CN104857902B - A kind of preparation method of silver/carbon composite hollow nanosphere - Google Patents
A kind of preparation method of silver/carbon composite hollow nanosphere Download PDFInfo
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- CN104857902B CN104857902B CN201510173671.2A CN201510173671A CN104857902B CN 104857902 B CN104857902 B CN 104857902B CN 201510173671 A CN201510173671 A CN 201510173671A CN 104857902 B CN104857902 B CN 104857902B
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Abstract
The invention discloses a kind of preparation method of silver/carbon composite hollow nanosphere.Under agitation, glucose solution is added in silver nitrate aqueous solution；Appropriate trioctylamine is slowly added dropwise while stirring, and mixed solution is obtained into milky white solution through ultrasonic disperse；Emulsion after ultrasound is transferred into reactor carries out hydro-thermal reaction, and reaction is cooled to room temperature after terminating, and black solid particle is obtained after centrifugation；Composite hollow nanosphere is obtained after washing, dry, the lower annealing of argon gas protection.The material has good application prospect at aspects such as SERS, antibacterials.
Description
Technical field
The invention belongs to nano composite material technical field, it is related to a kind of silver/carbon composite hollow for possessing high-specific surface area
The preparation method of nanosphere.
Background technology
The development of nanometer technology may largely be determined by the novel nano material that synthesis possesses ad hoc structure and functional characteristic
The ability of material.Nano-hollow ball is exactly the novel nano-material of such a ad hoc structure, due to special, low close with shape
The characteristics such as degree, large specific surface area and high voidage, its developmental research has caused the concern of many field scientific research personnel.Example
Such as, it is possible to use its hollow-core construction and good mobility are as a kind of unique pharmaceutical carrier or in contrast agent；Profit
Catalyst, fuel cell etc. are used it for its larger specific surface area；Can also utilize it as lightweight structural material, every
Hot, sound insulation and electrically insulating material, pigment, catalyst carrier etc..The method for preparing such nano-hollow ball at this stage has template
Method, adsorption technology, spraying high-temperature decomposition, sonochemical method, hydro-thermal method etc..Various nothings are successfully prepared using these methods
Machine Material cladding nano-hollow ball.
Silver nano material has the optical of uniqueness, high conductivity, height because of the property of its own and nanometer size effect
Catalytic and antibiotic property high, critical role is occupied in the fields such as photoelectricity, photocatalysis and antibacterial.However, nanometer silver surface is lived
Property high, thermodynamic instability, in the composite easily reunite, therefore, nano silver particles scattering problem in the composite is still
It is a major challenge of ongoing research area.At present, the report of the preparation method on silver-colored carbon composite is also fewer, method
It is relatively simple.Have using metal smelting process, vacuum infusion techniques or chemical vapour deposition technique to prepare load silver earlier
Absorbent charcoal material, but these methods high cost, and substantially is all two kinds of mixing of solid matter.In recent years, Shu-
Hong Yu et al. starch is carbon source and reducing agent, and carbon shell has been synthesized with hydro-thermal method and silver nitrate wraps up silver core Nanowire
Dimension composite.Although this method reduces preparation cost, but silver is wrapped up by carbon completely in obtained silver-colored carbon composite
, it is impossible to give full play to the performances such as surface-enhanced Raman, the antibacterial of silver nano material.Liu Lan etc. is same CNT and silver acetate
When be incorporated into epoxy resin-imidazoles curing system, thermal degradation silver-imidazole complex in situ, generates nanometer in the curing process
The CNT of modified by silver.Although this method solves Nano Silver scattering problem in the composite, but preparation process mistake
In cumbersome.
Preparation on nano-hollow ball, Gilles R.Bourret etc. adopt microemulsion method in H2O/CH2Cl2Two phase boundaries
Kocide SD nanofiber is generated at face, then these nanofibers are in the self assembly of water droplet interface under conditions of butanol is added
Porous spherical reticulated, porous Kocide SD net is obtained after the treatment such as centrifugation, dry.Again by the heat treatment of different temperatures
Various sizes of cupric oxide spherical shell can also be obtained.N.Jayaprakash etc. has synthesized porous hollow using die version method
Sulphur/carbon ball composite.The terminal hydroxy group polystyrene latex such as Robin J.White is that template is prepared for many work(through hydro-thermal reaction
The hollow carbon sphere of energy.Zhou Xiaoliang etc. employs soft template method and hydro-thermal method is prepared for copper carbon compound hollow microballoon.However, silver-colored carbon is answered
Close hollow Nano ball material and yet there are no relevant report so far.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the silver/carbon composite hollow nanosphere for possessing high-specific surface area.
Realizing the technical solution of the object of the invention is：A kind of preparation method of silver/carbon composite hollow nanosphere, including
Following steps：Under agitation, glucose solution is added in silver nitrate aqueous solution；It is pungent that appropriate three are slowly added dropwise while stirring
Amine, milky white solution is obtained by mixed solution through ultrasonic disperse；Emulsion after ultrasound is transferred into reactor carries out hydro-thermal reaction, instead
Room temperature is cooled to after should terminating, black solid particle is obtained after centrifugation；Answered after washing, dry, the lower annealing of argon gas protection
Close hollow nano-sphere.
In above-mentioned steps, silver nitrate aqueous solution concentration is 0.025mol/L, and glucose concentration is 0.25-2.5mol/
L, glucose is 1~10 with the proportioning of silver nitrate, the volume ratio 50-150 of mixed solution and trioctylamine, the ultrasonic disperse time 10~
30min, hydrothermal temperature is 140~200 DEG C, and the time is 10~24h, and the heating rate of annealing is 10 DEG C/min at 500 DEG C
Lower annealing, is incubated 2h.
Advantages of the present invention is as follows：(1) raw material is common is easy to get, and product is nontoxic to be easy to directly application.Silver nitrate is system
Standby silver-colored most common raw material, glucose is easy to get and cheap food in also living, and by its through Hydrothermal Synthesiss carbon
Nontoxic to human body and environment, the trioctylamine used by emulsion template can substantially be removed in the cyclic washing eccentric phase；(2) operate
Process is very simple, preparation method deft design.Experimental technique of the invention comes mainly in conjunction with emulsion masterplate method and hydro-thermal method
Prepare silver-colored carbon hollow nano-sphere.The raw material and emulsion masterplate for being used nearly all " as many duties ", reaction each stage all
Essential effect will be played.Trioctylamine prepares D/W/argent-amine complex/trioctylamine oil-in-water type for oil phase
Microemulsion system, is interior masterplate using the microemulsion system, and integrated application microemulsion technology and Hydrothermal Synthesiss technology prepare silver
Carbon composite hollow nanosphere.Glucose is the source of carbon in product of the present invention, at the same it be again reducing agent in hydro-thermal reaction, point
Powder.The silver-colored source of product is AgNO3, it can be complexed with trioctylamine, and this is one of key of hollow ball forming, while anti-in hydro-thermal
The stage silver of answering is again the catalyst of glucose carburizing reagent；(3) the easy agglomeration traits of Nano Silver are dexterously solved, it is improve
Utilization ratio.Silver-colored carbon composite hollow ball size distribution obtained by the present invention is uniform, and nano-Ag particles are embedded in spherical shell, and spherical shell is thick
The size for spending and being supported on the Argent grain on spherical shell is nanoscale, and good dispersion is easy to give full play to the superior function of silver.
Brief description of the drawings
Fig. 1 is the preparation flow schematic diagram of silver-colored carbon composite hollow nanosphere of the invention.
Fig. 2 is the structural characterization figure Raman spectrograms of the silver/carbon composite hollow nanosphere prepared by present example 1.
Fig. 3 is the structural characterization figure XRD spectrum figure of the silver/carbon composite hollow nanosphere prepared by present example 2.
Fig. 4 is the morphology characterization figure SEM photograph of the silver/carbon composite hollow nanosphere prepared by present example 3.
Fig. 5 is that the silver/carbon composite hollow nanosphere obtained by present example 2 is 10 to concentration-5The 4- sulfydryl pyrroles of mol/L
Pyridine surface-enhanced Raman design sketch.
Specific embodiment
The invention will be further described below in conjunction with the accompanying drawings.
As shown in accompanying drawing 1, silver of the invention/carbon composite hollow nanosphere preparation flow is as follows：
Embodiment 1：
The first step：It is respectively configured the silver nitrate solution of 0.025M and the D/W of 0.25M；
Second step：The above-mentioned solution of 30ml is taken respectively to mix under magnetic stirring；
3rd step：0.5ml trioctylamines are slowly added dropwise while stirring toward above-mentioned mixed solution；
4th step：Above-mentioned solution is put into and is cleaned by ultrasonic ultrasound 15min in instrument；
5th step：Above-mentioned suspension is transferred quickly in 100ml polytetrafluoroethyllining lining stainless steel cauldrons, 180 DEG C
Reaction 12h；
6th step：After reactor naturally cools to room temperature, by reaction solution centrifugation, black solid particle is obtained；
7th step：Alternate repetition water and washes of absolute alcohol precipitation are each 3 times, and 60 DEG C of vacuum drying 10h obtain final product nanometer sky
Bulbus cordis；Accompanying drawing 2 is the structural characterization Raman light collection of illustrative plates of resulting silver/carbon composite hollow nanosphere, as we can clearly see from the figure
The Raman peaks of carbon, it was confirmed that the presence of carbon.
Embodiment 2：
The first step：It is respectively configured the silver nitrate solution of 0.025M and the D/W of 0.25M；
Second step：The above-mentioned solution of 30ml is taken respectively to mix under magnetic stirring；
3rd step：0.5ml trioctylamines are slowly added dropwise while stirring toward above-mentioned mixed solution；
4th step：Above-mentioned solution is put into and is cleaned by ultrasonic ultrasound 15min in instrument；
5th step：(cumulative volume is during above-mentioned suspension is transferred quickly into polytetrafluoroethyllining lining stainless steel cauldron
100ml), 180 DEG C of reaction 10h；
6th step：After reactor naturally cools to room temperature, by reaction solution centrifugation, black solid particle is obtained；
7th step：Alternate repetition water and washes of absolute alcohol are precipitated 3 times, and 60 DEG C of vacuum drying 10h obtain nano-hollow ball；
Accompanying drawing 3 is the structural characterization XRD spectra of resulting silver/carbon composite hollow nanosphere.Can be obvious from figure
Find out the diffractive features peak of silver, it was confirmed that the presence of silver.
Accompanying drawing 5 is that the silver/carbon composite hollow nanosphere obtained by embodiment 2 is 10 to concentration-5The 4- sulfydryl pyrroles of mol/L
Pyridine surface-enhanced Raman design sketch.
Embodiment 3：
The first step：It is respectively configured the silver nitrate solution of 0.025M and the D/W of 0.50M；
Second step：The above-mentioned solution of 30ml is taken respectively to mix under magnetic stirring；
3rd step：It is slowly added dropwise 0.75ml trioctylamines while stirring in above-mentioned mixed solution；
4th step：Above-mentioned solution is put into and is cleaned by ultrasonic ultrasound 15min in instrument；
5th step：(cumulative volume is during above-mentioned suspension is transferred quickly into polytetrafluoroethyllining lining stainless steel cauldron
100ml), 180 DEG C of reaction 20h；
6th step：After reactor naturally cools to room temperature, by reaction solution centrifugation, black solid particle is obtained；
7th step：Alternate repetition water and washes of absolute alcohol are precipitated 3 times, and 60 DEG C of vacuum drying 10h obtain that silver-colored carbon is compound to be received
Rice hollow ball；
8th step：Product under Ar gas shieldeds, for 10 DEG C/min at 500 DEG C anneal by heating rate, and insulation 2h obtains nanometer
Hollow ball.
Accompanying drawing 4 is the morphology characterization SEM photograph of resulting silver/carbon composite hollow nanosphere.Be can see from picture
Argent grain is embedded in the surface of carbon ball, carbon ball surface irregularity, and hole to be present.Such shape characteristic phase exactly of the invention
Hope, this can also increase the popularity and performance advantage of the materials application.
Claims (4)
1. the preparation method of a kind of silver/carbon composite hollow nanosphere, it is characterised in that comprise the following steps：
The first step, under agitation, glucose solution is added in silver nitrate aqueous solution；
Second step, is slowly added dropwise trioctylamine while stirring, and mixed solution is obtained into milky white solution through ultrasonic disperse；
3rd step, the emulsion after ultrasound is transferred into reactor carries out hydro-thermal reaction, and reaction is cooled to room temperature, centrifugation after terminating
Black solid particle is obtained afterwards；Composite hollow nanosphere is obtained after washing, dry, the lower annealing of argon gas protection.
2. the preparation method of silver as claimed in claim 1/carbon composite hollow nanosphere, it is characterised in that in the first step, nitric acid
Silver-colored concentration of aqueous solution is 0.025-0.05mol/L, and glucose concentration is 0.25-2.5mol/L, glucose and silver nitrate
Match is 1 ~ 10.
3. the preparation method of silver as claimed in claim 1/carbon composite hollow nanosphere, it is characterised in that in second step, mixing
The volume ratio 50-150,10 ~ 30min of ultrasonic disperse time of solution and trioctylamine.
4. the preparation method of silver as claimed in claim 1/carbon composite hollow nanosphere, it is characterised in that in the 3rd step, hydro-thermal
Reaction temperature is 140 ~ 200 DEG C, and the time is 10 ~ 24h, and anneal 2h at 500 DEG C, and the heating rate of annealing is 10 DEG C/min.
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| CN105660620B (en) * | 2016-01-13 | 2018-01-26 | 南昌航空大学 | A kind of preparation method of embedded silver nano-grain carbosphere |
| CN105717091B (en) * | 2016-01-29 | 2019-01-18 | 南京理工大学 | Durable and efficient SERS substrate and preparation method thereof |
| CN106111030B (en) * | 2016-08-03 | 2019-01-04 | 南京理工大学 | A kind of gold/carbon complex microsphere and preparation method thereof |
| CN108663348A (en) * | 2017-03-30 | 2018-10-16 | 南京理工大学 | A kind of preparation method of silver carbon composite porous film |
| CN106984307B (en) * | 2017-05-05 | 2020-06-26 | 苏州楚捷新材料科技有限公司 | Ag-Pt @ C nanosphere with Yolk-Shell structure and preparation method thereof |
| CN107755691B (en) * | 2017-10-13 | 2019-10-01 | 上海应用技术大学 | A kind of preparation method of carbon coating copper micro-nano granules composite material |
| CN108232212B (en) * | 2018-03-26 | 2020-06-09 | 济南大学 | Hollow carbon nanosphere-loaded nano Ag particle fuel cell oxygen reduction catalyst and preparation method and application thereof |
| CN110277563A (en) * | 2019-06-10 | 2019-09-24 | 北京科技大学 | A kind of preparation method of N doping hollow carbon sphere elctro-catalyst |
| CN111646426B (en) * | 2020-05-15 | 2023-03-31 | 扬州大学 | Method for preparing carbon nanochain @ gold network film |
| CN112427016B (en) * | 2020-11-23 | 2023-05-02 | 南通市金达菱新材料科技有限公司 | Silver-loaded porous carbon microsphere and preparation method thereof |
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| GB1450012A (en) * | 1974-04-06 | 1976-09-22 | Bayer Ag | Process for the production of free-flowing hollow beads |
| CN103331452A (en) * | 2013-06-27 | 2013-10-02 | 北京科技大学 | Copper and carbon composite hollow sphere particle material and preparation method thereof |
| WO2014111477A2 (en) * | 2013-01-18 | 2014-07-24 | Commissariat à l'énergie atomique et aux énergies alternatives | Reinforced gel capsules, and reinforced lyophilized gel capsules, containing nano-objects and processes for preparing same |
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| WO2013103322A1 (en) * | 2012-01-05 | 2013-07-11 | Nanyang Technological University | Methods of preparing monodispersed polydopamine nano- or microspheres, and methods of preparing nano-or microstructures based on the polydopamine nano- or microspheres |
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| GB1450012A (en) * | 1974-04-06 | 1976-09-22 | Bayer Ag | Process for the production of free-flowing hollow beads |
| WO2014111477A2 (en) * | 2013-01-18 | 2014-07-24 | Commissariat à l'énergie atomique et aux énergies alternatives | Reinforced gel capsules, and reinforced lyophilized gel capsules, containing nano-objects and processes for preparing same |
| CN103331452A (en) * | 2013-06-27 | 2013-10-02 | 北京科技大学 | Copper and carbon composite hollow sphere particle material and preparation method thereof |
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