CN113049718B - Preparation of carbon-supported metal oxide composite microspheres and extraction of malachite green and crystal violet from aquatic products by using same - Google Patents
Preparation of carbon-supported metal oxide composite microspheres and extraction of malachite green and crystal violet from aquatic products by using same Download PDFInfo
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Abstract
The invention discloses a preparation method of carbon-supported metal oxide composite microspheres (NiO/ZnO @ C) and an extraction method of the carbon-supported metal oxide composite microspheres for malachite green and crystal violet in aquatic products. The invention firstly takes glucose as a carbon source to prepare the carbon spheres, and then the carbon spheres are put intoSoaking in nitric acid solution, cleaning, drying, and soaking carbon spheres in nitric acid, ni (NO) 3 ) 2 ·6H 2 O and Zn (NO) 3 ) 2 ·6H 2 Adding O into deionized water, uniformly mixing, carrying out hydrothermal reaction at 120 ℃ for 3-12h, washing, drying, and carbonizing in air for 3h to obtain the carbon-supported metal oxide composite microsphere NiO/ZnO @ C. The carbon-supported metal oxide composite microsphere NiO/ZnO @ C is used as an adsorbent to extract malachite green and crystal violet in the aquatic products, and the sensitive analysis of the malachite green and the crystal violet in the aquatic products is realized by matching with ultra-high performance liquid chromatography.
Description
Technical Field
The invention belongs to the technical field of food analysis, and particularly relates to preparation of carbon-supported metal oxide composite microspheres (NiO/ZnO @ C) and extraction and analysis of Malachite Green (MG) and Crystal Violet (CV) in aquatic products.
Background
MG and CV are used as artificially synthesized triphenylmethane dyes, and are widely used in aquaculture industry due to their high-efficiency antibacterial and bactericidal effects. MG and CV can cause harm to the human immune system and reproductive system, thus threatening human health. In view of food safety and public health, our country and many countries have banned the use of MG and CV in aquaculture and transportation. However, MG and CV are often prohibited due to their high efficiency, low cost, and the like, and their illegal use in aquatic products often occurs.
The detection method of MG and CV in aquatic products mainly comprises a chromatography method, an enzyme linked immunosorbent assay method and the like. Among the methods, high Performance Liquid Chromatography (HPLC) is widely used due to its advantages such as good separation performance, high accuracy and sensitivity. In the case of residual levels detected by HPLC, the target analyte needs to be extracted and purified. The Dispersive Solid Phase Extraction (DSPE) has the advantages of large contact area between the adsorbent and a sample to be analyzed, short extraction time, small adsorbent consumption, simple and convenient operation and the like. The selection of the adsorbent is a key factor in determining the extraction efficiency and selectivity.
The carbon material has the advantages of large specific surface area, easiness in modification and the like, the metal oxide NiO/ZnO is modified on the surface of a carbon sphere soaked by nitric acid to obtain a DSPE adsorbent with a shell-core structure and selective extraction performance on MG and CV, and a DSPE-UPLC analysis method suitable for MG and CV analysis in aquatic products is established by combining ultra-high performance liquid chromatography (UPLC).
Disclosure of Invention
The invention aims to provide a preparation method and application of carbon-supported metal oxide composite microspheres NiO/ZnO @ C for extracting MG and CV in aquatic products. The purpose of the invention is realized by the following technical scheme:
a preparation method of carbon-supported metal oxide composite microspheres NiO/ZnO @ C comprises the following steps: weighing 1.0g of carbon spheres, placing the carbon spheres in 10mL of nitric acid solution (6 mol/L) under the ultrasonic condition, soaking the carbon spheres for 12 hours under the room temperature condition, cleaning the obtained material with deionized water and absolute ethyl alcohol, and drying the material for 8 hours in a vacuum drying oven at 60 ℃ to obtain the nitric acid-soaked carbon spheres. Then 0.15g of nitric acid impregnated carbon spheres was weighed, and the molar ratio of Ni (NO 3 ) 2 ·6H 2 O and Zn (NO) 3 ) 2 ·6H 2 O (the total mole number of metal ions is 1.25 mmol), placing the mixture in 33mL deionized water under an ultrasonic condition, uniformly mixing, transferring the mixture into a 50mL hydrothermal synthesis kettle, reacting for 3-12h under a sealing condition at 120 ℃, cooling to room temperature, cleaning the obtained material with deionized water and absolute ethyl alcohol, drying for 8h at 60 ℃ in a vacuum drying oven, and carbonizing the obtained product in air at 350 ℃ for 3h to obtain the microsphere NiO/ZnO @ C.
The other purpose of the invention is realized by the following technical scheme:
a method of extracting MG and CV from a water product using the above NiO/zno @ c, the method comprising the steps of:
adding the NiO/ZnO @ C into an aquatic product sample solution, performing vortex oscillation for 40min to enable a target to be fully adsorbed, performing centrifugal separation to discard a supernatant, adding 3mL of cleaning solution (methanol: water =30, 70, v/v), performing vortex oscillation for 5min to wash away interferents, performing centrifugal separation to discard a supernatant, adding eluent 4mL of acidic methanol (acetic acid: methanol =10, 90, v/v), performing vortex oscillation for 30min to enable MG and CV on the surface of the adsorbent to be desorbed, performing centrifugal separation to take a supernatant, drying by using nitrogen, and fixing the volume to a preset volume by using a mobile phase, namely completing extraction of MG and CV in the aquatic product. The concentration of MG and CV was measured by ultra performance liquid chromatography-variable wavelength ultraviolet detector (UPLC-TUV).
Further, the pH value of the sample solution is 2-9, and the preferable pH value is 3.
Further, the amount of NiO/ZnO @ C is 5 to 20mg, and the preferable amount of NiO/ZnO @ C is 15mg.
Furthermore, MG and CV standard samples with different mass concentrations are added into the aquatic product extracting solution, niO/ZnO @ C is added, MG and CV in the target solution are extracted under the optimal extraction condition, a DSPE-UPLC analysis method for measuring MG and CV in aquatic products based on the microsphere NiO/ZnO @ C is established, and the detection Limits (LODs) of the method are 1.0 mu g/kg (MG) and 0.7 mu g/kg (CV) respectively.
Compared with the prior art, the invention has the beneficial effects that:
1. the microsphere NiO/ZnO @ C is spherical and has a shell-core structure. Compared with the existing reported NiO/ZnO material, the nano microsphere NiO/ZnO @ C has the advantages of uniform size, regular shape and the like, and is suitable for being used as a DSPE adsorbent to be applied to analysis of MG and CV in aquatic products.
2. The adsorption capacity is an important index for measuring the performance of the extraction material, and compared with a carbon ball (the saturated adsorption capacity to MG is 12.6 MG/g), the adsorption capacity of NiO/ZnO @ C is obviously improved (52.3 MG/g);
3. the NiO/ZnO @ C is used as an adsorbent, conditions such as pH, cleaning solution and the addition amount of the adsorbent are optimized, MG and CV in the aquatic product are extracted, and therefore the sensitivity of UPLC-TUV on MG and CV detection in the aquatic product is improved, and meanwhile, detection limits of MG (1.0 ug/kg) and CV (0.7 ug/kg) methods established by the method are lower than those of the high performance liquid chromatography (GB/T19857-2005 measurement of residual quantity of malachite green and crystal violet in the aquatic product) on MG and CV in the aquatic product (2.0 ug/kg).
Drawings
FIG. 1 is an SEM image of NiO/ZnO @ C of the present invention;
FIG. 2 is an XRD spectrum of NiO/ZnO @ C of the present invention;
FIG. 3 is a schematic of the effect of pH on extraction efficiency of a sample solution;
FIG. 4 is a schematic diagram showing the effect of the addition of NiO/ZnO @ C on the extraction efficiency;
FIG. 5 is a schematic diagram showing the adsorption effect of NiO/ZnO @ C prepared from carbon spheres and metal ions in different proportions on MG.
Detailed Description
Example 1
Weighing 8.0g of glucose, dissolving in 35mL of water, uniformly mixing by ultrasonic waves, transferring into a 50mL hydrothermal synthesis kettle, reacting for 24 hours at 180 ℃ under a sealed condition, cooling to room temperature, cleaning the obtained material by deionized water and absolute ethyl alcohol, and drying for 8 hours at 60 ℃ in a vacuum drying oven to obtain the carbon spheres. Weighing 1.0g of carbon spheres, placing the carbon spheres in 10mL of nitric acid solution (6 mol/L) under the ultrasonic condition, soaking the carbon spheres for 12 hours under the room temperature condition, cleaning the obtained material with deionized water and absolute ethyl alcohol, and drying the material in a vacuum drying oven for 8 hours at 60 ℃ to obtain the nitric acid-soaked carbon spheres. 0.15g nitric acid impregnated carbon spheres, 0.83mmol Ni (NO) were weighed 3 ) 2 ·6H 2 O and 0.42mmol Zn (NO) 3 ) 2 ·6H 2 And O, placing the mixture into 33mL of deionized water under an ultrasonic condition, uniformly mixing, transferring the mixture into a 50mL hydrothermal synthesis kettle, reacting for 6h under a sealing condition at 120 ℃, cooling to room temperature, cleaning the obtained material with deionized water and absolute ethyl alcohol, drying for 8h at 60 ℃ in a vacuum drying oven, and carbonizing the product for 3h at 350 ℃ in the air to obtain the microsphere NiO/ZnO @ C.
Hereinafter, the physicochemical properties of NiO/ZnO @ C were characterized by means of Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), and the like.
As can be seen from FIG. 1, niO/ZnO @ C has a regular and spherical morphology, a shell-core structure, and a size of about 4-7 μm.
As can be seen from FIG. 2, niO/ZnO @ C has characteristic lattice diffraction peaks of ZnO and NiO, indicating that the NiO/ZnO shell is successfully modified on the surface of the carbon sphere.
Example 2
The embodiment provides a method for extracting MG and CV from aquatic products by using the carbon-supported metal oxide composite microspheres NiO/ZnO @ C described in embodiment 1, which comprises the following steps:
dispersing 15MG of the microsphere NiO/ZnO @ C in a aquatic product extracting solution with the pH =3, carrying out vortex oscillation for 40min to ensure that MG and CV are fully adsorbed on the NiO/ZnO @ C, carrying out centrifugal separation, then discarding a supernatant, adding 3mL of 30% methanol water (methanol: water = 30.
Example 3
The embodiment provides an analysis method for extracting MG and CV in aquatic products by using the carbon-supported metal oxide composite microsphere NiO/ZnO @ C, which comprises the following steps:
dispersing 15MG of the microsphere NiO/ZnO @ C in the extraction liquid of MG and CV standard aquatic products with different mass concentrations and added with standards and pH =3, performing vortex oscillation for 40min to enable MG and CV to be fully adsorbed on the NiO/ZnO @ C, performing centrifugal separation, then discarding supernatant, adding 3mL of 30% methanol water (methanol: water =30, 70, v/v) as a cleaning solution, performing vortex oscillation for 5min to wash off interferents, performing centrifugal separation to discard supernatant, adding 4mL of eluent (methanol: acetic acid =90, 10, v/v), performing vortex oscillation for 30min again, performing centrifugal separation, taking supernatant, drying with nitrogen, performing volume fixing by using a liquid chromatography mobile phase, and then taking 500 mu L of the solution for UPLC analysis. Establishing a working curve of the method, wherein the detection Limits (LODs) of the method are respectively 1.0 mu g/kg (MG) and 0.7 mu g/kg (CV), and the detection limits are lower than the national standard (2.0 mu g/kg). Therefore, the established method is suitable for analyzing MG and CV in aquatic products.
Comparative example
The adsorption performance of the carbon-supported metal oxide composite microspheres NiO/ZnO @ C prepared from metal ions with different proportions and the MG adsorbed in the solution by the NiO/ZnO @ C and the carbon spheres in the example 1 under the same conditions were compared. The method specifically comprises the following steps:
accurately weighing 3mg of adsorbent, adding into 10 mM MG solution (concentration of 20 mg/L), and placingShaking in a constant temperature water bath at 25 deg.C for 6 hr, centrifuging to separate adsorbent, transferring 500 μ L of supernatant into a sample bottle, and performing UPLC analysis. The results are shown in FIG. 5, unmodified carbon spheres (i.e., ni in FIG. 5) 2+ /Zn 2+ = 0) the adsorption amount of the target substance is much lower than that of nickel-zinc-modified carbon spheres, and the metal ion ratio is Ni 2+ /Zn 2+ The microsphere prepared by the method is characterized in that the microsphere prepared by the method in the following step 1 has the highest adsorption capacity on MG, so that Ni is selected 2+ /Zn 2+ And (2) =1, preparing the carbon-supported metal oxide composite microspheres according to the optimal metal ion proportion.
Claims (4)
1. A preparation method of carbon-supported metal oxide composite microspheres NiO/ZnO @ C capable of extracting malachite green and crystal violet from aquatic products is characterized by comprising the following steps: weighing 1.0g of carbon spheres, placing the carbon spheres in 10mL of 6mol/L nitric acid solution under the ultrasonic condition, dipping the carbon spheres for 12h at room temperature, cleaning the obtained material with deionized water and absolute ethyl alcohol, drying the material for 8h at 60 ℃ in a vacuum drying oven to obtain nitric acid dipped carbon spheres, weighing 0.15g of nitric acid dipped carbon spheres, wherein the total mole number of the carbon spheres is 1.25mmol of Ni (NO) 3 ) 2 ·6H 2 O and Zn (NO) 3 ) 2 ·6H 2 O, placing the mixture in 33mL deionized water under the ultrasonic condition, uniformly mixing, transferring the mixture to a 50mL hydrothermal synthesis kettle, reacting for 3-12h under the sealing condition of 120 ℃, cooling to room temperature, cleaning the obtained material with deionized water and absolute ethyl alcohol, drying the material in a vacuum drying oven at 60 ℃ for 8h, and carbonizing the product in air at 350 ℃ for 3h to obtain the microsphere NiO/ZnO @ C, wherein the Ni (NO) is 3 ) 2 ·6H 2 O and Zn (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1.
2. The carbon-supported metal oxide composite microsphere NiO/ZnO @ C prepared in the claim 1 is applied to extraction of malachite green and crystal violet in aquatic products, and is characterized by comprising the following steps:
adding the NiO/ZnO @ C into the aquatic product extracting solution, carrying out vortex oscillation for 40min to enable the target to be fully adsorbed, carrying out centrifugal separation to discard a supernatant, adding 3mL of a methanol-water mixed solution with a volume ratio of 30: and (3) taking methanol as eluent, performing vortex oscillation for 30min to desorb malachite green and crystal violet from the adsorbent, performing centrifugal separation, taking supernate, drying by using nitrogen, and fixing the volume to a preset volume by using a mobile phase, thus finishing the extraction of the malachite green and the crystal violet in the aquatic product.
3. Use of NiO/zno @ c in accordance with claim 2, characterised in that the pH of the sample solution containing malachite green and crystal violet is in the range 2-9.
4. Use of NiO/ZnO @ C according to claim 3, characterized in that the amount of NiO/ZnO @ C added is 5-20mg.
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