CN105289514B - A kind of preparation and application of the magnetic oxygenated graphene adsorbent of 1-hydroxy ethylidene-1,1-diphosphonic acid modification - Google Patents
A kind of preparation and application of the magnetic oxygenated graphene adsorbent of 1-hydroxy ethylidene-1,1-diphosphonic acid modification Download PDFInfo
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Abstract
The present invention relates to a kind of preparation and application for being used to remove the magnetic oxygenated graphene adsorbent that heavy metal ion 1-hydroxy ethylidene-1,1-diphosphonic acid is modified in waste water solution, it is characterized in preparing magnetic oxygenated grapheme material using solvent-thermal method, make magnetic oxygenated grapheme material surface amination using silane coupler, amidized magnetic oxygenated grapheme material surface grafting 1-hydroxy ethylidene-1,1-diphosphonic acid is made using polypeptide condensing agent and base catalyst, a kind of magnetic oxygenated graphene adsorbent of 1-hydroxy ethylidene-1,1-diphosphonic acid modification is made.The sorbent preparation method is simple, and adsorption capacity is high, green, is easy to separate, and repeats and utilizes.
Description
Technical field
The present invention relates to the technical field of Heavy-metal Polluted Environment reparation, and in particular to a kind of adsorbent for heavy metal
Preparation method and application.
Background technology
The fast development of infant industry, although the life to people brings great convenience, industrial wastewater, especially
It is that the waste water containing plurality of heavy metal ion imports rivers and lakes, serious pollution is caused to water resource, and then threatened warp
The sustainable development of Ji and the health existence of the mankind.Therefore the waste water containing plurality of heavy metal ion how is efficiently handled to cause
People more and more pay attention to, and this also has become the emphasis and difficult point of current wastewater treatment.The processing being currently known is given up
The method of water has the methods of ion-exchange, membrane separation process, chemical precipitation method, flocculence and absorption method.Wherein, absorption method is with it
Simple to operate, the features such as cost is relatively low, application is wide, is widely used.Imitated however, traditional adsorbent has absorption
Rate is low and the shortcomings of adsorbance is small, it is impossible to meets the requirement of sewage health processing well.Therefore, new, efficient suction
Attached dose of exploitation just seems very critical.
Graphene oxide is a kind of new two-dimension nano materials, has higher specific surface area and abundant surface official
It can roll into a ball, and there is certain dispersiveness in water, this causes it to have certain sewage treatment capacity, but simple using oxidation
Graphene is not highly desirable as the effect of sorbing material.However, the reactable group of surface of graphene oxide causes it
Further it can be modified and be modified, so as to be expected to realize the improvement of its absorption property.Patent CN104707579A is announced
The preparation and application of a kind of hyperbranched polyetheramine grafted graphene oxide adsorbent for heavy metal adsorption.The adsorbent pair
The adsorbance of heavy metal ion is in more than 500mg/g.Patent CN103861564A discloses one kind and is based on dendrimer
The preparation of the graphene oxide sorbing material of modification, under normal temperature, the adsorbent is equal to lead ion, cadmium ion, manganese ion, copper ion
There is preferable suction-operated, especially there is stronger adsorption capacity to lead ion, maximal absorptive capacity reaches more than 300mg/g.So
And the adsorbent of above patent disclosure is all not easy to separate from waste water.Recent study focus be prepare not only adsorption efficiency height but also
It is easy to separate, the graphene oxide adsorbent that can be reused.Wherein, most widely studied is graphene oxide magnetic coupling
Material.Attachment magnetic nanoparticle causes the separation after absorption to become simple, only needs externally-applied magnetic field to carry out Magneto separate.
However, in order to further improve the adsorption effect of graphene oxide magnetic composite, report at present to oxidation
Most of material that the graft modification of graphene magnetic material uses all is organic mercaptan/ether, amine, miaow mile etc., unavoidably
The certain toxicity of presence.After the absorption that adsorbent completes heavy metal ion, it is likely that cause secondary pollution.And hydroxyl second
Pitching diphosphonic acid has abundant phosphonic functional groups, itself it is substantially nontoxic using metallic element easily with the hydroxyl containing particular functional group
Ethylidene diphosphonic acid generates the characteristics of stable comple, realizes the modification to graphene oxide magnetic material, harmful so as to remove
Heavy metal ion.
In order to develop a kind of environmentally friendly non-secondary pollution, while heavy metal ion has the segregative suction again of preferable adsorption effect
Attached dose, the present invention has carried out graft modification to graphene oxide magnetic material using 1-hydroxy ethylidene-1,1-diphosphonic acid first, resulting
The adsorbance of novel absorption material heavy metal ion is higher than the most of materials reported for work in 450 more than mg/g, adsorption effect
Material.The preparation method of the magnetic oxygenated graphene adsorbent of 1-hydroxy ethylidene-1,1-diphosphonic acid modification in the present invention is simple, adsorption capacity
Height, it is green, it is easy to separate, repeats and utilize, and not disclosed patent and document report.
The content of the invention
It is an object of the invention to provide the magnetic oxygenated stone that a kind of 1-hydroxy ethylidene-1,1-diphosphonic acid for heavy metal adsorption is modified
Black alkene adsorbent.The present invention also aims to provide a kind of magnetic oxygenated graphene suction of above-mentioned 1-hydroxy ethylidene-1,1-diphosphonic acid modification
Attached dose of preparation method and application.
The present invention is the principle based on chemical modification, using hydro-thermal method synthesizing magnetic graphene oxide composite material, using silane
Coupling agent makes magnetic oxygenated grapheme material surface amination, under conditions of polypeptide condensing agent and base catalyst, is grafted hydroxyl
Base ethylidene diphosphonic acid, the sorbing material of dual absorption is prepared, and then remove the heavy metal ion in waste water, it specifically includes following
Step.
The preparation of graphene oxide
Described graphene oxide is that laboratory is prepared using improved Hummers methods, tool prepared by graphene oxide
Body process is：
A. at room temperature, by 0.5 parts by weight sodium nitrate, 1 parts by weight of graphite powder and the wt% concentrated sulfuric acids of 46 parts by weight 98 in ice bath
Under the conditions of mix, stir 30 min, be then slow added into 3 parts by weight potassium permanganate, stir 30 min；
B. the reaction system in step a is heated to 35 DEG C, stirs 2 ~ 48 h, obtain brown suspension；To suspension
In be slowly added into 50 parts by weight of deionized water, stir, be warming up to 98 DEG C and continue the min of reaction 5 ~ 10, be cooled to room temperature；
C. step b reaction solution is poured into 167 parts by weight of deionized water while stirring, adds the wt% of 5 parts by weight 30
Hydrogen peroxide, stand 24 h；
D. take lower sediment, with deionized water under the conditions of 8000 rpm centrifuge washing three times, 5 ~ 10 min every time；Will
Precipitation is dialysed with deionized water, until BaCl2Detection is without SO4 2-, thick liquid is added in deionized water after dialysis, at ultrasound
1 h is managed, solution is then centrifuged into 5 ~ 10 min under conditions of 4000 ~ 8000 rpm, gained supernatant liquid is graphite oxide
Aqueous solution.Graphene oxide water solution will be obtained and obtain graphene oxide powder using freeze-drying.Thickness is 0.9 ~ 1.5
Nm, a diameter of 2 ~ 5 μm of lamella.
The preparation of magnetic oxygenated grapheme material
A. 1-2 parts FeCl is weighed3·6H2O is made into the solution of 0.05 g/ml concentration using magnetic agitation and ethylene glycol, claims
Measure 0.05-0.2 part graphene oxides, 1-10 part ammoniacal liquor, 0.05-0.3 parts polyvinylpyrrolidone (PVP);
B. to FeCl3·6H2In the mixed solution of O ethylene glycol, graphene oxide powder is added, stirring is uniformly mixed
After liquid, ammoniacal liquor is added dropwise, PVP is added after thing to be mixed is stable；
C. mixture is placed in polytetrafluoroethylliner liner reactor, 160-190 DEG C of heating 15-24 h；
D. after product is down to room temperature, replace washing 3 times with absolute ethyl alcohol using water, be freeze-dried, grinding.
The preparation of the magnetic oxygenated graphene adsorbent of 1-hydroxy ethylidene-1,1-diphosphonic acid modification
A. 1 part of silane coupler, the absolute ethyl alcohol of 2.5-10 parts and the water of 5-20 parts are weighed, is put into three-necked flask,
It is 4-5 with glacial acetic acid regulation pH value, after being stirred 2 hours under the rpm rotating speeds of room temperature 300, adds the graphene oxide of 1.5-3 parts
Magnetic material, stirred 4 hours under the rpm rotating speeds of room temperature 300, complete the amination modified of magnetic oxygenated graphene sorbing material,
After washing 3 times with absolute ethyl alcohol, it is freeze-dried, grinding；
B. it is the molten of 0.04 g/ml the 1-hydroxy ethylidene-1,1-diphosphonic acid powder of 0.5-1.5 parts to be added to and concentration is made into solvent
Liquid, then the base catalyst of the polypeptide condensing agent of 0.5-2 parts and 0.1-1 parts is added in above-mentioned solution successively, room temperature
Stirring is completely dissolved it, and the amidized magnetic oxygenated graphene powder prepared in step a finally is added into above-mentioned solution
In, after being stirred 24 hours under the rpm rotating speeds of room temperature 300, with water and absolute ethyl alcohol alternately washing 3 times, it is freeze-dried, grinding.
The removal of the magnetic oxygenated graphene adsorbent heavy metal ion of 1-hydroxy ethylidene-1,1-diphosphonic acid modification
Taking 50 ml, 80-200 mg/l heavy metal ion solution, regulation pH is 2-8, is added in 250 ml conical flask
Enter 7-12 mg adsorbent, 1-3 hours are vibrated in 25-45 DEG C of water bath chader, Magnetic Isolation, take supernatant detection weight
Residual concentration of the metal ion after absorption, the initial concentration C according to heavy metal ion in solution0With a huge sum of money in solution after absorption
Belong to the concentration C of ione, calculate the clearance of heavy metal ion.
Described silane coupler is APTES, γ-glycidyl ether oxygen propyl trimethoxy
Silane and γ-（Methacryloxypropyl）One or more in propyl trimethoxy silicane.
Described solvent is absolute ethyl alcohol, methanol, water, DMF, dimethyl sulfoxide (DMSO), dichloromethane, three
One or more in chloromethanes.
Described polypeptide condensing agent is N- hydroxy thiosuccinimides, dicyclohexylcarbodiimide, 1- ethyl -3- (3-
Dimethylaminopropyl) carbodiimide hydrochloride, N, N- DICs, 2- (7- azos BTA)-N, N, N ',
N '-tetramethylurea hexafluorophosphoric acid ester, 6- Chloro-Benzotriazoles -1,1, one kind or one kind in 3,3- tetramethylurea hexafluorophosphoric acid esters
More than.
Described base catalyst is potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, saleratus, sodium acid carbonate,
Caustic alcohol, the one or more in triethylamine.
Described heavy metal ion is Cu2+, Hg2+, Cd2+, Pb2+In one or more.
The magnetic oxygenated graphene adsorbent of 1-hydroxy ethylidene-1,1-diphosphonic acid modification prepared by the present invention, has the advantage that：
(1) the magnetic oxygenated graphene adsorbent that 1-hydroxy ethylidene-1,1-diphosphonic acid is modified in the present invention is a kind of novel magnetic nanometer
Composite；
(2) preparation technology of the magnetic oxygenated graphene adsorbent of 1-hydroxy ethylidene-1,1-diphosphonic acid modification of the present invention is simple；
(3) the efficient removal of heavy metal ion can be achieved in the present invention under smaller adsorbent addition；
(4) present invention is first using the magnetic oxygenated graphene of 1-hydroxy ethylidene-1,1-diphosphonic acid modification as adsorbent, to a huge sum of money
Belong to that the adsorbance of ion is high, and adsorption effect is excellent, and adsorption process is simple and easy to do, is easy to separate, non-secondary pollution after absorption, can be with
Recycling, is a kind of environmentally friendly friendly sorbing material.
Embodiment
The preparation method of the magnetic oxygenated graphene adsorbent of the 1-hydroxy ethylidene-1,1-diphosphonic acid of embodiment 1 modification
(1) preparation of magnetic oxygenated grapheme material
A. 1 part of FeCl is weighed3·6H2O is made into the solution of 0.05 g/ml concentration using magnetic agitation and ethylene glycol, weighs
0.05 part of graphene oxide, 1 part of ammoniacal liquor, 0.05 part of polyvinylpyrrolidone (PVP);
B. to FeCl3·6H2In the mixed solution of O ethylene glycol, graphene oxide powder is added, stirring is uniformly mixed
After liquid, ammoniacal liquor is added dropwise, PVP is added after thing to be mixed is stable；
C. mixture is placed in polytetrafluoroethylliner liner reactor, 160 DEG C of 15 h of heating；
D. after product is down to room temperature, replace washing 3 times with absolute ethyl alcohol using water, be freeze-dried, grinding；
(2) preparation of the magnetic oxygenated graphene adsorbent of 1-hydroxy ethylidene-1,1-diphosphonic acid modification
A. 1 part of silane coupler, 2.5 parts of absolute ethyl alcohol and 5 parts of water are weighed, is put into three-necked flask, with ice second
Acid for adjusting pH value is 4-5, after being stirred 2 hours under the rpm rotating speeds of room temperature 300, adds 1.5 parts of graphene oxide magnetic material
Material, stirs 4 hours under the rpm rotating speeds of room temperature 300, completes the amination modified of magnetic oxygenated graphene sorbing material, use is anhydrous
After ethanol washs 3 times, it is freeze-dried, grinding；
B., 0.5 part of 1-hydroxy ethylidene-1,1-diphosphonic acid powder is added to the solution for being made into that concentration is 0.04 g/ml in solvent,
Then 0.5 part of polypeptide condensing agent and 0.1 part of base catalyst are added in above-mentioned solution successively, being stirred at room temperature makes its complete
Fully dissolved, finally the amidized magnetic oxygenated graphene powder prepared in step a is added in above-mentioned solution, room temperature 300
After being stirred 24 hours under rpm rotating speeds, with water and absolute ethyl alcohol alternately washing 3 times, it is freeze-dried, grinding.
The preparation method of the magnetic oxygenated graphene adsorbent of the 1-hydroxy ethylidene-1,1-diphosphonic acid of embodiment 2 modification
(1) preparation of magnetic oxygenated grapheme material
A. 2 parts of FeCl are weighed3·6H2O is made into the solution of 0.05 g/ml concentration using magnetic agitation and ethylene glycol, weighs
0.16 part of graphene oxide, 3 parts of ammoniacal liquor, 0.2 part of polyvinylpyrrolidone (PVP);
B. to FeCl3·6H2In the mixed solution of O ethylene glycol, graphene oxide powder is added, stirring is uniformly mixed
After liquid, ammoniacal liquor is added dropwise, PVP is added after thing to be mixed is stable；
C. mixture is placed in polytetrafluoroethylliner liner reactor, 180 DEG C of 20 h of heating；
D. after product is down to room temperature, replace washing 3 times with absolute ethyl alcohol using water, be freeze-dried, grinding；
(2) preparation of the magnetic oxygenated graphene adsorbent of 1-hydroxy ethylidene-1,1-diphosphonic acid modification
A. 1 part of silane coupler, 5 parts of absolute ethyl alcohol and 10 parts of water are weighed, is put into three-necked flask, with ice second
Acid for adjusting pH value is 4-5, after being stirred 2 hours under the rpm rotating speeds of room temperature 300, adds 2.5 parts of graphene oxide magnetic material
Material, stirs 4 hours under the rpm rotating speeds of room temperature 300, completes the amination modified of magnetic oxygenated graphene sorbing material, use is anhydrous
After ethanol washs 3 times, it is freeze-dried, grinding；
B., 1.5 parts of 1-hydroxy ethylidene-1,1-diphosphonic acid powder is added to the solution for being made into that concentration is 0.04 g/ml in solvent,
Then 1.02 parts of polypeptide condensing agent and 0.5 part of base catalyst are added in above-mentioned solution successively, being stirred at room temperature makes it
It is completely dissolved, finally the amidized magnetic oxygenated graphene powder prepared in step a is added in above-mentioned solution, room temperature
After being stirred 24 hours under 300 rpm rotating speeds, with water and absolute ethyl alcohol alternately washing 3 times, it is freeze-dried, grinding.
The preparation method of the magnetic oxygenated graphene adsorbent of the 1-hydroxy ethylidene-1,1-diphosphonic acid of embodiment 3 modification
(1) preparation of magnetic oxygenated grapheme material
A. 1.5 parts of FeCl are weighed3·6H2O is made into the solution of 0.05 g/ml concentration using magnetic agitation and ethylene glycol, claims
Measure 0.2 part of graphene oxide, 10 parts of ammoniacal liquor, 0.3 part of polyvinylpyrrolidone (PVP);
B. to FeCl3·6H2In the mixed solution of O ethylene glycol, graphene oxide powder is added, stirring is uniformly mixed
After liquid, ammoniacal liquor is added dropwise, PVP is added after thing to be mixed is stable；
C. mixture is placed in polytetrafluoroethylliner liner reactor, 190 DEG C of 24 h of heating；
D. after product is down to room temperature, replace washing 3 times with absolute ethyl alcohol using water, be freeze-dried, grinding；
(2) preparation of the magnetic oxygenated graphene adsorbent of 1-hydroxy ethylidene-1,1-diphosphonic acid modification
A. 1 part of silane coupler, 10 parts of absolute ethyl alcohol and 20 parts of water are weighed, is put into three-necked flask, with ice second
Acid for adjusting pH value is 4-5, after being stirred 2 hours under the rpm rotating speeds of room temperature 300, adds 3 parts of graphene oxide magnetic material,
Stirred 4 hours under the rpm rotating speeds of room temperature 300, complete the amination modified of magnetic oxygenated graphene sorbing material, use absolute ethyl alcohol
After washing 3 times, it is freeze-dried, grinding；
B., 1 part of 1-hydroxy ethylidene-1,1-diphosphonic acid powder is added to the solution for being made into that concentration is 0.04 g/ml in solvent, so
2 parts of polypeptide condensing agent and 1 part of base catalyst are added in above-mentioned solution successively afterwards, being stirred at room temperature makes it completely molten
The amidized magnetic oxygenated graphene powder prepared in step a, is finally added in above-mentioned solution, the rpm of room temperature 300 by solution
After being stirred 24 hours under rotating speed, with water and absolute ethyl alcohol alternately washing 3 times, it is freeze-dried, grinding.
The magnetic oxygenated graphene adsorbent of the 1-hydroxy ethylidene-1,1-diphosphonic acid of embodiment 4 modification is to Cu2+Removal
Take 50ml, 80 mg/l Cu2+For solution in 250 ml conical flask, regulation pH is 2, adds 7 mg hydroxyl second
The magnetic oxygenated graphene adsorbent of diphosphonic acid modification is pitched, 1 h is vibrated in 25 DEG C of water bath chader, Magnetic Isolation, takes supernatant
Liquid detects Cu2+Residual concentration after absorption, according to Cu in solution2+Initial concentration C0With Cu in solution after absorption2+Concentration
CeCalculate Cu2+Adsorbance be 475.3 mg/g.
The magnetic oxygenated graphene adsorbent of the 1-hydroxy ethylidene-1,1-diphosphonic acid of embodiment 5 modification is to Hg2+Removal
Take 50ml, 100 mg/l Hg2+For solution in 250 ml conical flask, regulation pH is 4, adds 8 mg hydroxyl second
The magnetic oxygenated graphene adsorbent of diphosphonic acid modification is pitched, 1.5 h is vibrated in 35 DEG C of water bath chader, Magnetic Isolation, takes
Clear liquid detects Hg2+Residual concentration after absorption, according to Hg solution2+Initial concentration C0With Hg solution after absorption2+It is dense
Spend CeCalculate Hg2+Adsorbance be 508.9 mg/g.
The magnetic oxygenated graphene adsorbent of the 1-hydroxy ethylidene-1,1-diphosphonic acid of embodiment 6 modification is to Cd2+Removal
Take 50ml, 120 mg/l Cd2+For solution in 250 ml conical flask, regulation pH is 5, adds 9 mg hydroxyl second
The magnetic oxygenated graphene adsorbent of diphosphonic acid modification is pitched, 2 h is vibrated in 45 DEG C of water bath chader, Magnetic Isolation, takes supernatant
Liquid detects Cd2+Residual concentration after absorption, according to Cd in solution2+Initial concentration C0With Cd in solution after absorption2+Concentration
CeCalculate Cd2+Adsorbance be 501.5 mg/g.
The magnetic oxygenated graphene adsorbent of the 1-hydroxy ethylidene-1,1-diphosphonic acid of embodiment 7 modification is to Pb2+Removal
Take 50ml, 200 mg/l Pb2+For solution in 250 ml conical flask, regulation pH is 8, adds 12 mg hydroxyl
The magnetic oxygenated graphene adsorbent of ethylidene diphosphonic acid modification, vibrates 3 h in 35 DEG C of water bath chader, Magnetic Isolation, takes
Clear liquid detects Pb2+Residual concentration after absorption, according to Pb in solution2+Initial concentration C0With Pb in solution after absorption2+It is dense
Spend CeCalculate Pb2+Adsorbance be 487.9 mg/g.
Claims (4)
- A kind of 1. preparation method of the magnetic oxygenated graphene adsorbent of 1-hydroxy ethylidene-1,1-diphosphonic acid modification, it is characterised in that including Following steps：(1) preparation of magnetic oxygenated grapheme materialA. 1-2 parts FeCl is weighed3·6H2O is made into the solution of 0.05 g/mL concentration using magnetic agitation and ethylene glycol, weighs 0.05-0.2 part graphene oxides, 1-10 part ammoniacal liquor, 0.05-0.3 part polyvinylpyrrolidones；B. to FeCl3•6H2In the mixed solution of O ethylene glycol, graphene oxide powder is added, stirring is uniformly mixed after liquid, Ammoniacal liquor is added dropwise, polyvinylpyrrolidone is added after thing to be mixed is stable；C. mixture is placed in polytetrafluoroethylliner liner reactor, 160-190 DEG C of heating 15-24 h；D. after product is down to room temperature, replace washing 3 times with absolute ethyl alcohol using water, be freeze-dried, grinding；(2) preparation of the magnetic oxygenated graphene adsorbent of 1-hydroxy ethylidene-1,1-diphosphonic acid modificationA. 1 part of silane coupler, the absolute ethyl alcohol of 2.5-10 parts and the water of 5-20 parts are weighed, is put into three-necked flask, uses ice Second acid for adjusting pH value is 4-5, after being stirred 2 hours under the rpm rotating speeds of room temperature 300, adds the graphene oxide magnetic of 1.5-3 parts Material, stirred 4 hours under the rpm rotating speeds of room temperature 300, the amination modified of magnetic oxygenated graphene sorbing material is completed, with nothing After water-ethanol washs 3 times, it is freeze-dried, grinding；Described silane coupler is APTES；B., the 1-hydroxy ethylidene-1,1-diphosphonic acid powder of 0.5-1.5 parts is added to the solution for being made into that concentration is 0.04 g/mL in solvent, Then the base catalyst of the polypeptide condensing agent of 0.5-2 parts and 0.1-1 parts is added in above-mentioned solution successively, be stirred at room temperature It is completely dissolved, finally the amidized magnetic oxygenated graphene powder prepared in step a is added in above-mentioned solution, room After being stirred 24 hours under warm 300 rpm rotating speeds, with water and absolute ethyl alcohol alternately washing 3 times, it is freeze-dried, grinding；Described is more Peptide condensing agent is N- hydroxy thiosuccinimides, dicyclohexylcarbodiimide, the Asia of 1- ethyls -3- (3- dimethylaminopropyls) carbon two Amine hydrochlorate, N, N- DICs, 2- (7- azos BTA)-N, N, N ', N '-tetramethylurea hexafluorophosphoric acid One or more in ester, 6- Chloro-Benzotriazole -1,1,3,3- tetramethylurea hexafluorophosphoric acid esters；Described base catalysis Agent be potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, saleratus, sodium acid carbonate, caustic alcohol, one kind in triethylamine or More than one.
- 2. a kind of magnetic oxygenated graphene of 1-hydroxy ethylidene-1,1-diphosphonic acid modification prepared by preparation method as claimed in claim 1 is inhaled Attached dose, it is characterised in that as follows for the removal of heavy metal ion in water, step：50 mL, 80-200 mg/L heavy metal ion solution are taken in 250 mL conical flask, regulation pH is 2-8, adds 7- 12 mg adsorbent, 1-3 hours are vibrated in 25-45 DEG C of water bath chader, Magnetic Isolation, take supernatant to detect heavy metal Residual concentration of the ion after absorption, the initial concentration C according to heavy metal ion in solution0With heavy metal in solution after absorption from The concentration C of sone, calculate the clearance of heavy metal ion.
- A kind of 3. preparation side of the magnetic oxygenated graphene adsorbent of 1-hydroxy ethylidene-1,1-diphosphonic acid modification as claimed in claim 1 Method, it is characterised in that described solvent is absolute ethyl alcohol, methanol, water, DMF, dimethyl sulfoxide (DMSO), dichloromethane One or more in alkane, chloroform.
- 4. a kind of magnetic oxygenated graphene adsorbent of 1-hydroxy ethylidene-1,1-diphosphonic acid modification as claimed in claim 2, its feature exist In described heavy metal ion is Cu2+、Hg2+、Cd2+、Pb2+In one or more.
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