CN113588625A - Preparation method of solid-phase SERS nano-substrate - Google Patents
Preparation method of solid-phase SERS nano-substrate Download PDFInfo
- Publication number
- CN113588625A CN113588625A CN202110934763.3A CN202110934763A CN113588625A CN 113588625 A CN113588625 A CN 113588625A CN 202110934763 A CN202110934763 A CN 202110934763A CN 113588625 A CN113588625 A CN 113588625A
- Authority
- CN
- China
- Prior art keywords
- solution
- glass sheet
- nano
- solid
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Peptides Or Proteins (AREA)
Abstract
The invention discloses a preparation method of a solid-phase SERS nano-substrate, which comprises the steps of preparing a nano-gold seed solution, fixing a nano-gold seed on a glass sheet and growing a seed in situ to grow a single-layer nano-gold structure on the surface of a plane glass carrier, thereby obtaining the solid-phase SERS nano-substrate. The method effectively controls the gaps of the nano particles by adjusting the growth conditions, the prepared single-layer nanogold film solid-phase SERS nano substrate has high-density small nano gaps, good surface uniformity and strong absorption in a near-infrared region, has excellent surface enhanced Raman activity when being matched with a portable Raman spectrometer with an excitation wavelength in the near-infrared region, and has a detection limit lower than 1mg/kg by taking dibenzyl disulfide as a probe molecule.
Description
Technical Field
The invention relates to the technical field of surface enhanced Raman detection, in particular to a preparation method of a solid-phase SERS nano-substrate.
Background
The conventional SERS substrate is mainly prepared on the basis of precious metal nanoparticles such as nanogold, nanosilver and the like. Due to the relationship between morphology and size, the electromagnetic field intensity on the surface of the noble metal nanoparticle cannot achieve completely uniform distribution, so that the SERS substrate is required to have a high-density SERS hotspot. The preparation of the SERS substrate with this feature can be generally realized in three ways: firstly, anisotropic noble metal nanoparticles can be obtained by regulating the growth of metal single crystals, polycrystals and twins, and the special morphology often has a sharp end or a hot spot of a particle inner gap; second, hot spots created by inducing nanoparticle aggregation in the solution phase via chemical means (e.g., increasing ionic strength); third, the hot spots in the nanoparticle space are physically or chemically modulated/fabricated in two or even three dimensions. The first point is the basis of the SERS substrate, which is the ultimate form of the SERS substrate, i.e., the SERS substrate in the liquid phase and the SERS substrate in the solid phase. However, since SERS detection relies on the near-field enhancement effect, both the noble metal nanoparticles and the object to be detected are in an uncontrollable state in the solution phase, and it is difficult to capture an optical signal of the object to be detected at a hot spot; finally, to avoid the interference of background signals, the surface of the sol particles must be kept chemically pure, which inevitably affects the physical stability of the SERS reagent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a solid-phase SERS nano-substrate. The preparation method is simple to operate, the preparation can be completed by soaking different solutions in a few simple steps, and the obtained solid-phase SERS nano substrate is stable in structure, high in nano particle density and high in detection sensitivity.
The invention provides a preparation method of a solid-phase SERS nano substrate, which comprises the following steps:
preparing a nano gold seed solution: adding a chloroauric acid solution with a first preset concentration into ultrapure water, stirring, then adding a trisodium citrate solution as a protective agent, finally adding a sodium borohydride solution as a reducing agent, and continuously stirring for a first preset time to perform a reduction reaction to obtain a nanogold seed solution;
fixing the nano gold seeds on the glass sheet: cleaning a glass sheet, soaking the glass sheet in a 3-aminopropyltrimethoxysilane adsorbent solution for a second preset time, taking out the glass sheet, washing the glass sheet with ultrapure water, drying the glass sheet with nitrogen to obtain a pretreated glass sheet, placing the pretreated glass sheet in the nanogold solution, vertically suspending and soaking the glass sheet for a third preset time, taking out the glass sheet, washing the surface of the glass sheet with ultrapure water to remove redundant nanogold solution, and drying the glass sheet with nitrogen to obtain an adsorbed glass sheet;
growth of in situ seeds: and placing the adsorbed glass sheet in a centrifugal tube, adding ultrapure water, a chloroauric acid solution with a second preset concentration and a hydroxylamine hydrochloride solution as solutions required for growth, taking out the solutions after oscillating for a fourth preset time at a preset rotating speed in a constant-temperature mixing instrument, cleaning the solutions by using the ultrapure water, completing a growth cycle, and obtaining the solid-phase SERS nano substrate after 3-9 growth cycles.
Adding a chloroauric acid solution with a first preset concentration into ultrapure water, stirring, then adding a trisodium citrate solution as a protective agent, and finally adding a sodium borohydride solution as a reducing agent, wherein the steps of:
adding a chloroauric acid solution with the concentration of 25-35 mmol/L into ultrapure water, stirring, then adding a trisodium citrate solution with the concentration of 30-40 mmol/L as a protective agent, and finally adding a sodium borohydride solution with the concentration of 20-25 mmol/L as a reducing agent.
The volume ratio of the chloroauric acid solution with the concentration of 25-35 mmol/L to the sodium borohydride solution with the concentration of 20-25 mmol/L is 1:2 to 1: 1;
the volume ratio of the chloroauric acid solution with the concentration of 25-35 mmol/L to the trisodium citrate solution with the concentration of 30-40 mmol/L is 1: 5-1: 2.
Adding a sodium borohydride solution as a reducing agent, and continuously stirring for a first preset time to perform a reduction reaction, wherein the reduction reaction comprises the following steps:
and taking a sodium borohydride solution as a reducing agent, and continuously stirring for 2-3 hours after the sodium borohydride solution is added to carry out reduction reaction.
The glass sheet is cleaned and placed in a 3-aminopropyltrimethoxysilane adsorbent solution to be soaked for a second preset time, and the method comprises the following steps:
soaking the glass sheet in aqua regia for 10 minutes, washing the glass sheet with ultrapure water, soaking the glass sheet in an ethanol saturated solution of sodium hydroxide for 2 hours, washing the glass sheet with ultrapure water again, and soaking the glass sheet in a 3-aminopropyltrimethoxysilane adsorbent solution for 5-60 minutes.
The mass fraction of the 3-aminopropyl trimethoxy silane adsorbent solution is 0.1-1.5%.
Placing the pretreated glass sheet in the nanogold seed solution to be vertically suspended and soaked for a third preset time, wherein the third preset time comprises the following steps:
and placing the pretreated glass sheet in the nanogold seed solution to be vertically suspended and soaked for 1-30 hours.
Adding ultrapure water, a chloroauric acid solution with a second preset concentration and a hydroxylamine hydrochloride solution into a centrifugal tube as solutions required for growth, wherein the solutions comprise:
adding ultrapure water, 5-25 mmol/L chloroauric acid solution and 10-100 mmol/L hydroxylamine hydrochloride solution into a centrifugal tube as solutions required for growth.
The volume ratio of the chloroauric acid solution with the concentration of 5-25 mmol/L to the hydroxylamine hydrochloride solution with the concentration of 10-100 mmol/L is 1: 1-3: 1.
The centrifuging tube is in the fourth preset time of vibration under the rotational speed of predetermineeing in the constant temperature blending appearance, include:
the centrifugal tube is oscillated for 10-20 minutes at the rotating speed of 1000-2000 rpm in a constant-temperature blending instrument.
According to the preparation method of the solid-phase SERS nano-substrate, a single-layer nano-gold structure grows on the surface of a plane glass carrier through preparation of a nano-gold seed solution, fixation of a nano-gold seed on a glass sheet and growth of an in-situ seed, so that the solid-phase SERS nano-substrate is obtained. The preparation method is simple to operate, and the single-layer nanogold film with high density and small nanogap is prepared on the surface of the plane glass by adjusting the growth conditions of the nanogold seeds, so that the solid-phase SERS nano substrate is obtained. The preparation method is simple to operate and low in preparation cost, and the obtained solid-phase SERS nano substrate is stable in structure, high in detection sensitivity and good in surface uniformity.
Drawings
FIG. 1 is a flow chart of a method for preparing a solid-phase SERS nano-substrate according to an embodiment of the invention;
FIG. 2 is an SEM image of a solid-phase SERS nano-substrate according to a first embodiment of the invention;
FIG. 3 is a graph showing the comparison of nanoparticle density of a solid-phase SERS nano-substrate under different growth conditions in an embodiment of the present invention;
FIG. 4 is a graph of the UV-absorption spectra of a solid phase SEERS nanomatrix c and a glass plate used to prepare the same according to a second embodiment of the invention;
FIG. 5 is a diagram illustrating the detection results of the solid-phase SERS nano-substrate c according to the second embodiment of the present invention on ethanol solutions of dibenzyl disulfide (DBDS) with different concentrations;
fig. 6 is a graph illustrating the evaluation of the surface uniformity of the solid-phase SERS nano-substrate d according to the second embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
Fig. 1 shows a flow of a method for preparing a solid-phase SERS nano-substrate according to an embodiment of the present invention, where the method includes:
s11: preparing a nano gold seed solution: adding a chloroauric acid solution with a first preset concentration into ultrapure water, stirring, then adding a trisodium citrate solution as a protective agent, finally adding a sodium borohydride solution as a reducing agent, and continuously stirring for a first preset time to perform a reduction reaction to obtain a nanogold seed solution;
specifically, 50mL of ultrapure water is added into a round-bottom flask with the volume of 150mL, then 500 mu L of chloroauric acid solution with the concentration of 37.8mmol/L is added and continuously stirred, 1.5mL of trisodium citrate solution with the concentration of 38.8mmol/L is added as a protective agent, finally 900 mu L of sodium borohydride solution with the concentration of 21.2mmol/L is added, and the reaction is continuously stirred for 2 hours, so that the solution turns to wine red to obtain the required nanogold seed solution. And transferring the nano gold seed solution into a clean wide-mouth bottle for storage for later use.
Optionally, the first preset concentration may be any value within a range from 25mmol/L to 35mmol/L, the concentration of the trisodium citrate solution may be any value within a range from 30 mmol/L to 40mmol/L, and the concentration of the sodium borohydride solution may be any value within a range from 20 mmol/L to 25 mmol/L.
Optionally, the first preset time is 2-3 hours.
Optionally, the volume ratio of the 25-35 mmol/L chloroauric acid solution to the 30-40 mmol/L trisodium citrate solution is 1 (2-5); the volume ratio of the 25-35 mmol/L chloroauric acid solution to the 20-25 mmol/L sodium borohydride solution is 1:2 to 1: 1.
S12: fixing the nano gold seeds on the glass sheet: cleaning a glass sheet, soaking the glass sheet in a 3-aminopropyltrimethoxysilane adsorbent solution for a second preset time, taking out the glass sheet, washing the glass sheet with ultrapure water, drying the glass sheet with nitrogen to obtain a pretreated glass sheet, placing the pretreated glass sheet in the nanogold solution, vertically suspending and soaking the glass sheet for a third preset time, taking out the glass sheet, washing the surface of the glass sheet with ultrapure water to remove redundant nanogold solution, and drying the glass sheet with nitrogen to obtain an adsorbed glass sheet;
specifically, a glass sheet having a size of 10mm × 20mm was immersed in aqua regia for 10 minutes, washed with ultrapure water, immersed in an ethanol saturated solution of sodium hydroxide for 2 hours, washed again with ultrapure water, and immersed in a 0.2 mass% 3-aminopropyltrimethoxysilane adsorbent solution for 30 minutes. And taking out the glass sheet, washing with ultrapure water, drying with nitrogen, soaking the glass sheet in the nanogold seed solution, and vertically hanging and soaking for 10 hours. And taking out the glass sheet, washing away the excessive nano-gold seed solution on the surface by using ultrapure water, and drying by using nitrogen to finish the fixation of the nano-gold seeds on the glass sheet.
Optionally, the second preset time is 5-60 minutes, and the third preset time is 1-30 hours.
Optionally, the mass fraction of the 3-aminopropyltrimethoxysilane adsorbent solution is 0.1-1.5%.
Optionally, the area of the glass sheet is 30-100 mm2。
S13: growth of in situ seeds: and placing the adsorbed glass sheet in a centrifugal tube, adding ultrapure water, a chloroauric acid solution with a second preset concentration and a hydroxylamine hydrochloride solution as solutions required for growth, taking out the solutions after oscillating for a fourth preset time at a preset rotating speed in a constant-temperature mixing instrument, cleaning the solutions by using the ultrapure water, completing a growth cycle, and obtaining the solid-phase SERS nano substrate after 3-9 growth cycles.
Specifically, a glass sheet is placed in a 5mL centrifuge tube, 3mL of ultrapure water is added, 40 muL of chloroauric acid solution with the concentration of 7.6mmol/L and 20 muL of hydroxylamine hydrochloride solution with the concentration of 40mmol/L are added to serve as solutions required for primary growth, the solution is taken out after oscillation for 15 minutes at the rotation speed of a constant-temperature mixer at 1500rpm, the growth process is repeated after the solution is cleaned by the ultrapure water, and the SERS nano substrate is obtained after 5 growth cycles.
Optionally, the second preset concentration may be any value of 5 to 25mmol/L, and the concentration of the hydroxylamine hydrochloride solution is 10 to 100 mmol/L. Optionally, the preset rotating speed is 1000-2000 rpm. The fourth preset time is 10-20 minutes.
Optionally, the volume ratio of the chloroauric acid solution with the concentration of 5-25 mmol/L to the hydroxylamine hydrochloride solution with the concentration of 10-100 mmol/L is 1: 1-3: 1.
Optionally, the number of growth cycles is 3-9.
Fig. 2 shows an SEM image of the solid-phase SERS nano-substrate according to the embodiment of the present invention, and as shown in the figure, the solid-phase SERS nano-substrate prepared according to the embodiment has high density of small nano-gaps, and no filling molecules are filled between the gaps, so that the detection sensitivity is high.
In the preparation method of the solid-phase SERS nano-substrate in this embodiment, a single-layer nano-gold structure is grown on the surface of the planar glass carrier by preparing a nano-gold seed solution, fixing the nano-gold seeds on the glass sheet, and growing the in-situ seeds, so as to obtain the solid-phase SERS nano-substrate. The preparation method is simple to operate, the required reagent dosage is small, the preparation can be completed by simply soaking different solutions in several steps in the preparation process, and the obtained solid-phase SERS nano substrate is stable in structure, high in nano particle density and high in detection sensitivity.
Example two:
fig. 1 illustrates a method for preparing a solid-phase SERS nano-substrate according to an embodiment of the present invention, the method comprising:
s11: preparing a nano gold seed solution: adding a chloroauric acid solution with a first preset concentration into ultrapure water, stirring, then adding a trisodium citrate solution as a protective agent, finally adding a sodium borohydride solution as a reducing agent, and continuously stirring for a first preset time to perform a reduction reaction to obtain a nanogold seed solution;
specifically, 50mL of ultrapure water is added into a round-bottom flask with the volume of 150mL, then 500 mu L of chloroauric acid solution with the concentration of 37.8mmol/L is added and continuously stirred, 1.5mL of trisodium citrate solution with the concentration of 38.8mmol/L is added as a protective agent, finally 900 mu L of sodium borohydride solution with the concentration of 21.2mmol/L is added, and the reaction is continuously stirred for 2 hours, so that the solution turns to wine red to obtain the required nanogold seed solution. And transferring the nano gold seed solution into a clean wide-mouth bottle for storage for later use.
S12: fixing the nano gold seeds on the glass sheet: cleaning a glass sheet, soaking the glass sheet in a 3-aminopropyltrimethoxysilane adsorbent solution for a second preset time, taking out the glass sheet, washing the glass sheet with ultrapure water, drying the glass sheet with nitrogen to obtain a pretreated glass sheet, placing the pretreated glass sheet in the nanogold solution, vertically suspending and soaking the glass sheet for a third preset time, taking out the glass sheet, washing the surface of the glass sheet with ultrapure water to remove redundant nanogold solution, and drying the glass sheet with nitrogen to obtain an adsorbed glass sheet;
specifically, a glass sheet a, a glass sheet b, a glass sheet c and a glass sheet d, which are 10mm × 20mm in size, are soaked in aqua regia for 10 minutes, washed with ultrapure water, soaked in an ethanol saturated solution of sodium hydroxide for 2 hours, washed again with ultrapure water, and soaked in a 3-aminopropyltrimethoxysilane adsorbent solution with a mass fraction of 0.2% for 30 minutes. And taking out the glass sheet, washing with ultrapure water, drying with nitrogen, immersing the glass sheet a, the glass sheet b, the glass sheet c and the glass sheet d in the nanogold seed solution, and vertically hanging and immersing for 10 hours. And taking out the glass sheet, washing away the excessive nano gold seed solution on the surface by using ultrapure water, and drying by using nitrogen to finish the fixation of the nano gold seeds on the glass sheet a, the glass sheet b, the glass sheet c and the glass sheet d.
S13: growth of in situ seeds: and placing the adsorbed glass sheet in a centrifugal tube, adding ultrapure water, a chloroauric acid solution with a second preset concentration and a hydroxylamine hydrochloride solution as solutions required for growth, taking out the solutions after oscillating for a fourth preset time at a preset rotating speed in a constant-temperature mixing instrument, cleaning the solutions by using the ultrapure water, completing a growth cycle, and obtaining the solid-phase SERS nano substrate after 3-9 growth cycles.
Specifically, the glass sheet a is placed in a 5mL centrifuge tube, 3mL of ultrapure water is added, 80 muL of chloroauric acid solution with the concentration of 7.6mmol/L and 40 muL of hydroxylamine hydrochloride solution with the concentration of 40mmol/L are added to serve as solutions required for primary growth, the solution is taken out after oscillation for 15 minutes at the rotation speed of 1500rpm of a constant-temperature mixer, the growth process is repeated after the solution is cleaned by the ultrapure water, and the SERS nano-substrate a is obtained after 5 growth cycles. Specifically, during the first growth cycle, the glass sheet b is placed in a 5mL centrifuge tube, 3mL of ultrapure water is added, 160 μ L of chloroauric acid solution with the concentration of 7.6mmol/L and 80 μ L of hydroxylamine hydrochloride solution with the concentration of 40mmol/L are added as solutions required for the first growth, the solution is taken out after oscillation at the rotation speed of 1500rpm of a constant temperature mixer for 15 minutes, the first growth is completed after the solution is washed by the ultrapure water, then the growth process is repeated, from the beginning of the second growth, 80 μ L of chloroauric acid solution with the concentration of 7.6mmol/L and 40 μ L of hydroxylamine hydrochloride solution with the concentration of 40mmol/L are added as solutions required for the first growth, and the SERS nano substrate b is obtained after 5 growth cycles.
Specifically, during the first growth cycle, the glass sheet c is placed in a 5mL centrifuge tube, 3mL of ultrapure water is added, 240 μ L of chloroauric acid solution with the concentration of 7.6mmol/L and 120 μ L of hydroxylamine hydrochloride solution with the concentration of 40mmol/L are added as solutions required for the first growth, the solution is taken out after oscillation at the rotation speed of 1500rpm of a constant temperature mixer for 15 minutes, the first growth is completed after the solution is washed by the ultrapure water, then the growth process is repeated, from the beginning of the second growth, 80 μ L of chloroauric acid solution with the concentration of 7.6mmol/L and 40 μ L of hydroxylamine hydrochloride solution with the concentration of 40mmol/L are added as solutions required for the first growth, and the SERS nano-substrate c is obtained after 5 growth cycles.
Specifically, during the first growth cycle, the glass sheet d is placed in a 5mL centrifuge tube, 3mL of ultrapure water is added, 320 μ L of chloroauric acid solution with the concentration of 7.6mmol/L and 160 μ L of hydroxylamine hydrochloride solution with the concentration of 40mmol/L are added as solutions required for the first growth, the solution is taken out after oscillation at the rotation speed of 1500rpm of a constant temperature mixer for 15 minutes, the first growth is completed after the solution is washed by the ultrapure water, then the growth process is repeated, from the beginning of the second growth, 80 μ L of chloroauric acid solution with the concentration of 7.6mmol/L and 40 μ L of hydroxylamine hydrochloride solution with the concentration of 40mmol/L are added as solutions required for the first growth, and the SERS nano substrate d is obtained after 5 growth cycles.
Fig. 3 shows a comparison diagram of nanoparticle density of the solid-phase SERS nano-substrate according to the embodiment of the present invention under different growth conditions, as shown in fig. 3, the solid-phase SERS nano-substrate having higher density of nanoparticles than the solid-phase SERS nano-substrate according to the first embodiment is prepared by adjusting the growth conditions, and in the embodiment of the present invention, the nanoparticle densities of the solid-phase SERS nano-substrate a, the solid-phase SERS nano-substrate b, the solid-phase SERS nano-substrate c, and the solid-phase SERS nano-substrate d are sequentially increased.
Fig. 4 is a graph of ultraviolet-visible absorption spectrums of the glass sheet with the prepared substrate and the solid-phase SERS nano-substrate d, as shown in the figure, the glass sheet with the prepared substrate absorbs very weakly in the range of wavelength of 400-800 nm, and the solid-phase SERS nano-substrate d has strong absorption in the range of wavelength of 400-800 nm, so that the absorption of the solid-phase SERS nano-substrate d in the waveband comes from a single-layer nanogold film with high density and small nanogaps on the surface of the glass sheet.
Specifically, the solid-phase SERS nano substrate d has a good coupling effect with Raman excitation light with the wavelength of about 800nm, and is convenient to be matched with a common portable Raman spectrometer with the excitation wavelength of about 800nm in a near-infrared region for use.
FIG. 5 shows the detection results of solid-phase SERS nano-substrate d in different concentrations of ethanol dibenzyldisulfide (DBDS) solution, which is detected by using ethanol solution of dibenzyldisulfide (DBDS) with concentration of 1mg/kg, ethanol solution of dibenzyldisulfide (DBDS) with concentration of 10mg/kg, and ethanol solution of dibenzyldisulfide (DBDS) with concentration of 100 mg/kg.
Specifically, the detection instrument is a portable Raman spectrometer, the excitation wavelength is 785nm, the laser intensity is 200mW, the collection time is 1 second, the collection frequency is 2 times, and the collection spectral range is 400-1800 cm-1。
Specifically, as shown in the figure, the detection limit of the solid-phase SERS nano substrate d on dibenzyl disulfide is lower than 1 mg/kg. Specifically, 4-mercaptobenzoic acid is used as a probe molecule for testing, a 4-mercaptobenzoic acid standard substance is dissolved in absolute ethyl alcohol to prepare 1mmol/L mother liquor, and then the mother liquor is diluted step by the absolute ethyl alcohol to obtain the 4-mercaptobenzoic acid standard liquor with the concentration of 1 mu mol/L. Completely immersing the solid-phase SERS nano substrate d in standard liquid, taking out after 30 minutes, and carrying out 400-1800 cm alignment on different areas on the substrate by using the same Raman spectrometer under the same test parameters-1Raman signal collection is carried out in the spectral range, and the size of a test area is 300 multiplied by 150 mu m. The intensity distribution of the obtained SERS signal is shown in FIG. 6, and it can be seen that the substrate has good uniformity.
According to the preparation method of the solid-phase SERS nano-substrate in the embodiment of the invention, a single-layer nano-gold structure grows on the surface of a plane glass carrier through the preparation of a nano-gold solution, the fixation of nano-gold seeds on a glass sheet and the growth of in-situ seeds, so that the solid-phase SERS nano-substrate is obtained. The preparation method is simple to operate, and the single-layer nanogold film with high density and small nanogap is prepared on the surface of the plane glass by adjusting the growth conditions of the nanogold seeds, so that the solid-phase SERS nano substrate is obtained. The preparation method is simple to operate, and the obtained solid-phase SERS nano substrate is stable in structure, good in surface uniformity and high in detection sensitivity, has stronger absorption in a near-infrared region, and is convenient to be matched with a common portable Raman spectrometer with the excitation wavelength of about 800 nm.
The above embodiments of the present invention are described in detail, and the principle and the implementation of the present invention are described herein by using specific embodiments, and the description of the above embodiments is only used to help understanding the method of the present invention and the core idea thereof; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (10)
1. A preparation method of a solid-phase SERS nano-substrate is characterized by comprising the following steps:
preparing a nano gold seed solution: adding a chloroauric acid solution with a first preset concentration into ultrapure water, stirring, then adding a trisodium citrate solution as a protective agent, finally adding a sodium borohydride solution as a reducing agent, and continuously stirring for a first preset time to perform a reduction reaction to obtain a nanogold seed solution;
fixing the nano gold seeds on the glass sheet: cleaning a glass sheet, soaking the glass sheet in a 3-aminopropyltrimethoxysilane adsorbent solution for a second preset time, taking out the glass sheet, washing the glass sheet with ultrapure water, drying the glass sheet with nitrogen to obtain a pretreated glass sheet, placing the pretreated glass sheet in the nanogold solution, vertically suspending and soaking the glass sheet for a third preset time, taking out the glass sheet, washing the surface of the glass sheet with ultrapure water to remove redundant nanogold solution, and drying the glass sheet with nitrogen to obtain an adsorbed glass sheet;
growth of in situ seeds: and placing the adsorbed glass sheet in a centrifugal tube, adding ultrapure water, a chloroauric acid solution with a second preset concentration and a hydroxylamine hydrochloride solution as solutions required for growth, taking out the solutions after oscillating for a fourth preset time at a preset rotating speed in a constant-temperature mixing instrument, cleaning the solutions by using the ultrapure water, completing a growth cycle, and obtaining the solid-phase SERS nano substrate after 3-9 growth cycles.
2. The method for preparing a solid-phase SERS nano substrate according to claim 1, wherein the steps of adding chloroauric acid solution with a first preset concentration into ultrapure water, stirring, adding trisodium citrate solution as a protective agent, and adding sodium borohydride solution as a reducing agent comprise:
adding a chloroauric acid solution with the concentration of 25-35 mmol/L into ultrapure water, stirring, then adding a trisodium citrate solution with the concentration of 30-40 mmol/L as a protective agent, and finally adding a sodium borohydride solution with the concentration of 20-25 mmol/L as a reducing agent.
3. The method for preparing the solid-phase SERS nano-substrate according to claim 2, wherein the volume ratio of the chloroauric acid solution with the concentration of 25-35 mmol/L to the sodium borohydride solution with the concentration of 20-25 mmol/L is 1:2 to 1: 1;
the volume ratio of the chloroauric acid solution with the concentration of 25-35 mmol/L to the trisodium citrate solution with the concentration of 30-40 mmol/L is 1: 5-1: 2.
4. The method for preparing a solid-phase SERS nano-substrate according to claim 1, wherein the adding sodium borohydride solution as a reducing agent and the stirring for the first predetermined time for the reduction reaction comprises:
and taking the sodium borohydride solution as a reducing agent, and continuously stirring for 2-3 hours after the sodium borohydride solution is added to carry out reduction reaction.
5. The method for preparing a solid-phase SERS nano-substrate according to claim 1, wherein the step of cleaning the glass sheet and immersing the glass sheet in a 3-aminopropyltrimethoxysilane adsorbent solution for a second predetermined time comprises:
soaking the glass sheet in aqua regia for 10 minutes, washing the glass sheet with ultrapure water, soaking the glass sheet in an ethanol saturated solution of sodium hydroxide for 2 hours, washing the glass sheet with ultrapure water again, and soaking the glass sheet in a 3-aminopropyltrimethoxysilane adsorbent solution for 5-60 minutes.
6. The method for preparing the solid-phase SERS nano-substrate according to claim 5, wherein the mass fraction of the 3-aminopropyltrimethoxysilane adsorbent solution is 0.1-1.5%.
7. The method for preparing a solid-phase SERS nano-substrate according to claim 1, wherein the placing the pretreated glass sheet in the nanogold seed solution and vertically suspending and soaking the glass sheet for a third preset time comprises:
and placing the pretreated glass sheet in the nanogold seed solution to be vertically suspended and soaked for 1-30 hours.
8. The method for preparing a solid-phase SERS nano-substrate according to claim 1, wherein the step of adding ultrapure water, a chloroauric acid solution with a second predetermined concentration and a hydroxylamine hydrochloride solution into a centrifuge tube as growth-required solutions comprises:
adding ultrapure water, 5-25 mmol/L chloroauric acid solution and 10-100 mmol/L hydroxylamine hydrochloride solution into a centrifugal tube as solutions required for growth.
9. The method for preparing the solid-phase SERS nano-substrate according to claim 8, wherein the volume ratio of the chloroauric acid solution with the concentration of 5-25 mmol/L to the hydroxylamine hydrochloride solution with the concentration of 10-100 mmol/L is 1:1 to 3: 1.
10. The method for preparing the solid-phase SERS nano-substrate according to claim 1, wherein the oscillating of the centrifugal tube in the constant-temperature mixer at a preset rotation speed for a fourth preset time comprises:
the centrifugal tube is oscillated for 10-20 minutes at the rotating speed of 1000-2000 rpm in a constant-temperature blending instrument.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110934763.3A CN113588625A (en) | 2021-08-16 | 2021-08-16 | Preparation method of solid-phase SERS nano-substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110934763.3A CN113588625A (en) | 2021-08-16 | 2021-08-16 | Preparation method of solid-phase SERS nano-substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113588625A true CN113588625A (en) | 2021-11-02 |
Family
ID=78257969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110934763.3A Pending CN113588625A (en) | 2021-08-16 | 2021-08-16 | Preparation method of solid-phase SERS nano-substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113588625A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115586170A (en) * | 2022-09-26 | 2023-01-10 | 广西电网有限责任公司电力科学研究院 | SERS (surface enhanced Raman scattering) determination method for content of dibenzyl disulfide in mineral insulating oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108645835A (en) * | 2018-04-24 | 2018-10-12 | 扬州大学 | Gold nanoparticle SERS active-substrate of highly branchedization and preparation method thereof |
| CN108802007A (en) * | 2018-06-19 | 2018-11-13 | 云南师范大学 | A kind of surface enhanced Raman substrate and preparation method of large-area nano membrane structure |
-
2021
- 2021-08-16 CN CN202110934763.3A patent/CN113588625A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108645835A (en) * | 2018-04-24 | 2018-10-12 | 扬州大学 | Gold nanoparticle SERS active-substrate of highly branchedization and preparation method thereof |
| CN108802007A (en) * | 2018-06-19 | 2018-11-13 | 云南师范大学 | A kind of surface enhanced Raman substrate and preparation method of large-area nano membrane structure |
Non-Patent Citations (2)
| Title |
|---|
| "On-site and quantitative SERS detection of trace 1, 2, 3-benzotriazole in transformer oil with colloidal lignin particles-based green pretreatment reagents", SPECTROCHIMICA ACTA PART A: MOLECULAR AND BIOMOLECULAR SPECTROSCOPY * |
| YOUXING FANG ET AL: ""Self-Assembly of Cationic Polyelectrolyte-Functionalized Graphene Nanosheets and Gold Nanoparticles: A Two-Dimensional Heterostructure for Hydrogen Peroxide Sensing", LANGMUIR * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115586170A (en) * | 2022-09-26 | 2023-01-10 | 广西电网有限责任公司电力科学研究院 | SERS (surface enhanced Raman scattering) determination method for content of dibenzyl disulfide in mineral insulating oil |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Munro et al. | Characterization of the surface of a citrate-reduced colloid optimized for use as a substrate for surface-enhanced resonance Raman scattering | |
| Li et al. | High surface‐enhanced Raman scattering performance of individual gold nanoflowers and their application in live cell imaging | |
| Chen et al. | Sensing of hydrogen sulfide gas in the Raman-silent region based on gold nano-bipyramids (Au NBPs) encapsulated by zeolitic imidazolate framework-8 | |
| WO2022142109A1 (en) | Preparation method for sers substrate, sers substrate, and application | |
| CN102661944A (en) | Preparation method of surface-enhanced Raman scattering substrate of metal particle array | |
| Puente et al. | Silver-chitosan and gold-chitosan substrates for surface-enhanced Raman spectroscopy (SERS): Effect of nanoparticle morphology on SERS performance | |
| CN106940310B (en) | Substrate and preparation method thereof is immunized in a kind of self assembly gold nanorods SERS | |
| CN112730375A (en) | Method for detecting VOC gas by using MOF-coated gold nanoparticles through enhanced Raman spectroscopy | |
| CN108120709A (en) | A kind of capillary microlayer model metal ball detection method for Surface enhanced Raman spectroscopy | |
| CN113588625A (en) | Preparation method of solid-phase SERS nano-substrate | |
| CN110064360A (en) | Superparamagnetism Fe3O4@SiO2The preparation method of@Ag nanocomposite | |
| CN108414495A (en) | The preparation method of iron oxide synergic nano silver/graphene oxide SERS substrates | |
| Zheng et al. | Gel-assisted synthesis of oleate-modified Fe 3 O 4@ Ag composite microspheres as magnetic SERS probe for thiram detection | |
| CN110455769A (en) | Shell is interior target core-shell nano Surface enhanced Raman spectroscopy quantitative analysis method | |
| CN102980879B (en) | Preparation method of surface enhancement raman scattering substrate | |
| US20050186129A1 (en) | Metallic colloid particles and process for producing same | |
| CN110530842B (en) | Fe 3 O 4 @SiO 2 Preparation method and application of Au NPs particles | |
| Dong et al. | Capillary-force-assisted self-assembly of gold nanoparticles into highly ordered plasmonic thin films for ultrasensitive SERS | |
| CN103357885B (en) | A kind of Raman strengthens preparation method and the application thereof of elargol | |
| CN110907426B (en) | Method for enhancing SERS activity of silver decahedral nanoparticles by chloroauric acid | |
| CN107914022A (en) | A kind of preparation method of the nano silver wire with surface Raman enhancement effect | |
| CN112697770A (en) | Method for measuring glutaraldehyde in water based on metal organic framework material composite substrate surface enhanced Raman spectroscopy | |
| CN110220869A (en) | A kind of method of mercury ion in detection water | |
| CN111422896B (en) | Preparation method of bitter gourd-shaped CuO nanoparticle SERS substrate | |
| CN115144382A (en) | SERS active substrate formed by three-dimensional self-assembly and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |