CN114073938A - Nickel ferrite based magnetic nanocomposite material and preparation method thereof, and method for enriching organophosphorus pesticide residues - Google Patents

Nickel ferrite based magnetic nanocomposite material and preparation method thereof, and method for enriching organophosphorus pesticide residues Download PDF

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CN114073938A
CN114073938A CN202010819686.2A CN202010819686A CN114073938A CN 114073938 A CN114073938 A CN 114073938A CN 202010819686 A CN202010819686 A CN 202010819686A CN 114073938 A CN114073938 A CN 114073938A
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nickel ferrite
based magnetic
polydopamine
magnetic nanocomposite
nanocomposite material
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王学东
王慧利
杜力阳
高明
李捷意
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Suzhou University of Science and Technology
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Abstract

The invention belongs to the technical field of magnetic nano composite materials, and particularly relates to a nickel ferrite based magnetic nano composite material, a preparation method thereof and an enrichment method of organophosphorus pesticide residues. The nickel ferrite-based magnetic nano composite material is of a core-shell structure, the core is nickel ferrite nano particles, and the shell is polydopamine and a magnesium/aluminum double hydroxide nano layer coated on the surface of the polydopamine. The nickel ferrite based magnetic nano composite material overcomes the defects of small surface area and easy caking of the traditional iron-based crystal nano particles, polydopamine has high dispersibility and biocompatibility, and the magnesium/aluminum double hydroxide nano layer has larger specific surface area, so that the composite material has good dispersibility and adsorption performance, can be used as an adsorbent in a magnetic solid phase extraction system, and greatly improves the efficiency of magnetic solid phase extraction.

Description

Nickel ferrite based magnetic nanocomposite material and preparation method thereof, and method for enriching organophosphorus pesticide residues
Technical Field
The invention belongs to the technical field of magnetic nano composite materials, and particularly relates to a nickel ferrite based magnetic nano composite material, a preparation method thereof and an enrichment method of organophosphorus pesticide residues.
Background
Magnetic Solid Phase Extraction (MSPE) is a dispersed solid phase extraction technique using magnetic or magnetizable materials as the adsorbent matrix. In the magnetic solid phase extraction process, a magnetic adsorbent is not directly filled into an adsorption column, but is added into a solution or suspension of a sample, a target analyte is adsorbed to the surface of the dispersed magnetic adsorbent, the target analyte migrates along with the adsorbent under the action of an external magnetic field, and finally the target analyte is eluted by a suitable solvent, so that the target analyte is separated from a matrix of the sample. The magnetic adsorbent is usually Magnetic Nanoparticles (MNPs), and because the specific surface area is large and the diffusion distance is short, the low-concentration micro-extraction can be realized only by using a small amount of adsorbent and short balance time, and the extraction capacity and the extraction efficiency are higher.
The magnetic solid phase extraction has the advantages of large contact area, complete separation and collection by using an external magnet and the like, so that the magnetic solid phase extraction is a target analyte pretreatment method widely applied in recent years, and particularly, in the aspects of sensing and trace substance detection, the sample treatment process can be greatly simplified, so that the target analyte loss in the treatment process is avoided to cause inaccurate or undetectable detection results. The food safety is closely related to the life safety, so that the requirement on the accuracy of a detection result is relatively high in the detection of pesticide residues, and higher requirements are provided for the extraction and adsorption capacity of an adsorbent.
NiFe2O4The iron-based nano material is considered to be an iron-based nano material with a great application prospect due to the ultrahigh paramagnetism, low synthesis cost, good chemical stability and integrity. However, the conventional NiFe2O4The nano particles are easy to oxidize and corrode and are easy to agglomerate in water, and the detection requirement of pesticide residue cannot be met.
Disclosure of Invention
The invention aims to provide a nickel ferrite based magnetic nanocomposite material for improving NiFe2O4Dispersibility, adsorptivity and biocompatibility of the nanoparticles.
The second purpose of the invention is to provide a preparation method of nickel ferrite based magnetic nanocomposite material, so as to improve the existing NiFe2O4Dispersibility, adsorptivity and biocompatibility of the nanoparticles.
The third purpose of the invention is to provide an enrichment method of organophosphorus pesticide residues, so as to improve the enrichment efficiency of organophosphorus pesticide residues.
The fourth purpose of the invention is to provide the application of the nickel ferrite based magnetic nanocomposite material in the detection of organophosphorus pesticide residues, which can accurately detect organophosphorus pesticide residues, has high reusability and is environment-friendly.
In order to realize the purpose, the nickel ferrite based magnetic nano composite material has the specific technical scheme that:
the nickel ferrite-based magnetic nanocomposite material is of a core-shell structure, the core is a nickel ferrite nanoparticle, the shell is polydopamine and a magnesium/aluminum double hydroxide nano layer coated on the surface of the polydopamine, and the mass ratio of the core to the shell is 1: 3-5, wherein the mass ratio of the polydopamine layer to the magnesium/aluminum double hydroxide nano layer in the shell is 1: 2-4.
The nickel ferrite based magnetic nano composite material adopts a core-shell structure, overcomes the defects of easy agglomeration and easy corrosion of the traditional iron-based crystal nano particle magnetic core, and polydopamine has high dispersibility and biocompatibility, the magnesium/aluminum double hydroxide nano layer consists of a metal hydroxide layer with positive charges and water molecules, and has the advantages of high porosity, large specific surface area, good anion exchange capacity, easy preparation and the like, and the composite of the three substances ensures that the composite material has good dispersion and adsorption properties, can be used as an adsorbent in a magnetic solid phase extraction system, and greatly improves the efficiency of magnetic solid phase extraction.
Further, the molar ratio of aluminum to magnesium in the magnesium/aluminum double hydroxide nano layer is 1: 1.5-4.5.
The specific technical scheme of the preparation method of the nickel ferrite based magnetic nanocomposite material is as follows:
a preparation method of a nickel ferrite based magnetic nanocomposite material comprises the following steps: (1) mixing nickel ferrite nano particles and polydopamine in a buffer solution, reacting, and separating to obtain a polydopamine-nickel ferrite nano compound, wherein the pH value of the buffer solution is 7.0-9.0; (2) dripping the aqueous alkali of the polydopamine-nickel ferrite nano compound into the mixed aqueous solution of soluble aluminum salt and magnesium salt, and separating after uniform mixing.
The preparation method of the nickel ferrite based magnetic nanocomposite material has simple preparation process, and polydopamine prepared by polymerizing polyfunctional group dopamine can improve the existing NiFe2O4Dispersibility, adsorptivity and biocompatibility of the nanoparticles.
It can be understood that the poly-dopamine-nickel ferrite nanocomposite is a core-shell structure nanocomposite formed by wrapping poly-dopamine (PDA) on the surface of a nickel ferrite nanoparticle.
In order to ensure that the nickel ferrite nanoparticles can be completely wrapped by the polydopamine, the mass ratio of the nickel ferrite nanoparticles to the polydopamine in the step (1) is 1: 1-2, preferably the mass ratio of 1: 1.
generally, the buffer solution formed by tris and hydrochloric acid has an effective buffer pH of 7.0 to 9.2, and in order to further improve the adhesion between polydopamine and nickel ferrite nanoparticles, the buffer solution in step (1) is a mixed solution of tris and hydrochloric acid.
It can be understood that the generation of magnesium/aluminum double hydroxide requires the combination of aluminum ions and magnesium ions in soluble aluminum salt and magnesium salt with hydroxide ions, preferably, the alkaline solution in step (2) is an alkaline buffer solution, and the pH of the alkaline solution is 9-11.
Further, the alkali solution is a mixed solution of sodium carbonate and sodium hydroxide.
In order to completely wrap the generated magnesium/aluminum double hydroxide nano layer on the surface of the poly-dopamine-nickel ferrite nano composite, every 0.2g of the poly-dopamine-nickel ferrite nano composite in the step (2) corresponds to 0.96mmol of aluminum in the soluble aluminum salt and 2.89mmol of magnesium in the soluble magnesium salt.
The dropping speed in the step (2) is 35 to 45 drops/min, preferably 40 drops/min.
It can be understood that the nickel ferrite nanoparticles can be obtained by the existing preparation method, and preferably, the nickel ferrite nanoparticles are obtained by the hydrothermal reaction of a solution of a soluble ferric salt and a divalent nickel salt, wherein the solution contains a dispersing agent, and the pH value of the solution is 6-8. Preferably, the solution has a pH of 7. The addition of the dispersing agent can avoid the generated nickel ferrite nanoparticles from agglomerating.
Preferably, the temperature of the hydrothermal reaction is 140-180 ℃ for 10-15h to ensure that the reaction is complete.
The amount of the dispersant can be selected conventionally, preferably, 3-15 g of the dispersant is used for every 1mol of nickel in the divalent nickel salt, and further preferably, 8-12 g of the dispersant is used for every 1mol of nickel. The dispersant is polyethylene glycol or beta-cyclodextrin.
The specific technical scheme of the method for enriching the organophosphorus pesticide residue comprises the following steps:
the method for enriching the organophosphorus pesticide residue comprises the steps of extracting a sample solution by using the nickel ferrite based magnetic nanocomposite material and eluting the nickel ferrite based magnetic nanocomposite material adsorbed with the organophosphorus pesticide after extraction so as to separate the organophosphorus pesticide.
Specifically, the method comprises the following steps: (1) adding the nickel ferrite based magnetic nanocomposite material into a sample solution to enable organophosphorus pesticide to be adsorbed on the surface of the nickel ferrite based magnetic nanocomposite material; (2) separating the nickel ferrite-based magnetic nanocomposite material adsorbed with the organophosphorus pesticide from an aqueous solution through an external magnetic field; (3) and eluting the separated nickel ferrite based magnetic nanocomposite material by using an eluant so as to achieve the purposes of extracting and separating the organophosphorus pesticide residues in the sample liquid.
Preferably, the eluent used for elution is methanol, acetonitrile, acetone, ethanol or ethyl acetate.
The nickel ferrite based magnetic nano composite material is applied to detection of organophosphorus pesticide residues, and particularly can be used for detecting organophosphorus pesticides commonly used in agricultural production, such as methamidophos, parathion, phoxim, omethoate, acephate and the like.
Drawings
FIG. 1 is a SEM and TEM image of three materials in an experimental example of the present invention;
FIG. 2 is an XRD pattern of three materials in an experimental example of the present invention;
FIG. 3 shows FT-IR spectra of three materials in an experimental example of the present invention;
FIG. 4 is a graph showing the BET test results of three materials in an experimental example of the present invention;
FIG. 5 is a graph showing the results of VSM tests on three materials in an experimental example of the present invention;
FIG. 6 is a Zeta potential test result chart of the nanocomposite in the experimental example of the present invention;
FIG. 7 is a graph showing the results of an experiment for optimizing the types of eluates in the experimental example of the present invention;
FIG. 8 is a graph showing the results of an experiment for optimizing pH in an experimental example of the present invention;
FIG. 9 is a graph showing the results of an experiment for optimizing the volume of an eluate in an experimental example of the present invention;
FIG. 10 is a graph showing the results of an experiment for optimizing the amount of nanocomposite used in the experimental examples of the present invention;
FIG. 11 is a graph showing the result of an experiment for optimizing the ultrasonic time in the experimental example of the present invention;
FIG. 12 is a graph showing the results of an experiment for optimizing the extraction time in the experimental example of the present invention;
FIG. 13 is a chromatogram for detection of three pesticides in an experimental example of the present invention;
wherein, A, B in figure 1 are respectively NiFe2O4SEM and TEM test result chart of (C, D) is NiFe respectively2O4SEM and TEM test result chart of @ PDA, E, F is NiFe respectively2O4SEM and TEM test result graphs of @ PDA @ Mg/Al-LDH.
Detailed Description
The application of the method of the present invention will be specifically described with reference to the following examples. It should be noted that the examples given in this specification are only for the purpose of facilitating understanding of the present invention, and they are not intended to be limiting, i.e., the present invention may be embodied in other forms than those shown in the specification. Therefore, any technical solutions formed by equivalent substitution or equivalent transformation fall within the protection scope of the present invention.
First, a specific embodiment of the nickel ferrite-based magnetic nanocomposite material of the invention
Example 1
The nickel ferrite-based magnetic nanocomposite material of the embodiment is of a core-shell structure, wherein the core is nickel ferrite nanoparticles, the shell is a polydopamine layer and a magnesium/aluminum double hydroxide nano layer wrapped on the surface of the polydopamine layer, and the mass ratio of the core to the shell is 0.1: 0.34, the mass ratio of the polydopamine layer to the magnesium/aluminum double hydroxide nano-layer in the shell is 0.1: 0.24, wherein the molar ratio of aluminum to magnesium in the magnesium/aluminum double hydroxide nano layer is 1: 3, the preparation method comprises the following steps:
(1) preparation of nickel ferrite nanoparticles
(ii) 5.4g (0.02mol) of FeCl3·6H2O and 2.9g (0.01mol) of Ni (NO)3)2·6H2Dissolving O in 100mL of ultrapure water, performing ultrasonic treatment for 10min, adding 0.11g of polyethylene glycol (PEG), and further performing ultrasonic treatment for 5 min;
② use 0.9 mol. L-1Adjusting the pH value of the obtained solution to 7.0 by using NaOH solution to obtain a mixture;
transferring the mixture into a 100mL stainless steel autoclave lined with Teflon, heating at 160 ℃ for 12h, and then cooling to room temperature;
centrifuging the reaction product to obtain a brown solid product, sequentially washing the brown solid product with ultrapure water and ethanol for 3 times, and drying the washed product in a vacuum oven at the temperature of 60 ℃ for 6 hours to obtain nickel ferrite nanoparticles, which are marked as NiFe2O4；
(2) Preparation of poly-dopamine-nickel ferrite nano-composite
Adding 0.4g of nickel ferrite nano particles (NiFe)2O4) And 0.4g Polydopamine (PDA) was added to 200mL of tris buffer (10mM, pH 8.5) and stirred at room temperature for 12 hours to give a mixture;
separating solid product with outer magnet, washing with ultrapure water and ethanol repeatedly for 3 times, and drying in vacuum oven at 60 deg.C for 6 hr to obtain polydopamine-nickel ferrite nano composite, denoted as NiFe2O4@PDA；
(3) Preparation of nickel ferrite based magnetic nano composite material
Firstly, 0.2g of NiFe2O4@ PDA was added to 80mL of ultrapure water, and buffered (0.64g Na)2CO3And 0.8g naoh dissolved in 20mL of ultrapure water) to adjust the pH of the solution to 10.0, obtaining solution a;
② 0.74g (2.89mmol) of Mg (NO)3)2·6H2O and 0.36g (0.96mmol) of Al (NO)3)3·9H2Mixing O in 50mL of deionized water uniformly to obtain solution B;
dripping the solution A into the solution B at the speed of 40 drops/min (60 ℃), and carrying out ultrasonic treatment for 2 hours to obtain a mixture;
repeatedly washing the mixture with ethanol and water for 3 times, drying the mixture in a vacuum oven at 100 ℃ for 12 hours, and grinding the dried mixture into powder to obtain the nickel ferrite-based magnetic nano composite material which is marked as NiFe2O4@PDA@Mg/Al-LDH。
Example 2
The nickel ferrite based magnetic nanocomposite material of the embodiment is of a core-shell structure, wherein the core is nickel ferrite nanoparticles, the shell is a polydopamine layer and a magnesium/aluminum double hydroxide nano layer wrapped on the surface of the polydopamine layer, and the mass ratio of the core to the shell is 0.175: 0.405, the mass ratio of the polydopamine layer to the magnesium/aluminum double hydroxide nano layer in the shell is 0.35:0.23, the molar ratio of aluminum to magnesium in the magnesium/aluminum double hydroxide nano layer is 1:2.9, and the preparation method comprises the following steps:
(1) preparation of nickel ferrite nanoparticles
Fifthly, 5g of FeCl3·6H2O and 3g of Ni (NO)3)2·6H2Dissolving O in 100mL of ultrapure water, performing ultrasonic treatment for 10min, adding 0.2g of polyethylene glycol (PEG), and further performing ultrasonic treatment for 5 min;
use 0.9 mol.L-1Adjusting the pH value of the obtained solution to 7.0 by using NaOH solution to obtain a mixture;
the mixture is transferred into a 100mL stainless steel autoclave lined with Teflon, heated for 15h at 180 ℃, and then cooled to room temperature;
obtaining a brown solid product through centrifugation, sequentially washing the brown solid product with ultrapure water and ethanol for 3 times, and then drying the product in a vacuum oven at the temperature of 60 ℃ for 6 hours to obtain nickel ferrite nano particles which are marked as NiFe2O4；
(2) Preparation of poly-dopamine-nickel ferrite nano-composite
Adding 0.6g of nickel ferrite nano particles (NiFe)2O4) And 0.6g Polydopamine (PDA) was added to 200mL of tris buffer (10mM, pH 8.5) and stirred at room temperature for 12 hours to give a mixture;
separating the obtained product by using an external magnet, repeatedly washing the product by using ultrapure water and ethanol for 3 times, and drying the product in a vacuum oven at the temperature of 60 ℃ for 5 hours to obtain the poly-dopamine-nickel ferrite nano compositeCompound, denoted as NiFe2O4@PDA；
(3) Preparation of nickel ferrite based magnetic nano composite material
Adding 0.35g of NiFe2O4@ PDA was added to 80mL of ultrapure water, and buffered (0.0.7 gNa)2CO3And 0.7g naoh dissolved in 20mL of ultrapure water) to adjust the pH of the solution to 10.0, obtaining solution a;
② 0.7g of Mg (NO)3)2·6H2O and 0.35g of Al (NO)3)3·9H2Mixing O in 50mL of deionized water uniformly to obtain solution B;
dripping the solution A into the solution B at the speed of 40 drops/min (60 ℃), and carrying out ultrasonic treatment for 2 hours to obtain a mixture;
repeatedly washing the mixture with ethanol and water for 3 times, drying the mixture in a vacuum oven at 100 ℃ for 5 hours, and grinding the dried mixture into powder to obtain the nickel ferrite-based magnetic nano composite material which is marked as NiFe2O4@PDA@Mg/Al-LDH。
Second, a specific embodiment of the preparation method of the nickel ferrite based magnetic nanocomposite material of the present invention
Example 3
The preparation method of this embodiment is specifically the preparation method of the nickel ferrite based magnetic nanocomposite material in embodiment 1, and is not described again.
Example 4
The preparation method of this embodiment is specifically the preparation method of the nickel ferrite based magnetic nanocomposite material in embodiment 2, and is not described again.
Third, specific examples of the method for enriching organophosphorus pesticide residues according to the present invention
Example 5
The method for enriching organophosphorus pesticide residues in the embodiment uses the nickel ferrite based magnetic nanocomposite material in the embodiment 1, and specifically comprises the following steps:
samples of fresh fruit juice (grape, apple, orange, peach and mango) were collected in 30mL portions and centrifuged at 5,000rpm for 10 minutes, and then the supernatant was filtered through a 0.45- μm membrane. Finally, the filtrate was purified with ultrapure water in a ratio of 1:2 dilution ofAnd stored at-4 ℃ and used within three days. 17.8mg of NiFe2O4@ PDA @ Mg/Al-LDH nanocomposite and 6mL tris buffer (pH 6.4) were added to a 15mL centrifuge tube. The sample solution was then vortexed to allow for complete contact and adsorption. Next, the nanocomposite extractant/adsorbent was collected by placing an external magnet at the bottom of the centrifuge tube and the supernatant was removed to isolate the settled MNPs. An appropriate amount of acetonitrile was added to elute the precipitated MNPs. After vortexing and sonication, the adsorbent was collected again using an external magnet at the bottom of the tube. The collected eluate was filtered through a 0.45m filter membrane to remove potential particles and N was used2The gas stream was dried and redissolved in 400. mu.L of methanol. Finally, 20. mu.L of the resulting solution was used for HPLC analysis.
In other embodiments, for the enrichment of organophosphorus pesticide residues in other vegetables or fruits, reference may be made to the method in example 5, which is not described in detail.
The method for enriching organophosphorus pesticide residues in example 5 was used to treat fruit juice samples (peach juice, pear juice, mango juice, orange juice, etc.), and then HPLC-DAD detection was used. HPLC-DAD detection conditions were as follows: using A Shim-pack GIST C18Column (250 mm. times.4.6 mm, 5 μm). The flow rate was 0.9 mL/min-1The column oven temperature is 30 ℃, and the mobile phase is methanol: 85% of water: 15% (volume ratio), the detection wavelength is 265nm, and the sample injection amount is 20 μ L.
Fourth, comparative example
The method of the invention was systematically compared with previously reported methods on various analytical criteria (e.g. RSD, LOD, extraction time, amount of adsorption, type and volume of eluent and adsorption efficiency) (table 1).
Under the same HPLC detection conditions as those of the Fe-based3O4@SiO2@(PSS-PIL)10MSPE method (0.5 μ g L)-1)，mSiO2@Fe3O4Method for MSPE of G (0.5-3.3. mu.g L)-1)，Fe3O4@SiO2MSPE method of MIL-101 (0.3-1.5. mu. g L)-1) And Fe3O4/CP[5]A-based MSPE method(5.0-11.3μgL-1) The LOD provided by the invention is lower (0.06-0.13 mu gL)-1)。
Furthermore, the extraction/adsorption times (6 min) of the process according to the invention are significantly lower than those based on mSiO2@Fe3O4MSPE method of G (20 min), Fe3O4@SiO2MIL-101MSPE (20 min.) and Fe3O4/CP[5]MSPE method of A (20 min). Recovery (81.8-94.4%) and based on Fe3O4@SiO2@(PSS-PIL)10MSPE (58.9-85.8%) and based on Fe3O4/CP[5]The results for A were similar for MSPE (70.6-106.8%). Furthermore, with the PIL-MNPs-based MSPE (4.5-11.3%) and mSiO-based2@Fe3O4Compared to the MSPE of G (9.7%), the new method has a higher accuracy (RSD, 2.7-4.5%).
The above results indicate that the synthesized NiFe2O4The @ PDA @ Mg/Al-LDH nanocomposite material has better pre-concentration/extraction efficiency than the previously reported nanomaterial. The higher efficiency can be explained by the combined effect of high dispersion and stability of the PDA coating and increased specific surface area due to the addition of Mg/Al-LDH. Overall, the MSPE-NPML pretreatment process is simple, rapid and environmentally friendly, and shows great potential in routinely monitoring trace OPs in juice samples and other potential food products.
Table 1 compares the pretreatment method to other methods for detecting OPs by microextraction
Figure BDA0002634012440000071
Figure BDA0002634012440000081
Fifth, example of experiment
Characterization experiment
Experimental work was conducted on NiFe in example 12O4、NiFe2O4@ PDA and NiFe2O4@ PDA @ Mg/Al-LDH three nano-materialsA series of characterization tests were performed on the material, as follows.
(1) SEM and TEM testing
The SEM and TEM test results are shown in fig. 1. For NiFe2O4(FIG. 1-A/D), since it exists as a single magnetic core, it has weak acid and alkali resistance in an aqueous solution. Therefore, PDA is compounded in NiFe2O4The surface of the nano composite material is used as a protective layer, so that the stability and the magnetism of the nano composite material are effectively improved. With non-complexed NiFe2O4Similar shape of the magnetic core, NiFe2O4The morphology of @ PDA did not change significantly. However, in NiFe2O4The ultra-thin amorphous nano-platelets can be observed (fig. 1-B/E). For further improving NiFe2O4The extraction/adsorption efficiency of the @ PDA composite material to organophosphorus pesticide is that Mg/Al-LDH is introduced to the surface of the composite material as a functional layer. As shown in FIG. 1-C/F, in NiFe2O4A large number of plate-like substances were observed on the surface of @ PDA, indicating that Mg/AL-LDH was successfully attached to the synthesized NiFe2O4@ PDA @ Mg/Al-LDH nanocomposite surface.
(2) Crystal form testing
The XRD test results are shown in fig. 2. As can be seen from the figure, for NiFe2O4(a)，NiFe2O4@ PDA (b) and NiFe2O4@ PDA @ Mg/Al-LDH (c), peaks at about 30.3 °, 35.7 °, 43.4 °, 53.8 °, 57.4 ° and 63.0 ° corresponding to NiFe2O4The cubic spinel structures (220), (311), (400), (422), (511) and (440) planes (PDF # 74-2081). NiFe2O4(a) And NiFe2O4No significant difference in XRD pattern between @ PDA (b), indicating that the PDA film is paired with NiFe2O4Has no influence on the crystal structure of (2). With NiFe2O4(a) And NiFe2O4@ PDA (b) comparison, NiFe2O4The peaks of @ PDA @ Mg/Al-LDH (c) were located around 11.2 °, 23.4 ° and 61.6 ° of the (003), (006) and (110) planes of Mg/Al-LDH, respectively, indicating that the magnetic nanocomposite was successfully synthesized.
(3) FT-IR test
The FT-IR test results are shown in FIG. 3, which shows that NiFe2O4(a) At 602, 410, 1369, 1625 and 3400cm-1The absorption bands of (B) are Fe-O and Ni-O, C ═ O, NO3 -Stretching vibration peaks of ions and hydroxyl groups. With NiFe2O4(a) In contrast, NiFe2O4@ PDA (b) appears at 1287, 1488 and 1616cm-1Some of the new peaks at (a) are due to the aromatic ring of PDA. Proves that PDA is successfully compounded in NiFe through physical and chemical adsorption2O4A surface. For NiFe2O4@ PDA @ Mg/Al-LDH (c), approximately 1384 and 3444cm-1The peak at (a) is due to the Mg/Al-LDH layer.
(4) BET test
The BET test results are shown in fig. 4, from which it can be seen that: NiFe2O4Specific surface area of @ PDA @ Mg/Al-LDH MNPs is 68.9m2·g-1Pore volume of 0.153cm3·g-1The average pore diameter was 8.9 nm. The specific surface area is higher than the previously reported specific surface area of 10-15m2·g-1(see, in particular, Zhang Osmunda, Wenzhou university of medicine, pages 24-26; Tan et al (2020) Core-shell magnetic scientific organic frame nanocomposites as an adsorbent for the expression reaction-enhanced microorganism extraction of end rings dispersions in liquid materials Chemical Engineering Journal 396,125191). The higher specific surface area can increase the interaction between the analyte and the nanomaterial, thereby improving the adsorption efficiency thereof.
(5) VSM testing
The results of the VSM (vibrating sample magnetometer) test are shown in FIG. 5, from which it can be seen that NiFe2O4@ PDA and NiFe2O4The saturation magnetizations of @ PDA @ Mg/Al-LDH were 25.93 and 22.36emu g, respectively-1Lower than NiFe2O4(31.83emu·g-1). This indicates that NiFe2O4The coating reduces its magnetic properties. Although the saturation magnetization of the prepared nanocomposite is reduced, it is due to NiFe2O4The saturation magnetization of @ PDA @ Mg/Al-LDH MNPs is relatively high and can still be quickly controlled fromSeparating out the aqueous solution.
(6) Zeta potential test
As shown in fig. 6, it is understood from the results of the Zeta potential test that the PZC value (point of zero charge, isoelectric point) of the nanocomposite was about pH 6.2. The test factor optimized solution (15mg adsorbent, 1.6mL eluent, pH 6.4, ionic strength 0% and extraction time 6min) was close to the PZC value of the composite nanomaterial. In this case, the surface of the nano-copolymer exhibits a neutral charge state, and thus has a high extraction efficiency.
(II) optimization experiment
NiFe2O4The @ PDA @ Mg/Al-LDH can be applied to magnetic solid phase micro-extraction, and in order to obtain the optimal extraction efficiency, optimization tests are carried out on the volume and the type of an eluted substance, the pH value, the volume of the eluted substance, the using amount of a nano composite material, the ultrasonic time and the extraction time, and the results are shown in figures 7-12.
In the filtered juice solution (volume 5mL,20mg adsorbent, 1.6mL eluent, pH 6.4, ionic strength 0% and extraction time 6min), the elution efficiency of five common eluents of methanol, acetonitrile, acetone, ethanol and ethyl acetate was compared, and the results are shown in fig. 7. Figure 7 shows that the average extraction recovery of the three organophosphorus pesticides was the highest (about 90%) using acetonitrile as eluent, much higher than that of methanol (about 70%) (figure 7). Acetone, ethanol and ethyl acetate gave relatively low recovery of methamidophos (about 65%). Therefore, acetonitrile was chosen as the best solvent for further study.
In the filtered juice solution (volume 5mL,20mg adsorbent, 0.8mL eluent, ionic strength 0% and extraction time 6min), fig. 8 shows that the extraction recovery of the three organophosphorus pesticides increases gradually with pH from 3 to 7 and decreases gradually with pH from 7 to 11. Extreme pH conditions can destroy the original structure and stability of the nanocomposite, leading to a decrease in extraction recovery. Therefore, pH 7 is the optimum pH for subsequent studies.
In the filtered juice solution (volume 5mL,20mg adsorbent, pH 6.4, ionic strength 0% and extraction time 6min), figure 9 shows that the average extraction recovery increases gradually as the eluent volume is changed from 0.2 to 1.6mL, reaching a maximum (> 85%) at 1.6 mL.
In the filtered juice solution (volume 5mL,1.6mL eluent, pH 6.4, ionic strength 0% and extraction time 6min), fig. 10 shows the amount of nanocomposite (NiFe) used (i.e. the amount of the nanocomposite used)2O4@ PDA @ Mg/Al-LDH) is another important factor affecting extraction performance. The average extraction recovery increased gradually from 65% to 85% as the amount of nanocomposite increased from 5mg to 20 mg. Furthermore, the extraction recovery did not change significantly when the amount of nanocomposite was increased from 20mg to 30 mg. Therefore, subsequent experiments used 20mg of nanocomposite as the adsorbent.
In the filtered juice solution (volume 5mL,1.6mL eluent, pH 6.4, ionic strength 0%, extraction time 6min), fig. 11 shows that the extraction recovery rate gradually increases with the sonication time from 2 to 4min, and then slightly decreases with the sonication time from 4 to 10min, within the range of 2 to 10 min. These results indicate that an ultrasonic time of 4min is sufficient to reach the adsorption-desorption equilibrium of the organophosphorus pesticide. Therefore, elution was performed with 4min sonication time.
In the filtered juice solution (volume 5mL,1.6mL eluent, pH 6.4, ionic strength 0%), fig. 12 shows that the extraction recovery gradually increases when the extraction time is increased from 2min to 6min, and that the recovery tends to decrease when the extraction time is increased from 6min to 10min, possibly because excessive extraction time may cause more desorption and dissolution of the organophosphorus pesticide in the sample solution, thereby decreasing the extraction recovery. Therefore, 6min is the optimum extraction time.
(III) accuracy and sensitivity
The method for enriching the organophosphorus pesticide residues in the example 5 is adopted to adsorb and extract trace organophosphorus pesticide residues in peach juice and apple juice, two samples (a) and (b) are respectively taken and then are detected by HPLC-DAD, and the detection results are shown in Table 2.
TABLE 2 results of organophosphorus pesticides in peach juice and apple juice (mean. + -. standard deviation, number of detection 3)
Figure BDA0002634012440000101
Figure BDA0002634012440000111
As can be seen from Table 2, the concentrations for the three different additions (5, 20 and 200. mu.g.L)-1) The extraction recovery rates of the 4 fruit juice samples are respectively in the ranges of 87.3-94.0%, 81.8-86.2% and 83.7-91.1%, and the detection chromatograms of the three pesticides are shown in figure 13. From the above results, it was found that the methamidophos concentration was 0.45. + -. 0.17. mu.g.L in the case of detecting the unlabeled peach juice sample-1. However, the concentrations of the residual organophosphorus pesticides in the other juice samples were all below the respective detection limits.
The trace organophosphorus pesticide residues in the peach juice and the apple juice are detected by the same treatment method and detection conditions, and the results of the two samples (a) and (b) are shown in Table 3.
TABLE 3 results of organophosphorus pesticides in orange, mango and pear juices (mean. + -. standard deviation, number of tests ═ 3)
Figure BDA0002634012440000112
Figure BDA0002634012440000121
Table 3 shows the concentrations for three different additions (5, 20 and 200. mu.g.L)-1) The extraction recovery rates of the 6 fruit juice samples of methamidophos, parathion and phoxim are respectively 88.4-94.4%, 81.8-86.2% and 83.4-91.5%, and the detection chromatograms of the three pesticides are shown in figure 13.
From the results, the newly developed pretreatment method based on the nano composite material can meet the technical requirements of detection of trace organophosphorus pesticides in complex fruit juice matrixes, and has high accuracy and sensitivity.

Claims (10)

1. The nickel ferrite based magnetic nanocomposite is characterized in that the nickel ferrite based magnetic nanocomposite is of a core-shell structure, the core is a nickel ferrite nanoparticle, the shell is a polydopamine layer and a magnesium/aluminum double hydroxide nano layer wrapped on the surface of the polydopamine layer, and the mass ratio of the core to the shell is 1: 3-5, wherein the mass ratio of the polydopamine layer to the magnesium/aluminum double hydroxide nano layer in the shell is 1: 2-4.
2. The nickel ferrite based magnetic nanocomposite material according to claim 1, wherein the molar ratio of aluminum to magnesium in the magnesium/aluminum double hydroxide nanolayer is 1: 1.5 to 4.5.
3. The method for preparing the nickel ferrite based magnetic nanocomposite material according to claim 1, comprising the steps of:
(1) mixing nickel ferrite nano particles and polydopamine in a buffer solution, reacting, and separating to obtain a polydopamine-nickel ferrite nano compound, wherein the pH value of the buffer solution is 7.0-9.0;
(2) dripping the aqueous alkali of the polydopamine-nickel ferrite nano compound into the mixed aqueous solution of soluble aluminum salt and soluble magnesium salt, and separating after uniform mixing.
4. The preparation method of the nickel ferrite based magnetic nanocomposite material according to claim 3, wherein the mass ratio of the nickel ferrite nanoparticles to the polydopamine in the step (1) is 1: 1-2.
5. The method for preparing the nickel ferrite based magnetic nanocomposite material according to claim 3, wherein the buffer solution in the step (1) is a mixed solution of tris (hydroxymethyl) aminomethane and hydrochloric acid.
6. The preparation method of the nickel ferrite based magnetic nanocomposite material according to claim 3, wherein the pH of the alkali solution in the step (2) is 9-11, and each 0.2g of the polydopamine-nickel ferrite nanocomposite in the step (2) corresponds to 0.5-1.5mmol of aluminum in the soluble aluminum salt and 1.5-4mmol of magnesium in the soluble magnesium salt.
7. The preparation method of the nickel ferrite based magnetic nanocomposite material according to any one of claims 3 to 6, wherein the nickel ferrite nanoparticles are obtained by hydrothermal reaction of a solution of a soluble ferric iron salt and a divalent nickel salt, the solution contains a dispersing agent, and the pH of the solution is 6 to 8.
8. The method for preparing the nickel ferrite based magnetic nanocomposite material as claimed in claim 7, wherein the temperature of the hydrothermal reaction is 140-180 ℃ and the time is 10-15 h.
9. The preparation method of the nickel ferrite based magnetic nanocomposite material according to claim 7, wherein each 1mol of nickel in the divalent nickel salt corresponds to 3-15 g of a dispersant, and the dispersant is polyethylene glycol or beta-cyclodextrin.
10. A method for enriching organophosphorus pesticide residues, which comprises the steps of extracting a sample solution by using the nickel ferrite based magnetic nanocomposite material of claim 1, and eluting the nickel ferrite based magnetic nanocomposite material adsorbed with organophosphorus pesticide after extraction to separate organophosphorus pesticide.
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