WO2022142109A1 - Preparation method for sers substrate, sers substrate, and application - Google Patents

Preparation method for sers substrate, sers substrate, and application Download PDF

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WO2022142109A1
WO2022142109A1 PCT/CN2021/096596 CN2021096596W WO2022142109A1 WO 2022142109 A1 WO2022142109 A1 WO 2022142109A1 CN 2021096596 W CN2021096596 W CN 2021096596W WO 2022142109 A1 WO2022142109 A1 WO 2022142109A1
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mil
agnps
sers substrate
nanomaterials
sers
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Chinese (zh)
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邹明强
郑杰爽
齐小花
张晓华
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中国检验检疫科学研究院
中检国研(北京)科技有限公司
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    • 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

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  • the invention belongs to the technical field of Raman spectrum detection, and in particular relates to a preparation method, SERS substrate and application of a SERS substrate based on AgNPs/MIL-101(Fe) nanomaterials.
  • SERS Surface-enhanced Raman scattering
  • SERS surface-enhanced Raman spectroscopy
  • SERS is a fast and non-destructive spectroscopy technique, which has the characteristics of high sensitivity, high accuracy, fingerprint spectroscopy, and no interference from water molecules, which can realize the detection of single molecules.
  • SERS With the rapid development of laser technology and the growing maturity of nanomaterial preparation technology, SERS not only plays an important role in scientific research such as single crystal surface molecular adsorption, chemical reaction mechanism, and in vivo cell behavior, but also plays an increasingly important role in food safety. It has been widely used in real life, such as environmental pollution chemical weapons and artwork identification.
  • the SERS mechanism generally recognized by the academic community mainly includes two types: physical enhancement mechanism and chemical enhancement mechanism: the physical enhancement mode is Electromagnetic Mechanis (EM) and the chemical enhancement mode is Charge Transfer enhancement (CT).
  • the electromagnetic field mechanism is a physical model that believes that the SERS effect originates from the enhancement of the localized electric field on the metal surface.
  • the models of electromagnetic field enhancement mechanisms mainly include the following three surface plasmon resonance models (SPR), antenna resonator sub-models and mirror field models. Among them, the surface plasmon resonance (SPR) enhancement mechanism is considered to be the most important contributor to electromagnetic field enhancement.
  • Chemical enhancement mainly includes the following three mechanisms: off-resonance enhancement due to chemical bonding between adsorbates and metal substrates; resonance enhancement due to the formation of surface complexes between adsorbed molecules and surface adatoms; excitation light on the molecule-metal system. Resonance-like enhancement of light-induced charge transfer.
  • MOFs is the abbreviation of metal organic framework compounds (English name Metal organic Frameworks). It is a class of crystalline porous materials with periodic network structure formed by inorganic metal centers (metal ions or metal clusters) and bridged organic ligands connected to each other through self-assembly. It is not only different from inorganic porous materials, but also different. Compared with general organic complexes, it has both the rigidity of inorganic materials and the flexibility of organic materials, which makes it show great development potential and attractive development prospects in modern materials research. MOFs have many properties such as porosity, large specific surface area, and multi-metallic sites, so they have many applications in chemical and chemical fields, such as gas storage, molecular separation, catalysis, and sustained drug release. Because of the unique characteristics of MOFs, some researchers have extended the application of this material to the field of SERS, enriching the application prospects of MOFs.
  • Cao Xiaolin et al. prepared a variety of SERS active materials of AuNPs/MOFs by in situ reduction and embedding of metals in MOF by solution impregnation.
  • the use of SERS technology to detect pesticides provides a new approach which was introduced in the opening report.
  • this preparation method cannot control the size and morphology of metal particles due to the in-situ reduction, which makes it difficult to optimize the SERS performance.
  • Yang Haifei et al. successfully synthesized core-shell gold nanoparticles through layer-by-layer assembly, and the detection limit of hexamethylenetetramine was 10 -8 M.
  • the disadvantage of this method is that the distance between metal particles is not easy to control, and the optimal state of "hot spot" cannot be achieved.
  • Xiaowei Cao's group also adopted the solution immersion reduction method to prepare AgNPs/MIL-101(Cr) nanocomposites, and used it as a SERS substrate to perform SERS spectral analysis of ultra-trace glucose in aqueous solution, and the detection limit was about 10 - 14 M.
  • the present invention provides a SERS substrate based on AgNPs/MIL-101(Fe) nanomaterials prepared by the above preparation method;
  • the invention also provides a Raman spectrum detection method based on the AgNPs/MIL-101(Fe) nano-material SERS substrate and its application.
  • the SERS substrate based on AgNPs/MIL-101(Fe) nanomaterials includes AgNPs/MIL-101(Fe) nanomaterials;
  • the AgNPs/MIL-101(Fe) nanomaterial is prepared by a physical self-assembly method between the AgNPs material and the MIL-101(Fe) material;
  • the MIL-101(Fe) material is dispersed in a dispersant to prepare a MIL-101(Fe) dispersion, and then the MIL-101(Fe) dispersion is uniformly mixed with the AgNPs material, and mixed After incubation at room temperature, the AgNPs/MIL-101(Fe) nanomaterials were prepared.
  • the AgNPs material is AgNPs glue
  • the volume ratio of the MIL-101(Fe) dispersion to the AgNPs glue is 1:(1-3).
  • the dispersant is methanol
  • the MIL-101(Fe) material is dispersed in the dispersant to obtain a MIL-101(Fe) dispersion of 0.8-1.2 mg/mL.
  • the specific process of the AgNPs/MIL-101(Fe) nanomaterial is as follows: dispersing the MIL-101(Fe) material in the dispersant to obtain a 0.8-1.2 mg/mL MIL-101(Fe) dispersion, Then, the MIL-101(Fe) dispersion was mixed with the AgNPs glue, the volume ratio of the two was 1:(1-3), and then mixed at a high speed, and then incubated at room temperature for 1.3-2 hours to obtain AgNPs/MIL - 101(Fe) nanomaterials.
  • the molar ratio of silver atoms to iron atoms is 1:(4-13).
  • the MIL-101(Fe) material is prepared by the following method.
  • the iron source and terephthalic acid are dissolved in a solvent, and then treated by a solvothermal synthesis method. After cooling and washing, the crude product is obtained.
  • the MIL-101(Fe) material is obtained after the crude product is activated and dried.
  • the molar ratio of the terephthalic acid to the iron ions in the iron source is (1-1.3):2.45.
  • the solvent is DMF
  • the iron source is ferric chloride or ferric chloride hexahydrate.
  • the specific preparation process of the MIL-101 (Fe) material is as follows, adding ferric chloride and terephthalic acid into a sufficient amount of DMF, then dissolving to generate a transparent solution, placing the transparent solution in an autoclave, and at 100 °C. -130°C for 18-30 hours, cooled to room temperature and centrifuged to obtain a solid, then the solid was washed with DMF and sewage ethanol for several times to completely remove impurities in it to obtain a crude product, and the crude product was heated at a temperature of not lower than 70°C. Activated in ethanol for at least 2.5 hours, centrifuged to obtain an activated solid and dried to obtain MIL-101(Fe) material.
  • the AgNPs glue solution is prepared by the following method, taking the silver source solution and heating the silver source solution to boiling, adding sodium citrate solution to the silver source solution and mixing, continuing to heat for a period of time, and then cooling to AgNPs glue solution was obtained at room temperature.
  • the added amount of the sodium citrate solution is at least such that the silver in the silver source solution is completely reduced.
  • the silver source solution is a silver nitrate solution.
  • the specific preparation process of the AgNPs glue solution is as follows: the silver nitrate solution is heated, and the sodium citrate solution is rapidly added to the silver nitrate solution when the silver nitrate solution is boiled and stirred rapidly, and the AgNPs glue solution is kept in a boiling state for at least 40 minutes, and finally cooled to room temperature to obtain the AgNPs glue solution, The AgNPs glue solution was stored at low temperature in the dark.
  • a SERS substrate based on AgNPs/MIL-101(Fe) nanomaterials is prepared by the above-mentioned preparation method based on AgNPs/MIL-101(Fe) nanomaterials SERS substrates.
  • a Raman spectroscopic detection method based on AgNPs/MIL-101 (Fe) nanomaterial SERS substrate using the above-mentioned SERS substrate based on AgNPs/MIL-101 (Fe) nanomaterial for Raman spectroscopic detection.
  • the Raman spectroscopic detection method is as follows: after the AgNPs/MIL-101(Fe) nanomaterial-based SERS substrate is evenly mixed with the liquid to be tested, sampling is performed on a sample carrier, and Raman spectroscopic detection is performed after drying.
  • the AgNPs/MIL-101(Fe) nanomaterial and the liquid to be tested are mixed at a high speed in a volume ratio of 1:2, and then 10 ⁇ L is sampled and dropped on the Raman spectrum sample carrier, and the Raman detection is performed after natural drying. .
  • the Raman spectrum detection method is applied to the determination of paraquat in a sample to be tested in an environment with a pH value of 3-11
  • the present invention has the following beneficial effects:
  • the Raman spectroscopic detection method based on AgNPs/MIL-101(Fe) nanomaterial SERS substrate in the present invention has high sensitivity and lower detection limit, detects rhodamine 6G and calculates 10 -6 mol/L R6G
  • Fig. 1 is the XRD spectrum of MIL-101(Fe) nanomaterial, AgNPs material and finally synthesized AgNPs/MIL-101(Fe) nanomaterial in Example 2 of the present invention;
  • Example 2 is a 100,000 times electron microscope photo of the MIL-101(Fe) nanomaterial prepared in Example 2 of the present invention
  • Example 3 is a 500,000 times electron microscope photo of the MIL-101(Fe) nanomaterial prepared in Example 2 of the present invention
  • Figure 4 shows the detection results of AgNPs/MIL-101(Fe) nanomaterials prepared in Examples 1-3 for R6G; the figures from top to bottom are the AgNPs prepared in Example 2, Example 3 and Example 1, respectively. / MIL-101(Fe) nanomaterials test results for R6G;
  • Example 5 is a scanning electron microscope image of AgNPs/MIL-101(Fe) nanomaterials prepared in Example 1;
  • Example 6 is a scanning electron microscope image of AgNPs/MIL-101(Fe) nanomaterials prepared in Example 2;
  • Example 7 is a scanning electron microscope image of AgNPs/MIL-101(Fe) nanomaterials prepared in Example 3;
  • Figure 8 is a graph showing the Raman detection results of four different common SERS probe molecules for AgNPs/MIL-101(Fe) nanomaterials prepared in Example 2, in which Figure 8-a shows Rhodamine 6G as the SERS probe molecule , Figure 8-b shows crystal violet as SERS probe molecule, Figure 8-c shows 4-mercaptobenzoic acid as SERS probe molecule, Figure 8-d shows 5,5'-dithiobis(2-nitrobenzene) Formic acid) as the SERS probe molecule; the curves in Figure 8-a, Figure 8-b, Figure 8-c and Figure 8-d are AgNPs/MIL-101(Fe) nanomaterials, AgNPs materials and MIL from top to bottom, respectively Raman detection curve of -101(Fe) material;
  • Fig. 9 is a graph showing the detection result of the SERS signal reproducibility of AgNPs/MIL-101(Fe) nanomaterials; wherein, Fig. 9-a shows the AgNPs/MIL-101(Fe) nanomaterials obtained in Example 2 using Rhodamine 6G As the Raman detection reproducibility results of SERS probe molecules, Figure 9-b shows the Raman detection characteristics of AgNPs/MIL-101(Fe) nanomaterials prepared in Example 2 using rhodamine 6G as SERS probe molecules Peak signal intensity histogram analysis chart;
  • Figure 10 shows the detection results of paraquat using AgNPs/MIL-101(Fe) nanomaterials as a SERS substrate; among them, Figure 10-a shows the Laman detection spectrum of different paraquat concentrations, and Figure 10-b shows the paraquat The Raman detection spectrum of paraquat at a concentration of 10 -12 M, Figure 10-c is the Raman detection spectrum of paraquat at a concentration of 10 -6 M under different pH conditions, and Figure 10-d is under different pH conditions Histogram of Raman detection results of paraquat at 1650cm -1 at the detection concentration of 10 -6 M.
  • a SERS substrate based on AgNPs/MIL-101(Fe) nanomaterials the SERS substrate is AgNPs/MIL-101(Fe) nanomaterials, and in the AgNPs/MIL-101(Fe) nanomaterials, the moles of silver atoms and iron atoms are The ratio is 1:(4-13);
  • AgNPs/MIL-101(Fe) nanomaterials are prepared from AgNPs glue and MIL-101(Fe) material by physical self-assembly method.
  • MIL-101(Fe) materials are dispersed in methanol to obtain 0.8-1.2 mg/mL MIL-101(Fe) dispersions, and then MIL-101(Fe) dispersions are prepared.
  • the 101(Fe) dispersion was mixed with the AgNPs glue at a volume ratio of 1:(1-3), then mixed at high speed, and incubated at room temperature for 1.3-2 hours to obtain AgNPs/MIL-101(Fe) )nanomaterials.
  • the specific preparation process of the MIL-101(Fe) material is as follows, adding ferric chloride and terephthalic acid into a sufficient amount of DMF, and the molar ratio of terephthalic acid and iron ions in the iron source is (1-1.3): 2.45, Then dissolve to generate a transparent solution, which is placed in an autoclave, treated by solvothermal synthesis at 100-130 ° C for 18-30 hours, cooled to room temperature and centrifuged to obtain a solid, and then the solid is treated with DMF and sewage ethanol Washing for several times to completely remove impurities in the crude product, the crude product is activated in hot ethanol at a temperature of not lower than 70°C for at least 2.5 hours, centrifuged to obtain an activated solid and dried to obtain MIL-101(Fe) material;
  • the specific preparation process of the AgNPs glue solution is as follows: heating the silver nitrate solution, rapidly adding sodium citrate solution to it when the silver nitrate solution boils and stirring rapidly, and the addition amount of the sodium citrate solution is at least so that the silver in the silver source solution is completely Reduction, keep in a boiling state for at least 40 minutes, and finally cool to room temperature to obtain the AgNPs glue solution, which is stored in the dark and low temperature.
  • a Raman spectroscopic detection method based on AgNPs/MIL-101(Fe) nanomaterial SERS substrate using the above-mentioned SERS substrate based on AgNPs/MIL-101(Fe) nanomaterial for Raman spectroscopic detection; the Raman spectroscopic detection method is specifically In order to mix the SERS substrate based on AgNPs/MIL-101(Fe) nanomaterials with the liquid to be tested uniformly, take samples to the sample carrier, and perform Raman spectrum detection after drying; in the specific detection, AgNPs/MIL- The 101(Fe) nanomaterial and the liquid to be tested were mixed at a high speed in a volume ratio of 1:2, and then 10 ⁇ L was sampled and dropped on the Raman spectrum sample carrier, and the Raman detection was performed after natural drying.
  • the Raman spectrum detection method is applied to the detection of the paraquat content in the sample to be tested, and the detection is performed in an environment with a pH value of 3-11.
  • a SERS substrate based on AgNPs/MIL-101(Fe) nanomaterial is AgNPs/MIL-101(Fe) nanomaterial, and the AgNPs/MIL-101(Fe) nanomaterial is specifically prepared by the following method:
  • the specific preparation method of AgNPs material is as follows: prepare 100mL solution of AgNO3 concentration of 18mg/mL, stir while heating, and immediately add 4mL mass fraction of 1 % trisodium citrate solution when the AgNO3 solution boils and speed up the stirring. Continue to heat for 40 minutes at the same temperature, and finally cool to room temperature to obtain the AgNPs glue solution, which is then stored at 4 °C in the dark for future use.
  • MIL-101(Fe) material is as follows: Weigh 0.675g FeCl 3 ⁇ 6H 2 O and 0.206g terephthalic acid in 15mL DMF, and accelerate the dissolution on a high-speed vortexer to form a clear transparent yellow solution, and then mix The solution was transferred to a polytetrafluoroethylene-lined stainless steel autoclave, placed in a blast drying oven at 110°C for 20 hours, cooled to room temperature, and centrifuged to obtain a yellow solid, which was washed three times with DMF and anhydrous ethanol to obtain crude product, the obtained crude product solid was stirred and activated in hot ethanol (70°C) for 3 hours, and finally the solid was obtained by centrifugation and placed in a 60°C vacuum drying oven overnight, and finally a yellow powder was obtained and stored under drying conditions at room temperature for later use.
  • the specific preparation process of AgNPs/MIL-101(Fe) nanomaterials is as follows: the obtained MIL-101(Fe) powder is dispersed in methanol solution to prepare a MIL-101(Fe) dispersion with a dispersion content of 1 mg/mL. The MIL-101(Fe) dispersion was mixed with the prepared AgNPs glue at a volume ratio of 1:1, and then mixed at a high speed on a high-speed vortexer for 5 minutes, and incubated at room temperature for 1.5 h after mixing. AgNPs/MIL-101(Fe) nanomaterials were prepared.
  • Example 2 except for the preparation of AgNPs/MIL-101(Fe) nanomaterials, the volume ratio of MIL-101(Fe) dispersion and AgNPs glue is 1:2, other process steps and parameters are the same as those in Example 1. same.
  • Example 3 except for the preparation of AgNPs/MIL-101(Fe) nanomaterials, the volume ratio of MIL-101(Fe) dispersion to AgNPs glue is 1:3, other process steps and parameters are the same as those of Example 1. same.
  • the XRD patterns of the MIL-101(Fe) nanomaterials, AgNPs materials and the final synthesized AgNPs/MIL-101(Fe) nanomaterials synthesized in the present invention are shown in FIG. 1 .
  • the main diffraction peaks of Ag nanoparticles are consistent with the published literature, which confirms the structural integrity of MIL-101(Fe) and is consistent with the reports in related literatures; Ag nanoparticles appear after the composite of MIL-101(Fe), and the crystal plane diffraction peaks of Ag appear, which Consistent with relevant literature reports, the diffraction peaks of MIL-101 did not change before and after, which indicated that as a support for Ag nanoparticles, MIL-101(Fe) crystal structure was well preserved without obvious crystal loss.
  • Figures 2 and 3 are SEM images of MIL-101(Fe) under different magnifications. From the macroscopic and microscopic observation, it can be seen that this material presents a regular octahedron, which is a MIL-101 type structure, and the surface is relatively smooth.
  • Figure 4 shows the detection results of AgNPs/MIL-101(Fe) nanomaterials on R6G in Example 1-3
  • Figures 5 to 7 show the results of AgNPs/MIL-101(Fe) nanomaterials prepared in Example 1-3 in turn.
  • 101(Fe) nanomaterials have a relatively better detection effect.
  • the AgNPs/MIL-101(Fe) nanomaterials prepared in Example 2 have better surface morphology.
  • the surface distribution of MIL-101(Fe) is more uniform; at the same time, in the surface morphology of AgNPs/MIL-101(Fe) nanomaterials prepared in Example 3, there is a problem of slight detachment of AgNPs, which also makes the AgNPs prepared in Example 3.
  • the SRES effect of the /MIL-101(Fe) nanomaterial is inferior.
  • the AgNPs/MIL-101(Fe) nanomaterials prepared in Examples 1-3 of the present invention all have good surface morphology and SRES effect, but relatively speaking, the AgNPs/MIL-101(Fe) prepared in Example 2 ) nanomaterials have relatively better Raman enhancement effects.
  • AgNPs/MIL-101(Fe) nanomaterials prepared in Example 2 were selected as the SERS substrate.
  • SERS probe molecules Four common SERS probe molecules, rhodamine 6G, crystal violet, 4-mercaptobenzoic acid, and 5,5'-dithiobis(2-nitrobenzoic acid), were selected. 10 -6 M) of SERS probe molecules to preliminarily evaluate the SERS enhancement effect of the AgNPs/MIL-101(Fe) nanocomposites prepared in Example 2, using Ag nanosols with a particle size of about 30 nm and pure MIL-101(Fe) dispersion was used as reference.
  • Fig. 8-a shows Rhodamine 6G as SERS probe molecule
  • Fig. 8-b shows crystal violet as SERS probe molecule
  • Fig. 8-c shows 4-mercaptobenzoic acid as SERS probe molecule
  • Fig. 8-d is 5,5'-dithiobis(2-nitrobenzoic acid) as the SERS probe molecule
  • the low concentration SERS probe molecule (1 ⁇ 10 -6 M) and AgNPs/MIL-101 (Fe )
  • the SERS probe molecule has almost no Raman signal on pure MIL-101(Fe); this result shows that AgNPs and After MIL-101(Fe) is compounded, due to the strong adsorption of MIL-101(Fe), the analyte is adsorbed and aggregated and its surface plasmon coupling effect with AgNPs, so its Raman signal is significantly enhanced; and we choose 1 ⁇ 10 -6 M R6G 1646cm -1 characteristic peak, compared with the single Ag nanosol, it is found that its Raman signal is enhanced by about 10 times, and the corresponding EF calculation is carried out, the EF of 1 ⁇ 10 -6 M R6G can be calculated. The value is 2.09 ⁇ 10 9 .
  • the reproducibility of surface-enhanced Raman spectroscopy detection signals is also an important factor in examining the application performance of SERS substrates.
  • the SERS signal reproducibility of AgNPs/MIL-101(Fe)) nanocomposites was estimated from the relative standard deviation (RSD) value of the main Raman signal of the R6G molecule at a concentration of 1 ⁇ 10 -6 M. As shown in Fig. 9-a, 20 points were randomly selected from this independent substrate for testing, thereby obtaining 1 ⁇ 10 -6 M SERS spectral detection signals of R6G, and superimposing them.
  • the signal intensity of one of the characteristic peaks is selected for histogram analysis (as shown in Figure 9-b), and the calculated RSD is 7.55%, which is less than 15%; therefore, it can be shown that AgNPs/MIL-101(Fe) nanocomposite as a detection substrate has Good detection signal reproducibility.
  • AgNPs and MIL-101(Fe) are synthesized by the simplest physical self-assembly method to obtain SERS-based AgNPs/MIL-101(Fe) nanomaterials, and four kinds of low-concentration probe molecules are detected. Strong enhancement effect.
  • RSD Raman assigned peak position
  • EF enhancement factor EF

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Abstract

An SERS substrate, and a Raman spectrum detection method based on a AgNPs/MIL-101 (Fe) nano material-based SERS substrate and an application thereof in measuring the content of paraquat in a sample under test. The SERS substrate comprises an AgNPs/MIL-101 (Fe) nano material; the AgNPs/MIL-101 (Fe) nano material is prepared from a AgNPs material and an MIL-101 (Fe) material by means of a physical self-assembly method. The Raman spectrum detection method based on a AgNPs/MIL-101 (Fe) nano material-based SERS substrate has high sensitivity and a lower limit of detection, rhodamine 6G is detected and the EF value of 10-6 mol/L of rhodamine 6G is calculated to be 2.09×109, and the Raman attribution peak intensity RSD of rhodamine 6G is 7.55%; paraquat is detected and upon detection, the lowest concentration of paraquat is 10-12 mol/L, 10-6 mol/L of paraquat and the substrate are combined in different pH values for Raman signal detection comparison, the Raman signal value of paraquat is relatively stable, and paraquat can be detected in the environment having the pH value of 3-11.

Description

一种SERS基底的制备方法、SERS基底及其应用A kind of preparation method of SERS substrate, SERS substrate and application thereof 技术领域technical field
本发明属于拉曼光谱检测技术领域，尤其是涉及一种基于AgNPs/MIL-101(Fe)纳米材料SERS基底的制备方法、SERS基底及应用。The invention belongs to the technical field of Raman spectrum detection, and in particular relates to a preparation method, SERS substrate and application of a SERS substrate based on AgNPs/MIL-101(Fe) nanomaterials.
背景技术Background technique
表面增强拉曼散射(SERS)是在普通拉曼散射的基础上发展起来的一种技术。众所周知，表面增强拉曼光谱(SERS)是一门快速无损检测的光谱技术，具有高灵敏度、高准确度、指纹光谱以及不受水分子干扰等特点，可以实现单分子的检测。随着激光技术的迅速发展和纳米材料制备技术的日益成熟，SERS不仅在单晶表面分子吸附、化学反应机理以及生物体内细胞行为等科学研究中发挥重要作用，也越来越多的在食品安全、环境污染化学武器和艺术品鉴定等实际生活中得到广泛应用。Surface-enhanced Raman scattering (SERS) is a technique developed on the basis of ordinary Raman scattering. As we all know, surface-enhanced Raman spectroscopy (SERS) is a fast and non-destructive spectroscopy technique, which has the characteristics of high sensitivity, high accuracy, fingerprint spectroscopy, and no interference from water molecules, which can realize the detection of single molecules. With the rapid development of laser technology and the growing maturity of nanomaterial preparation technology, SERS not only plays an important role in scientific research such as single crystal surface molecular adsorption, chemical reaction mechanism, and in vivo cell behavior, but also plays an increasingly important role in food safety. It has been widely used in real life, such as environmental pollution chemical weapons and artwork identification.
目前学术界普遍认同的SERS机理主要有物理增强机理和化学增强机理两类：物理增强模式即电磁场增强(Electromagnetic Mechanis,EM)和化学增强模式即电荷转移增强(Charge Transfer,CT)。电磁场机理是一种物理模型，它认为SERS效应起源于金属表面局域电场的增强。电磁场增强机理的模型主要有以下三种表面等离子体共振模型(SPR)、天线共振子模型和镜像场模型，其中表面等离子体共振(SPR)增强机理被认为是电磁场增强的最主要贡献者，这种机理认为粗糙的贵金属表面受到激光照射时，表面的等离子体可以被激发到较高的能级并与光波电场耦合产生共振，使金属表面的电场增强，由于拉曼散射的强度和所处光电场的强度的平方成正比，因此使得拉曼散射效应也极大增强。化学增强主要包括以下三种机理：由于吸附物和金属基底的化学成键导致非共振增强；由于吸附分子和表面吸附原子形成表面络合物而导致的共振增强；激发光对分子-金属体系的光诱导电荷转移的类共振增强。At present, the SERS mechanism generally recognized by the academic community mainly includes two types: physical enhancement mechanism and chemical enhancement mechanism: the physical enhancement mode is Electromagnetic Mechanis (EM) and the chemical enhancement mode is Charge Transfer enhancement (CT). The electromagnetic field mechanism is a physical model that believes that the SERS effect originates from the enhancement of the localized electric field on the metal surface. The models of electromagnetic field enhancement mechanisms mainly include the following three surface plasmon resonance models (SPR), antenna resonator sub-models and mirror field models. Among them, the surface plasmon resonance (SPR) enhancement mechanism is considered to be the most important contributor to electromagnetic field enhancement. This mechanism believes that when the rough precious metal surface is irradiated by laser, the surface plasmon can be excited to a higher energy level and resonate with the light wave electric field coupling, so that the electric field on the metal surface is enhanced. The intensity of the field is proportional to the square of the square, so the Raman scattering effect is also greatly enhanced. Chemical enhancement mainly includes the following three mechanisms: off-resonance enhancement due to chemical bonding between adsorbates and metal substrates; resonance enhancement due to the formation of surface complexes between adsorbed molecules and surface adatoms; excitation light on the molecule-metal system. Resonance-like enhancement of light-induced charge transfer.
MOFs是金属有机骨架化合物(英文名称Metal organic Frameworks)的简称。是由无机金属中心(金属离子或金属簇)与桥连的有机配体通过自组装相互连接，形成的一类具有周期性网络结构的晶态多孔材料,它既不同于无机多孔材料，也不同于一般的有机配合物，兼有无机材料的刚性和有机材料的柔性特征，使其在现代材料研究方面呈现出巨大的发展潜力和诱人的发展前景。MOFs具有多孔、大比表面积和多金属位点等诸多性能，因此在化学化工领域得到许多应用，例如气体贮存、分子分离、催化和药物缓释等。正因MOFs的独特特点，有研究者将此材料应用拓展到SERS领域，更加丰富MOFs材料的应用前景。MOFs is the abbreviation of metal organic framework compounds (English name Metal organic Frameworks). It is a class of crystalline porous materials with periodic network structure formed by inorganic metal centers (metal ions or metal clusters) and bridged organic ligands connected to each other through self-assembly. It is not only different from inorganic porous materials, but also different. Compared with general organic complexes, it has both the rigidity of inorganic materials and the flexibility of organic materials, which makes it show great development potential and attractive development prospects in modern materials research. MOFs have many properties such as porosity, large specific surface area, and multi-metallic sites, so they have many applications in chemical and chemical fields, such as gas storage, molecular separation, catalysis, and sustained drug release. Because of the unique characteristics of MOFs, some researchers have extended the application of this material to the field of SERS, enriching the application prospects of MOFs.
2017年曹小林等人采用溶液浸渍将金属原位还原包埋在MOF中所制备得到多种 AuNPs/MOFs的SERS活性材料，这些新型复合材料具有较高的灵敏度、稳定性和重现性，为利用SERS技术检测农药提供了一条新的途径开题报告里面有引入。但此制备方法由于原位还原不能控制金属粒子的尺寸和形貌，导致实现SERS性能优化比较困难。2018年杨海飞等人通过层层组装成功合成了核-壳型金纳米颗粒，其检测六亚甲基四胺的检测限为10 -8M。这种方式的缺陷在于金属粒子间距不易控制，达不到“热点”最佳状态。 In 2017, Cao Xiaolin et al. prepared a variety of SERS active materials of AuNPs/MOFs by in situ reduction and embedding of metals in MOF by solution impregnation. The use of SERS technology to detect pesticides provides a new approach which was introduced in the opening report. However, this preparation method cannot control the size and morphology of metal particles due to the in-situ reduction, which makes it difficult to optimize the SERS performance. In 2018, Yang Haifei et al. successfully synthesized core-shell gold nanoparticles through layer-by-layer assembly, and the detection limit of hexamethylenetetramine was 10 -8 M. The disadvantage of this method is that the distance between metal particles is not easy to control, and the optimal state of "hot spot" cannot be achieved.
2018年曹晓伟课题组同样采取溶液浸渍还原法制备AgNPs/MIL-101(Cr)纳米复合材料，用其作为SERS基底，在水溶液中进行超痕量葡萄糖的SERS光谱分析，其检测限约为10 -14M。其研究中制备MIL-101(Cr)晶型较为难控制，并且Cr是有毒物质，对环境有一定的影响。 In 2018, Xiaowei Cao's group also adopted the solution immersion reduction method to prepare AgNPs/MIL-101(Cr) nanocomposites, and used it as a SERS substrate to perform SERS spectral analysis of ultra-trace glucose in aqueous solution, and the detection limit was about 10 - 14 M. In his research, it is difficult to control the preparation of MIL-101 (Cr) crystal form, and Cr is a toxic substance, which has a certain impact on the environment.
发明内容SUMMARY OF THE INVENTION
为解决现有技术中所采用的MOFs材料合成及性能优化难度大，无法控制金属离子微观形貌的问题，同时采用MOFs材料作为SERS基底材料时检测灵敏度不高等问题；为实现优化作为SERS基底材料的MOFs材料的合成过程及相应性能，降低SERS过程中的检测限，本发明提供了一种基于AgNPs/MIL-101(Fe)纳米材料SERS基底的制备方法；In order to solve the problem that the synthesis and performance optimization of MOFs materials used in the prior art are difficult, and the microscopic morphology of metal ions cannot be controlled, and the detection sensitivity is low when using MOFs materials as SERS substrate materials; in order to achieve optimization as SERS substrate materials The synthesis process and corresponding properties of the MOFs material are provided, and the detection limit in the SERS process is reduced, and the invention provides a preparation method based on the AgNPs/MIL-101(Fe) nanomaterial SERS substrate;
本发明提供给了一种由上述制备方法制备的基于AgNPs/MIL-101(Fe)纳米材料SERS基底；The present invention provides a SERS substrate based on AgNPs/MIL-101(Fe) nanomaterials prepared by the above preparation method;
本发明还提供了一种基于AgNPs/MIL-101(Fe)纳米材料SERS基底的拉曼光谱检测方法及其应用。The invention also provides a Raman spectrum detection method based on the AgNPs/MIL-101(Fe) nano-material SERS substrate and its application.
为实现上述目的，本发明采用的技术方案如下：For achieving the above object, the technical scheme adopted in the present invention is as follows:
一种基于AgNPs/MIL-101(Fe)纳米材料SERS基底的制备方法，A preparation method based on AgNPs/MIL-101(Fe) nanomaterial SERS substrate,
所述基于AgNPs/MIL-101(Fe)纳米材料SERS基底包括AgNPs/MIL-101(Fe)纳米材料；The SERS substrate based on AgNPs/MIL-101(Fe) nanomaterials includes AgNPs/MIL-101(Fe) nanomaterials;
所述AgNPs/MIL-101(Fe)纳米材料通过AgNPs材料与MIL-101(Fe)材料通过物理自组装方法制得；The AgNPs/MIL-101(Fe) nanomaterial is prepared by a physical self-assembly method between the AgNPs material and the MIL-101(Fe) material;
具体为，将所述MIL-101(Fe)材料分散于分散剂中制得MIL-101(Fe)分散液，然后将所述MIL-101(Fe)分散液与所述AgNPs材料混合均匀，混合后室温下孵育制得所述AgNPs/MIL-101(Fe)纳米材料。Specifically, the MIL-101(Fe) material is dispersed in a dispersant to prepare a MIL-101(Fe) dispersion, and then the MIL-101(Fe) dispersion is uniformly mixed with the AgNPs material, and mixed After incubation at room temperature, the AgNPs/MIL-101(Fe) nanomaterials were prepared.
作为优选，所述AgNPs材料为AgNPs胶液，所述MIL-101(Fe)分散液与所述AgNPs胶液的体积比为1：(1-3)。Preferably, the AgNPs material is AgNPs glue, and the volume ratio of the MIL-101(Fe) dispersion to the AgNPs glue is 1:(1-3).
作为优选，所述分散剂为甲醇，所述MIL-101(Fe)材料分散于所述分散剂中制得0.8-1.2mg/mL的MIL-101(Fe)分散液。Preferably, the dispersant is methanol, and the MIL-101(Fe) material is dispersed in the dispersant to obtain a MIL-101(Fe) dispersion of 0.8-1.2 mg/mL.
所述AgNPs/MIL-101(Fe)纳米材料的具体过程为，将MIL-101(Fe)材料分散于所述分散剂中制得0.8-1.2mg/mL的MIL-101(Fe)分散液，然后将MIL-101(Fe)分散液与AgNPs胶液混合，两者体积比为1：(1-3)，然后进行高速混合，混合后在室温下孵育1.3-2小时，制得AgNPs/MIL- 101(Fe)纳米材料。The specific process of the AgNPs/MIL-101(Fe) nanomaterial is as follows: dispersing the MIL-101(Fe) material in the dispersant to obtain a 0.8-1.2 mg/mL MIL-101(Fe) dispersion, Then, the MIL-101(Fe) dispersion was mixed with the AgNPs glue, the volume ratio of the two was 1:(1-3), and then mixed at a high speed, and then incubated at room temperature for 1.3-2 hours to obtain AgNPs/MIL - 101(Fe) nanomaterials.
所述AgNPs/MIL-101(Fe)纳米材料中，银原子与铁原子的摩尔比为1：(4-13)。In the AgNPs/MIL-101(Fe) nanomaterial, the molar ratio of silver atoms to iron atoms is 1:(4-13).
作为优选，所述MIL-101(Fe)材料由以下方法制得，取铁源和对苯二甲酸溶解于溶剂中，然后采用溶剂热合成法处理，冷却后并洗涤处理得粗产品，将所述粗产品活化处理并干燥后得到所述MIL-101(Fe)材料。Preferably, the MIL-101(Fe) material is prepared by the following method. The iron source and terephthalic acid are dissolved in a solvent, and then treated by a solvothermal synthesis method. After cooling and washing, the crude product is obtained. The MIL-101(Fe) material is obtained after the crude product is activated and dried.
作为优选，所述对苯二甲酸与所述铁源中铁离子的摩尔比为(1-1.3)：2.45。Preferably, the molar ratio of the terephthalic acid to the iron ions in the iron source is (1-1.3):2.45.
作为优选，所述溶剂为DMF，所述铁源为氯化铁或六水氯化铁。Preferably, the solvent is DMF, and the iron source is ferric chloride or ferric chloride hexahydrate.
所述MIL-101(Fe)材料的具体制备过程为，将氯化铁与对苯二甲酸加入到足量DMF中，然后溶解生成透明溶液，将该透明溶液置于高压反应釜中，在100-130℃处理18-30小时，冷却至室温后离心得到固体，再将该固体用DMF和污水乙醇洗涤多次使其中的杂质完全清除得到粗产品，将粗产品于不低于70℃的热乙醇中活化处理至少2.5小时，离心得到活化固体并干燥，得MIL-101(Fe)材料。The specific preparation process of the MIL-101 (Fe) material is as follows, adding ferric chloride and terephthalic acid into a sufficient amount of DMF, then dissolving to generate a transparent solution, placing the transparent solution in an autoclave, and at 100 °C. -130°C for 18-30 hours, cooled to room temperature and centrifuged to obtain a solid, then the solid was washed with DMF and sewage ethanol for several times to completely remove impurities in it to obtain a crude product, and the crude product was heated at a temperature of not lower than 70°C. Activated in ethanol for at least 2.5 hours, centrifuged to obtain an activated solid and dried to obtain MIL-101(Fe) material.
作为优选，所述AgNPs胶液由以下方法制得，取银源溶液并将银源溶液加热至沸腾，向所述银源溶液中加入柠檬酸钠溶液并混合，继续加热一段时间，之后冷却至室温得AgNPs胶液。Preferably, the AgNPs glue solution is prepared by the following method, taking the silver source solution and heating the silver source solution to boiling, adding sodium citrate solution to the silver source solution and mixing, continuing to heat for a period of time, and then cooling to AgNPs glue solution was obtained at room temperature.
作为优选，所述柠檬酸钠溶液的添加量至少为使所述银源溶液中银被完全还原。Preferably, the added amount of the sodium citrate solution is at least such that the silver in the silver source solution is completely reduced.
作为优选，所述银源溶液为硝酸银溶液。Preferably, the silver source solution is a silver nitrate solution.
所述AgNPs胶液得具体制备过程为，将硝酸银溶液加热，硝酸银溶液沸腾时向其中快速加入柠檬酸钠溶液并快速搅拌，保持沸腾状态至少40分钟，最后冷却至室温得AgNPs胶液，AgNPs胶液避光低温保存。The specific preparation process of the AgNPs glue solution is as follows: the silver nitrate solution is heated, and the sodium citrate solution is rapidly added to the silver nitrate solution when the silver nitrate solution is boiled and stirred rapidly, and the AgNPs glue solution is kept in a boiling state for at least 40 minutes, and finally cooled to room temperature to obtain the AgNPs glue solution, The AgNPs glue solution was stored at low temperature in the dark.
一种基于AgNPs/MIL-101(Fe)纳米材料的SERS基底，其由上述基于AgNPs/MIL-101(Fe)纳米材料SERS基底的制备方法制得。A SERS substrate based on AgNPs/MIL-101(Fe) nanomaterials is prepared by the above-mentioned preparation method based on AgNPs/MIL-101(Fe) nanomaterials SERS substrates.
一种基于AgNPs/MIL-101(Fe)纳米材料SERS基底的拉曼光谱检测方法，采用上述基于AgNPs/MIL-101(Fe)纳米材料的SERS基底进行拉曼光谱检测。A Raman spectroscopic detection method based on AgNPs/MIL-101 (Fe) nanomaterial SERS substrate, using the above-mentioned SERS substrate based on AgNPs/MIL-101 (Fe) nanomaterial for Raman spectroscopic detection.
作为优选，拉曼光谱检测方法具体为，将所述基于AgNPs/MIL-101(Fe)纳米材料的SERS基底与待测液混合均匀后，取样至载样器，干燥后进行拉曼光谱检测。Preferably, the Raman spectroscopic detection method is as follows: after the AgNPs/MIL-101(Fe) nanomaterial-based SERS substrate is evenly mixed with the liquid to be tested, sampling is performed on a sample carrier, and Raman spectroscopic detection is performed after drying.
具体检测时，将AgNPs/MIL-101(Fe)纳米材料与待测液按体积比1：2进行高速混合，然后取样10μL滴在拉曼光谱载样器上，待自然干燥后进行拉曼检测。During the specific detection, the AgNPs/MIL-101(Fe) nanomaterial and the liquid to be tested are mixed at a high speed in a volume ratio of 1:2, and then 10 μL is sampled and dropped on the Raman spectrum sample carrier, and the Raman detection is performed after natural drying. .
一种所述拉曼光谱检测方法的应用，将所述拉曼光谱检测方法应用于pH值为3-11环境下待测样品中百草枯的测定An application of the Raman spectrum detection method, the Raman spectrum detection method is applied to the determination of paraquat in a sample to be tested in an environment with a pH value of 3-11
因此，本发明具有以下有益效果：Therefore, the present invention has the following beneficial effects:
本发明中的基于AgNPs/MIL-101(Fe)纳米材料SERS基底的拉曼光谱检测方法具有高的敏感度和更低的检测限，对罗丹明6G进行检测并计算10 -6mol/L R6G的EF数值为2.09×10 9，在此研究并计算R6G拉曼归属峰强RSD＝7.55％；对百草枯进行检测，其检测最低浓度为10 -12mol/L，并将10 -6mol/L百草枯与此基底结合在不同pH中进行拉曼信号检测对比，其拉曼信号值相对稳定，在pH＝3-11的环境下均可进行百草枯的检测。 The Raman spectroscopic detection method based on AgNPs/MIL-101(Fe) nanomaterial SERS substrate in the present invention has high sensitivity and lower detection limit, detects rhodamine 6G and calculates 10 -6 mol/L R6G The EF value of paraquat is 2.09×10 9 , and the R6G Raman assigned peak intensity RSD=7.55% is studied and calculated here; the detection of paraquat, its lowest concentration is 10 -12 mol/L, and 10 -6 mol/ The Raman signal value of L paraquat combined with this substrate was compared at different pH, and the Raman signal value was relatively stable, and paraquat could be detected in the environment of pH=3-11.
附图说明Description of drawings
图1为本发明实施例2中MIL-101(Fe)纳米材料、AgNPs材料及最终合成的AgNPs/MIL-101(Fe)纳米材料的XRD谱图；Fig. 1 is the XRD spectrum of MIL-101(Fe) nanomaterial, AgNPs material and finally synthesized AgNPs/MIL-101(Fe) nanomaterial in Example 2 of the present invention;
图2为本发明实施例2制得MIL-101(Fe)纳米材料的100000倍电镜照片；2 is a 100,000 times electron microscope photo of the MIL-101(Fe) nanomaterial prepared in Example 2 of the present invention;
图3为本发明实施例2制得MIL-101(Fe)纳米材料的500000倍电镜照片；3 is a 500,000 times electron microscope photo of the MIL-101(Fe) nanomaterial prepared in Example 2 of the present invention;
图4为为实施例1-3制得AgNPs/MIL-101(Fe)纳米材料对R6G的检测结果；图中由上至下分别为实施例2、实施例3和实施例1中制得AgNPs/MIL-101(Fe)纳米材料对R6G的检测结果；Figure 4 shows the detection results of AgNPs/MIL-101(Fe) nanomaterials prepared in Examples 1-3 for R6G; the figures from top to bottom are the AgNPs prepared in Example 2, Example 3 and Example 1, respectively. / MIL-101(Fe) nanomaterials test results for R6G;
图5为实施例1制得AgNPs/MIL-101(Fe)纳米材料的扫描电镜图；5 is a scanning electron microscope image of AgNPs/MIL-101(Fe) nanomaterials prepared in Example 1;
图6为实施例2制得AgNPs/MIL-101(Fe)纳米材料的扫描电镜图；6 is a scanning electron microscope image of AgNPs/MIL-101(Fe) nanomaterials prepared in Example 2;
图7为实施例3制得AgNPs/MIL-101(Fe)纳米材料的扫描电镜图；7 is a scanning electron microscope image of AgNPs/MIL-101(Fe) nanomaterials prepared in Example 3;
图8为针对实施例2制得AgNPs/MIL-101(Fe)纳米材料采用四种不同常见的SERS探针分子的拉曼检测结果图，其中图8-a为罗丹明6G作为SERS探针分子，图8-b为结晶紫作为SERS探针分子，图8-c为4-巯基苯甲酸作为SERS探针分子，图8-d为5,5'-二硫代双(2-硝基苯甲酸)作为SERS探针分子；图8-a、图8-b、图8-c和图8-d中曲线由上至下分别为AgNPs/MIL-101(Fe)纳米材料、AgNPs材料和MIL-101(Fe)材料的拉曼检测曲线；Figure 8 is a graph showing the Raman detection results of four different common SERS probe molecules for AgNPs/MIL-101(Fe) nanomaterials prepared in Example 2, in which Figure 8-a shows Rhodamine 6G as the SERS probe molecule , Figure 8-b shows crystal violet as SERS probe molecule, Figure 8-c shows 4-mercaptobenzoic acid as SERS probe molecule, Figure 8-d shows 5,5'-dithiobis(2-nitrobenzene) Formic acid) as the SERS probe molecule; the curves in Figure 8-a, Figure 8-b, Figure 8-c and Figure 8-d are AgNPs/MIL-101(Fe) nanomaterials, AgNPs materials and MIL from top to bottom, respectively Raman detection curve of -101(Fe) material;
图9为AgNPs/MIL-101(Fe)纳米材料SERS信号重现性的检测结果图；其中，图9-a为针对实施例2制得AgNPs/MIL-101(Fe)纳米材料采用罗丹明6G作为SERS探针分子的拉曼检测重现性结果图，图9-b为针对实施例2制得AgNPs/MIL-101(Fe)纳米材料采用罗丹明6G作为SERS探针分子的拉曼检测特征峰信号强度柱状图分析图；Fig. 9 is a graph showing the detection result of the SERS signal reproducibility of AgNPs/MIL-101(Fe) nanomaterials; wherein, Fig. 9-a shows the AgNPs/MIL-101(Fe) nanomaterials obtained in Example 2 using Rhodamine 6G As the Raman detection reproducibility results of SERS probe molecules, Figure 9-b shows the Raman detection characteristics of AgNPs/MIL-101(Fe) nanomaterials prepared in Example 2 using rhodamine 6G as SERS probe molecules Peak signal intensity histogram analysis chart;
图10为AgNPs/MIL-101(Fe)纳米材料作为SERS基底对百草枯的检测结果图；其中，图10-a其不同百草枯浓度下拉曼检测谱图，如图10-b所示为百草枯浓度为10 -12M的拉曼检测谱图，图10-c为不同pH值条件下检测浓度为10 -6M百草枯的拉曼检测谱图，图10-d为不同pH值条件下检测浓度为10 -6M百草枯在1650cm -1处的拉曼检测结果柱状图。 Figure 10 shows the detection results of paraquat using AgNPs/MIL-101(Fe) nanomaterials as a SERS substrate; among them, Figure 10-a shows the Laman detection spectrum of different paraquat concentrations, and Figure 10-b shows the paraquat The Raman detection spectrum of paraquat at a concentration of 10 -12 M, Figure 10-c is the Raman detection spectrum of paraquat at a concentration of 10 -6 M under different pH conditions, and Figure 10-d is under different pH conditions Histogram of Raman detection results of paraquat at 1650cm -1 at the detection concentration of 10 -6 M.
具体实施方式Detailed ways
下面结合具体实施方式对本发明的技术方案作进一步的说明。The technical solutions of the present invention will be further described below in conjunction with specific embodiments.
显然，所描述的实施例仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。Obviously, the described embodiments are only some, but not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
在本发明中，若非特指，所有的设备和原料均可从市场上购得或是本行业常用的，下述实施例中的方法，如无特别说明，均为本领域常规方法。In the present invention, unless otherwise specified, all equipment and raw materials can be purchased from the market or are commonly used in the industry. The methods in the following examples are conventional methods in the art unless otherwise specified.
总实施例General Example
一种基于AgNPs/MIL-101(Fe)纳米材料的SERS基底，SERS基底为AgNPs/MIL-101(Fe)纳米材料，AgNPs/MIL-101(Fe)纳米材料中，银原子与铁原子的摩尔比为1：(4-13)；A SERS substrate based on AgNPs/MIL-101(Fe) nanomaterials, the SERS substrate is AgNPs/MIL-101(Fe) nanomaterials, and in the AgNPs/MIL-101(Fe) nanomaterials, the moles of silver atoms and iron atoms are The ratio is 1:(4-13);
AgNPs/MIL-101(Fe)纳米材料由AgNPs胶液与MIL-101(Fe)材料通过物理自组装方法制得，AgNPs/MIL-101(Fe) nanomaterials are prepared from AgNPs glue and MIL-101(Fe) material by physical self-assembly method.
AgNPs/MIL-101(Fe)纳米材料制备的具体过程为，将MIL-101(Fe)材料分散于甲醇中制得0.8-1.2mg/mL的MIL-101(Fe)分散液，然后将MIL-101(Fe)分散液与AgNPs胶液混合，两者体积比为1：(1-3)，然后进行高速混合，混合后在室温下孵育1.3-2小时，制得AgNPs/MIL-101(Fe)纳米材料。The specific preparation process of AgNPs/MIL-101(Fe) nanomaterials is as follows: MIL-101(Fe) materials are dispersed in methanol to obtain 0.8-1.2 mg/mL MIL-101(Fe) dispersions, and then MIL-101(Fe) dispersions are prepared. The 101(Fe) dispersion was mixed with the AgNPs glue at a volume ratio of 1:(1-3), then mixed at high speed, and incubated at room temperature for 1.3-2 hours to obtain AgNPs/MIL-101(Fe) )nanomaterials.
MIL-101(Fe)材料的具体制备过程为，将氯化铁与对苯二甲酸加入到足量DMF中，对苯二甲酸与铁源中铁离子的摩尔比为(1-1.3)：2.45，然后溶解生成透明溶液，将该透明溶液置于高压反应釜中，采用溶剂热合成法在100-130℃处理18-30小时，冷却至室温后离心得到固体，再将该固体用DMF和污水乙醇洗涤多次使其中的杂质完全清除得到粗产品，将粗产品于不低于70℃的热乙醇中活化处理至少2.5小时，离心得到活化固体并干燥，得MIL-101(Fe)材料；The specific preparation process of the MIL-101(Fe) material is as follows, adding ferric chloride and terephthalic acid into a sufficient amount of DMF, and the molar ratio of terephthalic acid and iron ions in the iron source is (1-1.3): 2.45, Then dissolve to generate a transparent solution, which is placed in an autoclave, treated by solvothermal synthesis at 100-130 ° C for 18-30 hours, cooled to room temperature and centrifuged to obtain a solid, and then the solid is treated with DMF and sewage ethanol Washing for several times to completely remove impurities in the crude product, the crude product is activated in hot ethanol at a temperature of not lower than 70°C for at least 2.5 hours, centrifuged to obtain an activated solid and dried to obtain MIL-101(Fe) material;
AgNPs胶液得具体制备过程为，将硝酸银溶液加热，硝酸银溶液沸腾时向其中快速加入柠檬酸钠溶液并快速搅拌，柠檬酸钠溶液的添加量至少为使所述银源溶液中银被完全还原，保持沸腾状态至少40分钟，最后冷却至室温得AgNPs胶液，AgNPs胶液避光低温保存。The specific preparation process of the AgNPs glue solution is as follows: heating the silver nitrate solution, rapidly adding sodium citrate solution to it when the silver nitrate solution boils and stirring rapidly, and the addition amount of the sodium citrate solution is at least so that the silver in the silver source solution is completely Reduction, keep in a boiling state for at least 40 minutes, and finally cool to room temperature to obtain the AgNPs glue solution, which is stored in the dark and low temperature.
一种基于AgNPs/MIL-101(Fe)纳米材料SERS基底的拉曼光谱检测方法，采用上述基于AgNPs/MIL-101(Fe)纳米材料的SERS基底进行拉曼光谱检测；拉曼光谱检测方法具体为，将所述基于AgNPs/MIL-101(Fe)纳米材料的SERS基底与待测液混合均匀后，取样至载样器，干燥后进行拉曼光谱检测；具体检测时，将AgNPs/MIL-101(Fe)纳米材料与待测液按体积比1：2进行高速混合，然后取样10μL滴在拉曼光谱载样器上，待自然干燥后进行拉曼检测。A Raman spectroscopic detection method based on AgNPs/MIL-101(Fe) nanomaterial SERS substrate, using the above-mentioned SERS substrate based on AgNPs/MIL-101(Fe) nanomaterial for Raman spectroscopic detection; the Raman spectroscopic detection method is specifically In order to mix the SERS substrate based on AgNPs/MIL-101(Fe) nanomaterials with the liquid to be tested uniformly, take samples to the sample carrier, and perform Raman spectrum detection after drying; in the specific detection, AgNPs/MIL- The 101(Fe) nanomaterial and the liquid to be tested were mixed at a high speed in a volume ratio of 1:2, and then 10 μL was sampled and dropped on the Raman spectrum sample carrier, and the Raman detection was performed after natural drying.
一种所述拉曼光谱检测方法的应用，将所述拉曼光谱检测方法应用于检测待测样品中百草枯含量，检测在pH值为3-11环境下进行。An application of the Raman spectrum detection method, the Raman spectrum detection method is applied to the detection of the paraquat content in the sample to be tested, and the detection is performed in an environment with a pH value of 3-11.
实施例1Example 1
一种基于AgNPs/MIL-101(Fe)纳米材料的SERS基底，SERS基底为AgNPs/MIL-101(Fe)纳米材料，AgNPs/MIL-101(Fe)纳米材料具体由以下方法制得：A SERS substrate based on AgNPs/MIL-101(Fe) nanomaterial, the SERS substrate is AgNPs/MIL-101(Fe) nanomaterial, and the AgNPs/MIL-101(Fe) nanomaterial is specifically prepared by the following method:
AgNPs材料具体制备方法如下：配制AgNO 3浓度为18mg/mL的100mL溶液，边加热边搅拌，等到AgNO 3溶液沸腾时立刻加入4mL质量分数为1％的柠檬酸三钠溶液并且加快搅拌，在此温度下继续加热40分钟，最后冷却到室温制得AgNPs胶液，之后避光在4℃下保存备用。 The specific preparation method of AgNPs material is as follows: prepare 100mL solution of AgNO3 concentration of 18mg/mL, stir while heating, and immediately add 4mL mass fraction of 1 % trisodium citrate solution when the AgNO3 solution boils and speed up the stirring. Continue to heat for 40 minutes at the same temperature, and finally cool to room temperature to obtain the AgNPs glue solution, which is then stored at 4 °C in the dark for future use.
MIL-101(Fe)材料的具体制备过程如下：称取0.675gFeCl 3·6H 2O和0.206g对苯二甲酸于15mLDMF中，并在高速漩涡器上加速溶解形成澄清的透明黄色溶液，然后将此溶液转移到聚四氟乙烯内衬不锈钢高压反应釜中，在110℃鼓风干燥箱中放置20小时，冷却至室温以后，离心得到黄色固体，再用DMF和无水乙醇分别洗涤三次得到粗产品，将得到的粗产品固体于热乙醇(70℃)中搅拌活化3小时，最后离心得到固体在60℃真空干燥箱中放置过夜，最后得到黄色粉末在室温干燥条件下保存备用。 The specific preparation process of MIL-101(Fe) material is as follows: Weigh 0.675g FeCl 3 ·6H 2 O and 0.206g terephthalic acid in 15mL DMF, and accelerate the dissolution on a high-speed vortexer to form a clear transparent yellow solution, and then mix The solution was transferred to a polytetrafluoroethylene-lined stainless steel autoclave, placed in a blast drying oven at 110°C for 20 hours, cooled to room temperature, and centrifuged to obtain a yellow solid, which was washed three times with DMF and anhydrous ethanol to obtain crude product, the obtained crude product solid was stirred and activated in hot ethanol (70°C) for 3 hours, and finally the solid was obtained by centrifugation and placed in a 60°C vacuum drying oven overnight, and finally a yellow powder was obtained and stored under drying conditions at room temperature for later use.
AgNPs/MIL-101(Fe)纳米材料制备的具体过程为，将得到的MIL-101(Fe)粉末分散于甲醇溶液中，配制分散液含量为1mg/mL的MIL-101(Fe)分散液。将MIL-101(Fe)分散液与所制备好的AgNPs胶液进行混合，其体积比分别为1:1，然后在高速漩涡器上进行5分钟高速混合，混合后在室温下孵育1.5h，制得AgNPs/MIL-101(Fe)纳米材料。The specific preparation process of AgNPs/MIL-101(Fe) nanomaterials is as follows: the obtained MIL-101(Fe) powder is dispersed in methanol solution to prepare a MIL-101(Fe) dispersion with a dispersion content of 1 mg/mL. The MIL-101(Fe) dispersion was mixed with the prepared AgNPs glue at a volume ratio of 1:1, and then mixed at a high speed on a high-speed vortexer for 5 minutes, and incubated at room temperature for 1.5 h after mixing. AgNPs/MIL-101(Fe) nanomaterials were prepared.
实施例2Example 2
实施例2中除了AgNPs/MIL-101(Fe)纳米材料制备制备时，MIL-101(Fe)分散液与AgNPs胶液的体积比为1：2外，其他工艺步骤及参数都与实施例1相同。In Example 2, except for the preparation of AgNPs/MIL-101(Fe) nanomaterials, the volume ratio of MIL-101(Fe) dispersion and AgNPs glue is 1:2, other process steps and parameters are the same as those in Example 1. same.
实施例3Example 3
实施例3中除了AgNPs/MIL-101(Fe)纳米材料制备制备时，MIL-101(Fe)分散液与AgNPs胶液的体积比为1：3外，其他工艺步骤及参数都与实施例1相同。In Example 3, except for the preparation of AgNPs/MIL-101(Fe) nanomaterials, the volume ratio of MIL-101(Fe) dispersion to AgNPs glue is 1:3, other process steps and parameters are the same as those of Example 1. same.
效果表征Effect representation
1.AgNPs/MIL-101(Fe)纳米材料的表征：1. Characterization of AgNPs/MIL-101(Fe) nanomaterials:
本发明中所合成的MIL-101(Fe)纳米材料、AgNPs材料及最终合成的AgNPs/MIL-101(Fe)纳米材料的XRD谱图如图1所示，MIL-101(Fe)在低角度的主要衍射峰与已发表文献相符，证实了MIL-101(Fe)结构的完整性，与相关文献报导吻合；Ag纳米粒子与MIL-101(Fe)复合后出现Ag的晶面衍射峰，其与相关文献报道吻合，MIL-101的衍射峰前后无变化，这表明作为Ag纳米粒子的支撑物，MIL-101(Fe)晶体结构有很好保留，没有明显的晶体损失。图2和图3为不同放大倍数下的MIL-101(Fe)扫描电镜图，从宏观和微观角度观察可以看到此材料呈现正八面体，是MIL-101型的结构，且表面较为光滑。The XRD patterns of the MIL-101(Fe) nanomaterials, AgNPs materials and the final synthesized AgNPs/MIL-101(Fe) nanomaterials synthesized in the present invention are shown in FIG. 1 . The main diffraction peaks of Ag nanoparticles are consistent with the published literature, which confirms the structural integrity of MIL-101(Fe) and is consistent with the reports in related literatures; Ag nanoparticles appear after the composite of MIL-101(Fe), and the crystal plane diffraction peaks of Ag appear, which Consistent with relevant literature reports, the diffraction peaks of MIL-101 did not change before and after, which indicated that as a support for Ag nanoparticles, MIL-101(Fe) crystal structure was well preserved without obvious crystal loss. Figures 2 and 3 are SEM images of MIL-101(Fe) under different magnifications. From the macroscopic and microscopic observation, it can be seen that this material presents a regular octahedron, which is a MIL-101 type structure, and the surface is relatively smooth.
图4为实施例1-3中AgNPs/MIL-101(Fe)纳米材料对R6G的检测结果，图5-图7依次为实施例1-3制得AgNPs/MIL-101(Fe)纳米材料的扫描电镜图；将图4与图5-图7结合对比，可以得知本发明实施例1-3制备获得的AgNPs/MIL-101(Fe)纳米材料都具有良好的检测结果，并且也具有比较好的表面形貌；但实施例1-3三个不同实施例制备获得的AgNPs/MIL-101(Fe)纳米材料也存在一定差距，由图4可知其中实施例2制得的AgNPs/MIL-101(Fe)纳米材料具有相对更好的检测效果，同样的由图5-图7可知，实施例2制得的AgNPs/MIL-101(Fe)纳米材料具有更好的表面形貌，AgNPs在MIL-101(Fe)表面分布更加均匀；同时实施例3制得的AgNPs/MIL-101(Fe)纳米材料表面形貌中，存在AgNPs轻微脱落的问题，这也使得实施例3制得的AgNPs/MIL-101(Fe)纳米材料SRES效果相对于实施例2制得的AgNPs/MIL-101(Fe)纳米材料差一些。Figure 4 shows the detection results of AgNPs/MIL-101(Fe) nanomaterials on R6G in Example 1-3, and Figures 5 to 7 show the results of AgNPs/MIL-101(Fe) nanomaterials prepared in Example 1-3 in turn. Scanning electron microscope image; by comparing Fig. 4 with Fig. 5-Fig. 7, it can be known that the AgNPs/MIL-101(Fe) nanomaterials prepared in Examples 1-3 of the present invention all have good detection results, and also have comparative However, there is a certain gap between the AgNPs/MIL-101(Fe) nanomaterials prepared by the three different examples of Examples 1-3. 101(Fe) nanomaterials have a relatively better detection effect. Similarly, it can be seen from Figures 5 to 7 that the AgNPs/MIL-101(Fe) nanomaterials prepared in Example 2 have better surface morphology. The surface distribution of MIL-101(Fe) is more uniform; at the same time, in the surface morphology of AgNPs/MIL-101(Fe) nanomaterials prepared in Example 3, there is a problem of slight detachment of AgNPs, which also makes the AgNPs prepared in Example 3. Compared with the AgNPs/MIL-101(Fe) nanomaterial prepared in Example 2, the SRES effect of the /MIL-101(Fe) nanomaterial is inferior.
本发明实施例1-3制得的AgNPs/MIL-101(Fe)纳米材料都具有较好表面形貌和SRES效果，但是相对而言，其中实施例2制得的AgNPs/MIL-101(Fe)纳米材料具有相对更好的拉曼增强效果。The AgNPs/MIL-101(Fe) nanomaterials prepared in Examples 1-3 of the present invention all have good surface morphology and SRES effect, but relatively speaking, the AgNPs/MIL-101(Fe) prepared in Example 2 ) nanomaterials have relatively better Raman enhancement effects.
2.AgNPs/MIL-101(Fe)纳米材料作为SERS基底进行拉曼光谱检测的效果表征2.Characterization of AgNPs/MIL-101(Fe) nanomaterials as SERS substrate for Raman spectroscopy detection
该部分选用实施例2制得的AgNPs/MIL-101(Fe)纳米材料作为SERS基底。In this part, AgNPs/MIL-101(Fe) nanomaterials prepared in Example 2 were selected as the SERS substrate.
2.1 AgNPs/MIL-101(Fe)纳米材料在拉曼中的增强作用2.1 Enhancement of AgNPs/MIL-101(Fe) nanomaterials in Raman
选用了罗丹明6G、结晶紫、4-巯基苯甲酸、5,5'-二硫代双(2-硝基苯甲酸)这四种常见的SERS探针分子，采用低浓度(浓度为1×10 -6M)的SERS探针分子对实施例2中制得的AgNPs/MIL-101(Fe)纳米复合材料的SERS增强效应进行初步评估，同时使用粒径约30nm的Ag纳米溶胶和单纯的MIL-101(Fe)分散液作为参照。 Four common SERS probe molecules, rhodamine 6G, crystal violet, 4-mercaptobenzoic acid, and 5,5'-dithiobis(2-nitrobenzoic acid), were selected. 10 -6 M) of SERS probe molecules to preliminarily evaluate the SERS enhancement effect of the AgNPs/MIL-101(Fe) nanocomposites prepared in Example 2, using Ag nanosols with a particle size of about 30 nm and pure MIL-101(Fe) dispersion was used as reference.
如图8所示，图8-a为罗丹明6G作为SERS探针分子，图8-b为结晶紫作为SERS探针分子，图8-c为4-巯基苯甲酸作为SERS探针分子，图8-d为5,5'-二硫代双(2-硝基苯甲酸)作为SERS探针分子；低浓度的SERS探针分子(1×10 -6M)与AgNPs/MIL-101(Fe)纳米复合材料混合后，拉曼信号强度增强，其增强效果比单独Ag纳米溶胶效果好，SERS探针分子在单纯的MIL-101(Fe)上几没有拉曼信号；这种结果说明AgNPs和MIL-101(Fe)复合以后，由于MIL-101(Fe)具有较强吸附性，将其待测物吸附聚集并且与AgNPs的表面等离子耦合效应，所以使其拉曼信号显著增强；并且我们选用1×10 -6M R6G 1646cm -1特征峰，与单独Ag纳米溶胶对比发现其拉曼信号大约增强了10倍，并且进行了相应的EF计算，计算可得1×10 -6M R6G的EF数值为2.09×10 9。 As shown in Fig. 8, Fig. 8-a shows Rhodamine 6G as SERS probe molecule, Fig. 8-b shows crystal violet as SERS probe molecule, Fig. 8-c shows 4-mercaptobenzoic acid as SERS probe molecule, Fig. 8-d is 5,5'-dithiobis(2-nitrobenzoic acid) as the SERS probe molecule; the low concentration SERS probe molecule (1×10 -6 M) and AgNPs/MIL-101 (Fe ) After the nanocomposites are mixed, the Raman signal intensity is enhanced, and the enhancement effect is better than that of the Ag nanosol alone. The SERS probe molecule has almost no Raman signal on pure MIL-101(Fe); this result shows that AgNPs and After MIL-101(Fe) is compounded, due to the strong adsorption of MIL-101(Fe), the analyte is adsorbed and aggregated and its surface plasmon coupling effect with AgNPs, so its Raman signal is significantly enhanced; and we choose 1×10 -6 M R6G 1646cm -1 characteristic peak, compared with the single Ag nanosol, it is found that its Raman signal is enhanced by about 10 times, and the corresponding EF calculation is carried out, the EF of 1×10 -6 M R6G can be calculated. The value is 2.09×10 9 .
2.2 AgNPs/MIL-101(Fe)纳米材料SERS信号重现性2.2 SERS signal reproducibility of AgNPs/MIL-101(Fe) nanomaterials
表面增强拉曼光谱检测信号能否进行重现也是检验SERS基底应用性能方面的一个重要 因素。由浓度为1×10 -6M的R6G分子主要拉曼信号的相对标准偏差(RSD)值估算AgNPs/MIL-101(Fe))纳米复合物的SERS信号重现性。如图9-a所示，从此独立基底上随意选择20个点进行测试，从而获得1×10 -6M的R6G的SERS光谱检测信号，并进行叠加。其选取其中一个的特征峰信号强度进行柱状图(如图9-b)分析，计算RSD＝7.55％，小于15％；因此，可以说明AgNPs/MIL-101(Fe)纳米复合材料作为检测基底具有良好的检测信号重现性。 The reproducibility of surface-enhanced Raman spectroscopy detection signals is also an important factor in examining the application performance of SERS substrates. The SERS signal reproducibility of AgNPs/MIL-101(Fe)) nanocomposites was estimated from the relative standard deviation (RSD) value of the main Raman signal of the R6G molecule at a concentration of 1×10 -6 M. As shown in Fig. 9-a, 20 points were randomly selected from this independent substrate for testing, thereby obtaining 1×10 -6 M SERS spectral detection signals of R6G, and superimposing them. The signal intensity of one of the characteristic peaks is selected for histogram analysis (as shown in Figure 9-b), and the calculated RSD is 7.55%, which is less than 15%; therefore, it can be shown that AgNPs/MIL-101(Fe) nanocomposite as a detection substrate has Good detection signal reproducibility.
2.3 AgNPs/MIL-101(Fe)纳米材料作为SERS基底对百草枯的检测2.3 Detection of paraquat using AgNPs/MIL-101(Fe) nanomaterials as SERS substrates
如图10-a所示，我们将此新型基底对百草枯进行了检测，其拉曼特征峰与百草枯特征峰相符，研究发现检测百草枯的最低浓度为10 -12M(如图10-b所示)；我们还在不同酸碱条件下检测浓度为10 -6M的百草枯，如图10-c和图10-d所示，在pH为3-11之间其在偏酸或偏碱条件下信号有所降低，但相对稳定，这说明此新型基底受环境影响较小，也体现出此材料的稳定性较佳。不同酸碱条件下依旧能检测出百草枯的信号，再次突显出了MOFs材料和贵金属各自的优异性能，体现出了MOFs材料的吸附性能。从另一方面来讲，氯离子有助于纳米粒子的重排，并能有效地促进Ag纳米粒子的表面活化，提高等离子体共振的能量传递效率，从而产生优越的SERS效应。 As shown in Figure 10-a, we tested this new substrate for paraquat, and its Raman characteristic peaks were consistent with those of paraquat. The study found that the lowest concentration of paraquat detected was 10 -12 M (Figure 10- b); we also tested paraquat at a concentration of 10 -6 M under different acid-base conditions, as shown in Figure 10-c and Figure 10-d, between pH 3-11, it was in a partial acid or The signal decreased under the alkaline condition, but it was relatively stable, which indicated that the new substrate was less affected by the environment, and also reflected the better stability of the material. The signal of paraquat can still be detected under different acid-base conditions, which once again highlights the excellent properties of MOFs and precious metals, and reflects the adsorption performance of MOFs. On the other hand, chloride ions contribute to the rearrangement of nanoparticles and can effectively promote the surface activation of Ag nanoparticles and improve the energy transfer efficiency of plasmonic resonance, resulting in a superior SERS effect.
3.结论3. Conclusion
综上，本发明中利用最简单的物理自组装法将AgNPs和MIL-101(Fe)合成得到SERS基底AgNPs/MIL-101(Fe)纳米材料，检测四种低浓度的探针分子，其表现出较强的增强效果。检测R6G结果表明该基底稳定性和均一性较佳，其拉曼归属峰位RSD＝7.55％，增强因子EF＝2.09×10 9，与单独Ag纳米溶胶对比发现其拉曼信号大约增强了10倍。同时AgNPs/MIL-101(Fe)纳米材料作为SERS基底能检测百草枯最低浓度为10 -12M，并在不同酸碱环境下拉曼信号较为稳定。 To sum up, in the present invention, AgNPs and MIL-101(Fe) are synthesized by the simplest physical self-assembly method to obtain SERS-based AgNPs/MIL-101(Fe) nanomaterials, and four kinds of low-concentration probe molecules are detected. Strong enhancement effect. The detection results of R6G show that the substrate has better stability and uniformity, its Raman assigned peak position RSD=7.55%, and the enhancement factor EF=2.09×10 9 . Compared with the single Ag nanosol, it is found that its Raman signal is enhanced by about 10 times. . Meanwhile, AgNPs/MIL-101(Fe) nanomaterials can detect paraquat at a minimum concentration of 10 -12 M as a SERS substrate, and the Raman signal is relatively stable in different acid-base environments.
应当理解的是，对于本领域普通技术人员来说，可以根据上述说明加以改进或变换，而所有这些改进和变换都应属于本发明所附权利要求的保护范围。It should be understood that for those skilled in the art, improvements or changes can be made according to the above description, and all these improvements and changes should fall within the protection scope of the appended claims of the present invention.

Claims (10)

  1. 一种SERS基底的制备方法，其特征在于：A preparation method of a SERS substrate, characterized in that:
    所述SERS基底为基于AgNPs/MIL-101(Fe)纳米材料SERS基底；The SERS substrate is a SERS substrate based on AgNPs/MIL-101(Fe) nanomaterials;
    所述基于AgNPs/MIL-101(Fe)纳米材料SERS基底包括AgNPs/MIL-101(Fe)纳米材料；The SERS substrate based on AgNPs/MIL-101(Fe) nanomaterials includes AgNPs/MIL-101(Fe) nanomaterials;
    所述AgNPs/MIL-101(Fe)纳米材料通过AgNPs材料与MIL-101(Fe)材料通过物理自组装方法制得；The AgNPs/MIL-101(Fe) nanomaterial is prepared by a physical self-assembly method between the AgNPs material and the MIL-101(Fe) material;
    具体为，将所述MIL-101(Fe)材料分散于分散剂中制得MIL-101(Fe)分散液，然后将所述MIL-101(Fe)分散液与所述AgNPs材料混合均匀，混合后室温下孵育制得所述AgNPs/MIL-101(Fe)纳米材料。Specifically, the MIL-101(Fe) material is dispersed in a dispersant to prepare a MIL-101(Fe) dispersion, and then the MIL-101(Fe) dispersion is uniformly mixed with the AgNPs material, and mixed After incubation at room temperature, the AgNPs/MIL-101(Fe) nanomaterials were prepared.
  2. 根据权利要求1所述的一种SERS基底的制备方法，其特征在于：The preparation method of a kind of SERS substrate according to claim 1, is characterized in that:
    所述AgNPs材料为AgNPs胶液，所述MIL-101(Fe)分散液与所述AgNPs胶液的体积比为1：(1-3)。The AgNPs material is AgNPs glue, and the volume ratio of the MIL-101(Fe) dispersion to the AgNPs glue is 1:(1-3).
  3. 根据权利要求2所述的一种SERS基底的制备方法，其特征在于：The preparation method of a kind of SERS substrate according to claim 2, is characterized in that:
    所述MIL-101(Fe)材料由以下方法制得，取铁源和对苯二甲酸溶解于溶剂中，然后采用溶剂热合成法处理，冷却后并洗涤处理得粗产品，将所述粗产品活化处理并干燥后得到所述MIL-101(Fe)材料。The MIL-101(Fe) material is prepared by the following method. The iron source and terephthalic acid are dissolved in a solvent, and then processed by a solvothermal synthesis method. After cooling, the crude product is washed and processed to obtain a crude product. The MIL-101(Fe) material is obtained after activation treatment and drying.
  4. 根据权利要求3所述的一种SERS基底的制备方法，其特征在于：The preparation method of a kind of SERS substrate according to claim 3, is characterized in that:
    所述对苯二甲酸与所述铁源中铁离子的摩尔比为(1-1.3)：2.45。The molar ratio of the terephthalic acid to the iron ions in the iron source is (1-1.3):2.45.
  5. 根据权利要求2所述的一种SERS基底的制备方法，其特征在于：The preparation method of a kind of SERS substrate according to claim 2, is characterized in that:
    所述AgNPs胶液由以下方法制得，取银源溶液并将银源溶液加热至沸腾，向所述银源溶液中加入柠檬酸钠溶液并混合，继续加热一段时间，之后冷却至室温得AgNPs胶液。The AgNPs glue solution is prepared by the following method, taking the silver source solution and heating the silver source solution to boiling, adding sodium citrate solution to the silver source solution and mixing, continuing to heat for a period of time, and then cooling to room temperature to obtain AgNPs glue.
  6. 根据权利要求5所述的一种SERS基底的制备方法，其特征在于：The preparation method of a kind of SERS substrate according to claim 5, is characterized in that:
    所述柠檬酸钠溶液的添加量至少为使所述银源溶液中银被完全还原。The addition amount of the sodium citrate solution is at least so that the silver in the silver source solution is completely reduced.
  7. 一种SERS基底，其特征在于：A SERS substrate, characterized in that:
    所述SERS基底由权利要求1-6任一所述的基于AgNPs/MIL-101(Fe)纳米材料SERS基底的制备方法制得。The SERS substrate is prepared by the preparation method based on the AgNPs/MIL-101(Fe) nanomaterial SERS substrate according to any one of claims 1-6.
  8. 一种基于SERS基底的拉曼光谱检测方法，其特征在于：A Raman spectroscopy detection method based on SERS substrate, characterized in that:
    采用如权利要求7所述SERS基底进行拉曼光谱检测。Raman spectroscopic detection is performed using the SERS substrate as claimed in claim 7 .
  9. 根据权利要求8所述的一种基于SERS基底的拉曼光谱检测方法，其特征在于：A kind of Raman spectrum detection method based on SERS substrate according to claim 8, is characterized in that:
    所述拉曼光谱检测方法具体为，将所述基于AgNPs/MIL-101(Fe)纳米材料的SERS基底与待测液混合均匀后，取样至载样器，干燥后进行拉曼光谱检测。The Raman spectroscopic detection method is specifically as follows: after the SERS substrate based on AgNPs/MIL-101(Fe) nanomaterials is evenly mixed with the liquid to be tested, sampling is carried out to a sample carrier, and Raman spectroscopic detection is performed after drying.
  10. 一种根据权利要求8或9所述拉曼光谱检测方法的应用，其特征在于：A kind of application according to the described Raman spectrum detection method of claim 8 or 9, is characterized in that:
    将所述拉曼光谱检测方法应用于pH值为3-11环境下待测样品中百草枯的测定。The Raman spectroscopic detection method is applied to the determination of paraquat in a sample to be tested in an environment with a pH value of 3-11.
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