CN113466205B - Preparation method of surface enhanced Raman sensor based on metal organic framework structure - Google Patents
Preparation method of surface enhanced Raman sensor based on metal organic framework structure Download PDFInfo
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Abstract
The invention discloses a preparation method of a surface enhanced Raman sensor based on a metal organic framework structure, wherein the surface enhanced Raman sensor is prepared from a rod-shaped Ag-MOF material with silver as a metal coordination ion and 2-amino terephthalic acid as a ligand, the material is uniformly coated on the surface of a substrate during preparation, silver ions are reduced into uniform silver simple substance particles through high-temperature carbonization reduction, and an organic matter is carbonized, so that the interference of a functional group in a Raman spectrum of the functional group in a low-wave-number section is removed, and the sensor has a good surface enhanced Raman sensing effect. The sensor has the advantages of simple preparation process, low cost, uniform grid structure of MOF materials, fixed distance between silver particles, good surface enhanced Raman effect, high sensitivity and small background interference signal, and can be used for low-concentration detection of various organic matters in water.
Description
Technical Field
The invention relates to the field of aquaculture and sewage detection, in particular to a preparation method of a surface enhanced Raman sensor based on a Metal Organic Framework (MOF).
Background
Methylene Blue (MB), Malachite Green (MG) and Crystal Violet (CV) are three common organic dyes, have good effects of killing fungi, bacteria and parasites and the like under low dosage, and are often used for improving the survival rate of fishes in aquatic product cultivation and transportation. The malachite green and the crystal violet are triphenylmethane organic matters, are reported to have high toxicity, high residue, three-cause harm and the like, are listed as edible animal drugs in China, are not detected by European Union requirements, and are forbidden due to low price. In addition, methylene blue is a phenothiazine organic substance with relatively low toxicity, so that malachite green and crystal violet are replaced, but the methylene blue still has certain toxicity and teratogenicity, and is prohibited from being used for aquaculture in some countries.
The traditional detection methods include spectrophotometry, liquid chromatography, immunoadsorption analysis and the like. The traditional method usually needs complex pretreatment on the sample, so that the whole detection process is slow, the instrument cost is high, and the portability is poor. The surface enhanced Raman is a low-cost, rapid, portable and non-invasive detection method, has higher sensitivity and can carry out trace detection. The methylene blue, malachite green and crystal violet molecules have larger Raman cross sections, and are suitable for detection by a surface enhanced Raman method, and the Raman fingerprint spectrum can distinguish different substances and can also effectively detect a mixed solution of the substances. However, gaps among the nano particles forming hot spots of the traditional surface enhanced Raman substrate are difficult to control, when the sensor is used for detecting the low concentration of organic dye in aquaculture and sewage, the Raman spectrum signal intensity cannot be effectively improved, and the silver nano particles are easy to oxidize, so that the sensor is not favorable for being used for detecting the low concentration of organic dye in aquaculture and sewage.
Disclosure of Invention
The invention aims to solve the problems and provide a preparation method of a surface Raman enhancement sensor, which has higher sensitivity and can be used for detecting low concentration of organic dye in aquaculture and sewage.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a surface enhanced Raman sensor based on a metal organic framework structure comprises the following steps:
dissolving silver nitrate in deionized water, dissolving 2-amino terephthalic acid in a DMF solution, adding the DMF in which the 2-amino terephthalic acid is dissolved into the deionized water in which the silver nitrate is dissolved, and heating and refluxing the mixed solution to obtain a dispersion liquid;
washing and drying the dispersion liquid to obtain Ag-MOF solid powder, dispersing the Ag-MOF solid powder in a solution, coating the solution on the surface of a substrate, and drying;
and step three, performing high-temperature carbonization reduction on the spin-coated substrate, heating to a certain temperature under the protection of inert gas, keeping for a period of time, and naturally cooling to room temperature to obtain the surface-enhanced Raman sensor.
The surface-enhanced Raman sensor is prepared from a rod-shaped Ag-MOF material with silver as a metal coordination ion and 2-amino terephthalic acid as a ligand, the material is uniformly coated on the surface of a substrate during preparation, silver ions are reduced into uniform silver elementary substance particles through high-temperature carbonization reduction, and organic matters are carbonized, so that the interference of a functional group in a Raman spectrum of the functional group in a low-wave band is removed, and the sensor has a good surface-enhanced Raman sensing effect. The sensor has the advantages of simple preparation process, low cost, high sensitivity and small background interference signal, exerts the advantages of uniform grid structure of MOF materials, and can be used for low-concentration detection of organic dyes in aquaculture and sewage.
Preferably, the molar ratio of silver nitrate to 2-aminoterephthalic acid in step one is 1: 0.5-2, and fully reacting silver nitrate and 2-amino terephthalic acid.
Preferably, the mixed solution is heated to reflux at 125 ℃ for 2 hours in step one.
Preferably, in step two, the dispersion liquid is centrifugally washed with DMF and ethanol for a plurality of times, and dried under vacuum at 60 ℃ to make the residual solvent in the gaps more volatile.
Preferably, the substrate in the second step comprises glass, silicon wafer, ITO glass and the like, and the surface of the substrate is flat, so that the sensitive material can be distributed more uniformly.
Preferably, the surface of the substrate is sputtered by magnetron sputtering of a metal simple substance with the thickness of 100-1500 nm, so that the Raman characteristic peak is few and background interference is not easy to generate.
Preferably, the metal element comprises gold, silver, copper, aluminum, nickel and chromium.
Preferably, before the substrate surface is used, acetone, isopropanol and ethanol are respectively used for ultrasonic cleaning, and impurities and organic matters on the surface of the silicon wafer are removed.
Preferably, the coating method in the second step includes drop coating, spin coating, liquid phase epitaxy and the like, so that the sensitive material can be uniformly and flatly distributed, and the thickness of the material can be controlled.
Preferably, the temperature range of the high-temperature carbonization reduction in the third step is 200-.
According to the invention, silver with high sensitivity is selected as a noble metal ion to construct MOF, 2-amino terephthalic acid is used as an organic ligand, compact and uniform simple substance silver nanoparticles are formed on the rod-shaped surface of the Ag-MOF, organic matters are carbonized through heat treatment, functional groups are destroyed, characteristic peaks of the functional groups in Raman spectra are removed, the interference on a sensor is reduced, the adsorbability of a carbon material and the hot spot effect of the silver nanoparticles are effectively combined, the sensor with the surface enhanced Raman effect is obtained, and therefore, the sensor can be used for low-concentration detection of organic dyes in aquaculture and sewage.
The MOF is composed of metal ions and organic ligands, has an ordered grid structure, changes the metal ions by adjusting the types of the metal ions and the organic ligands, controls the distance between the metal ions, and finally can obtain a structure with uniform particle size and compact arrangement by a high-temperature reduction mode, thereby generating better surface enhanced Raman effect.
The preparation method has the advantages that the preparation method is simple and rapid, the cost is low, the ordered grid structure of the MOF material is used, the hot spot distance can be controlled, the interference of the use of an organic reagent in the preparation process is treated through high temperature, the obtained silver nanoparticles are regular in shape, uniform in size and compact in arrangement, have a good hot spot effect, and can effectively improve the Raman spectrum signal intensity, and the silver nanoparticles contain some carbon elements, so that the oxidation of the silver nanoparticles can be slowed down, the sensor can be stably stored in the air for a period of time, and the sensor is favorably used for low-concentration detection of organic dyes in aquaculture and sewage.
Drawings
FIG. 1 is a SEM image of a prepared sensor;
FIG. 2 is a TEM image of the prepared sensor;
FIG. 3 is an X-ray spectrum of the prepared sensor;
fig. 4 is an EDX image in STEM mode of a single particle; a is HAADF-STEM, B is a silver element surface scanning image, and C is a carbon element surface scanning image;
FIG. 5 is a Raman spectrum of a blank sensor processed using different temperatures; wherein, the curve a is a group without high temperature treatment, the curve b is a group treated at 300 ℃ and the curve c is a group treated at 350 ℃;
FIG. 6 is a Raman spectrum of R6G detected after the sensor was placed in air for various days; wherein, the curve a is the detection result of the sensor after being placed in the air for 1 day, the curve b is the detection result of the sensor after being placed in the air for 30 days, and the curve c is the detection result of the sensor after being placed in the air for 60 days;
FIG. 7 is a Raman spectrum of a sensor detecting different concentrations of R6G and a blank sensor; wherein, a is that the sensor detects that the concentration of R6G is 10 -6 Raman spectrum at M, b is the concentration of R6G detected by the sensor as 10 -8 Raman spectrum at M, c is the concentration of R6G detected by the sensor as 10 -9 A Raman spectrogram at M, and d is a Raman spectrogram of the blank sensor;
FIG. 8 is a Raman spectrum of a lake water with sensors for detecting different concentrations of MB, MG and CV; wherein, A is MB solution for detecting different concentrations, B is MG solution for detecting different concentrations, and C is CV solution for detecting different concentrations; the concentration of the solution to be measured in the curve a is 10 -3 The concentration of the solution to be measured in M and b is 10 -5 The concentration of the solution to be measured in M and c is 10 -6 The concentration of the solution to be measured in M and d is 10 -7 M。
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
In this example, all chemical reagents were analytically pure and above. 2-amino terephthalic acid, silver nitrate AgNO3, DMF, acetone, isopropanol, ethanol, rhodamine 6G (R6G) were purchased from Sigma Aldrich (Sigma, USA). The deionized water used in the experiment was prepared in real time from a Millipore-Q ultrapure water system (Millipore Corp., USA) and had a conductivity of not less than 18.2 M.OMEGA.cm.
Preparation of the sensor
Step one, weighing 169.87mg (1mmol) of silver nitrate, fully dissolving in 50m L deionized water, weighing 181.15mg (1mmol) of 2-amino terephthalic acid, dissolving in 5 ml of DMF, slowly adding the DMF dissolved with the 2-amino terephthalic acid into the deionized water dissolved with the silver nitrate by using a syringe, and heating and refluxing for 2 hours at 125 ℃ to obtain a dispersed dark gray liquid. Centrifuging and washing the obtained solution respectively with DMF and ethanol for 3 times, and vacuum-drying at 60 ℃ for one night to obtain black gray solid powder Ag-MOF;
step two, ultrasonically cleaning the silicon wafer for 2 times by respectively using acetone, isopropanol and ethanol, removing impurities, organic matters and the like on the surface of the silicon wafer, sputtering a gold simple substance with the thickness of 300nm on the silicon wafer by using magnetron sputtering, taking chromium as a transition layer, and cutting to obtain a gold sheet with the thickness of 5mm x 5 mm;
and step three, weighing 20mg of Ag-MOF, ultrasonically dispersing in 1ml of deionized water, dropwise adding 10ul of the dispersion liquid on the surface of the gold plate cleaned by plasma at a low speed of 900r and a high speed of 3000r, placing the gold plate on a heating table at 45 ℃ for drying, and repeating the steps for 3 times. Carrying out high-temperature carbonization reduction on the spin-coated substrate in a tube furnace, introducing argon for protection, raising the temperature to 350 ℃ at the speed of 3 ℃/min, keeping the temperature for 2h, and naturally cooling to room temperature;
and step four, dripping the liquid to be detected on the surface of the sensor, waiting for the liquid to be detected to be dried, and detecting by using a Renishaw inVia Qontor Raman spectrometer under the conditions of 532nm of excitation light wavelength, 1.25mw of laser power and 10s of integration time.
FIG. 1 is an SEM image of the sensor, and FIG. 2 is a TEM image of the sensor, which shows that the sensor has a hollow nanorod structure, and a large number of compact and uniform particles are distributed on the surface of the sensor, so that a hot spot is formed, and the surface enhanced Raman effect is generated.
From the X-ray spectroscopy (XPS) in FIG. 3, it can be seen that there are significant C1S, Ag3d, Ag3p3/2, Ag3p1/2, indicating that the sensor has a large amount of silver nanoparticles on the surface in addition to carbon.
In fig. 4, EDX elemental analysis in STEM mode was performed on a single sensor particle, and it can be observed that the particle is composed of silver and a small amount of carbon element, and can block the sensor signal attenuation caused by silver oxidation in air.
Compared with the graph in FIG. 5, it is seen that different high-temperature treatment temperatures are used in the third step, when the high-temperature treatment is not performed, the blank sensor has more organic functional group peak positions in the low-band part of the Raman spectrum, the organic functional groups are destroyed and carbonized along with the increase of the high-temperature treatment temperature, and the Raman spectrum only has obvious D peak and G peak after the treatment at 350 ℃.
By comparing the sensor of FIG. 6 after different days of exposure to air 10 -6 M R6G water solution, it was found that the sensor could be stored stably in air for a period of time.
In the raman spectrum in fig. 7, it can be seen that the sensor is relatively clean, the background interference signal is less, and the R6G solution with the concentration of 10-9M can be detected, which indicates that the sensor has a relatively strong surface enhanced raman effect and relatively high sensitivity.
As can be seen from the detection of different concentrations MB, MG and CV in lake water by the sensor in FIG. 8, the sensor can detect the concentration of 10 -7 The MB, MG and CV solution of M can be used for detecting the low concentration of organic dye in aquaculture and sewage.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. A preparation method of a surface enhanced Raman sensor based on a metal organic framework structure is characterized by comprising the following steps:
dissolving silver nitrate in deionized water, dissolving 2-amino terephthalic acid in a DMF solution, adding the DMF in which the 2-amino terephthalic acid is dissolved into the deionized water in which the silver nitrate is dissolved, and heating and refluxing the mixed solution to obtain a dispersion liquid;
washing and drying the dispersion liquid to obtain Ag-MOF solid powder, dispersing the Ag-MOF solid powder in a solution, coating the solution on the surface of a substrate, and drying;
step three, performing high-temperature carbonization reduction on the spin-coated substrate, heating to a certain temperature under the protection of inert gas, keeping for a period of time, and naturally cooling to room temperature to obtain the surface-enhanced Raman sensor;
the temperature range of the high-temperature carbonization reduction in the third step is 200-450 ℃, and the time is 1-3 hours.
2. The method for preparing a surface-enhanced Raman sensor based on a metal-organic framework structure according to claim 1, wherein the molar ratio of silver nitrate to 2-aminoterephthalic acid in the first step is 1: 0.5-2.
3. The method for preparing a surface-enhanced Raman sensor based on a metal-organic framework structure according to claim 1, wherein the mixed solution is heated and refluxed at 125 ℃ for 2 hours in the first step.
4. The method for preparing a surface-enhanced Raman sensor based on a metal-organic framework structure according to claim 1, wherein in the second step, the dispersion liquid is centrifugally washed with DMF and ethanol respectively, and dried under vacuum at 60 ℃.
5. The method for preparing a surface-enhanced Raman sensor based on a metal-organic framework structure according to claim 1, wherein the substrate in the second step comprises glass, silicon wafer and ITO glass.
6. The method as claimed in claim 5, wherein the substrate surface is sputtered by magnetron sputtering a metal element with a thickness of 100-1500 nm.
7. The method for preparing the surface-enhanced Raman sensor based on the metal-organic framework structure according to claim 6, wherein the metal element comprises gold, silver, copper, aluminum, nickel, or chromium.
8. The method for preparing the surface-enhanced Raman sensor based on the metal-organic framework structure according to claim 5, wherein the surface of the substrate is ultrasonically cleaned by acetone, isopropanol and ethanol respectively before use to remove impurities and organic matters on the surface of the silicon wafer.
9. The method for preparing a surface-enhanced Raman sensor based on a metal-organic framework structure according to claim 1, wherein the coating method in the second step comprises drop coating, spin coating, and liquid phase epitaxy.
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