CN112798571A - A kind of preparation method of SERS substrate, SERS substrate and application thereof - Google Patents
A kind of preparation method of SERS substrate, SERS substrate and application thereof Download PDFInfo
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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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- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
本发明属于拉曼光谱检测技术领域。本发明公开了一种SERS基底，SERS基底包括AgNPs/MIL‑101(Fe)纳米材料；AgNPs/MIL‑101(Fe)纳米材料由AgNPs材料与MIL‑101(Fe)材料通过物理自组装方法制得；本发明还公开了一种基于AgNPs/MIL‑101(Fe)纳米材料SERS基底的拉曼光谱检测方法及将其用于检测待测样品中百草枯含量的应用。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2.09×109，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 invention belongs to the technical field of Raman spectrum detection. The invention discloses a SERS substrate. The SERS substrate comprises AgNPs/MIL-101(Fe) nanomaterials; the AgNPs/MIL-101(Fe) nanomaterials are prepared from AgNPs materials and MIL-101(Fe) materials through a physical self-assembly method The invention also discloses a Raman spectrum detection method based on AgNPs/MIL-101(Fe) nano-material SERS substrate and its application for detecting the paraquat content in a sample to be tested. The Raman spectrum 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 is 2.09×10 9 , and the R6G Raman attribution peak intensity RSD=7.55% is studied and calculated here; the detection of paraquat is carried out at a minimum concentration of 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.
Description
Technical Field
The invention belongs to the technical field of Raman spectrum detection, and particularly relates to a preparation method of an AgNPs/MIL-101(Fe) nanomaterial-based SERS substrate, the SERS substrate and application.
Background
Surface Enhanced Raman Scattering (SERS) is a technology developed on the basis of ordinary raman scattering. As is known, Surface Enhanced Raman Spectroscopy (SERS) is a spectroscopic technology for rapid nondestructive detection, has the characteristics of high sensitivity, high accuracy, fingerprint spectrum, no interference of water molecules and the like, and can realize the detection of single molecules. With the rapid development of laser technology and the increasing maturity of nano-material preparation technology, SERS not only plays an important role in scientific research such as single crystal surface molecular adsorption, chemical reaction mechanism and cell behavior in vivo, but also is increasingly widely applied in food safety, environmental pollution chemical weapons and artwork identification and other practical lives.
Currently, there are two main types of SERS mechanisms generally recognized by academia, namely physical enhancement mechanism and chemical enhancement mechanism: physical enhancement mode, i.e. Electromagnetic field Enhancement (EM), and chemical enhancement mode, i.e. Charge Transfer enhancement (CT). The electromagnetic field mechanism is a physical model that suggests that the SERS effect originates from an enhancement of the local electric field at the metal surface. The electromagnetic field enhancement mechanism mainly comprises the following three Surface Plasmon Resonance (SPR) models, antenna resonance submodels and mirror image field models, wherein the Surface Plasmon Resonance (SPR) enhancement mechanism is considered to be the most main contributor of electromagnetic field enhancement, and the mechanism is that when a rough noble metal surface is irradiated by laser, surface plasmas can be excited to a higher energy level and coupled with an optical wave electric field to generate resonance, so that the electric field of the metal surface is enhanced, and the Raman scattering effect is greatly enhanced because the intensity of Raman scattering is in direct proportion to the square of the intensity of the optical electric field. Chemical enhancement mainly involves the following three mechanisms: non-resonant enhancement due to chemical bonding of adsorbates and metal substrates; enhanced resonance due to the formation of surface complexes of adsorbed molecules and surface adsorbed atoms; the quasi-resonance enhancement of light-induced charge transfer of excitation light to the molecule-metal system.
MOFs are short for Metal organic Frameworks (Metal organic Frameworks). The material is a crystalline porous material with a periodic network structure formed by connecting an inorganic metal center (metal ion or metal cluster) and a bridged organic ligand through self-assembly, is different from an inorganic porous material and a common organic complex, has the rigidity of the inorganic material and the flexibility of the organic material, and has great development potential and attractive development prospect in the aspect of modern material research. MOFs have many properties such as porosity, large specific surface area, and multi-metal sites, and thus have many applications in the chemical and chemical fields, such as gas storage, molecular separation, catalysis, and drug release. Due to the unique characteristics of MOFs, researchers expand the application of the material to the SERS field, and the application prospect of the MOFs material is enriched.
In 2017, Cao Xiaolin and the like adopt solution impregnation to carry out in-situ reduction and embedding on metal in MOF to prepare various SERS active materials of AuNPs/MOFs, and the novel composite materials have high sensitivity, stability and reproducibility, so that a new approach problem report is provided for detecting pesticides by utilizing an SERS technology and is introduced in the SERS active materials. However, in the preparation method, the size and the morphology of the metal particles cannot be controlled due to in-situ reduction, so that the optimization of SERS performance is difficult to realize. In 2018, the core-shell gold nanoparticles are successfully synthesized by Populus sieversii et al through layer-by-layer assembly, and the detection limit of detecting hexamethylenetetramine is 10-8And M. The disadvantage of this approach is that the metal particle spacing is not easily controlled and does not achieve the "hot spot" optimum.
The AgNPs/MIL-101(Cr) nanocomposite is prepared by a solution dipping reduction method in the Zao Wei task group in 2018, and is used as an SERS substrate to perform SERS spectrum analysis of ultra-trace glucose in an aqueous solution, wherein the detection limit is about 10-14And M. It is researchedIn the preparation process, the MIL-101(Cr) crystal form is difficult to control, and Cr is a toxic substance and has certain influence on the environment.
Disclosure of Invention
The method aims to solve the problems that MOFs materials adopted in the prior art are difficult to synthesize and optimize in performance and cannot control the metal ion micro-morphology, and meanwhile, the detection sensitivity is low and the like when the MOFs materials are adopted as SERS substrate materials; in order to optimize the synthesis process and corresponding performance of MOFs materials serving as SERS substrate materials and reduce the detection limit in the SERS process, the invention provides a preparation method of an AgNPs/MIL-101(Fe) nano material-based SERS substrate;
the invention provides an AgNPs/MIL-101(Fe) -based nanomaterial SERS substrate prepared by the preparation method;
the invention also provides a Raman spectrum detection method based on the AgNPs/MIL-101(Fe) nanomaterial SERS substrate and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of an SERS substrate based on AgNPs/MIL-101(Fe) nano material,
the AgNPs/MIL-101(Fe) -based nanomaterial SERS substrate comprises AgNPs/MIL-101(Fe) nanomaterials;
the AgNPs/MIL-101(Fe) nano material is prepared by an AgNPs material and an MIL-101(Fe) material through a physical self-assembly method;
specifically, the MIL-101(Fe) material is dispersed in a dispersing agent to prepare MIL-101(Fe) dispersion liquid, then the MIL-101(Fe) dispersion liquid and the AgNPs material are uniformly mixed, and the AgNPs/MIL-101(Fe) nano material is prepared by incubation at room temperature after mixing.
Preferably, the AgNPs material is AgNPs glue solution, and the volume ratio of the MIL-101(Fe) dispersion solution to the AgNPs glue solution is 1: (1-3).
Preferably, the dispersant is methanol, and the MIL-101(Fe) material is dispersed in the dispersant to obtain 0.8-1.2mg/mL MIL-101(Fe) dispersion.
The AgNPs/MIL-101(Fe) nano material is prepared by dispersing an MIL-101(Fe) material in a dispersing agent to prepare 0.8-1.2mg/mL MIL-101(Fe) dispersion liquid, and then mixing the MIL-101(Fe) dispersion liquid with AgNPs glue liquid, wherein the volume ratio of the MIL-101(Fe) dispersion liquid to the AgNPs glue liquid is 1: (1-3), then high-speed mixing is carried out, and after mixing, incubation is carried out for 1.3-2 hours at room temperature, so as to prepare the AgNPs/MIL-101(Fe) nano material.
In the AgNPs/MIL-101(Fe) nano material, the molar ratio of silver atoms to iron atoms is 1: (4-13).
Preferably, the MIL-101(Fe) material is prepared by dissolving an iron source and terephthalic acid in a solvent, treating by a solvothermal synthesis method, cooling, washing to obtain a crude product, activating and drying the crude product to obtain the MIL-101(Fe) material.
Preferably, the molar ratio of the terephthalic acid to the iron ions in the iron source is (1-1.3): 2.45.
preferably, the solvent is DMF, and the iron source is ferric chloride or ferric chloride hexahydrate.
The specific preparation process of the MIL-101(Fe) material comprises the steps of adding ferric chloride and terephthalic acid into sufficient DMF, dissolving to generate a transparent solution, placing the transparent solution in a high-pressure reaction kettle, treating at 100 ℃ and 130 ℃ for 18-30 hours, cooling to room temperature, centrifuging to obtain a solid, washing the solid with DMF and sewage ethanol for multiple times to completely remove impurities in the solid to obtain a crude product, activating the crude product in hot ethanol at the temperature of not lower than 70 ℃ for at least 2.5 hours, centrifuging to obtain an activated solid, and drying to obtain the MIL-101(Fe) material.
Preferably, the AgNPs glue solution is prepared by taking a silver source solution, heating the silver source solution to boiling, adding a sodium citrate solution into the silver source solution, mixing, continuing to heat for a period of time, and then cooling to room temperature to obtain the AgNPs glue solution.
Preferably, the sodium citrate solution is added in an amount at least to completely reduce the silver in the silver source solution.
Preferably, the silver source solution is a silver nitrate solution.
The specific preparation process of the AgNPs glue solution comprises the steps of heating a silver nitrate solution, quickly adding a sodium citrate solution into the silver nitrate solution when the silver nitrate solution is boiled, quickly stirring, keeping the boiling state for at least 40 minutes, and finally cooling to room temperature to obtain the AgNPs glue solution, wherein the AgNPs glue solution is stored in a dark place at a low temperature.
An AgNPs/MIL-101(Fe) nanomaterial-based SERS substrate is prepared by the preparation method of the AgNPs/MIL-101(Fe) nanomaterial-based SERS substrate.
A Raman spectrum detection method based on an AgNPs/MIL-101(Fe) nanomaterial SERS substrate is adopted to carry out Raman spectrum detection.
Preferably, the raman spectroscopy detection method specifically comprises the steps of uniformly mixing the SERS substrate based on the AgNPs/MIL-101(Fe) nanomaterial with the liquid to be detected, sampling to a sample carrier, drying, and performing raman spectroscopy detection.
During detection, the AgNPs/MIL-101(Fe) nano material and a liquid to be detected are mixed according to the volume ratio of 1: 2, mixing at high speed, sampling 10 mu L, dripping on a Raman spectrum sample carrier, and performing Raman detection after natural drying.
The application of the Raman spectrum detection method in determination of paraquat in a sample to be detected under the environment of pH value of 3-11
Therefore, the invention has the following beneficial effects:
the Raman spectrum detection method based on the AgNPs/MIL-101(Fe) nanomaterial SERS substrate has high sensitivity and lower detection limit, detects rhodamine 6G and calculates 10-6The EF value of mol/L R6G is 2.09X 109R6G raman peak intensity RSD was studied and calculated to be 7.55%; detecting paraquat with the minimum detection concentration of 10-12mol/L, and is mixed with 10-6And the Raman signal value of the combination of mol/L paraquat and the substrate is relatively stable in comparison with Raman signal detection in different pH values, and paraquat can be detected in the environment of pH 3-11.
Drawings
FIG. 1 is an XRD spectrum of the MIL-101(Fe) nanomaterial, AgNPs material and the finally synthesized AgNPs/MIL-101(Fe) nanomaterial in example 2 of the present invention;
FIG. 2 is a 100000-fold electron micrograph of an MIL-101(Fe) nano-material prepared by example 2 of the invention;
FIG. 3 is a 500000 times electron micrograph of the MIL-101(Fe) nano-material prepared in example 2 of the present invention;
FIG. 4 is a graph showing the detection result of the AgNPs/MIL-101(Fe) nanomaterial prepared in example 1-3 on R6G; the detection results of the AgNPs/MIL-101(Fe) nano-materials prepared in example 2, example 3 and example 1 on R6G are shown from top to bottom respectively;
FIG. 5 is a scanning electron microscope image of AgNPs/MIL-101(Fe) nanomaterial prepared in example 1;
FIG. 6 is a scanning electron microscope image of AgNPs/MIL-101(Fe) nanomaterial prepared in example 2;
FIG. 7 is a scanning electron microscope image of AgNPs/MIL-101(Fe) nanomaterial prepared in example 3;
FIG. 8 is a graph of Raman detection results of four different common SERS probe molecules adopted for AgNPs/MIL-101(Fe) nanomaterials prepared in example 2, wherein FIG. 8-a shows rhodamine 6G as the SERS probe molecule, FIG. 8-b shows crystal violet as the SERS probe molecule, FIG. 8-c shows 4-mercaptobenzoic acid as the SERS probe molecule, and FIG. 8-d shows 5,5' -dithiobis (2-nitrobenzoic acid) as the SERS probe molecule; FIGS. 8-a, 8-b, 8-c, and 8-d show the Raman detection curves of AgNPs/MIL-101(Fe) nanomaterial, AgNPs material, and MIL-101(Fe) material, respectively, from top to bottom;
FIG. 9 is a graph of the detection result of the reproducibility of the SERS signal of AgNPs/MIL-101(Fe) nanomaterials; wherein, fig. 9-a is a raman detection reproducibility result diagram of the AgNPs/MIL-101(Fe) nanomaterial prepared in example 2 using rhodamine 6G as the SERS probe molecule, and fig. 9-b is a raman detection characteristic peak signal intensity histogram analysis diagram of the AgNPs/MIL-101(Fe) nanomaterial prepared in example 2 using rhodamine 6G as the SERS probe molecule;
FIG. 10 is a graph of the detection results of AgNPs/MIL-101(Fe) nanomaterials as SERS substrates for paraquat; wherein, in FIG. 10-a, the Raman detection spectra under different paraquat concentrations are shown, as shown in FIG. 10-b, the concentration of paraquat is 10-12Raman detection of MFIG. 10-c shows the measured concentration of 10 at different pH values-6Raman spectrum of M paraquat, FIG. 10-d shows the detected concentration of 10 under different pH values-6M Paraquat is 1650cm-1A histogram of raman measurements.
Detailed Description
The technical solution of the present invention will be further described with reference to the following embodiments.
It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all 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.
In the present invention, all the equipments and materials are commercially available or commonly used in the industry, and the methods in the following examples are conventional in the art unless otherwise specified.
General examples
The AgNPs/MIL-101(Fe) nanomaterial-based SERS substrate is prepared from AgNPs/MIL-101(Fe) nanomaterials, wherein the molar ratio of silver atoms to iron atoms in the AgNPs/MIL-101(Fe) nanomaterials is 1: (4-13);
the AgNPs/MIL-101(Fe) nano material is prepared from AgNPs glue solution and an MIL-101(Fe) material by a physical self-assembly method,
the specific process for preparing the AgNPs/MIL-101(Fe) nano material comprises the steps of dispersing the MIL-101(Fe) material in methanol to prepare 0.8-1.2mg/mL MIL-101(Fe) dispersion liquid, and then mixing the MIL-101(Fe) dispersion liquid with AgNPs glue liquid, wherein the volume ratio of the MIL-101(Fe) dispersion liquid to the AgNPs glue liquid is 1: (1-3), then high-speed mixing is carried out, and after mixing, incubation is carried out for 1.3-2 hours at room temperature, so as to prepare the AgNPs/MIL-101(Fe) nano material.
The MIL-101(Fe) material is specifically prepared by adding ferric chloride and terephthalic acid to DMF in sufficient quantity, wherein the molar ratio of terephthalic acid to iron ions in the iron source is (1-1.3): 2.45, dissolving to generate a transparent solution, placing the transparent solution in a high-pressure reaction kettle, treating for 18-30 hours at the temperature of 100-130 ℃ by adopting a solvothermal synthesis method, cooling to room temperature, centrifuging to obtain a solid, washing the solid for multiple times by using DMF (dimethyl formamide) and sewage ethanol to completely remove impurities in the solid to obtain a crude product, activating the crude product in hot ethanol at the temperature of not less than 70 ℃ for at least 2.5 hours, centrifuging to obtain an activated solid, and drying to obtain an MIL-101(Fe) material;
the specific preparation process of the AgNPs glue solution comprises the steps of heating a silver nitrate solution, quickly adding a sodium citrate solution into the silver nitrate solution when the silver nitrate solution is boiled, quickly stirring, keeping the boiling state for at least 40 minutes when the addition amount of the sodium citrate solution is at least enough to completely reduce silver in the silver source solution, and finally cooling to room temperature to obtain the AgNPs glue solution, wherein the AgNPs glue solution is stored in a dark place and at a low temperature.
A Raman spectrum detection method based on AgNPs/MIL-101(Fe) nanomaterial SERS substrate is provided, wherein the AgNPs/MIL-101(Fe) nanomaterial SERS substrate is adopted for Raman spectrum detection; the Raman spectrum detection method comprises the steps of uniformly mixing the SERS substrate based on the AgNPs/MIL-101(Fe) nano material with a liquid to be detected, sampling to a sample carrier, drying and performing Raman spectrum detection; during detection, the AgNPs/MIL-101(Fe) nano material and a liquid to be detected are mixed according to the volume ratio of 1: 2, mixing at high speed, sampling 10 mu L, dripping on a Raman spectrum sample carrier, and performing Raman detection after natural drying.
The application of the Raman spectrum detection method is to detect the content of paraquat in a sample to be detected, and the detection is carried out in an environment with a pH value of 3-11.
Example 1
An AgNPs/MIL-101(Fe) nanomaterial-based SERS substrate is prepared by the following steps:
the specific preparation method of the AgNPs material is as follows: preparation of AgNO3Heating and stirring 100mL of 18mg/mL solution until AgNO3When the solution is boiled, 4mL of trisodium citrate solution with the mass fraction of 1% is added immediately and the stirring is accelerated, the solution is heated for 40 minutes at the temperature, and finally the solution is cooled to the room temperature to prepare AgNPs glue solution, and then the AgNPs glue solution is stored at the temperature of 4 ℃ in a dark place for standby.
The specific preparation process of the MIL-101(Fe) material is as follows: weighing 0.675g FeCl3·6H2Dissolving O and 0.206g terephthalic acid in 15ml DMF (dimethyl formamide) in a high-speed vortex device at an accelerated speed to form a clear transparent yellow solution, transferring the solution into a polytetrafluoroethylene-lined stainless steel high-pressure reaction kettle, placing the reaction kettle in a 110 ℃ forced air drying box for 20 hours, cooling the reaction kettle to room temperature, centrifuging the reaction kettle to obtain a yellow solid, washing the yellow solid with DMF (dimethyl formamide) and absolute ethyl alcohol for three times respectively to obtain a crude product, stirring and activating the obtained crude product solid in hot ethyl alcohol (70 ℃) for 3 hours, finally centrifuging the obtained solid, placing the obtained solid in a 60 ℃ vacuum drying box for overnight, and finally obtaining yellow powder and storing the yellow powder for later use under the drying condition of room temperature.
The specific process for preparing the AgNPs/MIL-101(Fe) nano material comprises the steps of dispersing the obtained MIL-101(Fe) powder into a methanol solution, and preparing an MIL-101(Fe) dispersion liquid with the dispersion liquid content of 1 mg/mL. And mixing the MIL-101(Fe) dispersion liquid with the prepared AgNPs glue solution according to the volume ratio of 1:1, then carrying out high-speed mixing on a high-speed vortex device for 5 minutes, and incubating for 1.5 hours at room temperature after mixing to obtain the AgNPs/MIL-101(Fe) nano material.
Example 2
In example 2, except for the preparation of AgNPs/MIL-101(Fe) nano-materials, the volume ratio of the MIL-101(Fe) dispersion liquid to the AgNPs glue liquid is 1: except for 2, other process steps and parameters were the same as those of example 1.
Example 3
In example 3, except for the preparation of AgNPs/MIL-101(Fe) nano-materials, the volume ratio of the MIL-101(Fe) dispersion liquid to the AgNPs glue liquid is 1: except for 3, other process steps and parameters were the same as those of example 1.
Effect characterization
Characterization of AgNPs/MIL-101(Fe) nanomaterials:
XRD spectrograms of the synthesized MIL-101(Fe) nano material, the AgNPs material and the finally synthesized AgNPs/MIL-101(Fe) nano material are shown in figure 1, and the main diffraction peak of the MIL-101(Fe) at a low angle is consistent with published documents, so that the structural integrity of the MIL-101(Fe) is verified and is consistent with the reports of related documents; the Ag nano particle and MIL-101(Fe) are compounded to form a crystal face diffraction peak of Ag, which is consistent with related literature reports, and the diffraction peak of MIL-101 is unchanged before and after, which shows that the MIL-101(Fe) crystal structure is well preserved without obvious crystal loss as a support of the Ag nano particle. FIGS. 2 and 3 are scanning electron microscope images of MIL-101(Fe) under different magnifications, and the material can be seen from macroscopic and microscopic angles to be in a regular octahedron shape, be in a MIL-101 type structure and be relatively smooth in surface.
FIG. 4 is a result of detecting R6G by AgNPs/MIL-101(Fe) nano-materials in examples 1-3, and FIGS. 5-7 are scanning electron micrographs of AgNPs/MIL-101(Fe) nano-materials prepared in examples 1-3 in sequence; comparing fig. 4 with fig. 5 to fig. 7, it can be seen that the AgNPs/MIL-101(Fe) nanomaterials prepared by embodiments 1 to 3 of the present invention all have good detection results and also have relatively good surface morphologies; however, the AgNPs/MIL-101(Fe) nano-materials prepared in the three different embodiments of examples 1-3 have certain differences, and as can be seen from FIG. 4, the AgNPs/MIL-101(Fe) nano-material prepared in example 2 has relatively better detection effect, and as can be seen from FIG. 5-7, the AgNPs/MIL-101(Fe) nano-material prepared in example 2 has better surface appearance, and AgNPs are more uniformly distributed on the surface of MIL-101 (Fe); meanwhile, the AgNPs/MIL-101(Fe) nano-material prepared in the embodiment 3 has the problem that the AgNPs slightly falls off in the surface morphology, so that the SRES effect of the AgNPs/MIL-101(Fe) nano-material prepared in the embodiment 3 is slightly poorer than that of the AgNPs/MIL-101(Fe) nano-material prepared in the embodiment 2.
The AgNPs/MIL-101(Fe) nano-material prepared in the embodiment 1-3 of the invention has better surface morphology and SRES effect, but relatively speaking, the AgNPs/MIL-101(Fe) nano-material prepared in the embodiment 2 has relatively better Raman enhancement effect.
Effect characterization of AgNPs/MIL-101(Fe) nano material as SERS substrate for Raman spectrum detection
The AgNPs/MIL-101(Fe) nano material prepared in example 2 is used as an SERS substrate.
2.1 enhancement of AgNPs/MIL-101(Fe) nanomaterials in Raman
Choose and useFour common SERS probe molecules of danmine 6G, crystal violet, 4-mercaptobenzoic acid and 5,5' -dithiobis (2-nitrobenzoic acid) are adopted at low concentration (the concentration is 1 multiplied by 10)-6M) SERS probe molecules the SERS enhancement effect of the AgNPs/MIL-101(Fe) nanocomposites prepared in example 2 was initially evaluated, using Ag nanosol with a particle size of about 30nm and a simple MIL-101(Fe) dispersion as reference.
As shown in fig. 8, fig. 8-a shows rhodamine 6G as the SERS probe molecule, fig. 8-b shows crystal violet as the SERS probe molecule, fig. 8-c shows 4-mercaptobenzoic acid as the SERS probe molecule, and fig. 8-d shows 5,5' -dithiobis (2-nitrobenzoic acid) as the SERS probe molecule; low concentration SERS probe molecules (1X 10)-6M) and AgNPs/MIL-101(Fe) nanocomposite, the Raman signal intensity is enhanced, the enhancement effect is better than that of single Ag nanosol, and SERS probe molecules hardly have Raman signals on single MIL-101 (Fe); the result shows that after AgNPs and MIL-101(Fe) are compounded, the MIL-101(Fe) has strong adsorbability, and the object to be detected is adsorbed and gathered and is coupled with the surface plasma of the AgNPs, so that the Raman signal of the AgNPs is obviously enhanced; and we choose to use 1 × 10-6M R6G 1646cm-1The characteristic peak is compared with the single Ag nano sol, the Raman signal of the single Ag nano sol is approximately enhanced by 10 times, and the corresponding EF calculation is carried out, so that the calculation can obtain 1 multiplied by 10-6M R6 EF value of 6G is 2.09X 109。
2.2 reproducibility of AgNPs/MIL-101(Fe) nanomaterial SERS signal
Whether the detection signal of the surface enhanced Raman spectrum can be reproduced is also an important factor for testing the application performance of the SERS substrate. With a concentration of 1X 10-6The Relative Standard Deviation (RSD) value of the principal Raman signal of the R6G molecule of M estimates the SERS signal reproducibility of the AgNPs/MIL-101(Fe)) nanocomplex. As shown in FIG. 9-a, 20 spots were arbitrarily selected from the independent substrate for testing, thereby obtaining 1X 10-6The SERS spectra of R6G of M are detected and superposed. Selecting one of the characteristic peak signal intensities to carry out histogram analysis (as shown in figure 9-b), and calculating that RSD is 7.55 percent and is less than 15 percent; thus, AgNPs/MIL-101(Fe) nanocomposite can be demonstratedThe material has good detection signal reproducibility as a detection substrate.
2.3 detection of Paraquat by AgNPs/MIL-101(Fe) nanomaterial as SERS substrate
As shown in FIG. 10-a, the Raman characteristic peak of the novel substrate is consistent with the characteristic peak of paraquat when paraquat is detected, and the lowest concentration of the detected paraquat is 10-12M (as shown in FIG. 10-b); we also tested the concentration to be 10 under different acid and alkali conditions-6M paraquat, as shown in FIGS. 10-c and 10-d, shows a reduced signal at pH 3-11 under meta-acid or meta-base conditions, but is relatively stable, indicating that the novel substrate is less environmentally affected and also shows better stability of the material. The signals of paraquat can be still detected under different acid-base conditions, the respective excellent performances of the MOFs material and noble metal are highlighted again, and the adsorption performance of the MOFs material is reflected. On the other hand, the chloride ions contribute to the rearrangement of the nanoparticles, effectively promote the surface activation of the Ag nanoparticles, and improve the energy transfer efficiency of plasma resonance, thereby generating a superior SERS effect.
3. Conclusion
In conclusion, AgNPs and MIL-101(Fe) are synthesized by the simplest physical self-assembly method to obtain the SERS substrate AgNPs/MIL-101(Fe) nano material, four probe molecules with low concentration are detected, and the enhancement effect is strong. The result of detecting R6G shows that the substrate has better stability and uniformity, the Raman attributive peak position RSD is 7.55%, and the enhancement factor EF is 2.09 × 109The raman signal was found to be approximately 10-fold enhanced compared to the Ag nanosol alone. Meanwhile, the AgNPs/MIL-101(Fe) nano material as an SERS substrate can detect that the minimum concentration of paraquat is 10-12M, and Raman signals are stable under different acid-base environments.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (10)
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