CN113649590A - Preparation method of nano-silver inverse opal SERS (surface enhanced Raman Scattering) probe for bipyridine herbicide detection - Google Patents
Preparation method of nano-silver inverse opal SERS (surface enhanced Raman Scattering) probe for bipyridine herbicide detection Download PDFInfo
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- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 82
- 238000001514 detection method Methods 0.000 title claims abstract description 71
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- 239000011022 opal Substances 0.000 title claims abstract description 44
- 239000004009 herbicide Substances 0.000 title claims abstract description 40
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 title claims abstract description 37
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
A preparation method of a nano-silver inverse opal SERS probe for bipyridine herbicide detection comprises the steps of preparing a titanium dioxide inverse opal structure and preparing a silver nanoparticle modified titanium dioxide inverse opal structure. The preparation process of the invention comprises two steps: firstly, forming a hexagonal close-packed colloidal crystal template by using PS microspheres as a template through a gravity settling method, then filling a titanium source solution into a gap of the template, and preparing the template after aging and heat treatmentObtaining a titanium dioxide inverse opal film, wherein the surface of the film is rich in hydroxyl groups to enable silver ammonia ions to be adsorbed on the surface of the film, reducing silver ammonia solution into silver nano particles through the dual functions of PVP stabilization and reduction, adhering paraquat and diquat molecules on the surface of the nano silver inverse opal through electrostatic action, and enhancing the conventional Raman signal of the bipyridyl herbicide molecules by utilizing the local surface plasmon resonance field of the metal surface, wherein the detection limit is 10‑8mol·L‑1. The SERS probe prepared by the method has good stability, good selectivity and high SERS responsivity.
Description
Technical Field
The invention relates to the field of material science, in particular to a preparation method of a nano silver inverse opal SERS probe for detecting trace bipyridyl herbicide.
Background
The bipyridyl herbicides diquat and paraquat have the characteristics of broad spectrum and high efficiency, and are widely applied to agricultural production. Diquat (DQ) and Paraquat (PQ) are contact-type quick-acting herbicides with the same action mode and weeding mechanism, and due to the reasons of strong water solubility, large use amount, moderate toxicity and the like, when the Diquat and Paraquat are applied to farmlands, water source pollution can be caused by rainwater washing and water flowing into water bodies, so that fishes, algae and other aquatic organisms in the water bodies are damaged; the direct contact can cause irritation, sensitization and even ulcer to the skin; a large amount of mistaken eating and biological accumulation can poison the organs of the animal body, such as the lung, the heart, the liver, the kidney and the like. The content of DQ and PQ in drinking water is strictly regulated in many countries, and therefore, the amount of residual DQ and PQ in drinking water and agricultural products needs to be accurately monitored.
At present, the commonly used analytical methods include gas chromatography, liquid chromatography, capillary electrophoresis, square wave voltammetry, spectrometry, and a technique of combining these methods with mass spectrometry. However, most of the methods require complicated sample pretreatment processes, have long detection time or do not have ideal minimum detection limits, so that the establishment of a rapid and sensitive method for detecting the DQ and PQ contents in drinking water has important significance.
Surface Enhanced Raman (SERS), from the discovery of laser, has been widely used for the detection of various metal ions, pesticide residues and the preparation of active molecular probes due to its high detection sensitivity. And the SERS detection method using the nano metal material as the substrate can greatly enhance the Raman signal. The patent of invention (CN 112730372A) of YangLiang Bao, national academy of sciences and college of science, and the like, discloses a flexible surface enhanced Raman substrate, a preparation method thereof and a paraquat detection method. The method comprises the steps of depositing gold nanorods on the surface of a cellulose membrane through an in-situ synthesis method to prepare a flexible surface-enhanced Raman substrate, adding a sample containing paraquat into a centrifugal tube, adding methanol and acetonitrile to obtain a mixed solution, shaking up, centrifuging, taking supernate, and carrying out SERS detection. 2011, du crystal, et al, the ecological environment research center of the academy of sciences of china, discloses a new paraquat detection method (CN 102087216A). The invention uses core-shell type Fe3O4The silver magnetic nanoparticles are used as an SERS substrate and used for enriching and detecting paraquat in a water body. With the continuous and deep research of semiconductor nano materials, the research of the composite semiconductor core-shell nano SERS substrate gradually gets attention. Min-Hui Lin et al established a novel, simple and rapid test technique using Surface Enhanced Raman Spectroscopy (SERS) in combination with a gold nanostar as the SERS substrate. SERS performance was evaluated by detecting the widely used pesticide paraquat in green tea samples. The tips of the gold nanostars may act as SERS hot spots to enhance the raman signal of the analyte molecules. In addition, the rough morphology of the gold nanostars increases the surface area, enabling good substrate-analyte interactions. MiningThe gold nanostar substrate was characterized by electron microscopy and Zetasizer. The detection limit of the SERS method to paraquat in green tea is 0.2mg/kg (Food Control.2021:130:108280). Ho Sang Junga et al prepared a Cellulose Filter Paper (CFP) paper-based surface enhanced raman scattering sensor for label-free molecular detection. Pretreating the apple surface with diquat and paraquat herbicides, then simply attaching a sensor on the apple peel, and carrying out SERS detection by a portable Raman spectrometer with the detection limit concentration of 1ppm (Sensors & Actuators: B. Chemical 2019:291:369–377). Firstly, the uniformity of the distribution of metal nanoparticles serving as an SERS active substrate is difficult to control, and the uniformity and reproducibility of an SERS signal are difficult to guarantee, so that quantitative or semi-quantitative detection is difficult to realize; secondly, the detected SERS spectrum has obvious background interference signals, which is not beneficial to the qualitative detection of the residue of the low-concentration bipyridyl herbicide; and thirdly, the detection process is too complicated, and the trace residue of the bipyridyl herbicide cannot be detected easily and quickly.
Due to the great development potential of the SERS technology, the technology has been focused and widely researched in recent years. The surface-enhanced Raman overcomes the defect of low Raman spectrum sensitivity, can obtain structural information which is not easily obtained by the conventional Raman spectrum, is widely used for surface research, adsorption interfaces and the like, and can obtain the characteristics of some adsorbed molecules. However, surface modification often results in a reduction in SERS signal intensity due to separation of hot spots in the analyte and substrate and background noise caused by the presence of a modulating layer prior to detection, which can make signal interpretation difficult or poor, and despite the long history of SERS has since its discovery, it has not been a complex tool for practical applications. One major obstacle is the poor reproducibility and stability of the widely used metal colloid matrix, limiting its application in quantitative analysis. Furthermore, when the SERS technique is put to practical use, cost is another major problem. For practical applications, the sample matrix interference is also not negligible. Since usually low concentrations of target molecules and matrix have the same access to hot spots, significant spectral "contamination" can often be observed in complex sample matrices, which leads to difficult analytical results. In conclusion, the method selects the silver nano-modified titanium dioxide inverse opal film without any modification as the surface Raman enhancement substrate, has simple procedure, and realizes the detection of the bipyridyl herbicide with low cost, high speed, high selectivity and high sensitivity.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to overcome the defects in the prior art and provides the nano-silver inverse opal SERS probe which is reasonable and practical in structure and convenient for rapidly detecting the trace bipyridyl herbicide.
The technical scheme of the invention is as follows: a preparation method of a nano-silver inverse opal SERS probe for bipyridine herbicide detection is characterized by comprising the following steps: the SERS probe is a monodisperse polystyrene microsphere which is self-assembled by a gravity sedimentation method to form a hexagonal close-packed colloidal crystal template, then a titanium source solution is filled in a gap of a polystyrene photonic crystal, a titanium dioxide inverse opal film is prepared after aging and heat treatment, the surface of the film is rich in hydroxyl groups to ensure that silver ammonia ions are adsorbed on the surface of the film, the silver ammonia solution is reduced into silver nano particles by the dual action of stabilization and reduction of polyvinylpyrrolidone (PVP), paraquat molecules and diquat molecules are adhered on the surface of the nano silver inverse opal through electrostatic interaction, and the conventional Raman signal of the bipyridyl herbicide molecules is enhanced by utilizing a local surface plasmon resonance field of a metal surface, so that the detection of the trace bipyridyl herbicide is realized, and the preparation process of the invention comprises the following two steps:
the first step is the preparation of titanium dioxide inverse opal film: firstly, preparing monodisperse polystyrene microspheres into a 2% PS colloidal solution by using 10mL of deionized water, placing the PS colloidal solution into a 50mL beaker, ultrasonically dispersing for 10 minutes, then sequentially cleaning a glass slide by using water and ethanol for 15 minutes each time, then soaking the glass slide into a mixed solution of hydrogen peroxide and concentrated sulfuric acid with a volume ratio of 3:7 for 12 hours, taking out the glass slide, and washing the glass slide by using a large amount of deionized waterBlow-drying with dry nitrogen, vertically inserting into PS colloidal solution, standing in an electrothermal constant temperature blast drying oven at 50 deg.C to obtain polystyrene colloidal crystal template, sequentially adding anhydrous ethanol 10mL, concentrated hydrochloric acid 2mL, tetrabutyl titanate 2.5mL, and distilled water 4mL into a 100 mL beaker, stirring for 1h to obtain TiO2The method comprises the following steps of preparing a precursor solution, vertically suspending and inserting a prepared polystyrene colloidal crystal template into the precursor solution, standing for 4 minutes, quickly and vertically taking out a film, wiping the back of the film, placing the film in a room temperature for 4 hours, placing the film in a muffle furnace, heating to 120 ℃ at 1 ℃/min, keeping for 2 hours, heating to 240 ℃ at 1 ℃/min, keeping for 2 hours, heating to 450 ℃ at 1 ℃/min, keeping for 2 hours, and obtaining the titanium dioxide inverse opal film by changing the amount of the solution, the proportion of added materials and reaction conditions;
the second step is the preparation of the nano silver inverse opal SERS probe: dispersing the prepared titanium dioxide inverse opal film in 10mL of ethanol to control the concentration of the titanium dioxide inverse opal film to be 2.5%, dissolving 1g of PVP in 50mL of ethanol, magnetically stirring to form a uniform solution, adding 10g of titanium dioxide inverse opal film dispersion solution in a 250mL three-neck flask, then transferring into 10mL of newly prepared silver ammonia solution with the concentration of 0.59mol/L, enabling silver ammonia ions to be adsorbed on the surface of the film due to the fact that hydroxyl groups are rich in the surface of the film, reducing the silver ammonia solution into silver nanoparticles through the dual effects of PVP stabilization and reduction, magnetically stirring for 1 hour, adding the PVP solution, stirring at 300rpm, reacting at 70 ℃ for 7 hours at constant temperature, preparing a nano-silver inverse opal SERS probe, and realizing detection of the bipyridine herbicide.
As a further improvement to the prior art, the titanium dioxide inverse opal film is cured and calcined, the color is changed from purple to green, the aperture is reduced to 200nm, and the aperture is reduced by 25%; the silver-ammonia solution is prepared by dissolving silver nitrate in deionized water, dropwise adding 28% ammonia water to generate brick-red precipitate, and continuously dropwise adding until the color becomes clear; the particle size of the surface nano silver seed crystal of the titanium dioxide inverse opal film modified by the silver nano particles is 10-50 nm, and the thickness of a silver shell layer formed by the nano silver seed crystal is 10-90 nm; the surface-enhanced Raman scattering active substrate is a titanium dioxide inverse opal film modified by silver nanoparticles, and a Raman spectrometer with the laser wavelength of 532nm is used for measuring the content of paraquat or diquat attached to the silver nanoparticles.
Compared with the prior art, the method has the beneficial effects that:
surface Enhanced Raman (SERS), from the discovery of laser, has been widely used for the detection of various metal ions, pesticide residues and the preparation of active molecular probes due to its high detection sensitivity. And the SERS detection method using the nano metal material as the substrate can greatly enhance the Raman signal. The patent of invention (CN 112730372A) of YangLiang Bao, national academy of sciences and college of science, and the like, discloses a flexible surface enhanced Raman substrate, a preparation method thereof and a paraquat detection method. The method comprises the steps of depositing gold nanorods on the surface of a cellulose membrane through an in-situ synthesis method to prepare a flexible surface-enhanced Raman substrate, adding a sample containing paraquat into a centrifugal tube, adding methanol and acetonitrile to obtain a mixed solution, shaking up, centrifuging, taking supernate, and carrying out SERS detection. 2011, du crystal, et al, the ecological environment research center of the academy of sciences of china, discloses a new paraquat detection method (CN 102087216A). The invention uses core-shell type Fe3O4The silver magnetic nanoparticles are used as an SERS substrate and used for enriching and detecting paraquat in a water body. With the continuous and deep research of semiconductor nano materials, the research of the composite semiconductor core-shell nano SERS substrate gradually gets attention. Min-Hui Lin et al established a novel, simple and rapid test technique using Surface Enhanced Raman Spectroscopy (SERS) in combination with a gold nanostar as the SERS substrate. SERS performance was evaluated by detecting the widely used pesticide paraquat in green tea samples. The tips of the gold nanostars may act as SERS hot spots to enhance the raman signal of the analyte molecules. In addition, the rough morphology of the gold nanostars increases the surface area, enabling good substrate-analyte interactions. The gold nanostar substrate was characterized using an electron microscope and a Zetasizer. The detection limit of the SERS method to paraquat in green tea is 0.2mg/kg (Food Control.2021:130:108280). A Cellulose Filter Paper (CFP) paper-based form for label-free molecular detection was prepared by Ho Sangg Junga et alA surface enhanced Raman scattering sensor. Pretreating the apple surface with diquat and paraquat herbicides, then simply attaching a sensor on the apple peel, and carrying out SERS detection by a portable Raman spectrometer with the detection limit concentration of 1ppm (Sensors & Actuators: B. Chemical 2019:291:369–377). Firstly, the uniformity of the distribution of metal nanoparticles serving as an SERS active substrate is difficult to control, and the uniformity and reproducibility of an SERS signal are difficult to guarantee, so that quantitative or semi-quantitative detection is difficult to realize; secondly, the detected SERS spectrum has obvious background interference signals, which is not beneficial to the qualitative detection of the residue of the low-concentration bipyridyl herbicide; and thirdly, the detection process is too complicated, and the trace residue of the bipyridyl herbicide cannot be detected easily and quickly.
Due to the great development potential of the SERS technology, the technology has been focused and widely researched in recent years. The surface-enhanced Raman overcomes the defect of low Raman spectrum sensitivity, can obtain structural information which is not easily obtained by the conventional Raman spectrum, is widely used for surface research, adsorption interfaces and the like, and can obtain the characteristics of some adsorbed molecules. However, surface modification often results in a reduction in SERS signal intensity due to separation of hot spots in the analyte and substrate and background noise caused by the presence of a modulating layer prior to detection, which can make signal interpretation difficult or poor, and despite the long history of SERS has since its discovery, it has not been a complex tool for practical applications. One major obstacle is the poor reproducibility and stability of the widely used metal colloid matrix, limiting its application in quantitative analysis. Furthermore, when the SERS technique is put to practical use, cost is another major problem. For practical applications, the sample matrix interference is also not negligible. Since usually low concentrations of target molecules and matrix have the same access to hot spots, significant spectral "contamination" can often be observed in complex sample matrices, which leads to difficult analytical results. In conclusion, the method selects the silver nano-modified titanium dioxide inverse opal film without any modification as the surface Raman enhancement substrate, has simple procedure, and realizes the detection of the bipyridyl herbicide with low cost, high speed, high selectivity and high sensitivity.
The invention firstly prepares the titanium dioxide inverse opal film: preparing monodisperse polystyrene microspheres into a 2-3% PS colloidal solution by using 10-20 mL of deionized water, placing the PS colloidal solution into a 50mL beaker, ultrasonically dispersing for 10-30 minutes, then sequentially carrying out ultrasonic cleaning on a glass slide by using water and ethanol for 15-30 minutes each time, then placing the glass slide into a mixed solution of hydrogen peroxide and concentrated sulfuric acid with a volume ratio of 3:7, soaking for 12-24 hours, taking out the glass slide, washing the glass slide by using a large amount of deionized water, blow-drying the glass slide by using dry nitrogen, vertically inserting the glass slide into the PS colloidal solution, standing the glass slide in an electrothermal constant-temperature blast drying box at 50-70 ℃ to obtain a polystyrene colloidal crystal template, finally taking 10-30 mL of anhydrous ethanol, 2-4 mL of concentrated hydrochloric acid, 2.5-5.0 mL of tetrabutyl titanate and 4-8 mL of distilled water, sequentially adding the glass slide into the 100 mL beaker, and stirring for 1-3 hours to obtain TiO2The method comprises the following steps of (1) vertically suspending and inserting a prepared polystyrene colloidal crystal template into the precursor solution, stopping the solution for 4-10 minutes, quickly and vertically taking out the film, wiping the back of the film, placing the film in a muffle furnace for 4-5 hours at room temperature, heating the film to 120 ℃ at the speed of 1-3 ℃/min, keeping the temperature for 2-3 hours, heating the film to 240 ℃ at the speed of 1-3 ℃/min, keeping the film for 2-3 hours, heating the film to 450 ℃ at the speed of 1-3 ℃/min, keeping the film for 2-3 hours, and obtaining the titanium dioxide inverse opal film by changing the amount of the solution, the proportion of added materials and reaction conditions;
the second step is the preparation of the nano silver inverse opal SERS probe: dispersing the prepared titanium dioxide inverse opal film in 10-30 mL of ethanol to control the concentration of the titanium dioxide inverse opal film to be 1-4%, dissolving 0.8-1.2 g of PVP in 30-70 mL of ethanol, magnetically stirring to form a uniform solution, adding 7-12 g of titanium dioxide inverse opal film dispersion liquid into a 250mL three-neck flask, then transferring 8-14 mL of newly prepared silver ammonia solution with the concentration of 0.4-1.0 mol/L, enabling silver ammonia ions to be adsorbed on the surface of the film due to rich hydroxyl groups on the surface of the film, reducing the silver ammonia solution into silver nanoparticles through the dual effects of PVP stabilization and reduction, magnetically stirring for 1-3 hours, adding the PVP solution, stirring at 300-500 rpm, reacting at a constant temperature of 65-80 ℃ for 5-8 hours, preparing a nano silver inverse opal SERS probe, and realizing detection of the bipyridine herbicide.
In conclusion, the titanium dioxide inverse opal SERS probe modified by nano silver, particularly the silver nanoparticles of which the target products are loaded on the titanium dioxide inverse opal structure, not only has extremely strong electromagnetic field enhancement effect, but also enables the structure of the target products to be stable, and greatly improves the SERS activity of the target products.
The second step is as follows: according to the invention, silver nanoparticles grow on the surface of the titanium dioxide inverse opal film through an in-situ synthesis method, so that a novel SERS substrate is successfully prepared, and the bipyridyl herbicide has high selectivity.
And thirdly: the prepared target product is used as an SERS active substrate, and is used for carrying out repeated multi-batch tests on paraquat and diquat under different concentrations respectively, when the concentration of the tested paraquat is as low as 10-8When the concentration is mol/L, the method can still effectively detect the concentration, and the detection consistency and repeatability are very good at multiple points and any point on a target product.
Fourthly, the method comprises the following steps: the preparation method is simple, scientific and effective. The titanium dioxide inverse opal structure modified by the silver nanoparticles has a stable structure, avoids the interference of background signals during detection, is more beneficial to the industrial preparation, and further enables a target product to be easily applied to the rapid detection of the bipyridyl herbicide in a commercial and more extensive manner.
Drawings
Fig. 1 is a schematic diagram of the preparation of a silver nanoparticle modified titanium dioxide inverse opal SERS substrate used in the present invention.
FIG. 2 is an SEM image of a polystyrene colloidal crystal template employed in the present invention.
Fig. 3 is an SEM image of a titanium dioxide inverse opal film employed in the present invention.
Fig. 4 is an SEM image of a silver nanoparticle modified titanium dioxide inverse opal SERS substrate employed in the present invention.
FIG. 5 is an XRD pattern of the titanium dioxide inverse opal SERS substrate modified by the titanium dioxide inverse opal film and silver nanoparticles adopted by the invention.
FIG. 6 is a surface enhanced Raman spectrum of paraquat detection employed in the present invention.
FIG. 7 is a surface enhanced Raman spectrum of diquat detection employed in the present invention.
The embodiments are further explained with reference to the drawings
Fig. 1 is a schematic diagram of the preparation of a silver nanoparticle modified titanium dioxide inverse opal SERS substrate used in the present invention. The method comprises the steps of self-assembling monodisperse polystyrene microspheres by a gravity settling method to form a hexagonal close-packed colloidal crystal template, filling a titanium source solution into gaps of polystyrene photonic crystals, aging, performing heat treatment to prepare a titanium dioxide inverse opal film, enabling silver ammonia ions to be adsorbed on the surface of the film due to rich hydroxyl groups on the surface of the film, reducing the silver ammonia solution into silver nano particles through the dual action of stabilization and reduction of polyvinylpyrrolidone, adhering paraquat molecules and diquat molecules on the surface of nano silver inverse opal through electrostatic interaction, and enhancing the conventional Raman signal of bipyridyl herbicide molecules by utilizing a local surface plasmon resonance field on a metal surface to realize the detection of trace bipyridyl herbicide.
FIG. 2 is an SEM image of a polystyrene colloidal crystal template employed in the present invention. The monodisperse polystyrene microspheres are self-assembled by a gravity sedimentation method to form a hexagonal close-packed colloidal crystal template. The polystyrene colloid crystal templates shown as a and b in the figure 2 are regularly arranged and have uniform structures, and the particle size of the microspheres is 200-300 nm.
Fig. 3 is an SEM image of a titanium dioxide inverse opal film employed in the present invention. After the titanium dioxide inverse opal film is solidified and calcined, the color is changed from purple to green, the aperture is reduced to 200nm, and the aperture is reduced by 25%.
Fig. 4 is an SEM image of a silver nanoparticle modified titanium dioxide inverse opal SERS substrate employed in the present invention. The particle size of the silver nano-particles on the surface layer of the titanium dioxide inverse opal film modified by the silver nano-particles shown in a and b in fig. 4 is 10-50 nm, and the thickness of the silver shell layer formed by the silver nano-particles is 10-90 nm.
FIG. 5 is an XRD pattern of the titanium dioxide inverse opal SERS substrate modified by the titanium dioxide inverse opal film and silver nanoparticles adopted by the invention. The titanium dioxide inverse opal XRD pattern shown in fig. 5 a, at 2 theta =25.6 °, 38.4 °, 48.4 °, 54.2 °, 62.9 ° and 69.1 °, are typical titanium dioxide anatase phase planes (101), (004), (200), (105), (204) and (220). The XRD pattern of the silver nanoparticle modified titanium dioxide inverse opal film shown in b in fig. 5 is typical of silver nanoparticles having a face-centered cubic structure at 2 θ =38.1 °, 44.3 °, 64.4 ° and 77.4 °, corresponding to crystal planes (111), (200), (220) and (311).
FIG. 6 is a surface enhanced Raman spectrum of paraquat detection employed in the present invention. Taking a glass slide, sequentially carrying out ultrasonic cleaning with water and ethanol for 15 minutes each time, then putting the glass slide into a mixed solution of hydrogen peroxide and concentrated sulfuric acid with a volume ratio of 3:7, soaking for 12 hours, taking out the glass slide, washing with a large amount of deionized water, and drying with dry nitrogen; then, 0.5mL of nano-silver inverse opal dispersion is absorbed by a pipette gun and dripped at the central position of the glass slide, after natural drying, 0.5mL of nano-silver inverse opal dispersion with the concentration of 10 is absorbed by the pipette gun-3Dripping mol/L paraquat solution at the center of the glass slide, drying, and performing SERS detection by using a Raman spectrometer 10-4mol/L~10-8The mol/L paraquat solution is detected sequentially according to the method. As shown in FIG. 6, the Raman characteristic peak of paraquat molecule is 840cm-1Corresponding to N-CH3Stretching vibration, 1197cm-11309cm corresponding to symmetric stretching vibration of C = C bond of benzene ring skeleton-11685cm corresponding to C-C telescopic vibration of biphenyl-1Corresponding to C = N stretching vibration in the pyridine ring, the characteristic peak intensity of paraquat molecules is obviously reduced along with the reduction of the solution concentration, and the detection limit is 10-8mol/L, reaching the lowest detection level of the common detection method.
FIG. 7 is a surface enhanced Raman spectrum of diquat detection employed in the present invention. Taking a glass slide, sequentially carrying out ultrasonic cleaning with water and ethanol for 15 minutes each time, then putting the glass slide into a mixed solution of hydrogen peroxide and concentrated sulfuric acid with a volume ratio of 3:7, soaking for 12 hours, taking out the glass slide, washing with a large amount of deionized water, and drying with dry nitrogen; then theSucking 0.5mL of nano silver inverse opal dispersion liquid by using a pipette, dripping the nano silver inverse opal dispersion liquid at the central position of the glass slide, naturally drying the nano silver inverse opal dispersion liquid, sucking 0.5mL of nano silver inverse opal dispersion liquid with the concentration of 10 by using the pipette-3Dripping mol/L diquat solution at the central position of the glass slide, drying, and performing SERS detection by using a Raman spectrometer 10-4mol/L~10-8The mol/L diquat solution is sequentially detected according to the method, and as shown in figure 6, the Raman characteristic peak of the diquat molecule is 733cm-1Corresponding to in-plane bending vibration (delta)ring)，1559cm-1Corresponding to vring+ delta (CH) vibration, 1615cm-1Corresponding to pyridine ring stretching vibration (v)ring+ v (C = N)) the intensity of the characteristic peak of the diquat molecule is obviously reduced along with the reduction of the solution concentration, and the detection limit is 10-8mol/L, reaching the lowest detection level of the common detection method.
The specific implementation mode is as follows: a preparation method of a nano-silver inverse opal SERS probe for bipyridine herbicide detection is characterized by comprising the following steps: the SERS probe is a monodisperse polystyrene microsphere which is self-assembled by a gravity sedimentation method to form a hexagonal close-packed colloidal crystal template, then a titanium source solution is filled in a gap of a polystyrene photonic crystal, a titanium dioxide inverse opal film is prepared after aging and heat treatment, the surface of the film is rich in hydroxyl groups to ensure that silver ammonia ions are adsorbed on the surface of the film, the silver ammonia solution is reduced into silver nano particles by the dual action of stabilization and reduction of polyvinylpyrrolidone (PVP), paraquat molecules and diquat molecules are adhered on the surface of the nano silver inverse opal through electrostatic interaction, and the conventional Raman signal of the bipyridyl herbicide molecules is enhanced by utilizing a local surface plasmon resonance field of a metal surface, so that the detection of the trace bipyridyl herbicide is realized, and the preparation process of the invention comprises the following two steps:
the first step is the preparation of titanium dioxide inverse opal film: firstly, preparing monodisperse polystyrene microspheres into a PS colloidal solution with the concentration of 2-3% by using 10-20 mL of deionized water, placing the PS colloidal solution into a 50mL beaker, ultrasonically dispersing for 10-30 minutes, then taking a glass slide, sequentially cleaning the glass slide with water and ethanol for 15-30 minutes each time, and then placing the glass slide into a container with the volume ratio of 3:7 and peroxideSoaking the mixed solution of hydrogen and concentrated sulfuric acid for 12-24 hours, taking out, washing with a large amount of deionized water, drying by using dry nitrogen, vertically inserting the washed solution into a PS colloidal solution, standing in an electrothermal constant-temperature blast drying oven at 50-70 ℃ to obtain a polystyrene colloidal crystal template, and finally sequentially adding 10-30 mL of absolute ethyl alcohol, 2-4 mL of concentrated hydrochloric acid, 2.5-5.0 mL of tetrabutyl titanate and 4-8 mL of distilled water into a 100 mL beaker, and stirring for 1-3 hours to obtain TiO2The method comprises the following steps of (1) vertically suspending and inserting a prepared polystyrene colloidal crystal template into the precursor solution, stopping the solution for 4-10 minutes, quickly and vertically taking out the film, wiping the back of the film, placing the film in a muffle furnace for 4-5 hours at room temperature, heating the film to 120 ℃ at the speed of 1-3 ℃/min, keeping the temperature for 2-3 hours, heating the film to 240 ℃ at the speed of 1-3 ℃/min, keeping the film for 2-3 hours, heating the film to 450 ℃ at the speed of 1-3 ℃/min, keeping the film for 2-3 hours, and obtaining the titanium dioxide inverse opal film by changing the amount of the solution, the proportion of added materials and reaction conditions;
the second step is the preparation of the nano silver inverse opal SERS probe: dispersing the prepared titanium dioxide inverse opal film in 10-30 mL of ethanol to control the concentration of the titanium dioxide inverse opal film to be 1-4%, dissolving 0.8-1.2 g of PVP in 30-70 mL of ethanol, magnetically stirring to form a uniform solution, adding 7-12 g of titanium dioxide inverse opal film dispersion liquid into a 250mL three-neck flask, then transferring 8-14 mL of newly prepared silver ammonia solution with the concentration of 0.4-1.0 mol/L, enabling silver ammonia ions to be adsorbed on the surface of the film due to rich hydroxyl groups on the surface of the film, reducing the silver ammonia solution into silver nanoparticles through the dual effects of PVP stabilization and reduction, magnetically stirring for 1-3 hours, adding the PVP solution, stirring at 300-500 rpm, reacting at a constant temperature of 65-80 ℃ for 5-8 hours, preparing a nano silver inverse opal SERS probe, and realizing detection of the bipyridine herbicide.
Example (b): the monodisperse polystyrene microspheres are self-assembled by a gravity sedimentation method to form a hexagonal close-packed colloidal crystal template, then a titanium source solution is filled in a gap of a polystyrene photonic crystal, a titanium dioxide inverse opal film is prepared after aging and heat treatment, the surface of the film is rich in hydroxyl groups to enable silver ammonia ions to be adsorbed on the surface of the film, the silver ammonia solution is reduced into silver nano particles through the dual actions of polyvinylpyrrolidone (PVP) stabilization and reduction, paraquat molecules and diquat molecules are adhered on the surface of the nano silver inverse opal through electrostatic interaction, and the conventional Raman signal of the bipyridyl herbicide molecules is enhanced by utilizing a local surface plasmon resonance field on the metal surface, so that the detection of the trace bipyridyl herbicide is realized.
The first step is the preparation of titanium dioxide inverse opal film: firstly, preparing monodisperse polystyrene microspheres into a 2% PS colloidal solution by using 10mL of deionized water, placing the PS colloidal solution into a 50mL beaker, ultrasonically dispersing for 10 minutes, then, taking a glass slide, sequentially cleaning the glass slide by using water and ethanol for 15 minutes each time, then, putting the glass slide into a mixed solution of hydrogen peroxide and concentrated sulfuric acid with the volume ratio of 3:7, soaking the glass slide for 12 hours, taking the glass slide out, washing the glass slide by using a large amount of deionized water, drying the glass slide by using dry nitrogen, vertically inserting the glass slide into the PS colloidal solution, standing the glass slide in an electrothermal constant-temperature blast drying box at 50 ℃ to obtain a polystyrene colloidal crystal template, finally, sequentially adding 10mL of absolute ethyl alcohol, 2mL of concentrated hydrochloric acid, 2.5mL of tetrabutyl titanate and 4mL of distilled water into a 100 mL beaker, and stirring the glass slide for 1 hour to obtain TiO2The method comprises the following steps of preparing a precursor solution, vertically suspending and inserting a prepared polystyrene colloidal crystal template into the precursor solution, standing for 4 minutes, quickly and vertically taking out a film, wiping the back of the film, placing the film in a room temperature for 4 hours, placing the film in a muffle furnace, heating to 120 ℃ at 1 ℃/min, keeping for 2 hours, heating to 240 ℃ at 1 ℃/min, keeping for 2 hours, heating to 450 ℃ at 1 ℃/min, keeping for 2 hours, and obtaining the titanium dioxide inverse opal film by changing the amount of the solution, the proportion of added materials and reaction conditions;
the second step is the preparation of the nano silver inverse opal SERS probe: dispersing the prepared titanium dioxide inverse opal film in 10mL of ethanol to control the concentration of the titanium dioxide inverse opal film to be 2.5%, dissolving 1g of PVP in 50mL of ethanol, magnetically stirring to form a uniform solution, adding 10g of titanium dioxide inverse opal film dispersion solution in a 250mL three-neck flask, then transferring into 10mL of newly prepared silver ammonia solution with the concentration of 0.59mol/L, enabling silver ammonia ions to be adsorbed on the surface of the film due to the fact that hydroxyl groups are rich in the surface of the film, reducing the silver ammonia solution into silver nanoparticles through the dual effects of PVP stabilization and reduction, magnetically stirring for 1 hour, adding the PVP solution, stirring at 300rpm, reacting at 70 ℃ for 7 hours at constant temperature, preparing a nano-silver inverse opal SERS probe, and realizing detection of the bipyridine herbicide.
The detection method of paraquat comprises the following steps: firstly, taking a glass slide, sequentially carrying out ultrasonic cleaning by using water and ethanol for 15 minutes each time, then putting the glass slide into a mixed solution of hydrogen peroxide and concentrated sulfuric acid with a volume ratio of 3:7, soaking the glass slide for 12 hours, taking out the glass slide, washing the glass slide by using a large amount of deionized water, and drying the glass slide by using dry nitrogen; then, 0.5mL of nano-silver inverse opal dispersion is absorbed by a pipette gun and dripped at the central position of the glass slide, after natural drying, 0.5mL of nano-silver inverse opal dispersion with the concentration of 10 is absorbed by the pipette gun-3Dripping a mol/L paraquat solution at the central position of the glass slide, drying, and performing SERS detection by using a Raman spectrometer with the concentration of 10-4mol/L~10-8Paraquat solution with mol/L concentration of 10-3mol/L~10-8The mol/L diquat solution is sequentially detected according to the method, and the detection results are shown in FIGS. 6 and 7.
Claims (5)
1. A preparation method of a nano-silver inverse opal SERS probe for bipyridine herbicide detection is characterized by comprising the following steps: the SERS probe is a monodisperse polystyrene microsphere (PS) which is self-assembled by a gravity sedimentation method to form a hexagonal close-packed colloidal crystal template, then a titanium source solution is filled in a gap of a polystyrene photonic crystal, a titanium dioxide inverse opal film is prepared after aging and heat treatment, the surface of the film is rich in hydroxyl groups to enable silver ammonia ions to be adsorbed on the surface of the film, the silver ammonia solution is reduced into silver nano particles through the dual action of stabilization and reduction of polyvinylpyrrolidone (PVP), paraquat molecules and diquat molecules are adhered on the surface of the nano silver inverse opal through electrostatic interaction, and the conventional Raman signal of the bipyridyl herbicide molecules is enhanced by utilizing a local surface plasmon resonance field of a metal surface, so that the detection of the trace bipyridyl herbicide is realized, and the preparation process of the invention comprises the following two steps:
1.1 the first step is the preparation of titanium dioxide inverse opal film: firstly, preparing monodisperse polystyrene microspheres into a PS colloidal solution with the concentration of 2-3% by using 10-20 mL of deionized water, placing the PS colloidal solution into a 50mL beaker, and ultrasonically dispersing for 10-30 minutesThe method comprises the following steps of taking a glass slide, sequentially carrying out ultrasonic cleaning with water and ethanol for 15-30 minutes each time, then putting the glass slide into a mixed solution of hydrogen peroxide and concentrated sulfuric acid with a volume ratio of 3:7, soaking for 12-24 hours, taking out, washing with a large amount of deionized water, drying with dry nitrogen, vertically inserting the glass slide into a PS colloidal solution, standing in an electric heating constant-temperature air blast drying box at 50-70 ℃ to obtain a polystyrene colloidal crystal template, finally, taking 10-30 mL of absolute ethyl alcohol, 2-4 mL of concentrated hydrochloric acid, 2.5-5.0 mL of tetrabutyl titanate and 4-8 mL of distilled water, sequentially adding the anhydrous ethyl alcohol, the concentrated hydrochloric acid, the tetrabutyl titanate and the distilled water into a 100 mL beaker, and stirring for 1-3 hours to obtain TiO2The method comprises the following steps of (1) vertically suspending and inserting a prepared polystyrene colloidal crystal template into the precursor solution, stopping the solution for 4-10 minutes, quickly and vertically taking out the film, wiping the back of the film, placing the film in a muffle furnace for 4-5 hours at room temperature, heating the film to 120 ℃ at the speed of 1-3 ℃/min, keeping the temperature for 2-3 hours, heating the film to 240 ℃ at the speed of 1-3 ℃/min, keeping the film for 2-3 hours, heating the film to 450 ℃ at the speed of 1-3 ℃/min, keeping the film for 2-3 hours, and obtaining the titanium dioxide inverse opal film by changing the amount of the solution, the proportion of added materials and reaction conditions;
1.2 the second step is the preparation of the nano silver inverse opal SERS probe: dispersing the prepared titanium dioxide inverse opal film in 10-30 mL of ethanol to control the concentration of the titanium dioxide inverse opal film to be 1-4%, dissolving 0.8-1.2 g of PVP in 30-70 mL of ethanol, magnetically stirring to form a uniform solution, adding 7-12 g of titanium dioxide inverse opal film dispersion liquid into a 250mL three-neck flask, then transferring 8-14 mL of newly prepared silver ammonia solution with the concentration of 0.4-1.0 mol/L, enabling silver ammonia ions to be adsorbed on the surface of the film due to rich hydroxyl groups on the surface of the film, reducing the silver ammonia solution into silver nanoparticles through the dual effects of PVP stabilization and reduction, magnetically stirring for 1-3 hours, adding the PVP solution, stirring at 300-500 rpm, reacting at a constant temperature of 65-80 ℃ for 5-8 hours, preparing a nano silver inverse opal SERS probe, and realizing detection of the bipyridine herbicide.
2. The preparation method of the nano-silver inverse opal SERS probe for bipyridine herbicide detection according to claim 1, wherein the preparation method comprises the following steps: the titanium dioxide inverse opal film is cured and calcined, the color is changed from purple to green, the aperture is reduced to 200nm, and the aperture is reduced by 25%.
3. The preparation method of the nano-silver inverse opal SERS probe for bipyridine herbicide detection according to claim 1, wherein the preparation method comprises the following steps: the silver-ammonia solution is prepared by dissolving silver nitrate in deionized water, dropwise adding 28% ammonia water to generate brick-red precipitate, and continuously dropwise adding until the color becomes clear.
4. The preparation method of the nano-silver inverse opal SERS probe for bipyridine herbicide detection according to claim 1, wherein the preparation method comprises the following steps: the particle size of the surface nano silver seed crystal of the titanium dioxide inverse opal film modified by the silver nano particles is 10-50 nm, and the thickness of a silver shell layer formed by the nano silver seed crystal is 10-90 nm.
5. The preparation method of the nano-silver inverse opal SERS probe for bipyridine herbicide detection according to claim 1, wherein the preparation method comprises the following steps: the surface-enhanced Raman scattering active substrate is a titanium dioxide inverse opal film modified by silver nanoparticles, and a Raman spectrometer with the laser wavelength of 532nm is used for measuring the content of paraquat or diquat attached to the silver nanoparticles.
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