CN104857902A - Preparation method of silver/carbon composite hollow nanospheres - Google Patents
Preparation method of silver/carbon composite hollow nanospheres Download PDFInfo
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- CN104857902A CN104857902A CN201510173671.2A CN201510173671A CN104857902A CN 104857902 A CN104857902 A CN 104857902A CN 201510173671 A CN201510173671 A CN 201510173671A CN 104857902 A CN104857902 A CN 104857902A
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Abstract
The invention discloses a preparation method of silver/carbon composite hollow nanospheres. According to the method, under a stirring condition, a glucose solution is added into a silver nitrate aqueous solution; a proper amount of trioctylamine is slowly dropped in while stirring is carried out; the mixed solution is subjected to ultrasonic dispersion, such that a milky while solution is obtained; the emulsion obtained after ultrasonic treatment is delivered into a reaction kettle, and a hydrothermal reaction is carried out; when the reaction is finished, the obtained product is cooled to room temperature; centrifugal separation is carried out, such that black solid particles are obtained; washing and drying are carried out; and annealing is carried out under the protection of argon gas, such that the composite hollow nanospheres are obtained. The material has good application prospects in the aspects of surface-enhanced Raman scattering, antibiosis and the like.
Description
Technical field
The invention belongs to nano composite material technical field, relate to a kind of preparation method possessing the silver/carbon composite hollow nanosphere of high-specific surface area.
Background technology
The large absolutely degree of development of nanometer technology depends on that synthesis possesses the ability of the novel nano-material of ad hoc structure and functional characteristic.Nano-hollow ball is exactly a kind of like this novel nano-material of ad hoc structure, and the characteristics such as shape is special owing to having, low-density, comparatively Large ratio surface sum high voidage, its developmental research has caused the concern of a lot of field scientific research personnel.Such as, its hollow-core construction and good mobility can be utilized to it can be used as a kind of unique pharmaceutical carrier or in contrast preparation; The specific area utilizing it larger uses it for catalyst, fuel cell etc.; Can also utilize its as lightweight structural material, heat insulation, sound insulation and electrically insulating material, pigment, catalyst carrier etc.The method that present stage prepares such nano-hollow ball has template, adsorption technology, spraying high-temperature decomposition, sonochemical method, hydro-thermal method etc.These methods are adopted successfully to prepare multiple inorganic material compound nano-hollow sphere.
Silver nano material has unique optical, high conductivity, high catalytic property and high antibiotic property because of himself character and nanometer size effect, in photoelectricity, photocatalysis and the field such as antibacterial, occupy critical role.But Nano Silver surface-active is high, thermodynamic instability is easily reunited in the composite, and therefore, nano silver particles scattering problem is in the composite still a major challenge of ongoing research area.At present, the report about the preparation method of silver-colored carbon composite is also fewer, and method is also more single.Having comparatively early adopts metal smelting process, vacuum infusion techniques or chemical vapour deposition technique to prepare the absorbent charcoal material of load silver, but the high cost of these methods, and be in fact all the mixing of two kinds of solid matters.In recent years, people's starch such as Shu-Hong Yu are carbon source and reducing agent, wrap up silver-colored core nano-fiber composite material with hydro-thermal method and silver nitrate Reactive Synthesis carbon shell.Although this method reduces preparation cost, in obtained silver-colored carbon composite, silver has been wrapped up by carbon completely, cannot give full play to the surface-enhanced Raman of silver nano material, the performance such as antibacterial.Liu Lan etc. are incorporated into CNT and silver acetate in epoxy resin-imidazoles curing system simultaneously, and in-situ heat degraded silver-imidazole complex, generates the CNT that Nano Silver is modified in the curing process.Although this method solves Nano Silver scattering problem in the composite, preparation process is too loaded down with trivial details.
About the preparation of nano-hollow ball, Gilles R.Bourret etc. adopts microemulsion method at H
2o/CH
2cl
2two-phase interface place generate Kocide SD nanofiber, then under the condition adding butanols, these nanofibers are the spherical reticulated of porous in the self assembly of water droplet interface, obtain the Kocide SD net of porous after the process such as centrifugal, dry.The cupric oxide spherical shell of different size can also be obtained again by the heat treatment of different temperatures.N.Jayaprakash etc. adopt die version method to synthesize the sulphur/carbon ball composite of porous hollow.Robin J.White etc. are that template has prepared multi-functional hollow carbon sphere through hydro-thermal reaction with terminal hydroxy group polystyrene latex.Zhou Xiaoliangs etc. have employed soft template method and hydro-thermal method has prepared copper carbon compound hollow microballoon.But silver-colored carbon composite hollow nanosphere material yet there are no relevant report so far.
Summary of the invention
The object of this invention is to provide a kind of preparation method possessing the silver/carbon composite hollow nanosphere of high-specific surface area.
The technical solution realizing the object of the invention is: the preparation method of a kind of silver/carbon composite hollow nanosphere, comprises the steps: under agitation, to add glucose solution at silver nitrate aqueous solution; Slowly drip appropriate trioctylamine while stirring, mixed solution is obtained milky white solution through ultrasonic disperse; Emulsion after ultrasonic is proceeded to reactor and carries out hydro-thermal reaction, after reaction terminates, be cooled to room temperature, after centrifugation black solid particle; Composite hollow nanosphere is obtained after annealing under washing, drying, argon shield.
In above-mentioned steps, silver nitrate aqueous solution concentration is 0.025mol/L, glucose concentration is 0.25-2.5mol/L, the proportioning of glucose and silver nitrate is 1 ~ 10, the volume ratio 50-150 of mixed solution and trioctylamine, ultrasonic disperse time 10 ~ 30min, hydrothermal temperature is 140 ~ 200 DEG C, time is 10 ~ 24h, and the heating rate of annealing is that 10 DEG C/min anneals at 500 DEG C, insulation 2h.
Advantage of the present invention is as follows: (1) raw material is common to be easy to get, and product is nontoxic is convenient to direct application.Silver nitrate is the silver-colored modal raw material of preparation, and glucose is easy to get in also living and cheap food, and by its carbon through Hydrothermal Synthesis also to human body and environment nontoxic, emulsion template trioctylamine used can be removed substantially in the cyclic washing eccentric phase; (2) operating process is very simple, preparation method's deft design.Experimental technique of the present invention mainly prepares silver-colored carbon hollow nano-sphere in conjunction with emulsion masterplate method and hydro-thermal method.The raw material used and emulsion masterplate nearly all " hold many duties ", all will play requisite effect in each stage of reaction.Trioctylamine is that oil phase prepares D/W/argent-amine complex/trioctylamine oil-in-water microemulsion system, and utilize this Emulsions to be internal mold version, integrated application microemulsion technology and Hydrothermal Synthesis technology prepare silver-colored carbon composite hollow nanosphere.Glucose is the source of carbon in product of the present invention, and it is again reducing agent, the dispersant in hydro-thermal reaction simultaneously.The silver-colored source of product is AgNO
3, it can with trioctylamine complexing, this is one of shaping key of hollow ball, is again the catalyst of glucose carburizing reagent at hydro-thermal reaction stage silver simultaneously; (3) solve the easy agglomeration traits of Nano Silver dexterously, improve its utilization ratio.The silver-colored carbon composite hollow ball size distribution of gained of the present invention is even, and nano-Ag particles is embedded in spherical shell, and the size of shell thickness and the load Argent grain on spherical shell is nanoscale, good dispersion, is convenient to the superior function giving full play to silver.
Accompanying drawing explanation
Accompanying drawing 1 is the preparation flow schematic diagram of silver-colored carbon composite hollow nanosphere of the present invention.
Accompanying drawing 2 is structural characterization figure Raman spectrograms of the silver/carbon composite hollow nanosphere prepared by example 1 of the present invention.
Accompanying drawing 3 is structural characterization figure XRD spectrum figure of the silver/carbon composite hollow nanosphere prepared by example 2 of the present invention.
Accompanying drawing 4 is morphology characterization figure SEM photos of the silver/carbon composite hollow nanosphere prepared by example 3 of the present invention.
The silver that accompanying drawing 5 obtains for example 2 of the present invention/carbon composite hollow nanosphere is 10 to concentration
-5the 4-mercaptopyridine surface-enhanced Raman design sketch of mol/L.
Detailed description of the invention
Below in conjunction with accompanying drawing, the invention will be further described.
Shown in accompanying drawing 1, silver of the present invention/carbon composite hollow nanosphere preparation flow is as follows:
Embodiment 1:
The first step: configure the liquor argenti nitratis ophthalmicus of 0.025M and the D/W of 0.25M respectively;
Second step: get the above-mentioned solution of 30ml respectively and mix under magnetic stirring;
3rd step: slowly drip 0.5ml trioctylamine while stirring in above-mentioned mixed solution;
4th step: above-mentioned solution is put into the ultrasonic 15min of ultrasonic cleaning instrument;
5th step: above-mentioned suspension is transferred to rapidly in 100ml polytetrafluoroethyllining lining stainless steel cauldron, 180 DEG C of reaction 12h;
6th step: after reactor naturally cools to room temperature, by reactant liquor centrifugation, obtains black solid particle;
7th step: alternate repetition water and washes of absolute alcohol precipitate each 3 times, and namely 60 DEG C of vacuum drying 10h obtain nano-hollow ball; The structural characterization Raman light collection of illustrative plates that accompanying drawing 2 is obtained silver/carbon composite hollow nanosphere, the Raman peaks of carbon as we can clearly see from the figure, confirms the existence of carbon.
Embodiment 2:
The first step: configure the liquor argenti nitratis ophthalmicus of 0.025M and the D/W of 0.25M respectively;
Second step: get the above-mentioned solution of 30ml respectively and mix under magnetic stirring;
3rd step: slowly drip 0.5ml trioctylamine while stirring in above-mentioned mixed solution;
4th step: above-mentioned solution is put into the ultrasonic 15min of ultrasonic cleaning instrument;
5th step: above-mentioned suspension is transferred to rapidly (cumulative volume is 100ml) in polytetrafluoroethyllining lining stainless steel cauldron, 180 DEG C of reaction 10h;
6th step: after reactor naturally cools to room temperature, by reactant liquor centrifugation, obtains black solid particle;
7th step: alternate repetition water and washes of absolute alcohol precipitate 3 times, 60 DEG C of vacuum drying 10h obtain nano-hollow ball;
Accompanying drawing 3 is the structural characterization XRD spectra of obtained silver/carbon composite hollow nanosphere.Significantly can find out the diffractive features peak of silver from figure, confirm the existence of silver.
The silver that accompanying drawing 5 obtains for embodiment 2/carbon composite hollow nanosphere is 10 to concentration
-5the 4-mercaptopyridine surface-enhanced Raman design sketch of mol/L.
Embodiment 3:
The first step: configure the liquor argenti nitratis ophthalmicus of 0.025M and the D/W of 0.50M respectively;
Second step: get the above-mentioned solution of 30ml respectively and mix under magnetic stirring;
3rd step: slowly drip 0.75ml trioctylamine while stirring in above-mentioned mixed solution;
4th step: above-mentioned solution is put into the ultrasonic 15min of ultrasonic cleaning instrument;
5th step: above-mentioned suspension is transferred to rapidly (cumulative volume is 100ml) in polytetrafluoroethyllining lining stainless steel cauldron, 180 DEG C of reaction 20h;
6th step: after reactor naturally cools to room temperature, by reactant liquor centrifugation, obtains black solid particle;
7th step: alternate repetition water and washes of absolute alcohol precipitate 3 times, 60 DEG C of vacuum drying 10h obtain silver-colored carbon composite nano hollow ball;
8th step: product is under Ar gas shielded, and heating rate is that 10 DEG C/min anneals at 500 DEG C, insulation 2h obtains nano-hollow ball.
Accompanying drawing 4 is the morphology characterization SEM photo of obtained silver/carbon composite hollow nanosphere.Can see that from picture Argent grain is embedded in the surface of carbon ball, carbon ball surface irregularity, and have hole to exist.Such shape characteristic just the present invention expect, this also can increase popularity and the performance advantage of this materials application.
Claims (4)
1. a preparation method for silver/carbon composite hollow nanosphere, is characterized in that, comprise the steps:
The first step, under agitation, adds glucose solution at silver nitrate aqueous solution;
Second step, slowly drips trioctylamine while stirring, and mixed solution is obtained milky white solution through ultrasonic disperse;
3rd step, proceeds to reactor by the emulsion after ultrasonic and carries out hydro-thermal reaction, is cooled to room temperature after reaction terminates, after centrifugation black solid particle; Composite hollow nanosphere is obtained after annealing under washing, drying, argon shield.
2. the preparation method of silver/carbon composite hollow nanosphere as claimed in claim 1, it is characterized in that, in the first step, silver nitrate aqueous solution concentration is 0.025-0.05mol/L, glucose concentration is 0.25-2.5mol/L, and the proportioning of glucose and silver nitrate is 1 ~ 10.
3. the preparation method of silver/carbon composite hollow nanosphere as claimed in claim 1, is characterized in that, in second step, and the volume ratio 50-150 of mixed solution and trioctylamine, ultrasonic disperse time 10 ~ 30min.
4. the preparation method of silver/carbon composite hollow nanosphere as claimed in claim 1, it is characterized in that, in the 3rd step, hydrothermal 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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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105660620A (en) * | 2016-01-13 | 2016-06-15 | 南昌航空大学 | Silver nanoparticle-embedded carbon microsphere preparation method |
| CN105717091A (en) * | 2016-01-29 | 2016-06-29 | 南京理工大学 | Long-lasting efficient SERS substrate and preparation method thereof |
| CN106111030A (en) * | 2016-08-03 | 2016-11-16 | 南京理工大学 | A kind of gold/carbon complex microsphere and preparation method thereof |
| CN106984307A (en) * | 2017-05-05 | 2017-07-28 | 董可轶 | One kind has York Shell structure Ag Pt@C nano balls and preparation method thereof |
| CN107755691A (en) * | 2017-10-13 | 2018-03-06 | 上海应用技术大学 | A kind of preparation method of carbon coating copper micro-nano granules composite |
| CN108232212A (en) * | 2018-03-26 | 2018-06-29 | 济南大学 | A kind of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst and preparation method and application |
| 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 |
| 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 |
| CN111646426A (en) * | 2020-05-15 | 2020-09-11 | 扬州大学 | Method for preparing carbon nanochain @ gold network film |
| CN112427016A (en) * | 2020-11-23 | 2021-03-02 | 南通科源新材料有限公司 | Silver-loaded porous carbon microsphere and preparation method thereof |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105660620A (en) * | 2016-01-13 | 2016-06-15 | 南昌航空大学 | Silver nanoparticle-embedded carbon microsphere preparation method |
| CN105717091A (en) * | 2016-01-29 | 2016-06-29 | 南京理工大学 | Long-lasting efficient SERS substrate and preparation method thereof |
| CN105717091B (en) * | 2016-01-29 | 2019-01-18 | 南京理工大学 | A kind of SERS substrate of persistent high efficiency 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 |
| CN106111030A (en) * | 2016-08-03 | 2016-11-16 | 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 |
| CN106984307A (en) * | 2017-05-05 | 2017-07-28 | 董可轶 | One kind has York Shell structure Ag Pt@C nano balls and preparation method thereof |
| CN107755691A (en) * | 2017-10-13 | 2018-03-06 | 上海应用技术大学 | A kind of preparation method of carbon coating copper micro-nano granules composite |
| 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 |
| CN108232212A (en) * | 2018-03-26 | 2018-06-29 | 济南大学 | A kind of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst and preparation method and application |
| 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 |
| CN111646426A (en) * | 2020-05-15 | 2020-09-11 | 扬州大学 | Method for preparing carbon nanochain @ gold network film |
| CN111646426B (en) * | 2020-05-15 | 2023-03-31 | 扬州大学 | Method for preparing carbon nanochain @ gold network film |
| CN112427016A (en) * | 2020-11-23 | 2021-03-02 | 南通科源新材料有限公司 | Silver-loaded porous carbon microsphere and preparation method thereof |
| 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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