CN100467115C - Method for preparing nano granules based on water base foam template - Google Patents
Method for preparing nano granules based on water base foam template Download PDFInfo
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- CN100467115C CN100467115C CNB2006100687866A CN200610068786A CN100467115C CN 100467115 C CN100467115 C CN 100467115C CN B2006100687866 A CNB2006100687866 A CN B2006100687866A CN 200610068786 A CN200610068786 A CN 200610068786A CN 100467115 C CN100467115 C CN 100467115C
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- nano particle
- surfactant
- water base
- vertical tube
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Abstract
The present invention provides a simple method for preparing nano (metal elementary substance, oxide and compound) granules. It is characterized by that said invention adopts gas-liquid interface technique, and uses the water base foam as template to prepare nano granules. Said invention also provides the basic principle of said method and its concrete steps.
Description
Technical field
The invention belongs to field of nanometer technology, relate to the method that a kind of simple and convenient prepares the nano particle of metal simple-substance, oxide and compound.
Background technology
Nanometer technology is brand-new, an epoch-making science and technology, is one of three fields may obtaining important breakthrough 21 century (life science, biotechnology and obtain the energy from outer celestial body).
At present, the method for preparing nano particle is a lot, mainly is divided into physics method, chemical method.So-called physics method is utilized physical force that particle is ground to form exactly and is of a size of nano level particle.Chemical method mainly contains sol-gel processing, chemical vapour deposition technique, the precipitation method and microemulsion method.
The research of sol-gel process can be traced back to 1846 the earliest, J.J.Ebelmen[Briuker C J at that time, Scherer G W.Sol-gel Science:The Physics and Chemistry of S-G Processing[M] .Academic Press, INC, 1990.] find that mixing the back with SiCl4 with ethanol in humid air hydrolysis takes place and generate gel.It is to be predecessor with the metal alkoxide, is hydrolyzed in organic media, polycondensation reaction, makes solution obtain the hydrosol through the solation process, and the hydrosol is again through heat drying, and sintering forms superfine powder then.But in roasting process, easily reunite, adopt metal alkoxide as raw material, the cost height, emission has pollution to environment.Chemical vapour deposition technique (CVD) is to utilize gaseous material under uniform temperature, pressure, reacts at the surface of solids, generates the solid deposited thing, and deposit at first is a nano particle, forms film then.The shortcoming of this method is very high to equipment and ingredient requirement.In containing the salting liquid of one or more metal ions, add people's precipitating reagent (OH
-, C
2O
4 2-, CO
3 2-Deng), or under certain temperature, make the solution hydrolysis, form insoluble hydroxide, hydrous oxide or salt from solution, to separate out, the method that obtains nano-oxide or complex chemical compound through washing, thermal decomposition, dehydration etc. claims the precipitation method then.This method is big or small wayward to nano particle, easily is agglomerated into bigger particle.
Microemulsion claims reverse micelle again, utilize reverse micelle to prepare nano particle and can trace back to early 1980s Boutonner[Boutonner M, Kizling J, et al.The Perpartion of Monodisperse Colloidal Metal Particlefrom Microemulsion.Colloidsand Surfaces, 1982,5:209] etc. work, they have synthesized metal nanoparticles such as monodispersed platinum, rhodium, palladium first in nineteen eighty-two.Microemulsion method is to utilize two kinds of immiscible solvents to form a kind of uniform breast bubble under the effect of surfactant, the solvent that dosage is little is wrapped in and forms a microvesicle in the big solvent of dosage, the surface of microvesicle is made up of surfactant, the processes such as solid phase can make nucleation, grows, condenses, reunion that generate from microvesicle are confined in the small spherical droplets, thereby the formation spheric granules has been avoided the further reunion between the particle again.Wherein the nucleation of nano particle and growth are most crucial steps, very easily are subjected to the influence of factor such as mass transfer, heat transfer in the process in the real process, thereby make nucleation process be difficult to control.
Summary of the invention:
The purpose of this invention is to provide a kind of chemical method (abbreviation foam method) of coming the synthesis of nano particle with water base foam as template.
Foam is to be gathered in the gas/liquid interface, to be formed single dispersing molecule layer of similar Langmuir film in essence by surfactant molecule.Surfactant molecule is arranged with water closely mutually towards the mode of lining with polar head and is separated.Each bubble in the foam (generally be that three bubbles intersect, this is rock-steady structure) intersection forms plateau boundary (the P district in the accompanying drawing 1).Equally also have a liquid film district (the A district in the accompanying drawing 1) between two bubbles, analyse after liquid reaches certain hour at foam in these two zones, and thickness can reach tens even several nanometer, and this just provides possibility for the generation of nano particle.Because the interaction of redox reaction or electrostatic attraction takes place, the molecule of the generation solid sediment that can react or ion are (as HAuCl
4And NaNH
4Au, Ti (SO are produced in reaction
4)
2(NH
4)
3PO
3Reaction generates TiO
2, Ca
2+And CO
3 2Reaction generates CaCO
3, Zn
2+And S
2-Reaction generates ZnS etc.) the generation nano particle reacts in the formed foam by surfactant solution.
The invention provides a kind ofly, the steps include: with the method for water base foam as template synthesis of nano particle
A) have in the lower end and add the aqueous surfactant solution that contains the differential responses thing in the glass vertical tube (1) of core and (2) respectively;
B) in band core glass vertical tube (1) and (2), pour nitrogen respectively simultaneously, the formed foam of surfactant solution can carry reactant solution and rise along (1) pipe and (2) pipe respectively, in push pipe (3), meet then, when foam meets in its liquid film entrained reactant react to each other, generate nano particle;
C) nano particle of Sheng Chenging receives from the glass vertical tube (5) of the lower end of push pipe (3).Under TEM (transmission electron microscope), it is observed then.
Described surfactant is one or both in cloudy surfactant, positive surfactant, non-ionic surface active agent, the amphoteric surfactant.
Described push pipe (3) is " M " shape glass-tube.
Described nano particle is the nano particle of metal simple-substance, oxide and metallic compound.Nanoparticle size can be regulated and control very easily by changing experiment condition, can obtain from several nanometers to tens, hundreds of nanometers.
Preferably, described differential responses thing is HAuCl
4And NaNH
4
Preferably, described differential responses thing is NH
3H
2The FeCl of O and certain mol proportion
2With FeCl
3
Preferably, described differential responses thing is CaCl
2And Na
2CO
3
Preferably, described differential responses thing is Zn (AC)
2And Na
2S.
Preferably, described concentration of reactants scope is 1-25mmol/L.
Preferably, described concentration of reactants scope is 1-5mmol/L.
Preferably, described cloudy surfactant is AE
2S (AEO); Described positive surfactant is AEAC (an alkyl polyoxyethylene ammonium chloride); Described non-ionic surface active agent is TX-100 (NONIN HS 240); Described amphoteric surfactant is Betaine (betaine).
Preferably, described cloudy surfactant concentration ranges is 1-10mmol/L; Described positive surfactant concentration ranges is 1-10mmol/L; Described non-ionic surface active agent concentration range is for being 1-10mmol/L; Described amphoteric surfactant concentration range is for being 1-10mmol/L.
Preferably, the stream of nitrogen gas injection rate is 60ml/min.
The present invention also provides a kind of device of realizing the described method of claim 1, it is characterized in that, described device comprises:
A nitrogen cylinder (6) is used for storing and supplying nitrogen;
Two band core glass vertical tubes, core glass vertical tube (1) and be with core glass vertical tube (2) is used for holding the aqueous surfactant solution of different inorganic salts; Its lower end links to each other with nitrogen cylinder (6) by conduit;
" M " shape glass-tube (3) is as the conversion zone of the aqueous surfactant solution of different inorganic salts; Two ends link to each other with band core glass vertical tube (2) with core glass vertical tube (1) respectively;
A receiving vessel (4) is used to receive the nano particle of generation; It links to each other with the mid portion of " M " shape glass-tube (3) by glass vertical tube (5).
The present invention adopts a kind of simple mechanism, utilizes the liquid-vapor interface technology, has prepared uniform particle diameter, good dispersion and size adjustable nano particle with water base foam as template.This method is simple, and can regulate and control effectively the yardstick of nano particle, is a kind of efficient and have a nano particle synthesizing process of potentiality.
Description of drawings
Fig. 1 is a foam reactant district schematic diagram, and wherein A is the liquid film district, and P is the plateau junctional area.
Fig. 2 is a nano particle generating apparatus schematic diagram, and wherein 1 is band core glass vertical tube, and 2 are band core glass vertical tube, and 3 is " M " shape glass-tube, and 4 is beaker, and 5 is the glass vertical tube, and 6 is nitrogen cylinder.
Fig. 3 is nanometer CaCO
3The transmission electron microscope photo of particle.
Fig. 4 is nanometer CaCO
3Particle size is with the inorganic salt concentration variation diagram.Wherein C is inorganic salts (CaCl
2And Na
2CO
3) concentration, unit is mol/L; D is the nano particle average diameter size, and unit is nm.
Fig. 5 is the transmission electron microscope photo of nanometer ZnS particle.
Fig. 6 is that the nanometer ZnS particle size is with the surfactant concentration variation diagram.Wherein C is for being surfactant concentration, and unit is mol/L; D is the nano particle average diameter size, and unit is nm.
The specific embodiment:
Following examples are to further specify of the present invention, but invention is not limited thereto.
Add respectively in (1) in accompanying drawing 2 and (2) two pipes and contain the CaCl that concentration is 10mmol/L
2The anion surfactant AE2S aqueous solution and contain the Na that concentration is 10mmol/L
2CO
3The cationic surfactant AEAC aqueous solution (surfactant concentration is 10mmol/L), in two pipes, pour nitrogen (60ml/min) respectively simultaneously then, the formed foam of surfactant solution can carry inorganic salt solution and rise along (1) pipe and (2) pipe respectively, the place meets in the middle of " M " type glass-tube (3) then, foam entrained Ca in its liquid film when meeting
2+And CO
3 2-Owing to the interaction of electrostatic attraction reacts, generate nanometer CaCO
3Particle receives its product with a beaker (4).With means such as TEM products therefrom is characterized then.The result shows that the nano particle of gained is spheric granules, particle diameter distribution homogeneous, and decentralization is fine.Fig. 3 is experiment gained nanometer CaCO
3The TEM of particle (transmission electron microscope) photo.
As implement 1 described method, different is to change reactant (CaCl
2And Na
2CO
3) concentration.By changing reactant (CaCl
2And Na
2CO
3) concentration, can regulate and control nanometer CaCO easily
3The size of particle.In this experiment, fix two kinds of surfactant (AE
2S and AEAC) concentration is 1mmol/L, change two kinds of reactant concentrations, be respectively 1mmol/L, 2mmol/L, 3mmol/L, 4mmol/L, in two pipes, pour nitrogen (60ml/min) respectively simultaneously, then products therefrom is characterized with TEM, the diameter of discovery gained nano particle increases with the increase of inorganic salt concentration.Accompanying drawing 4 is nanoparticle size variation diagrams with inorganic salt concentration.
Add respectively in (1) in accompanying drawing 2 and (2) two pipes and contain the Zn that concentration is 10mmol/L (AC)
2Anion surfactant AE
2The S aqueous solution and contain the Na that concentration is 10mmol/L
2The cationic surfactant AEAC aqueous solution (surfactant concentration is 2mmol/L) of S, experimental technique is with embodiment 1.Fig. 5 is the TEM photo of experiment gained nanometer ZnS particle.
As embodiment 3 described methods, different is the fixation reaction substrate concentration, changes surfactant concentration.Products therefrom is characterized with TEM, find the size almost not influence of the change of surfactant concentration nano particle.Accompanying drawing 6 has illustrated this point, and wherein reactant concentration is fixed as 10mmol/L, changes two kinds of surfactant concentrations, is respectively 2mmol/L, 4mmol/L, 8mmol/L, and the nitrogen injection rate still is 60ml/min.Nano particle is of a size of 31 ± 2nm.
As embodiment 3 described methods, different is the fixed surface surfactant concentration, changes reactant concentration.Products therefrom is characterized with TEM, and the size of discovery nano particle increases with the increase of reactant concentration.
As embodiment 3 described methods, different is to add polymer in solution, investigates polymer to producing the influence of nano particle.The result shows: high polymer forms even band, and nano particle is distributed in wherein uniformly, and uniform particle diameter, and is big slightly when average grain diameter does not more add high polymer.
Embodiment 7
As embodiment 3 described methods, different be to use single surfactant.Surfactant at (1) and (2) two pipe use same types for example all uses anion surfactant, cationic surfactant, amphoteric surfactant or all uses non-ionic surface active agent.Experimental result shows: the pattern of the nano particle that the kind variable effect of surfactant generates, and little to the nano particle diameter influence that generates.
Embodiment 8
As embodiment 3 described methods, different is to change the stream of nitrogen gas injection rate, has investigated foam and has analysed under the liquid situation producing the influence of nano particle pattern and size in difference.Stream of nitrogen gas speed is respectively 20ml/min, 40ml/min, 60ml/min and 80ml/min, and experimental result shows: the change of air velocity has certain influence to the pattern of nano particle, is not very big to the size impact of nano particle.
Embodiment 9
Add respectively in (1) in accompanying drawing 2 and (2) two pipes and contain the Ti (SO that concentration is 10mmol/L
4)
2Anion surfactant AE
2The S aqueous solution the and contain (NH that concentration is 10mmol/L
4)
3PO
3AE
2The S aqueous solution (surfactant solution concentration is 10mmol/L).Experimental technique is the same.The result shows, the spherical TiO of gained
2Particle is in the nanoscale scope, and uniform particle diameter, and decentralization is better.
Add the FeCl that mol ratio is 2:1 respectively in (1) in accompanying drawing 2 and (2) two pipes
2And FeCl
3Anion surfactant AE
2The S aqueous solution and contain NH
3H
2The AE of O
2The S aqueous solution (surfactant solution concentration is 10mmol/L).Experimental technique is the same.The result shows, the spherical Fe of gained
3O
4Particle is in the nanoscale scope, and uniform particle diameter, and decentralization is better.
Claims (6)
1. one kind with the method for water base foam as template synthesis of nano particle, the steps include:
A) be with core glass vertical tube (1) and second to be with first and add the aqueous surfactant solution that contains different inorganic salts in the core glass vertical tube (2) respectively;
B) in the first band core glass vertical tube (1) and the second band core glass vertical tube (2), pour nitrogen respectively simultaneously, the formed foam of aqueous surfactant solution can carry inorganic salt solution and rise along the first band core glass vertical tube (1) and the second band core glass vertical tube (2) respectively, locate to meet at push pipe (3) then, foam when meeting in its liquid film entrained inorganic ion react to each other, generate nano particle;
C) nano particle of Sheng Chenging receives from the glass vertical tube (5) of push pipe (3) lower end;
Described surfactant is one or both in anion surfactant, cationic surfactant, non-ionic surface active agent, the amphoteric surfactant.
2. as claimed in claim 1 with the method for water base foam as template synthesis of nano particle, it is characterized in that described push pipe (3) is a M shape glass-tube.
3. as claimed in claim 1 with the method for water base foam as template synthesis of nano particle, it is characterized in that described different inorganic salts are Zn (CH
3COO)
2And Na
2S; Or CaCl
2And Na
2CO
3
4. as claimed in claim 1ly it is characterized in that with the method for water base foam the concentration range of described inorganic salts is 1-25mmol/L as template synthesis of nano particle.
5. as claimed in claim 1 with the method for water base foam as template synthesis of nano particle, it is characterized in that described anionic surfactant concentration scope is 1-10mmol/L; Described cationic surfactant concentration scope is 1-10mmol/L; Described non-ionic surface active agent concentration range is 1-10mmol/L; Described amphoteric surfactant concentration range is 1-10mmol/L.
6. as claimed in claim 1 with the method for water base foam as template synthesis of nano particle, it is characterized in that the stream of nitrogen gas injection rate is 60ml/min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100687866A CN100467115C (en) | 2006-09-12 | 2006-09-12 | Method for preparing nano granules based on water base foam template |
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|---|---|---|---|
| CNB2006100687866A CN100467115C (en) | 2006-09-12 | 2006-09-12 | Method for preparing nano granules based on water base foam template |
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| CN1935351A CN1935351A (en) | 2007-03-28 |
| CN100467115C true CN100467115C (en) | 2009-03-11 |
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| CN102581300A (en) * | 2012-03-23 | 2012-07-18 | 武汉大学 | Gold nano particle preparation method |
| CN107442081B (en) * | 2017-08-18 | 2021-03-26 | 中国科学院兰州化学物理研究所 | Method for constructing porous heavy metal adsorbent by taking Pickering water-based foam as template |
| CN115124983B (en) * | 2021-03-29 | 2023-11-28 | 中国石油天然气股份有限公司 | Water-based cleaning agent and preparation method and application thereof |
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