CN109926578A - A kind of surface enhanced Raman scattering substrate material, preparation method and application - Google Patents
A kind of surface enhanced Raman scattering substrate material, preparation method and application Download PDFInfo
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- CN109926578A CN109926578A CN201910142987.3A CN201910142987A CN109926578A CN 109926578 A CN109926578 A CN 109926578A CN 201910142987 A CN201910142987 A CN 201910142987A CN 109926578 A CN109926578 A CN 109926578A
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Abstract
The invention discloses a kind of surface enhanced Raman scattering substrate material, preparation method and applications.Surface enhanced Raman scattering substrate material forms (Ag@Co-Ni LDH) by the core-shell structure of the cobalt nickel bimetal hydroxide (Co-Ni LDH) of silver nanowires and hollow structure, the substrate material surface modifies p-aminophenyl thiophenol, the capture of aldehydes molecule can be achieved, realize the qualitative and quantitative detection of aldehydes molecule.To 1623cm‑1The Raman peak intensity at place carries out the RGB imaging of intensity.Color Range is 0-300.Tri- bit value of R, G, B of RGB image is read respectively.Using 9 bit digitals and testing molecule concentration information of RGB, bar code or two dimensional code coding are carried out.
Description
Technical field
The present invention relates to a kind of base materials, and in particular to a kind of surface enhanced Raman scattering substrate material, its preparation side
Method and application.
Background technique
The cell metabolism of cancerous tumor cell changes, and leads to the volatile organic gases (VOCs) in lung cancer patient exhalation object
Type differs greatly with content and ordinary person.Aldehydes molecule is molecule important in VOCs, can be used as breathing marker, according to
Its content judges histiocytic metabolic condition, and then realizes the early diagnosis to cancer.Currently, mainly passing through solid phase microextraction
Joint gas chromatography-mass spectrography (GC-MS) technology, pyrolysis analyzer joint gas-chromatography etc. carry out VOCs detection and analysis.It is such
Method pre-treatment is cumbersome, instrument and equipment requires height.
Surface enhanced Raman scattering (SERS) is a kind of to realize determinand according to different molecular vibration level and structural information
Detection analytical technology.The technology has many advantages, such as high sensitivity, high specificity, non-destructive testing in situ, is widely used in object
The fields such as reason, chemistry, biology.But testing molecule needs to be adsorbed on plasma hot spot region, and the gas strong for mobility is difficult
With absorption, and then it cannot achieve the detection of gaseous aldehyde molecule.
Summary of the invention
The present invention provides a kind of base material, and the base material includes the cobalt nickel bimetal of silver nanowires and hollow structure
Hydroxide Co-Ni LDH, the base material have core-shell structure: core is silver nanowires, and shell is the Co-Ni LDH；It is excellent
Selection of land, the base material can be indicated with Ag@Co-Ni LDH.
The length of base material according to the present invention, the silver nanowires can be 1.5-7 μm, such as length can be
2.3-5.6 μm, as an example, length is 2.5 μm, 3 μm, 3.6 μm, 4 μm, 4.5 μm, 5 μm.The diameter of the silver nanowires can be with
For 30-120nm, such as diameter can be 50-100nm, 55-90nm, as an example, diameter can be 60nm, 70nm, 80nm.
Base material according to the present invention, the silver nanowires account for the 24-49% of the base material quality, such as 25-
45%, 30-40%；As an example, the silver nanowires accounts for 29%, 33%, the 36% of the base material quality.
Base material according to the present invention, the Co-Ni LDH account for the 50-75% of the base material quality, such as 55-
70%, 60-65%；As an example, the Co-Ni LDH accounts for 63%, 66%, the 70% of the base material quality.
Base material according to the present invention, the partial size of the cobalt nickel bimetal hydroxide of the hollow structure are 150-
400nm, for example, partial size can be 200-300nm, as an example, partial size can for 220nm, 240nm, 250nm, 275nm,
290nm。
The silver nanowires of base material according to the present invention, the base material can also be repaired using p-aminophenyl thiophenol
Decorations.Preferably, the modification is the sulfydryl by p-aminophenyl thiophenol in conjunction with the silver atoms on the silver nanowires surface.It is preferred that
Ground, grafting amount of the p-aminophenyl thiophenol on the silver nanowires surface (can be received for 0.0002-0.4wt ‰ relative to silver
The mass ratio of rice noodles).
The present invention also provides the preparation methods of above-mentioned base material, and described method includes following steps:
(1) it disperses silver nanowires in methanol, 2-methylimidazole, cobalt nitrate is added thereto, ultrasound is collected purple ash and produced
Object；It dispersing the purplish grey product after washing in ethyl alcohol, nickel nitrate is added thereto, celadon product is collected in heating reaction,
Obtain the Ag@Co-Ni LDH；
(2) it disperses the Ag@Co-Ni LDH in the ethanol solution of p-aminophenyl thiophenol, is ultrasonically treated, collect grayish green
Color product obtains the base material.
Preparation method according to the present invention, in step (1), the silver nanowires can voluntarily prepare or directly buy city
Sell product.For example, the preparation process of shown silver nanowires includes: that polyvinylpyrrolidone is added in ethylene glycol, will mix
Object heating, and silver chlorate and silver nitrate are rapidly joined into the mixture with vigorous stirring, insulation reaction is completed wait react
Afterwards, Off-white product and washed product is collected by centrifugation.Wherein, the quality volume of the polyvinylpyrrolidone and the ethylene glycol
Than that can be 5-30mg/mL, such as 10-20mg/mL, as an example, the mass volume ratio can be 10mg/mL, 15mg/
mL.Wherein, the silver chlorate can be added in the form of the ethylene glycol mixture of silver chlorate, for example, the second two of the silver chlorate
The concentration of silver chlorate can be 0.02-0.04g/mL, such as 0.025-0.03g/mL in alcohol mixture.Wherein, the silver nitrate can
In the form of the ethylene glycol mixture by silver nitrate be added, for example, in the ethylene glycol mixture of the silver nitrate silver nitrate it is dense
Degree can be 0.03-0.08g/mL, such as 0.04-0.06g/mL, as an example, concentration can be 0.05g/mL.Wherein, the chlorine
The mass ratio for changing silver and the polyvinylpyrrolidone can be (0.03-0.2): 1, such as (0.05-0.15): 1, (0.07-
0.12): 1, as an example, mass ratio can be 0.083:1,0.1:1.Wherein, the silver nitrate and the polyvinylpyrrolidine
The mass ratio of ketone can be (0.05-0.8): 1, such as (0.1-0.7): 1, (0.15-0.5): 1, as an example, mass ratio can be with
For 0.1:1,0.33:1.Preferably, the silver chlorate and silver nitrate can be added simultaneously or successively be added, for example, first adding
Enter silver chlorate, adds silver nitrate.Wherein, it is 160-190 DEG C that heating, which needs temperature to be achieved, such as 170-180 DEG C.Wherein,
The temperature of the insulation reaction is 160-190 DEG C, such as 170-180 DEG C；The time of the insulation reaction can be 0.3-1.5h,
Such as 0.5-1h.
Preparation method according to the present invention, in step (1), the mass volume ratio of the silver nanowires and the methanol can be with
For 1-20mg/mL, such as 1-10mg/mL, as an example, mass volume ratio can be 2mg/mL, 4mg/mL, 6mg/mL, 8mg/
mL。
Preparation method according to the present invention, in step (1), the mass volume ratio of the 2-methylimidazole and the methanol can
5-25mg/mL, such as 10-20mg/mL are thought, as an example, the mass volume ratio of the 2-methylimidazole and the methanol can
Think 5mg/mL, 10mg/mL.After the completion of the 2-methylimidazole addition, 0.3-1.5h, such as ultrasound 0.5- can be ultrasonically treated
1h。
Preparation method according to the present invention, in step (1), the mass volume ratio of the cobalt nitrate and the methanol can be
5-25mg/mL, such as 10-20mg/mL, as an example, the mass volume ratio of the cobalt nitrate and the methanol can be 5mg/
mL,10mg/mL.After the completion of the cobalt nitrate addition, 1-3h, such as 1.5-2.5h can be ultrasonically treated.Preferably, the nitric acid
Cobalt is added after 2-methylimidazole.
Preparation method according to the present invention, in step (1), the mass volume ratio of the purplish grey product and ethyl alcohol can be
5-50mg/mL, such as 8-40mg/mL, 15-30mg/mL, as an example, mass volume ratio can for 10mg/mL, 20mg/mL,
25mg/mL、35mg/mL。
Preparation method according to the present invention, in step (1), the mass volume ratio of the nickel nitrate and ethyl alcohol can be 5-
25mg/mL, such as 10-20mg/mL, as an example, the mass volume ratio of the nickel nitrate and ethyl alcohol can for 5mg/mL,
10mg/mL.The temperature of the heating reaction can be 50-70 DEG C, such as 55-65 DEG C, as an example, temperature can be 60 DEG C.
The time of the heating reaction can be 50-200 minutes, such as 60-180 minutes, 80-150 minutes, 100-130 minutes.
Preparation method according to the present invention, in step (2), the second of the Ag@Co-Ni LDH and the p-aminophenyl thiophenol
The mass volume ratio of alcoholic solution can be 1-50mg/mL, such as 8-40mg/mL, 15-30mg/mL, as an example, quality volume
Than that can be 10mg/mL, 20mg/mL, 25mg/mL, 35mg/mL.
Preparation method according to the present invention, in step (2), p-aminophenyl sulphur in the ethanol solution of the p-aminophenyl thiophenol
The concentration of phenol can be (0.5-1.5) × 10-4Mol/L, such as concentration can be (0.8-1.2) × 10-4Mol/L, as showing
Example, concentration are 1.0 × 10-4mol/L。
Preparation method according to the present invention, in step (2), the time of the ultrasonic treatment can be 0.5-3h, such as 1-
2h、1.3-1.8h。
Preparation method according to the present invention, in step (1) and (2), those skilled in the art can according to need selection and close
Suitable dispersing mode, such as ultrasonic disperse mode can be used.
Preparation method according to the present invention, in step (1) and (2), obtained product can be carried out using centrifugation
It collects, the operation that product is collected by centrifugation can be identical or different, and those skilled in the art can select according to the actual situation,
For example, the revolving speed of the centrifugation can be 2000-5000rpm, for example revolving speed is 3000-4000rpm.For example, the centrifugation
Time can be 3-10 minutes, for example the time can be 5-8 minutes.
Preparation method according to the present invention in step (1) and (2), can also carry out carrying out washing treatment to obtained product, this
Field technical staff can according to need the number of selection washing solvent and washing used, for example, the solvent of the washing
It can be ethyl alcohol, the number of the washing can be for once, twice, three times or more times.
The preparation method of illustrative technical solution according to the present invention, the surface enhanced Raman scattering substrate material includes
Following steps:
1) synthesis of silver nanowires
0.3-0.5g polyvinylpyrrolidone is added in 20-50mL ethylene glycol.Then, 180 are heated the mixture to
DEG C, and rapidly join the ethylene glycol mixture 1-2mL of the silver chlorate of 0.02-0.04g/mL with vigorous stirring, continuously add to
180℃；And the ethylene glycol mixture 1-2ml of the silver nitrate of 0.03-0.08g/mL is added dropwise with vigorous stirring；At 180 DEG C
After lower stirring 0.5-1 hours, 5-8 minutes collection Off-white products are centrifuged with 2000-5000rpm and use ethanol washing；
2) synthesis of the core-shell structure of the cobalt nickel bimetal hydroxide of silver nanowires and hollow structure
Silver nanowires made of step 1) is dispersed in 10-20mL methanol by ultrasonic treatment, is added into mixture
The 2-methylimidazole of 0.1-0.2g continues ultrasound 0.5h-1h；The cobalt nitrate of 0.1-0.2g, ultrasonic 1- is added into mixture again
3h；The purple grey product of collection in 5-8 minutes is centrifuged with 2000-5000rpm and uses ethanol washing；Purplish grey product is passed through into ultrasonic treatment
It is dispersed in 10-20mL ethyl alcohol, the nickel nitrate of 0.1-0.2g is added, after being heated to 60 DEG C, reaction 60-180 minutes, with 2000-
5000rpm is centrifuged 5-8 minutes collection celadon products and with ethanol washing, and the cobalt nickel for obtaining silver nanowires and hollow structure is double golden
Belong to the core-shell structure (Ag@Co-Ni LDH) of hydroxide；
3) modification of Ag@Co-Ni LDH
The core-shell structure of the cobalt nickel bimetal hydroxide of silver nanowires and hollow structure that step 2) is obtained passes through super
Sonication is dispersed in 10-20mL, (0.5-1.5) × 10-4In the ethanol solution of mol/L p-aminophenyl thiophenol, continue ultrasound 1-2h,
5-8 minutes collection celadon products are centrifuged with 2000-5000rpm and with ethanol washing, the base material.
The present invention also provides base materials prepared by the preparation method.
The present invention also provides the base materials in Surface enhanced Raman scattering, gaseous aldehyde Raman detection, test result
The application of bar code or two dimensional code the coding display aspect of the RGB of Raman image method, Raman image result.
The detection method of present invention offer aldehydes molecule, which comprises the base material is coated on silicon wafer,
Then silicon wafer is placed in aldehydes atmosphere and is reacted, the silicon wafer after reaction carries out Raman signal acquisition with Raman spectrometer.For example, this
Field technical staff can according to need the specification of adjustment silicon wafer, such as the specification of silicon wafer can be 1cm × 1cm.For example, described
The concentration of aldehyde can be 1ppb-1000ppm, preferably 1ppb-500ppm, 1ppb-100ppm in aldehydes atmosphere；As an example,
The concentration of aldehyde can be 1ppb, 10ppb, 100ppb, 1ppm, 10ppm, 50ppm.For example, the temperature of the reaction can be 50-
70 DEG C, preferably 55-65 DEG C, as an example, temperature is 60 DEG C；The time of the reaction can be 0.5-4h, preferably 1-3h, as
Example, time 1h, 1.5h, 2h, 2.5h, 3h.For example, the aldehyde in the aldehydes atmosphere can be 4- ethylo benzene formaldehyde, benzene first
Aldehyde, salicylide, glutaraldehyde, paranitrobenzaldehyde etc..
The present invention provides the method for encoding the testing result of aldehydes molecule, which comprises to 1060-
1080cm-1The Raman peak intensity at place is standardized, and makes its intensity value 1000；To 1600-1650cm-1The Raman at place
Peak intensity carries out the RGB imaging of intensity, and Color Range 0-300 reads tri- bit value of R, G, B of RGB image respectively, utilizes
9 bit digitals of RGB, aldehydes molecular species to be measured and its concentration information, are encoded.For example, the detection knot of the aldehydes molecule
Fruit is obtained by above-mentioned detection method.For example, available bar code or two dimensional code after coding.
Beneficial effects of the present invention:
Surface enhanced Raman scattering substrate material provided by the invention, since hollow structure imitates the confinement of gas molecule
It answers, so that the adsorption efficiency of the material for gaseous molecule is promoted, the absorption and detection of minimum gas molecule may be implemented.Substrate material
Expect that the modification of the p-aminophenyl thiophenol on surface can effectively capture gaseous aldehyde molecule, realizes the qualitative and quantitative detection of aldehydes.Together
When, to the rgb value reading of the Raman image figure after raman spectral signal standardization and the bar code or two dimension of test result
Code coding, it can be achieved that the visualization of complex data, it is simple read, and realize the portable display of information of test result.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph for the Ag@Co-Ni LDH being prepared in the embodiment of the present invention 1；
Fig. 2 is the Raman spectrum that the 4- ethylo benzene formaldehyde of various concentration is detected in the embodiment of the present invention 1；
Fig. 3 is the linear relationship of concentration of aldehyde species and raman scattering intensity to be measured in the embodiment of the present invention 1；
Fig. 4 is the Raman image figure and barcode encoding of 100ppm 4- ethylo benzene formaldehyde in the embodiment of the present invention 1；
Fig. 5 is the schematic diagram of testing result cataloged procedure in the embodiment of the present invention 1.
Specific embodiment
Crystalline material and its preparation method and application of the invention is done further below in conjunction with specific embodiment
It is described in detail.It should be appreciated that the following example is merely illustrative the ground description and interpretation present invention, and it is not necessarily to be construed as to this hair
The limitation of bright protection scope.All technologies realized based on above content of the present invention are encompassed by the range the present invention is directed to protection
It is interior.
Unless otherwise indicated, raw materials and reagents used in the following embodiment are commercial goods, or can be by
Perception method preparation.
Following embodiment and comparative example instrument information:
Scanning electron microscope (SEM): the S-4800 of Hitachi, Japan.
Raman spectrometer: the LabRAM HR Evolution of Horiba company.
Embodiment 1
1) synthesis of silver nanowires
0.3g polyvinylpyrrolidone is added in 20mL ethylene glycol, then, heats the mixture to 180 DEG C, and
It is vigorously stirred down the ethylene glycol mixture 1mL for rapidly joining the silver chlorate of 0.025g/mL, continues to be heated to 180 DEG C.And violent
The ethylene glycol mixture 2mL of the silver nitrate of 0.05g/mL is added dropwise under stirring.After being stirred 1 hour at 180 DEG C, with
5000rpm be centrifuged 5 minutes collection Off-white products and with ethanol washing three times.
2) synthesis of the core-shell structure of the cobalt nickel bimetal hydroxide of silver nanowires and hollow structure
Silver nanowires made of step 1) is dispersed in 20mL methanol by ultrasonic treatment, 0.1g is added into mixture
2-methylimidazole continue ultrasound 0.5h.The cobalt nitrate of 0.1g, ultrasound 1 hour is added into mixture again.It is centrifuged with 5000rpm
The purple grey product of collection in 5 minutes and with ethanol washing three times.Purplish grey product is dispersed in 10mL ethyl alcohol by ultrasonic treatment, is added
The nickel nitrate for entering 0.1 is heated to 60 DEG C.Reaction after sixty minutes, is centrifuged 5 minutes collection celadon products with 2000rpm and uses second
Alcohol washs three times.Obtain core-shell structure (the Ag@Co-Ni of the cobalt nickel bimetal hydroxide of silver nanowires and hollow structure
LDH).Wherein, silver nanowires accounts for the 29% of quality of materials, and cobalt nickel bimetal hydroxide accounts for the 70% of quality of materials.
3) modification of Ag@Co-Ni LDH
The core-shell structure of the cobalt nickel bimetal hydroxide of silver nanowires and hollow structure that step 2) obtains passes through ultrasound
It handles and is dispersed in 10mL, 1 × 10-4In the ethanol solution of mol/L p-aminophenyl thiophenol, continue ultrasound 1 hour, with 5000rpm from
5 minutes collection celadon products of the heart and with ethanol washing three times.Obtain the silver nanowires and hollow knot that p-aminophenyl thiophenol is modified
The core-shell structure of the cobalt nickel bimetal hydroxide of structure.
4) barcode encoding of the detection of aldehydes molecule and test structure
The silver nanowires for the p-aminophenyl thiophenol modification that step 3) is obtained and the cobalt nickel bimetal hydroxide of hollow structure
The core-shell structure primary coat of object is on the silicon wafer of 1cm × 1cm.Silicon wafer is placed in the 4- ethylo benzene formaldehyde containing 1ppb-1000ppm
In atmosphere, 60 DEG C of reaction 1h.Silicon wafer after reaction is subjected to Raman signal acquisition with Raman spectrometer.To 1070cm-1The drawing at place
Graceful peak intensity is standardized, and makes its intensity value 1000.To 1623cm-1The Raman peak intensity at place carries out the RGB of intensity
Imaging.Color Range is 0-300.Tri- bit value of R, G, B of RGB image is read respectively.Utilize 9 bit digitals and concentration of RGB
Information carries out barcode encoding.By bar code scanning test result can be shown in other equipment.
It is Ag@Co-Ni LDH scanning electron microscope (SEM) photograph prepared by embodiment 1 as shown in Figure 1, the length of silver nanowires is 4 μm,
Diameter is 60nm, and the cobalt nickel bimetal hydroxide partial size of hollow structure is 250nm.
Fig. 2 gives the Ag@Co-Ni LDH detection various concentration of the modification of p-aminophenyl thiophenol prepared by embodiment 1
The Raman spectrum of 4- ethylo benzene formaldehyde.The result shows that: in 1623cm-1The corresponding stretching vibration peak of appearance C=N double bond, and with
Concentration enhancing, peak intensity gradually increases.
Fig. 3 gives the Ag@Co-Ni LDH detection various concentration of the modification of p-aminophenyl thiophenol prepared by embodiment 1
The raman spectrum strength of 4- ethylo benzene formaldehyde and the linear relationship of concentration.The result shows that: 10-4~10-8(v/v, volumetric concentration)
In range, linear relationship, variance R is presented in corresponding C=N double bond stretching vibration peak intensity and concentration2=0.996.
Fig. 4 gives the 4- of the Ag@Co-Ni LDH detection 100ppm of the modification of p-aminophenyl thiophenol prepared by embodiment 1
The raman spectrum strength image of ethylo benzene formaldehyde, obtained intensity is for R=255, G=031, B=000.Using to be measured
Molecule 4- ethylo benzene formaldehyde and concentration 100ppm and rgb value carry out barcode encoding, and cataloged procedure is as shown in Figure 5.
Embodiment 2
1) synthesis of silver nanowires
0.5g polyvinylpyrrolidone is added in 50mL ethylene glycol.Then, 180 DEG C are heated the mixture to, and
It is vigorously stirred down the ethylene glycol mixture 2mL for rapidly joining the silver chlorate of 0.025g/mL, is continuously added to 180 DEG C.And violent
The ethylene glycol mixture 2mL of the silver nitrate of 0.05g/mL is added dropwise under stirring.After being stirred 0.5-1 hours at 180 DEG C, with
2000rpm be centrifuged 8 minutes collection Off-white products and with ethanol washing three times.
2) synthesis of the core-shell structure of the cobalt nickel bimetal hydroxide of silver nanowires and hollow structure
Silver nanowires made of step 1) is dispersed in 20mL methanol by ultrasonic treatment, 0.2g is added into mixture
2-methylimidazole continue ultrasound 1h.The cobalt nitrate of 0.2g, ultrasonic 3h is added into mixture again.With 2000rpm centrifugation 8 minutes
Collect purple grey product and with ethanol washing three times.Purplish grey product is dispersed in 10-20mL ethyl alcohol by ultrasonic treatment, is added
The nickel nitrate of 0.2g is heated to 60 DEG C.After reaction 180 minutes, 8 minutes collection celadon products are centrifuged with 2000rpm and use second
Alcohol washs three times.Obtain core-shell structure (the Ag@Co-Ni of the cobalt nickel bimetal hydroxide of silver nanowires and hollow structure
LDH)。
3) modification of Ag@Co-Ni LDH
The core-shell structure of the cobalt nickel bimetal hydroxide of silver nanowires and hollow structure that step 2) obtains passes through ultrasound
It handles and is dispersed in 20mL, 1 × 10-4In the ethanol solution of mol/L p-aminophenyl thiophenol, continue ultrasound 2h, with 2000rpm centrifugation 8
Minute collect celadon product and with ethanol washing three times.Obtain the silver nanowires and hollow structure of the modification of p-aminophenyl thiophenol
The core-shell structure of cobalt nickel bimetal hydroxide.
4) two dimensional code of the detection of aldehydes molecule and test result encodes
The silver nanowires for the p-aminophenyl thiophenol modification that step 3) is obtained and the cobalt nickel bimetal hydroxide of hollow structure
The core-shell structure primary coat of object is on the silicon wafer of 1cm × 1cm.By silicon wafer be respectively placed in containing 1ppb, 10ppb, 100ppb, 1ppm,
In the atmosphere of the 4- ethylo benzene formaldehyde of 100ppm, 1000ppm, 60 DEG C of reaction 3h.By the silicon wafer Raman spectrometer after reaction into
The acquisition of row Raman signal.To 1070cm-1The Raman peak intensity at place is standardized, and makes its intensity value 1000.It is right
1623cm-1The Raman peak intensity at place carries out the RGB imaging of intensity.Color Range is 0-300.Respectively read RGB image R,
G, tri- bit value of B.Using 9 bit digitals and concentration information of RGB, two dimensional code coding is carried out.It can be at it by two-dimensional code scanning
He shows test result at equipment.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of base material, which is characterized in that the base material includes the cobalt nickel bimetal of silver nanowires and hollow structure
Hydroxide Co-Ni LDH, the base material have core-shell structure: core is silver nanowires, and shell is the Co-Ni LDH；
Preferably, the base material is indicated with Ag@Co-Ni LDH.
2. base material according to claim 1, which is characterized in that the length of the silver nanowires is 1.5-7 μm, described
The diameter of silver nanowires is 30-120nm；
Preferably, the silver nanowires accounts for the 24-49% of the base material quality.
3. base material according to claim 1 or 2, which is characterized in that the cobalt nickel bimetal hydrogen of the hollow structure
The partial size of oxide is 150-400nm；
Preferably, the Co-Ni LDH accounts for the 50-75% of the base material quality.
4. base material according to claim 1-3, which is characterized in that the silver nanowires of the base material is adopted
It is modified with p-aminophenyl thiophenol；
Preferably, the modification is the sulfydryl by p-aminophenyl thiophenol in conjunction with the silver atoms on the silver nanowires surface；
Preferably, grafting amount of the p-aminophenyl thiophenol on the silver nanowires surface is 0.0002-0.4wt ‰.
5. the preparation method of any one of the claim 1-4 base material, which is characterized in that the method includes walking as follows
It is rapid:
(1) it disperses silver nanowires in methanol, 2-methylimidazole, cobalt nitrate is added thereto, ultrasound is collected by centrifugation purple ash and produces
Object；It disperses the purplish grey product in ethyl alcohol, nickel nitrate is added thereto, heating reaction is collected celadon product, obtained
The Ag@Co-Ni LDH；
(2) it disperses the Ag@Co-Ni LDH in the ethanol solution of p-aminophenyl thiophenol, is ultrasonically treated, collect product, obtain
To the base material.
6. preparation method according to claim 5, which is characterized in that in step (1), the preparation process of the silver nanowires
Include: that polyvinylpyrrolidone is added in ethylene glycol, mixture is heated, and with vigorous stirring into the mixture
Rapidly join silver chlorate and silver nitrate, insulation reaction, to which Off-white product and washed product after the reaction was completed, is collected by centrifugation；
Preferably, the mass volume ratio of the silver nanowires and the methanol is 1-20mg/mL；
Preferably, the mass volume ratio of the 2-methylimidazole and the methanol is 5-25mg/mL；
Preferably, the mass volume ratio of the cobalt nitrate and the methanol is 5-25mg/mL；
Preferably, the mass volume ratio of the purplish grey product and ethyl alcohol can be 5-50mg/mL；
Preferably, the mass volume ratio of the nickel nitrate and ethyl alcohol is 5-25mg/mL；
Preferably, the temperature of step (1) the heating reaction is 50-70 DEG C, and the time of the heating reaction is 50-200 minutes.
7. preparation method according to claim 5 or 6, which is characterized in that in step (2), the Ag@Co-Ni LDH with
The mass volume ratio of the ethanol solution of the p-aminophenyl thiophenol is 1-50mg/mL；
Preferably, the concentration of p-aminophenyl thiophenol is (0.5-1.5) × 10 in the ethanol solution of the p-aminophenyl thiophenol-4mol/
L；
Preferably, the time of the ultrasonic treatment is 0.5-3h.
8. any one of the claim 1-4 base material is in Surface enhanced Raman scattering, gaseous aldehyde Raman detection, test knot
The application of bar code or two dimensional code the coding display aspect of the RGB of fruit Raman image method, Raman image result.
9. the detection method of aldehydes molecule, which is characterized in that the described method includes: by the described in any item bases of claim 1-4
Bottom material is coated on silicon wafer, and then silicon wafer is placed in aldehydes atmosphere and is reacted, and the silicon wafer after reaction is drawn with Raman spectrometer
Graceful signal acquisition；
Preferably, the concentration of aldehyde is 1ppb-1000ppm in the aldehydes atmosphere；
Preferably, the temperature of the reaction is 50-70 DEG C, and the time of the reaction is 0.5-4h；
Preferably, the aldehyde in the aldehydes atmosphere is 4- ethylo benzene formaldehyde, benzaldehyde, salicylide, glutaraldehyde and p-nitrophenyl first
At least one of aldehyde.
10. the method that the testing result of aldehydes molecule is encoded, which is characterized in that the described method includes: to 1060-1080cm-1The Raman peak intensity at place is standardized, and makes its intensity value 1000；To 1600-1650cm-1The Raman peak intensity at place
The RGB imaging of intensity is carried out, Color Range 0-300 reads tri- bit value of R, G, B of RGB image respectively, utilizes the 9 of RGB
Bit digital, aldehydes molecular species to be measured and its concentration information, are encoded；
Preferably, the testing result of the aldehydes molecule is obtained by detection method as claimed in claim 9；
Preferably, bar code or two dimensional code are obtained after coding.
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| CN111982881A (en) * | 2020-08-19 | 2020-11-24 | 东南大学 | Magnetic recyclable surface-enhanced Raman substrate and preparation method thereof |
| CN112381899A (en) * | 2020-10-10 | 2021-02-19 | 天津工业大学 | SERS spectrum anti-counterfeiting combined coding method based on compound Raman probe |
| CN112697770A (en) * | 2020-12-10 | 2021-04-23 | 广西民族大学 | Method for measuring glutaraldehyde in water based on metal organic framework material composite substrate surface enhanced Raman spectroscopy |
| CN114082410A (en) * | 2021-11-01 | 2022-02-25 | 佛山市高明佛水供水有限公司 | SERS substrate based on novel composite material and preparation method thereof |
| CN114643364A (en) * | 2022-03-01 | 2022-06-21 | 厦门大学 | Synthesis method of core-shell structure nanoparticles of nickel-cobalt composite metal oxide coated nanogold |
| CN115194147A (en) * | 2022-07-18 | 2022-10-18 | 中国计量大学 | SERS substrate material Au @ ZnAl-LDHs and preparation method and application thereof |
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| CN110879223A (en) * | 2019-11-20 | 2020-03-13 | 厦门华厦学院 | Rapid detection reagent and detection method for formaldehyde in beer |
| CN111850523A (en) * | 2020-07-15 | 2020-10-30 | 澳门大学 | Surface-enhanced Raman scattering substrate and preparation method and application thereof |
| CN111982881A (en) * | 2020-08-19 | 2020-11-24 | 东南大学 | Magnetic recyclable surface-enhanced Raman substrate and preparation method thereof |
| CN112381899A (en) * | 2020-10-10 | 2021-02-19 | 天津工业大学 | SERS spectrum anti-counterfeiting combined coding method based on compound Raman probe |
| CN112697770A (en) * | 2020-12-10 | 2021-04-23 | 广西民族大学 | Method for measuring glutaraldehyde in water based on metal organic framework material composite substrate surface enhanced Raman spectroscopy |
| CN114082410A (en) * | 2021-11-01 | 2022-02-25 | 佛山市高明佛水供水有限公司 | SERS substrate based on novel composite material and preparation method thereof |
| CN114082410B (en) * | 2021-11-01 | 2024-02-06 | 佛山市高明佛水供水有限公司 | SERS substrate based on composite material and preparation method thereof |
| CN114643364A (en) * | 2022-03-01 | 2022-06-21 | 厦门大学 | Synthesis method of core-shell structure nanoparticles of nickel-cobalt composite metal oxide coated nanogold |
| CN115194147A (en) * | 2022-07-18 | 2022-10-18 | 中国计量大学 | SERS substrate material Au @ ZnAl-LDHs and preparation method and application thereof |
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