A kind of preparation method of magnetic nanometer composite material
The application is the applying date are as follows: on 01 07th, 2016, application No. is a kind of 201610010126.6, titles are as follows: magnetic
The divisional application of the patent of invention of property graphene polyaniline nano-composite material and preparation method thereof.
Technical field
The invention belongs to technical field of composite materials, are related to a kind of modified composite adsorbing material more particularly to one of graphene
Kind magnetic graphene polyaniline nano-composite material and preparation method thereof and the material answering in the enrichment of phenols environmental estrogens
With.
Background technique
Nonyl phenol, octyl phenol and bisphenol-A belong to phenols environmental estrogens, to the potential risk of environment and human health
It has attracted wide attention.Nonyl phenol and octyl phenol can accumulate in vivo as endocrine disruptor, and pass through food
Chain enters human body, to human cancer cell growth and fecundity can generate and seriously affect, because due to preferential danger has been classified as by European Union
Evil substance.The content of nonyl phenol must not be higher than 0.1% in the commodity such as European Union 2003/53/EC instruction regulation textile.International Environmental Protection
Clearly stipulate that forbidding during textile production in " Oeko-TexStandard 1000 " that weaving association works out and promulgates
Use nonyl phenol.Bisphenol-A is also a kind of incretion interferent, will cause difference to the reproductive development of mammal and aquatic animal
The influence of degree.On October 18th, 2008, Her Majesty the Queen in right of Canada as represented by the minister of Healt announce that bisphenol-A is hazardous substance, and nonimportation and pin
Sell the polycarbonate baby bottles containing bisphenol-A.What Norway's contamination control administration promulgated " is consuming about limitation special harmful substance
Use in product " (PoHS instruction) the also use of limitation bisphenol-A in the consumer goods.
Currently used for detect phenols environmental estrogens Main Analysis detection method have spectrophotometry, fluorimetry,
Gas chromatography, gas chromatographymass spectrum, liquid chromatography, liquid-mass chromatography method etc..Wherein color-matter joint technology detection limit is low, clever
Sensitivity is high, selectivity is good, but instrument price is expensive, and testing cost is very high.Swash further, since phenols present in environmental sample is female
Cellulose content is very low, and background interference is big, and even expensive chromatograph-mass spectrometer coupling technology is also incompetent to the detection of some samples
For power, other existing analysis methods more can not meet the detection of micro phenolic estrogen in environment, therefore develop with height
The sample pretreating method of effect selectivity and accumulation rate, wherein key is the adsorbent material that exploitation has high efficiency of additive capability.
Summary of the invention
There is the π-πconjugation rich in electronics in graphene, provides possibility for the induced adsorption of organic matter.But graphite
Alkene lamellar structure is easy to reunite, and cannot effectively embody its high specific surface area advantage, and graphene surface official in actual use
Can single group one, for the characteristic of phenols environmental estrogens, inventor by pay creative labor selectivity in graphene
Amino polymer in surface modification, with the hydrogen bond of the amino and the hydroxyl in phenols environmental estrogens that are protonated by material surface
And inducing action power, improve absorption of the material to phenols environmental estrogens.Therefore the present invention has following three goal of the invention:
The first purpose of this invention is to provide a kind of magnetic graphene polyaniline for the above technical problems to receive
Nano composite material.
Another object of the present invention is to provide a kind of magnetic graphene polyaniline for the above technical problems to receive
The preparation method of nano composite material.
A further object of the invention is to provide a kind of utilization magnetic graphene polyphenyl for the above technical problems
The method that amine nanocomposite is enriched with phenols environmental estrogens
The purpose of the present invention can be achieved through the following technical solutions:
A kind of magnetic graphene polyaniline nano-composite material, the material are to be prepared via a method which to obtain:
Using the alcohol containing 1~5 carbon atom as solvent, mass ratio is followed successively by 1~5:1~10:1~10 graphene/poly-
Aniline composite material, FeCl3It is dissolved in the solvent and is ultrasonically treated with sodium acetate, carry out in a high pressure reaction kettle later anti-
It answers, magnetic graphene polyaniline nano-composite material can be obtained.
A kind of preparation method of magnetic graphene polyaniline nano-composite material, this method is with the alcohol containing 1~5 carbon atom
For solvent, mass ratio is followed successively by 1~5:1~10:1~10 grapheme/polyaniline composite material, FeCl3It is molten with sodium acetate
It in the solvent and is ultrasonically treated, is reacted in a high pressure reaction kettle later, magnetic graphene polyaniline can be obtained
Nanocomposite.
As preferred: in magnetic graphene polyaniline nano-composite material and preparation method thereof, graphene/polyaniline is compound
Material: FeCl3: the mass ratio of sodium acetate is 1~3:1~5:5~10;The power of ultrasonic treatment is 300~500W, and the time is
0.5~1.5h;The temperature reacted in autoclave is 150~250 DEG C, and the time of reaction is 4~48h, preferably reaction under high pressure
The temperature reacted in kettle is 180~200 DEG C, and the time of reaction is 4~10h.The alcohol containing 1~5 carbon atom is selected from first
At least one of alcohol, ethyl alcohol, ethylene glycol and diethylene glycol, the alcohol for preferably comprising 1~5 carbon atom is ethylene glycol and diethylene glycol
Mixed liquor.
Grapheme/polyaniline composite material described in technical solution of the present invention is to be prepared via a method which to obtain: by oxygen
It is ultrasonically treated after graphite and solvent mixing, obtains graphene oxide solution;It is added and contains in the graphene oxide solution
The hydrochloric acid solution of aniline simultaneously stirs evenly, and obtains mixed liquor;(NH4) will be contained2S2O8Hydrochloric acid solution be added to the mixed liquor
In reacted, obtain grapheme/polyaniline composite material after reaction.
As preferred: in the preparation method of grapheme/polyaniline composite material, the solvent is selected from water, ethyl alcohol, second two
At least one of pure and mild diethylene glycol;Graphite oxide: aniline: (NH4)2S2O8Mass ratio be 1~5:1~5:4~10.Institute
The mass ratio of aniline and hydrochloric acid is 1.5~3:1 in the hydrochloric acid solution containing aniline stated, and is contained (NH4)2S2O8Hydrochloric acid solution in
(NH4)2S2O8Mass ratio with hydrochloric acid is 15~35:1.The power of ultrasonic treatment is 300~500W, and the time is 0.5~1.5h.
It is a kind of rich to phenols environmental estrogens using the above-mentioned magnetic graphene polyaniline nano-composite material being prepared
The method of collection, this method using magnetic graphene polyaniline nano-composite material as adsorbent material, by adsorbent material be added to containing
It in the solution of phenols environmental estrogens and is uniformly mixed, to guarantee that absorption is abundant;Use magnet by adsorbent material after absorption sufficiently
It is separated with solution;The adsorbent material for having adsorbed phenols environmental estrogens is eluted using eluting solvent after separation, is washed
Solution after collecting elution after de- is to get the phenols environmental estrogens to after being enriched with;It is preferred that the eluant, eluent is selected from first
At least one of alcohol, ethyl alcohol and acetic acid.
GO/PANI described in technical solution of the present invention is graphene polyaniline composite material, and the MGO/PANI is magnetic
Property graphene polyaniline nano-composite material, the M/PANI be magnetic polyaniline composite material, the M/GO be magnetism
Grapheme material.
Beneficial effects of the present invention:
Magnetic graphene polyaniline nano-composite material stable chemical performance prepared by the present invention, large specific surface area, absorption
Performance is strong.Graphene is modified using aniline and magnetic material, graphene sheet layer is overcome and easily stacks and simple polyphenyl
Amine disadvantage easy to reunite.With phenolic estrogen in this kind of adsorbent absorption water, show better than magnetic graphene material and magnetism
The absorption property of polyaniline material.Graphene through magnetic material and Polyaniline-modified not only increases the suction to phenolic estrogen
Attached efficiency keeps its separation relatively easy as well as magnetism possessed by the material itself.Therefore, the present invention has absorption
Efficiently, advantage easy to operate.
Detailed description of the invention
Fig. 1 (a) is graphene oxide transmission electron microscope picture used in embodiment 1, and Fig. 1 (b) is the graphite that embodiment 1 is prepared
Alkene/polyaniline composite material transmission electron microscope picture, Fig. 1 (c) are the transmission electricity for the MGO/PANI-1 material that embodiment 1 is prepared
Mirror figure.
Fig. 2 be the magnetic graphene polyaniline nano-composite material that is prepared of embodiment 1 under condition of different pH to several
The adsorption efficiency curve of kind phenolic estrogen.
Fig. 3 is the magnetic graphene polyaniline nano-composite material hysteresis graph that embodiment 1 is prepared.
Fig. 4 is effect pair before and after the magnetic graphene polyaniline nano-composite material Magnetic Isolation that embodiment 1 is prepared
Than figure.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, and but the scope of the present invention is not limited thereto:
Embodiment 1
The graphite oxide for weighing 0.14g is placed in the three-neck flask equipped with 60mL deionized water, super with ultrasonic power 300W
Sonication 1h obtains graphene oxide solution.0.28g aniline is added in the graphene oxide solution and 0.2mol/L hydrochloric acid is molten
Liquid 20mL, electric stirring 30min.It is added dropwise under ice-water bath later and enters to contain 0.68g (NH4)2S2O80.05mol/L hydrochloric acid
There is color change in reaction solution in solution 20mL, 5min, becomes blackish green.Electric stirring stops reaction after reacting 6h, respectively
Several times with water and ethyl alcohol eccentric cleaning, 60 DEG C of vacuum drying obtain blackish green product, as grapheme/polyaniline composite material.
It is the ethylene glycol of 1:1 and the mixed liquor of diethylene glycol as solvent using volume ratio, 0.1g graphene/polyaniline is compound
Material, 0.4gFeCl3It is dissolved in solvent with 0.7g sodium acetate, 1h is ultrasonically treated with ultrasonic power 300W, has been transferred to later poly-
In the stainless steel autoclave of tetrafluoroethene liner, autoclave is heated to 190 DEG C, reaction 6h is maintained, is cooled to room
Temperature.Product progress Magnetic Isolation collection for several times with second alcohol and water wash products can be obtained for 60 DEG C in a vacuum drying oven
MGO/PANI-1 material.Its saturation magnetization is 48.14emu/g, as shown in Figure 3.
In addition, surface is smooth and deposits as can be seen that graphene oxide (GO) is very thin lamellar structure from Fig. 1 (a)
In more fold;As can be seen that graphene Polyaniline (GO/PANI) is also lamellar structure, polyphenyl from Fig. 1 (b)
Amine is uniformly covered on graphene surface and does not destroy lamellar structure, but can be seen that lamellar spacing increases from the shade of gauffer;
As can be seen that magnetic graphene Polyaniline (MGO/PANI-1) is still lamellar structure from Fig. 1 (c), surface distribution
Fe3O4Magnetic-particle, particle diameter is between 100-200nm.
Embodiment 2
The graphite oxide for weighing 0.14g is placed in the three-neck flask equipped with 60mL deionized water, super with ultrasonic power 450W
Sonication 1h obtains graphene oxide solution.0.42g aniline and 0.2mol/L hydrochloric acid solution 20mL, electric stirring 30min is added.
It is added dropwise under ice-water bath later and enters to contain 1.24g (NH4)2S2O80.05mol/L hydrochloric acid solution 20mL, 5min in reaction it is molten
There is color change in liquid, becomes blackish green.Electric stirring stops reaction after reacting 6h, uses water and ethyl alcohol eccentric cleaning number respectively
Time, 60 DEG C of vacuum drying obtain blackish green product, as grapheme/polyaniline composite material.
It is the ethylene glycol of 1:1 and the mixed liquor of diethylene glycol as solvent using volume ratio, 0.2g graphene/polyaniline is compound
Material, 0.4gFeCl3It is dissolved in solvent with 0.9g sodium acetate, 1h is ultrasonically treated with ultrasonic power 450W, has been transferred to later poly-
In the stainless steel autoclave of tetrafluoroethene liner, autoclave is heated to 190 DEG C, reaction 6h is maintained, is cooled to room
Temperature.For several times with second alcohol and water wash products MGO/PANI-2 material is can be obtained into for 60 DEG C in a vacuum drying oven in collection of products
Material.
Comparative example 1
Electric stirring 30min after 0.42g aniline and 0.2mol/L hydrochloric acid solution 20mL mixing.It is added dropwise under ice-water bath
Contain 1.24g (NH4)2S2O80.05mol/L hydrochloric acid solution 20mL, electric stirring stops reaction after reacting 6h, respectively with water and
Several times, 60 DEG C of vacuum drying obtain PANI material to ethyl alcohol eccentric cleaning.
Be the ethylene glycol of 1:1 and the mixed liquor of diethylene glycol as solvent using volume ratio, by 0.2gPANI material,
0.4gFeCl3It is dissolved in solvent with 0.9g sodium acetate, 1h is ultrasonically treated with ultrasonic power 450W, has been transferred to polytetrafluoroethyl-ne later
In the stainless steel autoclave of alkene liner, autoclave is heated to 190 DEG C, reaction 6h is maintained, is cooled to room temperature.It will produce
Object is collected, and for several times with second alcohol and water wash products, M/PANI material can be obtained for 60 DEG C in a vacuum drying oven.
Comparative example 2
It is the ethylene glycol of 1:1 and the mixed liquor of diethylene glycol as solvent using volume ratio, by 0.2g graphene, 0.4gFeCl3
It is dissolved in solvent with 0.9g sodium acetate, 1h is ultrasonically treated with ultrasonic power 450W, is transferred to polytetrafluoroethyllining lining later
In stainless steel autoclave, autoclave is heated to 190 DEG C, reaction 6h is maintained, is cooled to room temperature.By collection of products,
For several times with second alcohol and water wash products, M/GO material can be obtained for 60 DEG C in a vacuum drying oven.
Performance detection
The material that embodiment 1, embodiment 2, comparative example 1 and comparative example 2 are prepared is respectively applied to nonyl phenol, octyl
The measurement of phenol and bisphenol-A absorption property, specific as follows:
The MGO/PANI-2 that MGO/PANI-1 material that 4mg embodiment 1 is prepared, embodiment 2 are prepared respectively
The M/GO material that the M/PANI and comparative example 2 that material, comparative example 1 are prepared are prepared is placed in 15mL teat glass, is added
The mixed standard solution 0.5mL for entering nonyl phenol, octyl phenol and bisphenol-A that concentration is 1mg/mL, is settled to 5mL with water, obtains
Concentration C0For the prepare liquid of 100mg/L, cap.At room temperature in vortex instrument with 2200rpm/min be vortexed one section
Time guarantees that absorption is abundant.The material for having adsorbed determinand is separated with water sample using magnet, with supernatant after HPLC measurement absorption
The mass concentration of liquid, according to formulaCalculate adsorbance.Obtain the adsorbance (mg/g) of each material.C0, C difference
For the mass concentration of absorption front and back solution, mg/L;M is the quality of adsorbent material, unit g;Q is the adsorbance of adsorbent, mg/
g。
The concentration of nonyl phenol, octyl phenol and bisphenol-A supernatant after table 1 adsorbs
The adsorbance of 2 n nonylphenol of table, octyl phenol and bisphenol-A
Material |
Nonyl phenol |
Octyl phenol |
Bisphenol-A |
MGO/PANI-1 |
70.5mg/g |
79.8mg/g |
60.38mg/g |
MGO/PANI-2 |
73.4mg/g |
82.1mg/g |
64.26mg/g |
M/PANI |
22.8mg/g |
23.4mg/g |
18.2mg/g |
M/GO |
40.5mg/g |
42.7mg/g |
38.3mg/g |
We can see that the material phenolic estrogen being prepared with the method for the present invention from the content of Tables 1 and 2
Absorption in, the adsorbance of each substance magnetic polyaniline nano material more compound than unused graphene oxide has 50mg/g or so
Raising.Compared with also not having mentioning close to 20-30mg/g with the adsorbance of the magnetic graphene nano material of Polyaniline-modified
It is high.Change the product absorption property slight difference that different material ratio is prepared, adsorbance is all significantly increased.
2. the survey that the material that embodiment 1 and embodiment 2 are prepared is applied to nonyl phenol, octyl phenol and bisphenol-A clearance rate
It is fixed
Weigh 4mg MGO/PANI-1 respectively, MGO/PANI-2, M/PANI and M/GO material are placed in 15mL teat glass,
The mixed standard solution 0.5mL that concentration is the nonyl phenol of 0.1mg/mL, octyl phenol and bisphenol-A is added, 5mL is settled to water,
Obtain the prepare liquid that concentration is 10mg/L, cap.At room temperature in vortex instrument with 2200rpm/min be vortexed one section
Time guarantees that absorption is abundant.The material for having adsorbed determinand is separated with water sample using magnet, with supernatant after HPLC measurement absorption
The mass concentration of liquid, according to formula clearance rate=(c0-c)/c0, calculate clearance rate (%).c0, c be respectively to adsorb front and back solution
Mass concentration, mg/L.
Nonyl phenol, octyl phenol and bisphenol-A supernatant mass concentration after table 3 adsorbs
The clearance rate of nonyl phenol, octyl phenol and bisphenol-A after table 4 adsorbs
Material |
Nonyl phenol |
Octyl phenol |
Bisphenol-A |
MGO/PANI-1 |
83% |
85% |
77% |
MGO/PANI-2 |
82% |
83% |
80% |
M/PANI |
27% |
30% |
23% |
M/GO |
38% |
40% |
35% |
From in the content of table 3 and table 4 we can see that the material being prepared with the method for the present invention is for a certain concentration
In the absorption of phenolic estrogen, the material magnetic polyaniline nanometer more compound than unused graphene oxide for the clearance rate of each substance
Material has 50% or more raising.Compared with also not having with the clearance rate of the magnetic graphene nano material of Polyaniline-modified
30% raising.Change the product that is prepared of different material ratio to the clearance rate slight difference of phenolic estrogen, but removes
Rate is all significantly increased.
3, the stability of enrichment environment
The nonyl that the MGO/PANI-1 material that embodiment 1 is prepared is 10mg/L to concentration under conditions of different pH
Phenol, octyl phenol and bisphenol-A are adsorbed respectively, and adsorption efficiency is as shown in Fig. 2, we can see that the variation pair of pH from Fig. 2
Adsorption effect has little effect, this illustrates that the material is used for the Adsorption of phenols environmental estrogens in environmental water sample hardly
It is influenced by the fluctuation of water quality acid-base property, embodies the stability applied to acid and alkali-resistance good in actual environment water sample.
4, separating effect
5mL is dispersed by the MGO/PANI-1 material that 4mg implementation 1 is prepared, the bisphenol-A absorption that concentration is 10mg/L is molten
In liquid, MGO/PANI/PAab-1 material can be completely segregated in≤1min, and separating effect is as shown in Figure 4.And existing centrifugation point
From needing to be centrifuged 15min at 5000rpm, similar separating effect can be only achieved, and the solution after centrifugation is when taking supernatant
There can't be vibration slightly, the particle otherwise precipitated down is easy to scatter again, the degree of difficulty of operation is increased, and
It cannot be guaranteed that the material of precipitating will not be got completely, therefore the application of magnetic material substantially increases separation in terms of separation process
Efficiency simplifies lock out operation.
5, concentration effect
MGO/PANI-1 the and M/PANI material being prepared in embodiment 1 and comparative example 1 is respectively weighed 4mg to be respectively placed in
It is to be placed under room temperature in vortex instrument in the nonyl phenol, octyl phenol and bisphenol-A solution of 1mg/L with 2000rpm's containing 10mL concentration
After velocity vortex 40min.Magnetic Isolation removes supernatant, retains magnetic material, and 1mL methanol solution is added in every pipe, and room temperature is underlying
It is dense with HPLC measurement eluent in the velocity vortex 30min of 2000rpm, after Magnetic Isolation, collecting eluent in vortex instrument
Degree, according to formula γ=C/C0Calculate enrichment times γ.C0, C be respectively the mass concentration of solution and the quality of eluent before adsorbing
Concentration, mg/L.
Table 5MGO/PANI-1 material is applied to eluate concentration and enrichment times in phenolic estrogen solution
|
C(mg/L) |
Enrichment times γ |
Nonyl phenol |
9.42 |
9.4 |
Octyl phenol |
9.28 |
9.3 |
Bisphenol-A |
9.03 |
9.0 |
Table 6M/PANI material is applied to eluate concentration and enrichment times in phenolic estrogen solution
|
C(mg/L) |
Enrichment times γ |
Nonyl phenol |
3.13 |
3.1 |
Octyl phenol |
3.28 |
3.3 |
Bisphenol-A |
2.83 |
2.8 |
By table 5 and table 6 it is found that the polyaniline material accumulation rate of composite graphite alkene has significant improvement, this is attributed to the fact that
The raising of its surface area and the enhancing of dispersibility.It can also be higher to obtain by the volume of raising adsorbent solution in this experiment
Enrichment times.