CN104308172A - Method for preparing hollow cubic micro-nano metal - Google Patents
Method for preparing hollow cubic micro-nano metal Download PDFInfo
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Abstract
The invention discloses a method for preparing hollow cubic micro-nano metal and belongs to the field of inorganic nano materials. The method comprises the following steps: by performing azeotropic distillation on reversed-phase microemulsion, enabling salt contained in each microemulsion drop to separate out in the form of a cubic crystal as a template; reacting the template with metal salt precursor solution to form a core-shell structure of coating the salt with metal compounds; after reducing, washing the salt crystal template and a surfactant to obtain the hollow cubic micro-nano metal. The particle size and the wall thickness of the prepared hollow cubic micro-nano metal can be adjusted; the hollow cubic micro-nano metal is good in monodispersity and uniform in size, and can be applied to the fields of catalysis, drug carriers, sensors and the like.
Description
Technical field
The present invention relates to a kind of method preparing hollow cubic micro-/ nano metal.Specifically, the present invention relates to and prepare a cube method for hollow micro-/ nano metal with azeotropic distillation.Belong to field of inorganic nano material.
Background technology
Hollow micro-/ nano nano metal material is owing to having the thick advantage such as controlled of low-density, high-specific surface area, higher chemical stability and thermodynamic stability, particle diameter and shell, be not only desirable new catalysts materials, and in fields such as drug delivery, photocatalysis, biomarker, sensor, energy storage material, light absorbents, there is great application potential.
At present, the general method preparing hollow nano metal material has: template, spray drying process, supercritical ultrasonics technology.
Template is the most frequently used method preparing hollow nano metal, and detailed process is: first cover one deck targeted precursor material or target material itself at template surface, then removes template by the method for high-temperature calcination or chemolysis, obtains hollow material.According to the difference adopting template, template can be divided into hard template method and soft template method again, conventional hard template has: polystyrene microsphere, resin cation, meso-porous alumina, porous silicon etc., and conventional soft template has: micella, vesica, microemulsion drop, block copolymer etc.[the Wang A such as Wang, Yin H, Ge C, et al. Applied Surface Science, 2010,256 (8): 2611-2615] adopt polystyrene-acrylic acid (PSA) microballoon to do template, take Sodium Polyacrylate as stabilizing agent, reduce silver nitrate by ascorbic acid, first prepared the microballoon that Ag wraps up PSA, finally washed away PSA with oxolane and prepared hollow ping-pong ball.[the Tang Y such as Tang; Jiang Z; Xing G; et al. Advanced Functional Materials; 2013; 23 (23): 2932-2940] first by ethanol injection close to saturated sodium chloride solution; in ethanol-water solution, the solubility of sodium chloride sharply reduces and separates out; obtain sodium chloride template, under the protection of polyvinylpyrrolidone (PVP), react with liquor argenti nitratis ophthalmicus; obtain the common salt particle of silver chlorate parcel; again by ultraviolet or propane diols reduction, and wash away common salt template, finally obtain hollow cubic silver bullion.[the Zhang D such as zhang, Qi L, Ma J, et al. Advanced Materials, 2002,14 (20): 1499-1502] hollow ball of argent that uses the block copolymer (PEO-block-PMAA) of oxygen ethene and methacrylic acid and the composite micelle (PEO-biock-PMAA-SDS) of surfactant 12 a heatable brick bed base sodium sulphate (SDS) to be Template preparation.Hard template method product pattern is better, but usually needs to modify template surface just can make core-shell structure copolymer compact siro spinning technology, makes removed template method comparatively difficult; Soft template method removed template method more for convenience, but soft template method is more responsive to solution environmental, the fluctuation of the pH of solution, ionic strength, solvent, temperature all can affect that the single dispersing of product is dispersed, pattern.
Spray heating decomposition is powder manufacturing technology conventional in industry.General spray-wall interaction process is: first by target presoma wiring solution-forming, then in sprayer unit, make solution atomization; The fine droplets formed through nozzle atomization enters in tube furnace, and the solvent on drop surface evaporates rapidly, and the chemical reaction of solute generation thermal decomposition or burning etc. simultaneously, forms hollow ball structure.The spray-wall interaction technology such as Fu Xixian has prepared hollow sphere CaTiO
3[Fu Xixian, Dan Zhixing. applied science journal, 1997,15 (2): 249-252].Spray drying process advantage to make solute separate out at short notice; preparation process is continuous, simple to operate; be applicable to large-scale production; but spray-wall interaction process is by the restriction of many factors; as solution viscosity, atomizer efficiency and heating-up temperature etc.; the powder body material monodispersity of the method production is simultaneously poor, and this limits the application of the method to a certain extent.
Supercritical ultrasonics technology is the method for the hollow micro/nano material of preparation grown up in recent years, its general principle is: produce an alternately positive and negative pressure when ultrasonic wave is propagated in liquid medium, medium is subject to positive and negative pressure action and ruptures, form microvesicle, microvesicle grows up into cavitation bubble, and last cavitation bubble disappears or collapse in media as well.The corresponding two reaction zones territory of cavitation: one is the gas phase in cavitation bubble, temperatures as high 5000 K, and another is the skim liquid phase of cavitation bubble outer surface, and temperature is at 1900 K.Dhas etc. [Dhas N A, Suslick K S. Journal of the American Chemical Society, 2005,127 (8): 2368-2369.] are with Mo (CO)
6, S
8for reactant, under hyperacoustic effect, define MoS
2and MoO
3hollow ball.The great advantage preparing material with ultrasonic method is that reaction can at room temperature be carried out, and the reaction time is short.In addition, the character of ultrasonic technique to system does not have particular/special requirement, as long as there is the liquid medium of transmitting energy, thus has very strong versatility to various reaction system.Although ultrasonic wave is simple, the pattern of products made thereby and the more difficult control of particle diameter, this limits the application of the method to a certain extent.
In sum, the main following points of preparation method of existing hollow micro-/ nano metal and metal oxide materials are not enough: one, synthesis technique relative complex, and condition is harsh; Two, monodispersity is poor, and product size, wall thickness can not easily regulate; Three, the pattern of product mostly is spherical, can not prepare single dispersion metal and the metal oxide materials of cube pattern.Based on above some, need a kind of step simple, lower-cost mode prepares specific morphology, and size, wall thickness are controlled, and the good method of monodispersity prepares hollow micro-/ nano metal and metal oxide materials.
summary of the invention:
For overcoming the deficiencies in the prior art, the invention provides a kind of method preparing hollow cubic micro-/ nano metal newly, the particle diameter of the hollow micro-/ nano metal that the method is produced, wall thickness can regulate, and monodispersity is good, and size is even.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method preparing the micro-nano metal of hollow cubic, carries out according to following step:
A) by soluble in water for one or more salt, and and organic solvent, surfactant is hybridly prepared into microemulsion.
B) raise the temperature of system, start azeotropic distillation and keep certain hour, period, progressively separate the water in reaction system, till distillate clear, now salt block crystal is present in the middle of system with cubic morphology.
C) precursor solution adding one or more metals and cube salt block crystal react and form metallic compound and wrap up the nucleocapsid structure of cubic metal salt block crystal as core as shell
D) remove cube salt block crystal nuclear gains in depth of comprehension to the hollow metal compound shell of cubic morphology, finally reduce this shell with reducing agent, and wash away surfactant and can obtain hollow cubic metal or alloy.
Wherein step a) described salt be the metallic salt containing halogen (Cl, Br, I), preferably, described salt is NaCl, KCI, NaBr, KBr, NaI, KI.
Wherein step a) described in organic solvent be that benzene, toluene, chloroform, oxolane, cyclohexane, benzinum etc. can form the organic matter of azeotropic mixture with water.
Wherein step a) described in surfactant include but not limited to softex kw (CTAB), 2-ethylhexyl Disodium sulfosuccinate (AOT), neopelex (SDS), n-octyl amine etc.
Wherein step a) described in salt and the mass ratio of surfactant be 0.1-20: 1 g/g, the volume mass of described organic solvent and surfactant is than being 10-1000: 1 ml/g.
Described step b) azeotropic distillation temperature is 50-250 DEG C, the time of azeotropic distillation is 5-48 hour.
Described step c) precursor solution that adds one or more metals be adopt triphenylphosphine, n-octyl amine, propylamine, ethanol, the nitrate of the metal such as Ag, Pb, Pt, Pd, Zn, Co, Fe, Ni, Cu, Ti, Sn, Cd of second eyeball or benzene complexing, chloride, hypochlorite, acetate, oxalates or sulfate one or more, wherein, metal precursor solutions and step a) described in the mass ratio of slaine be 0.1-2:1 g/g
Steps d) described in reducing agent be a kind of in hydrogen, hydrazine hydrate, natrium citricum, ascorbic acid, formaldehyde, glucose.After washing away surfactant, the particle of gained is hollow micro-/ nano particle.
A described cube average-size for salt block crystal of stating is 10nm-10 μm, and the external diameter of hollow cubic metal or alloy is 10nm-10 μm, and wall thickness is 2-5 μm.
The method of what the present invention was used prepare hollow cubic micro-/ nano metal can referred to as azeotropic distillation, its core content is by the azeotropic distillation to reverse micro emulsion, the salt contained in each microemulsion droplets is made to be that Cubic crystal is separated out as template, react with metal salt precursor solution again, become the nucleocapsid structure of metallic compound parcel salt, wash away salt crystal template after reduction and surfactant can obtain hollow cubic micro-/ nano metal.
The technical advantage of the preparation method of hollow cubic micro-/ nano metal of the present invention is mainly reflected in: adopt comparatively common salt as template, cost is lower, and raw material is easy to get.Because in microemulsion, water droplet is uniformly dispersed, size uniformity, so the crystal of the salt obtained after water in azeotropic distillation removing system is uniformly dispersed, size uniformity, which ensure that the size uniformity of final hollow micro-/ nano metal.By the size regulating the addition of salt in the size of micro emulsion drop and drop can regulate and control final hollow micro-/ nano metal.Simultaneously by regulate metal precursor solution addition and with a cube reaction time for salt block crystal, the wall thickness of final hollow cubic micro-/ nano metal can be controlled.
accompanying drawing illustrates:
Fig. 1 is the TEM figure of the hollow cubic silver bullion that embodiment 1 obtains;
Fig. 2 is the XRD figure of the hollow cubic silver bullion that embodiment 2 obtains;
Fig. 3 is the TEM figure of the hollow cubic silver bullion that embodiment 2 obtains;
Fig. 4 is the SEM figure of the hollow cubic silver bullion that embodiment 2 obtains.
detailed description of the invention:
Below in conjunction with specific embodiment, the present invention will be further described, but protection scope of the present invention is not limited thereto.
Embodiment 1
(1) take 0.5g sodium chloride and be dissolved in 5g water, pour there-necked flask into, add 2gAOT and 100ml toluene, there-necked flask is put into oil bath pan and stir 3 hours at 60 DEG C, form homogeneous microemulsion.
(2) temperature of oil bath pan be raised to 100 DEG C and keep azeotropic distillation 12h, period removes 1ml water every two little time-divisions, until distillate clarification.
(3) after solution cool to room temperature, take 0.17g silver nitrate and be dissolved in 2ml n-octyl amine, join in there-necked flask, after reaction 6h, then to add 100 μ L concentration be 5%(mass fraction) sodium citrate solution, reaction 2h.
(4) by above-mentioned product through centrifuge 5000(rev/min) centrifugal after get precipitation, wash sodium chloride with water, then through 5000(rev/min after washing away AOT with isooctane) centrifugal, dry after obtain a cube hollow silver bullion product.The average 25nm of nanometer silver bullion particle diameter collected, wall thickness 2nm.Fig. 1 is the TEM figure of the hollow cubic silver bullion that embodiment 1 obtains
Embodiment 2
(1) take 1g sodium chloride and be dissolved in 10g water, pour there-necked flask into, add 1gCTAB and 100ml benzene, there-necked flask is put into oil bath pan and stir 3 hours at 60 DEG C, form homogeneous microemulsion.
(2) temperature of oil bath pan be raised to 100 DEG C and keep azeotropic distillation 12h, period removes 1ml water every a little time-division, until distillate clarification.
(3) after solution cool to room temperature, take 0.17g chloroplatinic acid and be dissolved in 2ml n-octyl amine, join in there-necked flask, after reaction 6h, then to add 100 μ L concentration be 1%(mass fraction) hydrazine hydrate solution, reaction 2h.
(4) by above-mentioned product through centrifuge 5000(rev/min) centrifugal after get precipitation, wash sodium chloride with water, then through 5000(rev/min after washing away CTAB with isooctane) centrifugal, dry after obtain a cube hollow platinum block product.The average 200nm of Platinum Nanoparticles block particle diameter collected, wall thickness 20nm.Fig. 2 is the XRD figure of the hollow cubic silver bullion that embodiment 2 obtains, Fig. 3 is that the TEM of the hollow cubic silver bullion that embodiment 2 obtains schemes, and Fig. 4 is that the SEM of the hollow cubic silver bullion that embodiment 2 obtains schemes.
Embodiment 3
(1) take 0.5g sodium chloride and be dissolved in 5g water, pour there-necked flask into, add 2gCTAB and 100ml cyclohexane, there-necked flask is put into oil bath pan and stir 4 hours at 60 DEG C, form homogeneous microemulsion.
(2) temperature of oil bath pan be raised to 100 DEG C and keep azeotropic distillation 12h, period removes 1ml water every two little time-divisions, until distillate clarification.
(3) after solution cool to room temperature, take 0.1g gold chloride and be dissolved in 2ml n-octyl amine, join in there-necked flask, after reaction 6h, then to add 100 μ L concentration be 1%(mass fraction) sodium citrate solution, reaction 2h.
(4) by above-mentioned product through centrifuge 5000(rev/min) centrifugal after get precipitation, wash sodium chloride with water, then through 5000(rev/min after washing away AOT with isopropyl alcohol) centrifugal, dry after obtain a cube hollow gold bullion product.The average 25nm of nanometer gold bullion particle diameter collected, wall thickness 2nm.
Embodiment 4
(1) take 0.5g sodium chloride and be dissolved in 5g water, pour there-necked flask into, add 2gAOT and 100ml benzene, there-necked flask is put into oil bath pan and stir 3 hours at 60 DEG C, form homogeneous microemulsion.
(2) temperature of oil bath pan be raised to 100 DEG C and keep azeotropic distillation 12h, period removes 1ml water every two little time-divisions, until distillate clarification.
(3) after solution cool to room temperature, take 0.15g copper nitrate and be dissolved in 2ml acetonitrile, join in there-necked flask, after reaction 6h, then to add 100 μ L concentration be 1%(mass fraction) hydrazine hydrate solution, reaction 2h.
(4) by above-mentioned product through centrifuge 5000(rev/min) centrifugal after get precipitation, wash sodium chloride with water, then through 5000(rev/min after washing away AOT with isooctane) centrifugal, dry after obtain a cube hollow copper billet product.The average 25nm of nanometer copper billet particle diameter collected, wall thickness 2nm.
Embodiment 5
(1) take 0.5g sodium chloride and be dissolved in 5g water, pour there-necked flask into, add 2gCTAB and 100ml benzinum, there-necked flask is put into oil bath pan and stir 3 hours at 60 DEG C, form homogeneous microemulsion.
(2) temperature of oil bath pan be raised to 100 DEG C and keep azeotropic distillation 12h, period removes 1ml water every two little time-divisions, until distillate clarification.
(3) after solution cool to room temperature, take 0.1g zinc nitrate and be dissolved in 2ml aniline, join in there-necked flask, after reaction 6h, then to add 100 μ L concentration be 1%(mass fraction) sodium citrate solution, reaction 2h.
(4) by above-mentioned product through centrifuge 5000(rev/min) centrifugal after get precipitation, wash sodium chloride with water, then through 5000(rev/min after washing away CTAB with isopropyl alcohol) centrifugal, dry after obtain a cube hollow spelter product.The average 20nm of nanometer silver bullion particle diameter collected, wall thickness 2nm.
Embodiment 6
(1) take 0.5g sodium chloride and be dissolved in 5g water, pour there-necked flask into, add 2gSDS and 100ml benzene, there-necked flask is put into oil bath pan and stir 3 hours at 60 DEG C, form homogeneous microemulsion.
(2) temperature of oil bath pan be raised to 100 DEG C and keep azeotropic distillation 12h, period removes 1ml water every two little time-divisions, until distillate clarification.
(3) after solution cool to room temperature, take 0.1g palladium nitrate and be dissolved in 2ml n-octyl amine, join in there-necked flask, after reaction 6h, then to add 100 μ L concentration be 1%(mass fraction) formalin, reaction 2h.
(4) by above-mentioned product through centrifuge 5000(rev/min) centrifugal after get precipitation, wash sodium chloride with water, then through 5000(rev/min after washing away SDS with isooctane) centrifugal, dry after obtain a cube hollow palladium block product.The average 25nm of nanometer silver bullion particle diameter collected, wall thickness 2nm.
Embodiment 7
(1) take 0.5g sodium chloride and be dissolved in 5g water, pour there-necked flask into, add 2gSDS and 100ml benzene, there-necked flask is put into oil bath pan and stir 3 hours at 60 DEG C, form homogeneous microemulsion.
(2) temperature of oil bath pan be raised to 100 DEG C and keep azeotropic distillation 12h, period removes 1ml water every two little time-divisions, until distillate clarification.
(3) after solution cool to room temperature, take 0.3g ferric nitrate and be dissolved in 2ml n-octyl amine, join in there-necked flask, after reaction 6h, then to add 100 μ L concentration be 1%(mass fraction) sodium citrate solution, reaction 2h.
(4) by above-mentioned product through centrifuge 5000(rev/min) centrifugal after get precipitation, wash sodium chloride with water, then through 5000(rev/min after washing away SDS with isooctane) centrifugal, dry after obtain a cube hollow silver bullion product.The average 40nm of nanometer iron block particle diameter collected, wall thickness 5nm.
Embodiment 8
(1) take 0.5g sodium bromide and be dissolved in 5g water, pour there-necked flask into, add 2gAOT and 100ml benzene, there-necked flask is put into oil bath pan and stir 3 hours at 60 DEG C, form homogeneous microemulsion.
(2) temperature of oil bath pan be raised to 100 DEG C and keep azeotropic distillation 12h, period removes 1ml water every two little time-divisions, until distillate clarification.
(3) after solution cool to room temperature, take 0.17g cobalt nitrate and be dissolved in 2ml n-octyl amine, join in there-necked flask, after reaction 6h, then to add 100 μ L concentration be 1%(mass fraction) hydrazine hydrate solution, reaction 2h.
(4) by above-mentioned product through centrifuge 5000(rev/min) centrifugal after get precipitation, wash sodium bromide with water, then through 5000(rev/min after washing away AOT with isooctane) centrifugal, dry after obtain a cube hollow cobalt block product.The average 25nm of nanometer cobalt block particle diameter collected, wall thickness 2nm.
Claims (8)
1. prepare a method for the micro-nano metal of hollow cubic, it is characterized in that carrying out according to following step:
A) by soluble in water for one or more salt, and and organic solvent, surfactant is hybridly prepared into microemulsion;
B) raise the temperature of system, start azeotropic distillation and keep certain hour, period, progressively separate the water in reaction system, till distillate clear, now salt block crystal is present in the middle of system with cubic morphology;
C) precursor solution adding one or more metals and cube salt block crystal react and form metallic compound and wrap up the nucleocapsid structure of cubic metal salt block crystal as core as shell;
D) remove cube salt block crystal nuclear gains in depth of comprehension to the hollow metal compound shell of cubic morphology, finally reduce this shell with reducing agent, and wash away surfactant and can obtain hollow cubic metal or alloy.
2. a kind of method preparing the micro-nano metal of hollow cubic according to claim 1, it is characterized in that wherein step a) described salt be the metallic salt containing halogen (Cl, Br, I).
3. a kind of method preparing the micro-nano metal of hollow cubic according to claim 1, the organic solvent that it is characterized in that described in wherein step a) is that benzene, toluene, chloroform, oxolane, cyclohexane, benzinum etc. can form the organic matter of azeotropic mixture with water.
4. a kind of method preparing the micro-nano metal of hollow cubic according to claim 1, is characterized in that the surfactant described in wherein step a) includes but not limited to softex kw (CTAB), 2-ethylhexyl Disodium sulfosuccinate (AOT), neopelex (SDS), n-octyl amine etc.
5. a kind of method preparing the micro-nano metal of hollow cubic according to claim 1, it is characterized in that the mass ratio of the salt described in wherein step a) and surfactant is 0.1 ~ 20: 1 g/g, described organic solvent is 10 ~ 1000: 1 ml/g with the volume mass ratio of surfactant.
6. a kind of method preparing the micro-nano metal of hollow cubic according to claim 1, is characterized in that described step b) azeotropic distillation temperature is 50-250 DEG C, the time of azeotropic distillation is 5-48 hour.
7. a kind of method preparing the micro-nano metal of hollow cubic according to claim 1, it is characterized in that described step c) precursor solution that adds one or more metals be adopt triphenylphosphine, n-octyl amine, propylamine, ethanol, the nitrate of the metal such as Ag, Pb, Pt, Pd, Zn, Co, Fe, Ni, Cu, Ti, Sn, Cd of second eyeball or benzene complexing, chloride, hypochlorite, acetate, oxalates or sulfate one or more, metal precursor solutions and step a) described in the mass ratio of slaine be 0.1 ~ 2:1 g/g.
8. a kind of method preparing the micro-nano metal of hollow cubic according to claim 1, is characterized in that steps d) described in reducing agent be a kind of in hydrogen, hydrazine hydrate, natrium citricum, ascorbic acid, formaldehyde, glucose.
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