CN107115850A - The sodium alginate gel ball of graphene oxide Polyaniline synthesis is removed to the adsorptivity of lead in water body and cadmium heavy metal ion - Google Patents
The sodium alginate gel ball of graphene oxide Polyaniline synthesis is removed to the adsorptivity of lead in water body and cadmium heavy metal ion Download PDFInfo
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Abstract
The present invention provides a kind of method of graphene oxide polyaniline sodium alginate gel ball removing Heavy Metals in Waters lead ion, including：Graphene oxide polyaniline sodium alginate is added in the water body of the ion containing heavy metal lead, vibration absorption is produced.The present invention utilizes Polyaniline Doped graphene modified sodium alginate gel ball, effectively increases sodium alginate gel ball heavy metal lead, the adsorption efficiency of cadmium.The sodium alginate gel ball finally prepared disclosure satisfy that quick, the efficient requirement for removing Heavy Metals in Waters, it is to avoid the significantly diffusion of heavy metal pollution.The preparation method of the gel ball is simple, efficient, and particularly heavy metal lead and cadmium have higher adsorption efficiency.
Description
Technical field
The invention belongs to the alginic acid in heavy metal adsorption field, the more particularly to synthesis of graphene oxide-polyaniline compound
Sodium gel ball is removed to the adsorptivity of lead in water body and cadmium heavy metal ion.
Background technology
It is heavy metal-polluted to have a finger in every pie the environmental pollution caused by heavy metal or its compound.Mainly by mining, waste gas discharge, sewage
Irrigate and using caused by the human factors such as heavy metals exceeding standard product.The content of beary metal in environment is caused to increase because of mankind's activity,
Beyond normal range (NR), directly it is detrimental to health, and causes environmental quality to deteriorate.At the beginning of 4 months 2011, China is first " 12 "
Ad hoc planning ---《Heavy metal pollution integrated control " 12 " is planned》Obtain State Council formally to give an written reply, control program makes every effort to control
Make 5 heavy metal species.
Lead contamination is the toxic metals that can be put aside in human body and animal tissue.It is mainly derived from various paint, coating, storage
Battery, smelting, hardware, machinery, plating, cosmetics, hair dye, muffle painting dishes, tableware, fire coal, dilated food, running water pipe
Deng.It is to enter affine with a variety of organs in vivo by skin, alimentary canal, respiratory tract, and major toxicity effect is anemia, nerve
Dysfunction and injury of kidney, vulnerable crowd have children, old man, immunocompromised crowd.Safe concentration of the lead to aquatile
For 0.16mg/L, during with leaded 0.1~4.4mg/L water water for irrigation rice and wheat, lead content substantially increases in crop.In human body
Normal lead content should easily cause anaemia in 0.1 mg/litre, if content overproof, damage nervous system.And child is big
Brain is much more sensitive than adult by the infringement of lead, once blood lead content is exceeded, it should take the malicious measure of positive lead discharging.Children can
Take lead discharging oral liquid or carry out lead discharging by other products.
Cadmium is not the essential elements of human body.The toxicity of cadmium is very big, can be put aside in human body, mainly puts aside in kidney, causes
The changes of function of urinary system；Cadmium main source has the useless of the discharges such as plating, mining, smelting, fuel, battery and chemical industry
Water；Cadmium content is higher in old and useless battery, exist in fruits and vegetables, especially mushroom, also has in dairy produce and cereal
It is a small amount of to exist.Cadmium can replace calcium in bone, bone is seriously softened, and bone is broken into pieces, and can cause the dirty functional disturbance of stomach, disturb human body
With the enzyme system of zinc in organism, vascular hypertension is caused to rise.Vulnerable crowd is mining operations person, hypoimmunity people
Group.In water during 0.1mg/L containing cadmium, it can slightly suppress the self purification of the surface water, cadmium is to the safe concentration of Silver Carp
0.014mg/L, when being irrigated with the water of the 0.04Mg/L containing cadmium, soil and rice are substantially polluted, and agriculture contains cadmium in pouring water
During 0.007mg/L, you can pollute.Cadmium concentration in normal human blood, which is less than in 5 micrograms per litres, urine, is less than 1 micrograms per litre.Cadmium
Calcium in bone is can interfere with, if taking in Trace Cadmium for a long time, bone is seriously softened, bone is broken into pieces, causes Itai-itai diseases, it can also draw
The dirty functional disturbance of stomach is played, and disturbs the enzyme system of zinc in human body and organism, causes vascular hypertension to rise.Therefore, a preventing and treating huge sum of money
Category pollution, particularly lead, cadmium pollution is significant.
Conducting polymer is a kind of new functional macromolecule material, because with excellent physical and chemical performance, in recent years by section
The extensive concern of educational circles.Wherein, polyaniline (PANI) is used as a kind of typical conducting polymer, its good electroactive, environment
Stability and reversible doping, are widely used in ultracapacitor.Artificial muscle, electromagnetic screen and anti-corrosive paints and
The fields such as chemical sensor.But low conductivity and insoluble insoluble defect again limit further applying for PANI.In order to make up
This is not enough, and a kind of conductive material is generally combined by people with it, and to improve the electric conductivity of polyaniline, GO is one
Optimal conductive material is planted, it can produce cooperative effect to make up PANI deficiency with polyaniline.Meanwhile, PANI incorporation
Cause GN piece interlamellar spacings to significantly increase, effectively prevent GO agglomerations, and then add dispersivenesses of the GO in PANI matrix.
Therefore, the concern for enjoying people of graphene/polyaniline (GO/PANI) composite in recent years.
In recent years, sodium alginate is often applied to the embedding medium of immobilized cell, but its gel in terms of heavy metal improvement
Ball still suffers from the problem of adsorption time length, adsorption capacity are not enough, it is difficult to meet the emergent fast of paroxysmal heavy metal pollution accident
Speed disposal is required.
The content of the invention
In order to overcome above-mentioned deficiency, the present invention provides a kind of sodium alginate of graphene oxide-polyaniline compound synthesis
Gel ball, and it is have studied to lead in water body and the adsorptivity removal of cadmium heavy metal ion.As a result show：The sodium alginate
Gel ball disclosure satisfy that quick, the efficient requirement for removing Heavy Metals in Waters, it is to avoid the significantly diffusion of heavy metal pollution.The gel
The preparation method of ball is simple, efficient, and particularly heavy metal lead and cadmium have higher adsorption efficiency.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of graphene oxide-polyaniline-sodium alginate gel ball, including：
Sodium alginate gel ball；
And it is embedded in polyaniline and graphene in the sodium alginate gel ball.
Now there are some researches show：It can be uniformly deposited on after Polyaniline Doped graphene in the middle of graphene sheet layer, prevent stone
Accumulation between black alkene nanometer sheet, improves the decentralization of graphene oxide, increases its active surface area.The present invention is accidental in an experiment
It was found that, above-mentioned Polyaniline Doped graphene is used for modified sodium alginate gel ball, sodium alginate gel ball pair can be effectively improved
The adsorption efficiency of heavy metal lead, cadmium.
It is preferred that, sodium alginate, polyaniline, the mass ratio of graphene are 20 in the gel ball：5~20：0.3~1.8.
Present invention also offers a kind of preparation method of graphene oxide-polyaniline-sodium alginate gel ball, including：
Prepare the graphene oxide of Polyaniline-modified；
The graphene oxide of above-mentioned Polyaniline-modified, sodium alginate are added to the water, are uniformly dispersed, obtain graphene oxide-
Polyaniline-sodium alginate mixed liquor；
Above-mentioned mixed liquor is instilled into CaCl2In solution, solidification produces sodium alginate-polyaniline-graphite alkene gel ball.
It is preferred that, the sodium alginate, polyaniline, the mass ratio of graphene are 20：5~20：0.3~1.8.
It is preferred that, the mass concentration of sodium alginate is 2% in the graphene oxide-polyaniline-sodium alginate mixed liquor
~5%.
It is preferred that, the CaCl2The concentration of solution is 1%~2.5%.
It is preferred that, hardening time is 8-12h.
Present invention also offers sodium alginate-polyaniline-graphite alkene gel ball prepared by any above-mentioned method.
Heavy Metals in Waters is removed present invention also offers any above-mentioned sodium alginate-polyaniline-graphite alkene gel ball
In application.
Heavy Metals in Waters lead ion is being removed the invention provides a kind of sodium alginate-polyaniline-graphite alkene gel ball
Method, including：Sodium alginate-polyaniline-graphite alkene gel ball is added in the water body of the ion containing heavy metal lead, vibration is inhaled
It is attached, produce.
It is preferred that, the mass ratio of the sodium alginate-polyaniline-graphite alkene gel ball and heavy metal ion is 1000：7~
12。
It is preferred that, the concentration of the Heavy Metals in Waters lead ion is 10~50mg/L.
There is high adsorption efficiency in preparation heavy metal present invention also offers graphene oxide/polyaniline composite material
Application in sodium alginate gel ball.
Beneficial effects of the present invention:
(1) present invention utilizes Polyaniline Doped graphene modified sodium alginate gel ball, can effectively improve sodium alginate and coagulate
Glueballs heavy metal lead, the adsorption efficiency of cadmium.
(2) preparation method of the present invention is simple, adsorption efficiency is high, disclosure satisfy that the emergent of paroxysmal heavy metal pollution accident
Processing requirement.
Embodiment
It is noted that described further below is all exemplary, it is intended to provide further instruction to the application.Unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
Embodiment 1：
Take 0.55mL aniline to be dissolved in the dilute HCl of 20mL (1mol/L) and form uniform solution, 1h points of 30mg GO ultrasounds
It is dispersed in above-mentioned aniline solution.Take 0.3422g (NH4)2S2O8It is dissolved in the dilute HCl of 10mL 1mol/L, and the solution is fast
Speed is poured into above-mentioned ready aniline/GO dispersion soln, is stirred continuously, and polymerization quickly starts, the continuous greening of solution colour,
Holding is stirred overnight at room temperature.After completion of the reaction, the dilution of 75mL ultra-pure waters is added, obtained product is subjected to centrifugal treating, and
Cyclic washing is carried out with substantial amounts of water, ethanol, untill solution is without color, the product for then obtaining centrifugation is placed on baking oven
(60 DEG C) dryings, produce the GO of Polyaniline-modified.
GO, 20mg sodium alginate (viscosity 350) and 20mL distilled water of 40mg Polyaniline-modifieds, ultrasound are added into beaker
6h is uniform to solution, obtains graphene oxide-polyaniline-sodium alginate mixed liquor.It is another to take beaker, configure 10mg/mL CaCl2It is molten
Liquid, CaCl is instilled with peristaltic pump by 20mL graphene oxide-polyanilines-sodium alginate mixed liquor2After solution, solidification 8-12h, obtain
400 graphene oxide-polyaniline-sodium alginate gel balls.
40 above-mentioned different graphene oxide-polyanilines-sodium alginate gel balls are added to 50mL lead ions, cadmium ion
During concentration is all 10mg/L water, vibration absorption 1.5h is carried out on HY-4 speed governing multi-purpose type oscillators, with inductive etc. from
Daughter mass spectrograph (ICP) detects Heavy Metals in Waters content, as a result shows：Lead ion and Cd ionic adsorption effects to 10mg/L
Respectively up to 99%, more than 80%；Lead ion and Cd ionic adsorption effects to 1mg/L all reach more than 99%.
Embodiment 2：
Take 0.55mL aniline to be dissolved in the dilute HCl of 20mL (1mol/L) and form uniform solution, 1h points of 30mg GO ultrasounds
It is dispersed in above-mentioned aniline solution.Take 0.3422g (NH4)2S2O8It is dissolved in the dilute HCl of 10mL 1mol/L, and the solution is fast
Speed is poured into above-mentioned ready aniline/GO dispersion soln, is stirred continuously, and polymerization quickly starts, the continuous greening of solution colour,
Holding is stirred overnight at room temperature.After completion of the reaction, the dilution of 75mL ultra-pure waters is added, obtained product is subjected to centrifugal treating, and
Cyclic washing is carried out with substantial amounts of water, ethanol, untill solution is without color, the product for then obtaining centrifugation is placed on baking oven
(60 DEG C) dryings, produce the GO of Polyaniline-modified.
GO, 20mg sodium alginate (viscosity 350) and 20mL distilled water of 80mg Polyaniline-modifieds, ultrasound are added into beaker
6h is uniform to solution, obtains graphene oxide-polyaniline-sodium alginate mixed liquor.It is another to take beaker, configure 10mg/mL CaCl2It is molten
Liquid, CaCl is instilled with peristaltic pump by 20mL graphene oxide-polyanilines-sodium alginate mixed liquor2After solution, solidification 8-12h, obtain
Graphene oxide-polyaniline-sodium alginate gel ball.
0.25g graphene oxide-polyanilines-sodium alginate gel ball is taken to be added to 50mL lead ions, concentration of cadmium ions all
In 10mg/L water, to carry out vibration absorption 1.5h on HY-4 speed governing multi-purpose type oscillators, inductively coupled plasma matter is used
Spectrometer (ICP) detects Heavy Metals in Waters content, as a result shows：Lead ion and Cd ionic adsorptions effect to 10mg/L reach respectively
99%, more than 80%.
Embodiment 3：
Take 0.55mL aniline to be dissolved in the dilute HCl of 20mL (1mol/L) and form uniform solution, 1h points of 30mg GO ultrasounds
It is dispersed in above-mentioned aniline solution.Take 0.3422g (NH4)2S2O8It is dissolved in the dilute HCl of 10mL 1mol/L, and the solution is fast
Speed is poured into above-mentioned ready aniline/GO dispersion soln, is stirred continuously, and polymerization quickly starts, the continuous greening of solution colour,
Holding is stirred overnight at room temperature.After completion of the reaction, the dilution of 75mL ultra-pure waters is added, obtained product is subjected to centrifugal treating, and
Cyclic washing is carried out with substantial amounts of water, ethanol, untill solution is without color, the product for then obtaining centrifugation is placed on baking oven
(60 DEG C) dryings, produce the GO of Polyaniline-modified.
GO, 20mg sodium alginate (viscosity 350) and 20mL distilled water of 160mg Polyaniline-modifieds are added into beaker, is surpassed
Sound 6h is uniform to solution, obtains graphene oxide-polyaniline-sodium alginate mixed liquor.It is another to take beaker, configure 10mg/mL CaCl2
Solution, CaCl is instilled with peristaltic pump by 20mL graphene oxide-polyanilines-sodium alginate mixed liquor2After solution, solidification 8-12h,
Obtain graphene oxide-polyaniline-sodium alginate gel ball.
0.25g graphene oxide-polyanilines-sodium alginate gel ball is taken to be added to 50mL lead ions, concentration of cadmium ions all
In 10mg/L water, to carry out vibration absorption 1.5h on HY-4 speed governing multi-purpose type oscillators, inductively coupled plasma matter is used
Spectrometer (ICP) detects Heavy Metals in Waters content, as a result shows：Lead ion and Cd ionic adsorptions effect to 10mg/L reach respectively
99%, more than 80%.
Embodiment 4：
Take 0.55mL aniline to be dissolved in the dilute HCl of 20mL (1mol/L) and form uniform solution, 1h points of 30mg GO ultrasounds
It is dispersed in above-mentioned aniline solution.Take 0.3422g (NH4)2S2O8It is dissolved in the dilute HCl of 10mL 1mol/L, and the solution is fast
Speed is poured into above-mentioned ready aniline/GO dispersion soln, is stirred continuously, and polymerization quickly starts, the continuous greening of solution colour,
Holding is stirred overnight at room temperature.After completion of the reaction, the dilution of 75mL ultra-pure waters is added, obtained product is subjected to centrifugal treating, and
Cyclic washing is carried out with substantial amounts of water, ethanol, untill solution is without color, the product for then obtaining centrifugation is placed on baking oven
(60 DEG C) dryings, produce the GO of Polyaniline-modified.
GO, 35mg sodium alginate (viscosity 350) and 20mL distilled water of 40mg Polyaniline-modifieds, ultrasound are added into beaker
6h is uniform to solution, obtains graphene oxide-polyaniline-sodium alginate mixed liquor.It is another to take beaker, configure 10mg/mL CaCl2It is molten
Liquid, CaCl is instilled with peristaltic pump by 20mL graphene oxide-polyanilines-sodium alginate mixed liquor2After solution, solidification 8-12h, obtain
Graphene oxide-polyaniline-sodium alginate gel ball.
0.25g graphene oxide-polyanilines-sodium alginate gel ball is taken to be added to 50mL lead ions, concentration of cadmium ions all
In 10mg/L water, to carry out vibration absorption 1.5h on HY-4 speed governing multi-purpose type oscillators, inductively coupled plasma matter is used
Spectrometer (ICP) detects Heavy Metals in Waters content, as a result shows：Lead ion and Cd ionic adsorptions effect to 10mg/L reach respectively
99%, more than 80%.
Embodiment 5：
Take 0.55mL aniline to be dissolved in the dilute HCl of 20mL (1mol/L) and form uniform solution, 1h points of 30mg GO ultrasounds
It is dispersed in above-mentioned aniline solution.Take 0.3422g (NH4)2S2O8It is dissolved in the dilute HCl of 10mL 1mol/L, and the solution is fast
Speed is poured into above-mentioned ready aniline/GO dispersion soln, is stirred continuously, and polymerization quickly starts, the continuous greening of solution colour,
Holding is stirred overnight at room temperature.After completion of the reaction, the dilution of 75mL ultra-pure waters is added, obtained product is subjected to centrifugal treating, and
Cyclic washing is carried out with substantial amounts of water, ethanol, untill solution is without color, the product for then obtaining centrifugation is placed on baking oven
(60 DEG C) dryings, produce the GO of Polyaniline-modified.
GO, 50mg sodium alginate (viscosity 350) and 20mL distilled water of 40mg Polyaniline-modifieds, ultrasound are added into beaker
6h is uniform to solution, obtains graphene oxide-polyaniline-sodium alginate mixed liquor.It is another to take beaker, configure 10mg/mL CaCl2It is molten
Liquid, CaCl is instilled with peristaltic pump by 20mL graphene oxide-polyanilines-sodium alginate mixed liquor2After solution, solidification 8-12h, obtain
Graphene oxide-polyaniline-sodium alginate gel ball.
0.25g graphene oxide-polyanilines-sodium alginate gel ball is taken to be added to 50mL lead ions, concentration of cadmium ions all
In 10mg/L water, to carry out vibration absorption 1.5h on HY-4 speed governing multi-purpose type oscillators, inductively coupled plasma matter is used
Spectrometer (ICP) detects Heavy Metals in Waters content, as a result shows：Lead ion and Cd ionic adsorptions effect to 10mg/L reach respectively
99%, more than 80%.
Comparative example 1
0.25g sodium alginate gel balls are taken to be added in the water that 50mL lead ions, concentration of cadmium ions are all 10mg/L,
Vibration absorption 1.5h is carried out on HY-4 speed governing multi-purpose type oscillators, water body is detected with icp mses (ICP)
Middle content of beary metal, as a result shows：Lead ion and Cd ionic adsorptions effect to 10mg/L are 87%, 59% respectively.
The preferred embodiment of the application is the foregoing is only, the application is not limited to, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of graphene oxide-polyaniline-sodium alginate gel ball, it is characterised in that including：
Sodium alginate gel ball；
And it is embedded in polyaniline and graphene in the sodium alginate gel ball.
2. gel ball as claimed in claim 1, it is characterised in that sodium alginate in the gel ball, polyaniline, graphene
Mass ratio is 20：5~20：0.3~1.8.
3. a kind of preparation method of graphene oxide-polyaniline-sodium alginate gel ball, it is characterised in that including：
Prepare the graphene oxide of Polyaniline-modified；
The graphene oxide of above-mentioned Polyaniline-modified, sodium alginate are added to the water, are uniformly dispersed, graphene oxide-polyphenyl is obtained
Amine-sodium alginate mixed liquor；
Above-mentioned mixed liquor is instilled into CaCl2In solution, solidification produces sodium alginate-polyaniline-graphite alkene gel ball.
4. method as claimed in claim 3, it is characterised in that the sodium alginate, polyaniline, the mass ratio of graphene are
20：5~20：0.3~1.8.
5. method as claimed in claim 3, it is characterised in that in the graphene oxide-polyaniline-sodium alginate mixed liquor
The mass concentration of sodium alginate is 2%~5%.
6. method as claimed in claim 3, it is characterised in that the CaCl2The concentration of solution is 1%~2.5%；
Or the hardening time is 8-12h.
7. graphene oxide-polyaniline-sodium alginate gel ball prepared by the method described in claim 3-6.
8. graphene oxide-polyaniline-sodium alginate gel ball described in any one of claim 1,2,7 removes a huge sum of money in water body
The application of category.
9. a kind of graphene oxide-polyaniline-sodium alginate gel ball is in the method for removing Heavy Metals in Waters lead ion, it is special
Levy and be, including：Graphene oxide-polyaniline described in 1,2,7 any one-sodium alginate gel ball is added to containing heavy metal
In the water body of lead ion, vibration absorption is produced.
10. graphene oxide/polyaniline composite material has the sodium alginate gel ball of high adsorption efficiency in preparation heavy metal
In application.
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| GB2569462A (en) * | 2017-08-11 | 2019-06-19 | Univ Beijing Normal | Anti-corrosive coating with self-repairing ability, preparation method therefor, and application thereof. |
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