CN108663348A - A kind of preparation method of silver carbon composite porous film - Google Patents
A kind of preparation method of silver carbon composite porous film Download PDFInfo
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- CN108663348A CN108663348A CN201710202933.2A CN201710202933A CN108663348A CN 108663348 A CN108663348 A CN 108663348A CN 201710202933 A CN201710202933 A CN 201710202933A CN 108663348 A CN108663348 A CN 108663348A
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Abstract
The invention discloses a kind of preparation methods of silver-colored carbon composite porous film.The method is under the conditions of being protected from light, trioctylamine is added when stirring glucose solution, silver nitrate solution is slowly added dropwise again, it is placed at 160 DEG C~200 DEG C and carries out hydro-thermal reaction, after reaction, cooled to room temperature takes upper layer silvery white film, alternate repetition water and washes of absolute alcohol are dried to obtain silver-colored carbon composite porous film.Silver-colored carbon composite porous film prepared by the method for the present invention has even particle size, holey micro-nano structure, participating in compound hydro-thermal carbon component can not only effectively avoid the problem that SERS substrates are inactivated by oxidation, it will greatly prolong holding time, and nano silver can be helped to adsorb more probe molecules, to improve the sensitivity of detection, after placing 8 months, detection limit is up to 10‑9M has preferable application prospect in terms of Surface enhanced Raman scattering.
Description
Technical field
The invention belongs to composite nano materials fields, are related to a kind of silver-colored carbon composite porous film having efficient SERS effects
Preparation.
Background technology
Surface enhanced Raman scattering (SERS) is used as a kind of spectral analysis technique, selectivity good, sensitivity narrow with bands of a spectrum
High, anti-light bleaching, do not interfered by biological sample autofluorescence and water, quickly, in situ, real-time and lossless etc. many merits,
There is good application prospect in biochemistry, molecular biology, single molecule study field.In Surface enhanced Raman spectroscopy technology
In, laser wavelength of incidence, excitation intensity, metal SERS active-substrate are three heavy to closing to the analysis of Surface enhanced Raman spectroscopy
The factor wanted.Local electric field of the very big enhancing of the Raman scattering observed in experiment essentially from metallic nanostructured surface
Enhancing, secondly, Raman enhancing are also influenced by the special electron resonance of raman active molecule and its contacted with metal surface.Therefore
The preparation of SERS substrates seems most important.Existing SERS substrates are there is poor reproducibility, the holding time is short, the bad regulation and control of substrate
The shortcomings of, limit the application of SERS technologies.
Nanometer ultramicron (1~100nm) has quantum size effect, small-size effect, skin effect and macroscopic quantum
Tunnel-effect shows physics not available for many traditional materials, chemical property compared with common bulky grain material.Wherein
Nano silver particles are in researchs such as Surface enhanced Raman spectroscopy, surface enhanced resonance scattering spectoroscopy, molecular biology, supramolecular systems
Field occupies an important position, and is widely used in anti-biotic material, sensor design, electronic circuit, chemical fibre etc..It receives
Rice porous structure has the specific surface area and nanometer size effect of bigger, can be combined with silver, gold, copper etc. and generate more excellent increasing
It is potent to answer.
About the preparation of porous metals nano material, Lv Jing etc. (CN105506559A) passes through in physical method filming equipment
The method of upper shutter of the installation equipped with hole is prepared for porous thick Ag films.Song Tingting etc. (CN102296349A) is utilized and is gone
AB (C) alloy thin band prepared by amorphous alloy is put into the container equipped with electrolyte solution, is taken out after heating by alloyage,
It is prepared for that there is three-dimensional continuous nano-porous structure substrate.Metal simple-substance purity prepared by above method is high, can get higher
SERS performances, but silver is easily aoxidized in air, therefore the holding time of such substrate is extremely short.Wang Tianhe etc.
(CN105158229) method of collosol and gel and spin coating is used to prepare porous silica titanium coating in substrate, and porous two
Nano-Ag particles are deposited using photoreduction in titanium oxide, obtain silver/titanium dioxide composite coating material, it is such to be coagulated by colloidal sol
Poly- method prepares film, and particle aggregation easily occurs and performance is caused to decline.
Invention content
The object of the present invention is to provide a kind of preparation methods of silver-colored carbon composite porous film, are prepared using hydro-thermal-reduction method
Obtain silver layer and the compound porous membrane of carbon-coating, film obtained, which is easy to preserve and can be used as SERS substrates, directly to be applied, sensitive
The low magnitude of degree more existing SERS substrates.
Realizing the technical solution of the object of the invention is：
A kind of preparation method of silver carbon composite porous film, includes the following steps：
Trioctylamine is added dropwise in glucose solution, is uniformly mixed, by the molar ratio of glucose and silver nitrate be 5~
15:1, silver nitrate solution is slowly added dropwise and obtains mixed solution, wherein the total volume of glucose solution and silver nitrate solution is pungent with three
The volume ratio of amine is 15~40:1, hydro-thermal reaction is carried out at 160 DEG C~200 DEG C, is cooled to room temperature after reaction, by upper layer
Film takes out, with obtaining silver-colored carbon composite porous film after water and ethyl alcohol washes clean.
Preferably, the concentration of glucose in the mixed solution is 0.1-0.15M.
Preferably, a concentration of 0.01-0.015M of the silver nitrate in the mixed solution.
Preferably, the hydro-thermal reaction time is 6h~15h.
The present invention prepares silver-colored carbon composite porous film using hydro-thermal-reduction method, and used raw material is in each of reaction
Stage all plays an important role：Wherein, trioctylamine is as oil phase, solution upper layer by coordination adsorb a large amount of silver from
Son.Glucose is the reducing agent in hydro-thermal reaction, while being the hydro-thermal carbon source in product again, and the hydro-thermal carbon is in oil-water interfaces strata
Collection growth forms C film, supports upper layer Ag films.Different from common silver-colored carbon direct combination film, the product table in the present invention
Face is the nano silver of very high purity, can greatly improve the sensitivity of detection；In addition different from nano silver film is directly obtained
It is that the presence of lower layer's carbon can effectively prevent the oxidation of silver, to make the holding time greatly prolong.
Compared with prior art, advantages of the present invention is as follows：
(1) raw material that the method for the present invention utilizes is cheap, simple for process, easy to operate, prepares quickly, simplifies production technology
Process；
(2) silver-colored carbon composite porous film prepared by the method for the present invention has even particle size, holey micro-nano
Structure, participating in compound hydro-thermal carbon component can not only effectively avoid the problem that SERS substrates are inactivated by oxidation, by the holding time
It greatly prolongs, and nano silver can be helped to adsorb more probe molecules, to improve the sensitivity of detection, placing 8
After month, detection limit is still up to 10-9M, a more existing low magnitude；
(3) porous structure of nanoscale is conducive to generate more SERS " hot spot ", to further increase probe molecule
Signal strength；
(4) in the later stage is applied, compared with existing nucleocapsid composite particles, film prepared by the method for the present invention,
The appearance characteristics of multi-layer compound film eliminate the process of SERS substrates preparation, not only can be directly used for SERS tests, but also
Improve the reproducibility of different test point probe molecule Raman scattering signals.
Description of the drawings
Fig. 1 is the preparation flow schematic diagram of the silver-colored carbon composite porous film of the present invention.
Fig. 2 is the SEM morphology characterization figures after the silver-colored carbon composite porous film prepared by embodiment 1 is placed 8 months.
Fig. 3 is the EDS elemental analysis figures of the silver-colored carbon composite porous film piece prepared by embodiment 2.
Fig. 4 is the Raman spectrum structural characterization figure of the silver-colored carbon composite porous film prepared by embodiment 3.
Fig. 5 is after the silver-colored carbon composite porous film prepared by embodiment 4 is placed 8 months, using rhodamine 6G as probe molecule
SERS collection of illustrative plates.
Fig. 6 is after the silver-colored carbon composite porous film prepared by embodiment 5 is placed 8 months, using crystal violet as probe molecule
SERS collection of illustrative plates.
Specific implementation mode
With reference to embodiment and attached drawing, the invention will be further described.
Embodiment 1
1.0mL trioctylamines are added dropwise in 0.2M glucose solutions, after being uniformly mixed, by rubbing for glucose and silver nitrate
You are than being 10:1, which is slowly added dropwise 0.02M silver nitrate solutions, obtains mixed solution, wherein glucose solution and silver nitrate solution it is total
Volume and the volume ratio of trioctylamine are 30:1, the above-mentioned solution of 30mL is taken, hydro-thermal reaction 15h is carried out at 160 DEG C, after reaction
After being cooled to room temperature, topmost thin film is taken out, with obtaining silver-colored carbon composite porous film after water and ethyl alcohol washes clean.
Fig. 2 is the morphology characterization figure SEM photograph after silver-colored carbon composite porous film obtained is placed 8 months, can be with from figure
See the nano-Ag particles in reticular structure distribution.
Embodiment 2
1.5mL trioctylamines are added dropwise in 0.2M glucose solutions, after being uniformly mixed, by rubbing for glucose and silver nitrate
You are than being 5:1, which is slowly added dropwise 0.04M silver nitrate solutions, obtains mixed solution, wherein glucose solution and silver nitrate solution it is total
Volume and the volume ratio of trioctylamine are 20:1, the above-mentioned solution of 30mL is taken, hydro-thermal reaction 12h is carried out at 180 DEG C, after reaction
After being cooled to room temperature, topmost thin film is taken out, with obtaining silver-colored carbon composite porous film after water and ethyl alcohol washes clean.
Fig. 3 is silver-colored carbon composite porous film EDS elemental analysis figures obtained, it can be seen that the constituent of film surface is pure
Spend higher silver.
Embodiment 3
0.75mL trioctylamines are added dropwise in 0.3M glucose solutions, after being uniformly mixed, by glucose and silver nitrate
Molar ratio is 15:1, which is slowly added dropwise 0.02M silver nitrate solutions, obtains mixed solution, wherein glucose solution and silver nitrate solution
The volume ratio of total volume and trioctylamine is 40:1, the above-mentioned solution of 30mL is taken, hydro-thermal reaction 6h is carried out at 200 DEG C, reaction terminates
After postcooling to room temperature, topmost thin film is taken out, with obtaining silver-colored carbon composite porous film after water and ethyl alcohol washes clean.
Fig. 4 is the structural characterization figure Raman spectrograms of carbon composite porous film obtained bottom surface, and provable bottom exists
Carbon.
Embodiment 4
2mL trioctylamines are added dropwise in 0.2M glucose solutions, after being uniformly mixed, by mole of glucose and silver nitrate
Than being 10:1, which is slowly added dropwise 0.02M silver nitrate solutions, obtains mixed solution, wherein the totality of glucose solution and silver nitrate solution
Product and the volume ratio of trioctylamine are 15:1, the above-mentioned solution of 30mL is taken, progress hydro-thermal reaction 12h, cold after reaction at 180 DEG C
But to after room temperature, topmost thin film is taken out, with obtaining silver-colored carbon composite porous film after water and ethyl alcohol washes clean.
Fig. 5 is placed 8 months after silver-colored carbon composite porous film is made, and various concentration (10 is tested as SERS substrates-7, 10-8, 10-9M) the Raman spectrogram of rhodamine 6G, it is seen that minimum test concentrations are up to 10-9M。
Embodiment 5
1.0mL trioctylamines are added dropwise in 0.2M glucose solutions, after being uniformly mixed, by rubbing for glucose and silver nitrate
You are than being 7:1, which is slowly added dropwise 0.03M silver nitrate solutions, obtains mixed solution, wherein glucose solution and silver nitrate solution it is total
Volume and the volume ratio of trioctylamine are 30:1, the above-mentioned solution of 30mL is taken, hydro-thermal reaction 8h is carried out at 200 DEG C, after reaction
After being cooled to room temperature, topmost thin film is taken out, with obtaining silver-colored carbon composite porous film after water and ethyl alcohol washes clean.
Fig. 6 is placed 8 months after silver-colored carbon composite porous film is made, and various concentration (10 is tested as SERS substrates-6, 10-7, 10-8M) the Raman spectrogram of crystal violet, it is seen that minimum test concentrations are up to 10-8M。
Comparative example 1
1.0mL trioctylamines are added dropwise in 0.2M glucose solutions, after being uniformly mixed, by rubbing for glucose and silver nitrate
You are than being 7:1, which is slowly added dropwise 0.03M silver nitrate solutions, obtains mixed solution, wherein glucose solution and silver nitrate solution it is total
Volume and the volume ratio of trioctylamine are 30:1, the above-mentioned solution of 30mL is taken, hydro-thermal reaction 8h is carried out at 220 DEG C, after reaction
It is cooled to room temperature, desired silver-colored carbon compound film is not made under the hydrothermal temperature.
Claims (4)
1. a kind of preparation method of silver carbon composite porous film, which is characterized in that include the following steps：
Trioctylamine is added dropwise in glucose solution, is uniformly mixed, is 5~15 by the molar ratio of glucose and silver nitrate:1,
Silver nitrate solution is slowly added dropwise and obtains mixed solution, wherein the total volume and trioctylamine of glucose solution and silver nitrate solution
Volume ratio is 15~40:1, hydro-thermal reaction is carried out at 160 DEG C~200 DEG C, is cooled to room temperature after reaction, by topmost thin film
It takes out, with obtaining silver-colored carbon composite porous film after water and ethyl alcohol washes clean.
2. preparation method according to claim 1, which is characterized in that the concentration of glucose in the mixed solution is
0.1-0.15M。
3. preparation method according to claim 1, which is characterized in that silver nitrate in the mixed solution it is a concentration of
0.01-0.015M。
4. preparation method according to claim 1, which is characterized in that the hydro-thermal reaction time is 6h~15h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111175275A (en) * | 2020-01-06 | 2020-05-19 | 宁波大学 | Silver-based modified MoO for SERS3-xOf a multilayer structure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104857902A (en) * | 2015-04-13 | 2015-08-26 | 南京理工大学 | Preparation method of silver/carbon composite hollow nanospheres |
| CN105717091A (en) * | 2016-01-29 | 2016-06-29 | 南京理工大学 | Durable and efficient SERS substrate and preparation method thereof |
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- 2017-03-30 CN CN201710202933.2A patent/CN108663348A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104857902A (en) * | 2015-04-13 | 2015-08-26 | 南京理工大学 | Preparation method of silver/carbon composite hollow nanospheres |
| CN105717091A (en) * | 2016-01-29 | 2016-06-29 | 南京理工大学 | Durable and efficient SERS substrate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| PENGPENG JIANG, ET.AL.: ""Study of Preparation，Growth Mechanism and Catalytic Performance of Carbon Based Embedded Silver Nano Composite Materials"", 《EURASIAN CHEMICO-TECHNOLOGICAL JOURNAL》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111175275A (en) * | 2020-01-06 | 2020-05-19 | 宁波大学 | Silver-based modified MoO for SERS3-xOf a multilayer structure |
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