CN107324297A - 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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- CN107324297A CN107324297A CN201710662614.XA CN201710662614A CN107324297A CN 107324297 A CN107324297 A CN 107324297A CN 201710662614 A CN201710662614 A CN 201710662614A CN 107324297 A CN107324297 A CN 107324297A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000009413 insulation Methods 0.000 claims abstract description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 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
- 230000008901 benefit Effects 0.000 abstract description 2
- 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
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 20
- 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
- 239000000463 material Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 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
- 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
- 230000015556 catabolic process Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000010438 heat treatment Methods 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
- 238000006243 chemical reaction Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 229940011871 estrogen Drugs 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- 230000005284 excitation Effects 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
- 150000007974 melamines Chemical class 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
- 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
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002604 ultrasonography 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
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- 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
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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
- C01P2004/04—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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the nitridation adjustable preparation method of carbon atomic layer number, 3~9g Bulk g C are weighed3N4It is rapidly heated to 550~580 DEG C and taken out after the 20min of thermal expansion 10 in container, liquid nitrogen is added immediately to sample is submerged, LN is treated2Volatilization is finished, and repeats above step totally 5~10 times, obtains superthin section；The preparation of carbonitride superthin section：Weigh the g C that 0.12~1.2g steps (1) are obtained3N4Superthin section is rapidly heated in container to 550~580 DEG C of TE temperature, is naturally cooled to room temperature after the 10 20min times of insulation, is obtained monoatomic layer and multilayer g C3N4.It is an advantage of the invention that：The ultrasonic stripping means of organic reagent generally used using cheap, nontoxic stripping reagent substitution, makes preparation g C3N4Superthin section process is fast, cost is low, environmental protection, it is adaptable to which industrialization is extensive to be prepared.
Description
Technical field
The present invention relates to photoelectrocatalysimaterial material field, specifically with visible light-responded carbon material-class graphite-phase nitridation
Carbon (g-C3N4) the adjustable preparation method of the atom number of plies.
Background technology
Superthin section is an a kind of class 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 produce the new property that some corresponding bulks do not possess,
As optics, it is electrical and mechanical in terms of characteristic, future be expected to energy conversion with energy storage, electronics, catalyst, sensor and life
The various fields application such as thing 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 chemically and thermally stability, acid and alkali-resistance and organic solvent.But bulk g-C3N4(Bulk g-C3N4) deposit
In some defects, such as surface area is small, and photo-generate electron-hole recombination rate is high, medium band gap etc. limit its in practice should
With.At present, its catalytic activity is improved in order 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 be modified, the key problem that wherein pattern is modified is how a g-C3N4Peel off superthin section.It is existing
In conventional preparation g-C3N4The method of superthin section is stripping means (top-down method) from bottom to top, and the most frequently used has
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
The maximum shortcoming of stripping means is low yield, and splitting time is long, and g-C3N4The atom number of plies there is 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.
The content of the invention
The invention provides a kind of preparation method of the adjustable carbonitride superthin section of number of plies, its preparation process is fast, cost is low,
Environmental protection, it is adaptable to which industrialization is extensive to be prepared, and is applied to the photocatalytic degradation of dyestuff, hence it is evident that better than Bulk g-C3N4, and
There is obvious electro catalytic activity to environmental estrogens tetrabromobisphenol A.
The present invention solve the technical scheme that is used of above-mentioned technical problem for：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 are weighed3N4It is rapidly heated in container to 550~580 DEG C and carries out thermal expansion (thermal
Expansion, TE) take out after 10-20min, liquid nitrogen (liquid nitrogen, LN are added immediately2) to submergence sample, treat LN2
Volatilization is finished, 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：Weigh the g-C that 0.12~1.2g steps (1) are obtained3N4
Superthin section is rapidly heated in container to 550~580 DEG C of TE temperature, is naturally cooled to room temperature after the insulation 10-20min times, is obtained
To monoatomic layer or multilayer g-C3N4。
By such scheme, described g-C3N 4The preparation of superthin section：Weigh rich nitrogen presoma first to be placed in container, quickly
500~600 DEG C of insulation 4h are warming up to, room temperature is naturally cooled to, obtains Bulk g-C3N4。
By such scheme, the rich nitrogen presoma described in step (1) is melamine, dicyanodiamine or thiocarbamide.
By such scheme, when described rich nitrogen presoma is thiocarbamide or dicyanodiamine, the g-C obtained is peeled off3N4, its thickness
For 2.5-10nm, the number of plies is 7-30 layers；When described rich nitrogen presoma is melamine, peelable acquisition 1-8 layers of g-C3N4。
The present invention can control g-C by controlling TE temperature3N4The atom number of plies.When rich nitrogen presoma is melamine, control
TE processed is 580 DEG C, then TE-LN2Gasification can only be peeled off 5 times, obtain average thickness for 1.5nm, about 4 layers of g-C3N4Piece (580-TE-
LN2(5))；And it is 550 DEG C to control TE, then TE-LN2Gasify peelable 10 times, obtain average thickness for 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 times of required stripping is more；Temperature is higher, TE
Degree is bigger, adds LN2The peeling effect that gasifies is better, but g-C3N4Thermally decompose more serious, g-C3N4Fragment it is many, yield is corresponding
Reduction, but temperature does not exceed 580 DEG C yet, so, to obtain large stretch of ultra-thin g-C3N4, can control 550 DEG C and carry out 10 times
TE-LN2Gasification is peeled off, and temperature is lower to be needed to peel off number of times increase, and cost is also greatly increased；G- to obtain fragment individual layer
C3N4, then can control 580 DEG C of progress, 5 TE-LN2Gasification is peeled off, but temperature is no more than 580 DEG C, is otherwise difficult to obtain product.
The step (1) of the present invention peels off Bulk g-C by controlling3N4Quality, can control g-C3N4The atom number of plies.Point
Also known as take 6g and 9g Bulk g-C3N4, it is 580 DEG C of progress, 5 TE-LN to control TE2(5) peel off, obtaining average thickness is respectively
About 4 layers of 1.5nm and about 30 layers of 10nm g-C3N4.Under identical stripping conditions, sample size is fewer, g-C3N4TE speed after heated
Rate and the speed of thermal decomposition are accelerated, plus LN2Peel off fully, peelable number of times is fewer, but low yield, therefore, peel off Bulk g-
C3N4Quality minimum cannot be below 3g.Step (1) and (2) are by controlling TE-LN2Number of times and last TE samples are peeled off in gasification
Quality, it is controllable to obtain individual layer g-C3N4.Such as weigh 0.45g 580-TE-LN2(5)g-C3N4Thin slice carries out 580 DEG C of TE again,
Average thickness then be can obtain for 0.68nm monoatomic layers g-C3N4.But 580 DEG C of TE-LN2The number of times peeled off gasify no more than 5 times,
Otherwise will be without product, and the quality of last TE samples can not be more than 0.45g, otherwise cannot get individual layer g-C3N4.In identical peel strip
Under part, the amount of last TE samples 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 the LN of environmental protection2, joined by simply repeatedly TE
Close LN2The method of rapid gasification cooling is to Bulk g-C3N4Peeled off.The g-C under conditions of TE3N4Interlamellar spacing increase, LN2
It is quickly interspersed to enter g-C3N4Interlayer, and gasify rapidly, reach stripping g-C3N4Effect.
Compared with prior art, it is an advantage of the invention that：Using having that cheap, nontoxic stripping reagent substitution is generally used
Machine reagent ultrasound stripping means, makes preparation g-C3N4Superthin section process is fast, cost is low, environmental protection, it is adaptable to the extensive system of industrialization
It is standby.It the method overcome existing g-C3N4The shortcomings of ultra-thin piece preparation method, have found a low cost and prepare individual layer g-
C3N4" green " route.The g-C prepared by method of the present invention3N4Superthin section is photochemical catalyst, using visible ray as light
Source, it is adaptable to the degraded of environmental organic pollutant, at the same time as the sensor of environmental hormone tetrabromobisphenol A in water.
Brief description of the drawings
Fig. 1 is the g-C obtained by different stripping conditions3N4Superthin section atomic force microscopy diagram；
Fig. 2 is the g-C obtained by different stripping conditions3N4Superthin section, Bulk g-C3N4, bare electrode containing 1 × 10- 5molL-1Tetrabromobisphenol A cyclic voltammogram；
Fig. 3 is the g-C obtained by different stripping conditions3N4Superthin section visible light photocatalytic degradation RhB schemes；
Fig. 4 is the g-C obtained by different stripping conditions3N4Superthin section energy diagram；
Fig. 5 is the g-C obtained by different stripping conditions3N4Superthin section fluorescence emission spectrum.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Embodiment 1
3.0g melamines are weighed in container, are put into Muffle furnace, by room temperature to 550 DEG C in air, are risen
Warm speed is 5 DEG C/min, after constant temperature 4h, naturally cools to room temperature and obtains yellow Bulk g-C3N4Product.
Embodiment 2
3.0g dicyanodiamines are weighed in container, are put into Muffle furnace, by room temperature to 550 DEG C in air, heating
Speed is 5 DEG C/min, after constant temperature 4h, naturally cools to room temperature and obtains yellow Bulk g-C3N4Product.
Embodiment 3
6.0g thiocarbamides are weighed in container, are put into Muffle furnace, by room temperature to 550 DEG C, heating rate in air
For 5 DEG C/min, after constant temperature 4h, naturally cool to room temperature and obtain yellow Bulk g-C3N4Product.
Embodiment 4
Weigh the gained 6.0g Bulk g-C of embodiment 13N4In container, it 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.Treat LN2Above-mentioned behaviour is repeated after being evaporated completely
Make 9 times, obtain g-C3N4, its atomic force microscopy diagram such as Fig. 1, wherein shown in (a), g-C as seen from the figure3N4Superthin section is big
Sheet, its average thickness is 2.8nm, about 8 atomic layers.
Embodiment 5
Weigh the gained 6.0g Bulk g-C of embodiment 13N4With in container, being placed in Muffle furnace, it is warming up to 20 DEG C/min
20min is kept in 580 DEG C, LN is poured into taking-up immediately2Until submergence sample.Treat LN2Aforesaid operations are repeated after being evaporated completely 4 times, obtained
To g-C3N4, its atomic force microscopy diagram such as Fig. 1, wherein shown in (c), as can be seen from the figure g-C3N4Superthin section substantially becomes
Fractionlet, its average thickness is 1.5nm, about 4 atomic layers.
Embodiment 6
Weigh the g-C of the preparation of 0.15g embodiments 43N4Thin slice is placed in Muffle furnace in container, is warming up to 20 DEG C/min
20min is kept in 550 DEG C, room temperature is naturally cooled to, g-C is obtained3N4, its atomic force microscopy diagram such as Fig. 1, wherein shown in (b),
As can be seen from the figure g-C3N4Superthin section substantially diminishes, and its average thickness is about 1.0nm, about 2 atomic layers.
Embodiment 7
Weigh the g-C of the preparation of 0.45g embodiments 53N4Thin slice is placed in Muffle furnace in container, is warming up to 20 DEG C/min
20min is kept in 580 DEG C, room temperature is naturally cooled to, g-C is obtained3N4, its atomic force microscopy diagram such as Fig. 1, wherein shown in (d),
As can be seen from the figure average thickness about 0.68nm, the about g-C of monoatomic layer are obtained3N4。
Embodiment 8
Weigh the gained 1.0g Bulk g-C of embodiment 23N4In container, it 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, LN is treated2Aforesaid operations are repeated after being evaporated completely 4 times, obtained
g-C3N4Average thickness is 10nm, about 30 layers.
Embodiment 9
Weigh the gained 1.0g Bulk g-C of embodiment 33N4In 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, LN is treated2Aforesaid operations are repeated after being evaporated completely 4 times, obtained g-C3N4It is average
Thickness is 4.2nm, about 12 layers.
Embodiment 10
Weigh the g-C of the preparation of 0.45g embodiments 93N4Superthin section is placed in Muffle furnace in container, is heated up with 20 DEG C/min
20min is kept into 580 DEG C, room temperature is naturally cooled to, obtains g-C3N4Average thickness is about 2.5nm, 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 polished is clear with sulfuric acid
Wash activation, then the μ L of drop coating 5 the obtained g-C of different stripping conditions3N4Superthin section decorating liquid, illumination is to dry.To 4mL pH=5.8
Phosphate buffer solution in add 1mL 10-5molL-1Tetrabromobisphenol A as prepare liquid, as a result see accompanying drawing 2.580-TE-LN2
(5+1),550-TE-LN2(10+1),580-TE-LN2And 550-TE-LN (5)2(10) modified electrode, its peak current is respectively
Bulk g-C3N41.4 times, 1.2 times, 1.1 times and 1.06 times.This method peels off obtained g-C3N4Superthin section is double to tetrabromo
Phenol A electro catalytic activities are significantly improved (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 containing 1 × 10-5molL-1Tetrabromobisphenol A
The cyclic voltammogram of solution)
Embodiment 12
Photocatalysis performance is tested
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-C3N4Superthin section energy diagram (see accompanying 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 accompanying 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 stripping3N4Lamella is thinning, due to quantum limitation effect, band gap increase, compared with Bulk g-C3N4
0.25eV, 0.23eV, 0.13eV and 0.09eV are added respectively, then light excites the photo-generate electron-hole redox ability of generation
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, its ultra-thin g-C3N4The fluorescence intensity of generation is substantially reduced.Use it for visible light photocatalytic degradation rhodamine B
(RhB).25mg photochemical catalyst is added to the μ gmL of 50mL 10-1RhB solution in 300W xenon lamp irradiation lights shine 20min.Knot
Fruit sees the (g-C obtained by different stripping conditions of accompanying drawing 33N4Superthin section photocatalytic degradation RhB curves).In 15min to RhB's
Degradation rate is up to 93.5%, 91.7%, 90.3%, and 78.0%, its degradation rate constant is respectively 0.235,0.185,
0.171 and 0.137min-1, compared to Bulk g-C3N40.00238min-1, 98 times, 77 times, 72 times and 58 are added respectively
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 are weighed3N4It is rapidly heated after carrying out thermal expansion 10-20min to 550~580 DEG C and takes in container
Go out, liquid nitrogen is added immediately to sample is submerged, LN is treated2Volatilization is finished, and repeats above step totally 5~10 times, obtains g-C3N4It is ultra-thin
Piece；
(2) preparation of the adjustable carbonitride superthin section of the atom number of plies：Weigh the g-C that 0.12~1.2g steps (1) are obtained3N4It is ultra-thin
Piece is rapidly heated in container to 550~580 DEG C of TE temperature, is naturally cooled to room temperature after the insulation 10-20min times, is obtained list
Atomic layer or multilayer g-C3N4。
2. the preparation method of the adjustable carbonitride superthin section of the atom number of plies as described in claim 1, it is characterised in that described
g-C3N4The preparation of superthin section：Rich nitrogen presoma is weighed first to be placed in container, is rapidly heated to 500~600 DEG C of insulation 4h, from
Room temperature so is cooled to, Bulk g-C are obtained3N4。
3. the preparation method of the adjustable carbonitride superthin section of the atom number of plies as described in claim 1, it is characterised in that step (1)
Described 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 1, it is characterised in that when described
Rich nitrogen presoma be thiocarbamide or dicyanodiamine, peel off obtain g-C3N4, its thickness is 2.5-10nm, and the number of plies is 7-30 layers；When
Described rich nitrogen presoma is melamine, peelable acquisition 1-8 layers of g-C3N4。
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