CN103254200B - C3N4 nanosheet with molecular-scale thickness as well as preparation method and application thereof - Google Patents
C3N4 nanosheet with molecular-scale thickness as well as preparation method and application thereof Download PDFInfo
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- CN103254200B CN103254200B CN201310190678.6A CN201310190678A CN103254200B CN 103254200 B CN103254200 B CN 103254200B CN 201310190678 A CN201310190678 A CN 201310190678A CN 103254200 B CN103254200 B CN 103254200B
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Abstract
The invention discloses a C3N4 nanosheet with a molecular-scale thickness as well as a preparation method and an application thereof, which belong to the technical fields of material preparation and photocatalysis. The C3N4 nanosheet photocatalyst with a molecular-scale thickness disclosed by the invention is prepared in a water/ethanol mixed system via an ultrasonic treatment-stirring combination method. The preparation method of the catalyst comprises the following two steps of: step 1, synthesising a bulk-phase C3N4 precursor via a solid-phase thermal polymerization method; and step 2, stripping via ultrasonic treatment-stirring combination to prepare the C3N4 nanosheet. The C3N4 nanosheet photocatalyst prepared by the preparation method is high in specific surface area and photon-generated carrier separation efficiency, capable of efficiently degrading organic pollutants, and particularly efficiently decolouring printing and dyeing wastewater, and high in activity in the aspects of hydrogen production from photocatalytic water splitting and photocatalytic selective oxidation for alcohols simultaneously. The catalyst is simple in preparation process, low in cost, green and environment-friendly in production process, high in stability, capable of meeting actual production needs, and high in application potential.
Description
Technical field
The invention belongs to material preparation and photocatalysis technology field, be specifically related to a kind of C of molecular level thickness
3n
4nanometer sheet and the preparation method and application in water/ethanol mixed system thereof.
Background technology
Photocatalysis technology, because its reaction is thorough, reaction conditions is gentle, have the advantages such as redox ability concurrently, develops rapidly in recent years as a kind of new technology utilizing sun power to carry out environmental purification and energy conversion, becomes study hotspot of greatest concern at present.But still there is problem in science such as key core such as quantum yield low grade in conductor photocatalysis at present, makes it develop and be subject to very big restriction.And the key solved still is on photocatalyst, therefore, Chinese scholars has done a large amount of exploration work in the photo-quantum efficiency improving photocatalyst: as, in the modification, modification etc. of titanium dioxide optical catalyst, do a large amount of explorations and achieved certain progress, simultaneously the also novel non-titanium dioxide optical catalyst of active development.Although these research work have promoted photochemical catalysis development greatly, photocatalyst has increased for specific its quantum yield of reaction, in practical application the activity of catalyzer and stability still undesirable.Therefore find and the efficient photocatalyst of development of new, remain current and even research focus in the quite a long period from now in photocatalysis field.
In the various new photocatalyst material developed, nonmetal organic polymer semiconductor--graphite phase carbon nitride because its raw material sources are extensive, stability is high, there is suitable energy band structure, be considered to the up-and-coming photocatalyst of a class to visible light-responded etc., be applied in visible light photocatalysis hydrogen production by water decomposition and organism conversion, realize the conversion of sun power to chemical energy.But the carbon nitride photocatalyst of the body phase reported also exists some intrinsic defects, makes its photocatalytic activity lower.At present, the carbonitride of body phase is mainly prepared by the solid-phase synthesis of high temperature, high pressure, and this makes prepared sample there is a large amount of boundary defects, and the Interface composites causing photo-generated carrier is serious.Although some investigators by exploitation mesoporous carbonitride (
energy Environ. Sci. 2011,4,4668-4674), nonmetal doping modification (Angew. Chem. Int. Ed.2010
,
49, 441-444;
j. Am. Chem. Soc.2010
,
132, 11642-11648) change the energy band structure of carbonitride and strengthen its absorbing properties, and then improve its photocatalytic activity, but the quantum yield of carbonitride is still quite low.
Research shows, the two-dimensional nano sheet of molecular level thickness (0.5-3 nm) has high electric conductivity and photoresponse due to quantum size effect and surface tissue effect, photo-generated carrier separation rate is high, and the avtive spot of superelevation exposes ratio (close to 100%), large specific surface area.Therefore, if the two-dimensional nano sheet that carbon nitride photocatalyst exploitation can be prepared into molecular level thickness effectively will solve above-mentioned carbon nitride photocatalyst Problems existing, its photocatalysis performance will be improved greatly.Based on this thinking, had been found that some carbonitride two-dimensional nano sheets show excellent photocatalytic activity in photolysis water hydrogen, as Liu etc. (
adv. Funct. Mater.2012,
22, 4763-4770) and utilize the method for heat etching to prepare carbonitride two-dimensional nano sheet, its photocatalytic water H2-producing capacity improves 4.4 times, and the life-span of the photo-generated carrier of 70% is extended.Although this method technique is simple, also there is a lot of problem, as controllability is not strong, the nanometer sheet of preparation is thicker, productive rate very low (<6%).Xie(
j. Am. Chem. Soc. 2012,135,18-21) and Yang(Adv. Mater.2013,
25, 2452-2456) etc. adopt liquid phase method, in single water, Virahol, methane amide, acetone equal solvent, the body phase carbon nitride of commodity is made carbonitride two-dimensional nano sheet.The visible ray photocatalytic water ability of prepared azotized carbon nano sheet is effectively strengthened.Although the method that they grow up can prepare azotized carbon nano sheet, the key issues such as the nanometer sheet turbid liquid concentration prepared low (≤0.15 mg/mL), lamellar spacing large (>=3 nm), productive rate are low are still unresolved.
Summary of the invention
The object of the present invention is to provide a kind of C of molecular level thickness
3n
4nanometer sheet and its preparation method and application, solves and prepares C at present
3n
4the problems such as the charge stripping efficiency that nanometer sheet exists is low, turbid liquid concentration is too low, nanometer sheet productive rate is low, toxic organic solvent use.The C of molecular level thickness of the present invention
3n
4nanometer sheet, the separation efficiency of photo-generated carrier is high, all shows very high photocatalytic activity in fields such as photochemical catalysis wastewater treatment, photocatalytic water and selective oxidation alcohols.This preparation method is simple, production process environmental protection, the equipment not needing complex and expensive, synthesis condition are gentle, and cost is low, and catalyst stability is good, has larger application potential.
For achieving the above object, the present invention adopts following technical scheme:
A kind of C of molecular level thickness
3n
4nanometer sheet is graphite-phase C
3n
4organic polymer semiconductor, its specific surface area is 50-300 m
2/ g, sheet thickness is 0.5-3 nm, and length and width are 100-2000 nm, and energy gap is greater than 2.8 eV, effectively can be separated photo-generated carrier.
Prepare the C of molecular level thickness as above
3n
4the method of nanometer sheet is the C of the stratiform obtained with trimeric cyanamide thermopolymerization
3n
4for precursor, in water/ethanol mixed system by ultrasonic-stir the method that combines and prepare the C that concentration is the molecular level thickness of 0.3-3 mg/mL
3n
4nanometer sheet suspension liquid, obtains C finally by centrifugal means
3n
4nanometer sheet pressed powder.Comprise the following steps: (1) gets the trimeric cyanamide of 1-20 g in crucible, be placed in retort furnace 550 DEG C calcining 4 h, prepare the stratiform C of body phase
3n
4presoma; (2) the stratiform C of 0.2-1 g body phase is got
3n
4presoma puts into 500 mL beakers, adds the deionized water of 20-150 mL and the ethanol of 10-205 mL, then first ultrasonication 1-6 h in beaker, rear stirring 0.5-24 h, ultrasonication 1-6 h again, finally centrifugal with the rotating speed of 3000 revs/min, remove the C of stratiform
3n
4precipitation, obtains the C of the molecular level thickness of high density
3n
4nanometer sheet suspension liquid, finally obtains the C of molecular level thickness under 10000 revs/min of high speed centrifugations
3n
4nanometer sheet.
The C of described molecular level thickness
3n
4nanometer sheet is used for degradation of contaminant, particularly to the efficient decolorizing of dyeing waste water as photocatalyst; Or be applied to photolysis water hydrogen and photocatalysis to selectively oxidize alcohols.
Remarkable advantage of the present invention is:
(1) the present invention utilizes water/alcohol mixed solvent first, the stripping means combined by ultrasonication-stirring, prepares the C of the molecular level thickness of high density
3n
4nanometer sheet, prepared nanometer sheet has large specific surface area, and photo-generated carrier such as to be effectively separated at the feature.
(2) compared with the method for bibliographical information, the solvent environment that the present invention uses is friendly, and the nanometer sheet turbid liquid concentration prepared is high, and nanometer sheet productive rate is high, avoids the use of toxic organic solvents, and obtained nanometer sheet size uniform, size is adjustable, and thickness is less.
(3) whole technological process of the present invention is simple and easy to control, production process environmental protection, and energy consumption is low, and do not need the equipment of complex and expensive, synthesis condition gentle, cost is low, and catalyst stability is good, has larger application potential.
(4) C of molecular level thickness
3n
4nanometer sheet can photocatalysis treatment dyeing waste water, photodissociation aquatic products hydrogen and selective oxidation alcohols etc. efficiently, has good activity stability simultaneously.In light-catalyzed reaction system, photocatalyst renewable is strong, and repeating utilization factor is high, has very high practical value and application prospect.
Accompanying drawing explanation
Fig. 1 is the C of molecular level thickness
3n
4the preparation flow schematic diagram of nanometer sheet.
Fig. 2 is the C of the molecular level thickness of embodiment 1 gained
3n
4the X-ray powder diffraction figure (XRD) of nanometer sheet.
Fig. 3 is the C of the molecular level thickness of embodiment 1 gained
3n
4the atomic power flying-spot microscope figure (AFM) of nanometer sheet.
Fig. 4 is the C of the molecular level thickness of embodiment 1 gained
3n
4the C of nanometer sheet, stratiform
3n
4with commodity TiO
2to the degradation effect comparison diagram of RhB.
Embodiment
Be below several embodiments of the present invention, further illustrate the present invention, but the present invention is not limited only to this.
embodiment 1
First be body phase C
3n
4the preparation of presoma, the trimeric cyanamide taking 15 g, in crucible, is placed in retort furnace 550 DEG C calcining 4 h, for subsequent use after grinding; By the body phase C of 0.5 g in beaker
3n
4presoma adds the deionized water of 90 mL and the ethanol of 105 mL, then beaker is placed in ultrasonic 4 h of ultrasonic machine, after beaker be placed in agitator stir 14 h, ultrasonic 4 h again, obtain suspension liquid, centrifugal under the rotating speed of 3000 revs/min, remove precipitation, last again under the high speed centrifugation of 10000 revs/min, the C of molecular level thickness can be obtained
3n
4nanosheet photocatalyst.
embodiment 2
First be body phase C
3n
4the preparation of presoma, the trimeric cyanamide taking 10 g, in crucible, is placed in retort furnace 550 DEG C calcining 4 h, for subsequent use after grinding; By the body phase C of 0.3 g in beaker
3n
4presoma adds the deionized water of 60 mL and the ethanol of 70 mL, then beaker is placed in ultrasonic 4 h of ultrasonic machine, after beaker be placed in agitator stir 5 h, ultrasonic 4 h obtain suspension liquid again, centrifugal under the rotating speed of 3000 revs/min, remove precipitation, finally again under the high speed centrifugation of 10000 revs/min, the C of molecular level thickness can be obtained
3n
4nanosheet photocatalyst.
embodiment 3
First be body phase C
3n
4the preparation of presoma, the trimeric cyanamide taking 15 g, in crucible, is placed in retort furnace 550 DEG C calcining 4 h, for subsequent use after grinding; By the body phase C of 1.0 g in beaker
3n
4presoma adds the deionized water of 90 mL and the ethanol of 105 mL, then beaker is placed in ultrasonic 5 h of ultrasonic machine, after beaker be placed in agitator stir 14 h, ultrasonic 3 h again, obtain suspension liquid, centrifugal under the rotating speed of 3000 revs/min, remove precipitation, last again under the high speed centrifugation of 10000 revs/min, the C of molecular level thickness can be obtained
3n
4nanometer sheet glue photocatalyst.
The C of molecular level thickness can be found from Fig. 2
3n
4the XRD diffraction peak of nanometer sheet significantly weakens and even disappears, and the C of body phase is described
3n
4the nanometer sheet of successful coverlet molecular layers thick.The C of prepared molecular level thickness can be found from Fig. 3
3n
4the thickness of nanometer sheet is about 1 nm.
The C of molecular level thickness
3n
4nanometer sheet photocatalysis performance is tested, and characterizes under irradiating at xenon lamp to the degraded of RhB.Adopt batch reactor, be about the RhB of 10 ppm with concentration for reaction substrate.Using the xenon lamp of 300 W as light source, the consumption of catalyzer is 0.04 g.Before reaction of turning on light, absorption in advance makes RhB turn on light illumination after adsorption-desorption balance on a catalyst.As can be seen from Figure 4, after the illumination 70min that turns on light, the C of molecular level thickness
3n
4nanosheet photocatalyst to the degradation rate of RhB up to 100%.By contrast, body phase C
3n
4catalyzer is low to the degradation efficiency of RhB in 90 min light application times.More also obviously can find out that the azotized carbon nano piece performance of the molecular level thickness that the present invention prepares is more excellent with the titanium dioxide of commodity simultaneously.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (2)
1. the C of a molecular level thickness
3n
4the preparation method of nanometer sheet, is characterized in that: described C
3n
4nanometer sheet is graphite-phase C
3n
4organic polymer semiconductor;
Described C
3n
4the specific surface area of nanometer sheet is 50-300 m
2/ g, sheet thickness is 0.5-1nm, and length and width are 100-2000 nm, and energy gap is greater than 2.8 eV, effectively can be separated photo-generated carrier;
The C of the stratiform obtained with trimeric cyanamide thermopolymerization
3n
4for precursor, in water/ethanol mixed system by ultrasonic-stir the method that combines and prepare the C that concentration is the molecular level thickness of 0.3-3 mg/mL
3n
4nanometer sheet suspension liquid, obtains C finally by centrifugal means
3n
4nanometer sheet pressed powder.
2. the C of molecular level thickness according to claim 1
3n
4the preparation method of nanometer sheet, is characterized in that: comprise the following steps:
(1) trimeric cyanamide getting 1-20 g, in crucible, is placed in retort furnace 550 DEG C calcining 4 h, prepares the stratiform C of body phase
3n
4presoma;
(2) the stratiform C of 0.2-1 g body phase is got
3n
4presoma puts into 500 mL beakers, adds the deionized water of 20-150 mL and the ethanol of 10-205 mL, then first ultrasonication 1-6 h in beaker, rear stirring 0.5-24 h, ultrasonication 1-6 h again, finally centrifugal with the rotating speed of 3000 revs/min, remove the C of stratiform
3n
4precipitation, obtains the C of the molecular level thickness of high density
3n
4nanometer sheet suspension liquid, finally obtains the C of molecular level thickness under 10000 revs/min of high speed centrifugations
3n
4nanometer sheet.
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| CN201310190678.6A CN103254200B (en) | 2013-05-22 | 2013-05-22 | C3N4 nanosheet with molecular-scale thickness as well as preparation method and application thereof |
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| CN201310190678.6A CN103254200B (en) | 2013-05-22 | 2013-05-22 | C3N4 nanosheet with molecular-scale thickness as well as preparation method and application thereof |
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| CN103254200B true CN103254200B (en) | 2015-06-03 |
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| CN103787290B (en) * | 2014-01-16 | 2016-01-20 | 大连民族学院 | Based on intercalation configuration C 3n 4nanometer sheet high-performance humidity-sensitive material and preparation method |
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| CN105925954B (en) * | 2016-05-27 | 2020-04-14 | 清华大学 | Preparation method of semiconductor carbon nitride film |
| 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 |
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| CN112717973A (en) * | 2020-11-16 | 2021-04-30 | 中北大学 | Preparation of rod-like g-C by microwave hydrothermal method3N4Method and application of nanosheet |
| CN113321818A (en) * | 2021-05-11 | 2021-08-31 | 中山大学 | Composite hydrogel and preparation method and application thereof |
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