CN110302822A - A kind of N doping carbon dots zinc oxide microcapsules and preparation method thereof - Google Patents
A kind of N doping carbon dots zinc oxide microcapsules and preparation method thereof Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 106
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 52
- 239000003094 microcapsule Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007764 o/w emulsion Substances 0.000 claims abstract description 25
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000011162 core material Substances 0.000 claims abstract description 13
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000006227 byproduct Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 15
- 239000004246 zinc acetate Substances 0.000 claims description 15
- 235000013904 zinc acetate Nutrition 0.000 claims description 15
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 9
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 2
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 claims 1
- 239000012153 distilled water Substances 0.000 abstract description 17
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000010907 mechanical stirring Methods 0.000 description 11
- 238000013019 agitation Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- -1 Sodium alkyl sulfate Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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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- Physics & Mathematics (AREA)
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Abstract
The present invention provides a kind of N doping carbon dots zinc oxide microcapsules and preparation method thereof, belongs to field of nanometer material technology.It as water phase, lauryl sodium sulfate is first that surfactant prepares oil-in-water emulsion so as to be dispersed with the dehydrated alcohols of N doping carbon dots and hexamethylene be oily phase, distilled water, then nano zine oxide is coated on emulsion droplets surface using Electrostatic Absorption and in situ Precipitation, finally by product centrifuge washing, obtaining by core material, nano zine oxide of N doping carbon dots is the N doping carbon dots zinc oxide microcapsules of wall material.The present invention does not need that directly N doping carbon dots can be loaded in nano zine oxide by subsidiary conditions such as thermal energy, simple process, energy conservation and environmental protection, and repeatability is strong；And it is more regular using N doping carbon dots zinc oxide microcapsule structure prepared by the present invention, and the slow release effect of N doping carbon dots is preferable.
Description
Technical field
The invention belongs to field of nanometer material technology, in particular to a kind of preparation method of N doping carbon dots zinc oxide microcapsules.
Background technique
Carbon dots (Carbon dots, CDs) are because having excellent biocompatibility, photoelectric conversion and being easy to chemical modification
Equal good characteristics and the extensive concern for causing scientific circles.Especially N doping carbon dots (N-doped Carbon dots, NCDs)
Show excellent fluorescence intensity, anti-microbial property, Corrosion Protection etc. due to having defect relevant to N, ion probe,
It has made important progress in the fields such as photoelectrocatalysis, antibacterial and mouldproof, anticorrosive metal.Zinc oxide (ZnO) has wide prohibit as a kind of
The semiconductor material of band equally has excellent photoelectrocatalysis, antibacterial and mouldproof, anticorrosion ability.Therefore, by carbon dots and zinc oxide
It is compound to obtain the composite material haveing excellent performance.Such as, Ding etc. pass through the ZnO foam dispersion that will burn into CDs solution at
It is prepared for function ZnO foam/CDs nanocomposite, which has good ultraviolet and visible light photocatalysis active
(Materials Science in Semiconductor Processing,2016,47,25-31).Liu et al. passes through in ZnO
CDs is impregnated at the top of nano-chip arrays to prepare ZnO/CDs hetero-junctions, further improves the separative efficiency of charge, is advanced electricity
Pole material high-performance water oxidation application in provide new chance (Ceramics International, 2017,43 (6),
5329-5333).However, CDs is easy to be gone bad by external environmental interference, to influence there are unstability in above-mentioned report
The actual use performance of composite material.
Summary of the invention
The purpose of the present invention is to provide a kind of N doping carbon dots zinc oxide microcapsules and preparation method thereof, and this method can
Directly N doping carbon dots are loaded in zinc oxide microcapsules, solve the problems, such as that CDs is unstable.
The present invention is to be achieved through the following technical solutions:
A kind of preparation method of N doping carbon dots zinc oxide microcapsules, includes the following steps:
Step 1, N doping carbon dots are prepared；
Step 2, it disperses N doping carbon dots in the mixed liquor of dehydrated alcohol and hexamethylene, forms solution 1；By dodecane
Base sodium sulphate, dehydrated alcohol and water, which are mixed evenly to bubble-free, to be occurred, and solution 2 is formed；Then, solution 1 is added to molten
In liquid 2, stirring is obtained using water as continuous phase, and dehydrated alcohol, hexamethylene and N doping carbon dots are the oil-in-water type emulsus of dispersed phase
Liquid；
Step 3, zinc acetate aqueous solution is added dropwise in step 2 oil-in-water emulsion obtained, is stirred to react, obtains
Solution 3；Then sodium hydrate aqueous solution is added dropwise into solution 3, continues to be stirred to react, products therefrom centrifuge washing is obtained with nitrogen
Adulterate carbon dots be core material, the N doping carbon dots zinc oxide microcapsules that nano zine oxide is wall material.
Preferably, step 1 specifically: o-phenylenediamine is added to absolute ethanol, is stirred evenly, then at 170-190 DEG C
Lower progress 12~14h of solvent thermal reaction obtains N doping carbon dots after products therefrom is dry.
Preferably, in step 2,2 preparation process of solution specifically: mix lauryl sodium sulfate, dehydrated alcohol and water
Uniformly occur to bubble-free, 300~400r/min stirs 10~20min and forms solution 2 at 15~25 DEG C.
Preferably, in step 2, oil-in-water emulsion preparation process specifically: solution 1 is added into solution 2, in 15
300~400r/min stirs 15~25min at~25 DEG C, obtains oil-in-water emulsion.
Preferably, in the solution 1 of step 2, the mass ratioes of N doping carbon dots, dehydrated alcohol and hexamethylene be (0.021~
0.042): (1.882~3.765): (0.149~0.298).
Preferably, in the solution 2 of step 2, the mass ratio of lauryl sodium sulfate, dehydrated alcohol and water be (0.060~
0.120): (7.599~15.198): (20.250~40.500).
Preferably, in step 2, the mass ratio of the quality and water of dehydrated alcohol and hexamethylene in the oil-in-water emulsion
For (3.2:6.8)~(1.9:8.1).
Preferably, step 3 specifically: by Zinc diacetate dihydrate formation zinc acetate aqueous solution soluble in water, at 15~25 DEG C
It is lower that zinc acetate aqueous solution is added dropwise in oil-in-water emulsion, and 2~4h is stirred to react with 300~400r/min, obtain solution
3；Then sodium hydrate aqueous solution is added dropwise into solution 3, and 300~400r/min is stirred to react 1~1.5h at 15~25 DEG C,
By product centrifuge washing, N doping carbon dots zinc oxide microcapsules are obtained.
Preferably, the mass ratio of N doping carbon dots and zinc acetate is (0.021~0.042): (0.660~1.320).
The N doping carbon dots zinc oxide microcapsules obtained using the preparation method.
Compared with prior art, the invention has the following beneficial technical effects:
(1) present invention is dripped with the oil-in-water microemulsion containing N doping carbon dots for template, Zn2+It is adsorbed by electrostatic interaction
In the micro emulsion droplet surface for having negative electricity, alkali source is then added, makes OH-With Zn2+In-situ precipitate generates zinc oxide, thus aoxidizing
The loading of N doping carbon dots is directly realized by the preparation process of zinc, simple process, energy conservation and environmental protection, repeatability is by force.
(2) more regular using N doping carbon dots zinc oxide microcapsule structure prepared by the present invention, N doping carbon dots cladding
In zinc oxide microcapsules, do not go bad vulnerable to environmental disturbances, improves stability, and N doping carbon dots can be in different solutions
It realizes and stablizes and constantly discharge.
Detailed description of the invention
Fig. 1 (a), (b) are respectively the TEM photo of N doping carbon dots prepared by embodiment 2,5.
Fig. 2 is the SEM photograph of N doping carbon dots zinc oxide microcapsules prepared by embodiment 1.
Fig. 3 is the TEM photo of N doping carbon dots zinc oxide microcapsules prepared by embodiment 3.
Fig. 4 is the EDS photo of N doping carbon dots zinc oxide microcapsules prepared by embodiment 4.
Fig. 5 is the N doping carbon dots zinc oxide microcapsules of the preparation of embodiment 4 in distilled water, 1%, 3%, 5%NaCl solution
In elution profiles figure.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
The present invention the following steps are included:
Step 1: o-phenylenediamine is added to absolute ethanol, and 10~20min of magnetic agitation is then transferred to polytetrafluoroethyl-ne
In alkene reaction kettle, 12~14h is reacted at 170~190 DEG C, and N doping carbon dots are obtained after vacuum drying.O-phenylenediamine and anhydrous
The ratio of ethyl alcohol is (0.550~0.650) g:(55~65) mL.
Step 2: dispersing N doping carbon dots in the mixed liquor of dehydrated alcohol and hexamethylene, forms solution 1；By 12
Sodium alkyl sulfate, dehydrated alcohol, which are uniformly mixed to bubble-free with distilled water, to be occurred, and 300~400r/min is mechanical at 15~25 DEG C
It stirs 10~20min and forms solution 2；Then, the solution 1 of above-mentioned formation is added into solution 2,300 at 15~25 DEG C~
400r/min 15~25min of mechanical stirring is obtained using water as continuous phase, and dehydrated alcohol, hexamethylene and N doping carbon dots are dispersion
The oil-in-water emulsion of phase.The mass ratio of N doping carbon dots, dehydrated alcohol and hexamethylene is (0.021~0.042): (1.882
~3.765): (0.149~0.298).The mass ratio of lauryl sodium sulfate, dehydrated alcohol and distilled water be (0.060~
0.120): (7.599~15.198): (20.250~40.500).
Step 3: Zinc diacetate dihydrate is dissolved in the aqueous solution that zinc acetate is formed in distilled water, by it at 15~25 DEG C
It is added dropwise in step 2 oil-in-water emulsion obtained, and 2~4h is stirred to react with 300~400r/min, then thereto
The aqueous solution (3~6mol/L) of 2~3mL sodium hydroxide is added dropwise, and at 15~25 DEG C 300~400r/min be stirred to react 1~
Product centrifuge washing is obtained and is aoxidized using N doping carbon dots as core material, nano zine oxide for the N doping carbon dots of wall material by 1.5h
Zinc microcapsules.The mass ratio of Zinc diacetate dihydrate and distilled water is (0.660~1.320): (1.800~3.600).
Wherein:
In oil-in-water emulsion described in step 2 the mass ratio of the quality and water of dehydrated alcohol and hexamethylene be (3.2:
6.8)~(1.9:8.1).
The alcohol-soluble of N doping carbon dots described in step 2 is higher than water solubility.
The mass ratio of step 3 N doping carbon dots and zinc acetate is (0.021~0.042): (0.660~1.320), gained
The partial size of N doping carbon dots zinc oxide microcapsules is between 100~200nm.
Embodiment 1
Step 1: 0.550g o-phenylenediamine is added in 55mL dehydrated alcohol, magnetic agitation 10min is then transferred to poly-
In tetrafluoroethene reaction kettle, 14h is reacted at 170 DEG C, and N doping carbon dots are obtained after vacuum drying.
Step 2: 0.021g N doping carbon dots are dispersed in the mixed liquor of 1.882g dehydrated alcohol Yu 0.149g hexamethylene
In, form solution 1；0.060g lauryl sodium sulfate, 7.599g dehydrated alcohol are uniformly mixed with 20.250g distilled water to nothing
Bubble occurs, and 300r/min mechanical stirring 10min forms solution 2 at 15 DEG C；Then, the solution 1 of above-mentioned formation is added extremely
In solution 2, the 300r/min mechanical stirring 15min at 15 DEG C is obtained using water as continuous phase, and dehydrated alcohol, hexamethylene and nitrogen are mixed
Miscellaneous carbon dots are the oil-in-water emulsion of dispersed phase.
Step 3: 0.660g Zinc diacetate dihydrate is dissolved in the aqueous solution that zinc acetate is formed in 1.800g distilled water, 15
It is added dropwise at DEG C in step 2 oil-in-water emulsion obtained, and 2h is stirred to react with 300r/min, then thereto
The aqueous solution (3mol/L) of 2mL sodium hydroxide is added dropwise, and 300r/min is stirred to react 1h at 15 DEG C, by product centrifuge washing,
Obtaining by core material, nano zine oxide of N doping carbon dots is the N doping carbon dots zinc oxide microcapsules of wall material.
Embodiment 2
Step 1: 0.600g o-phenylenediamine is added in 60mL dehydrated alcohol, magnetic agitation 20min is then transferred to poly-
In tetrafluoroethene reaction kettle, 12h is reacted at 180 DEG C, and N doping carbon dots are obtained after vacuum drying.
Step 2: 0.021g N doping carbon dots are dispersed in the mixed liquor of 1.882g dehydrated alcohol Yu 0.298g hexamethylene
In, form solution 1；0.060g lauryl sodium sulfate, 7.599g dehydrated alcohol are uniformly mixed with 40.500g distilled water to nothing
Bubble occurs, and 400r/min mechanical stirring 20min forms solution 2 at 25 DEG C；Then, the solution 1 of above-mentioned formation is added extremely
In solution 2, the 400r/min mechanical stirring 25min at 25 DEG C is obtained using water as continuous phase, and dehydrated alcohol, hexamethylene and nitrogen are mixed
Miscellaneous carbon dots are the oil-in-water emulsion of dispersed phase.
Step 3: 0.660g Zinc diacetate dihydrate is dissolved in the aqueous solution that zinc acetate is formed in 1.800g distilled water, 25
It is added dropwise at DEG C in step 2 oil-in-water emulsion obtained, and 4h is stirred to react with 400r/min, then thereto
The aqueous solution (6mol/L) of 3mL sodium hydroxide is added dropwise, and 400r/min is stirred to react 1.5h at 25 DEG C, product centrifugation is washed
It washs, obtaining by core material, nano zine oxide of N doping carbon dots is the N doping carbon dots zinc oxide microcapsules of wall material.
Embodiment 3
Step 1: 0.550g o-phenylenediamine is added in 55mL dehydrated alcohol, magnetic agitation 15min is then transferred to poly-
In tetrafluoroethene reaction kettle, 12h is reacted at 185 DEG C, and N doping carbon dots are obtained after vacuum drying.
Step 2: 0.021g N doping carbon dots are dispersed in the mixed liquor of 3.765g dehydrated alcohol Yu 0.298g hexamethylene
In, form solution 1；0.060g lauryl sodium sulfate, 9.599g dehydrated alcohol are uniformly mixed with 40.500g distilled water to nothing
Bubble occurs, and 300r/min mechanical stirring 15min forms solution 2 at 20 DEG C；Then, the solution 1 of above-mentioned formation is added extremely
In solution 2, the 300r/min mechanical stirring 15min at 20 DEG C is obtained using water as continuous phase, and dehydrated alcohol, hexamethylene and nitrogen are mixed
Miscellaneous carbon dots are the oil-in-water emulsion of dispersed phase.
Step 3: 1.320g Zinc diacetate dihydrate is dissolved in the aqueous solution that zinc acetate is formed in 3.600g distilled water, 20
It is added dropwise at DEG C in step 2 oil-in-water emulsion obtained, and 3h is stirred to react with 300r/min, then thereto
The aqueous solution (3mol/L) of 2mL sodium hydroxide is added dropwise, and 300r/min is stirred to react 1.5h at 20 DEG C, product centrifugation is washed
It washs, obtaining by core material, nano zine oxide of N doping carbon dots is the N doping carbon dots zinc oxide microcapsules of wall material.
Embodiment 4
Step 1: 0.600g o-phenylenediamine is added in 60mL dehydrated alcohol, magnetic agitation 20min is then transferred to poly-
In tetrafluoroethene reaction kettle, 13h is reacted at 185 DEG C, and N doping carbon dots are obtained after vacuum drying.
Step 2: 0.042g N doping carbon dots are dispersed in the mixed liquor of 1.882g dehydrated alcohol Yu 0.149g hexamethylene
In, form solution 1；0.120g lauryl sodium sulfate, 7.599g dehydrated alcohol are uniformly mixed with 20.250g distilled water to nothing
Bubble occurs, and 350r/min mechanical stirring 20min forms solution 2 at 25 DEG C；Then, the solution 1 of above-mentioned formation is added extremely
In solution 2, the 350r/min mechanical stirring 25min at 25 DEG C is obtained using water as continuous phase, and dehydrated alcohol, hexamethylene and nitrogen are mixed
Miscellaneous carbon dots are the oil-in-water emulsion of dispersed phase.
Step 3: 0.660g Zinc diacetate dihydrate is dissolved in the aqueous solution that zinc acetate is formed in 1.800g distilled water, 25
It is added dropwise at DEG C in step 2 oil-in-water emulsion obtained, and 3h is stirred to react with 350r/min, then thereto
The aqueous solution (6mol/L) of 2mL sodium hydroxide is added dropwise, and 350r/min is stirred to react 1.5h at 25 DEG C, product centrifugation is washed
It washs, obtaining by core material, nano zine oxide of N doping carbon dots is the N doping carbon dots zinc oxide microcapsules of wall material.
Embodiment 5
Step 1: 0.600g o-phenylenediamine is added in 60mL dehydrated alcohol, magnetic agitation 20min is then transferred to poly-
In tetrafluoroethene reaction kettle, 12h is reacted at 190 DEG C, and N doping carbon dots are obtained after vacuum drying.
Step 2: 0.042g N doping carbon dots are dispersed in the mixed liquor of 1.882g dehydrated alcohol Yu 0.298g hexamethylene
In, form solution 1；0.120g lauryl sodium sulfate, 7.599g dehydrated alcohol are uniformly mixed with 40.500g distilled water to nothing
Bubble occurs, and 400r/min mechanical stirring 20min forms solution 2 at 25 DEG C；Then, the solution 1 of above-mentioned formation is added extremely
In solution 2, the 400r/min mechanical stirring 25min at 25 DEG C is obtained using water as continuous phase, and dehydrated alcohol, hexamethylene and nitrogen are mixed
Miscellaneous carbon dots are the oil-in-water emulsion of dispersed phase.
Step 3: 0.660g Zinc diacetate dihydrate is dissolved in the aqueous solution that zinc acetate is formed in 1.800g distilled water, 25
It is added dropwise at DEG C in step 2 oil-in-water emulsion obtained, and 3h is stirred to react with 400r/min, then thereto
The aqueous solution (6mol/L) of 2mL sodium hydroxide is added dropwise, and 400r/min is stirred to react 1.5h at 25 DEG C, product centrifugation is washed
It washs, obtaining by core material, nano zine oxide of N doping carbon dots is the N doping carbon dots zinc oxide microcapsules of wall material.
Fig. 1 is the TEM photo of N doping carbon dots.It shows the structural integrity of N doping carbon dots, favorable dispersibility, partial size point
Cloth is more uniform, about 5nm.
Fig. 2 is the SEM photograph of N doping carbon dots zinc oxide microcapsules.There it can be seen that N doping carbon dots zinc oxide
The pattern of microcapsules is in class cubic, and partial size is between 100~170nm, and the part by irising out in figure is it is observed that nitrogen
Adulterating carbon dots zinc oxide microcapsules has apparent cavity structure.
Fig. 3 is the TEM photo of N doping carbon dots zinc oxide microcapsules.There it can be seen that N doping carbon dots zinc oxide
Be the biggish black of intensity on the outside of microcapsules, and internal then color is relatively shallower, suggest the formation of using N doping carbon dots as core material,
Zinc oxide is the microcapsules of wall material, almost the same with the result of SEM photograph.
Fig. 4 is the EDS photo of N doping carbon dots zinc oxide microcapsules.It can be seen from the figure that N doping carbon dots aoxidize
In zinc microcapsules mainly as composed by zinc, oxygen, nitrogen these three elements, and nitrogen is evenly distributed on zinc oxide microcapsules
On, this shows that N doping carbon dots are successfully loaded on zinc oxide microcapsules.
Fig. 5 is elution profiles of the N doping carbon dots zinc oxide microcapsules in distilled water, 1%, 3%, 5%NaCl solution
Figure.As seen from the figure, in the buffer solutions of different salinity, N doping carbon dots can be slowly released.
Microcapsules technology both can be improved by the way that a kind of material to be embedded in another material by the stabilization of protection core material
Property, increase core material utilization rate, additionally it is possible to the release of core material in certain circumstances is controlled, to realize mentioning for material comprehensive performance
It rises.N doping carbon dots zinc oxide microcapsule structure prepared by the present invention is more regular, improves the stability of N doping carbon dots,
Slow release effect is preferable.
The contents of the present invention are not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention
And to any equivalent transformation that technical solution of the present invention is taken, all are covered by the claims of the invention.
Claims (10)
1. a kind of preparation method of N doping carbon dots zinc oxide microcapsules, which comprises the steps of:
Step 1, N doping carbon dots are prepared；
Step 2, it disperses N doping carbon dots in the mixed liquor of dehydrated alcohol and hexamethylene, forms solution 1；By dodecyl sulphur
Sour sodium, dehydrated alcohol and water, which are mixed evenly to bubble-free, to be occurred, and solution 2 is formed；Then, solution 1 is added to solution 2
In, stirring is obtained using water as continuous phase, and dehydrated alcohol, hexamethylene and N doping carbon dots are the oil-in-water emulsion of dispersed phase；
Step 3, zinc acetate aqueous solution is added dropwise in step 2 oil-in-water emulsion obtained, is stirred to react, obtains solution
3；Then sodium hydrate aqueous solution is added dropwise into solution 3, continues to be stirred to react, products therefrom centrifuge washing is obtained with N doping
The N doping carbon dots zinc oxide microcapsules that carbon dots are core material, nano zine oxide is wall material.
2. the preparation method of N doping carbon dots zinc oxide microcapsules according to claim 1, which is characterized in that step 1 tool
Body are as follows: o-phenylenediamine is added to absolute ethanol, is stirred evenly, then at 170-190 DEG C carry out solvent thermal reaction 12~
14h obtains N doping carbon dots after products therefrom is dry.
3. the preparation method of N doping carbon dots zinc oxide microcapsules according to claim 1, which is characterized in that step 2
In, 2 preparation process of solution specifically: lauryl sodium sulfate, dehydrated alcohol and water are uniformly mixed to bubble-free and occurred, in 15
300~400r/min stirs 10~20min and forms solution 2 at~25 DEG C.
4. the preparation method of N doping carbon dots zinc oxide microcapsules according to claim 1, which is characterized in that step 2
In, oil-in-water emulsion preparation process specifically: 300~400r/ at 15~25 DEG C into solution 2 is added in solution 1
Min stirs 15~25min, obtains oil-in-water emulsion.
5. the preparation method of N doping carbon dots zinc oxide microcapsules according to claim 1, which is characterized in that step 2
In solution 1, the mass ratio of N doping carbon dots, dehydrated alcohol and hexamethylene is (0.021~0.042): (1.882~3.765):
(0.149~0.298).
6. the preparation method of N doping carbon dots zinc oxide microcapsules according to claim 1, which is characterized in that step 2
In solution 2, the mass ratio of lauryl sodium sulfate, dehydrated alcohol and water is (0.060~0.120): (7.599~15.198):
(20.250~40.500).
7. the preparation method of N doping carbon dots zinc oxide microcapsules according to claim 1, which is characterized in that step 2
In, in the oil-in-water emulsion mass ratio of the quality and water of dehydrated alcohol and hexamethylene be (3.2:6.8)~(1.9:
8.1)。
8. the preparation method of N doping carbon dots zinc oxide microcapsules according to claim 1, which is characterized in that step 3 tool
Body are as follows: by Zinc diacetate dihydrate formation zinc acetate aqueous solution soluble in water, be added dropwise to zinc acetate aqueous solution at 15~25 DEG C
In oil-in-water emulsion, and 2~4h is stirred to react with 300~400r/min, obtains solution 3；Then hydrogen-oxygen is added dropwise into solution 3
Change sodium water solution, and 300~400r/min is stirred to react 1~1.5h at 15~25 DEG C, by product centrifuge washing, obtains nitrogen and mix
Miscellaneous carbon dots@zinc oxide microcapsules.
9. the preparation method of N doping carbon dots zinc oxide microcapsules according to claim 1, which is characterized in that N doping
The mass ratio of carbon dots and zinc acetate is (0.021~0.042): (0.660~1.320).
10. the N doping carbon dots zinc oxide microcapsules obtained using the described in any item preparation methods of claim 1-9.
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