption of visible region.With terephthalic acid (TPA) as molecular probe, pass through
Fluorescent technique contrasts g-C3N4Polymeric material and the present invention prepare g-C3N4The photocatalysis performance of nanometer sheet.Fig. 5 is visible
Under light light irradiation the fluorescence intensity of photocatalysis product 2- hydroxyterephthalic acids with light application time change curve.Can by Fig. 5
See, with g-C3N4When nanometer sheet is photochemical catalyst, the fluorescence intensity of 2- hydroxyterephthalic acids is significantly higher than g-C3N4Polymeric material
Material, illustrates the g-C that the present invention is prepared under illumination condition3N4Nanometer sheet can produce more OH, urge with more excellent light
Change performance.
Embodiment 2
In the ceramic crucible with cover of 50mL add 8.43g dicyanodiamines, crucible is placed in Muffle furnace, with 2.5 DEG C/
The speed of min is increased to 550 DEG C from room temperature, two hours of constant temperature.Calcining is cooled to room temperature after terminating, by sample in agate mortar
Middle grinding obtains yellow powder, i.e. g-C3N4Polymeric material.Under nitrogen protective condition, 71.2mg g-C are weighed3N4Polymer
Material is added in the tetrahydrofuran solution that 100mL fresh drieds are crossed, ultrasonic 5min, then adds 0.81g golden in the dispersion liquid
Category lithium and 5.22g naphthalenes, solution be changed into it is blackish green after persistently stir a hour, then with automatic injector with the speed of 10mL/h to
1- bromines normal butane is added in above-mentioned solution until solution green disappearance, continues to react 12h under nitrogen protection.After reaction terminates,
Add ethanol to remove unreacted lithium metal in above-mentioned reactant, 5min, gained solid are centrifuged with the rotating speed of 8000rpm/min
Product uses successively toluene, ethanol, water washing, finally obtains g-C3N4Nanometer sheet material.
Embodiment 3
10g dicyanodiamines are added in the ceramic crucible with cover of 50mL, crucible is placed in Muffle furnace, with 2.5 DEG C/min
Speed be increased to 550 DEG C from room temperature, two hours of constant temperature.Calcining is cooled to room temperature after terminating, by sample in agate mortar
Grinding obtains yellow powder, i.e. g-C3N4Polymeric material.Under nitrogen protective condition, 368mg g-C are weighed3N4Polymeric material
Material is added in the tetrahydrofuran solution that 120mL fresh drieds are crossed, ultrasonic 5min, and 0.21g metals are then added in the dispersion liquid
Lithium and 2.56g naphthalenes, solution be changed into it is blackish green after persistently stir a hour, then with automatic injector with the speed of 10mL/h upwards
State and add 1- bromines n-hexane in solution until solution green disappearance, continues to react 12h under nitrogen protection.After reaction terminates,
Add ethanol to remove unreacted lithium metal in above-mentioned reactant, 5min is centrifuged with the rotating speed of 8000rpm/min, gained solid is produced
Thing uses successively toluene, ethanol, water washing, finally obtains g-C3N4Nanometer sheet material.
Claims (8)
1. a kind of method that solution prepares graphite phase carbon nitride nanometer sheet, comprises the following steps：
1) with dicyanodiamine as raw material, calcined, obtained the g-C of yellow3N4Polymeric material；
2) by step 1) gained g-C3N4Polymeric material is dispersed in tetrahydrofuran solution, the ultrasound point under nitrogen protective condition
Dissipate, obtain g-C3N4Dispersion liquid, in g-C3N4Alkali metal and naphthalene are sequentially added in dispersion liquid, is persistently stirred, being subsequently adding halo has
Machine reagent, reacts under nitrogen protective condition, after reaction terminates, gained solid product is carried out successively with toluene, second alcohol and water
Washing, obtains g-C3N4Nanometer sheet.
2. a kind of method that as claimed in claim 1 solution prepares graphite phase carbon nitride nanometer sheet, it is characterised in that step 1)
In, the temperature of the calcining is 450～550 DEG C, and the time of calcining is 2～4h.
3. a kind of method that as claimed in claim 1 solution prepares graphite phase carbon nitride nanometer sheet, it is characterised in that step 2)
In, the alkali metal is lithium metal or metallic sodium.
4. a kind of method that as claimed in claim 1 solution prepares graphite phase carbon nitride nanometer sheet, it is characterised in that step 2)
In, the g-C3N4Polymeric material and alkali-metal mol ratio (C3N4: alkali metal) it is 1: 7～150, alkali metal rubs with naphthalene
You compare>1.
5. a kind of method that as claimed in claim 1 solution prepares graphite phase carbon nitride nanometer sheet, it is characterised in that step 2)
In, the halogenated organic reagent is brominated alkanes Br (CH2)nCH3, n is integer, 4≤n≤12；Or alkane iodide I (CH2)nCH3,
N is integer, 4≤n≤12.
6. a kind of method that as claimed in claim 1 solution prepares graphite phase carbon nitride nanometer sheet, it is characterised in that step 2)
In, the halo organic reagent is 1: 1 with alkali-metal mol ratio.
7. a kind of method that as claimed in claim 1 solution prepares graphite phase carbon nitride nanometer sheet, it is characterised in that step 2)
In, the time of the reaction is 5～24h.
8. a kind of method that as claimed in claim 1 solution prepares graphite phase carbon nitride nanometer sheet, it is characterised in that step 2)
In, the time persistently stirred is 30～120min.
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| CN105417507B (en) * | 2015-12-10 | 2018-03-06 | 济南大学 | A kind of preparation method and products obtained therefrom of azotized carbon nano particle |
| CN105540557A (en) * | 2015-12-17 | 2016-05-04 | 榆林学院 | Method for preparing graphite-like carbon nitride in ultrasonic field |
| CN105688969A (en) * | 2016-02-19 | 2016-06-22 | 厦门大学 | Preparation method of catalyst for photo-catalytically splitting water to produce hydrogen |
| CN105800571B (en) * | 2016-02-26 | 2018-04-27 | 浙江大学 | A kind of preparation method of two-dimensional nano piece carbon-nitrogen material |
| CN105772056A (en) * | 2016-04-28 | 2016-07-20 | 成都理工大学 | Preparation method and application of graphite-phase carbon nitride photocatalysis material |
| CN107098323B (en) * | 2017-04-25 | 2019-08-30 | 中南大学 | A kind of g-C3N4Nanometer sheet and the preparation method and application thereof |
| CN108584892A (en) * | 2018-04-26 | 2018-09-28 | 福州大学 | A kind of preparation method and applications of crystalline phase azotized carbon nano particle |
| CN108927197B (en) * | 2018-07-09 | 2021-04-20 | 江苏大学 | g-C with high catalytic performance3N4Preparation method and use of |
| CN112126946B (en) * | 2020-09-15 | 2021-08-27 | 中国科学院大连化学物理研究所 | Composite membrane for acid-base water electrolysis and preparation method and application thereof |
| CN112897484B (en) * | 2021-01-14 | 2023-10-31 | 华南理工大学 | Defect-free g-C 3 N 4 Nanoplatelets, two-dimensional g-C 3 N 4 Nanosheet film and preparation method and application thereof |
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| CN103232458B (en) * | 2013-04-25 | 2015-10-14 | 大连理工大学 | A kind of preparation method with the graphite phase carbon nitride material of monoatomic layer structure |
| CN103848405B (en) * | 2014-03-07 | 2016-01-20 | 西北大学 | A kind of individual layer g-C with monoatomic thickness 3n 4the preparation method of nano material |
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