CN107324297B - A kind of preparation method of the adjustable carbonitride superthin section of the atom number of plies - Google Patents
A kind of preparation method of the adjustable carbonitride superthin section of the atom number of plies Download PDFInfo
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- CN107324297B CN107324297B CN201710662614.XA CN201710662614A CN107324297B CN 107324297 B CN107324297 B CN 107324297B CN 201710662614 A CN201710662614 A CN 201710662614A CN 107324297 B CN107324297 B CN 107324297B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000002604 ultrasonography Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 16
- 238000010586 diagram Methods 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 238000002309 gasification Methods 0.000 description 6
- 238000004630 atomic force microscopy Methods 0.000 description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical group C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229940011871 estrogen Drugs 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
-
- 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
-
- 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
Abstract
The present invention relates to the nitridation adjustable preparation methods of carbon atomic layer number, weigh 3~9g Bulk g-C3N4It is rapidly heated after carrying out thermal expansion 10-20min to 550~580 DEG C and takes out in container, liquid nitrogen is added immediately to sample is submerged, to LN2Volatilization finishes, and repeats above step totally 5~10 times, obtains superthin section；The preparation of carbonitride superthin section: the g-C that 0.12~1.2g step (1) obtains is weighed3N4Superthin section is rapidly heated to 550~580 DEG C of TE temperature in container, and cooled to room temperature after keeping the temperature the 10-20min time obtains monoatomic layer and multilayer g-C3N4.The invention has the advantages that replacing the organic reagent ultrasound stripping means generally used using cheap, nontoxic removing reagent, make to prepare g-C3N4Superthin section process is fast, at low cost, environmentally friendly, is suitable for industrialization large scale preparation.
Description
Technical field
The present invention relates to photoelectrocatalysimaterial material fields, specifically have visible light-responded carbon material-class graphite-phase nitridation
Carbon (g-C3N4) the adjustable preparation method of the atom number of plies.
Background technique
Superthin section is a kind of a kind of new material with atomic-level thickness.Because of its distinctive two-dimensional structure feature and thickness
Size can not only cause the enhancing of the intrinsic performance of its material, but also can generate the new property that some corresponding bulks do not have,
As optics, it is electrical and mechanical in terms of characteristic, future be expected to energy convert with energy storage, electronics, catalyst, sensor and life
The various fields application such as object medical treatment, it may be said that be one of following most promising advanced material.
g-C3N4It is a kind of two-dimensional sheet structure for being connected to form infinite expanding by nitrogen-atoms by 5-triazine units.This
Shape structure has preferable chemical and thermal stability, acid and alkali-resistance and organic solvent.But bulk g-C3N4(Bulk g-C3N4) deposit
In some defects, if surface area is small, photo-generate electron-hole recombination rate is high, and medium band gap etc. limits its answering in practice
With.Currently, improving its catalytic activity to overcome one's shortcomings, people have carried out a series of study on the modification to it, such as: doping changes
Property, composite modified and pattern it is modified, wherein the modified key problem of pattern is how a g-C3N4Remove superthin section.It is existing
In commonly preparation g-C3N4The method of superthin section is stripping means (top-down method) from bottom to top, most common to have
Ultrasonic wave added liquid phase stripping method, hot stripping means, acid or aqueous slkali stripping method, and heat and ultrasonic method for combined use.But these
Stripping means is maximum the disadvantage is that low yield, splitting time is long, and g-C3N4The atom number of plies have uncontrollability, be its research
With the bottleneck of practical application.Therefore, a kind of adjustable g-C of the number of plies is found3N4The method that superthin section is largely prepared has critically important
Realistic meaning.
Summary of the invention
The present invention provides a kind of preparation method of the adjustable carbonitride superthin section of number of plies, preparation process is fast, it is at low cost,
Environmental protection is suitable for industrialization large scale preparation, is applied to the photocatalytic degradation of dyestuff, hence it is evident that is better than Bulk g-C3N4, and
There is apparent electro catalytic activity to environmental estrogens tetrabromobisphenol A.
The technical scheme of the invention to solve the technical problem is: a kind of adjustable carbonitride of the atom number of plies is ultra-thin
The preparation method of piece, includes following steps:
(1) 3~9g Bulk g-C is weighed3N4It is rapidly heated in container and is thermally expanded (thermal to 550~580 DEG C
Expansion, TE) it takes out after 10-20min, liquid nitrogen (liquid nitrogen, LN are added immediately2) to submergence sample, to LN2
Volatilization finishes, and repeats above step totally 5~10 times, obtains g-C3N4Superthin section；
(2) preparation of the adjustable carbonitride superthin section of the atom number of plies: the g-C that 0.12~1.2g step (1) obtains is weighed3N4
Superthin section is rapidly heated to 550~580 DEG C of TE temperature in container, and cooled to room temperature after keeping the temperature the 10-20min time obtains
To monoatomic layer or multilayer g-C3N4。
According to the above scheme, the g-C3N 4The preparation of superthin section: rich nitrogen presoma is weighed first and is placed in container, quickly
500~600 DEG C of heat preservation 4h are warming up to, cooled to room temperature obtains Bulk g-C3N4。
According to the above scheme, rich nitrogen presoma described in step (1) is melamine, dicyanodiamine or thiocarbamide.
According to the above scheme, when the rich nitrogen presoma be thiocarbamide or dicyanodiamine, remove the g-C of acquisition3N4, thickness
For 2.5-10nm, the number of plies is 7-30 layers；It is peelable to obtain 1-8 layers of g-C when the rich nitrogen presoma is melamine3N4。
The present invention can control g-C by control TE temperature3N4The atom number of plies.When rich nitrogen presoma is melamine, control
TE processed is 580 DEG C, then TE-LN2Gasification can only remove 5 times, and obtaining average thickness is 1.5nm, about 4 layers of g-C3N4Piece (580-TE-
LN2(5))；And controlling TE is 550 DEG C, then TE-LN2Gasify peelable 10 times, obtaining average thickness is 2.8nm, about 8 layers of g-C3N4
Piece (550-TE-LN2(10)).The lower g-C of temperature3N4TE degree it is smaller, the number of required removing is more；Temperature is higher, TE
Degree is bigger, and LN is added2The peeling effect that gasifies is better, but g-C3N4Thermally decompose more serious, g-C3N4Fragment it is more, yield is corresponding
It reduces, but temperature does not exceed 580 DEG C yet, so, to obtain large stretch of ultra-thin g-C3N4, can control 550 DEG C to carry out 10 times
TE-LN2Gasification removing, temperature is lower to need to remove number increase, and cost also greatly increases；To obtain the g- of fragment single layer
C3N4, then can control 580 DEG C of progress, 5 TE-LN2Gasification removing, but otherwise temperature is difficult to obtain product no more than 580 DEG C.
Step (1) of the invention passes through control removing Bulk g-C3N4Quality, can control g-C3N4The atom number of plies.Point
Also known as take 6g and 9g Bulk g-C3N4, control TE is 580 DEG C of progress, 5 TE-LN2(5) it removes, obtaining average thickness is respectively
The g-C that about 4 layers and about 30 layers of 10nm of 1.5nm3N4.Under identical stripping conditions, sample size is fewer, g-C3N4The speed of TE after heated
Rate and the rate of thermal decomposition are accelerated, and LN is added2Sufficiently, peelable number is fewer, but low yield for removing, therefore, removes Bulk g-
C3N4Quality minimum cannot be below 3g.Step (1) and (2) pass through control TE-LN2Gasification removing number and last TE sample
Quality, it is controllable to obtain single layer g-C3N4.Such as weigh 0.45g 580-TE-LN2(5)g-C3N4Thin slice carries out 580 DEG C of TE again,
It is 0.68nm monoatomic layer g-C that average thickness, which then can be obtained,3N4.But 580 DEG C of TE-LN2Gasify the number removed no more than 5 times,
Otherwise will be without product, and the quality of last TE sample cannot be greater than 0.45g, otherwise cannot get single layer g-C3N4.In identical peel strip
Under part, the amount of last TE sample is fewer, g-C3N4It is thinner, but sample size cannot be below 0.12g, then can control g-C3N4For 1-2
Layer.
The present invention takes high-temperature heat expansion (TE) to combine liquid nitrogen (LN2) low temperature gasification (TE-LN2) stripping means prepare it is former
The regulatable g-C of sublayer number3N4Superthin section.Specifically, the reagent of use is environmentally protective LN2, joined by simply repeatedly TE
Close LN2The cooling method of gasification is to Bulk g-C rapidly3N4It is removed.G-C under conditions of TE3N4Interlamellar spacing increase, LN2
It is quickly interspersed to enter g-C3N4Interlayer, and gasify rapidly, reach removing g-C3N4Effect.
Compared with prior art, the invention has the advantages that replacing what is generally used to have using cheap, nontoxic removing reagent
Machine reagent ultrasound stripping means makes to prepare g-C3N4Superthin section process is fast, at low cost, environmentally friendly, is suitable for the extensive system of industrialization
It is standby.The method overcome existing g-C3N4The shortcomings of ultra-thin piece preparation method have found a low cost and prepare single layer g-
C3N4" green " route.The g-C of method preparation through the invention3N4Superthin section is photochemical catalyst, using visible light as light
Source, suitable for the degradation of environmental organic pollutant, at the same time as the sensor of environmental hormone tetrabromobisphenol A in water.
Detailed description of the invention
Fig. 1 is the obtained g-C of different stripping conditions3N4Superthin section atomic force microscopy diagram；
Fig. 2 is the obtained g-C of different stripping conditions3N4Superthin section, Bulk g-C3N4, bare electrode contain 1 × 10- 5molL-1Tetrabromobisphenol A cyclic voltammogram；
Fig. 3 is the obtained g-C of different stripping conditions3N4Superthin section visible light photocatalytic degradation RhB figure；
Fig. 4 is the obtained g-C of different stripping conditions3N4Superthin section energy diagram；
Fig. 5 is the obtained g-C of different stripping conditions3N4Superthin section fluorescence emission spectrum.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
3.0g melamine is weighed in container, is put into Muffle furnace, by room temperature to 550 DEG C in air, is risen
Warm rate is 5 DEG C/min, and after constant temperature 4h, cooled to room temperature obtains yellow Bulk g-C3N4Product.
Embodiment 2
3.0g dicyanodiamine is weighed in container, is put into Muffle furnace, by room temperature to 550 DEG C in air, heating
Rate is 5 DEG C/min, and after constant temperature 4h, cooled to room temperature obtains yellow Bulk g-C3N4Product.
Embodiment 3
6.0g thiocarbamide is weighed in container, is put into Muffle furnace, by room temperature to 550 DEG C in air, heating rate
For 5 DEG C/min, after constant temperature 4h, cooled to room temperature obtains yellow Bulk g-C3N4Product.
Embodiment 4
Weigh 1 gained 6.0g Bulk g-C of embodiment3N4It in container, is placed in Muffle furnace, is warming up to 20 DEG C/min
20min is kept in 550 DEG C, takes out and LN is poured into crucible2, until flooding sample.To LN2Above-mentioned behaviour is repeated after being evaporated completely
Make 9 times, obtains g-C3N4, atomic force microscopy diagram such as Fig. 1, wherein shown in (a), g-C as seen from the figure3N4Superthin section is big
Sheet, average thickness 2.8nm, about 8 atomic layers.
Embodiment 5
Weigh 1 gained 6.0g Bulk g-C of embodiment3N4It in container, is placed in Muffle furnace, is warming up to 20 DEG C/min
20min is kept in 580 DEG C, LN is poured into taking-up immediately2Until submergence sample.To LN2It repeats aforesaid operations 4 times, obtains after being evaporated completely
To g-C3N4, atomic force microscopy diagram such as Fig. 1, wherein shown in (c), as can be seen from the figure g-C3N4Superthin section obviously becomes
Fractionlet, average thickness 1.5nm, about 4 atomic layers.
Embodiment 6
Weigh the g-C of the preparation of 0.15g embodiment 43N4Thin slice is placed in Muffle furnace in container, is warming up to 20 DEG C/min
20min is kept in 550 DEG C, cooled to room temperature obtains g-C3N4, atomic force microscopy diagram such as Fig. 1, wherein shown in (b),
As can be seen from the figure g-C3N4Superthin section obviously becomes smaller, and average thickness is about 1.0nm, about 2 atomic layers.
Embodiment 7
Weigh the g-C of the preparation of 0.45g embodiment 53N4Thin slice is placed in Muffle furnace in container, is warming up to 20 DEG C/min
20min is kept in 580 DEG C, cooled to room temperature obtains g-C3N4, atomic force microscopy diagram such as Fig. 1, wherein shown in (d),
As can be seen from the figure obtaining average thickness is about 0.68nm, about the g-C of monoatomic layer3N4。
Embodiment 8
Weigh 2 gained 1.0g Bulk g-C of embodiment3N4It in container, is placed in Muffle furnace, is warming up to 20 DEG C/min
20min is kept in 580 DEG C, LN is poured into taking-up immediately2To submergence sample, to LN2It repeats aforesaid operations 4 times, obtains after being evaporated completely
g-C3N4Average thickness is 10nm, about 30 layers.
Embodiment 9
Weigh 3 gained 1.0g Bulk g-C of embodiment3N4In container, it is warming up in 580 DEG C and is kept with 20 DEG C/min
LN is poured into 20min, taking-up immediately2To submergence sample, to LN2It is repeated aforesaid operations 4 times after being evaporated completely, obtained g-C3N4It is average
With a thickness of 4.2nm, about 12 layers.
Embodiment 10
Weigh the g-C of the preparation of 0.45g embodiment 93N4Superthin section is placed in Muffle furnace in container, with 20 DEG C/min heating
To 20min is kept in 580 DEG C, cooled to room temperature obtains g-C3N4Average thickness is about 2.5nm, and about 7 layers.
Embodiment 11
The test of electro catalytic activity:
g-C3N4Electrochemical response of the superthin section catalyst to tetrabromobisphenol A.It is first that the glass-carbon electrode sulfuric acid polished is clear
Wash activation, then the obtained g-C of different stripping conditions of 5 μ L of drop coating3N4Superthin section decorating liquid, illumination is to dry.To the pH=5.8 of 4mL
Phosphate buffer solution in be added 1mL 10-5molL-1Tetrabromobisphenol A as prepare liquid, the results are shown in attached figure 2.580-TE-LN2
(5+1),550-TE-LN2(10+1),580-TE-LN2(5) and 550-TE-LN2(10) modified electrode, peak current are respectively
Bulk g-C3N41.4 times, 1.2 times, 1.1 times and 1.06 times.The g-C that this method is removed3N4Superthin section is double to tetrabromo
Phenol A electro catalytic activity significantly improves (see Fig. 2, wherein (a) 580-TE-LN2(5+1),(b)550-TE-LN2(10+1),(c)580-
TE-LN2(5),(d)550-TE-LN2(10),(e)Bulk g-C3N4, (f) bare electrode is containing 1 × 10-5molL-1Tetrabromobisphenol A
The cyclic voltammogram of solution)
Embodiment 12
Photocatalysis performance test
580-TE-LN prepared by the present invention2(5+1) (embodiment 7), 550-TE-LN2(10+1) (embodiment 6), 580-TE-
LN2(5) (embodiment 5), 550-TE-LN2(10) (embodiment 4) g-C3N4The energy diagram of superthin section is (see attached drawing 4, wherein (a)
580-TE-LN2(5+1),(b)550-TE-LN2(10+1),(c)580-TE-LN2(5),(d)550-TE-LN2(10),(e)Bulk
g-C3N4Energy diagram) and fluorescence emission spectrum (see attached drawing 5, wherein (a) 580-TE-LN2(5+1),(b)550-TE-LN2(10+
1),(c)580-TE-LN2(5),(d)550-TE-LN2(10),(e)Bulk g-C3N4(excitation wavelength is fluorescence emission spectrogram of compound
270nm)).As a result illustrate: g-C after removing3N4Lamella is thinning, and due to quantum limitation effect, band gap increases, compared with Bulk g-C3N4
0.25eV, 0.23eV, 0.13eV and 0.09eV are increased separately, then the photo-generate electron-hole redox ability that light excitation generates
Enhancing.Another aspect lamella is thinning, and the time that the light induced electron of generation is transferred to surface shortens, and effectively reduces light induced electron
The recombination rate in hole, ultra-thin g-C3N4The fluorescence intensity of generation substantially reduces.It is used for visible light photocatalytic degradation rhodamine B
(RhB).The photochemical catalyst of 25mg is added to 10 μ gmL of 50mL-1RhB solution in 300W xenon lamp irradiation light shine 20min.Knot
Fruit sees (the different obtained g-C of stripping conditions of attached drawing 33N4Superthin section photocatalytic degradation RhB curve).In 15min to RhB's
Degradation rate has been up to 93.5%, 91.7%, 90.3% and 78.0%, degradation rate constant is respectively 0.235,0.185,
0.171 and 0.137min-1, compared to Bulk g-C3N40.00238min-1, increased separately 98 times, 77 times, 72 times and 58
Times.
Claims (4)
1. a kind of preparation method of the adjustable carbonitride superthin section of the atom number of plies, includes following steps:
(1) 3~9g bulk g-C is weighed3N4It is rapidly heated after carrying out thermal expansion 10-20min to 550~580 DEG C and takes in container
Out, liquid nitrogen is added immediately to sample is submerged, is finished to liquid nitrogen volatilization, repeats above step totally 5~10 times, obtain g-C3N4It is ultra-thin
Piece；
(2) preparation of the adjustable carbonitride superthin section of the atom number of plies: the g-C that 0.12~1.2g step (1) obtains is weighed3N4It is ultra-thin
Piece is rapidly heated to 550~580 DEG C of thermal expansion temperature in container, and cooled to room temperature after keeping the temperature the 10-20min time obtains
To monoatomic layer or multilayer g-C3N4。
2. the preparation method of the adjustable carbonitride superthin section of the atom number of plies according to claim 1, it is characterised in that described
g-C3N4The preparation of superthin section: weighing rich nitrogen presoma first and be placed in container, is rapidly heated to 500~600 DEG C of heat preservation 4h, from
It is so cooled to room temperature, obtains blocky g-C3N4。
3. the preparation method of the adjustable carbonitride superthin section of the atom number of plies as described in claim 2, it is characterised in that step (1)
The rich nitrogen presoma is melamine, dicyanodiamine or thiocarbamide.
4. the preparation method of the adjustable carbonitride superthin section of the atom number of plies as described in claim 2, it is characterised in that when described
Rich nitrogen presoma be thiocarbamide or dicyanodiamine, remove the g-C of acquisition3N4, with a thickness of 2.5-10nm, the number of plies is 7-30 layers；When
The rich nitrogen presoma is melamine, the peelable g-C for obtaining 1-8 layers3N4。
Priority Applications (1)
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| CN111644131B (en) * | 2020-06-12 | 2021-07-06 | 中国科学院生态环境研究中心 | Method for degrading hexabromocyclododecane by using graphite-phase carbon nitride |
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| CN113996327A (en) * | 2021-11-11 | 2022-02-01 | 扬州大学 | MoS2/g-C3N4Preparation method of composite hydrogen evolution material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105883734A (en) * | 2016-04-08 | 2016-08-24 | 山东大学 | Graphite phase carbon nitride quantum dot and preparation method thereof |
| CN106477539A (en) * | 2016-09-22 | 2017-03-08 | 西安交通大学 | A kind of preparation method of ultra-thin graphite phase carbon nitride |
| CN106732707A (en) * | 2016-11-10 | 2017-05-31 | 梅庆波 | A kind of preparation method of catalytic efficiency carbon nitride photocatalyst high |
-
2017
- 2017-08-04 CN CN201710662614.XA patent/CN107324297B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105883734A (en) * | 2016-04-08 | 2016-08-24 | 山东大学 | Graphite phase carbon nitride quantum dot and preparation method thereof |
| CN106477539A (en) * | 2016-09-22 | 2017-03-08 | 西安交通大学 | A kind of preparation method of ultra-thin graphite phase carbon nitride |
| CN106732707A (en) * | 2016-11-10 | 2017-05-31 | 梅庆波 | A kind of preparation method of catalytic efficiency carbon nitride photocatalyst high |
Non-Patent Citations (3)
| Title |
|---|
| A Graphitic-C3N4 "Seaweed" Architecture for Enhanced Hydrogen Evolution;Qing Han et al.;《Angewandte Chemie》;20150715;第127卷(第39期);第11595-11599页 |
| Atomically Thin Mesoporous Nanomesh of Graphitic C3N4 for High-Efficiency Photocatalytic Hydrogen Evolution;Qing Han et al.;《ACS NANO》;20160114;第16卷(第2期);第2745-2751页 |
| 超薄类石墨相氮化碳纳米片剥离技术的研究进展;张宇航等;《武汉工程大学学报》;20170630;第39卷(第3期);第223-230页 |
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