CN110286115B - SERS substrate based on paper fiber substrate and preparation method - Google Patents
SERS substrate based on paper fiber substrate and preparation method Download PDFInfo
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- CN110286115B CN110286115B CN201910606295.XA CN201910606295A CN110286115B CN 110286115 B CN110286115 B CN 110286115B CN 201910606295 A CN201910606295 A CN 201910606295A CN 110286115 B CN110286115 B CN 110286115B
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- 239000000758 substrate Substances 0.000 title claims abstract description 107
- 239000000835 fiber Substances 0.000 title claims abstract description 78
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 94
- 229910052737 gold Inorganic materials 0.000 claims abstract description 91
- 239000010931 gold Substances 0.000 claims abstract description 91
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000001514 detection method Methods 0.000 claims abstract description 27
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000000084 colloidal system Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 23
- 239000000725 suspension Substances 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 239000013557 residual solvent Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000000007 visual effect Effects 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 9
- 239000002082 metal nanoparticle Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
Abstract
A SERS substrate based on a paper fiber substrate and a preparation method thereof belong to the technical fields of plasmon nanophotography and optical sensing. Gold nanoparticles coated with tetraoctylammonium bromide are adhered to the surface of the paper fiber substrate to form a detection area, wherein the particle size of the gold nanoparticles is 100-160nm; there is a gap between the gold nanoparticles in the detection region. Gold nanoparticle colloid coated with tetraoctylammonium bromide on the surface and synthesized based on common paper fiber and conventional chemical method, and low-temperature heat treatment process. The photophysics, SERS performance and detection sensitivity can reach the level of the current high-end preparation technology.
Description
Technical Field
The invention belongs to the technical field of plasmon nano photonics and optical sensing. The SERS substrate is realized by assembling metal nano particles on the paper fiber, which is simple and easy to implement and is used for trace detection of substances.
Background
Raman scattering is inelastic scattering, and the frequency shift of raman scattered light relative to incident light is independent of the incident light frequency, but corresponds to vibration and rotation information of molecular features. Thus, raman spectroscopy reveals the structure of a substance, and allows for the identification and content identification of the substance. However, identification and detection of microscale substances presents a significant challenge due to the weak intensity of scattered light.
SERS has very high sensitivity, and has the advantage that it has electromagnetic enhancement and chemical enhancement properties, which is a very good surface optical sensing technique. SERS detection is based primarily on metal nanostructure plasmonic localized field enhancement effects, which are primarily dependent on the size of the metal nanostructure, the gap, i.e., the density and intensity of SERS hot spots. The raman scattering intensity of the molecules at the "hot spot" can be greatly enhanced. Plasmon resonance spectrum of gold, silver, copper and other nano structures covers the whole visible light and near infrared band, and is widely applied to preparation of SERS substrates. The structure of the metal substrate material is optimized by various methods to obtain larger enhancement factors, for example, the metal nano particles with different sizes and shapes are prepared by chemical synthesis methods. In addition, SERS substrates prepared on substrates such as quartz plates, silicon wafers and the like based on technologies such as weather deposition, lithography, etching, nanoparticle assembly and the like also show excellent performance in trace substance detection. The SERS enhancement effect of the two-dimensional metal nano structure prepared on the flat substrate is limited relative to the plasmon of the three-dimensional structure and the SERS enhancement effect, and the problems of planarization, templating, non-uniformity, complex preparation process and the like exist.
The metal nano particles are assembled on the paper fiber substrate, and SERS 'hot spots' with three-dimensional distribution can be formed by utilizing the spatial three-dimensional distribution characteristic provided by the paper fibers. The spatial three-dimensional structure of the paper fiber not only can provide a large surface area for adsorbing more metal nanoparticles, but also enables gold nanoparticles and SERS' hot spots generated by the gold nanoparticles to be distributed in a three-dimensional space to a greater extent, thereby providing more SERS enhancement hot spots. Thereby remarkably improving the Raman signal of the molecule to be detected in the space three-dimensional structure and realizing the identification of trace substances and the detection of sensitivity.
Disclosure of Invention
The invention provides a SERS substrate for detecting trace substances and a preparation method thereof. The preparation method has the advantages of simplicity and low cost, and is based on common paper fiber and gold nanoparticle colloid with tetraoctyl ammonium bromide coated on the surface synthesized by a conventional chemical method and a low-temperature treatment process. The photophysics, SERS performance and detection sensitivity can reach the level of the current high-end preparation technology.
In order to achieve the above effects, the present invention is realized by the steps of:
the SERS substrate based on the paper fiber substrate is characterized in that gold nanoparticles coated with tetraoctylammonium bromide are adhered to the surface of the paper fiber substrate to form a detection area, and the particle size of the gold nanoparticles is 100-160nm; there is a gap between the gold nanoparticles in the detection region.
A plurality of detection areas are arranged on the surface of a paper fiber substrate, and the detection areas form an array structure; the size of the detection zone may be prepared as desired.
Further preferably, the surface density of the gold nanoparticle covered paper fiber substrate area within each detection area is: the projected area of the gold nanoparticles covers or occupies 0-100% of the area of the paper fiber substrate excluding 0 and 100%, preferably 10% -50%.
The appearance image of each monitoring area is circular, rectangular and the like.
The paper fiber is selected from filter paper, printing paper, envelope paper and the like.
The preparation of the SERS substrate based on the paper fiber substrate is characterized by comprising the following steps of:
(1) Preparation of gold nanoparticles coated with tetraoctylammonium bromide:
adding aqueous solution of chloroauric acid into toluene solution dissolved with tetraoctyl ammonium bromide, stirring the solution, adding aqueous solution of sodium borohydride after the completely dissolved and mixed solution of chloroauric acid is changed into orange, continuously stirring to prepare black nano-particle colloidal solution, and stopping stirring; separating the colloid solution to remove the water phase, and removing the organic phase by a reduced pressure distillation method; adding a high-polarity solvent into the black viscous liquid containing the gold nanoparticles, and settling the gold nanoparticles; separating the gold nanoparticles from the solution, and obtaining gold nanoparticles coated with tetraoctylammonium bromide after the residual solvent is completely volatilized;
(2) Dispersing the gold nanoparticles in the step (1) in an organic solvent to prepare gold nanoparticle suspension;
(3) Selection and preparation of paper fiber substrate
In order to prevent gold nanoparticles from falling from pores of a paper fiber substrate and enable the gold nanoparticles to have certain adsorptivity on the surface of fiber paper, a paper taking fiber substrate with the pore diameter smaller than the diameter of the gold nanoparticles is selected, and the surface of the paper taking fiber substrate has roughness;
(4) Preparation of SERS substrates
The gold nanoparticle suspension in the step (2) is dripped on the paper fiber substrate in the step (3), and different limiting templates can be adopted according to different appearance images formed by the gold nanoparticles on the surface of the paper fiber substrate; and (3) placing the paper fiber substrate sample with the gold nanoparticles on a heating plate at 110 ℃, and adsorbing and adhering the gold nanoparticles on the fiber paper after the solvent volatilizes to prepare the paper fiber SERS substrate.
The surface density of the gold nanoparticles on the substrate is controlled by controlling the concentration of the gold nanoparticle suspension in the step (2) and the dosage of the solution dripped in the step (4).
The optical physical characteristics, the SERS performance and the detection sensitivity of the SERS substrate based on the paper fiber substrate can reach the level of the current high-end preparation technology.
The invention has the advantages that:
1. the metal nano particles wrapped by the tetraoctyl ammonium bromide can be self-assembled to form Raman signal enhancement hot spots with smaller particle gaps, and the Raman signal enhancement hot spots have obvious enhancement effect on signals of molecules to be detected adsorbed on the Raman signal enhancement hot spots;
2. the metal nano-particle synthesis process is simple and efficient, and has good adhesion capability on various paper fiber substrates;
3. the space three-dimensional structure of the paper fiber can provide a large surface area for adsorbing more metal nano particles, the gold nano particles and SERS 'hot spots' generated by the gold nano particles can be distributed in a three-dimensional space to a greater extent, and the SERS enhancement performance is greatly improved;
4. the use of paper fibers as a substrate can greatly reduce the cost of preparing SERS substrates.
Drawings
FIG. 1 is a schematic front view of a SERS substrate based on a paper fiber substrate;
FIG. 2 is a schematic view of section A-A of FIG. 1;
FIG. 3 is a schematic view of gold nanoparticles.
Wherein the 1-paper fiber substrate, the 2-monitoring area, the 3-gold nanoparticle and the 4-tetraoctyl ammonium bromide modification layer.
FIG. 4 is a scanning electron micrograph of tetraoctylammonium bromide-coated gold nanoparticles dispersed on a glass substrate;
FIG. 5 is a scanning electron micrograph of a certain detection area of a filter paper SERS substrate with gold nanoparticles adsorbed thereon;
FIG. 6 is a scanning electron micrograph of a detection zone of a printing paper SERS substrate with gold nanoparticles adsorbed thereon;
FIG. 7 is a scanning electron micrograph of a detection zone of an envelope SERS substrate having gold nanoparticles adsorbed thereon;
FIG. 8, raman scattering spectra of rhodamine 6G on filter paper, printing paper, envelope paper SERS substrates with gold nanoparticles adsorbed thereon;
FIG. 9 is a scanning electron micrograph of a detection area of a SERS substrate with different gold nanoparticle coverage areas on filter paper; a-d respectively correspond to 10%,15%,30% and 50% in sequence.
FIG. 10 is a Raman enhancement spectrum of rhodamine 6G molecules on filter papers with different gold nanoparticle coverage areas;
FIG. 11 shows Raman enhancement spectra of filter paper SERS substrates adsorbed with gold nanoparticles on rhodamine 6G molecules with different concentrations.
The specific embodiment is as follows:
the invention will be further described with reference to specific examples, but the invention is not limited to the following examples.
The radii of the dripping areas of the filter paper, the printing paper and the envelope paper in the following examples are all 4mm.
Example 1: implementation of different paper fiber SERS substrates
To the toluene solution in which tetraoctylammonium bromide was dissolved, an aqueous chloroauric acid solution was added, and stirred. Wherein the mass of the tetraoctyl ammonium bromide is 1.5g, the volume of the toluene solvent is 80ml, the mass of the chloroauric acid is 0.32g, the volume of the water is 2ml, then 20ml of sodium borohydride aqueous solution with the concentration of 0.37mol/L is added into the mixed solution, and the stirring is stopped after 5min, and the chemical reaction is finished; wherein the mass ratio of the reactants of tetraoctylammonium bromide, chloroauric acid and sodium borohydride is 12:1:9; separating the mixed solution to remove the water phase, and removing the organic phase by a reduced pressure distillation method to obtain black viscous liquid containing gold nanoparticles; adding methanol into the black viscous liquid, settling gold nanoparticles, removing the solvent, and volatilizing the residual solvent among the particles to obtain gold nanoparticle powder; dispersed in a quartz baseThe morphology of gold nanoparticles on the sheet is shown in an SEM image of FIG. 4, and the particle diameter is about 100-160nm. Gold nanoparticles are dispersed in ethanol to prepare suspension with the concentration of 80mg/mL, and 40ul of the suspension is respectively dripped on filter paper, printing paper and envelope paper fiber substrates. The sample was placed on a heating plate at 110 c and after the solvent had evaporated to dryness, a paper fiber SERS substrate was prepared, see fig. 5-7. Concentration is set to 10 -3 A mol/L rhodamine 6G alcohol solution is dripped on the substrate, a 785nm excitation light source is used for exciting a Raman signal, the output power of the excitation light is 100mW, and the integration time is 1s. The enhanced Raman spectrum of the rhodamine 6G is shown as a long-dashed curve in fig. 8, and the method realizes the preparation of various fiber paper SERS substrates.
Example 2: influence of gold nanoparticle suspension concentration on raman enhancement performance of paper fiber SERS substrate
Referring to example 1, ethanol suspensions of gold nanoparticles at concentrations of 10mg/mL, 15mg/mL, 30mg/mL, 50mg/mL were drop-coated on filter paper to form four test areas on the fiber paper, and SERS substrates with different area coverage of gold nanoparticles in different areas. The sample was placed on a hot plate at 110 c and after the solvent had evaporated to dryness, a paper fiber SERS substrate was prepared, as shown in fig. 9 (a) - (d), with particle surface densities of about 10%,15%,30%, 50% projected coverage area ratios, respectively. Concentration is set to 10 -3 The rhodamine 6G alcohol solution with mol/L is dripped on the four substrates, and a 785nm excitation light source is used for exciting a Raman signal of the substrates, so that an enhanced Raman spectrum is obtained. Wherein the output power of the excitation light is 100mW, and the integration time is 1s. The raman enhancement properties of each particle-covered paper fiber SERS substrate are shown in fig. 10. When the concentration of the gold nanoparticle ethanol suspension is 15mg/mL, the Raman enhancement of the substrate is good.
Example 3: raman enhancement performance of paper fiber SERS substrates on rhodamine 6G at different concentrations
Referring to example 1, gold nanoparticles were prepared, 120mL of an ethanol suspension of gold nanoparticles having a mass volume concentration of 15mg/mL was prepared and applied dropwise to three filter papers, respectively (each corresponding to 40ul, i.e., three substrates were considered to be identical), and the sample was placed on a heating plate having a temperature of 110 °cAnd (5) after the solvent is volatilized, preparing the paper fiber SERS substrate. Concentration is set to 10 - 4 mol/L、10 -5 mol/L、10 -6 The rhodamine 6G ethanol solution with mol/L is respectively dripped on the filter paper, a 785nm excitation light source is used for exciting Raman signals, the laser power is set to be 100mW, the integration time is set to be 1s, and the obtained Raman enhancement spectra of rhodamine 6G with different concentrations are shown in figure 11. The SERS performance and the detection sensitivity of the substrate can reach the level of the current high-end preparation technology.
Claims (8)
1. The SERS substrate based on the paper fiber substrate is characterized in that gold nanoparticles coated with tetraoctylammonium bromide are adhered to the surface of the paper fiber substrate to form a detection area, and the particle size of the gold nanoparticles is 100-160nm; gaps are arranged among the gold nano particles in the detection area;
the substrate preparation method comprises the following steps:
(1) Preparation of gold nanoparticles coated with tetraoctylammonium bromide:
adding aqueous solution of chloroauric acid into toluene solution dissolved with tetraoctyl ammonium bromide, stirring the solution, adding aqueous solution of sodium borohydride after the completely dissolved and mixed solution of chloroauric acid is changed into orange, continuously stirring to prepare black nano-particle colloidal solution, and stopping stirring; separating the colloid solution to remove the water phase, and removing the organic phase by a reduced pressure distillation method; adding a high-polarity solvent into the black viscous liquid containing the gold nanoparticles, and settling the gold nanoparticles; separating the gold nanoparticles from the solution, and obtaining gold nanoparticles coated with tetraoctylammonium bromide after the residual solvent is completely volatilized;
(2) Dispersing the gold nanoparticles in the step (1) in an organic solvent to prepare gold nanoparticle suspension;
(3) Selection and preparation of paper fiber substrate
In order to prevent gold nanoparticles from falling from pores of a paper fiber substrate and enable the gold nanoparticles to have certain adsorptivity on the surface of fiber paper, a paper taking fiber substrate with the pore diameter smaller than the diameter of the gold nanoparticles is selected, and the surface of the paper taking fiber substrate has roughness;
(4) Preparation of SERS substrates
The gold nanoparticle suspension in the step (2) is dripped on the paper fiber substrate in the step (3), and different limiting templates are adopted according to different appearance images formed by the gold nanoparticles on the surface of the paper fiber substrate; placing a paper fiber substrate sample dropwise coated with gold nanoparticles on a heating plate at 110 ℃, and after the solvent volatilizes, adsorbing and adhering the gold nanoparticles on fiber paper to prepare a paper fiber SERS substrate;
the surface density of the gold nanoparticles on the substrate is controlled by controlling the concentration of the gold nanoparticle suspension in the step (2) and the dosage of the solution dripped in the step (4).
2. A SERS substrate based on a paper fibre substrate according to claim 1 wherein there are a plurality of detection areas on a surface of the paper fibre substrate, the plurality of detection areas forming an array structure.
3. A paper fiber substrate based SERS substrate according to claim 1, wherein the gold nanoparticles cover the paper fiber substrate areas at a surface density within each detection area of: the projected area of the gold nanoparticles covers or occupies 0-100% of the area of the paper fiber substrate, excluding 0 and 100%.
4. A SERS substrate based on a paper fibre substrate according to claim 3 wherein the gold nanoparticles cover the paper fibre substrate region with a surface density of: the projected area of the gold nanoparticles covers or accounts for 10% -50% of the area of the paper fiber substrate.
5. A SERS substrate based on a paper fibre substrate according to claim 1 wherein the visual image of each monitored area is selected from circular, rectangular.
6. A SERS substrate based on a paper fibre substrate according to claim 1 wherein the paper fibre is selected from filter paper, printing paper, envelope paper.
7. A method of preparing a SERS substrate based on a paper fibre substrate according to any one of claims 1 to 6, comprising the steps of:
(1) Preparation of gold nanoparticles coated with tetraoctylammonium bromide:
adding aqueous solution of chloroauric acid into toluene solution dissolved with tetraoctyl ammonium bromide, stirring the solution, adding aqueous solution of sodium borohydride after the completely dissolved and mixed solution of chloroauric acid is changed into orange, continuously stirring to prepare black nano-particle colloidal solution, and stopping stirring; separating the colloid solution to remove the water phase, and removing the organic phase by a reduced pressure distillation method; adding a high-polarity solvent into the black viscous liquid containing the gold nanoparticles, and settling the gold nanoparticles; separating the gold nanoparticles from the solution, and obtaining gold nanoparticles coated with tetraoctylammonium bromide after the residual solvent is completely volatilized;
(2) Dispersing the gold nanoparticles in the step (1) in an organic solvent to prepare gold nanoparticle suspension;
(3) Selection and preparation of paper fiber substrate
In order to prevent gold nanoparticles from falling from pores of a paper fiber substrate and enable the gold nanoparticles to have certain adsorptivity on the surface of fiber paper, a paper taking fiber substrate with the pore diameter smaller than the diameter of the gold nanoparticles is selected, and the surface of the paper taking fiber substrate has roughness;
(4) Preparation of SERS substrates
The gold nanoparticle suspension in the step (2) is dripped on the paper fiber substrate in the step (3), and different limiting templates are adopted according to different appearance images formed by the gold nanoparticles on the surface of the paper fiber substrate; placing a paper fiber substrate sample dropwise coated with gold nanoparticles on a heating plate at 110 ℃, and after the solvent volatilizes, adsorbing and adhering the gold nanoparticles on fiber paper to prepare a paper fiber SERS substrate;
the surface density of the gold nanoparticles on the substrate is controlled by controlling the concentration of the gold nanoparticle suspension in the step (2) and the dosage of the solution dripped in the step (4).
8. Use of a SERS substrate based on a paper fibre substrate as claimed in any one of claims 1 to 6 for trace detection of substances.
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