CN103318922B - Water-soluble sodium halide micro-particles, and preparation method and application thereof - Google Patents
Water-soluble sodium halide micro-particles, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to water-soluble sodium halide micro-particles, and a preparation method an application thereof. The water-soluble sodium halide micro-particles has a sodium-chloride-type crystal structure and at least one morphology and dimension of the following: the particles are cube, rhombic dodecahedron, regular octahedron, sphere or sphere-like shape, hexagonal-shaped petals or hexagonal star-shape, six-sided funnel-shape, octagonal-shaped petals, or nano-wires with three-dimensional size of 50 nanometers to 20 micrometers.
Description
Technical field
The present invention relates to a kind of halogenide with special appearance and receive micropartical, its preparation method and application thereof.Described micropartical of receiving can be used as a kind of new environmental friendliness section mould plate, for the preparation of micro-hollow structure of receiving of various material, the invention belongs to novel material and preparation field thereof, can Co ntrolled release be widely used in, the fields such as drug conveying, Selective absorber, catalysis and lithium ion battery.
Background technology
Having the material of hollow structure or compound, to have proportion little; specific surface area is large; other materials can be contained and realize protection; the functions such as slowly-releasing or increasing katalysis; at Co ntrolled release; the fields such as drug conveying, Selective absorber and catalysis have a good application prospect, wherein extensive with the preparation and application of oxide compound hollow structure.The means preparing oxide compound hollow structure are generally utilize the inorganic or previously prepared kernel templates of organic materials and coated institute earnest matter, recycle various method removing core, obtain the hollow structure of material.
Utilize the method for template synthesis oxide compound hollow structure more, but can be hard template method and soft template method two class by its classification.Wherein the monodispersed inorganics of the many fingers of hard template method, high molecular polymer or resin receive micropartical as core, nucleocapsid structure is formed in the various chemical substance of its Surface coating, and by method removings such as calcining or solvent extractions as the core of template, leave shell and form homogeneous hollow structure.And soft template method is generally carry out in the solution, utilize the material of flexible deformable such as (instead) micella or emulsion droplet etc. as template, the chemical reaction occurred by two-phase interface in the solution forms hollow structure, dry finally by separation, obtain determine hollow structure.
In the template that above-mentioned two classes are main, it is good that hard template method has monodispersity, repeatable high, the advantage such as granule-morphology and size uniformity.But also there is preparation process complexity, condition is harsh, long reaction time, and template is removed difficult, easily to remarkable shortcomings such as environments simultaneously.Soft template method has the advantages such as method is simple, mild condition, but it is single also to there is granule-morphology, and size is uneven, the significantly shortcoming such as monodispersity difference.
That is, although above-mentioned two kinds of template have been widely used in preparing various hollow structure, and be applied to Co ntrolled release, the multiple fields such as drug conveying, Selective absorber and catalysis, but still lack a kind of simple, reaction conditions is gentle, monodispersity is good, form is homogeneous, morphology controllable, particularly substances content enrich and more friendly to environment, prepare the new template of various hollow structure material.
Halogenide (such as sodium-chlor) is one of material that on the earth, content enriches the most, is widely used in daily life and completely harmless to human body.In addition, in halogenide, major part can be dissolved easily by water and is separated simply or remove, very friendly to global environment.But because most of halogenide is the ionic crystal of low melting point, there is pattern single (being generally only found to be cubes or similar), particle is extremely difficult realizes regulation and control in nanometer or submicron-scale, is not considered to a kind of potential new mould material so far.
Report more to the preparation method of superfine sodium chloride in Typical halogenated thing at present, such as, the technology of preparing of micron order superfine sodium chloride has ball mill pulverizing method method, spray-drying process, sonochemical method etc.Ball milled generally needs secondary ball milling, and the ball milling condition that the strong absorptive matter due to sodium-chlor is is harsh, the product needed high temperature dehydration process after ball milling.Superfine sodium chloride prepared by the method is easily reunited, and easily brings impurity into.
Within 2009, there is report anti-solvent legal system for micron-sized sodium chloride particle (a kind of preparation method of micron order superfine sodium chloride, number of patent application: 200910031335.9), but its size comparatively large (~ 10um), size distribution is wide, same so far, and this single shape cube shaped can only be obtained.
The hollow aggregate particles of the funnelform sodium-chlor of one side that had report to prepare in 2011, but it is for being permitted granose aggregate, it is not monodispersed small-particle, and size is very large, preparation process is complicated, and condition controls harsh (Hopper-LikeSingle Crystals of Sodium Chloride Grown at the Interface of Metastable Water Droplets, Angew.Chem.Int.Ed.2011,50,6044 ~ 6047).
In 2012, also be reported in and sodium-chlor deposited stannic oxide and obtain its hollow cubic body structure, but, stannic oxide is only deposited on the sodium-chlor crystal grain that is mixed in as chemical reaction intermediate product, any effective regulation and control are not done to sodium chloride crystal size and pattern, also be not directly separated from solution and obtain monodispersity and controlled sodium-chlor crystal grain (the Sodium Chloride Template Synthesis of Cubic Tin Dioxide Hollow Particles for Lithium IonBattery Applications of appearance and size, ACS Appl.Mater.Interfaces2012, 4, 1537-1542).
In sum, the pattern of current sodium chloride particle is only limited to cubes, almost there is no the controlled separable single dispersing sodium-chlor of appearance and size or other halid any reports, more do not propose the water-soluble substances that very enriched by this kind of earth content thinking as a kind of new Template preparation hollow structure.
Summary of the invention
In the face of prior art Problems existing, through well-planned and select, new mould material is focused on one of material that earth content enriches the most by first, to be widely used in daily life and completely harmless to human body, on the water-soluble halide very friendly to global environment.Through deliberate repetition test, first in nanometer, in submicron and micron size range, successfully synthesize this kind of halid single dispersing nano-particle of different morphologies, and realize the controlled of pattern and size.Utilize the water-soluble hollow structure preparing oxide compound of this class template, demonstrate operability and the superiority of template.
Compare with soft template method with traditional die version method, water soluble ion crystal template of the present invention is provided with the advantage of soft or hard template simultaneously and avoids its remarkable shortcoming.Particularly importantly, this kind of halid earth content is very abundant, to human and environment all without any detrimentally affect, achieves striding forward to complete Green synthesis.And up to now, never see any report this kind of water-soluble halide ionic crystal nano-particle being realized to pattern and size controlled synthesis, do not see the precedent proposing this Pseudohalides to be prepared hollow structure as a kind of new masterplate yet.
First, the invention provides a kind of water-soluble halide nano-particle, described water-soluble halide nano-particle has NaCl type crystalline structure and at least has following a kind of pattern and size:
Particle three-dimensional be of a size of 50 nanometers to 20 micron cubes, rhombic dodecahedron, regular octahedron, spherical or class is spherical, six rib petal-shaped or hexagonal star-shape, six funnel-forms, anistree petal-shaped or nano wires.
Wherein,
Described cubes is: surface is made up of { 100 } crystal face of 6 squares;
Described rhombic dodecahedron is: surface is made up of { 110 } crystal face of 12 parallelogram like;
Described regular octahedron is: surface is made up of { 111 } crystal face of 8 equilateral triangle shapes;
Described spherical or class is spherical comprise length-to-diameter ratio be less than 2 solid or hollow ball shape or class spherical, wherein, the wall thickness of hollow ball is 1/100 ~ 1/5 of its sphere diameter;
Described six rib petal-shaped or hexagonal star-shape are: be made up of six symmetric petal-shaped branches, its position can be described as, and in space three-dimensional cartesian coordinate, the positive and negative semiaxis of x, y, z coordinate axis respectively has a petal;
Described six funnel-forms are: profile exterior feature is the regular cube that { 100 } crystal face is formed, and its six faces all cave inward in funnel-form;
Described anistree petal-shaped is: gabarit pattern is similar to hexahedron, and the projection of hexahedron each all comprises the branched structure of four similar petals;
The length-to-diameter ratio of described nano wire is greater than 20.
In the present invention, described water-soluble halide can comprise sodium-chlor, Repone K, calcium chloride, magnesium chloride, ammonium chloride, Sodium Bromide, Potassium Bromide, Calcium Bromide and magnesium bromide.
The present invention provides first can have above-mentioned special appearance, and be of a size of the pattern of micron order or submicron order and the controlled monodispersity halogenide nano-particle of size, achieve the important breakthrough of basic science, these monodispersity halogenide nano-particles are expected to be used as the hollow structure of environmentally friendly water-soluble crystal template for the preparation of various material, and then medicine/gene Co ntrolled release, medicine/gene conveying, shape Selective absorber can be widely used in, catalyzer, lithium ion battery, the various uses such as pigment and makeup.
The present invention also provides a kind of method preparing above-mentioned dissolubility halogenide nano-particle, and described method comprises:
Steps A: water-soluble halide is dissolved in solvent orange 2 A to obtain halide solution C, described solvent orange 2 A is for being selected from ethylene glycol, 1,2 propylene glycol, 1,3 propylene glycol, glycerine, 1,2 butyleneglycols, 1, at least one polyvalent alcohol in 3 butyleneglycols and Isosorbide-5-Nitrae butyleneglycol or the mixed solvent be made up of this at least one polyvalent alcohol and water, in described halide solution C, halid volumetric molar concentration is between 0.1mol/L to this kind of halid saturation concentration in solvent orange 2 A;
Step B: described halide solution C is added at least with the solvent B of described solvent orange 2 A partial miscibility, described solvent B is for being selected from ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol, 2-amylalcohol, n-hexyl alcohol, isohexyl alcohol and N, the at least one polar organic solvent of dinethylformamide or the mixed solvent be made up of with hydrochloric acid or ammoniacal liquor this at least one polar organic solvent, the specified time is kept to reach balance to obtain the solution containing single dispersing halogenide nano-particle to make halogenide crystallization, the volume ratio of wherein said halide solution C and solvent B is 1:10 ~ 1:320, and
Step C: centrifugation, clean, drying obtains described water-soluble halide nano-particle.
Method of the present invention is simply controlled, the halogenide with special appearance can be prepared and receive micropartical, particle morphology at least comprises rhombic dodecahedron, regular octahedron, six rib petal-shaped, six funnel-forms, nanocubes, spherical, anistree petal-shaped, nano wire and hollow balls, size of particles can be nano level, submicron order or micron order.
Preferably, in stepb, the volume ratio of described halide solution C and solvent B is 1:10 ~ 1:30.
Preferably, in stepb, described specific time is 1 ~ 60 minute.
Again, in stepb, also comprise and add appropriate tensio-active agent, described tensio-active agent comprises Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, Trimethyllaurylammonium bromide, polyvinylpyrrolidone, bromohexadecane base Trimethylamine 99 and palmityl trimethyl ammonium chloride, wherein by weight, the addition of tensio-active agent is halid 0 ~ 10%.
Again, the present invention also provides a kind of above-mentioned water-soluble halide nano-particle preparing the application had in the material requested of hollow structure, and described material requested comprises oxide material, precious metal material and macromolecule polymer material, and described application comprises:
Make the solution reaction of the solution of containing water-soluble halogenide nano-particle and the presoma containing material requested material or material requested material with make material requested material be wrapped in water-soluble halide nano-particle with formed with water-soluble halide nano-particle be kernel, the material requested material nucleocapsid structure that is shell; And
Described nucleocapsid structure is scattered in remove the kernel of water-soluble halide nano-particle in water, to form the material requested with hollow structure.
The present invention using water-soluble halide nano-particle as the hollow structure of a kind of new soluble template for the preparation of various material, for medicine/gene Co ntrolled release, medicine/gene conveying, shape Selective absorber, catalyzer, lithium ion battery, the various uses such as pigment and makeup.The present invention utilizes the material of earth rich content, achieves the new technology revolution of complete environmental protection, and template of the present invention is easily removed.
In one example, material requested is oxide material, and described application comprises:
Step D: the solution to containing water-soluble halogenide nano-particle adds oxide precursor, ammoniacal liquor and water successively, stir, the reaction specified time, be wrapped on water-soluble halide nano-particle to make oxide compound, wherein, by weight, the addition of described oxide precursor is described halid 1 ~ 10 times;
Step e: add water and stir to remove water-soluble halide nano-particle; And
Step F: centrifugation, clean, drying obtains the oxide material with hollow structure.
Again, described oxide compound is silicon oxide, and described oxide precursor is tetraethoxy.
Again, described oxide compound is titanium oxide, and described oxide precursor is tetrabutyl titanate.
In another example, material requested is precious metal material, and described application comprises:
Step G: the aqueous solution of preparation containing precious metal material material;
Step H: the aqueous solution of the precious metal material material prepared by step G adds in the solution of step containing water-soluble halogenide nano-particle, stirring reaction is wrapped on water-soluble halide nano-particle to make described precious metal material material, wherein, by weight, the addition of described precious metal material material is described halid 1 ~ 15 times;
Step I: add water and stir to remove water-soluble halide nano-particle mould; And
Step J: centrifugation, the precious metal material that clean, dry, thermal treatment has hollow structure.
Again, described precious metal material is gold copper-base alloy, and described step G is: adopt reductive agent reduction hydrochloro-auric acid and be separated removal organic solution wherein with the aqueous solution of preparation containing nanometer gold.
Again, in step G, described reductive agent is sodium borohydride, and the mol ratio of described hydrochloro-auric acid and sodium borohydride is 1:1 ~ 1:1.5.
Again, in step J, described heat treated temperature is 200 ~ 400 DEG C, and the heat treated time is 10 ~ 60min.
In another example, material requested is polythene material, and described application comprises:
Step K: the solution of mixing containing water-soluble halogenide nano-particle and polyethylene imine based butanol solution, be uniformly mixed, centrifugal, clean gained powder, wherein, volumetric molar concentration polyethylene imine based in described polyethylene imine based butanol solution is 1 ~ 5mM, by weight, described polyethylene imine based addition is described halid 5 ~ 50 times.
Step L: step K gained powder is dispersed in 10 ~ 20ml propyl carbinol by 0.2g powder again, add polyacrylic acid butanol solution, be uniformly mixed, centrifugal, clean gained powder, wherein, in described polyacrylic acid butanol solution, polyacrylic volumetric molar concentration is 10 ~ 20mM, and by weight, described polyacrylic consumption is 5 ~ 50 times of step K gained powder;
Step M: be again dispersed in by 0.2g powder the system that 10 ~ 20ml propyl carbinol obtains with step L gained powder and replace the solution of described containing water-soluble halogenide nano-particle to repeat step K, step L5 ~ 20 time;
Step N: add water and stir to remove water-soluble halide nano-particle; And
Step O: centrifugation, clean, drying obtains the polythene material with hollow structure.
The present invention utilizes the common feature of this kind of water-soluble halide, proposes first as the new approaches of environmentally friendly water soluble ion crystal template for the preparation of various hollow structure, achieves the important breakthrough on basic science.The present invention selects single dispersing that modal sodium-chlor, Potassium Bromide etc. prepare various appearance and size and receives micropartical in above-mentioned halogenide group, successfully prepares silicon oxide and the representative oxide compound of this two class of titanium oxide, gold, polyethylene receive micro-hollow structure with it for template.Micropartical and the described template received of the present invention, environmental friendliness is nontoxic, can be widely used in Co ntrolled release, the fields such as drug conveying, Selective absorber, catalysis, pigment, makeup and lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrum (XRD) of various pattern sodium chloride crystal;
Fig. 2 is the scanning sub-microscope photo (SEM) of rhombic dodecahedron sodium chloride crystal;
Fig. 3 is the SEM picture of regular octahedron sodium chloride crystal;
Fig. 4 is the SEM picture of six rib petal-shaped sodium chloride crystals;
Fig. 5 is the SEM picture of six funnel sodium chloride crystals;
Fig. 6 is the SEM picture of nanocubes shape sodium chloride crystal;
Fig. 7 is the SEM picture of the spherical sodium chloride crystal of class;
Fig. 8 is the SEM picture of anistree petal-shaped sodium chloride crystal;
Fig. 9 is the SEM picture of nanometer wire sodium chloride crystal;
Figure 10 is the SEM picture of hollow ball-shape sodium chloride crystal;
Figure 11,12 SEM picture and the transmission electron microscope photos (TEM) being respectively six rib petal-shaped silicon oxide hollow balls;
Figure 13,14 SEM picture and the TEM pictures being respectively hollow ball-shape silicon oxide;
Figure 15,16 SEM picture and the TEM pictures being respectively hollow ball-shape titanium oxide.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
Particularly sodium chloride crystal pattern is single to the present invention is directed to existing halogenide, size can not realize more greatly controlled, there is no the present situation of single dispersing nano-particle, invent the monodispersity halogenide nano-particle that appearance and size is controlled, and using this compounds as the hollow structure of a kind of new soluble template for the preparation of various material.The present invention utilizes the material of earth rich content, achieves the new technology revolution of complete environmental protection.
Water-soluble halide nano-particle provided by the invention has NaCl type crystalline structure and at least has following a kind of pattern:
1) rhombic dodecahedron: surface is made up of { 110 } crystal face of 12 parallelogram like, and particle size is that nano level is to submicron order (50 nanometer ~ 1 micron) or micron order (1 ~ 20 micron);
2) regular octahedron: surface is made up of { 111 } crystal face of 8 equilateral triangle shapes, and particle size is that nano level is to submicron order (50 nanometer ~ 1 micron) or micron order (1 ~ 20 micron);
3) spherical or class is spherical: pattern subglobular, comprise ellipsoid or other any three-dimensional dimensions are more spherical than the class being not more than 2, diameter is that nano level is to submicron order (50 nanometer ~ 1 micron) or micron order (1 ~ 20 micron);
4) six rib petal-shaped (or hexagonal star-shape): be made up of six symmetric petal-shaped branches, its position can be described as, in space three-dimensional cartesian coordinate, the positive and negative semiaxis of x, y, z coordinate axis respectively has a petal; Particle overall dimensions is that nano level is to submicron order (50 nanometer ~ 1 micron) or micron order (1 ~ 20 micron);
5) nano level is to submicron order (50 nanometer ~ 1 micron) or micron order (1 ~ 20 micron) cubes, preferred nanocubes: 6 square { 110 } crystal faces that surface is not more than 200nm by the length of side are formed;
6) six funnel-forms: it is regular cube that its feature can be described as profile exterior feature, and its six faces all cave inward in funnel-form; The cubes length of side is that nano level is to submicron order (50 nanometer ~ 1 micron) or micron order (1 ~ 20 micron);
7) anistree petal-shaped: gabarit pattern is similar to hexahedron, hexahedral each the branched structure all comprising four similar petals; The length of side of hexahedron profile is that nano level is to submicron order (50 nanometer ~ 1 micron) or micron order (1 ~ 20 micron);
8) nano wire: its diameter is submicron order (100 nanometer ~ 1 micron), and length-to-diameter ratio is greater than 20;
9) hollow ball: the wall thickness of hollow ball is 1/100 ~ 1/5 of its sphere diameter, such as diameter is micron order (1 ~ 20 micron), and wall thickness is submicron order (100 nanometer ~ 1 micron).
Above-mentioned various nano-particle size comprises nano level (0 ~ 100nm), submicron order (100 nanometer ~ 1 micron) or micron order (1 ~ 20 micron), and all can obtain by monodisperse status.
Water-soluble halide of the present invention comprises sodium-chlor, Repone K, calcium chloride, magnesium chloride, ammonium chloride, Sodium Bromide, Potassium Bromide, Calcium Bromide and magnesium bromide, the common halogenide such as first-selected sodium-chlor, Repone K Sodium Bromide and Potassium Bromide.
In the present invention, described water-soluble halide nano-particle extremely simple method can obtain monodispersity nano-particle, and preparation method include, but are not limited to following steps:
1) select two kinds of organic solvent A and B, halogenide is solvable or easily molten to solvent orange 2 A, and to solvent B indissoluble or insoluble, and solvent orange 2 A dissolves each other at least partly with B is satisfied.Such as, organic solvent A can be polyvalent alcohol, such as ethylene glycol, 1,2 propylene glycol, 1,3 propylene glycol, glycerine, 1,2 butyleneglycols, 1, the alcohols such as 3 butyleneglycols and Isosorbide-5-Nitrae butyleneglycol, preferably 1,2 propylene glycol, 1,2 butyleneglycols and glycerine; Organic solvent B can be the organic polar solvent such as alcohol or acid amides, such as ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol, 2-amylalcohol, n-hexyl alcohol, isohexyl alcohol and N, dinethylformamide etc., preferred n-propyl alcohol, sec-butyl alcohol, propyl carbinol, Pentyl alcohol.Above-mentioned solvent orange 2 A or B also can be comprised a certain proportion of water, ammoniacal liquor or hydrochloric acid as required.Such as, in above-mentioned solvent orange 2 A or B can containing 0 ~ 25% water, ammoniacal liquor or hydrochloric acid.
2) halogenide is dissolved in solvent orange 2 A completely, as required, to obtain solution C concentration be 0.1mol/L until this kind of halid saturation concentration in A under relevant temperature.
3) solution C is added solvent B, the volume ratio of solution C and solvent B is 1:10 ~ 1:320, and preferably, 1:10 ~ 1:30, can add suitable tensio-active agent if desired; Tensio-active agent can be Sodium dodecylbenzene sulfonate (SDBS), sodium laurylsulfonate (SDS), Trimethyllaurylammonium bromide (DTAB), polyvinylpyrrolidone (PVP), bromohexadecane base Trimethylamine 99 (CTAB) and palmityl trimethyl ammonium chloride (CTAC) etc.By weight, the addition of tensio-active agent is halid 0 ~ 10%, and maintenance specified time (such as 5 ~ 60 minutes) obtains the solution containing single dispersing halogenide nano-particle.
By the solution containing halogenide nano-particle through centrifugation, collect, vacuum-drying, obtains various halogenide nano-particle.
Obtain nano-particle and namely can be used as a kind of water-soluble template newly.Because above-mentioned reaction soln is simultaneously containing organic solvent and monodispersity halogenide nano-particle, also directly can add various material (such as oxide compound, precious metal, high molecular polymer) in the solution to wrap up halide mixture pellet, for the preparation of the hollow structure of various material.
The method of the hollow structure of the various material of this preparation comprises the steps: 1) obtained halide mixture pellet is mixed with the organic solution containing required preparation hollow structure material, make material be wrapped in halide mixture pellet surface formed stable nucleocapsid structure (with water-soluble halide nano-particle be kernel, the material requested material nucleocapsid structure that is shell); 2) in above-mentioned solution, appropriate water is added, until the halogenide as core is dissolved in liquid the hollow structure obtaining institute's earnest matter completely; 3) hollow structure is separated from solution, cleans, reclaim, and drying and thermal treatment obtain the hollow structure of determined inorganic or organic substance.The most common and the broad-spectrum silica of this hollow structure and titanium oxide, the former is generally used for as carrier, and latter is a kind of useful photocatalyst material or optical material or cosmetics additive.These materials with hollow structure can be widely used in medicine/gene Co ntrolled release, medicine/gene conveying, shape Selective absorber, catalyzer, lithium ion battery, the various uses such as pigment and makeup.
In one example, material requested is oxide material, and its preparation method can comprise:
Solution to containing water-soluble halogenide nano-particle adds oxide precursor, ammoniacal liquor and water successively, stirring reaction (reaction times can be 2 ~ 12h) is wrapped on water-soluble halide nano-particle to make oxide compound, wherein, by weight, the addition of described oxide precursor is described halid 1 ~ 10 times;
Add water and stir to remove water-soluble halide nano-particle; And
Centrifugation, clean, drying obtains the oxide material with hollow structure.
Such as, when preparing hollow silicon oxide, oxide precursor used can be tetraethoxy.When such as preparing again hollow titanium oxide, oxide precursor used can be tetrabutyl titanate.The addition of ammoniacal liquor can be 0.5 ~ 2 times of oxide precursor consumption.
In another example, material requested is precious metal (such as gold) material, and its preparation method comprises:
The aqueous solution of preparation containing precious metal material material; Such as, when preparing gold copper-base alloy, can adopt reductive agent reduction hydrochloro-auric acid and be separated removal organic solution wherein to prepare the aqueous solution containing nanometer gold, wherein said reductive agent can be sodium borohydride, and the mol ratio of hydrochloro-auric acid and sodium borohydride can be 1:1 ~ 1:1.5;
The aqueous solution of precious metal material material is added in the solution of step containing water-soluble halogenide nano-particle, stirring reaction (reaction times can be 20 ~ 40min) is wrapped on water-soluble halide nano-particle to make described precious metal material material, wherein, by weight, the addition of described precious metal material material is described halid 1 ~ 15 times;
Add water and stir to remove water-soluble halide nano-particle mould; And
Centrifugation, the precious metal material that clean, dry, thermal treatment has hollow structure, wherein heat treated temperature is 200 ~ 400 DEG C, and the heat treated time is 10 ~ 60min.
In another example, material requested is macromolecule polymer material, and for polyethylene, its preparation method comprises:
1) solution of containing water-soluble halogenide nano-particle and polyethylene imine based butanol solution is mixed, be uniformly mixed, centrifugal, clean gained powder, wherein, volumetric molar concentration polyethylene imine based in described polyethylene imine based butanol solution is 1 ~ 5mM, by weight, described polyethylene imine based addition is described halid 5 ~ 50 times
2) step 1) gained powder is dispersed in 10 ~ 20ml propyl carbinol by 0.2g powder again, add polyacrylic acid butanol solution, be uniformly mixed, centrifugal, clean gained powder, wherein, in described polyacrylic acid butanol solution, polyacrylic volumetric molar concentration is 10 ~ 20mM, and by weight, described polyacrylic consumption is 5 ~ 50 times of step 1) gained powder;
3) with step 2) L gained powder is again dispersed in by 0.2g powder the system that 10 ~ 20ml propyl carbinol obtains and replaces the solution of described containing water-soluble halogenide nano-particle to repeat step 1), step 2) 5 ~ 20 times;
4) stirring is added water to remove water-soluble halide nano-particle; And
5) centrifugation, clean, drying obtains the polythene material with hollow structure.
Exemplify embodiment below further to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The temperature that following example is concrete, time etc. are also only examples in OK range, and namely, those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1: the preparation of rhombic dodecahedron sodium-chlor, preparation method comprises the following steps:
1) take 5g sodium-chlor (Aladdin, top grade is pure) to add and 50ml1, in 2 propylene glycol (Aladdin, top grade is pure), keep 60min at 100-140 DEG C, the insoluble part of elimination, obtains sodium chloride saturated solution;
2) the another 30ml Virahol for preparing to add in 50ml beaker and under magnetic agitation condition, slowly beaker is instilled with the above-mentioned sodium chloride saturated solution of pipette, extract 1ml, precipitated sodium chloride crystallization in the solution, keeps 5min to make crystallization reach balance, obtains sodium-chlor crystalline deposit;
3) above-mentioned reactant solution is removed supernatant liquid through centrifugation, add ethanol in proper amount, 5 minutes clean with ultrasonic oscillation, and recentrifuge is separated; Repeat said process 3-5 time;
4) centrifugal rear obtained sodium-chlor crystallization is placed on filter paper, keeps 24 hours in 70 DEG C of vacuum drying ovens, collect and obtain determined sodium-chlor crystallization 0.1g aggregate and be put in vacuum and preserve.
Utilize XRD(X x ray diffraction analysis x) and SEM(scanning electronic microscope) obtained particle is analyzed.Wherein, comprise obtained sodium-chlor crystallization X-ray diffraction spectrum in Fig. 1, the crystallization that obtains is the pure crystalline phase of sodium-chlor; Fig. 2 is by being obtained sodium-chlor crystallization SEM photo, and be the single dispersing rhombic dodecahedron that pattern is homogeneous, mean sizes is about 1.8 microns.
Embodiment 2
Under the equal conditions of embodiment 1, in 1,2 propylene glycol of 50ml, add 0.5ml deionized water in advance; The sodium chloride particle that obtains is the pure crystalline phase of sodium-chlor through X-ray diffraction analysis, adopt sem observation to obtain sodium chloride crystal be similar to the homogeneous single dispersing rhombic dodecahedron of the pattern of Fig. 1, but size comparatively embodiment 1 diminishes, and median size is about 1.2 microns.
Embodiment 3: the preparation of regular octahedron sodium-chlor, its preparation method comprises the following steps:
1) take 5g sodium-chlor (Aladdin, top grade is pure) to add and 50ml1, in 2 propylene glycol (Aladdin, top grade is pure), keep 60min at 100-140 DEG C, the insoluble part of elimination, obtains sodium chloride saturated solution;
2) the another 30ml sec-butyl alcohol for preparing to add in 50ml beaker and under magnetic agitation condition, slowly beaker is instilled with the above-mentioned sodium chloride saturated solution of pipette, extract 1ml, precipitated sodium chloride crystallization in the solution, (reaction times is 30 minutes to keep certain hour, magnetic agitation speed is 500rpm) make crystallization reach balance, obtain sodium-chlor crystalline deposit;
3) above-mentioned reactant solution is removed supernatant liquid through centrifugation, add ethanol in proper amount, 5 minutes clean with ultrasonic oscillation, and recentrifuge is separated; Repeat said process 3-5 time;
4) ageing 72h in sodium-chlor powder granule step 3) prepared and vacuum, obtains the sodium chloride particle 0.1g of regular octahedron.
Utilize XRD(X line diffraction analysis) and SEM(scanning electronic microscope) obtained particle is analyzed.Fig. 3 is by being obtained sodium-chlor crystallization SEM photo, and be the single dispersing regular octahedron that pattern is homogeneous, the mean sizes of the length of side is about 1.0 microns.
The preparation of embodiment 4: six rib petal-shaped Potassium Bromide, its preparation method comprises the following steps:
1) take 5g Potassium Bromide (Aladdin, top grade is pure) to add and 50ml1, in 2 butyleneglycols (Aladdin, top grade is pure), keep 60min at 100-140 DEG C, the insoluble part of elimination, obtains Potassium Bromide saturated solution;
2) the another 30ml sec-butyl alcohol for preparing to add in 50ml beaker and under magnetic agitation condition, slowly beaker is instilled with the above-mentioned Potassium Bromide saturated solution of pipette, extract 3ml, separate out Potassium Bromide crystallization in the solution, (reaction times is 5 minutes to keep certain hour, magnetic agitation speed is 500rpm) make crystallization reach balance, obtain crystalline deposit;
3) above-mentioned reactant solution is removed supernatant liquid through centrifugation, add ethanol in proper amount, 5 minutes clean with ultrasonic oscillation, and recentrifuge is separated; Repeat said process 3-5 time;
4) centrifugal rear obtained Potassium Bromide crystallization is placed on filter paper, keeps 24 hours in 70 DEG C of vacuum drying ovens, collect and obtain determined Potassium Bromide crystallization 0.3g aggregate and be put in vacuum and preserve.
Utilize XRD(X line diffraction analysis) and SEM(scanning electronic microscope) obtained particle is analyzed.Fig. 4 is by being obtained Potassium Bromide crystallization SEM photo, and be the single dispersing six rib petal-shaped that pattern is homogeneous, the mean sizes of the overall length of side is about 10 microns.
The preparation of embodiment 5: six funnel-form sodium-chlor, its preparation method comprises the following steps:
1) take 5g sodium-chlor (Aladdin, top grade is pure) to add and 50ml1, in 2 propylene glycol (Aladdin, top grade is pure), keep 60min at 100-140 DEG C, the insoluble part of elimination, obtains sodium chloride saturated solution;
2) concentrated hydrochloric acid of 7ml and the n-propyl alcohol of 23ml are stirred 10 minutes, fully mix;
3) slowly instill step 2 with the sodium chloride saturated solution of pipette, extract 2ml step 1)) beaker in, precipitated sodium chloride crystallization in the solution, keep certain hour (reaction times is 5 minutes, and magnetic agitation speed is 500rpm) to make crystallization reach balance, obtain sodium-chlor crystalline deposit;
4) reaction times is 5 minutes, and magnetic agitation speed is 500rpm;
5) above-mentioned reactant solution is removed supernatant liquid through centrifugation, add ethanol in proper amount, 5 minutes clean with ultrasonic oscillation, and recentrifuge is separated; Repeat said process 3-5 time;
6) centrifugal rear obtained sodium-chlor crystallization is placed on filter paper, keeps 24 hours in 70 DEG C of vacuum drying ovens, collect and obtain determined Potassium Bromide crystallization 0.2g aggregate and be put in vacuum and preserve.
Utilize XRD(X line diffraction analysis) and SEM(scanning electronic microscope) obtained particle is analyzed.Fig. 5 is by being obtained sodium-chlor crystallization SEM photo, and be single dispersing six funnel-forms that pattern is homogeneous, the mean sizes of the overall length of side is about 5 microns.
Embodiment 6: the preparation of nanocubes Repone K, its preparation method comprises the following steps:
1) taking 5g Repone K (Aladdin, top grade is pure) adds with 50ml glycerine (Aladdin, top grade is pure), and keep 60min at 100-140 DEG C, the insoluble part of elimination, obtains saturated potassium chloride solution;
2) the another 30ml sec-butyl alcohol for preparing to add in 50ml beaker and under magnetic agitation condition, slowly beaker is instilled with the above-mentioned saturated potassium chloride solution of pipette, extract 1ml, separate out Repone K crystallization in the solution, (reaction times is 5 minutes to keep certain hour, magnetic agitation speed is 500rpm) make crystallization reach balance, obtain crystalline deposit;
3) above-mentioned reactant solution is removed supernatant liquid through centrifugation, add ethanol in proper amount, 5 minutes clean with ultrasonic oscillation, and recentrifuge is separated; Repeat said process 3-5 time;
4) centrifugal rear obtained Repone K crystallization is placed on filter paper, keeps 24 hours in 70 DEG C of vacuum drying ovens, collect and obtain determined Potassium Bromide crystallization 0.1g aggregate and be put in vacuum and preserve.
Utilize XRD(X line diffraction analysis) and SEM(scanning electronic microscope) obtained particle is analyzed.Fig. 6 is by being obtained Repone K crystallization SEM photo, and be the dispersed nano cubes that pattern is homogeneous, the mean sizes of the length of side is about 100 nanometers.
Embodiment 7: the preparation of the spherical Sodium Bromide of class, its preparation method comprises the following steps:
1) take 5g Sodium Bromide (Aladdin, top grade is pure) to add and 50ml1, in 2 butyleneglycols (Aladdin, top grade is pure), keep 60min at 100-140 DEG C, the insoluble part of elimination, obtains Sodium Bromide saturated solution;
2) the another 30ml Virahol for preparing to add in 50ml beaker and under magnetic agitation condition, slowly beaker is instilled with the above-mentioned Sodium Bromide saturated solution of pipette, extract 2ml, separate out Sodium Bromide crystallization in the solution, (reaction times is 5 minutes to keep certain hour, magnetic agitation speed is 500rpm) make crystallization reach balance, obtain crystalline deposit;
3) above-mentioned reactant solution is removed supernatant liquid through centrifugation, add ethanol in proper amount, 5 minutes clean with ultrasonic oscillation, and recentrifuge is separated; Repeat said process 3-5 time;
4) centrifugal rear obtained Sodium Bromide crystallization is placed on filter paper, keeps 24 hours in 70 DEG C of vacuum drying ovens, collect and obtain determined Potassium Bromide crystallization 0.2g aggregate and be put in vacuum and preserve.
Utilize XRD(X line diffraction analysis) and SEM(scanning electronic microscope) obtained particle is analyzed.Fig. 7 is by being obtained Sodium Bromide crystallization SEM photo, and the single dispersing class homogeneous for pattern is spherical, and the mean sizes of the overall length of side is about 1 micron.
Embodiment 8: the preparation of anistree petal-shaped sodium-chlor, its preparation method comprises the following steps:
1) take 5g sodium-chlor (Aladdin, top grade is pure) to add and 50ml1, in 2 propylene glycol (Aladdin, top grade is pure), keep 60min at 100-140 DEG C, the insoluble part of elimination, obtains sodium chloride saturated solution;
2) strong aqua of 7ml and the n-propyl alcohol of 23ml are stirred 10 minutes, fully mix.
3) slowly instill step 2 with the sodium chloride saturated solution of pipette, extract 2ml step 1)) beaker in, precipitated sodium chloride crystallization in the solution, keep certain hour (reaction times is 5 minutes, and magnetic agitation speed is 500rpm) to make crystallization reach balance, obtain crystalline deposit;
4) above-mentioned reactant solution is removed supernatant liquid through centrifugation, add ethanol in proper amount, 5 minutes clean with ultrasonic oscillation, and recentrifuge is separated; Repeat said process 3-5 time;
5) centrifugal rear obtained sodium-chlor crystallization is placed on filter paper, keeps 24 hours in 70 DEG C of vacuum drying ovens, collect and obtain determined Potassium Bromide crystallization 0.2g aggregate and be put in vacuum and preserve.
Utilize XRD(X line diffraction analysis) and SEM(scanning electronic microscope) obtained particle is analyzed.Fig. 8 is by being obtained sodium-chlor crystallization SEM photo, and be the anistree petal-shaped of single dispersing that pattern is homogeneous, the mean sizes of the overall length of side is about 5 microns.
Embodiment 9: the preparation of nanometer wire Repone K, its preparation method comprises the following steps:
1) taking 5g Repone K (Aladdin, top grade is pure) adds with 50ml glycerine (Aladdin, top grade is pure), and keep 60min at 100-140 DEG C, the insoluble part of elimination, obtains saturated potassium chloride solution;
2) the another 30ml sec-butyl alcohol for preparing to add in 50ml beaker and under magnetic agitation condition, slowly beaker is instilled with the above-mentioned saturated potassium chloride solution of pipette, extract 3ml, separate out Repone K crystallization in the solution, (reaction times is 5 minutes to keep certain hour, magnetic agitation speed is 500rpm) make crystallization reach balance, obtain crystalline deposit;
3) above-mentioned reactant solution is removed supernatant liquid through centrifugation, add ethanol in proper amount, 5 minutes clean with ultrasonic oscillation, and recentrifuge is separated; Repeat said process 3-5 time;
4) centrifugal rear obtained Repone K crystallization is placed on filter paper, keeps 24 hours in 70 DEG C of vacuum drying ovens, collect and obtain determined Potassium Bromide crystallization 0.3g aggregate and be put in vacuum and preserve;
Utilize XRD(X line diffraction analysis) and SEM(scanning electronic microscope) obtained particle is analyzed.Fig. 9 is by being obtained Repone K crystallization SEM photo, and be the dispersed nano line that pattern is homogeneous, nanowire diameter is about 200 nanometers, and length is about 5 microns.
Embodiment 10: the preparation of the Sodium Bromide of hollow ball-shape, its preparation method comprises the following steps:
1) taking 5g Sodium Bromide (Aladdin, top grade is pure) adds with 50ml glycerine (Aladdin, top grade is pure), and keep 60min at 100-140 DEG C, the insoluble part of elimination, obtains Sodium Bromide saturated solution;
2) the another 30ml sec-butyl alcohol for preparing to add in 50ml beaker and under magnetic agitation condition, slowly beaker is instilled with the above-mentioned Sodium Bromide saturated solution of pipette, extract 3ml, separate out Sodium Bromide crystallization in the solution, (reaction times is 5 minutes to keep certain hour, magnetic agitation speed is 500rpm) make crystallization reach balance, obtain crystalline deposit;
3) above-mentioned reactant solution is removed supernatant liquid through centrifugation, add ethanol in proper amount, 5 minutes clean with ultrasonic oscillation, and recentrifuge is separated; Repeat said process 3-5 time;
4) centrifugal rear obtained Sodium Bromide crystallization is placed on filter paper, keeps 24 hours in 70 DEG C of vacuum drying ovens, collect and obtain determined Potassium Bromide crystallization 0.3g aggregate and be put in vacuum and preserve.
Utilize XRD(X line diffraction analysis) and SEM(scanning electronic microscope) obtained particle is analyzed.Figure 10 is by being obtained Sodium Bromide crystallization SEM photo, and be the monodisperse hollow ball that pattern is homogeneous, the diameter of hollow ball is at about 10um, and wall thickness is about 200nm.
Embodiment 11: the preparation being Template preparation silicon oxide hollow structure with six rib petal-shaped Potassium Bromides, its preparation method comprises the following steps:
1) take 5g Potassium Bromide (Aladdin, top grade is pure) to add and 50ml1, in 2 butyleneglycols (Aladdin, top grade is pure), keep 60min at 100-140 DEG C, the insoluble part of elimination, obtains Potassium Bromide saturated solution;
2) the another 30ml sec-butyl alcohol for preparing to add in 50ml beaker and under magnetic agitation condition, slowly beaker is instilled with the above-mentioned Potassium Bromide saturated solution of pipette, extract 3ml, separate out Potassium Bromide crystallization in the solution, (reaction times is 5 minutes to keep certain hour, magnetic agitation speed is 500rpm) make crystallization reach balance, obtain crystalline deposit;
3) tetraethoxy (TEOS), ammoniacal liquor and each 2ml of deionized water, stirring reaction 4h is dripped successively with ratio in order;
4) in step 3) solution in add 4ml deionized water, stir 5min, template Potassium Bromide is dissolved;
5) solution centrifugal of step 4) is separated, rotating speed 10000rpm, 5 minutes time.By the powder collected in vacuum drying oven 70 DEG C dry 24 hours, obtain the hollow silicon oxide 0.53g of six rib petal-shaped.
Utilize SEM(scanning electronic microscope) and TEM(transmission electron microscope) obtained particle is analyzed.Figure 11,12 SEM picture and the transmission electron microscope photos (TEM) being respectively six rib petal-shaped silicon oxide hollow balls.
Embodiment 12: the preparation being Template preparation silicon oxide hollow ball with the spherical Sodium Bromide of class, its preparation method comprises the following steps:
1) take 5g Sodium Bromide (Aladdin, top grade is pure) to add and 50ml1, in 2 butyleneglycols (Aladdin, top grade is pure), keep 60min at 100-140 DEG C, the insoluble part of elimination, obtains sodium chloride saturated solution;
2) the another 30ml Virahol for preparing to add in 50ml beaker and under magnetic agitation condition, slowly beaker is instilled with the above-mentioned Sodium Bromide saturated solution of pipette, extract 2ml, separate out Sodium Bromide crystallization in the solution, (reaction times is 5 minutes to keep certain hour, magnetic agitation speed is 500rpm) make crystallization reach balance, obtain crystalline deposit;
3) each 1.5ml of TEOS, ammoniacal liquor and deionized water is dripped successively with ratio in order, stirring reaction 4h;
4) step 3) is prepared in solution the deionized water adding 3ml, stir 5min, template Sodium Bromide is dissolved;
5) solution centrifugal of step 4) is separated, rotating speed 10000rpm, 5 minutes time, repeats 2 times; By the powder collected in vacuum drying oven 70 DEG C dry 24 hours, obtain class spherical hollow silicon oxide 0.41g.
Utilize SEM(scanning electronic microscope) and TEM(transmission electron microscope) obtained particle is analyzed.Figure 13,14 SEM picture and the transmission electron microscope photos (TEM) being respectively hollow ball-shape silicon oxide hollow ball.
Embodiment 13: the preparation being Template preparation titanium oxide hollow ball with the spherical Sodium Bromide of class, its preparation method comprises the following steps:
1) take 5g Sodium Bromide (Aladdin, top grade is pure) to add and 50ml1, in 2 butyleneglycols (Aladdin, top grade is pure), keep 60min at 100-140 DEG C, the insoluble part of elimination, obtains sodium chloride saturated solution;
2) the another 30ml Virahol for preparing to add in 50ml beaker and under magnetic agitation condition, slowly beaker is instilled with the above-mentioned Sodium Bromide saturated solution of pipette, extract 2ml, separate out Sodium Bromide crystallization in the solution, (reaction times is 5 minutes to keep certain hour, magnetic agitation speed is 500rpm) make crystallization reach balance, obtain crystalline deposit;
3) add tetrabutyl titanate 1ml and ammoniacal liquor 4ml in order successively, the reaction times is 1h;
4) solution of step 3) is heated to 50 DEG C, continues reaction 2h;
5) in the solution of step 4), drip the water of 5ml, stir 5min, Sodium Bromide template is removed;
6) be separated by the solution centrifugal of step 5), rotating speed 10000rpm, 5 minutes time, then add ethanol purge, evenly ultrasonic, centrifugation, repeats 3 times, by the powder collected in vacuum drying oven 70 DEG C dry 12 hours, obtain class spherical alumina titanium hollow ball 0.21g.
Utilize SEM(scanning electronic microscope) and TEM(transmission electron microscope) obtained particle is analyzed.Figure 15,16 SEM picture and the transmission electron microscope photos (TEM) being respectively hollow ball-shape titanium oxide hollow ball.
Embodiment 14: with the preparation of the spherical Sodium Bromide of class for Template preparation gold (Au) hollow ball, its preparation method comprises the following steps:
1) take 5g Sodium Bromide (Aladdin, top grade is pure) to add and 50ml1, in 2 butyleneglycols (Aladdin, top grade is pure), keep 60min at 100-140 DEG C, the insoluble part of elimination, obtains sodium chloride saturated solution;
2) the another 30ml Virahol for preparing to add in 50ml beaker and under magnetic agitation condition, slowly beaker is instilled with the above-mentioned Sodium Bromide saturated solution of pipette, extract 2ml, separate out Sodium Bromide crystallization in the solution, (reaction times is 5 minutes to keep certain hour, magnetic agitation speed is 500rpm) make crystallization reach balance, obtain crystalline deposit;
3) preparation method of nanometer gold: get the HAuCl that concentration is 30mM
4solution 1.5ml joins in the mixing solutions of 2ml tetra-n-octyl brometo de amonio and 50ml toluene, stirs 30min;
4) in the solution of step 3), add the NaBH of 0.4M
4solution 1.3ml, the reaction times is 20min;
5) organic solvent of the solution of step 4) is removed, the solution of remaining nanometer Au;
6) solution of step 5) being got 1ml joins in the spherical sodium bromide solution of class prepared by step 3), stirs 20min(stirring velocity 500rpm);
7) in the solution of step 6), add the deionized water of 5ml, stir 5min, remove Sodium Bromide template;
8) be separated (rotating speed 10000rpm, 10min) by the solution centrifugal of step 7), then add ethanol purge, evenly ultrasonic, centrifugation, repeats 3 times, by the powder collected in vacuum drying oven 70 DEG C dry 12 hours.
9) by the golden hollow ball powder of step 8) under air conditions, during temperature 300 DEG C, calcining 30min, obtain nanometer gold form hollow ball 0.01g.
Embodiment 15: with the method for the spherical Sodium Bromide of class for Template preparation polyethylene (PE) hollow ball, its preparation method comprises the following steps:
1) take 5g Sodium Bromide (Aladdin, top grade is pure) to add and 50ml1, in 2 butyleneglycols (Aladdin, top grade is pure), keep 60min at 100-140 DEG C, the insoluble part of elimination, obtains sodium chloride saturated solution;
2) the another 30ml Virahol for preparing to add in 50ml beaker and under magnetic agitation condition, slowly beaker is instilled with the above-mentioned Sodium Bromide saturated solution of pipette, extract 2ml, separate out Sodium Bromide crystallization in the solution, (reaction times is 5 minutes to keep certain hour, magnetic agitation speed is 500rpm) make crystallization reach balance, obtain crystalline deposit;
3) by step 2) polyethylene imine based (PEI) butanol solution (PEI is dissolved in propyl carbinol, and concentration is 1mM) of the spherical sodium bromide solution of class prepared and 1ml stirs 2h, mixes;
4) solution centrifugal step 3) prepared is separated (10000rpm, 10min), and with propyl carbinol, the powder of collection is cleaned 3 times;
5) by step 4) powder prepared is scattered in 10ml propyl carbinol again, and polyacrylic acid (PAA) butanol solution (PAA is dissolved in propyl carbinol, and concentration is 10mM) adding 1ml stirs 2h, mixes;
6) solution centrifugal step 5) prepared is separated (10000rpm, 10min), and with propyl carbinol, the powder of collection is cleaned 3 times;
7) by step 3)-6) experiment repeat 10 times;
8) solution step 7) prepared adds the deionized water of 5ml, stirs 5min, removes the spherical Sodium Bromide template of class;
9) be separated by the solution centrifugal of step 8), rotating speed 10000rpm, 5 minutes time, then add propyl carbinol cleaning, evenly ultrasonic, centrifugation, repeats 3 times, by the 70 DEG C of oven dry 12 hours in vacuum drying oven of the powder collected, obtains PE hollow ball 0.02g.
Industrial applicability
Micropartical and the described template received of the present invention, environmental friendliness is nontoxic, can be widely used in Co ntrolled release, the fields such as drug conveying, Selective absorber, catalysis, pigment, makeup and lithium ion battery.
Claims (16)
1. a water-soluble halide nano-particle, is characterized in that, described water-soluble halide nano-particle has NaCl type crystalline structure and at least has following a kind of pattern and size:
Particle three-dimensional is of a size of the cubes of 50 nanometer to 200 nanometers, particle three-dimensional is of a size of 50 nanometers to 20 micron rhombic dodecahedron, regular octahedron, spherical or class is spherical, six rib petal-shaped or hexagonal star-shape, six funnel-forms, anistree petal-shaped or nano wires.
2. water-soluble halide nano-particle according to claim 1, is characterized in that,
Described cubes is: surface is made up of { 100 } crystal face of 6 squares;
Described rhombic dodecahedron is: surface is made up of { 110 } crystal face of 12 parallelogram like;
Described regular octahedron is: surface is made up of { 111 } crystal face of 8 equilateral triangle shapes;
Described spherical or class is spherical comprise length-to-diameter ratio be less than 2 solid or hollow ball shape or class spherical, wherein, the wall thickness of hollow ball is 1/100 ~ 1/5 of its sphere diameter;
Described six rib petal-shaped or hexagonal star-shape are: be made up of six symmetric petal-shaped branches, its position can be described as, and in space three-dimensional cartesian coordinate, the positive and negative semiaxis of x, y, z coordinate axis respectively has a petal;
Described six funnel-forms are: profile exterior feature is the regular cube that { 100 } crystal face is formed, and its six faces all cave inward in funnel-form;
Described anistree petal-shaped is: gabarit pattern is similar to hexahedron, and the projection of hexahedron each all comprises the branched structure of four similar petals;
The length-to-diameter ratio of described nano wire is greater than 20.
3. water-soluble halide nano-particle according to claim 1 and 2, is characterized in that, described water-soluble halide comprises sodium-chlor, Repone K, Sodium Bromide and Potassium Bromide.
4. prepare a method for the water-soluble halide nano-particle according to any one of claims 1 to 3, it is characterized in that, described method comprises:
Steps A: water-soluble halide is dissolved in solvent orange 2 A to obtain halide solution C, described solvent orange 2 A is for being selected from ethylene glycol, 1,2-propylene glycol, 1, ammediol, glycerine, 1,2-butyleneglycol, 1, at least one polyvalent alcohol in 3-butyleneglycol and BDO or the mixed solvent be made up of this at least one polyvalent alcohol and water, in described halide solution C, halid volumetric molar concentration is between 0.1mol/L to this kind of halid saturation concentration in solvent orange 2 A;
Step B: described halide solution C is added at least with the solvent B of described solvent orange 2 A partial miscibility, described solvent B is for being selected from ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol, 2-amylalcohol, n-hexyl alcohol, isohexyl alcohol and N, the at least one polar organic solvent of dinethylformamide or the mixed solvent be made up of with hydrochloric acid or ammoniacal liquor this at least one polar organic solvent, the specified time is kept to reach balance to obtain the solution containing single dispersing halogenide nano-particle to make halogenide crystallization, the volume ratio of wherein said halide solution C and solvent B is 1:10 ~ 1:320, and
Step C: centrifugation, clean, drying obtains described water-soluble halide nano-particle.
5. method according to claim 4, is characterized in that, in stepb, the volume ratio of described halide solution C and solvent B is 1:10 ~ 1:30.
6. the method according to claim 4 or 5, is characterized in that, in stepb, described specific time is 1 ~ 60 minute.
7. the method according to claim 4 or 5, it is characterized in that, in stepb, also comprise and add appropriate tensio-active agent, described tensio-active agent comprises Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, Trimethyllaurylammonium bromide, polyvinylpyrrolidone, bromohexadecane base Trimethylamine 99 and palmityl trimethyl ammonium chloride, wherein by weight, the addition of tensio-active agent is halid 0 ~ 10%.
8. the water-soluble halide nano-particle according to any one of a claims 1 to 3 is preparing the application had in the material requested of hollow structure, it is characterized in that, described material requested comprises oxide material, precious metal material and macromolecule polymer material, and described application comprises:
Make the solution reaction of the solution of containing water-soluble halogenide nano-particle and the presoma containing material requested material or material requested material, with make material requested material be wrapped in water-soluble halide nano-particle with formed with water-soluble halide nano-particle be kernel, the material requested material nucleocapsid structure that is shell; And
Described nucleocapsid structure is scattered in remove the kernel of water-soluble halide nano-particle in water, to form the material requested with hollow structure.
9. application according to claim 8, is characterized in that, material requested is oxide material, and described application comprises:
Step D: the solution to containing water-soluble halogenide nano-particle adds oxide precursor, ammoniacal liquor and water successively, stir, the reaction specified time, be wrapped on water-soluble halide nano-particle to make oxide compound, wherein, by weight, the addition of described oxide precursor is described halid 1 ~ 10 times;
Step e: add water and stir to remove water-soluble halide nano-particle; And
Step F: centrifugation, clean, drying obtains the oxide material with hollow structure.
10. application according to claim 9, is characterized in that, described oxide compound is silicon oxide, and described oxide precursor is tetraethoxy.
11. application according to claim 9, is characterized in that, described oxide compound is titanium oxide, and described oxide precursor is tetrabutyl titanate.
12. application according to claim 8, is characterized in that, material requested is precious metal material, and described application comprises:
Step G: the aqueous solution of preparation containing precious metal material material;
Step H: the aqueous solution of the precious metal material material prepared by step G adds in the solution of containing water-soluble halogenide nano-particle, stirring reaction is wrapped on water-soluble halide nano-particle to make described precious metal material material, wherein, by weight, the addition of described precious metal material material is described halid 1 ~ 15 times;
Step I: add water and stir to remove water-soluble halide nano-particle mould; And
Step J: centrifugation, the precious metal material that clean, dry, thermal treatment has hollow structure.
13. application according to claim 12, is characterized in that, described precious metal material is gold copper-base alloy, and described step G is: adopt reductive agent reduction hydrochloro-auric acid and be separated removal organic solution wherein with the aqueous solution of preparation containing nanometer gold.
14. application according to claim 13, is characterized in that, in step G, described reductive agent is sodium borohydride, and the mol ratio of described hydrochloro-auric acid and sodium borohydride is 1:1 ~ 1:1.5.
15. application according to any one of claim 12 ~ 14, it is characterized in that, in step J, described heat treated temperature is 200 ~ 400 DEG C, and the heat treated time is 10 ~ 60min.
16. application according to claim 8, is characterized in that, material requested is polythene material, and described application comprises:
Step K: the solution of mixing containing water-soluble halogenide nano-particle and polyethylene imine based butanol solution, be uniformly mixed, centrifugal, clean gained powder, wherein, volumetric molar concentration polyethylene imine based in described polyethylene imine based butanol solution is 1 ~ 5mM, by weight, described polyethylene imine based addition is described halid 5 ~ 50 times;
Step L: step K gained powder is dispersed in 10 ~ 20ml propyl carbinol by 0.2g powder again, add polyacrylic acid butanol solution, be uniformly mixed, centrifugal, clean gained powder, wherein, in described polyacrylic acid butanol solution, polyacrylic volumetric molar concentration is 10 ~ 20mM, and by weight, described polyacrylic consumption is 5 ~ 50 times of step K gained powder;
Step M: be again dispersed in by 0.2g powder the system that 10 ~ 20ml propyl carbinol obtains with step L gained powder and replace the solution of described containing water-soluble halogenide nano-particle to repeat step K, step L5 ~ 20 time; Step N: add water and stir to remove water-soluble halide nano-particle; And
Step O: centrifugation, clean, drying obtains the polythene material with hollow structure.
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