CN109158125A - A kind of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis material and preparation method thereof - Google Patents
A kind of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- -1 carbon quantum dot modified zinc oxide Chemical class 0.000 title claims abstract description 29
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000011787 zinc oxide Substances 0.000 claims abstract description 37
- 239000002096 quantum dot Substances 0.000 claims abstract description 27
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000011324 bead Substances 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 24
- 238000000227 grinding Methods 0.000 claims description 22
- 238000010008 shearing Methods 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 2
- 238000003701 mechanical milling Methods 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000004482 other powder Substances 0.000 abstract description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 abstract 2
- 238000007605 air drying Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 17
- 238000007146 photocatalysis Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000004044 response Effects 0.000 description 8
- 230000003595 spectral effect Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
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- 239000010865 sewage Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000009514 concussion Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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Classifications
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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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- B01J35/39—
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Abstract
The present invention relates to a kind of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis materials and preparation method thereof, first prepare g-C3N4Quantum dot disperses solution；Then by crude zinc oxide materials and g-C3N4Quantum dot disperses solution mixing, and ball milling is dry, obtains the modified zinc oxide catalysis material of graphitic nitralloy carbon quantum dot.The present invention is not needed using special device and solvent; method, which is shaken, by mechanical ultrasonic prepares graphitic nitralloy carbon quantum dot; and the method for directly utilizing mechanical ball mill; promote the formation of the modified oxidized zinc powder of graphitic nitralloy carbon quantum dot by mechanical force and chemical; then the modified zinc oxide visible light catalytic material of graphitic nitralloy carbon quantum dot is prepared with forced air drying method; simplify preparation process; reduce experimental cost; preparation process environmental protection; industrialized production can be achieved, while also will provide an effective path for the other powder body materials of prepare with scale.
Description
Technical field
The present invention relates to a kind of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis materials and preparation method thereof, belong to light and urge
Change field.
Background technique
Zinc oxide minerals are widely distributed in nature, rich content, cheap, and due to its special electronic structure
With excellent photoelectric property, it is made to show good application prospect in fields such as photocatalysis, paint filler, chemical colors.To the greatest extent
Pipe Zinc oxide minerals excellent in optical properties, it is cheap, it is extensive in industrial applications, but the forbidden bandwidth of zinc oxide is wider, only
The ultraviolet portion in sunlight can be absorbed, and the photo-generated carrier that light excitation generates is easily compound, to limit it in photocatalysis
Application in industry.It therefore, is necessary by the modified spectral response range for improving zinc oxide and photocatalytic activity.
Semiconductors coupling is to widen the compound one kind of zinc oxide catalysis material spectral response range, reduction photo-generated carrier to have
Effect means are widely used in the fields such as sewage treatment, environmental protection.In numerous narrowband based semiconductors, graphite-phase nitridation
Carbon (g-C3N4) be forbidden bandwidth be 2.74 eV, itself can absorb visible light formed photo-generated carrier, show to be catalyzed well
Characteristic；Meanwhile it has many advantages, such as good stability, resistance to acid and alkali and excellent electrochemical properties, and source is numerous, storage
Amount is abundant, receives the concern of more and more researchers.Utilize the modified light for being remarkably improved zinc oxide of graphite phase carbon nitride
Catalytic activity and spectral response range improve photocatalysis efficiency, promote in fields such as environmental protection, sewage treatment, air cleanings
Application.
Currently, there are many method for obtaining modified zinc oxide catalysis material, but there are preparation process complexity, it is not easy to realize production
Industry large-scale production, production prices are somewhat expensive, are not easy large-scale production and application, thus obtain a kind of simple, easily industrial metaplasia
The method for producing modified zinc oxide catalysis material is necessary.
Summary of the invention
Present invention solves the technical problem that being to prepare visible light-responded Zinc oxide-base catalysis material at present frequently with chemistry
Synthetic method is reacted, is needed using organic solvent, preparation process is complicated, at high cost, it is understood that there may be the problems such as environmental pollution, this
The purpose of invention is to pass through machinery on the basis of preparing graphitic nitralloy carbon quantum dot using mechanical stirring and ultrasonic vibration method
Ball grinding method realizes the modified oxidized zinc powder of graphitic nitralloy carbon quantum, widens the spectral response range of zinc oxide and improves photocatalysis
Activity, to provide a kind of simple process, at low cost, and the graphitic nitralloy carbon quantum dot modified zinc oxide of easily preparation of industrialization is urged
Change material and preparation method thereof.
In order to solve the above-mentioned technical problem, technical scheme is as follows:
A kind of preparation method of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis material, includes the following steps:
S1, by g-C3N4Powder is added in the mixed liquor of deionized water and alcohol, after ultrasonic disperse 20-40min, generally 25-
35min stirs 20-40min, generally 25-35min, obtains g-C3N4Dispersion liquid；
Wherein, deionized water and the volume ratio of alcohol are 96:4 ~ 98:2, add 0.3-2g g-C in every 100mL mixed liquor3N4Powder
Body, it is preferable that 0.6-1.7g g-C is added in every 100mL mixed liquor3N4Powder；
Under sonic oscillation, with mechanical shearing machine to the g-C3N4Dispersion liquid carries out 5 ~ 6 h of shearing, and it is evenly dispersed to obtain solution
G-C3N4Solution；Then, with centrifuge to the g-C3N4Processing is centrifuged in solution, obtains g-C3N4Quantum dot dispersion
Solution；
S2, the g-C that will be obtained in crude zinc oxide materials and S13N4Quantum dot disperses solution mixing, and ball milling is dry, obtains graphite nitrogen
Change carbon quantum dot modified zinc oxide catalysis material.
In S1, g-C3N4Raw powder's production technology are as follows: nitrogenous compound is placed in Muffle furnace, is warming up to 500-600 DEG C,
Preferably, heating rate is 3 ~ 5 DEG C/min, and after keeping the temperature 1.5-7h, generally 2-6h, preferably 2.5-5h are cooling, obtains g-
C3N4Powder.
The nitrogenous compound is at least one of melamine, urea, thiocarbamide.
In S1, the alcohol is at least one of methanol, ethyl alcohol, propyl alcohol.
In S1, in shear history, the revolving speed of mechanical shearing machine is 2000 ~ 6000 r/min, generally 3000 ~ 5000 r/
Min, preferably 3500 ~ 4500 r/min；During centrifuging treatment, centrifuge speed be 10000 ~ 12000 r/min, one
As be 11000 ~ 12000 r/min.
In S2,1-10mL g-C is mixed into every 1g crude zinc oxide materials3N4Quantum dot disperses solution, it is preferable that every 1g zinc oxide
2-8mL g-C is mixed into raw material3N4Quantum dot disperses solution.
In S2, the crude zinc oxide materials are the Zinc oxide powders that partial size is 0.5-3 μm.Further, the zinc oxide is former
Zinc oxide miberal powder can also be used in material, can also prepare target product, and can reduce cost of material.
Graphitic nitralloy carbon quantum dot not only possesses the performance of block graphitic nitralloy carbon, but also imitates with special quantum size
It answers, shows superior performance, there is better reinforcing effect than carbonitride stratified material, show good industrial application
Prospect.It is raw material with zinc oxide miberal powder, water is solvent, and graphite phase carbon nitride quantum dot is that reinforcing material obtains spectral response range
Wide, high catalytic efficiency Zinc oxide minerals catalysis material, preparation process is simple and environmentally-friendly, and preparation cost is low, can yield, have
Good industrial applications prospect.
In S2, in mechanical milling process, the grinding bead of selection includes big grinding bead and small grinding bead, the big grinding bead and small is ground
The quantity ratio for grinding pearl is 1:3-5, it is preferable that the diameter ratio of the big grinding bead and small grinding bead is 2:1, and the grinding bead is preferred
For zirconium oxide abrasive pearl.Big grinding bead and small grinding bead gradation promote ball milling effect.
In S2, ball milling uses way traffic mode, i.e. 30 ~ 40min of positive operation, stops 3 ~ 5 min, then inverted running 30
~ 40 min stop 3 ~ 5 min, and repeatedly, runing time is 3 ~ 5h in total.Preferably, rotational speed of ball-mill is 300 ~ 500 r/min.
Further, in S2, ball milling is carried out using horizontal ball mill.
Further, it in S2, after ball milling, is dried in such a way that air blast dries up.
Based on the same inventive concept, the present invention also provides a kind of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis material,
It is prepared by preparation method as described above.
Technical concept of the invention is: using graphitic nitralloy carbon quantum dot special structure and photoelectric properties, widening oxidation
The spectral response range and raising photocatalytic activity of zinc.In addition, the use of Zinc oxide powder being directly raw material, water is solvent, is used
Simple mechanical ball mill method is made to realize that Zinc oxide powder and graphitic nitralloy carbon quantum dot are uniformly mixed by mechanochemistry
Possess the hetero-junctions of " synergistic effect " with building, to prepare what the excellent graphitic nitralloy carbon quantum dot of photocatalysis performance was modified
Zinc oxide catalysis material.
Present invention Zinc oxide powder, nitrogenous compound are raw material, and water is solvent, use simple mechanical concussion method system
Standby graphitic nitralloy carbon quantum dot, and mechanical ball mill method is relied on, obtain the graphite nitrogen that spectral response range is wide, catalytic activity is high
Change carbon quantum dot modified zinc oxide visible light catalytic material.
The principle of the present invention is: utilizing simple mechanical ball mill method, does not need special device and organic solvent and obtain
Graphitic nitralloy carbon quantum dot and its zinc oxide visible light catalytic material of modification.Its principle is the machinery formed using mechanical ball mill
Chemical action forms graphitic nitralloy carbon quantum dot modified zinc oxide catalysis material, is on the one hand to reduce zinc oxide using mechanical ball mill
The partial size of raw material, while it is uniformly mixed graphitic nitralloy carbon quantum dot and crude zinc oxide materials, obtain performance more preferably composite catalyzing
Material.It on the other hand is to utilize graphitic nitralloy carbon quantum dot using graphitic nitralloy carbon quantum dot modified zinc oxide powder raw material
Special construction and excellent properties widen the spectral response range of crude zinc oxide materials, and the light quantum for increasing zinc oxide catalysis material produces
Rate, and the fault energy level formed between zinc oxide by it, accelerate the separation of photo-generated carrier, improve the photocatalysis of zinc oxide
Activity.
Maximum feature of the invention is: preparing finely dispersed graphitic nitralloy carbon quantum dot water using mechanical shearing method
Then solution passes through the quantum-dot modified oxide powder and zinc powder stock of method synthetic graphite carbonitride of mechanical ball mill, does not need other
Additive and solvent, preparation process is simple, at low cost, preparation process environmental protection, and is easy to large-scale production.In addition, this method
Using graphitic nitralloy carbon quantum dot modified zinc oxide raw material, the zinc oxide for obtaining more excellent performance of natural sun photoresponse is urged
Change material, the modified zinc oxide catalysis material of the graphitic nitralloy carbon quantum dot can be applied to sewage treatment, light degradation water, sky
The field of environment protection such as gas purification.
Compared with prior art, present invention has an advantage that the present invention does not need to pass through using special device and solvent
Mechanical ultrasonic concussion method prepares graphitic nitralloy carbon quantum dot, and the method for directly utilizing mechanical ball mill, by mechanical force and chemical
Promote graphitic nitralloy carbon quantum dot modified zinc oxide raw material, forms the compound system for being uniformly dispersed, being firmly combined, then use air blast
Seasoning prepares the modified zinc oxide visible light catalytic material of graphitic nitralloy carbon quantum dot, simplifies preparation process, reduces experiment
Cost, preparation process environmental protection also will provide one for the other powder body materials of prepare with scale and have, it can be achieved that industrialized production
The path of effect.
Detailed description of the invention
Fig. 1 is the g-C that embodiment 1 obtains3N4Quantum-dot modified ZnO catalysis material (g-C3N4 ) and other phases QDs/ZnO
Close photocatalysis performance comparative situation figure of the material under ultraviolet light.C is the concentration of organic dyestuff in solution, C0For in solution
The initial concentration of organic dyestuff.
Fig. 2 is the g-C that embodiment 2 obtains3N4The XRD spectrum of quantum-dot modified ZnO catalysis material.
Fig. 3 is the g-C that embodiment 3 obtains3N4Quantum-dot modified ZnO catalysis material (g-C3N4 ) and other correlations QDs/ZnO
The photocatalysis performance comparative situation figure of material under visible light illumination.
In Fig. 1 and Fig. 3, Blank group refers to that the natural degradation situation of organic dyestuff under light illumination, ZnO group refer to pure zirconia
Zinc under light illumination degradating organic dye the case where, g-C3N4 / ZnO group is g-C3N4Modified ZnO catalysis material drops under light illumination
The case where solving organic dyestuff, g-C3N4QDs/ZnO group is g-C3N4Quantum-dot modified ZnO catalysis material degrades have under light illumination
The case where engine dyeing material.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Embodiment 1
In the present embodiment, g-C3N4Quantum-dot modified ZnO catalysis material the preparation method is as follows:
(1) urea is placed in Muffle furnace, is heated with the heating rate of 4 DEG C/min, is heated to 500 DEG C, then keeps the temperature 4
H after natural cooling, obtains g-C by mortar grinder3N4Powder.
(2) g-C of 5 g steps (1) preparation is weighed3N4Powder is added to 1000 mL deionized waters and methyl alcohol mixed liquor (body
Product is than being 98:2) in, 40 min are stirred for after ultrasonic disperse 20min；Obtain g-C3N4Dispersion liquid；
(3) under sonic oscillation, with the g-C that is obtained to above-mentioned steps (2) of mechanical shearing machine that revolving speed is 2000 r/min3N4Point
Dispersion liquid carries out 5 h of shearing, obtains the evenly dispersed g-C of solution3N4Solution；
(4) g-C is obtained after being centrifuged with the supercentrifuge that revolving speed is 10000 r/min3N4Quantum dot disperses solution.
(5) it takes 25 g ZnO powder raw materials (partial size is 3 μm) to be placed in ball grinder, 50 mLg-C is added3N4Quantum dot point
Solution is dissipated, while ready grinding bead is put into ball grinder, the gradation of ball is that the ratio between big ball bead is 1:3, the radius of big ball
For 20 mm, the radius of bead is 10 mm.
(6) above-mentioned ball grinder being placed on horizontal ball mill, revolving speed is 300 r/min, first ball milling is set and rotates forward 30 min,
Then stop 5 min, reverse 40 min later, controlling entire Ball-milling Time is 3 h.Uniformly mixed powder is dried and is answered
Light combination catalyst.And detection can be carried out to its photocatalytic, as described in Fig. 1.
Fig. 1 is the photocatalysis performance of related catalysis material under ultraviolet light.As can be seen from FIG., g-C3N4Quantum dot
Modification can greatly improve the photocatalysis performance of ZnO powder, and the time that photocatalytic degradation same concentrations dyestuff uses reduces one
Half.In addition, g-C3N4Quantum dot modifies sample ratio g-C3N4Modification sample shows better photocatalysis performance.
Embodiment 2
In the present embodiment, g-C3N4Quantum-dot modified ZnO catalysis material the preparation method is as follows:
(1) thiocarbamide is placed in Muffle furnace, is heated with the heating rate of 3 DEG C/min, is heated to 600 DEG C, then keeps the temperature 5
H after natural cooling, obtains g-C by mortar grinder3N4Powder；
(2) g-C of 10 g above-mentioned steps (1) preparation is weighed3N4Powder is added to 1000 mL deionized waters and alcohol mixeding liquid
In (volume ratio 96:4), 40 min are stirred for after 40 min of ultrasonic disperse；Obtain g-C3N4Dispersion liquid；
(3) under sonic oscillation, with the g-C that is obtained to above-mentioned steps (2) of mechanical shearing machine that revolving speed is 6000 r/min3N4Point
Dispersion liquid carries out 6 h of shearing, obtains the evenly dispersed g-C of solution3N4Solution；
(4) g-C is obtained after being centrifuged with the supercentrifuge that revolving speed is 12000 r/min3N4Quantum dot disperses solution；
(5) it takes 30 g ZnO raw materials (partial size is 1 μm) to be placed in ball grinder, 200 mLg-C is added3N4Quantum dot disperses solution,
Ready grinding bead is put into ball grinder simultaneously, the gradation of ball is that the ratio between big ball bead is 1:4, and the radius of big ball is 20 mm,
The radius of bead is 10 mm.
(6) above-mentioned ball grinder being placed on horizontal ball mill, revolving speed is 500 r/min, first ball milling is set and rotates forward 40 min,
Then stop 3 min, reverse 30 min later, whole Ball-milling Time is 5 h.It dries uniformly mixed powder to obtain complex light
Catalyst.Attached drawing 3 is the XRD of composite photo-catalyst.
Fig. 2 is g-C3N4The XRD diagram of quantum-dot modified ZnO catalysis material.As can be seen from FIG., graphitic nitralloy carbon quantum dot
Modification front and back sample show as fine zinc cubic structure zinc oxide, but after modification in sample 2 θ=27.4 ° at discovery one newly
Diffraction maximum, this correspond to g-C3N4(002) crystallographic plane diffraction peak.This result proves to include g-C in the sample obtained3N4。
Embodiment 3
In the present embodiment, g-C3N4Quantum-dot modified ZnO catalysis material the preparation method is as follows:
(1) melamine is placed in Muffle furnace, is heated with the heating rate of 5 DEG C/min, is heated to 550 DEG C, then protects
3 h of temperature after natural cooling, obtain g-C by mortar grinder3N4Powder.
(2) g-C of 8 g above-mentioned steps (1) preparation is weighed3N4Powder is added to 800 mL deionized waters and propyl alcohol mixed liquor
In (volume ratio 97:3), 20 min are stirred for after 20 min of ultrasonic disperse；Obtain g-C3N4Dispersion liquid；
(3) under sonic oscillation, with the g-C that is obtained to above-mentioned steps (2) of mechanical shearing machine that revolving speed is 5000 r/min3N4Point
Dispersion liquid carries out 6 h of shearing, obtains the evenly dispersed g-C of solution3N4Solution；
(4) g-C is obtained after being centrifuged with the supercentrifuge that revolving speed is 11000 r/min3N4Quantum dot disperses solution.
(5) it takes 50 g ZnO powder raw materials (partial size is 0.5 μm) to be placed in ball grinder, 150 mLg-C is added3N4Quantum dot
To disperse solution, while ready grinding bead is put into ball grinder, the gradation of ball is that the ratio between big ball bead is 1:5, the half of big ball
Diameter is 20 mm, and the radius of bead is 10 mm.
(6) above-mentioned ball grinder being placed on horizontal ball mill, revolving speed is 400 r/min, and setting ball milling first rotates forward 35 min,
Stop 4 min later, then reverse 35 min, whole Ball-milling Time is 4 h.It dries uniformly mixed powder to obtain complex light
Catalyst.Attached drawing 3 is the cycle performance of composite photo-catalyst.
Fig. 3 is photocatalysis performance of the associated catalytic material under sunlight.It is seen that changing compared with ZnO powder
Performance of the sample under sunlight has great promotion after property, and photocatalytic degradation capability is doubled, wherein g-C3N4Amount
The sample of son point modification shows better photocatalysis performance, and photocatalytic activity about improves 15%.This illustrates graphitic nitralloy
Carbon quantum dot can effectively improve the visible light catalysis activity of Zinc oxide powder, be expected to be applied in actual industrial.
To sum up, present invention Zinc oxide powder and graphitic nitralloy carbon are raw material, and water is solvent, prepare it is visible light-responded,
The modified zinc oxide catalysis material of the high graphitic nitralloy carbon quantum dot of catalytic activity, this method preparation process is simple, and raw material is easy to get,
Cost is relatively low, easy to industrialized production.
The content that above-described embodiment illustrates should be understood as that these embodiments are only used for being illustrated more clearly that the present invention, without
For limiting the scope of the invention, after the present invention has been read, those skilled in the art are to various equivalent forms of the invention
Modification each fall within the application range as defined in the appended claims.
Claims (10)
1. a kind of preparation method of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis material, which is characterized in that including walking as follows
It is rapid:
S1, by g-C3N4Powder is added in the mixed liquor of deionized water and alcohol, after ultrasonic disperse 20-40min, stirs 20-
40min obtains g-C3N4Dispersion liquid；
Wherein, deionized water and the volume ratio of alcohol are 96:4 ~ 98:2, add 0.3-2g g-C in every 100mL mixed liquor3N4Powder；
Under sonic oscillation, with mechanical shearing machine to the g-C3N4Dispersion liquid carries out 5 ~ 6 h of shearing, and it is evenly dispersed to obtain solution
G-C3N4Solution；Then, with centrifuge to the g-C3N4Processing is centrifuged in solution, obtains g-C3N4Quantum dot dispersion
Solution；
S2, the g-C that will be obtained in crude zinc oxide materials and S13N4Quantum dot disperses solution mixing, and ball milling is dry, obtains graphitic nitralloy
Carbon quantum dot modified zinc oxide catalysis material.
2. the preparation method of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis material according to claim 1, feature
It is, in S1, g-C3N4Raw powder's production technology are as follows: nitrogenous compound is placed in Muffle furnace, is warming up to 500-600 DEG C, preferably
Ground, heating rate is 3 ~ 5 DEG C/min, cooling after keeping the temperature 1.5-7h, obtains g-C3N4Powder.
3. the preparation method of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis material according to claim 2, feature
It is, the nitrogenous compound is at least one of melamine, urea, thiocarbamide.
4. the preparation method of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis material according to claim 1, feature
It is, in S1, the alcohol is at least one of methanol, ethyl alcohol, propyl alcohol.
5. the preparation method of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis material according to claim 1, feature
It is, in S1, in shear history, the revolving speed of mechanical shearing machine is 2000 ~ 6000 r/min；During centrifuging treatment, from
Scheming revolving speed is 10000 ~ 12000 r/min.
6. the preparation method of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis material according to claim 1, feature
It is, in S2, is mixed into 1-10mL g-C in every 1g crude zinc oxide materials3N4Quantum dot disperses solution.
7. the preparation method of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis material according to claim 1, feature
It is, in S2, the crude zinc oxide materials are the Zinc oxide powders that partial size is 0.5-3 μm.
8. the preparation method of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis material according to claim 1, feature
It is, in S2, in mechanical milling process, the grinding bead of selection includes big grinding bead and small grinding bead, the big grinding bead and small grinding
The quantity ratio of pearl is 1:3-5, it is preferable that the diameter ratio of the big grinding bead and small grinding bead is 2:1, and the grinding bead is preferably
Zirconium oxide abrasive pearl.
9. the preparation method of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis material according to claim 1, feature
It is, in S2, ball milling uses way traffic mode, i.e. 30 ~ 40min of positive operation, stops 3 ~ 5 min, then inverted running 30 ~ 40
Min stops 3 ~ 5 min, and repeatedly, runing time is 3 ~ 5h in total, it is preferable that revolving speed is 300 ~ 500 r/min.
10. a kind of graphitic nitralloy carbon quantum dot modified zinc oxide catalysis material, which is characterized in that any by such as claim 1-9
Preparation method described in is prepared.
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