CN106824234B - The method for preparing sea urchin shape Ag/AgCl/ZnO nanocomposite - Google Patents
The method for preparing sea urchin shape Ag/AgCl/ZnO nanocomposite Download PDFInfo
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- CN106824234B CN106824234B CN201710053128.8A CN201710053128A CN106824234B CN 106824234 B CN106824234 B CN 106824234B CN 201710053128 A CN201710053128 A CN 201710053128A CN 106824234 B CN106824234 B CN 106824234B
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- 229910021607 Silver chloride Inorganic materials 0.000 title claims abstract description 43
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 34
- 241000257465 Echinoidea Species 0.000 title claims abstract description 27
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 60
- 229910001868 water Inorganic materials 0.000 claims abstract description 53
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 45
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 32
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011780 sodium chloride Substances 0.000 claims abstract description 20
- 230000032683 aging Effects 0.000 claims abstract description 13
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 13
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001509 sodium citrate Substances 0.000 claims abstract description 11
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 11
- 230000005514 two-phase flow Effects 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 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 4
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- 239000012530 fluid Substances 0.000 claims description 20
- 101710134784 Agnoprotein Proteins 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 3
- YCSMVPSDJIOXGN-UHFFFAOYSA-N CCCCCCCCCCCC[Na] Chemical compound CCCCCCCCCCCC[Na] YCSMVPSDJIOXGN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 230000008676 import Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 11
- 239000002086 nanomaterial Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000005119 centrifugation Methods 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 8
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 7
- 229940012189 methyl orange Drugs 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- -1 Sodium dialkyl sulfate Chemical class 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OQUFOZNPBIIJTN-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;sodium Chemical compound [Na].OC(=O)CC(O)(C(O)=O)CC(O)=O OQUFOZNPBIIJTN-UHFFFAOYSA-N 0.000 description 1
- ADDFGXAESAZSBJ-UHFFFAOYSA-N CC=1NC=CN1.[Cl] Chemical compound CC=1NC=CN1.[Cl] ADDFGXAESAZSBJ-UHFFFAOYSA-N 0.000 description 1
- WUNVTWGPFJFCPH-UHFFFAOYSA-N [Cl].C(CCC)N1CN(C=C1)C Chemical compound [Cl].C(CCC)N1CN(C=C1)C WUNVTWGPFJFCPH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000003862 health status Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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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
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/34—Organic compounds containing oxygen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The method that the present invention provides a kind of continuously to prepare sea urchin shape Ag/AgCl/ZnO nanocomposite in micro passage reaction using oil-water two-phase flow.Specifically: first by AgNO3、Zn(NO3)2, sodium citrate, lauryl sodium sulfate be configured to water solution A, NaCl and NaOH are configured to aqueous solution B.Water solution A, aqueous solution B, normal octane are then passed through capillary microreactor simultaneously, water solution A is quickly mixed with aqueous solution B, and is independent drop by normal octane dispersion, and being formed by continuous phase, aqueous solution of normal octane is the two-phase flow of dispersed phase.Above-mentioned capillary microreactor is placed under xenon lamp, and reaction mass reacts under certain temperature.Sea urchin shape Ag/AgCl/ZnO nanocomposite is finally prepared through centrifugation, washing, aging after capillary microreactor outflow in reaction mass.The present invention has many advantages, such as that process is continuous, simple process, reaction condition are mild, reproducible between batch, and avoids blockage problem of the micro passage reaction in nano material preparation process.
Description
Technical field
The invention belongs to Materials Science and Engineering fields, are related to one kind and utilize oil-water two-phase flow system in micro passage reaction
The method of standby sea urchin shape Ag/AgCl/ZnO nanocomposite.
Background technique
Water is one of valuable source for the survival of mankind, and the quality of water environment directly affects the health status of human body.With
The fast development of modern industry, water pollution problems grow in intensity, caused the extensive concern of whole world researcher.Organic matter
How (dyestuff, pesticide etc.) realizes that its efficient, green, low consumption degradation have become solution water as one of water body major pollutants
The key of pollution problem.Photocatalytic degradation of organic matter because reaction condition is mild, using solar energy the advantages that, be considered as one it is capable it
The new way of effective degradation of organic substances.Currently, researcher has developed many patterns and performance based on semiconductor material
Different photochemical catalyst.ZnO makes it have as a kind of broad stopband, the semiconductor material of high excitation energy, special electronic structure
The effects such as excellent electricity, magnetic, light have the advantages such as resourceful, at low cost, nontoxic, it has also become photochemical catalyst it is preferred.So
And ZnO have the shortcomings that surface photoinduced electron-hole to easily it is compound, limit the photocatalysis performance of ZnO.
In order to improve the photocatalysis performance of ZnO, researcher often on zno-based body doped precious metal, base metal or its
His semiconductor.For example, by Ag/AgX (X=Cl, Br, I) and the compound photocatalysis performance for being remarkably improved ZnO of ZnO.In Ag/
In AgX/ZnO (X=Cl, Br, I) system, the photoinduced electron that ZnO and AgX (X=Cl, Br, I) conduction band generate can be to its surface
The transfer of Ag nanoparticle, effectively prevents photoinduced electron and the compound of hole to bury in oblivion, to greatly improve the photocatalytic of ZnO
Energy.Meanwhile being organically combined the two in a manner of doping, the agglomeration traits of Ag nanoparticle can be effectively improved, and then reduce Ag
Dosage.In addition, also can get the table significantly increased using ZnO as base load Ag/AgX (X=Cl, Br, I) nanoparticle
Surface plasma resonance effect improves photo-quantum efficiency, increases spectral absorption range.
Meng et al. research " Ag/AgCl/ZnO nano-networks:preparation,
characterization,
mechanism and photocatalytic activity,J Mol Catal A-Chem,2016,411:
290-298 " has synthesized Ag/AgCl/ZnO with the technique that calcining combines using coordination precipitation, and detailed process is anti-at 60 DEG C
After answering 4.5h, 0.5h is first calcined in air environment at 200 DEG C, is then warming up to 350 DEG C of holding 4h.This method is intermittent behaviour
Make, time-consuming, limits the extensive use of this method.Research " the Enhanced photocatalytic of Xu et al.
Activity of new photocatalyst Ag/AgCl/ZnO, J Alloy Compd, 2011,509:3285-3292 ",
Ag/AgCl/ZnO nano material has been synthesized using two-step method.ZnO is synthesized under 140 DEG C of hydrothermal conditions first, then on ZnO
Ag is supported, being finally introducing 1- butyl -3- methylimidazole chlorine makes part Ag be converted into AgCl.This method agents useful for same 1- butyl -3-
Not environmentally, subsequent processing is cumbersome for methylimidazole chlorine, and can not continuous production.Research " the Controlled of Begum et al.
orientation in a bio-inspired assembly of Ag/AgCl/ZnO nanostructures enables
enhancement in visible-light-induced photocatalytic performance,Chem Eur J,
2012,18:6847-6853 " are mediated the mineralising of ZnO with polyamines, are prepared for Ag/AgCl/ZnO nanometers of materials by biological excitation method
Material.The process carries out in polyamines system, and low output, last handling process is cumbersome, and this method also cannot achieve continuous production.
To sum up, the preparation process of Ag/AgX/ZnO (X=Cl, Br, I) nanocomposite is mostly in traditional reactor at present
The intermittently operated of progress, production efficiency is low, and granularity is inhomogenous, poor repeatability between batch.To overcome disadvantages mentioned above, one kind need to be developed
Not only it can continuously produce in enormous quantities, but also make method reproducible between gained nano material uniform particle diameter and batch.Micro- Chemical Engineering Technology
As the model for the process intensification technology that nineties 21 century rises, compared with traditional technology, there is small in size, specific surface area
Greatly, transfer performance is good, the advantages that being easily integrated.Have unique advantage in field of inorganic material preparing technology: reacting fluid can be quick
Mixing, forms the reaction environment of stable uniform, and product can remove in time, to reduce reunion, makes gained nano material partial size point
It is reproducible between cloth is narrow and batch.In addition, the nano material preparation process based on micro- Chemical Engineering Technology is continuous operation mode, it is easy to
Large-scale production.However, being difficult to avoid blocking during preparing nano material since micro passage reaction channel size is smaller
Problem.For this purpose, the application is prepared for sea urchin shape Ag/AgCl/ZnO, Ji Keti using oil-water two-phase flow in micro passage reaction
High nano particle diameter homogeneity, and can avoid the blocking of micro passage reaction.
Summary of the invention
It is an object of the invention to be based on micro passage reaction, provides and a kind of prepare sea urchin shape Ag/ using oil-water two-phase flow
The method of AgCl/ZnO nanocomposite.It is an advantage of the invention that process is continuous, simple process, reaction condition are mild, Ag/
AgCl/ZnO pattern and uniform particle diameter, without blockage problem.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
(1) under the conditions of being protected from light, by AgNO3、Zn(NO3)2, sodium citrate, lauryl sodium sulfate and water be configured to it is water-soluble
Liquid A；
(2) NaCl and NaOH and water are configured to aqueous solution B；
(3) water solution A, aqueous solution B, normal octane are passed through capillary microreactor, water solution A is quickly mixed with aqueous solution B
It closes, and drop is independent by normal octane dispersion, being formed by continuous phase, aqueous solution of normal octane is the two-phase flow of dispersed phase；
The microreactor or be transparent capillary microreactor that capillary microreactor is reaction channel side with transparent window, reaction
The transparent window or transparent capillary microreactor in channel are placed under xenon lamp (300-500W, preferably 400W), and reaction mass is anti-
It answers；For reaction mass after capillary microreactor outflow, sea urchin shape Ag/ is finally prepared in the aging after being centrifuged and washing
AgCl/ZnO nanocomposite.
In above-mentioned technical proposal, AgNO in water solution A3The molar concentration of Yu Shuizhong is 0.0005-0.0015mol/L, excellent
Select 0.0007-0.0012mol/L；Zn(NO3)2With AgNO3Molar ratio be 10:1-40:1, preferably 15:1-30:1；Citric acid
Sodium and AgNO3Molar ratio range be 1:1-5:1, preferably 1.2:1-3.5:1；Lauryl sodium sulfate and AgNO3Molar ratio model
It encloses for 6:1-24:1, preferably 8:1-15:1.
In above-mentioned technical proposal, in aqueous solution B the molar concentration of NaCl Yu Shuizhong be 0.025-0.75mol/L, NaOH in
Molar concentration in water is 0.025-1.8mol/L.
In above-mentioned technical proposal, the flow of water solution A and aqueous solution B are 0.1-1.5mL/min, preferably 0.3-
0.9mL/min；Normal octane flow is 0.3-2.5mL/min, preferably 0.6-1.5mL/min.
In above-mentioned technical proposal, water solution A is identical as the flow of aqueous solution B.
In above-mentioned technical proposal, NaCl and AgNO3Molar ratio range be 50:1-500:1, preferably 150:1-350:1；
NaOH and Zn (NO3)2Molar ratio range be 5:1:-30:1, preferably 10:1-20:1.
In above-mentioned technical proposal, reaction temperature is 10-60 DEG C, preferably 20-40 DEG C.
In above-mentioned technical proposal, aging temperature is 100-150 DEG C, ageing time 3-5h.
In above-mentioned technical proposal, capillary microreactor have reaction channel and three intake channels, respectively liquid into
Mouth channel I, fluid inlet channel II, fluid inlet channel III, three intake channel hydraulic diameters are identical or different, respectively
0.2-1.2mm；The outlet end of three fluid inlet channels is connected to the arrival end of reaction channel respectively, fluid inlet channel I with
Fluid inlet channel II, fluid inlet channel II are identical as the angle of fluid inlet channel III, are 30-90 °；The water of reaction channel
Power diameter and intake channel hydraulic diameter are identical or different, are 0.2-1.2mm, and reaction channel length is 2-10m.Water solution A, water
The arrival end that solution B and normal octane pass through three fluid inlet channels respectively enters, reaction channel arrival end start mixing with
Reaction.
Product of the invention is sea urchin shape Ag/AgCl/ZnO composite nanoparticle, the mass ratio 1:1.4:15.1- of each substance
1:12.3-301.4。
The particle size range of sea urchin shape Ag/AgCl/ZnO nanocomposite prepared by the present invention is 300-800nm.
Compared with prior art, the present invention the substantive distinguishing features outstanding and significant progress that have are as follows:
1. based on micro passage reaction one-step synthesis sea urchin shape Ag/AgCl/ZnO, simple process, reaction condition be mild,
Process is continuous, the Ag/AgCl/ZnO pattern and uniform particle diameter being prepared, reproducible between batch.
2. forming oil-water two-phase flow by introducing normal octane as oily phase, avoiding microchannel blockage problem.
Detailed description of the invention
Fig. 1 is process flow chart of the invention, wherein 1,2,3 be syringe pump, and 4 be capillary microreactor, and 5 be liquid
Intake channel I, 6 be fluid inlet channel II, and 7 be fluid inlet channel III, and 8 be reaction channel, and 9 be xenon source.
Fig. 2 is the transmission electron microscope photo of sea urchin shape Ag/AgCl/ZnO nanocomposite prepared by embodiment 1.
Fig. 3 is the XRD spectra of Ag/AgCl/ZnO nanoparticle prepared by embodiment 1.
Fig. 4 is the transmission electron microscope photo of sea urchin shape Ag/AgCl/ZnO nanocomposite prepared by embodiment 2.
Fig. 5 is the transmission electron microscope photo of sea urchin shape Ag/AgCl/ZnO nanocomposite prepared by embodiment 3.
Fig. 6 is the transmission electron microscope photo of sea urchin shape Ag/AgCl/ZnO nanocomposite prepared by embodiment 4.
Fig. 7 is that the transmission electron microscope of random pattern Ag/AgCl/ZnO nanocomposite prepared by comparative example 1 shines
Piece.
Fig. 8 is that the transmission electron microscope of random pattern Ag/AgCl/ZnO nanocomposite prepared by comparative example 2 shines
Piece.
Fig. 9 is photo-catalytic degradation of methyl-orange curve.
Specific embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1
(1) by 0.01268g AgNO under the conditions of being protected from light3、0.36g Zn(NO3)2It is dissolved in 50mL deionized water, is made into
AgNO3With Zn (NO3)2Molar concentration is respectively the water solution A of 0.0015 and 0.025mol/L, and 0.15g ten is then added thereto
Sodium dialkyl sulfate, 0.025g sodium citrate stir 10 minutes, are allowed to be sufficiently mixed；
(2) 1.2g NaOH, 0.5g NaCl are dissolved in 50mL deionized water, are made into NaOH and NaCl molar concentration difference
For the aqueous solution B of 0.6 and 0.17mol/L；
(3) by water solution A, aqueous solution B, normal octane respectively with 0.2,0.2, the flow of 0.6mL/min passes through syringe pump and infuses
Enter in capillary microreactor, is reacted under the irradiation of 400W xenon lamp in 20 DEG C；
(4) capillary microreactor outlet gained precipitating is after water replaces washing with ethyl alcohol, and aging 5h, obtains at 120 DEG C
To sea urchin shape Ag/AgCl/ZnO nanocomposite, as shown in Figure 2.The XRD spectra of gained sample is as shown in Figure 3, it can be seen that
Gained sea urchin shape Ag/AgCl/ZnO is by cubic phase Ag, cubic phase AgCl and wurtzite ZnO.
Embodiment 2
(1) by 0.01268g AgNO under the conditions of being protected from light3、0.36g Zn(NO3)2It is dissolved in 50mL deionized water, is made into
AgNO3With Zn (NO3)2Molar concentration is respectively the water solution A of 0.0015 and 0.025mol/L, and 0.15g ten is then added thereto
Sodium dialkyl sulfate, 0.025g sodium citrate stir 10 minutes, are allowed to be sufficiently mixed；
(2) 1.2g NaOH, 0.5g NaCl are dissolved in 50mL deionized water, are made into NaOH and NaCl molar concentration difference
For the aqueous solution B of 0.6 and 0.17mol/L；
(3) by water solution A, aqueous solution B, normal octane respectively with 0.3,0.3, the flow of 0.4mL/min passes through syringe pump and infuses
Enter in capillary microreactor, is reacted under xenon lamp irradiation in 20 DEG C；
(4) capillary microreactor outlet gained precipitating is after water replaces washing with ethyl alcohol, and aging 5h, obtains at 120 DEG C
To sea urchin shape Ag/AgCl/ZnO nanocomposite, as shown in Figure 4.
Embodiment 3
(1) by 0.00845g AgNO under the conditions of being protected from light3、0.45g Zn(NO3)2It is dissolved in 50mL deionized water, is made into
AgNO3With Zn (NO3)2Molar concentration is respectively the water solution A of 0.001 and 0.03mol/L, and 0.15g 12 is then added thereto
Sodium alkyl sulfate, 0.025g sodium citrate stir 10 minutes, are allowed to be sufficiently mixed；
(2) 1.2g NaOH, 0.5g NaCl are dissolved in 50mL deionized water, are made into NaOH and NaCl molar concentration difference
For the aqueous solution B of 0.6 and 0.17mol/L；
(3) by water solution A, aqueous solution B, normal octane respectively with 0.2,0.2, the flow of 0.6mL/min passes through syringe pump and infuses
Enter in capillary microchannels reactor, is reacted under xenon lamp irradiation in 20 DEG C；
(4) capillary microreactor outlet gained precipitating is after water replaces washing with ethyl alcohol, and aging 5h, obtains at 120 DEG C
To sea urchin shape Ag/AgCl/ZnO nanocomposite, as shown in Figure 5.
Embodiment 4
(1) by 0.01268g AgNO under the conditions of being protected from light3、0.36g Zn(NO3)2It is dissolved in 50mL deionized water, is made into
AgNO3With Zn (NO3)2Molar concentration is respectively the water solution A of 0.0015 and 0.025mol/L, and 0.15g ten is then added thereto
Sodium dialkyl sulfate, 0.025g sodium citrate stir 10 minutes, are allowed to be sufficiently mixed；
(2) 1.2g NaOH, 0.5g NaCl are dissolved in 50mL deionized water, are made into NaOH and NaCl molar concentration difference
For the aqueous solution B of 0.6 and 0.17mol/L；
(3) by water solution A, aqueous solution B, normal octane respectively with 0.1,0.1, the flow of 0.3mL/min passes through syringe pump and infuses
Enter in capillary microchannels reactor, is reacted under xenon lamp (400W, similarly hereinafter) irradiation in 20 DEG C；
(4) capillary microreactor outlet gained precipitating is after water replaces washing with ethyl alcohol, and aging 5h, obtains at 120 DEG C
To sea urchin shape Ag/AgCl/ZnO nanocomposite, as shown in Figure 6.
Comparative example 1
(1) by 0.01268g AgNO under the conditions of being protected from light3、0.36g Zn(NO3)2It is dissolved in 50mL deionized water, is made into
AgNO3With Zn (NO3)2Molar concentration is respectively the water solution A of 0.0015 and 0.025mol/L, and 0.15g ten is then added thereto
Sodium dialkyl sulfate, 0.025g sodium citrate stir 10 minutes, are allowed to be sufficiently mixed；
(2) 0.2g NaOH, 0.5g NaCl are dissolved in 50mL deionized water, are made into NaOH and NaCl molar concentration difference
For the aqueous solution B of 0.1 and 0.17mol/L；
(3) by water solution A, aqueous solution B, normal octane respectively with 0.2,0.2, the flow of 0.6mL/min passes through syringe pump and infuses
Enter in capillary microchannels reactor, is reacted under xenon lamp irradiation in 20 DEG C；
(4) capillary microreactor outlet gained precipitating is after water replaces washing with ethyl alcohol, and aging 5h, obtains at 120 DEG C
To random pattern Ag/AgCl/ZnO nanocomposite, as shown in Figure 7.
Comparative example 2
(1) by 0.00845g AgNO under the conditions of being protected from light3、0.595g Zn(NO3)2It is dissolved in 50mL deionized water, is made into
AgNO3With Zn (NO3)2Molar concentration is respectively the water solution A of 0.001 and 0.04mol/L, and 0.15g 12 is then added thereto
Sodium alkyl sulfate, 0.025g sodium citrate stir 10 minutes, are allowed to be sufficiently mixed；
(2) 1.2g NaOH, 0.5g NaCl are dissolved in 50mL deionized water, are made into NaOH and NaCl molar concentration difference
For the aqueous solution B of 0.6 and 0.17mol/L；
(3) by water solution A, aqueous solution B, normal octane respectively with 0.2,0.2, the flow of 0.6mL/min passes through syringe pump and infuses
Enter in capillary microchannels reactor, is reacted under xenon lamp irradiation in 20 DEG C；
(4) capillary microreactor outlet gained precipitating is after water replaces washing with ethyl alcohol, and aging 5h, obtains at 120 DEG C
To random pattern Ag/AgCl/ZnO nanocomposite, as shown in Figure 8.
Application examples 1
Sea urchin shape Ag/AgCl/ZnO nanocomposite photo-catalytic degradation of methyl-orange prepared by embodiment 1:
(1) 2mg methyl orange is dissolved in 100mL deionized water under the conditions of being protected from light, is made into the methyl orange solution of 20mg/L, to
Sea urchin shape Ag/AgCl/ZnO nanocomposite 0.06g prepared by embodiment 1 is wherein added as photochemical catalyst, stirring 30
Minute, make up to adsorption equilibrium；
(2) it is stirred under xenon lamp irradiation, and keeps 20 DEG C of water-baths, take out 3mL mixed solution, centrifugation point at regular intervals
From taking supernatant to do UV-vis detection；
(3) it will test result treatment and do methyl orange degradation curve graph, as shown in Figure 9.
Application examples 2
Sea urchin shape Ag/AgCl/ZnO nanocomposite photo-catalytic degradation of methyl-orange prepared by embodiment 2:
(1) 2mg methyl orange is dissolved in 100mL deionized water under the conditions of being protected from light, is made into the methyl orange solution of 20mg/L, to
Sea urchin shape Ag/AgCl/ZnO nanoparticle 0.06g prepared by embodiment 2 is wherein added as photochemical catalyst, stirs 30 minutes,
Make up to adsorption equilibrium；
(2) it is stirred under xenon lamp irradiation, and keeps 20 DEG C of water-baths, take out 3mL mixed solution, centrifugation point at regular intervals
From taking supernatant to do UV-vis detection；
(3) it will test result treatment and do methyl orange degradation curve graph, as shown in Figure 9.
Claims (9)
1. the method for preparing sea urchin shape Ag/AgCl/ZnO nanocomposite utilizes oil-water two-phase flow in micro passage reaction
Continuously prepare sea urchin shape Ag/AgCl/ZnO nanocomposite, it is characterised in that:
(1) under the conditions of being protected from light, by AgNO3、Zn(NO3)2, sodium citrate, lauryl sodium sulfate and water be configured to water solution A；
Zn(NO3)2With AgNO3Molar ratio be 10:1-40:1, AgNO in water solution A3The molar concentration of Yu Shuizhong is 0.0005-
0.0015 mol/L, sodium citrate and AgNO3Molar ratio range be 1:1-5:1, lauryl sodium sulfate and AgNO3Mole
It is 6:1-24:1 than range,
(2) NaCl and NaOH and water are configured to aqueous solution B；The molar concentration of NaCl Yu Shuizhong is 0.025- in aqueous solution B
The molar concentration of 0.75 mol/L, NaOH Yu Shuizhong are 0.025-1.8 mol/L；
(3) water solution A, aqueous solution B, normal octane being passed through capillary microreactor, water solution A is quickly mixed with aqueous solution B, and
Drop is independent by normal octane dispersion, being formed by continuous phase, aqueous solution of normal octane is the two-phase flow of dispersed phase；Capillary
The microreactor or be transparent capillary microreactor that microreactor is reaction channel side with transparent window, reaction channel
Transparent window or transparent capillary microreactor are placed under 300-500W xenon lamp, reaction mass reaction；Reaction mass is from capillary
After the outflow of pipe microreactor, the nano combined material of sea urchin shape Ag/AgCl/ZnO is finally prepared in the aging after being centrifuged and washing
Material, reaction temperature are 10-60 DEG C, and aging temperature is 100-150 DEG C, and ageing time is 3-5 h, the stream of water solution A and aqueous solution B
Amount is 0.1-1.5 mL/min；Normal octane flow is 0.3-2.5 mL/min；NaCl and AgNO3Molar ratio range be 50:
1-500:1；NaOH and Zn (NO3)2Molar ratio range be 5:1-30:1.
2. according to the method described in claim 1, it is characterized by: AgNO in water solution A3The molar concentration of Yu Shuizhong is
0.0007-0.0012 mol/L；Zn(NO3)2With AgNO3Molar ratio be 15:1-30:1；Sodium citrate and AgNO3Molar ratio
Range is 1.2:1-3.5:1；Lauryl sodium sulfate and AgNO3Molar ratio range be 8:1-15:1.
3. according to the method described in claim 1, it is characterized by: the flow of water solution A and aqueous solution B are 0.3-0.9
mL/min；Normal octane flow is 0.6-1.5 mL/min.
4. according to the method described in claim 1, it is characterized by: water solution A is identical as the flow of aqueous solution B.
5. according to the method described in claim 1, it is characterized by: NaCl and AgNO3Molar ratio range be 150:1-350:
1；NaOH and Zn (NO3)2Molar ratio range be 10:1-20:1.
6. according to the method described in claim 1, it is characterized by: reaction temperature is 20-40 DEG C.
7. according to the method described in claim 1, it is characterized by: capillary microreactor has reaction channel and three imports
Channel, respectively fluid inlet channel I, fluid inlet channel II, fluid inlet channel III, three intake channel hydraulic diameter phases
It is same or different, respectively 0.2-1.2 mm；The outlet end of three fluid inlet channels is connected to the arrival end of reaction channel respectively,
Fluid inlet channel I and fluid inlet channel II, fluid inlet channel II are identical as the angle of fluid inlet channel III, are 30-
90o；The hydraulic diameter of reaction channel and intake channel hydraulic diameter are identical or different, are 0.2-1.2 mm, reaction channel length
For 2-10 m, the arrival end that water solution A, aqueous solution B and normal octane pass through three fluid inlet channels respectively enters, logical in reaction
Road arrival end starts to mix and react.
8. according to the method described in claim 1, it is characterized by: product form is Ag/AgCl/ZnO composite nanoparticle, respectively
The mass ratio 1:1.4:15.1-1:12.3:301.4 of substance.
9. according to the method described in claim 1, it is characterized by: the wattage of xenon lamp is 400W.
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