CN104308172B - A kind of method preparing the micro-nano metal of hollow cubic - Google Patents
A kind of method preparing the micro-nano metal of hollow cubic Download PDFInfo
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Abstract
A kind of method preparing the micro-nano metal of hollow cubic of the present invention, belongs to field of inorganic nano material.By the azeotropic distillation to reverse micro emulsion, making the salt contained in each microemulsion droplets is that Cubic crystal separates 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 i.e. can get hollow cubic micro-/ nano metal with surfactant.The particle diameter of hollow micro-/ nano metal of preparation, wall thickness can regulate, and monodispersity is good, and size is uniform, can be applicable to the fields such as catalysis, pharmaceutical carrier, sensor.
Description
Technical field
The present invention relates to a kind of method preparing hollow cubic micro-/ nano metal.Specifically, the present invention relates to use azeotropic
Rectification method prepares a cube method for hollow micro-/ nano metal.Belong to field of inorganic nano material.
Background technology
Hollow micro-/ nano nano metal material is owing to having low-density, high-specific surface area, higher chemical stability and heat
The advantages such as mechanical stability, particle diameter and shell thickness are controlled, are not only preferable new catalysts materials, and at medicine conveying, light
The fields such as catalysis, biomarker, sensor, energy storage material, light absorbent have great application potential.
At present, the method for general preparation hollow nano metal material has: template, spray drying method, supercritical ultrasonics technology.
Template is the method for the most frequently used preparation hollow nano metal, and detailed process is: first cover at template surface
One layer of targeted precursor material or target material itself, then remove template by the method for high-temperature calcination or chemolysis, obtain
Hollow material.According to the difference of employing template, template can be divided into again hard template method and soft template method, conventional hard template
Having: polystyrene microsphere, cationic resin, meso-porous alumina, porous silicon etc., conventional soft template has: micelle, vesicle, microemulsion
Shape drop, block copolymer etc..[Wang A, Yin H, Ge C, the et al. Applied Surface such as Wang
Science, 2010,256 (8): 2611-2615] use polystyrene-acrylic acid (PSA) microsphere to do template, with polypropylene
Acid sodium is stabilizer, by ascorbic acid reduction silver nitrate, is first prepared for the microsphere of Ag parcel PSA, finally uses oxolane
Wash away PSA and be prepared for hollow ping-pong ball.[Tang Y, Jiang Z, Xing G, the et al. Advanced such as Tang
Functional Materials, 2013,23 (23): 2932-2940] first by ethanol injection close to saturated sodium chloride
Solution, in ethanol-water solution, the dissolubility of sodium chloride drastically reduces and separates out, and obtains sodium chloride template, at polyvinyl pyrrole
Under the protection of alkanone (PVP), react with silver nitrate solution, obtain the sodium chloride granule of silver chloride parcel, then by ultraviolet or
Propylene glycol reduces, and washes away sodium chloride template, finally gives hollow cubic silver bullion.Zhang etc. [Zhang D, Qi L, Ma J,
Et al. Advanced Materials, 2002,14 (20): 1499-1502] the embedding of oxygen ethylene and methacrylic acid is used
Section copolymer (PEO-block-PMAA) and the composite micelle (PEO-biock-of surfactant 12 a heatable brick bed base sodium sulphate (SDS)
PMAA-SDS) it is the template hollow ball that is prepared for argent.Hard template method product pattern is preferable, but typically requires template surface
Carry out modifying and just can make core-shell structure copolymer compact siro spinning technology so that removed template method is the most difficult；Soft template method removed template method is the most square
Just, but soft template method is more sensitive to solution environmental, and the pH of solution, ionic strength, solvent, the fluctuation of temperature all can affect product
The single dispersing dispersibility of product, pattern.
Spray heating decomposition is powder body manufacturing technology conventional in industry.General spray-wall interaction process is: first by mesh
Mark presoma wiring solution-forming, then makes solution atomization in sprayer unit；The fine droplets formed through nozzle atomization enters pipe
In formula stove, the solvent on drop surface evaporates rapidly, and solute occurs the chemical reactions such as thermal decomposition or burning simultaneously, forms hollow chou
Structure.The spray-wall interaction technology such as Fu Xixian is prepared for hollow sphere CaTiO3[Fu Xixian, Dan Zhixing. applied science
Report, 1997,15 (2): 249-252].Spray drying method advantage is to make solute separate out at short notice, and preparation process is even
Continuous, simple to operate, it is adaptable to large-scale production, but spray-wall interaction process is limited by many factors, such as solution viscosity, atomization
Device efficiency and heating-up temperature etc., the powder body material monodispersity that the method produces simultaneously is poor, and this limits to a certain extent
The application of the method.
Supercritical ultrasonics technology is the method preparing hollow micro/nano material grown up in recent years, and its ultimate principle is: ultrasonic
Producing an alternately positive and negative pressure when ripple is propagated in liquid medium, medium is ruptured by positive and negative pressure action, is formed micro-
Bubble, microvesicle grows up into cavitation bubble, and last cavitation bubble disappears or collapse in media as well.Cavitation correspondence two reaction zones
Territory: one is the gas phase in cavitation bubble, and temperature is up to 5000 K, another is a thin layer liquid phase of cavitation bubble outer surface,
Temperature is at 1900 K.[Dhas N A, the Suslick K S. Journal of the American Chemical such as Dhas
Society, 2005,127 (8): 2368-2369.] with Mo (CO)6、S8For reactant, formed under the effect of ultrasound wave
MoS2And MoO3Hollow ball.The great advantage preparing material with ultrasonic method is that reaction can at room temperature be carried out, and
Response time is short.Additionally, ultrasonic technique does not has particular/special requirement to the character of system, as long as having the liquid medium of transmission energy i.e.
Can, thus various reaction systems are had the strongest versatility.Although ultrasound wave is simple, but the pattern of products made thereby and grain
The more difficult control in footpath, this limits the application of the method to a certain extent.
In sum, the preparation method of existing hollow micro-/ nano metal and metal oxide materials mainly has the most several
Point deficiency: one, synthesis technique is relative complex, condition is harsh；Two, monodispersity is poor, and product size, wall thickness can not easily be adjusted
Joint；Three, the pattern of product mostly is spherical, it is impossible to the single dispersion metal of preparation cube pattern and metal oxide materials.Based on
Above some, need a kind of step simple, and lower-cost mode prepares specific morphology, and size, wall thickness are controlled, and monodispersity is good
Good method prepares hollow micro-/ nano metal and metal oxide materials.
Summary of the invention:
For overcoming the deficiencies in the prior art, the present invention provides a kind of new method preparing hollow cubic micro-/ nano metal,
The particle diameter of hollow micro-/ nano metal, wall thickness that the method produces can regulate, and monodispersity is good, and size is uniform.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows: one prepares the micro-nano gold of hollow cubic
The method belonged to, is carried out as steps described below:
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 time, period, progressively separating in reaction system
Water, 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 reacts formation metallic compound as shell with a cube salt block crystal
Layer parcel cubic metal salt block crystal is as the nucleocapsid structure of core
D) removing cube salt block crystal nuclear gains in depth of comprehension are to the hollow metal compound shell of cubic morphology, finally use reducing agent
Reduce this shell, and wash away surfactant and i.e. can get hollow cubic metal or alloy.
Wherein the described salt of step a) is the metallic salt containing halogen (Cl, Br, I), it is preferred that described salt is
NaCl、KCI、NaBr、KBr、NaI、KI。
Wherein the organic solvent described in step a) is that benzene, toluene, chloroform, oxolane, hexamethylene, petroleum ether etc. can be with
Water forms the Organic substance of azeotropic mixture.
Wherein the surfactant described in step a) includes but not limited to cetyl trimethylammonium bromide (CTAB), 2-second
Base hexyl Disodium sulfosuccinate (AOT), dodecylbenzene sodium sulfonate (SDS), 1-Aminooctane etc.
Wherein the salt described in step a) is 0.1-20: 1 g/g with the mass ratio of surfactant, and described is organic
The volume mass of solvent and surfactant is than for 10-1000: 1 ml/g.
Described step b) azeotropic distillation temperature is 50-250 DEG C, and the time of azeotropic distillation is 5-48 hour.
Described step c) adds the precursor solution of one or more metals for using triphenylphosphine, 1-Aminooctane, propylamine, second
The nitrate of metal such as Ag, Pb, Pt, Pd, Zn, Co, Fe, Ni, Cu, Ti, Sn, Cd of alcohol, second eyeball or benzene complexation, chloride, secondary
One or more of chlorate, acetate, oxalates or sulfate, wherein, metal precursor solutions and the gold described in step a)
The mass ratio belonging to salt is 0.1-2:1 g/g
Reducing agent described in step d) is a kind of in hydrogen, hydrazine hydrate, sodium citrate, ascorbic acid, formaldehyde, glucose.
After washing away surfactant, the granule of gained is hollow micro-/ nano granule.
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, wall thickness is 2-5 μm.
The method preparing hollow cubic micro-/ nano metal used by the present invention may be simply referred to as azeotropic distillation, in its core
Appearance is by the azeotropic distillation to reverse micro emulsion so that the salt contained in each microemulsion droplets is the analysis of Cubic crystal
Go out as template, then react with metal salt precursor solution, become the nucleocapsid structure of metallic compound parcel salt, wash after reduction
The crystal template that desalts i.e. can get hollow cubic micro-/ nano metal with surfactant.
The technical advantage of the preparation method of hollow cubic micro-/ nano metal of the present invention is mainly reflected in: use relatively
For common salt as template, cost is relatively low, and raw material is easy to get.Owing in microemulsion, water droplet is uniformly dispersed, size uniformity, so
The salt obtained after water in azeotropic distillation removing system crystalline dispersion uniformly, size uniformity, which ensure that the most hollow
The size uniformity of micro-/ nano metal.Can be regulated and controled by the addition of salt in the regulation size of microemulsion drop and drop
The size of hollow micro-/ nano metal eventually.Simultaneously by regulation metal precursor solution addition and with a cube salt block crystal
Response time, 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 prepares；
Fig. 2 is the XRD figure of the hollow cubic silver bullion that embodiment 2 prepares；
Fig. 3 is the TEM figure of the hollow cubic silver bullion that embodiment 2 prepares；
Fig. 4 is the SEM figure of the hollow cubic silver bullion that embodiment 2 prepares.
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 to this.
Embodiment 1
(1) weigh 0.5g sodium chloride and be dissolved in 5g water, pour there-necked flask into, add 2gAOT Yu 100ml toluene, by three mouthfuls of burnings
Bottle is put in oil bath pan and is stirred 3 hours at 60 DEG C, forms homogeneous microemulsion.
(2) temperature of oil bath pan being raised to 100 DEG C and keeps azeotropic distillation 12h, period removes 1ml water every two little time-divisions,
Until distillate clarification.
(3) after solution is cooled to room temperature, weigh 0.17g silver nitrate and be dissolved in 2ml 1-Aminooctane, join there-necked flask
In, reaction 6h after, adding 100 μ L concentration is 5%(mass fraction) sodium citrate solution, react 2h.
(4) by above-mentioned product 5000(rev/min of machine by centrifugation) centrifugal after take precipitation, wash sodium chloride with water, then use
Isobutyltrimethylmethane. wash away AOT after through 5000(rev/min) centrifugal, dry after obtain a cube hollow silver bullion product.The nanometer silver collected
The average 25nm of block particle diameter, wall thickness 2nm.Fig. 1 is the TEM figure of the hollow cubic silver bullion that embodiment 1 prepares
Embodiment 2
(1) weigh 1g sodium chloride and be dissolved in 10g water, pour there-necked flask into, add 1gCTAB Yu 100ml benzene, by there-necked flask
Put in oil bath pan and stir 3 hours at 60 DEG C, form homogeneous microemulsion.
(2) temperature of oil bath pan being raised to 100 DEG C and keeps azeotropic distillation 12h, period divides 1ml water the most every other hour,
Until distillate clarification.
(3) after solution is cooled to room temperature, weigh 0.17g chloroplatinic acid and be dissolved in 2ml 1-Aminooctane, join there-necked flask
In, reaction 6h after, adding 100 μ L concentration is 1%(mass fraction) hydrazine hydrate solution, react 2h.
(4) by above-mentioned product 5000(rev/min of machine by centrifugation) centrifugal after take precipitation, wash sodium chloride with water, then use
Isobutyltrimethylmethane. wash away CTAB after through 5000(rev/min) centrifugal, dry after obtain a cube hollow platinum block product.The Platinum Nanoparticles collected
The average 200nm of block particle diameter, wall thickness 20nm.Fig. 2 is the XRD figure of the hollow cubic silver bullion that embodiment 2 prepares, and Fig. 3 is that embodiment 2 is made
The TEM figure of the hollow cubic silver bullion obtained, Fig. 4 is the SEM figure of the hollow cubic silver bullion that embodiment 2 prepares.
Embodiment 3
(1) weigh 0.5g sodium chloride and be dissolved in 5g water, pour there-necked flask into, add 2gCTAB Yu 100ml hexamethylene, by three
Mouth flask is put in oil bath pan and is stirred 4 hours at 60 DEG C, forms homogeneous microemulsion.
(2) temperature of oil bath pan being raised to 100 DEG C and keeps azeotropic distillation 12h, period removes 1ml water every two little time-divisions,
Until distillate clarification.
(3) after solution is cooled to room temperature, weigh 0.1g gold chloride and be dissolved in 2ml 1-Aminooctane, join there-necked flask
In, reaction 6h after, adding 100 μ L concentration is 1%(mass fraction) sodium citrate solution, react 2h.
(4) by above-mentioned product 5000(rev/min of machine by centrifugation) centrifugal after take precipitation, wash sodium chloride with water, then use
Isopropanol wash away AOT after through 5000(rev/min) centrifugal, dry after obtain a cube hollow gold bullion product.The nanometer gold collected
The average 25nm of block particle diameter, wall thickness 2nm.
Embodiment 4
(1) weigh 0.5g sodium chloride and be dissolved in 5g water, pour there-necked flask into, add 2gAOT Yu 100ml benzene, by there-necked flask
Put in oil bath pan and stir 3 hours at 60 DEG C, form homogeneous microemulsion.
(2) temperature of oil bath pan being raised to 100 DEG C and keeps azeotropic distillation 12h, period removes 1ml water every two little time-divisions,
Until distillate clarification.
(3) after solution is cooled to room temperature, weigh 0.15g copper nitrate and be dissolved in 2ml acetonitrile, join in there-necked flask,
Reaction 6h after, adding 100 μ L concentration is 1%(mass fraction) hydrazine hydrate solution, react 2h.
(4) by above-mentioned product 5000(rev/min of machine by centrifugation) centrifugal after take precipitation, wash sodium chloride with water, then use
Isobutyltrimethylmethane. wash away AOT after through 5000(rev/min) centrifugal, dry after obtain a cube hollow copper billet product.The Nanometer Copper collected
The average 25nm of block particle diameter, wall thickness 2nm.
Embodiment 5
(1) weigh 0.5g sodium chloride and be dissolved in 5g water, pour there-necked flask into, add 2gCTAB Yu 100ml petroleum ether, by three
Mouth flask is put in oil bath pan and is stirred 3 hours at 60 DEG C, forms homogeneous microemulsion.
(2) temperature of oil bath pan being raised to 100 DEG C and keeps azeotropic distillation 12h, period removes 1ml water every two little time-divisions,
Until distillate clarification.
(3) after solution is cooled to room temperature, weigh 0.1g zinc nitrate and be dissolved in 2ml aniline, join in there-necked flask,
Reaction 6h after, adding 100 μ L concentration is 1%(mass fraction) sodium citrate solution, react 2h.
(4) by above-mentioned product 5000(rev/min of machine by centrifugation) centrifugal after take precipitation, wash sodium chloride with water, then use
Isopropanol wash away CTAB after through 5000(rev/min) centrifugal, dry after obtain a cube hollow spelter product.The nanometer silver collected
The average 20nm of block particle diameter, wall thickness 2nm.
Embodiment 6
(1) weigh 0.5g sodium chloride and be dissolved in 5g water, pour there-necked flask into, add 2gSDS Yu 100ml benzene, by there-necked flask
Put in oil bath pan and stir 3 hours at 60 DEG C, form homogeneous microemulsion.
(2) temperature of oil bath pan being raised to 100 DEG C and keeps azeotropic distillation 12h, period removes 1ml water every two little time-divisions,
Until distillate clarification.
(3) after solution is cooled to room temperature, weigh 0.1g Palladous nitrate. and be dissolved in 2ml 1-Aminooctane, join there-necked flask
In, reaction 6h after, adding 100 μ L concentration is 1%(mass fraction) formalin, react 2h.
(4) by above-mentioned product 5000(rev/min of machine by centrifugation) centrifugal after take precipitation, wash sodium chloride with water, then use
Isobutyltrimethylmethane. wash away SDS after through 5000(rev/min) centrifugal, dry after obtain a cube hollow palladium block product.The nanometer silver collected
The average 25nm of block particle diameter, wall thickness 2nm.
Embodiment 7
(1) weigh 0.5g sodium chloride and be dissolved in 5g water, pour there-necked flask into, add 2gSDS Yu 100ml benzene, by there-necked flask
Put in oil bath pan and stir 3 hours at 60 DEG C, form homogeneous microemulsion.
(2) temperature of oil bath pan being raised to 100 DEG C and keeps azeotropic distillation 12h, period removes 1ml water every two little time-divisions,
Until distillate clarification.
(3) after solution is cooled to room temperature, weigh 0.3g ferric nitrate and be dissolved in 2ml 1-Aminooctane, join there-necked flask
In, reaction 6h after, adding 100 μ L concentration is 1%(mass fraction) sodium citrate solution, react 2h.
(4) by above-mentioned product 5000(rev/min of machine by centrifugation) centrifugal after take precipitation, wash sodium chloride with water, then use
Isobutyltrimethylmethane. wash away SDS after through 5000(rev/min) centrifugal, dry after obtain a cube hollow silver bullion product.The Nanoscale Iron collected
The average 40nm of block particle diameter, wall thickness 5nm.
Embodiment 8
(1) weigh 0.5g sodium bromide and be dissolved in 5g water, pour there-necked flask into, add 2gAOT Yu 100ml benzene, by there-necked flask
Put in oil bath pan and stir 3 hours at 60 DEG C, form homogeneous microemulsion.
(2) temperature of oil bath pan being raised to 100 DEG C and keeps azeotropic distillation 12h, period removes 1ml water every two little time-divisions,
Until distillate clarification.
(3) after solution is cooled to room temperature, weigh 0.17g cobalt nitrate and be dissolved in 2ml 1-Aminooctane, join there-necked flask
In, reaction 6h after, adding 100 μ L concentration is 1%(mass fraction) hydrazine hydrate solution, react 2h.
(4) by above-mentioned product 5000(rev/min of machine by centrifugation) centrifugal after take precipitation, wash sodium bromide with water, then use
Isobutyltrimethylmethane. wash away AOT after through 5000(rev/min) centrifugal, dry after obtain a cube hollow cobalt block product.The nanometer cobalt collected
The average 25nm of block particle diameter, wall thickness 2nm.
Claims (1)
1. the method preparing the micro-nano metal of hollow cubic, it is characterised in that carry out as steps described below:
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 time, period, progressively separating 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 reacts formation metallic compound as shell bag with a cube salt block crystal
Wrap up in the cubic metal salt block crystal nucleocapsid structure as core；
D) removing cube salt block crystal nuclear gains in depth of comprehension are to the hollow metal compound shell of cubic morphology, finally reduce with reducing agent
This shell, and wash away surfactant and i.e. can get hollow cubic metal or alloy；
Wherein the described salt of step a) is the metallic salt containing halogen, and halogen is Cl, Br or I；
Wherein the organic solvent described in step a) is benzene, toluene, chloroform, oxolane, hexamethylene, petroleum ether；
Wherein the surfactant described in step a) is cetyl trimethylammonium bromide CTAB, 2-ethylhexyl succinate sulphur
Acid sodium AOT, dodecylbenzene sodium sulfonate SDS, 1-Aminooctane；
Wherein the salt described in step a) is 0.1 ~ 20: 1 g/g with the mass ratio of surfactant, described organic solvent
It is 10 ~ 1000: 1 ml/g with the volume mass ratio of surfactant；
Described step b) azeotropic distillation temperature is 50-250 DEG C, and the time of azeotropic distillation is 5-48 hour；
Described step c) add the precursor solution of one or more metals for use triphenylphosphine, 1-Aminooctane, propylamine, ethanol,
The nitrate of Ag, Pb, Pt, Pd, Zn, Co, Fe, Ni, Cu, Ti, Sn, Cd of second eyeball or benzene complexation, chloride, hypochlorite, vinegar
One or more of hydrochlorate, oxalates or sulfate, metal precursor solutions with the mass ratio of the slaine described in step a) is
0.1 ~ 2:1 g/g；
Reducing agent described in step d) is a kind of in hydrogen, hydrazine hydrate, sodium citrate, ascorbic acid, formaldehyde, glucose.
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| CN106881087B (en) * | 2015-12-16 | 2019-10-25 | 中国科学院大连化学物理研究所 | One kind cube skeletal porous silver and preparation method thereof |
| CN105965032B (en) * | 2016-07-26 | 2018-08-24 | 陕西师范大学 | The method that electrochemistry prepares Ag-Pd Nanoalloys in quaternary ion liquid microemulsion |
| CN106450350B (en) * | 2016-10-20 | 2019-04-30 | 绍兴文理学院 | A kind of synthetic method of platinum nano cubic block |
| CN106799229A (en) * | 2017-01-22 | 2017-06-06 | 南昌大学 | A kind of core shell structure Pd Ce@SiO2Catalyst and preparation method |
| CN108529681A (en) * | 2017-03-06 | 2018-09-14 | 中国科学院深圳先进技术研究院 | Hollow manganese dioxide nano particle and its preparation method and application |
| CN107755711B (en) * | 2017-10-20 | 2019-07-05 | 昆明理工大学 | A kind of pros' micro-nano silver powder, preparation method thereof |
| CN108298502B (en) * | 2018-01-15 | 2021-06-01 | 东南大学 | Method for preparing dispersed nano metal oxide and nano metal powder |
| CN110241438A (en) * | 2018-03-08 | 2019-09-17 | 天津大学 | Foam copper supports palladium-copper alloy nanocages catalyst and preparation method thereof |
| CN108907174A (en) * | 2018-06-05 | 2018-11-30 | 武汉工程大学 | A kind of silver palladium alloy nano material and its preparation method and application |
| CN109467108B (en) * | 2019-01-06 | 2020-12-01 | 中盐金坛盐化有限责任公司 | Preparation method of nano-grade superfine sodium chloride |
| CN110127654A (en) * | 2019-05-31 | 2019-08-16 | 天津大学 | A kind of preparation method of uniform micron pore size three-dimensional carbon network |
| CN111408734B (en) * | 2020-04-23 | 2021-08-03 | 华中科技大学 | Small hollow gold nanorod and preparation method and application thereof |
| CN115672305B (en) * | 2022-09-14 | 2023-12-19 | 南京工业大学 | CeVO (CeVO) 4 Preparation method and application of hollow cube structure |
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| CN1232377C (en) * | 2003-06-05 | 2005-12-21 | 中国科学院理化技术研究所 | Preparing method for cubic silver nanometer grain |
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