CN109650357A - A kind of method of the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour - Google Patents
A kind of method of the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 238000000034 method Methods 0.000 title claims abstract description 119
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 66
- 238000005530 etching Methods 0.000 title claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 73
- 239000010439 graphite Substances 0.000 claims abstract description 73
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 44
- 239000006260 foam Substances 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 35
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011261 inert gas Substances 0.000 claims abstract description 14
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 40
- 230000008569 process Effects 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 238000002791 soaking Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002957 persistent organic pollutant Substances 0.000 claims description 5
- 238000005538 encapsulation Methods 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims 1
- 230000031700 light absorption Effects 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 229920000877 Melamine resin Polymers 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000002135 nanosheet Substances 0.000 description 5
- 238000005286 illumination Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 229910017435 S2 In Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
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- 239000002341 toxic gas Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C01B21/076—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 with titanium or zirconium or hafnium
- C01B21/0768—After-treatment, e.g. grinding, purification
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- 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
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- 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
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- 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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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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Abstract
The present invention provides a kind of method of hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour; this method is using melamine as persursor material; blocky graphite phase carbon nitride is first prepared with high-temperature polycondensation method; then blocky graphite phase carbon nitride powder is wrapped up with nickel foam; using nickel foam as metal vapor source; it is heat-treated using inert gas shielding; prepare amorphous state azotized carbon nano piece; nanometer sheet thickness is 4~6nm; amorphous structure is showed, there is good light absorption in visible-range.Preparation method time-consuming provided by the invention is short, and technique is advanced, simple and effective, and the amorphous state azotized carbon nano piece of preparation has ultra-thin structure and good light absorption, is applied and shows good performance during photocatalysis degradation organic contaminant.
Description
Technical field
The invention belongs to the technical fields of catalysis material preparation and application, and in particular to a kind of hot etching method of metallic vapour
The method for preparing amorphous state azotized carbon nano piece.
Background technique
With the fast development of modern industrialization, demand of the people to the energy increasingly increases, and consumes a large amount of coal, stone
The non-renewable fossil fuel such as oil, natural gas, and give off CO2、SO2、NOxIsothermal chamber gas and toxic gas cause serious
Energy crisis and environmental pollution the problems such as.The efficient conversion and storage benefit of solar energy may be implemented in Photocatalitic Technique of Semiconductor
With, drive important chemical reaction in a mild condition, solve energy shortage and in terms of show it is huge latent
Power.Traditional semiconductor light-catalyst is opened because broad-band gap and low the efficiency of solar energy utilization seriously limit their application
It issues while there is high-quantum efficiency, high visible utilization rate, high stability and cheap novel photocatalyst to become current light
The research hotspot of catalytic field.Wherein, graphite phase carbon nitride (g-C3N4) it is used as a kind of novel metalloid polymer semiconductor material
Material, causes the extensive concern of people.From 2009, related scholar reported g-C for the first time3N4Water can be decomposed under visible light illumination
Since hydrogen manufacturing, g-C3N4Because of its unique semiconductor energy band structure and excellent chemical stability, as a kind of visible light photocatalysis
Agent is introduced in photocatalysis field, produces oxygen, the organic selectivity synthesis of photocatalysis, the organic dirt of photocatalytic degradation for photodissociation aquatic products hydrogen
Contaminate object etc..
However, due to the material property of polymer, by g-C3N4It there is also some problems as photochemical catalyst, such as specific surface
The compound serious, quantum efficiency of the small, photo-generate electron-hole of product is low and forbidden bandwidth is larger and cannot efficiently use sunlight etc., sternly
Recasting about its large-scale promotion application in the energy, environmental photocatlytsis field.In order to improve g-C3N4Photocatalysis performance, to it
A large amount of study on the modification work is carried out.Due to g-C3N4It is a kind of lamellar compound, there is strong C-N covalent bond in face, in layer
Between there is weak Van der Waals force, therefore by blocky g-C3N4Removing is that stratiform is reasonable.Obtained two-dimentional g-C3N4Nanometer sheet
Specific surface area with higher, accelerates electron-transport, reduces the compound of quantity of photogenerated charge carrier, enhances redox energy
Power, to be conducive to light-catalyzed reaction.However, g-C3N4Nanometer sheet is not still able to satisfy the requirement of high catalytic activity, amorphous state nitrogen
Change carbon nanosheet and g-C3N4Nanometer sheet is compared, and richer active site can be provided, be conducive to light-catalyzed reaction into
Row, to improve the photocatalytic activity of carbon nitride material.
In general, the method for synthesis nitridation carbon nanosheet has the removing of ultrasonic wave added liquid, thermal oxide etching etc., although can obtain
The higher azotized carbon nano piece of specific surface area is obtained, but these preparation methods have time-consuming, inefficient and low light absorpting ability etc.
Inherent defect, it is therefore desirable to the method for developing a kind of preparation amorphous state azotized carbon nano piece of high-efficient simple.
Accordingly, it is desirable to provide a kind of be directed to the insufficient improved technology scheme of the above-mentioned prior art.
Summary of the invention
The purpose of the present invention is to provide a kind of method of metallic vapour hot etching method preparation amorphous state azotized carbon nano piece,
It solves the disadvantage that removing at present and thermal oxide lithographic method time-consuming, low yield, while improving the light absorpting ability of material.This hair
Bright preparation method time-consuming is short, simple process, and the amorphous state azotized carbon nano piece of preparation has ultra-thin structure and good
Light absorption, for degradable organic pollutant under visible light illumination.
To achieve the goals above, the invention provides the following technical scheme:
A kind of method of the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour, the preparation method of the nanometer sheet
The following steps are included:
The preparation of S1, blocky graphite phase carbon nitride
S11, graphite phase carbon nitride is prepared using high-temperature polycondensation method；
S12, graphite phase carbon nitride obtained in step s11 is ground, is then sieved with sieve, is ground up, sieved anti-
It is multiple to carry out, evengranular blocky graphite phase carbon nitride powder is obtained, is collected spare；
The preparation of S2, heat treated sample
Blocky graphite phase carbon nitride powder obtained in step s12 is uniformly layered on nickel foam piece top, it then will be another
Foam nickel sheet is placed on the top of blocky graphite phase carbon nitride powder, the foam of position and lower part that another foam nickel sheet is placed
Nickel sheet parallel alignment, is then compacted, and heat treated sample is made；
The preparation of S3, amorphous state azotized carbon nano piece
Heat treated sample obtained in step S2 is laid flat in heatproof container, is then placed in high temperature furnace, it is closed, it extracts
Then furnace air is passed through inert gas into high temperature furnace, make invariablenes pressure of liquid in furnace, be then heat-treated, to natural cooling
To room temperature, stopping is passed through gas, and sample is taken out from high temperature furnace, tears two panels foam nickel sheet, collects pale yellow powder, obtains
To amorphous state azotized carbon nano piece, encapsulation is saved.
In the method for the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour as described above, it is preferable that step s11
Described in graphite phase carbon nitride the preparation method comprises the following steps: melamine powder is put into heatproof container, heatproof container is put into height
It is heat-treated in warm furnace, product is taken out from high temperature furnace, obtains graphite-phase by cooled to room temperature after keeping the temperature a period of time
Carbonitride.
In the method for the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour as described above, it is preferable that step s11
The additional amount of the melamine powder of middle addition is the 1/2~5/6 of heatproof container capacity.
In the method for the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour as described above, it is preferable that step s11
In the heating temperature that is heat-treated in the high temperature furnace be 520~600 DEG C, soaking time is 2~4h, heating rate 3
~5 DEG C/min；
Preferably, the heating temperature being heat-treated in the high temperature process furnances is 550 DEG C, soaking time 2h, is risen
Warm rate is 4 DEG C/min.
In the method for the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour as described above, it is preferable that step S2
The length and width of middle two panels foam nickel sheet and high size are all the same.
In the method for the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour as described above, it is preferable that step S2
In be layered on nickel foam on piece blocky graphite phase carbon nitride powder quality be 30~100mg/cm2；
Preferably, the quality for being layered on the blocky graphite phase carbon nitride powder of nickel foam on piece is 50mg/cm2。
In the method for the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour as described above, it is preferable that step S3
The middle inert gas being passed through into the high temperature furnace is argon gas；
Preferably, the rate that is passed through that inert gas is passed through into high temperature furnace is 100~120cm3/ min, invariablenes pressure of liquid in furnace
In 0.101MPa.
In the method for the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour as described above, it is preferable that step S3
In the heating temperature that is heat-treated in the high temperature furnace be 520~580 DEG C, soaking time is 2~4h, heating rate 3
~5 DEG C/min；
Preferably, the heating temperature being heat-treated in the high temperature process furnances is 550 DEG C, soaking time 2h, is risen
Warm rate is 4 DEG C/min.
A kind of amorphous state nitridation that the method with the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour is prepared
Carbon nanosheet.
A kind of amorphous state nitridation that the method with the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour is prepared
The application of carbon nanosheet, the amorphous state azotized carbon nano piece are applied to degradable organic pollutant under visible light illumination.
Compared with the immediate prior art, technical solution provided by the invention has following excellent effect:
The present invention is the physical and chemical performance and structure feature according to graphite phase carbon nitride, using melamine as presoma material
Material, nickel foam is metal vapor source, carries out high-temperature heat treatment using inert gas shielding, allows layer structure in the effect of nickel steam
Lower etching is separated into two-dimensional nano chip architecture, and nanometer sheet has ultra-thin pattern, while showing amorphous structure, to make
Standby amorphous state azotized carbon nano piece out.Preparation method time-consuming provided by the invention is short, simple process, the amorphous state carbonitride of preparation
Nanometer sheet has ultra-thin structure and good light absorption, shows during photocatalysis degradation organic contaminant good
Performance.Preparation method technique provided by the present invention is advanced, is a kind of preparation amorphous state azotized carbon nano piece of simple and effective
Method.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.Wherein:
Fig. 1 is the blocky graphite phase carbon nitride condition of heat treatment schematic diagram under inert gas protection of the embodiment of the present invention；
Fig. 2 is the schematic diagram of the heat treated sample of the embodiment of the present invention；
Fig. 3 is the scanning electron microscope (SEM) photograph and amorphous state azotized carbon nano piece of the blocky graphite phase carbon nitride of the embodiment of the present invention
(a is the scanning electron microscopic picture of blocky graphite phase carbon nitride in figure, and b is amorphous state nitrogen for scanning electron microscope (SEM) photograph, high-resolution-ration transmission electric-lens figure
Change the scanning electron microscopic picture of carbon nanosheet, c is the transmission electron microscope picture of amorphous state azotized carbon nano piece, and d is amorphous state carbonitride
The high resolution TEM picture of nanometer sheet)；
Fig. 4 is the blocky graphite phase carbon nitride of the embodiment of the present invention and the atomic force microscope of amorphous state azotized carbon nano piece
(a and b is the atomic force microscope images of blocky graphite phase carbon nitride to figure in figure, and c and d are amorphous state azotized carbon nano piece
Atomic force microscope images)；
Fig. 5 is the blocky graphite phase carbon nitride of the embodiment of the present invention and the ultraviolet-visible light of amorphous state azotized carbon nano piece
Absorb map；
Fig. 6 is the transmission electron microscope picture of the azotized carbon nano piece of reference examples 2 of the present invention.
In figure: 1, electric cabinet；2, display screen；3, indicator light；4, power switch；5, heating temperature control；6, vacuum pump
Controller；7, high temperature process furnances；8, bell；9, outlet pipe valve；10, workbench；11, alumina crucible；12, heat treated sample；
13, argon bottle；14, argon gas valve；15, tunger tube；16, argon gas；17, vacuum pump；18, vacuum valve；19, vacuum tube；20, conducting wire；
21, foam nickel sheet；22, blocky graphite phase carbon nitride powder.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff's every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention will be described in detail below with reference to the accompanying drawings and embodiments.It should be noted that in the feelings not conflicted
Under condition, the feature in embodiment and embodiment in the present invention be can be combined with each other.
The present invention provides a kind of methods of the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour, according to graphite
The physical and chemical performance and structure feature of phase carbon nitride pass through high-temperature polycondensation legal system first using melamine as persursor material
It is standby to obtain blocky graphite phase carbon nitride, then blocky graphite phase carbon nitride powder is pressed between two panels foam nickel sheet, is most passed through afterwards
Inert gas shielding in high temperature furnace is crossed to make annealing treatment to obtain amorphous state azotized carbon nano piece.Since the weak Van der Waals force of interlayer is insufficient
To resist the saturated vapor pressure of metal at high temperature, therefore layer structure etches under the action of nickel steam and is separated into two-dimensional nano
Chip architecture, while strong covalent bond of the nickel steam also in opposite generates certain influence makes nanometer sheet show a kind of amorphous
Structure, to prepare amorphous state azotized carbon nano piece.Preparation method technique provided by the present invention is advanced, is a kind of easy to be high
The method of the preparation amorphous state azotized carbon nano piece of effect.
The azotized carbon nano piece prepared in the present invention is presented ultra-thin amorphous state two-dimensional structure, and nanometer sheet thickness is 4~
6nm effectively improves the specific surface area of graphite phase carbon nitride, and the preparation method time-consuming is short, and simple process avoids biography
System method time-consuming, inefficient disadvantage, meanwhile, the nanometer sheet of preparation has good light absorpting ability, in photocatalytic degradation industry
It has a good application prospect in terms of organic pollutant in waste water.
A kind of method of the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour provided by the invention, including it is following
Step:
The preparation of S1, blocky graphite phase carbon nitride
S11, melamine powder is put into heatproof container, heatproof container is put into high temperature furnace and is heat-treated, so
Product is taken out from high temperature process furnances, obtains graphite phase carbon nitride by cooled to room temperature afterwards；
The additional amount of melamine powder is the 1/2~5/6 of heatproof container capacity in heatproof container in step s11.
The heating temperature being heat-treated in high temperature furnace in step s11 be 520~600 DEG C (such as 520 DEG C, 530 DEG C,
540 DEG C, 550 DEG C, 560 DEG C, 570 DEG C, 580 DEG C, 590 DEG C, 600 DEG C), soaking time be 2~4h (such as 2h, 2.5h, 3h,
3.5h, 4h), heating rate be 3~5 DEG C/min (such as 3 DEG C/min, 3.5 DEG C/min, 4 DEG C/min, 4.5 DEG C/min, 5 DEG C/
min)。
Preferably, the heating temperature being heat-treated in high temperature furnace is 550 DEG C, soaking time 2h, heating rate 4
℃/min。
S12, the graphite phase carbon nitride after heat treatment is ground, is then sieved with sieve, be ground up, sieved repeatedly into
Row obtains evengranular blocky graphite phase carbon nitride powder 22, collects spare.
Preferably, heatproof container is alumina crucible with cover.
It is the corundum crucible with cover of 50 × 20 × 20mm used in the present invention, the melamine powder quality of addition is suitable
In, it is 3~5g (such as 3g, 3.5g, 4g, 4.5g, 5g) that quality, which is added, in melamine powder；Preferably, melamine powder
Quality is 3g, and the ratio that the melamine powder amount of addition occupies corundum crucible capacity is 50%, melamine powder quality mistake
Few yield is too low, and excessively then heatproof container Sheng fails to lay down.
The preparation of S2, heat treated sample
Blocky graphite phase carbon nitride powder 22 obtained in step s12 is uniformly layered on 21 top of foam nickel sheet, then will
Another foam nickel sheet 21 is placed on 22 top of blocky graphite phase carbon nitride powder, and is aligned with the foam nickel sheet 21 of lower part, then presses
It is real, heat treated sample is made.
The quality that the blocky graphite phase carbon nitride powder 22 on nickel foam piece 21 is layered in step S2 is 30~100mg/cm2
(such as 30mg/cm2、40mg/cm2、50mg/cm2、60mg/cm2、70mg/cm2、80mg/cm2、90mg/cm2、100mg/cm2)；
Preferably, the quality for being layered on the blocky graphite phase carbon nitride powder 22 in foam nickel sheet 21 is 50mg/cm2。
More preferably, the length and width of two panels foam nickel sheet 21 and high size are all the same in step S2, and upper and lower two panels is steeped
Foam nickel sheet 21 is compacted, and is come into full contact with them, is prevented two panels foam nickel sheet when high-temperature heat treatment from separating, influence product
Quality.
The preparation of S3, amorphous state azotized carbon nano piece
Heat treated sample obtained in step S2 is laid flat in heatproof container, is then placed in high temperature furnace, it is closed, it extracts
Then furnace air is passed through inert gas into furnace with certain rate, make invariablenes pressure of liquid in furnace, be heat-treated, to nature
After being cooled to room temperature, stopping is passed through gas, and sample is taken out from high temperature process furnances, tears two panels foam nickel sheet 21, collects light
Yellow powder, obtains amorphous state azotized carbon nano piece, and encapsulation saves.
The inert gas being passed through in step S3 into high temperature furnace is argon gas, and the rate being passed through is 100~120cm3/ min (ratio
Such as 100cm3/min、102cm3/min、104cm3/min、106cm3/min、108cm3/min、110cm3/min、112cm3/min、
114cm3/min、116cm3/min、118cm3/ min), invariablenes pressure of liquid is in 0.101MPa in furnace.
The heating temperature being heat-treated in high temperature furnace in step S3 be 520~580 DEG C (such as 520 DEG C, 530 DEG C,
540 DEG C, 550 DEG C, 560 DEG C, 570 DEG C, 580 DEG C), soaking time is 2~4h (such as 2h, 2.5h, 3h, 3.5h, 4h), heating speed
Rate is 3~5 DEG C/min (such as 3 DEG C/min, 3.5 DEG C/min, 4 DEG C/min, 4.5 DEG C/min, 5 DEG C/min)；Preferably, in high temperature
The heating temperature being heat-treated in furnace is 550 DEG C, soaking time 2h, and heating rate is 4 DEG C/min.
What a kind of method of the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour provided by the invention was prepared
Amorphous state azotized carbon nano piece has ultra-thin structure and good light absorpting ability, can be applied to drop under visible light illumination
Solve organic pollutant.
Embodiment 1
A kind of method of the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour provided by the invention, including it is following
Step:
The preparation of S1, blocky graphite phase carbon nitride
S11, melamine powder 3g is put into alumina crucible with cover, crucible is put into high temperature process furnances, heated
550 DEG C of temperature, 2h, 4 DEG C/min of heating rate are kept the temperature, then cooled to room temperature, product is taken out from high temperature process furnances；
S12, the graphite phase carbon nitride after heat treatment is ground with agate mortar, is then sieved, is ground with 300 mesh screens
Mill, sieving are repeated, and obtain evengranular blocky graphite phase carbon nitride powder 22, collect spare.
The preparation of S2, heat treated sample
It is placed in the foam nickel sheet 21 of the 30mm*10mm*1.5mm cut is open and flat on pan paper, will be obtained in step s12
Blocky graphite phase carbon nitride powder 0.15g be uniformly layered on 21 top of foam nickel sheet, then by the nickel foam of another same size
Piece 21 is placed on 22 top of blocky graphite phase carbon nitride powder, and is aligned with the foam nickel sheet 21 of lower part, is then compacted, hot place is made
Manage sample.
The preparation of S3, amorphous state azotized carbon nano piece
Heat treated sample obtained in step S2 is laid flat in alumina crucible with cover, high temperature process furnances are then placed in
In, it is closed, furnace air is extracted, pressure in furnace is made to reach 2Pa, argon gas is then passed through into furnace, it is 100cm that argon gas, which is passed through rate,3/
Min is heat-treated invariablenes pressure of liquid in furnace in 0.101MPa, 550 DEG C of heating temperature, keeps the temperature 2h, 4 DEG C/min of heating rate,
Then cooled to room temperature, stopping are passed through gas, sample are taken out from high temperature process furnances, tears two panels foam nickel sheet, receive
Collect pale yellow powder, obtain amorphous state azotized carbon nano piece, encapsulation saves.
The pattern of blocky graphite phase carbon nitride and amorphous state azotized carbon nano piece to preparation, structure, absorbing properties into
Row test, analysis and characterization.
For blocky graphite phase carbon nitride, condition of heat treatment figure, each portion position are connected under inert gas protection as shown in Figure 1
Relationship correctly will be operated sequentially.The heat treatment of blocky graphite phase carbon nitride is carried out in high temperature process furnances 7, is to take out very
It is completed under empty, logical argon gas, heated condition.
High temperature process furnances 7 are vertical rectangle, and 7 top of high temperature process furnances is bell 8, and lower part is electric cabinet 1；High temperature process furnances
Bottom is equipped with workbench 10 in 7, places alumina crucible 11 on 10 top of workbench, heat treatment sample is placed in alumina crucible 11
Product 12；Outlet pipe valve 9 is equipped in 7 upper right quarter of high temperature process furnances；Argon bottle 13, argon bottle 13 are equipped in 7 left part of high temperature process furnances
Top is equipped with argon gas valve 14, tunger tube 15, and argon gas 16 is inputted into high temperature process furnances 7；It is equipped in 7 right part of high temperature process furnances true
Sky pump 17,17 top of vacuum pump is equipped with vacuum valve 18, vacuum tube 19, and is connected to 7 furnace chamber of high temperature process furnances；It is set on electric cabinet 1
There are display screen 2, indicator light 3, power switch 4, heating temperature control 5, controller for vacuum pump 6；Electric cabinet 1 by conducting wire 20 with
Vacuum pump 17 connects.
It is illustrated in figure 2 the schematic diagram of heat treated sample, blocky graphite phase carbon nitride powder 22 is uniformly layered on two panels
Between nickel foam 21, then two panels foam nickel sheet 21 is forced together.
It is as shown in Figures 3 to 6 respectively pattern, the knot to blocky graphite phase carbon nitride and amorphous state azotized carbon nano piece
Structure, light absorption can be carried out the picture obtained after test, analysis and characterization.
With scanning electron microscope and transmission electron microscope to blocky graphite phase carbon nitride and amorphous state azotized carbon nano
Piece carries out pattern and structural analysis obtains Fig. 3.As shown in figure 3, being blocky graphite phase carbon nitride and amorphous state azotized carbon nano piece
Microscopic appearance figure.Wherein figure a and figure b is respectively the SEM picture of blocky graphite phase carbon nitride and amorphous state azotized carbon nano piece,
As can be seen that figure a is the pattern of typical blocky graphite phase carbon nitride, layer structure is stacked with, and thickness is thicker, and it is non-to scheme b
Crystalline state azotized carbon nano piece shows ultra-thin two-dimensional nano piece pattern.Scheme c and schemes the TEM that d is amorphous state azotized carbon nano piece
With HRTEM picture, it can be seen that prepared nanometer sheet from figure c and show nearly transparent feature, show its ultra-thin thickness
Degree can be seen that the structure that nanometer sheet shows a kind of amorphous from figure d, can not observe apparent lattice fringe, show poor
Plane in crystallinity.
From in Fig. 3 c and d scheme it is found that azotized carbon nano piece prepared by the present invention shows ultra-thin two-dimensional nano piece shape
Looks and amorphous structure.
Thickness Analysis is carried out to blocky graphite phase carbon nitride and amorphous state azotized carbon nano piece with atomic force microscope to obtain
Fig. 4.As shown in figure 4, being the AFM picture of blocky graphite phase carbon nitride and amorphous state azotized carbon nano piece.Wherein figure a and figure b are
The AFM picture of blocky graphite phase carbon nitride, it can be seen that blocky graphite phase carbon nitride with a thickness of 104.62nm, scheme c and figure d be
The AFM picture of amorphous state azotized carbon nano piece, it can be seen that amorphous state azotized carbon nano piece with a thickness of 4.84nm.
From the c and d figure in Fig. 4 it is found that further showing that amorphous state azotized carbon nano piece prepared by the present invention is thick with data
Spending ultra-thin is only several nanometers.
With ultraviolet-visible spectrophotometer to the light absorption point of blocky graphite phase carbon nitride and amorphous state azotized carbon nano piece
Analysis obtains Fig. 5.As shown in figure 5, being the UV-Vis map of blocky graphite phase carbon nitride and amorphous state azotized carbon nano piece, can see
Out compared to blocky graphite phase carbon nitride, amorphous state azotized carbon nano piece has a better light absorption in visible-range.
Conclusion: the amorphous state azotized carbon nano piece as made from metallic vapour hot etching method is buff powder, is showed
Amorphous structure, with a thickness of 4~6nm, product purity is up to 99.9%.
Product storage
The amorphous state azotized carbon nano piece of preparation is stored in the vial of amber transparent, it is closed to be kept in dark place, to prevent
Damp, sun-proof, anti-acid-alkali salt corrodes, and 20 DEG C of storage temperature, relative humidity 10%.
Embodiment 2
The heating temperature being heat-treated in the high temperature process furnances in step s11 is changed to 520 in the present embodiment
DEG C, soaking time is changed to 3h, and other methods step is same as Example 1, and details are not described herein.
The pattern of the azotized carbon nano piece prepared in the present embodiment, structure are subjected to test, analysis and characterization, specific steps
It is same as Example 1 with method；The azotized carbon nano piece prepared in the present embodiment is buff powder, shows ultra-thin two dimension
Nanometer sheet pattern, nanometer sheet show a kind of structure of amorphous, can not observe apparent lattice fringe, show poor plane
Crystallinity, azotized carbon nano piece with a thickness of 4.92nm, equally compared to blocky graphite phase carbon nitride in visible-range
There is a good light absorption, the heating temperature of selection described above being heat-treated in the high temperature process furnances is in this hair
In bright scope of the claims, available thickness and the similar amorphous state azotized carbon nano piece of embodiment 1.
Embodiment 3
In the present embodiment more by the quality for the blocky graphite phase carbon nitride powder 22 being layered in step S2 on nickel foam piece 21
It is changed to 0.24g, other methods step is same as Example 1, and details are not described herein.
The pattern of the azotized carbon nano piece prepared in the present embodiment, structure are subjected to test, analysis and characterization, specific steps
It is same as Example 1 with method；The azotized carbon nano piece prepared in the present embodiment is buff powder, shows ultra-thin two dimension
Nanometer sheet pattern, nanometer sheet show a kind of structure of amorphous, can not observe apparent lattice fringe, show poor plane
Crystallinity is horizontal, azotized carbon nano piece with a thickness of 4.90nm, equally compared to blocky graphite phase carbon nitride in visible light model
There are a good light absorption, the matter of the blocky graphite phase carbon nitride powder for being layered on nickel foam on piece of selection described above in enclosing
It measures within the scope of the invention as claimed, available thickness and the similar amorphous state azotized carbon nano piece of embodiment 1.
Embodiment 4
The heating temperature being heat-treated in the high temperature process furnances in step S3 is changed to 520 in the present embodiment
DEG C, soaking time is changed to 3h, and other methods step is same as Example 1, and details are not described herein.
The pattern of the azotized carbon nano piece prepared in the present embodiment, structure are subjected to test, analysis and characterization, specific steps
It is same as Example 1 with method；The azotized carbon nano piece prepared in the present embodiment is buff powder, shows ultra-thin two dimension
Nanometer sheet pattern, nanometer sheet show a kind of structure of amorphous, can not observe apparent lattice fringe, show poor plane
Crystallinity is horizontal, azotized carbon nano piece with a thickness of 5.22nm, equally compared to blocky graphite phase carbon nitride in visible light model
There is a good light absorption in enclosing, the heating temperature of selection described above being heat-treated in the high temperature process furnances exists
In scope of the invention as claimed, available thickness and the similar amorphous state azotized carbon nano piece of embodiment 1.
Embodiment 5
In the present embodiment by the soaking time being heat-treated in the high temperature process furnances in step S3 be changed to 3h and
Heating rate is changed to 5 DEG C/min, and other methods step is same as Example 1, and details are not described herein.
The pattern of the azotized carbon nano piece prepared in the present embodiment, structure are subjected to test, analysis and characterization, specific steps
It is same as Example 1 with method；The azotized carbon nano piece prepared in the present embodiment is buff powder, shows ultra-thin two dimension
Nanometer sheet pattern, nanometer sheet show a kind of structure of amorphous, can not observe apparent lattice fringe, show poor plane
Crystallinity is horizontal, azotized carbon nano piece with a thickness of 4.88nm, equally compared to blocky graphite phase carbon nitride in visible light model
There is a good light absorption in enclosing, the soaking time of selection described above being heat-treated in the high temperature process furnances exists
In scope of the invention as claimed, available thickness and the similar amorphous state azotized carbon nano piece of embodiment 1.
Reference examples 1
Preparation in this reference examples without heat treated sample in step S2, directly by the blocky graphite phase nitrogen of phase homogenous quantities
Change carbon dust to be put into alumina crucible with cover, other methods step is same as Example 1, and details are not described herein.
The pattern of the azotized carbon nano piece prepared in this reference examples, structure are subjected to test, analysis and characterization, specific steps
It is same as Example 1 with method；The azotized carbon nano piece prepared in this reference examples is yellow powder, and microscopic appearance is shown as stratiform
Structure is stacked with, and does not have significant difference with blocky graphite phase carbon nitride, transmission photo is shown as crystal structure, there is apparent crystalline substance
Glazing bar line shows that crystal structure is not destroyed, azotized carbon nano piece with a thickness of 90.52nm, thickness does not subtract significantly
It is small to compare the light absorption in visible-range with blocky graphite phase carbon nitride and there is no significant difference.
Reference examples 2
The heating temperature being heat-treated in the high temperature process furnances in step S3 is changed to 500 in this reference examples
DEG C, other methods step is same as Example 1, and details are not described herein.
The pattern of the azotized carbon nano piece prepared in this reference examples, structure are subjected to test, analysis and characterization, specific steps
It is same as Example 1 with method；The azotized carbon nano piece prepared in this reference examples is yellow powder, is shown as multi-layer nano piece heap
Folded pattern, as shown in Figure 6.Nanometer sheet shows a kind of incomplete non crystalline structure, observes unconspicuous lattice fringe, shows
Metallic vapour does not also cause biggish destruction to the associative key in plane, azotized carbon nano piece with a thickness of 20.52nm, thickness is bright
It is aobvious to increase, compared to blocky graphite phase carbon nitride without good light absorption in visible-range.
There is significant difference in the structure of the azotized carbon nano piece prepared in the embodiment of the present invention, thickness and reference examples, implements
Example is relatively thin compared to the nanometer sheet thickness in reference examples, and the azotized carbon nano piece prepared in the embodiment of the present invention is amorphous state knot
Structure, and there is ultra-thin thickness, there is good light absorption in visible-range.
In summary: the present invention is successfully prepared amorphous state azotized carbon nano piece, using melamine as persursor material, bubble
Foam nickel is metal vapor source, carries out high-temperature heat treatment using inert gas shielding, layer structure is allowed to carve under the action of nickel steam
Erosion is separated into two-dimensional nano chip architecture, and nanometer sheet has ultra-thin pattern, and thickness shows amorphous only in 4~6nm
Structure has good light absorption in visible-range.
Preparation method time-consuming provided by the invention is short, simple process, and the amorphous state azotized carbon nano piece of preparation has ultra-thin
Structure and good light absorption, good performance is shown during photocatalysis degradation organic contaminant.The present invention
Provided preparation method technique is advanced, is a kind of method of the preparation amorphous state azotized carbon nano piece of simple and effective.
The above description is only a preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method of the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour, which is characterized in that the nanometer sheet
Preparation method the following steps are included:
The preparation of S1, blocky graphite phase carbon nitride
S11, graphite phase carbon nitride is prepared using high-temperature polycondensation method；
S12, graphite phase carbon nitride obtained in step s11 is ground, is then sieved with sieve, be ground up, sieved repeatedly into
Row obtains evengranular blocky graphite phase carbon nitride powder, collects spare；
The preparation of S2, heat treated sample
Blocky graphite phase carbon nitride powder obtained in step s12 is uniformly layered on nickel foam piece top, then by another foam
Nickel sheet is placed on the top of blocky graphite phase carbon nitride powder, the foam nickel sheet of position and lower part that another foam nickel sheet is placed
Then parallel alignment is compacted, heat treated sample is made；
The preparation of S3, amorphous state azotized carbon nano piece
Heat treated sample obtained in step S2 is laid flat in heatproof container, is then placed in high temperature furnace, it is closed, it extracts in furnace
Then air is passed through inert gas into high temperature furnace, make invariablenes pressure of liquid in furnace, be then heat-treated, after naturally cool to room
Wen Hou, stopping are passed through gas, sample are taken out from high temperature furnace, tear two panels foam nickel sheet, collect pale yellow powder, obtain non-
Crystalline state azotized carbon nano piece, encapsulation save.
2. the method for the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour as described in claim 1, feature exist
It, will be heat-resisting in, graphite phase carbon nitride described in step s11 the preparation method comprises the following steps: melamine powder is put into heatproof container
Container is put into high temperature furnace and is heat-treated, and cooled to room temperature after keeping the temperature a period of time takes out product from high temperature furnace,
Obtain graphite phase carbon nitride.
3. the method for the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour as claimed in claim 2, feature exist
In the additional amount for the melamine powder being added in step s11 is the 1/2~5/6 of heatproof container capacity.
4. the method for the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour as claimed in claim 2, feature exist
In the heating temperature being heat-treated in the high temperature furnace in step s11 is 520~600 DEG C, and soaking time is 2~4h, is risen
Warm rate is 3~5 DEG C/min；
Preferably, the heating temperature being heat-treated in the high temperature process furnances is 550 DEG C, soaking time 2h, heating speed
Rate is 4 DEG C/min.
5. the method for the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour as described in claim 1, feature exist
In the length and width of two panels foam nickel sheet and high size are all the same in step S2.
6. the method for the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour as described in claim 1, feature exist
In the quality for being layered on the blocky graphite phase carbon nitride powder of nickel foam on piece in step S2 is 30~100mg/cm2；
Preferably, the quality for being layered on the blocky graphite phase carbon nitride powder of nickel foam on piece is 50mg/cm2。
7. the method for the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour as described in claim 1, feature exist
In the inert gas being passed through in step S3 into the high temperature furnace is argon gas；
Preferably, the rate that is passed through that inert gas is passed through into high temperature furnace is 100~120cm3/ min, invariablenes pressure of liquid exists in furnace
0.101MPa。
8. the method for the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour as described in claim 1, feature exist
In the heating temperature being heat-treated in the high temperature furnace in step S3 is 520~580 DEG C, and soaking time is 2~4h, is risen
Warm rate is 3~5 DEG C/min；
Preferably, the heating temperature being heat-treated in the high temperature process furnances is 550 DEG C, soaking time 2h, heating speed
Rate is 4 DEG C/min.
9. a kind of as described in claim 1~8 is any with the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour
The amorphous state azotized carbon nano piece that method is prepared.
10. a kind of as described in claim 1~8 is any with the hot etching method preparation amorphous state azotized carbon nano piece of metallic vapour
The application for the amorphous state azotized carbon nano piece that method is prepared, the amorphous state azotized carbon nano piece are applied in radiation of visible light
Lower degradable organic pollutant.
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