CN108079978B

CN108079978B - Fe3O4-NH2Preparation method and application of-PEI magnetic nano material

Info

Publication number: CN108079978B
Application number: CN201711348616.8A
Authority: CN
Inventors: 娄大伟; 田媛媛; 祝波; 王希越; 连丽丽; 张�浩; 明明; 郭晓阳; 徐阳
Original assignee: Jilin Institute of Chemical Technology
Current assignee: Jilin Institute of Chemical Technology
Priority date: 2017-12-15
Filing date: 2017-12-15
Publication date: 2020-10-20
Anticipated expiration: 2037-12-15
Also published as: CN108079978A

Abstract

The invention discloses Fe₃O₄‑NH₂A preparation method and application of-PEI magnetic nano material, comprising 1) FeCl₃·6H₂Adding anhydrous sodium acetate and ethylene glycol into O, mixing, mechanically stirring at 75-85 ℃, dropwise adding ethanolamine to obtain a first mixed solution, transferring the first mixed solution into a reaction kettle, reacting at 190-210 ℃ for 7-10 hours, cleaning, and drying to obtain Fe₃O₄‑NH₂Nanoparticles; 2) mixing Fe₃O₄‑NH₂Adding the solution into a PEI methanol solution, performing ultrasonic treatment for 20-40 min, dropwise adding glutaraldehyde, mechanically stirring, precipitating, cleaning and drying to obtain Fe₃O₄‑NH₂-PEI magnetic nanomaterial. PEI functionalized Fe prepared by the invention₃O₄The magnetic nano material keeps the original crystal form, has good superparamagnetism and dispersibility, and can be used for enriching the organic phosphate tri (2-ethyl) hexyl phosphate (TEHP) in the environment.

Description

Preparation method and application of Fe3O4-NH2-PEI magnetic nano material

Technical Field

The invention belongs to the field of inorganic composite materials and technologies, and particularly relates to a preparation method of a novel magnetic nano material, wherein the material can be applied to enrichment of organic phosphate (TEHP) in the environment.

Background

Organic phosphates (ops) are an important class of phosphorus-based flame retardants, and are currently widely used as flame retardants or plasticizers in plastics, electronic devices, and furniture. As an additive flame retardant, the OPEs are mainly bonded with chemical materials, and are reported to be detected in ambient air, indoor air, surface water and sewage treatment plant discharge water. A large number of experimental researches find that the organic phosphate flame retardant has stable property, biological accumulation, carcinogenic toxicity, reproductive toxicity and mutagenicity, and threatens human health and an ecological system. Thus, the detection and control of OPEs in aqueous environments is becoming increasingly important.

Magnetic Solid Phase Extraction (MSPE) is used as a novel sample pretreatment technology, a magnetic adsorbent is directly added into a sample solution to be fully contacted with a target analyte, and after extraction balance is achieved, the target analyte is rapidly separated from a sample matrix by applying an external magnetic field. Magnetic solid phase extraction is introduced into an environmental sample pretreatment technology, and a magnetic adsorption material not only can be directly enriched and rapidly separated in an environmental medium, but also solves the problems that an SPE adsorbent needs to be filled with a column, loaded with samples in large volume and the like. The MSPE uses a magnetic nano material as a carrier of a target analyte, and has the advantages of easy functional modification, large specific surface area, strong dispersibility, convenience for solid-liquid separation and the like. MSPE is simple to operate and has high enrichment efficiency on analytes.

However, in the prior art, the technology of applying magnetic solid phase extraction to organic phosphate enrichment is few, and the technical limitation is to the truly suitable magnetic nano material.

Aiming at the problems, the invention prepares the magnetic nano-microsphere Fe with the shell-core structure₃O₄-NH₂PEI, the modified magnetic nano material has the advantages of stable chemical property, high selectivity and the like, the problem that the traditional adsorbent is difficult to separate solid from liquid is solved, the preparation process is environment-friendly and pollution-free, and the TEHP in an enriched environment water sample has unique advantages.

Disclosure of Invention

The invention aims to provide a preparation method of functionalized magnetic nanoparticles for adsorbing organic phosphate ester TEHP. The purpose of the invention is realized by the following technical scheme:

fe₃O₄-NH₂-a method for preparing PEI magnetic nanomaterial, comprising the following preparation steps:

1）Fe₃O₄-NH₂preparing nano particles: FeCl₃·6H₂Adding anhydrous sodium acetate, glycol and FeCl into O₃·6H₂The mass ratio of O to anhydrous sodium acetate is 3: 7-9, the mass volume ratio of anhydrous sodium acetate to ethylene glycol is 9g/100mL, the mixture is mixed and mechanically stirred at the temperature of 75-85 ℃, ethanolamine is added dropwise to obtain a first mixed solution, and ethanolamine and FeCl are added₃·6H₂The mass ratio of O is 5.0-7.0: 1.3-1.4; transferring the first mixed solution into a reaction kettle, reacting for 7-10 h at 190-210 ℃, cleaning the product after reaction by using deionized water and absolute ethyl alcohol, and drying for 22-26 h at 55-65 ℃ in a vacuum drying oven to obtain Fe₃O₄-NH₂Nanoparticles;

2）Fe₃O₄-NH₂-preparation of PEI nanomaterials: mixing Fe₃O₄-NH₂Adding into a methanol solution of PEI, Fe₃O₄-NH₂Performing ultrasonic treatment for 20-40 min, dropwise adding glutaraldehyde into the PEI methanol solution at a mass-volume ratio of 0.1-0.3 g/40-60 mL, performing mechanical stirring, cleaning the obtained black brown precipitate ultrapure water, and drying the cleaned black brown precipitate ultrapure water for 22-26 h at 55-65 ℃ in a vacuum drying oven to obtain the Fe₃O₄-NH₂-PEI magnetic nanomaterial.

Further, FeCl₃·6H₂The mass ratio of O to anhydrous sodium acetate is 3: 8.

Further, a mechanical stirrer is adopted for mechanical stirring in the step 1), the rotating speed of the mechanical stirrer is 300rpm, and the stirring time is 30-40 min.

Further, the temperature of mechanical stirring in the step 2) is 20-30 ℃, the rotating speed of a mechanical stirrer is 300rpm, and the stirring time is 30-40 min.

Preparation of the resulting Fe₃O₄-NH₂The PEI magnetic nano material is applied to adsorption and enrichment of organic phosphate in the environment. Is particularly suitable for adsorbing and enriching organic phosphate in liquid environment.

Using said Fe₃O₄-NH₂-method for adsorbing organic phosphate in liquid by PEI magnetic nano material: mixing Fe₃O₄-NH₂Adding the PEI magnetic nano material into liquid containing organic phosphate pollutants, oscillating or stirring for 10-30 min, and then recycling the magnetic nano material through an external magnetic field.

The invention has the beneficial effects that:

PEI functionalized Fe prepared by the invention₃O₄The magnetic nano material keeps the original crystal form, has good superparamagnetism and dispersibility, and can be used for enriching the organic phosphate tri (2-ethyl) hexyl phosphate (TEHP) in the environment. The method has the characteristics of simple method, mild reaction conditions, easily obtained raw materials and low cost, and has wide application prospect in the field of analytical chemistry.

Drawings

FIG. 1 shows the magnetic nanoparticles Fe obtained₃O₄-NH₂-PEI Scanning Electron Microscopy (SEM) images.

FIG. 2 shows the effect of particles made of 1, 6-hexanediamine and ethanolamine on the adsorption effect.

FIG. 3 influence of the addition of adsorbent on the adsorption results of TEHP.

Detailed Description

Example 1

1）Fe₃O₄-NH₂preparing nano particles: FeCl₃·6H₂Adding anhydrous sodium acetate, glycol and FeCl into O₃·6H₂The mass ratio of O to anhydrous sodium acetate is 3: 7-9 (preferably 3: 8), the mass volume ratio of anhydrous sodium acetate to ethylene glycol is 9g/100mL, the mixture is mixed and mechanically stirred at the temperature of 75-85 ℃, ethanolamine is added dropwise to obtain a first mixed solution, and ethanolamine and FeCl are added₃·6H₂The mass ratio of O is 5.0-7.0: 1.3-1.4; transferring the first mixed solution into a reaction kettle, reacting for 7-10 h at 190-210 ℃ (preferably 200 ℃), cleaning the product after reaction with deionized water and absolute ethyl alcohol, and drying for 22-26 h at 55-65 ℃ in a vacuum drying oven to obtain Fe₃O₄-NH₂Nanoparticles;

Example 2

The improvement is carried out on the basis of the embodiment 1.

1）Fe₃O₄-NH₂Preparing nano particles: 1.3-1.4 g FeCl₃·6H₂Adding anhydrous sodium acetate, glycol and FeCl into O₃·6H₂The mass ratio of O to anhydrous sodium acetate is 3: 7-9 (preferably 3: 8), the mass volume ratio of anhydrous sodium acetate to ethylene glycol is 9g/100mL, the mixture is uniformly mixed, the liquid is transferred into a 100mL three-neck flask and is mechanically stirred at the temperature of 80 ℃, and the mechanical stirring is carried out one by oneDropwise adding 5.0-6.0 g of ethanolamine to obtain a first mixed solution; transferring the first mixed solution into a reaction kettle, reacting for 8 hours at 190-210 ℃ (preferably 200 ℃), cleaning the product after reaction with deionized water and absolute ethyl alcohol, and drying for 24 hours at 60 ℃ in a vacuum drying oven to obtain Fe₃O₄-NH₂Nanoparticles;

2）Fe₃O₄-NH₂-preparation of PEI nanomaterials: 0.1-0.3 g Fe₃O₄-NH₂Adding the nanoparticles into 40-60 ml of an Alfa Aesar (Alfa Aesar) methanol solution (Product No.: 40331 Product: polyethylene imine, branched, M.W. 10,000, 99% Lot No.: R05C005 molecular weight:10,000 Amine value:18 meq/g Assay: 99.8% CAS:9002-98-6 specification: 25 g), performing ultrasonic treatment for 30min, dropwise adding 4-6 ml of glutaraldehyde, mechanically stirring, cleaning the obtained brown black precipitate with ultrapure water, drying in a vacuum drying box at 60 ℃ for 24h, and preparing the Fe₃O₄-NH₂-PEI magnetic nanomaterial.

In the research process, the temperature and the amount of the ethanolamine influence the particle size, but the effect is not linear due to the complexity of the growth process. Furthermore, the extension of the reaction time has no significant effect on the particle size.

FIG. 1 shows Fe prepared by this method₃O₄-NH₂PEI nano-particles, the composite material is in irregular bulk shape, the surface roughness can be seen from the appearance, the composite material is in a porous structure, and the roughness and the fold structure can obviously increase the surface area and the load capacity for extracting the target compound. Is particularly suitable for adsorbing organic phosphate.

Preparation of Fe₃O₄-NH₂In the case of nanoparticles, TEHP was adsorbed by 1, 6-hexanediamine and ethanolamine, respectively, as shown in FIG. 2, and the results of the experiment showed that Fe was produced by ethanolamine₃O₄-NH₂Nanoparticles adsorb organophosphates better.

Example 3

The modification is carried out on the basis of the embodiment 2, and other conditions are consistent with the embodiment 2.

The experiment shows that: step 1) FeCl₃·6H₂The optimum amount of O is 1.35g, the optimum amount of NaAc is 3.6g (3: 8), the volume of ethylene glycol is 40mL, the optimum amount of ethanolamine is 6.5g, the reaction is carried out at 200 ℃, and the granulation effect is the best.

Fe in step 2)₃O₄-NH₂The optimum amount of (2) is 0.2 g, the optimum amount of PEI methanol solution is 50 mL, and the optimum amount of glutaraldehyde is 5 mL, under which the prepared particles have the best effect.

Example 4

20 mg, 40 mg, 60 mg, 80 mg, 100 mg of Fe prepared in example 2 were weighed out separately₃O₄-NH₂And (2) putting PEI magnetic nanoparticles into 20 mL of mixed solution containing organic phosphate (TEHP) respectively, wherein the concentration of the TEHP in the solution is 1.25 ug/mL, performing vortex oscillation for 10 min, as PEI has polar group amino to form hydrogen bonds with the TEHP, then PEI has a hydrophobic group (vinyl) structure and the TEHP performs hydrophobic action, so that the TEHP is adsorbed on the magnetic nanoparticles, recovering the magnetic nanoparticles through an external magnetic field, adding 800 mu L of ethyl acetate into the magnetic nanoparticles, performing ultrasonic treatment for 10 min, recovering ethyl acetate eluent, drying and concentrating the ethyl acetate eluent by using nitrogen, adding 200 mu L of ethyl acetate to fix the volume, and detecting by using gas chromatography mass spectrometry, wherein the adsorption rate can reach 60-70%. The results are shown in FIG. 3.

Claims

1. Fe₃O₄-NH₂-a method for preparing PEI magnetic nanomaterial, comprising the following preparation steps:

1)Fe₃O₄-NH₂preparing nano particles: FeCl₃·6H₂Adding anhydrous sodium acetate, glycol and FeCl into O₃·6H₂The mass ratio of O to anhydrous sodium acetate is 3: 7-9, the mass volume ratio of anhydrous sodium acetate to ethylene glycol is 9g/100mL, the mixture is mixed and mechanically stirred at the temperature of 75-85 ℃, ethanolamine is added dropwise to obtain a first mixed solution, and ethanolamine and FeCl are added₃·6H₂The mass ratio of O is 5.0-7.0: 1.3-1.4; transferring the first mixed solution into a reaction kettle, and reacting for 7-10 h at 190-210 ℃ for reactionWashing the post product with deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 55-65 ℃ for 22-26 h to obtain Fe₃O₄-NH₂Nanoparticles; in the step 1), a mechanical stirrer is adopted for mechanical stirring, the rotating speed is 300rpm, and the stirring time is 30-40 min;

2)Fe₃O₄-NH₂-preparation of PEI nanomaterials: mixing Fe₃O₄-NH₂Adding into a methanol solution of PEI, Fe₃O₄-NH₂Performing ultrasonic treatment for 20-40 min, dropwise adding glutaraldehyde into the PEI methanol solution at a mass-volume ratio of 0.1-0.3 g/40-60 mL, performing mechanical stirring, cleaning the obtained black brown precipitate ultrapure water, and drying the cleaned black brown precipitate ultrapure water for 22-26 h at 55-65 ℃ in a vacuum drying oven to obtain the Fe₃O₄-NH₂-a PEI magnetic nanomaterial; the temperature of mechanical stirring in the step 2) is 20-30 ℃, the rotating speed of a mechanical stirrer is 300rpm, and the stirring time is 30-40 min.

2. Fe of claim 1₃O₄-NH₂-a method for preparing PEI magnetic nanomaterial, characterized in that: FeCl₃·6H₂The mass ratio of O to anhydrous sodium acetate is 3: 8.

3. Fe prepared by the preparation method of any one of claims 1-2₃O₄-NH₂-use of PEI magnetic nanomaterial for the adsorption and enrichment of organophosphates in a liquid environment.

4. Use according to claim 3, characterized in that: mixing Fe₃O₄-NH₂Adding the PEI magnetic nano material into liquid containing organic phosphate pollutants, oscillating or stirring for 10-30 min, and then recycling the magnetic nano material through an external magnetic field.

5. Use according to claim 4, characterized in that: the organic phosphate-containing compoundWhen the concentration of the organic phosphate in the liquid of the pollutants is 1-10 mg/L, Fe₃O₄-NH₂The addition amount of the PEI magnetic nano material added into the liquid containing the organic phosphate pollutants is 1-5 g/L.