CN108380237A - Nitrogen defect graphite phase carbon nitride nanosheet photocatalyst and the preparation method and application thereof - Google Patents
Nitrogen defect graphite phase carbon nitride nanosheet photocatalyst and the preparation method and application thereof Download PDFInfo
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- CN108380237A CN108380237A CN201810419179.2A CN201810419179A CN108380237A CN 108380237 A CN108380237 A CN 108380237A CN 201810419179 A CN201810419179 A CN 201810419179A CN 108380237 A CN108380237 A CN 108380237A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 230000007547 defect Effects 0.000 title claims abstract description 48
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 48
- 239000010439 graphite Substances 0.000 title claims abstract description 48
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 37
- 239000002135 nanosheet Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000012545 processing Methods 0.000 claims abstract description 9
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004202 carbamide Substances 0.000 claims abstract description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 16
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000005286 illumination Methods 0.000 abstract description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 230000006798 recombination Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000007974 melamines Chemical class 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
-
- 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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/60—
Abstract
The present invention discloses nitrogen defect graphite phase carbon nitride nanosheet photocatalyst and the preparation method and application thereof, and preparation method is as follows：1) by melamine, dicyandiamide, the nitrogen-rich organics object such as thiocarbamide urea, which is put into crucible, to carry out high-temperature calcination processing between 220 420 DEG C of temperature and keeps 0.5 10h, cooling, obtains presoma；2) presoma is ground, is calcined in an inert atmosphere, it is nitrogen defect graphite phase carbon nitride nanosheet photocatalyst to obtain product.Using the nano material of nitrogen defect graphite phase carbon nitride prepared by the method for the present invention, more catalysis reaction sites are capable of providing, while nitrogen defect can capture light induced electron, effectively photo-generate electron-hole be made to detach, and reduce recombination rate, improve photocatalytic activity.Obtained photochemical catalyst is utilized, it under visible light illumination can effectively degradable organic pollutant.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to nitrogen defect azotized carbon nano piece photochemical catalyst and its system
Preparation Method and application.
Background technology
With the development of human society, problem of environmental pollution becomes increasingly conspicuous, it would be highly desirable to solve, in numerous depollution of environment methods
In, photocatalysis depollution of environment technology is concerned.Photocatalysis technology is a kind of environmentally friendly technology, and sunlight can be utilized real
Existing degradable organic pollutant, has the characteristics that non-secondary pollution, recyclable regenerative.In recent years, graphite phase carbon nitride is as a kind of
No metal material receives the very big concern of researcher, the light that graphite phase carbon nitride has relatively small band gap and stablizes
Chemical characteristic, in degradable organic pollutant, the fields such as nitrogen oxides reduction have a wide range of applications.But current graphite-phase nitrogen
Change carbon causes photocatalytic activity not high the problems such as that there are specific surface areas is small, and light induced electron is easily compound, and quantum efficiency is low.Therefore scientific research
Worker done many research to improve the activity of graphite phase carbon nitride, such as by improving work with the compound of other materials
Property, also some improves activity using metal, nonmetal doping to change architecture.It is well known that inherent shortcoming can promote
Photocatalytic activity, defect can not only change electronic structure, but also can serve as reactivity site, can also improve photocatalysis
The quantum efficiency of material inhibits the compound of electronics and hole as trap capture electronics, therefore the research of defect is urged improving light
Changing material has important role.But the nitrogen defective material particle size of previous research report is big, specific surface area is small, pattern list
One, photocatalytic activity is low.In order to further increase the photocatalysis efficiency of nitrogen defect graphite phase carbon nitride material, we will improve stone
Black phase carbon nitride internal crystallization, obtain three kinds of element characteristics of best defective proportion and bigger serface assign a kind of materials it
In, to significantly improve the photocatalytic activity of graphite phase carbon nitride.
Invention content
The object of the present invention is to provide a kind of high surface area crystallite nitrogen defect graphite phase carbon nitride nanosheet photocatalyst and
Preparation method, this method is simple, conveniently, low cost, mild condition, be conducive to mass produce.
The technical solution adopted by the present invention is：
Nitrogen defect graphite phase carbon nitride nanosheet photocatalyst, preparation method are as follows：
1) nitrogen-rich organic object is put into crucible, high-temperature calcination processing is carried out between 220-420 DEG C of temperature and keeps 0.5-
Natural cooling after 10h, obtains precursor A；
2) precursor A is directly calcined under inert gas environment or air environment, obtains target product nitrogen defect
Graphite phase carbon nitride nanosheet photocatalyst；
Or precursor A is subjected to sour processing, precursor B is obtained, precursor B is ground, under inert gas or air environment
It is calcined, obtains target product nitrogen defect graphite phase carbon nitride nanosheet photocatalyst.
The nitrogen defect graphite phase carbon nitride nanosheet photocatalyst, acid processing described in step 2) are specially：First
Precursor A is dissolved in heating stirring in deionized water, oxalic acid is then added dropwise, gained mixed liquor is put into heat in baking oven and is dried
It is dry, obtain precursor B.
The nitrogen defect graphite phase carbon nitride nanosheet photocatalyst, the precursor A are dissolved in deionized water and are configured to
The solution of a concentration of 0.01-3mol/L.
The heating temperature of the nitrogen defect graphite phase carbon nitride nanosheet photocatalyst, the heating stirring is 40-99
℃。
The nitrogen defect graphite phase carbon nitride nanosheet photocatalyst, the temperature of heating, drying is 80- in the baking oven
250℃。
The nitrogen defect graphite phase carbon nitride nanosheet photocatalyst, every gram of precursor A, which corresponds to, is added 0.375-3g grass
Acid.
The nitrogen defect graphite phase carbon nitride nanosheet photocatalyst, nitrogen-rich organic object is melamine in the step 1)
Amine, dicyandiamide, thiocarbamide or urea.
The nitrogen defect graphite phase carbon nitride nanosheet photocatalyst, in inert gas environment or sky in the step 2)
Compression ring is calcined under border, and the temperature of calcining is 450-550 DEG C, calcination time 1-10h.
The nitrogen defect graphite phase carbon nitride nanosheet photocatalyst, in inert gas environment or sky in the step 2)
Compression ring is calcined under border in tube furnace, and calcination temperature is 450-600 DEG C, calcination time 1-8h.
A kind of nitrogen defect graphite phase carbon nitride nanosheet photocatalyst catalytic degradation gas pollutant under visible light
Application in isopropanol.
The beneficial effects of the invention are as follows：The present invention not only successfully constructs nitrogen defect sturcture, while also forming a graphite
Phase carbon nitride nanometer chip architecture is easier that photo-generate electron-hole is made to efficiently separate in this way, reduces recombination rate, can effectively carry
Highlight catalytic active.And preparation method provided by the present invention, raw material is cheap, easy to operate, and high degree is reduced into
This, and it is environmentally safe, realize Green Chemistry.The rate of degradation isopropanol generation acetone is pure stone under visible light
12 times or so of black phase carbon nitride.
Description of the drawings
Fig. 1 is the XRD tests of CNO photochemical catalysts prepared by embodiment 1.
Fig. 2 is the TEM figures of CNO photochemical catalysts prepared by embodiment 1.
Fig. 3 is the XRD tests of CN1 photochemical catalysts prepared by embodiment 2.
Fig. 4 is the TEM figures of CN1 photochemical catalysts prepared by embodiment 2.
Fig. 5 is the XRD tests of CN2 photochemical catalysts prepared by embodiment 3.
Fig. 6 is the TEM figures of CN2 photochemical catalysts prepared by embodiment 3.
Fig. 7 is the XRD tests of CN3 photochemical catalysts prepared by embodiment 4.
Fig. 8 is the TEM figures of CN3 photochemical catalysts prepared by embodiment 4.
Fig. 9 is the active comparison diagram of CNO, CN1, CN2 and CN3 photocatalytic degradation isopropanol gas.
Figure 10 is CNO, CN1, CN2 and CN3 photochemical catalyst EPR comparison diagrams.
Specific implementation mode
The pure g-C of embodiment 13N4(CNO) photochemical catalyst
(1) preparation method
Directly by the melamine of 2.52g, in the environment of nitrogen, 4h is calcined at 550 DEG C, heating rate is 5 DEG C/min,
Obtain pure g-C3N4(CNO) photochemical catalyst.
(2) it detects
Fig. 1 is the XRD test charts of CNO prepared by embodiment 1, and as seen from Figure 1, sample has two diffraction at 13 ° and 27 °
Peak.The crystallite dimension that sample is calculated according to formula is about 15.2nm.
The TEM figures that Fig. 2 is CNO prepared by embodiment 2, from Figure 2 it can be seen that pure graphite phase carbon nitride contains a small amount of hole,
It can approximately be considered a non-porous material.
2 nitrogen defect graphite phase carbon nitride nanosheet photocatalyst of embodiment
(1) preparation method
1) 2.5g melamines are put into crucible and carry out calcination processings in 350 DEG C of temperature and keeps natural cooling after 5h,
Obtain precursor A (solid)；
2) 2g precursor As are then dissolved in the solution that a concentration of 0.2mol/L is configured in 60mL deionized waters, at 60 DEG C
Under heating condition, then 0.75g oxalic acid is added dropwise in magnetic agitation, gained mixed liquor is put into baking oven, in 100-110 DEG C
Lower drying, obtains precursor B；Precursor B is put into mortar and is ground, grinding is placed in alumina crucible, in tube furnace,
In the environment of nitrogen, 550 DEG C of calcining 4h obtain target product nitrogen defect graphite phase carbon nitride g-C3N4Nanosheet photocatalyst
(CN1)；
3) target product GN1 is placed in Muffle furnace, in the environment of air, calcines 2h in 550 DEG C, remove the carbon of oxalic acid
Residual.
(2) it detects
Fig. 3 is the XRD test charts of CN1 prepared by embodiment 2, and as seen from Figure 3, sample has two diffraction at 13 ° and 27 °
Peak meets the diffraction maximum of graphite phase carbon nitride, with pure g-C3N4Diffraction maximum is similar, it was demonstrated that synthesized sample nitrogenizes for graphite-phase
Carbon.
The TEM figures that Fig. 4 is CN1 prepared by embodiment 2 show sample from fig. 4, it can be seen that there are many big holes for sample surfaces
It is a porous material, the quantity ratio CN0 in hole is more, and gained sample is thinner nanometer chip architecture.
Have determined that CN1 is graphite-phase nitrogen by XRD test charts, from fig. 4, it can be seen that crystallite dimension about 13.6nm can
Will become apparent from being obviously reduced in 13 ° of diffraction maximum this is because the addition of acid destroys crystal structure, however reduce sample
Crystallite dimension.The negligible amounts in the holes CNO as seen in Figure 2, a similar non-porous material, seems a thick painting
Layer.And CN1 has entirely different pattern, it is evident that be a very thin nanometer chip architecture, and particle size is obviously reduced
It is identical as the measurement result of XRD.
3 nitrogen defect graphite phase carbon nitride composite photo-catalyst of embodiment
(1) preparation method
1) 2.52g melamines are put into crucible and carry out calcination processings in 420 DEG C of temperature and keeps natural cooling after 5h,
Obtain precursor A (solid)；
2) 2g precursor As are then dissolved in the solution that a concentration of 0.2mol/L is configured in 60mL deionized waters, at 60 DEG C
Under heating condition, under magnetic agitation, 1.5g oxalic acid is added, gained mixed liquor is put into baking oven, is dried at 100-110 DEG C,
Obtain precursor B；Precursor B is put into mortar and is ground, is put into alumina crucible, in tube furnace, in the environment of nitrogen,
4h is calcined in 550 DEG C, obtains target product nitrogen defect graphite phase carbon nitride g-C3N4Nanosheet photocatalyst (GN2)；
3) by product GN2 in Muffle furnace, in the environment of air, 2h is calcined in 550 DEG C, removes the carbon residual of oxalic acid.
(2) it detects
Fig. 5 is the XRD test charts of CN2 prepared by embodiment 3, and as seen from Figure 5, sample has two diffraction at 13 ° and 27 °
Peak；The diffraction maximum for meeting graphite phase carbon nitride, with pure g-C3N4Diffraction maximum is similar.
Fig. 6 is TEM figures prepared by embodiment 3, and as seen from Figure 6, sample particle size ratio CNO is small.Pass through XRD test charts
Have determined that CN2 is graphite phase carbon nitride, crystallite dimension about 8.6nm, it should be noted that sample is several in 13 ° of diffraction maximum
It disappears, is equally to destroy aromatic structure due to adding oxalic acid, but it can be seen that reducing the crystallite dimension of sample.
By the negligible amounts in the holes Fig. 2 CNO, a similar non-porous material, seems a thick coating, and CN2 is with entirely different
The solid pattern of pattern, stratiform loses completely, and nanometer sheet is clear in structure as it can be seen that seeming that a circular particle forms a list
It is brilliant.The addition of oxalic acid is illustrated so that sample obtains different patterns, oxalic acid plays important angle during synthesis
Color.
4 nitrogen defect graphite phase carbon nitride nanosheet photocatalyst of embodiment
(1) preparation method
1) 2.52g melamines are put into crucible and are calcined in 400 DEG C of temperature and keeps natural cooling after 5h, before obtaining
Drive body A (solid)；；
2) precursor A is put into mortar and is ground, is put into alumina crucible, in tube furnace, in the environment of nitrogen,
4h is calcined in 550 DEG C, it is nitrogen defect graphite phase carbon nitride g-C to obtain target product3N4Nanosheet photocatalyst CN3.
(2) it detects
Fig. 7 is the XRD test charts of CN1 prepared by embodiment 4, and as seen from Figure 3, sample has two diffraction at 13 ° and 27 °
Peak meets the diffraction maximum of graphite phase carbon nitride, with pure g-C3N4Diffraction maximum is similar, it was demonstrated that synthesized sample nitrogenizes for graphite-phase
Carbon.
The TEM figures that Fig. 8 is CN1 prepared by embodiment 4, as seen from Figure 8, there are many big holes for sample surfaces, show sample
It is a porous material, the quantity ratio CN0 in hole is more, and gained sample is thinner nanometer chip architecture.
Have determined that CN1 is graphite-phase nitrogen by XRD test charts, as seen from Figure 7, crystallite dimension about 12.7nm,
It is higher than CN0 samples in 13 ° of diffraction peak-to-peak signals, this is because forming more large area when more melem polymerizations in polycondensation process
Triazine heterocycle caused by, it can be seen that step calcination can cause the crystal structure of sample to change, this is to be conducive to obtain
Obtain different patterns.The negligible amounts in the holes CNO as seen in Figure 2, a similar non-porous material, seems one thick
Coating.And CN1 has entirely different pattern, seems the superposition of some sheets, and more transparent compared to CN0, belongs to one
A very thin nanometer chip architecture, and particle size is obviously reduced, some folds on surface illustrate surface exist it is a large amount of not at
To electronics, illustrate defective presence, this is conducive to photocatalysis effect.
From embodiment 1-4：The sample for preparing out shows different shape characteristics, is either added
Oxalic acid still changes calcination condition.And compared with CN0, the crystallite dimension of CN1, CN2, CN3 are all reduced, especially CN2
It is the most apparent, and pattern feature is also significant different, and this is all conducive to obtain better catalytic activity.
Embodiment 5 is applied
Photochemical catalyst prepared by embodiment 1-4 carries out photocatalyst material performance test.
Test process is：Using 300W xenon lamps as light source, photoelectric current is adjusted to the positions 20A, is adjusted light intensity center and is just irradiated to
Sample surfaces, fixed good position, are put in 4cm by embodiment 1-3 CNO, CN1, CN2 and CN3 prepared respectively2It, will in glass guide channel
The glass guide channel of photocatalyst-bearing is respectively put into the 224ml reactors for including an atmospheric air, finally into reactor
5ul isopropanol liquids are injected, start timing after illumination 20min, sample extracted a needle every 20 minutes, tested, and recorded
The peak area of isopropanol, it is the rate for finding out degradation isopropanol per minute after recording 6 times by calculating that the results are shown in Figure 7.Knot
Fruit such as Fig. 9.
As seen from Figure 9, the nitrogen defect graphite phase carbon nitride of preparation and pure g-C3N4Degradation isopropanol rate per minute live
Property figure,.It can be seen that much higher than pure sample activity of the catalytic activity of the photochemical catalyst of prepared nitrogen defect, especially
CN2 samples are pure g-C3N48 times or so of isopropanol rate of degrading, also in that the presence of unique pattern and defect makes
The g-C prepared3N4With higher activity.It is a kind of mode of judgement sample existing defects by Figure 10, first EPR, passes through
The comparison diagram of EPR data can be seen that CN1, CN2, CN3 and CN0 have a typical Lorentz curve (g=2.0035),
CN1, CN2, CN3 possess the higher strength of resonance than CN0, also just illustrate CN1, CN2, CN3, have in sample on more carbon azacyclo-s
Not pairs of carbon atom is captured to, and extra not pairs of electronics is redistributed on neighbouring carbon atom, is further related to
Sample certain amount nitrogen defect, it can be said that the bright nitrogen defect photochemical catalyst prepared be more advantageous to charge point
From higher catalytic activity can be caused.
Claims (10)
1. nitrogen defect graphite phase carbon nitride nanosheet photocatalyst, which is characterized in that preparation method is as follows：
1) nitrogen-rich organic object is put into crucible, after high-temperature calcination processing is carried out between 220-420 DEG C of temperature and keeps 0.5-10h
Natural cooling obtains precursor A；
2) precursor A grinding is directly calcined under inert gas environment or air environment, obtains target product nitrogen defect
Graphite phase carbon nitride nanosheet photocatalyst；
Or precursor A is subjected to sour processing, precursor B is obtained, precursor B is ground, is carried out under inert gas or air environment
Calcining, obtains target product nitrogen defect graphite phase carbon nitride nanosheet photocatalyst.
2. nitrogen defect graphite phase carbon nitride nanosheet photocatalyst as described in claim 1, which is characterized in that institute in step 2)
Stating acid processing is specially：Precursor A is dissolved in heating stirring in deionized water first, oxalic acid is then added dropwise, gained is mixed
It closes liquid and is put into heating, drying in baking oven, obtain precursor B.
3. nitrogen defect graphite phase carbon nitride nanosheet photocatalyst as claimed in claim 2, which is characterized in that the presoma
A is dissolved in the solution that deionized water is configured to a concentration of 0.01-3mol/L.
4. nitrogen defect graphite phase carbon nitride nanosheet photocatalyst as claimed in claim 2, which is characterized in that the heating is stirred
The heating temperature mixed is 40-99 DEG C.
5. nitrogen defect graphite phase carbon nitride nanosheet photocatalyst as claimed in claim 2, which is characterized in that in the baking oven
The temperature of heating, drying is 80-250 DEG C.
6. nitrogen defect graphite phase carbon nitride nanosheet photocatalyst as claimed in claim 2, which is characterized in that every gram of presoma
A, which is corresponded to, is added 0.375-3g oxalic acid.
7. nitrogen defect graphite phase carbon nitride nanosheet photocatalyst as described in claim 1, which is characterized in that the step 1)
Middle nitrogen-rich organic object is melamine, dicyandiamide, thiocarbamide or urea.
8. nitrogen defect graphite phase carbon nitride nanosheet photocatalyst as described in claim 1, which is characterized in that the step 2)
In calcined under inert gas environment or air environment, the temperature of calcining is 450-550 DEG C, calcination time 1-10h.
9. nitrogen defect graphite phase carbon nitride nanosheet photocatalyst as described in claim 1, which is characterized in that the step 2)
In calcined in tube furnace under inert gas environment or air environment, calcination temperature is 450-600 DEG C, and calcination time is
1-8h。
10. nitrogen defect graphite phase carbon nitride nanosheet photocatalyst as described in claim 1 catalytic degradation gas under visible light
Application in pollutant isopropanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810419179.2A CN108380237B (en) | 2018-05-04 | 2018-05-04 | Nitrogen-defect graphite-phase carbon nitride nanosheet photocatalyst and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810419179.2A CN108380237B (en) | 2018-05-04 | 2018-05-04 | Nitrogen-defect graphite-phase carbon nitride nanosheet photocatalyst and preparation method and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN108380237A true CN108380237A (en) | 2018-08-10 |
| CN108380237B CN108380237B (en) | 2020-10-09 |
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