CN115990466A - Aminated spinel type ferrite/MXene composite material and preparation and application thereof - Google Patents
Aminated spinel type ferrite/MXene composite material and preparation and application thereof Download PDFInfo
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- CN115990466A CN115990466A CN202310001461.XA CN202310001461A CN115990466A CN 115990466 A CN115990466 A CN 115990466A CN 202310001461 A CN202310001461 A CN 202310001461A CN 115990466 A CN115990466 A CN 115990466A
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Abstract
The invention discloses an aminated spinel type ferrite/MXene composite material and a preparation method thereof. The composite material is used for separating and enriching vitamin B 2 It was found that a large number of hydroxyl/amino groups and metal centers in the aminated spinel ferrite/MXene composite material can be combined with vitamin B 2 The characteristics of hydrogen bond interaction and metal-pi complex interaction are generated, so that vitamin B is realized 2 High efficiency, low cost, specialThe method can be used as adsorbent for vitamin B in food 2 Is vitamin B in complex sample 2 Provides novel materials and technical methods.
Description
Technical Field
The invention relates to the technical field of analysis and detection, in particular to an aminated spinel type ferrite/MXene composite material and a preparation method thereof, and simultaneously relates to enrichment and detection of vitamin B by the composite material 2 Is used in the field of applications.
Background
Vitamin B 2 Also called riboflavin, has an important role in maintaining human health. The food is the main dietary source of human vitaminsFor vitamin B in food sample 2 The accurate determination of the content of (c) is of great significance in guiding a reasonable diet, quality evaluation and quality control. Currently, vitamin B 2 Common methods of measurement include High Performance Liquid Chromatography (HPLC), ultra high performance liquid chromatography (UPLC), fluorescence spectrophotometry (FL), ultraviolet visible spectroscopy (UV-Vis), capillary Electrophoresis (CE), electrochemical analysis (ECL), and the like. Among them, UPLC is a highly efficient and viable method in the quantitative analysis of vitamins due to its higher sensitivity and analysis throughput, better separation, shorter analysis time and lower solvent consumption. However, accurate determination of multivitamins in cereal samples still presents certain difficulties due to chemical instability of the analyte and the susceptibility to complex matrix interference. Therefore, development and establishment of a sample pretreatment material and a method which are green in preparation, good in selectivity and integrated with separation, extraction and detection have very important significance.
As a crucial step in complex sample analysis processes, advances in sample pretreatment technology have significant implications for the development of analytical chemistry. The magnetic solid phase extraction (magnetic solid phase extraction, MSPE) is a novel sample pretreatment technology using magnetic or magnetizable materials as adsorbents, and has the advantages of simple operation, short extraction time, strong impurity interference resistance, good biocompatibility and the like, thus having wide application prospect in the field of food sample pretreatment. In recent years, with the rapid development of various adsorption material preparation technologies, the magnetic solid phase extraction technology based on the novel magnetic nano material is increasingly widely applied to food safety detection. The MXene material is a layered two-dimensional carbon/nitride and is usually chemically etched to separate the MAX phase (M n+1 AX n N=1 to 3, m is a transition metal, a is a group IIIA or IVA element, and X is C or N). Because of its high specific surface area, hydrophilicity, adsorptivity and high surface reactivity, MXene has attracted considerable attention from researchers in many fields, and can be used in a number of fields such as adsorption of heavy metals, supercapacitors, lithium ion batteries, catalysis, and the like. Etching using an acidic solution containing fluorideThe surface of MXene prepared by etching MAX phase often contains groups such as-OH, -O-and-F, which are abbreviated as M n+1 X n T m Wherein T represents a surface end group. However, to date, no aminated spinel ferrite/MXene composite material has been applied to vitamin B in foods 2 Relevant reports of extraction separation.
Disclosure of Invention
The invention aims to provide an aminated spinel type ferrite/MXene composite material and a preparation method thereof, and the aminated spinel type ferrite/MXene composite material is used for separating and enriching vitamin B 2 . The amino spinel type ferrite/MXene composite material can be used with a large number of polar groups such as hydroxyl and amino, and the like 2 The characteristic of hydrogen bond formation between amino and hydroxyl, and the adsorption performance of metal-pi complexation of metal cation and conjugated structure, without damaging vitamin B 2 On the premise of structure, vitamin B is realized 2 High efficiency, low cost, and specific separation and enrichment.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides an aminated spinel type ferrite/MXene composite material, which consists of flaky MXene and aminated spinel type ferrite magnetic nano particles uniformly loaded on the MXene; the spinel type ferrite magnetic nano-particles are ZnFe 2 O 4 And (3) nanoparticles. The MXene is a single-layer or less-layer sheet structure, the thickness of the MXene is within 3 nm and the number of layers is less<A 5-layer laminate structure.
The preparation method of the aminated spinel type ferrite/MXene composite material comprises the following steps:
(1) Preparation of sheet MXene:
slowly adding lithium fluoride into a hydrochloric acid solution, stirring for 25-35 min at room temperature, and adding Ti 3 AlC 2 Stirring for 24-48 h at 35-40 ℃, centrifuging the obtained suspension, and washing the obtained precipitate with deionized water to be neutral; adding water into the precipitate, introducing nitrogen to deoxidize, ultrasonically stripping for 1-2 h, centrifuging the obtained suspension, collecting supernatant, and freeze-drying to obtain the flaky MXene. Wherein lithium fluoride and Ti 3 AlC 2 The mass ratio of (2) is 1:1-2:1. The MXene material prepared under the conditions of the raw material proportion, the reaction temperature and the time reaction is suitable in size, uniform in size, less in stripping layer number and not easy to oxidize.
(2) Preparation of aminated spinel type ferrite:
adding sodium acetate into ethylene glycol, stirring uniformly, adding ferric trichloride hexahydrate and zinc chloride, heating the mixed solution to 45-55 ℃ after ultrasonic treatment uniformly, continuously adding 1, 6-hexamethylenediamine into the mixed solution under stirring, stirring for 25-35 min, transferring the mixed solution to a hydrothermal reaction kettle, reacting for 8-24 h at 150-200 ℃, washing the product with absolute ethyl alcohol and deionized water, and drying in vacuum to obtain the amino spinel type ferrite magnetic nano particles. Wherein Zn is 2+ And Fe (Fe) 3+ The mass ratio of the substances is 1:1.8-1:2.2; fe (Fe) 3+ The concentration in the mixed solution is 0.01-0.03 mol/L. The mass ratio of the sodium acetate to the ferric trichloride hexahydrate is 1.5:1-2.5:1; the mass ratio of the sodium acetate to the 1, 6-hexamethylenediamine is 1:3-1:4. The spinel type ferrite magnetic nanomaterial prepared under the reaction system of limited temperature and time is suitable in size and uniform in size.
(3) Preparation of an aminated spinel ferrite/MXene composite material:
and (3) dissolving MXene in water and performing ultrasonic treatment to obtain MXene solution, dissolving the aminated spinel type ferrite magnetic nano particles in water to prepare an aminated spinel type ferrite magnetic nano particle aqueous solution, adding the aminated spinel type ferrite magnetic nano particle aqueous solution into the MXene solution, performing ultrasonic treatment on the mixed solution, washing a product with deionized water, performing magnetic separation from the solution containing excessive magnetic nano particles until supernatant is clear, and drying the obtained composite material in vacuum.
Wherein the mass ratio between the aminated spinel type ferrite magnetic nano particles and the MXene is 1:0.5-1:3. The magnetic separation capability and the vitamin B enrichment of the aminated spinel type ferrite/MXene composite material prepared under the reaction system with the raw material proportion limited by the invention 2 The effect of (2) is optimal.
The invention also provides ammoniaThe composite material of spinel ferrite/MXene as adsorbent for separating and enriching vitamin B 2 Is used in the field of applications. Separation and enrichment of vitamin B 2 The method of (1) comprises the following steps:
(1) Dispersing an aminated spinel ferrite/MXene composite material to contain vitamin B 2 In the sample extracting solution of (2), vibrating for 10-20 min to enrich vitamin B 2 The method comprises the steps of carrying out a first treatment on the surface of the The vitamin B-containing food contains vitamin B 2 The sample extract of (C) contains vitamin B 2 Dispersing the sample into 20mM/L acetic acid solution; the acetic acid aqueous solution with the concentration can fully extract the vitamin B in the sample 2 And is favorable for vitamin B 2 Is enriched in (2); meanwhile, the aminated spinel type ferrite/MXene composite material can be well dispersed.
The sample extract is a mixture of a plurality of water-soluble components. The invention examines the enrichment of vitamin B from the angles of various water-soluble components by the aminated spinel type ferrite/MXene composite material 2 High specificity enrichment, high anti-interference capability and wider application range.
(2) Magnetically separating the enriched liquid, and enriching vitamin B 2 Adding eluent into the aminated spinel type ferrite/MXene composite material for ultrasonic elution for 1-5 min and performing magnetic separation to obtain vitamin B 2 Enriching the solution; the eluent is methanol solution containing 1% of formic acid by mass fraction, and the pH of the eluent is 2.0. The invention limits the oscillation time range and the acidity of the eluent, and the vitamin B 2 The enriched amount is the largest. The magnetic separation method is to adopt a magnetic object to carry out adsorption separation on the aminated spinel type ferrite/MXene composite material. The magnetic object can be neodymium iron boron strong magnetism, a soft magnetic strip or magnet stone, etc.
The separation and enrichment method is simpler and more convenient to operate, is not limited by a large-scale instrument (such as a high-speed centrifugal machine), realizes thorough separation of materials and solutions, and is more beneficial to follow-up experiments.
The invention is used for enriching vitamin B 2 The kit comprises an aminated spinel type ferrite/MXene composite material,20mM/L acetic acid in water, methanol and formic acid.
The technical scheme of the invention has the beneficial effects that: the amino spinel type ferrite/MXene composite material of the invention has a large number of hydroxyl groups/amino groups and metal centers which can be combined with vitamin B 2 The characteristics of hydrogen bond interaction and metal-pi complex interaction are generated, so that vitamin B is realized 2 High efficiency, low cost, and specific separation and enrichment. Compared with a direct detection method without enrichment, the method provided by the invention has the advantages of mild enrichment conditions, low-cost and easily obtained materials, high enrichment specificity and remarkable effect. The method provided by the invention can be used for enriching, and can maintain vitamin B 2 The structural information of (2) improves the signal intensity, is beneficial to the subsequent mass spectrum analysis, and reflects the vitamin B in the food sample 2 Is the content of vitamin B in complex sample 2 Provides new materials, new methods and related theoretical basis for analysis and detection.
Drawings
FIG. 1 is a scanning electron microscope and a transmission electron microscope of the aminated spinel type ferrite and the aminated spinel type ferrite/MXene composite material obtained in example 1.
FIG. 2 is an XRD pattern of the aminated spinel type ferrite and the aminated spinel type ferrite/MXene composite material obtained in example 1.
FIG. 3 is a zeta potential plot of the aminated spinel ferrite and the aminated spinel ferrite/MXene composite material obtained in example 1.
FIG. 4 shows the results of example 1 for the aminated spinel ferrite/MXene composite against vitamin B 2 And (3) evaluating the adsorption anti-interference capability of the catalyst.
FIG. 5 is an evaluation of reusability of the aminated spinel ferrite/MXene composite material obtained in example 1.
Detailed Description
The following describes the technical scheme of the present invention in further detail with reference to examples, but the scope of the present invention is not limited thereto.
EXAMPLE 1 preparation of aminated spinel ferrite/MXene composite Material
(1) Preparation of sheet MXene:
(a) 1g of LiF was slowly added to hydrochloric acid containing 20. 20 mL mol/L hydrochloric acid and stirred at room temperature for 30min, followed by 1g of Ti 3 AlC 2 Adding a small amount of the above solution for multiple times, stirring at 35 ℃ for 24 hours, centrifuging the obtained suspension at 3500 rpm for 5 minutes, and washing the obtained precipitate with deionized water to neutrality;
(b) Adding water into the precipitate, introducing nitrogen to deoxidize, ultrasonically stripping for 1h, centrifuging the obtained suspension at 3500 rpm for 1h, collecting supernatant, and freeze-drying to obtain Ti 3 C 2 T x MXene；
(2) Preparation of aminated spinel type ferrite:
adding 6.0 g sodium acetate into 90 mL glycol, stirring, adding 3.0 g ferric trichloride hexahydrate (FeCl) 3 ·6H 2 O) and 0.756 g zinc chloride (ZnCl) 2 ) Heating the mixed solution to 50 ℃ after ultrasonic homogenization, continuously adding 20 mL of 1, 6-hexamethylenediamine into the mixed solution under stirring, stirring for 30min, transferring the mixed solution to a hydrothermal reaction kettle, reacting for 8h at 200 ℃, repeatedly washing the product with absolute ethyl alcohol and deionized water, and drying the solid in a vacuum drying oven at 70 ℃ for 12 h to obtain the aminated spinel type ferrite magnetic nanoparticles;
(3) Preparation of an aminated spinel ferrite/MXene composite material:
100 mg of MXene was dissolved in water and sonicated for 1h to obtain 1mg/mL of MXene solution, 100 mg of aminated spinel type ferrite magnetic nanoparticles were dissolved in water to prepare 2mg/mL of solution, 100 mL of aminated spinel type ferrite magnetic nanoparticles aqueous solution was added to 50 mLMXene solution, and after sonicating the mixed solution for 1h at room temperature, the product was washed with deionized water and magnetically separated from the solution containing the excessive magnetic nanoparticles until the supernatant was clear. The resulting composite was dried in vacuo and stored at 4 ℃ for the next use.
Scanning electron microscopy and transmission electron microscopy of the aminated spinel type ferrite and the aminated spinel type ferrite/MXene composite material prepared in this example are shown in FIG. 1. As can be seen from fig. 1: amino groupDissolving ZnFe 2 O 4 The nanoparticles were uniformly supported on the MXene, which was tissue-like, indicating that MXene was very successfully exfoliated; aminated ZnFe 2 O 4 The nanoparticle size is around 100 a nm a. The results show that: the resulting aminated spinel ferrite/MXene composite material was successfully prepared.
XRD patterns of the aminated spinel type zinc ferrite and the aminated spinel type zinc ferrite/MXene composite material prepared in this example are shown in FIG. 2. Pure aminated ZnFe shown from FIG. 2 2 O 4 The XRD pattern of (2) shows that: the product of the invention is pure aminated ZnFe 2 O 4 The diffraction peak of the crystal face of the (B) is consistent with the reported ZnFe 2 O 4 Reflecting the success of step (1) according to the present invention, it is helpful to synthesize an aminated spinel ferrite/MXene composite. The aminated ZnFe from FIG. 2 2 O 4 XRD patterns of/MXene can be observed at 6.0 °, 18.2 ° and 60.9 ° with Ti 3 C 2 T x The corresponding diffraction peaks of the (002), (004) and (110) crystal planes of MXene. In addition, no other miscellaneous peaks appear, which indicates the purity compound requirement of the product. XRD results indicated that: the aminated spinel ferrite/MXene composite material can be successfully prepared by the method.
The zeta potential of the aminated spinel ferrite and the aminated spinel ferrite/MXene composite material prepared in this example is shown in FIG. 3, from which it can be seen that the MXene surface has a large negative charge (-30.6 mV), aminated ZnFe 2 O 4 The surface is a large positive charge (+22.7 mV), the zeta potential is positive, and after the composite material is compounded, the zeta potential of the composite material is close to 0, and the result shows that: the aminated spinel ferrite/MXene composite material can be successfully prepared by the method.
Example 2 use of composite materials for separation and enrichment of vitamin B 2
1. Preparation of rice extract
5g of rice powder and 25mL of 20mM/L acetic acid solution were mixed, shaken for 1h, centrifuged, the supernatant was taken, filtered, and the filtrate was placed in a 25mL volumetric flask and scaled.
2. Enrichment of vitamin B from rice extract 2
(1) Ultrasonic dispersing 5 mg amino spinel ferrite/MXene composite material in 5mL rice extractive solution, and continuously oscillating to enrich vitamin B 2 The shaking enrichment time was 15 min.
(2) And (3) carrying out magnetic separation on the enriched dispersion liquid of the aminated spinel type ferrite/MXene composite material, and taking out supernatant after separation, namely enriched raffinate. The obtained aminated spinel type ferrite/MXene composite material precipitates, namely enriched vitamin B 2 The obtained aminated spinel type ferrite/MXene composite material.
(3) Adsorption of vitamin B 2 Adding eluent into the precipitation of the aminated spinel type ferrite/MXene composite material, and continuously carrying out ultrasonic treatment to adsorb the vitamin B on the surface of the aminated spinel type ferrite/MXene composite material 2 Eluting; the eluent is methanol solution of 1% formic acid, the pH of the eluent is 2.0, and the ultrasonic elution time is 2min.
(4) Magnetically separating the eluted solution, and collecting supernatant rich in vitamin B 2 Is used for eluting the eluent.
(5) Drying the eluent with nitrogen, re-dissolving with ultrapure water, and performing ultra-high performance liquid chromatography-mass spectrometry analysis.
The aminated ZnFe prepared in example 1 2 O 4 Use of/MXene composite material for vitamin B 2 The results of the selective enrichment ability test of (2) are shown in FIG. 4. In the case of the simultaneous presence of six other vitamins, it is specific for vitamin B 2 The adsorption capacity of (C) was still maintained at 30 mg/g, indicating that the aminated ZnFe prepared in example 1 2 O 4 Vitamin B pair of MXene composite material 2 Has good adsorption selectivity. As shown in fig. 5, the vitamin B is repeatedly used a plurality of times 2 Without a significant decrease in enrichment capacity.
Claims (10)
1. An aminated spinel ferrite/MXene composite material characterized by: the composite material of aminated spinel ferrite/MXene consists of sheetThe magnetic nano-particle consists of MXene and aminated spinel type ferrite magnetic nano-particles uniformly loaded on the MXene; the spinel type ferrite magnetic nano-particles are ZnFe 2 O 4 And (3) nanoparticles.
2. The aminated spinel ferrite/MXene composite material according to claim 1, characterized in that: the MXene is a single-layer or less-layer sheet structure, and the MXene is a sheet structure with the thickness of less than 3 nm and the number of layers of less than 5.
3. A method for preparing the aminated spinel ferrite/MXene composite material according to any one of claims 1 to 2, comprising the steps of:
(1) Preparation of sheet MXene:
slowly adding lithium fluoride into a hydrochloric acid solution, stirring for 25-35 min at room temperature, and adding Ti 3 AlC 2 Stirring for 24-48 h at 35-40 ℃, centrifuging the obtained suspension, and washing the obtained precipitate with deionized water to be neutral; adding water into the sediment, introducing nitrogen to deoxidize, ultrasonically stripping for 1-2 hours, centrifuging the obtained suspension, collecting supernatant, and freeze-drying to obtain flaky MXene;
(2) Preparation of aminated spinel type ferrite:
adding sodium acetate into ethylene glycol, uniformly stirring, adding ferric trichloride hexahydrate and zinc chloride, uniformly carrying out ultrasonic treatment, heating the mixed solution to 45-55 ℃, continuously adding 1, 6-hexamethylenediamine into the mixed solution under the stirring state, stirring for 25-35 min, transferring the mixed solution to a hydrothermal reaction kettle, reacting for 8-24 h at 150-200 ℃, washing the product with absolute ethyl alcohol and deionized water, and carrying out vacuum drying to obtain the aminated spinel type ferrite magnetic nano particles;
(3) Preparation of an aminated spinel ferrite/MXene composite material:
and (3) dissolving MXene in water and performing ultrasonic treatment to obtain MXene solution, dissolving the aminated spinel type ferrite magnetic nano particles in water to prepare an aminated spinel type ferrite magnetic nano particle aqueous solution, adding the aminated spinel type ferrite magnetic nano particle aqueous solution into the MXene solution, performing ultrasonic treatment on the mixed solution for 1-2 hours, washing a product with deionized water, performing magnetic separation from the solution containing excessive magnetic nano particles until supernatant is clear, and drying the obtained composite material in vacuum.
4. A method of preparing an aminated spinel ferrite/MXene composite material according to claim 3, characterized in that: in step (1), lithium fluoride and Ti 3 AlC 2 The mass ratio of (2) is 1:1-2:1.
5. A method of preparing an aminated spinel ferrite/MXene composite material according to claim 3, characterized in that: in the step (2), zn 2+ And Fe (Fe) 3+ The mass ratio of the substances is 1:1.8-1:2.2; fe (Fe) 3+ The concentration in the mixed solution is 0.01-0.03 mol/L.
6. A method of preparing an aminated spinel ferrite/MXene composite material according to claim 3, characterized in that: in the step (2), the mass ratio of the sodium acetate to the ferric trichloride hexahydrate is 1.5:1-2.5:1; the mass ratio of the sodium acetate to the 1, 6-hexamethylenediamine is 1:3-1:4.
7. A method of preparing an aminated spinel ferrite/MXene composite material according to claim 3, characterized in that: in the step (3), the mass ratio of the aminated spinel type ferrite magnetic nano particles to the MXene is 1:0.5-1:3.
8. An aminated spinel ferrite/MXene composite material as an adsorbent for separating and enriching vitamin B 2 Is used in the field of applications.
9. An aminated spinel ferrite/MXene composite material as an adsorbent for separating and enriching vitamin B 2 Is characterized in that: enrichment detection of vitamin B 2 The method of (1) comprises the following steps:
(1) Dispersing an aminated spinel ferrite/MXene composite material to contain vitamin B 2 In the sample extracting solution of (2), vibrating for 10-20 min to enrich vitamin B 2 The method comprises the steps of carrying out a first treatment on the surface of the The vitamin B-containing food contains vitamin B 2 The sample extract of (C) contains vitamin B 2 Dispersing the sample into 20mM/L acetic acid solution;
(2) Magnetically separating the enriched liquid, and enriching vitamin B 2 Adding eluent into the aminated spinel type ferrite/MXene composite material for ultrasonic elution for 1-5 min and performing magnetic separation to obtain vitamin B 2 Enriching the solution; the eluent is methanol solution containing 1% formic acid.
10. A kind of vitamin B used for enriching 2 Is characterized in that: an aqueous acetic acid solution comprising 20mM/L of the aminated spinel ferrite/MXene composite material of claim 1, methanol and formic acid.
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| CN116272871A (en) * | 2023-04-26 | 2023-06-23 | 中国科学院兰州化学物理研究所 | Application of multilayer MXene/zinc amide ferrite composite material as adsorbent in heavy metal mercury enrichment |
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| CN116272871A (en) * | 2023-04-26 | 2023-06-23 | 中国科学院兰州化学物理研究所 | Application of multilayer MXene/zinc amide ferrite composite material as adsorbent in heavy metal mercury enrichment |
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