CN110487772A - A kind of three-dimensional S nO2/ Ag NPs Raman enhances substrate and the preparation method and application thereof - Google Patents
A kind of three-dimensional S nO2/ Ag NPs Raman enhances substrate and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention relates to Raman enhancing substrate technical field more particularly to a kind of three-dimensional S nO2/ Ag NPs Raman enhances substrate and the preparation method and application thereof.The Raman enhancing substrate includes substrate, SnO2Film layer and Ag NPs；The SnO2Film layer is attached to substrate surface, the SnO2Film surface is coarse, forms three-dimensional vesicular texture, and the Ag NPs is dispersed in SnO2In film layer, and part is located at SnO2In the hole of film layer, SnO2Perovskite material is collectively formed with Ag NPs.Present invention SnO2The surface area bigger than smooth surface can be provided to adsorb nano-Ag particles as three-dimensional (3D) SERS active-substrate of substrate preparation, to provide more reflecting points to capture more probe molecules and improve detection sensitivities.Moreover, three-dimensional substrates structure has limit luminous effect, it can be with the scattering light in Heavy metal substrate, to generate higher Raman reinforcing effect.
Description
Technical field
The present invention relates to Raman enhancing substrate technical field more particularly to a kind of three-dimensional S nO2/ Ag NPs Raman enhances base
Bottom and the preparation method and application thereof.
Background technique
It is only intended to increase understanding of the overall background of the invention for information disclosed in background of invention, without
It is existing well known to persons skilled in the art so to be considered as recognizing or imply that information composition has become in any form
Technology.
From last century the seventies propose Surface enhanced Raman scattering (SERS) detection technique, because its is with higher
The advantages that detection sensitivity and specificity, allows SERS as a kind of sensor and spectral technique, in chemistry, bio-sensing, environment prison
The fields such as survey face are widely applied, but a series of disadvantages such as preparation process that traditional Raman detection substrate has is complicated, is prepared into
The requirement detected instantly is not achieved gradually and limits its scope of application for this valuableness, detection sensitivity, therefore Raman detection technology is compeled
It is essential and wants a kind of novel base material to improve its detectability and expand its application range.
Currently, there are mainly two types of the mechanism for improving substrate sensitivity generally to be received by everybody.One is electromagnetism (EM) enhancings
Mechanism, be derived from noble metal nano body structure surface local surface plasma resonance (LSPR), in particulate interspaces, tip or
The regions such as nanoaperture, ambient light shine the charge concentration generated in these regional areas, so that LSPR constantly enhances, to play
Very high Raman signal reinforcing effect.Another kind is chemical enhanced mechanism (CM), and this enhancing mechanism is present in semiconductor material
In, reinforcing effect is relatively low, it includes three processes: the electric charge transfer between substrate and probe molecule, molecular resonance and phase interaction
With non-resonance interaction.However, its material cost is high present inventor have discovered that although noble metal substrate reinforcing effect is significant
Expensive and preparation process is complicated, semiconductor base cost economy but reinforcing effect it is relatively low be not suitable for detect low concentration sample, these
The defect limitation of substrate seriously limits the development and application of Raman detection technology.Therefore, it is necessary to which developing one kind takes into account the Supreme People's Procuratorate
Survey the novel SERS substrate of sensitivity and cheap production cost.
Summary of the invention
For above-mentioned problem, the present invention is intended to provide a kind of three-dimensional S nO2/ Ag NPs Raman enhances substrate and its preparation
Method and application.The new substrates material SnO that the present invention designs2/ AgNPs is comprehensive electromagnetic enhancement mechanism and chemical enhanced mechanism
Form composite construction together to obtain higher SERS signal.
To achieve the above object, the present invention discloses following proposal:
A kind of three-dimensional S nO2/ Ag NPs Raman enhances substrate, including substrate, SnO2Film layer and Ag NPs (Nano silver grain)；
The SnO2Film layer is attached to substrate surface, the SnO2Film surface is coarse, forms three-dimensional vesicular texture, the Ag
NPs is dispersed in SnO2In film layer, and part is located at SnO2In the hole of film layer；SnO2Perovskite material is collectively formed with Ag NPs.
One of the characteristics of Raman enhancing substrate of the present invention are as follows: compared with other materials, the perovskite of Argent grain is added dropwise in surface
Material SnO2/ Ag has very superior electrical conductivity energy, is able to suppress the compound of carrier, makes carrier in SnO2With Ag nanometers
It is redistributed between grain, interfacial polarization occurs, enhanced CM and LSPR effect, improve detection sensitivity.
The two of the characteristics of Raman of the present invention enhancing substrate are as follows: the substrate possesses special three-dimensional microstructures: with it is traditional
Smooth flat substrate is compared, and substrate surface of the invention is coarse, as porous foam, is had very big surface area, be can be absorbed more
More probe molecules, and the structure can promote more nano-Ag particles to be adsorbed on SnO2Surface proposes the substrate
Strong graceful signal is enhanced for more conversion zones.
The three of the characteristics of Raman enhancing substrate of the present invention are as follows: this possesses photocatalysis energy more higher than ordinary semiconductor material
Power can decompose test sample in the sun, realize substrate secondary use；Test proves: the substrate can be irradiated in sunlight
The R6G dye content on substrate surface is reduced by 84% in lower 3 hours.
Compared with prior art, the present invention achieve it is following the utility model has the advantages that
(1) present invention SnO2It can be provided as three-dimensional (3D) SERS active-substrate of substrate preparation bigger than smooth surface
Surface area adsorb nano-Ag particles, to provide more reflecting points, to capture more probe molecules, to improve detection sensitive
Degree.Moreover, three-dimensional substrates structure has limit luminous effect, it can be with the scattering light in Heavy metal substrate, to generate higher drawing
Graceful reinforcing effect.
(2) active Raman base material prepared by the present invention has very high detection sensitivity: using R6G dyestuff as probe
Molecule observes the SERS signal measured by detecting the dyestuff of various concentration, and Raman substrate material of the invention can be low
To 10-12Powerful detection signal is obtained under the R6G solution concentration of M.
(3) active Raman base material prepared by the present invention has good repeatability, and the recycling of substrate may be implemented.In
Sunlight irradiated the lower conventional base active base material almost nil but of the invention to the decomposition of detection solution in 3 hours
80% or more can be decomposed to R6G dyestuff.The duplicate measurements to detection substance may be implemented in the active substrate.
(4) active Raman base material prepared by the present invention is with a wide range of applications.It is excellent in addition to having to R6G dyestuff
Different detection sensitivity, the active substrate can also realize the detection to MG and CV concentration of aqueous solution.Meanwhile activity of the invention is drawn
Graceful base material also has advantage at low cost.
Detailed description of the invention
The Figure of description for constituting a part of the invention is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.
Fig. 1 is three-dimensional S nO prepared by the embodiment of the present invention 12The SEM of/Ag NPs Raman enhancing substrate.
Fig. 2 is the three-dimensional S nO that various concentration R6G is prepared in the embodiment of the present invention 12/ Ag NPs Raman enhances in substrate
SERS spectra.
Fig. 3 is the three-dimensional S nO that the MG and CV solution of various concentration is prepared in the embodiment of the present invention 12The enhancing of/Ag NPs Raman
SERS spectra and Raman mapping in substrate.
Fig. 4 is the three-dimensional S nO that R6G is prepared in the embodiment of the present invention 12Light degradation in/Ag NPs Raman enhancing substrate is shown
It is intended to.
Fig. 5 is same concentrations R6G respectively in pure SnO2The three-dimensional S nO prepared with the embodiment of the present invention 12/ Ag NPs Raman increases
Photocatalytic degradation situation on strong basis bottom.
Specific embodiment
It is noted that unless otherwise specified, all technical and scientific terms used in the present invention have and institute of the present invention
Belong to the normally understood identical meanings of those of ordinary skill of technical field.
It should be noted that term used in the present invention is merely to describe specific embodiment, and be not intended to limit
System is according to an illustrative embodiment of the invention.As used herein, unless the context clearly indicates otherwise, otherwise singular
Form be also intended to include plural form, additionally, it should be understood that, when in the present specification use term "comprising" and/or
When " comprising ", existing characteristics, step, operation, device, component and/or their combination are indicated.
As previously mentioned, although noble metal substrate reinforcing effect is significant, its material cost is expensive and preparation process is multiple
It is miscellaneous, semiconductor base cost economy but reinforcing effect it is relatively low be not suitable for detect low concentration sample, these substrates defect limitation
Seriously limit the development and application of Raman detection technology.For this purpose, the present invention is based on new substrates material SnO2/ Ag NPs is proposed
A kind of Raman enhances substrate.
In some typical embodiments, the substrate is FTO electro-conductive glass, with tape-stripping FTO electro-conductive glass, In
It reserves square window above, smears slurry etc. in window blade.
In some typical embodiments, the SnO29-10 microns of the thickness of film layer.
In some typical embodiments, the SnO2It is 1.5-2.8:1 with the mass ratio of Ag NPs, preferably 1.7:
1。
In some typical embodiments, the SnO2With Ag NPs by the way that perovskite material is collectively formed after calcining.
In addition, present invention also proposes simple and economic method prepares the three-dimensional S nO2The enhancing of/Ag NPs Raman
Substrate includes the following steps:
(1) high-purity SnO2Preparation: the aqueous solution pH of tin source is adjusted to alkalinity, the solution is then placed in confined condition
Lower heat preservation isolates precipitating after generation completely to be precipitated, the SnO that will be obtained after freeze-drying2Powder is dispersed in n-butanol, so
First time calcining is carried out to dispersion liquid afterwards, obtains high-purity SnO2；
(2) pure SnO2Preparation: by the high-purity SnO2The is carried out after grinding under conditions of being higher than first time calcination temperature
Secondary clacining obtains pure SnO2, spare；
(3)SnO2Slurry preparation:
The mixed solution of ethyl cellulose and ethyl alcohol is thermally formed A colloidal sol；
By the pure SnO2It is dispersed in dehydrated alcohol with tetraethyl orthosilicate and forms B solution；
A colloidal sol and B solution are uniformly mixed, SnO is formed2Slurry, it is spare；
(4) three-dimensional S nO2/ Ag NPs Raman enhances substrate preparation: by the SnO2Slurry is formed coated in substrate surface
SnO2Film layer, then by Ag nanoparticle dispersion drop on the surface of the film layer after calcine, after the completion cool down to get.
In some typical embodiments, in step (1), the aqueous solution of the tin source is that stannic chloride tin tetrachloride is dissolved in
The tin chloride solution that distilled water is formed.
In some typical embodiments, in step (1), the pH control preferably increases the hydrogen in solution between 8-9
Oxygen root concentration makes tin tetrachloride that backward reaction occur, and generates white precipitate, at the pH, reaction effect is best, between 7-8
The very fast positive increase of conversion ratio, more than 9 after rise slowly, optionally, the adjusting of the pH, ammoniacal liquor mass concentration are carried out using ammonium hydroxide
For 20-26%.
In some typical embodiments, in step (1), the temperature of the heat preservation is 80-120 DEG C；The freezing is dry
The dry time is 22-25 hours.The too high leakproofness and crushing resistance to laboratory apparatus of reaction temperature requires excessive.
In some typical embodiments, in step (1), the SnO2Powder and n-butanol ratio are sequentially 0.3-
1.5g:15-40ml, preferably 0.5g:20ml.
In some typical embodiments, in step (1), the temperature of the first time calcining is 380-440 DEG C, the time
It is 4.5-5.5 hours, preferably 400 calcinings 5 hours.N-butanol ammonium hydroxide, dry speed are evaporated by the relatively low temperature calcination of first time
Degree is fast, prepared stannic oxide purity is high.
In some typical embodiments, in step (2), the temperature of second of calcining is 750-820 DEG C, the time
It is 2.5-4 hours；Preferably 800 calcinings 3 hours；Product is purified by secondary high-temperature calcination.
In some typical embodiments, in step (3), ethyl cellulose and ethyl alcohol addition are than column in the A colloidal sol
It is sequentially 1.8-3.5g:15-30ml；Preferably 2.5g:19ml.The three-dimensional structure to grow out under the ratio is more excellent.
In some typical embodiments, in step (3), SnO in the B solution2, tetraethyl orthosilicate, ethyl alcohol adds
Adding ratio is sequentially 0.6-0.8g, 1.2-2.5g, 14-28ml；Preferably 0.65g:1.5g:17ml.
In some typical embodiments, in step (3), the mixed solution of the ethyl cellulose and ethyl alcohol heats temperature
Degree is 65-80 DEG C, and the time is 2-3.5 hours.So that ethyl alcohol is volatilized by heating, forms three-dimensional structure.
In some typical embodiments, in step (3), the mixing mass ratio of the A colloidal sol and B solution is 4.2-
5.0:15-22g.Due to 3D shape to be grown, to guarantee that ethyl alcohol will be far more than stannic oxide, and ensure again mixed
Closing liquid cannot be too dilute, with obstruction free knifing.
In some typical embodiments, in step (3), the A colloidal sol and B solution are sufficiently stirred between 55-64 DEG C
It mixes 6-10 hours and SnO is made2Slurry.
In some typical embodiments, in step (4), the silver nano-grain of the dropwise addition is per unit basement membrane 0.4-
0.7ml。
In some typical embodiments, in step (4), the calcination temperature is 420-480 DEG C, time 1.2-2
Hour.It is helped to ensure that under the temperature and time and does not destroy substrate three-dimensional appearance, and Argent grain can be allowed to be attached in matrix
It is dried.
In some typical embodiments, the three-dimensional S nO2/ Ag NPs Raman enhances substrate and/or the system of the substrate
Preparation Method is also used for chemistry, bio-sensing, the fields such as environmental monitoring face.
The present invention is further illustrated now in conjunction with specification drawings and specific embodiments.
Embodiment 1
A kind of three-dimensional S nO2/ Ag NPs Raman enhances the preparation method of substrate, includes the following steps:
(1)SnO2Preparation:
Firstly, tin tetrachloride, which is dissolved in distilled water, forms tin chloride solution, being slowly added to ammonium hydroxide into the solution, (quality is dense
22%) and with pH meter degree measures solution acid alkalinity, until solution ph reaches 9, this is stirred continuously in the process.
Then the solution for having reconciled pH is moved in heating kettle, fastens heating kettle lid, and heating kettle is put into oven,
Place 1 hour generation white precipitate in 100 DEG C of environment, white depositions centrifugal filtration, be freeze-dried 24 hours, spend from
Sub- water and ethyl alcohol repeat the above steps, and wash by three times, obtain the SnO that alcohol washes system2Powder.
By the SnO2Powder and n-butanol are moved into three hole cucurbits after mixing according to the ratio of 0.5g:20ml and distill,
Solid in bottle is taken out the high-purity SnO that 5 hours systems are calcined in 400 DEG C of muffle furnaces2.With crucible by obtained high-purity SnO2It grinds
It is calcined 3 hours at 800 DEG C after wearing into fine powder mill, obtains pure SnO2, it is spare to be ground into powder；
(2) SnO is prepared2Slurry:
It is formed after being stirred 3 hours at 70 DEG C after ethyl cellulose and ethyl alcohol are mixed according to the additive amount of 2.5g, 19ml
Substance be known as A colloidal sol；
By pure SnO made from step (1)2Powder and tetraethyl orthosilicate, which are dispersed in dehydrated alcohol, forms B solution,
In, the SnO2, tetraethyl orthosilicate, ethyl alcohol additive amount be 0.65g, 1.5g, 17ml.
It is sufficiently stirred 8 hours, is made in 60 DEG C of environment after A colloidal sol and B solution are mixed in the ratio of 4.5g:16g
SnO2Slurry.
(3) three-dimensional S nO2The preparation of/Ag NPs Raman enhancing substrate: by adhesive tape by the SnO of step (2)2Slurry exists
Film is painted in FTO electro-conductive glass substrate, then Ag nano particles exist according to the ratio dispersion drop of per unit basement membrane 0.5ml
On the surface of the film, finally heated 1.5 hours in 450 DEG C of Muffle furnaces.Take out it is cooling dry after to get.
Embodiment 2
A kind of three-dimensional S nO2/ Ag NPs Raman enhances the preparation method of substrate, includes the following steps:
(1)SnO2Preparation:
Firstly, tin tetrachloride, which is dissolved in distilled water, forms tin chloride solution, being slowly added to ammonium hydroxide into the solution, (quality is dense
20%) and with pH meter degree measures solution acid alkalinity, until solution ph reaches 9, this is stirred continuously in the process.
Then the solution for having reconciled pH is moved in heating kettle, fastens heating kettle lid, and heating kettle is put into oven,
Place 50min in 120 DEG C of environment and generate white precipitate, white depositions centrifugal filtration, be freeze-dried 22 hours, spend from
Sub- water and ethyl alcohol repeat the above steps, and wash by three times, obtain the SnO that alcohol washes system2Powder.
By the SnO2Powder and n-butanol are moved into three hole cucurbits after mixing according to the ratio of 1.5g:40ml and distill,
Solid in bottle is taken out the high-purity SnO that 5.5 hours systems are calcined in 380 DEG C of muffle furnaces2.With crucible by obtained high-purity SnO2
It is calcined 4 hours at 750 DEG C after being ground into fine powder mill, obtains pure SnO2, it is spare to be ground into powder；
(2) SnO is prepared2Slurry:
Shape after being stirred 3.5 hours at 65 DEG C after ethyl cellulose and ethyl alcohol are mixed according to the additive amount of 3.5g, 30ml
At substance be known as A colloidal sol；
By pure SnO made from step (1)2Powder and tetraethyl orthosilicate, which are dispersed in dehydrated alcohol, forms B solution,
In, the SnO2, tetraethyl orthosilicate, ethyl alcohol additive amount be 0.6g, 2.5g, 14ml.
It is sufficiently stirred 6 hours, is made in 64 DEG C of environment after A colloidal sol and B solution are mixed in the ratio of 4.2g:15g
SnO2Slurry.
(3) three-dimensional S nO2The preparation of/Ag NPs Raman enhancing substrate: by adhesive tape by the SnO of step (2)2Slurry exists
Film is painted on FTO electro-conductive glass, then drips Ag nano particles in the film according to the ratio dispersion of per unit basement membrane 0.7ml
Surface on, finally heated 2 hours in 420 DEG C of Muffle furnaces.Take out it is cooling dry after to get.
Embodiment 3
A kind of three-dimensional S nO2/ Ag NPs Raman enhances the preparation method of substrate, includes the following steps:
(1)SnO2Preparation:
Firstly, tin tetrachloride, which is dissolved in distilled water, forms tin chloride solution, being slowly added to ammonium hydroxide into the solution, (quality is dense
26%) and with pH meter degree measures solution acid alkalinity, until solution ph reaches 8, this is stirred continuously in the process.
Then the solution for having reconciled pH is moved in heating kettle, fastens heating kettle lid, and heating kettle is put into oven,
Place 2 hours generation white precipitates in 80 DEG C of environment, white depositions centrifugal filtration, be freeze-dried 25 hours, spend from
Sub- water and ethyl alcohol repeat the above steps, and wash by three times, obtain the SnO that alcohol washes system2Powder.
By the SnO2Powder and n-butanol are moved into three hole cucurbits after mixing according to the ratio of 0.3g:15ml and distill,
Solid in bottle is taken out the high-purity SnO that 4.5 hours systems are calcined in 440 DEG C of muffle furnaces2.With crucible by obtained high-purity SnO2
It is calcined 2.5 hours at 820 DEG C after being ground into fine powder mill, obtains pure SnO2, it is spare to be ground into powder；
(2) SnO is prepared2Slurry:
It is formed after being stirred 2 hours at 80 DEG C after ethyl cellulose and ethyl alcohol are mixed according to the additive amount of 1.8g, 15ml
Substance be known as A colloidal sol；
By pure SnO made from step (1)2Powder and tetraethyl orthosilicate, which are dispersed in dehydrated alcohol, forms B solution,
In, the SnO2, tetraethyl orthosilicate, ethyl alcohol additive amount be 0.8g, 1.2g, 28ml.
It is sufficiently stirred 10 hours, is made in 55 DEG C of environment after A colloidal sol and B solution are mixed in the ratio of 5.0g:22g
SnO2Slurry.
(3) three-dimensional S nO2The preparation of/Ag NPs Raman enhancing substrate: by adhesive tape by the SnO of step (2)2Slurry exists
Film is painted on FTO electro-conductive glass, then drips Ag nano particles in the film according to the ratio dispersion of per unit basement membrane 0.4ml
Surface on, finally heated 1.2 hours in 480 DEG C of Muffle furnaces.Take out it is cooling dry after to get.
Performance test
The three-dimensional S nO prepared with embodiment 12/ Ag NPs Raman carries out its microscopic appearance, performance etc. for enhancing substrate
Test.
Fig. 1 is three-dimensional S nO2The SEM of/Ag NPs Raman enhancing substrate, it can be seen that Raman enhancing prepared by the present invention
Substrate has coarse surface, and as porous foam, wherein the part Ag NPs is located at SnO2In the hole of film layer.By testing,
Its surface area has reached ca.3.75m2/ g, the substrate of this structure can absorb more probe molecules, and the structure can be with
Promote more nano-Ag particles to be adsorbed on stannic oxide surface, so that the substrate is provided more conversion zones strong to enhance
Graceful signal.
Fig. 2 is three-dimensional S nO2/ Ag NPs Raman enhances in substrate, the SERS spectra of various concentration R6G solution.From figure
It can be seen that Raman substrate material of the invention can be down to 10-12Powerful detection letter is obtained under the R6G solution concentration of M
Number.This is because the perovskite material SnO of Argent grain is added dropwise in surface2/ Ag has very superior electrical conductivity energy, is able to suppress current-carrying
Sub is compound, makes carrier in SnO2Redistributed between Ag nano particle, interfacial polarization occur, enhance CM and
LSPR effect, improves detection sensitivity.In addition, this three-dimensional substrates structure has limit luminous effect, it can be with Heavy metal substrate
In scattering light, to generate higher Raman reinforcing effect.
In Fig. 3, (a) and (c) figure are respectively MG the and CV solution of various concentration in three-dimensional S nO2The enhancing of/Ag NPs Raman
SERS spectra in substrate.It can be seen that can reach 10 to the detection sensitivity of MG target detection thing-10Mol/L, to CV target
The detectable concentration of detectable substance is up to 10-9Mol/L illustrates that the substrate can have very high sensitivity to MG.CV context of detection.
(b) and (d) figure is MG, the Raman mapping of CV aqueous solution, it will thus be seen that in the different location of the substrate, to same
The detectability of detectable substance is similar, and there is no certain parts of only substrate just can achieve high detection sensitivity, substrate edge edge
Position detection sensitivity problem not up to standard.In addition, wherein same gray scale represents the same enhancing sensitivity of the substrate, can see
Out, in entire substrate detection faces, the variation of gray scale is very unobvious, the almost same gray scale, illustrates that the substrate is being examined
Survey target substance when, the detection sensitivity of different spatial be it is the same, uniformly, there is no only it is a certain specific in the substrate
Position just shows outstanding detection sensitivity, embodies the detection uniformity of the substrate.
Fig. 4 is R6G in three-dimensional S nO2/ Ag NPs Raman enhances the light degradation schematic diagram in substrate, wherein when horizontal axis is
Between (minute), the longitudinal axis is Raman signal intensity, it will thus be seen that the substrate can decompose test sample R6G under light illumination, and
And with the enhancing of light application time, detected Raman signal is lower and lower, Raman signal can be reduced in or so hour
To the value of a very little, illustrate that the substrate can be under light illumination test sample photodissociation, and photolysis efficiency is high, may be implemented to serve as a contrast
Bottom secondary use shows good repeatability.
Fig. 5 is same concentrations R6G respectively in pure SnO2With three-dimensional S nO2/ Ag NPs Raman enhances photocatalysis drop in substrate
Solve situation, it will thus be seen that adulterate foundation light degradation rate and the light degradation ability of Argent grain far more than the Argent grain that commonly undopes
Stannic oxide substrate, illustrating the substrate just has superior photo-catalysis capability.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in
Within protection scope of the present invention.Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not
Limiting the scope of the invention, those skilled in the art should understand that, based on the technical solutions of the present invention, this
Field technical staff does not need to make the creative labor the various modifications or changes that can be made still in protection scope of the present invention
Within.
Claims (10)
1. a kind of three-dimensional S nO2/ Ag NPs Raman enhances substrate, which is characterized in that including substrate, SnO2Film layer and Ag NPs；Institute
State SnO2Film layer is attached to substrate surface, the SnO2Film surface is coarse, forms three-dimensional vesicular texture, the Ag NPs
It is dispersed in SnO2In film layer, and part is located at SnO2In the hole of film layer, SnO2Perovskite material is collectively formed with Ag NPs.
2. Raman as described in claim 1 enhances substrate, which is characterized in that the SnO2Film layer with a thickness of 9-10 microns.
3. Raman as described in claim 1 enhances substrate, which is characterized in that the SnO2Mass ratio with Ag NPs is 1.5-
2.8:1 preferably 1.7:1.
4. Raman as described in any one of claims 1-3 enhances substrate, which is characterized in that the substrate is electro-conductive glass, such as
FTO electro-conductive glass etc..
5. a kind of three-dimensional S nO2The preparation method of/Ag NPs Raman enhancing substrate, which comprises the steps of:
(1) high-purity SnO2Preparation: the aqueous solution pH of tin source is adjusted to alkalinity, then the solution is placed in and is protected under confined conditions
Temperature isolates precipitating after generation completely to be precipitated, the SnO that will be obtained after freeze-drying2Powder is dispersed in n-butanol, then right
Dispersion liquid carries out first time calcining, obtains high-purity SnO2；
(2) pure SnO2Preparation: by the high-purity SnO2It is carried out under conditions of being higher than first time calcination temperature second after grinding
Calcining, obtains pure SnO2, spare；
(3)SnO2Slurry preparation:
The mixed solution of ethyl cellulose and ethyl alcohol is thermally formed A colloidal sol；
By the pure SnO2It is dispersed in dehydrated alcohol with tetraethyl orthosilicate and forms B solution；
A colloidal sol and B solution are uniformly mixed, SnO is formed2Slurry, it is spare；
(4) three-dimensional S nO2/ Ag NPs Raman enhances substrate preparation: by the SnO2Slurry is coated in substrate surface and forms SnO2Film
Layer, then by Ag nanoparticle dispersion drop on the surface of the film layer after calcine, after the completion cool down to get.
6. preparation method as claimed in claim 5, which is characterized in that the aqueous solution of the tin source is that stannic chloride tin tetrachloride is molten
In the tin chloride solution that distilled water is formed；
Preferably, the pH control is advisable (preferably 7-8) between 8-9, optionally, the tune of the pH is carried out using ammonium hydroxide
Section, ammoniacal liquor mass concentration 20-26%；
Preferably, in step (1), the temperature of the heat preservation is 80-120 DEG C；
Preferably, the time of the freeze-drying is 22-25 hours；
Preferably, the SnO2Powder and n-butanol ratio are sequentially 0.3-1.5g:15-40ml, preferably 0.5g:20ml.
7. preparation method as claimed in claim 5, which is characterized in that the temperature of the first time calcining is 380-440 DEG C, when
Between be 4.5-5.5 hour, more preferably 400 calcine 5 hours；
Preferably, the temperature of second of calcining is 750-820 DEG C, and the time is 2.5-4 hours；More preferably 800 calcinings 3 are small
When.
8. preparation method as claimed in claim 5, which is characterized in that ethyl cellulose and ethyl alcohol add ratio in the A colloidal sol
Leie order is 1.8-3.5g:15-30ml；Preferably 2.5g:19ml
Preferably, SnO in the B solution2, tetraethyl orthosilicate, ethyl alcohol adding proportion be sequentially 0.6-0.8g, 1.2-2.5g,
14-28ml；More preferably 0.65g:1.5g:17ml；
Preferably, the mixed solution heating temperature of the ethyl cellulose and ethyl alcohol is 65-80 DEG C, and the time is 2-3.5 hours；
Preferably, the A colloidal sol and the mixing mass ratio of B solution are 4.2-5.0:15-22g；
Preferably, the A colloidal sol and B solution are sufficiently stirred 6-10 hours between 55-64 DEG C and SnO are made2Slurry.
9. preparation method as claimed in claim 5, which is characterized in that the silver nano-grain of the dropwise addition is per unit basement membrane
0.4-0.7ml；
Preferably, in step (4), the calcination temperature is 420-480 DEG C, and the time is 1.2-2 hours.
10. three-dimensional S nO according to any one of claims 1-42/ Ag NPs Raman enhances substrate and/or such as claim 5-9
Application of described in any item preparation methods in chemistry, bio-sensing, environmental monitoring face field.
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| CN111189816A (en) * | 2020-01-20 | 2020-05-22 | 合肥工业大学 | Three-dimensional SiO2Preparation of-Ag porous structure and application thereof in volatile organic compound detection |
| CN111366571A (en) * | 2020-03-12 | 2020-07-03 | 华东师范大学 | CsPbBr 3-Au-based flexible photoinduced enhanced Raman sensor and preparation and application thereof |
| CN113324972A (en) * | 2021-05-17 | 2021-08-31 | 昆明理工大学 | Quantitative analysis method for formaldehyde in water environment |
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| CN109655443A (en) * | 2019-01-14 | 2019-04-19 | 中国人民解放军火箭军工程大学 | Silver-colored carried titanium dioxide nano-array laminated film, preparation method and its application in trace materials detection |
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| CN111366571A (en) * | 2020-03-12 | 2020-07-03 | 华东师范大学 | CsPbBr 3-Au-based flexible photoinduced enhanced Raman sensor and preparation and application thereof |
| CN113324972A (en) * | 2021-05-17 | 2021-08-31 | 昆明理工大学 | Quantitative analysis method for formaldehyde in water environment |
| CN113324972B (en) * | 2021-05-17 | 2022-09-13 | 昆明理工大学 | Quantitative analysis method for formaldehyde in water environment |
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