CN105080512B - A kind of preparation method and application of graphite oxide alkenyl cadmium ion imprinted polymer - Google Patents
A kind of preparation method and application of graphite oxide alkenyl cadmium ion imprinted polymer Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method and application of graphite oxide alkenyl cadmium ion imprinted polymer, category environment functional material is prepared and water process new technical field, using graphene oxide as matrix in the present invention, and Cd (II) is template, methyl methacrylate（MMA）For monomer, cetyl trimethylammonium bromide（CTAB）For surfactant, azodiisobutyronitrile (AIBN) is initiator, using S, and S ' two (α, α ' dimethyl α ' ' acetic acid) trithiocarbonate（BDAT）As RAFT auxiliary agents, reacted in microemulsion by Invertible ideal（RAFT polymerize）, a kind of cadmium ion imprinted polymer composite material adsorbent using graphene oxide as base material is prepared for, its absorption property to Cd (II) has been investigated；The adsorbent has the selectivity of height to Cd (II), and adsorption capacity is big, and can be simple to operate by controlling the proportioning of reactant to make polymerization process controllable, is had broad application prospects in environmental areas such as sewage disposals.
Description
Technical field
The present invention relates to a kind of preparation method and application of graphite oxide alkenyl cadmium ion imprinted polymer, belong to environmental functional
Material is prepared and water process new technical field.
Background technology
With rapid development of economy, the chemical reagent in industrial or agricultural field is largely used, China's major part surface water and ground
Lower water receives different degrees of pollution, and its pollutant mainly includes heavy metal and organic matter etc., wherein, cadmium is a main huge sum of money
Belong to one of pollutant.Heavy metal cadmium can not only influence growing for crop, and can not be biodegradable, in vivo
Biological half-life is up to 10-30, moreover it is possible to the health of the mankind is endangered by biological concentration and eventually through food chain, is taken the photograph by human body
The cadmium entered is combined with the sulfydryl of zymoprotein, the activity of inhibitory enzyme, can produce toxicity, and also carcinogenesis.Therefore handle
Cadmium wastewater eliminates cadmium pollution, and exploitation efficient metal ion adsorbent has caused the highest attention of the mankind.
At present, separation has a variety of with removing the method for cadmium ion in aqueous medium, as chemical precipitation method, chemical reduction method,
Ion-exchange, hyperfiltration, membrane separation process, biological treatment and absorption method.Absorption method because its operation operation is easy, into
This low, removal efficiency is high and renewable recycle receives extensive concern, and still, general adsorbent is for the target in water body
Ion is without recognition capability, therefore suction-operated lacks selectivity.And with ion imprinted polymer（Ion Imprinted
PoLymers, IIPs）During as sorbent treatment heavy metal ion, not only with specific selectivity, and adsorption capacity compared with
Height, is a kind of efficient adsorbent（Chen L, Xu S, Li J. Recent advances in molecular
imprinting technology: current status, challenges and highlighted
applications [J]. The Royal Society of Chemistry, 2011, 40:2922-2942.）.Surface from
Sub- engram technology is that it preferably resolves tradition with reference to the immunoblot method in stromal surface the imprinted layer with recognition site
Some major defects for integrally also existing of engram technology, such as avtive spot embeds too deep, the dynamics of mass transfer and charge transfer
Speed is slow etc.（Rao T P, Daniel R K S. Metal ion-imprinted polymers-Novel materials
for selective recognition of inorganics [J]. Analytica Chimica Acta, 2006,
578:105-116.）.Meanwhile, surface imprinted technology also has its advantage, such as selects appropriate matrix effectively to improve absorption
The adsorption capacity of agent.Compared with conventional silica-base material etc., graphene oxide（GO）Lamellar structure have higher ratio surface
Product, the oxygen-containing functional group containing high activities such as hydroxyl, carboxyl and epoxy radicals（Steurer P, wissert R, Thomann R,
et al. Functionalized graphenes and thermoplastic nanocomposites based upon
expanded graphite oxide [J]. Macromolecular Rapid Communications, 2009, 30:
316-327.）, and heavy metal ion has very strong interaction, can dramatically increase the adsorption capacity of composite material adsorbent,
Improve the absorption property of adsorbent.
In recent years, the method controllable/active free radical polymerization for preparing imprinted polymer gradually obtains more researchers'
Pay attention to and pay close attention to, and achieve important breakthrough.Primarily now there are three kinds of active free radical polymerization methods：Oxygen nitrogen regulates and controls radical polymerization
Close（NMP）, ATRP（ATRP）, and reversible addion-fragmentation chain transfer polymerization（RAFT polymerize）.Wherein RAFT
Polymerization remain conventional free radical polymerization multifunctionality, while the narrow polymer of relative molecular mass distribution can be prepared, can be more
Good control molecular weight, polydispersity and polymer architecture（Ma J, Yang C, Luo J, et al. Reversible
addition-fragmentation chain transfer polymerization of methyl methacrylate
in microemulsion: The Influence of Reaction Conditions on Polymerization [J].
Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, 2012,
49: 321-329.）.RAFT polymerizations are to add to have high chain transfer constant and specific knot in traditional radical polymerization system
The double thioesters of the chain-transferring agent of structure or three thioesters, when the concentration of chain-transferring agent is sufficiently large, chain transfer reaction is become by irreversible reaction
Into reversible reaction, polymerization process also becomes controllable by uncontrollable.RAFT living polymerizations, in the homogeneous system such as body and solution
In polymerization process in rate of polymerization it is very high, can have deactivation phenomenom；Polymerization in conventional emulsions and trickle emulsion system
There is latex unstability, molecular weight out of control, molecular weight in journey and particle diameter distribution is wide and the problem of slow rate of polymerization, therefore it is industrialized
Application be restricted（Zhou X, Ni P, Yu Z. Comparison of RAFT polymerization of
methyl methacrylate in conventional emulsion and miniemulsion systems [J].
Polymer, 2007, 48: 6262-6271.）.Due to the isotropism of microemulsion system, thermodynamic stability, dispersed phase chi
Very little small and specific surface area is big so that the RAFT polymerization processes quick and stable in microemulsion, it is possible to reduce or improvement polymerization is unstable
The problem of（Ma J, Zhang H. Kinetics study of living microemulsion polymerization
mediated by reversible addition-fragmentation chain transfer [J]. Journal of
Polymer Research, 2014, 21: 614.）.In microemulsion system, using graphene oxide as matrix, RAFT is used
The method of polymerization, the research for synthesizing the feature imprinted polymer of the PMA of cadmium ion trace not yet has been reported that.This hair
A kind of preparation method of graphite oxide alkenyl cadmium ion imprinted polymer of bright middle preparation, realizes the characteristic print to cadmium ion
Mark, the imprinted material contains substantial amounts of imprinted cavity, to cadmium ion（Cd(II)）With the single-minded Selective recognition of predetermined substance and
The function of absorption, adsorption capacity is big, and adsorption time is short, and this provides one for the Cd (II) in selective separation enrichment environmental sample
Class new method, and there is important Research Significance to effectively removing Cd (II) ion in waste water.
The content of the invention
The present invention relates to a kind of preparation method of graphite oxide alkenyl cadmium ion imprinted polymer, the technical scheme of use
It is：With graphene oxide（GO）For matrix, Cd (II) is template, methyl methacrylate（MMA）For monomer, cetyl front three
Base ammonium bromide（CTAB）For surfactant, azodiisobutyronitrile (AIBN) is initiator, using S, and S '-two (α, α '-diformazan
Base-α ' '-acetic acid) trithiocarbonate（BDAT）As RAFT auxiliary agents, pass through reversible addion-fragmentation chain transfer in microemulsion
Polymerisation（RAFT polymerize）, a kind of graphite oxide alkenyl cadmium ion imprinted polymer is prepared for, and investigated it to Cd (II)
Absorption property.
A kind of preparation method of graphite oxide alkenyl cadmium ion imprinted polymer is carried out according to the following steps：
（1）The preparation of graphene oxide：
In 250mL beaker, 23mL 98% concentrated sulfuric acid is added, ice-water bath is placed in.Then, under conditions of stirring, plus
Enter 1g aquadags powder and 0.5g sodium nitrate.Again under strong stirring, keeping temperature in 3g potassium permanganate, reaction is slowly added to
Less than 20 DEG C；Then ice-water bath is removed, temperature is increased to 35 DEG C, sustained response 30min.Under agitation, it is slowly added to
46mL deionized waters, and it is warming up to 98 DEG C, solution presentation brown, reaction 15min；Then add 140mL 60 DEG C of heat go from
30% hydrogen peroxide of sub- water and 4.5mL, until it is in brown color that reaction, which terminates solution,.Finally by centrifugation, first with 5% salt pickling
To sulfate radical-free, then it is washed with deionized water to neutrality, finally by ultrasonically treated, dried at 50 DEG C and can be prepared by graphite oxide
Alkene.
（2）The preparation of graphite oxide alkenyl cadmium ion imprinted polymer：
In 100mL three-necked flasks, deionized water, four nitric hydrate cadmiums, cetyl trimethylammonium bromide, oxidation are added
Graphene, ultrasound makes it be uniformly dispersed, and stirring at room temperature forms aqueous phase composition；In small beaker, methyl methacrylate is added
With RAFT auxiliary agents, it is uniformly dispersed to form oil phase composition；Oil phase is added in aqueous phase dropwise by dropping funel, after dripping off at room temperature
Stirring；Then lead to nitrogen and heat up, add azodiisobutyronitrile, sealing reaction；After reaction terminates, washed successively with water, methanol
For several times, it is dried in vacuo, you can obtain graphite oxide alkenyl cadmium ion imprinted polymer, be designated as Cd (II)-IIP.
Wherein, step（2）Described in aqueous phase composition in four nitric hydrate cadmiums, cetyl trimethylammonium bromide and oxidation stone
Black alkene
Ratio be 1.23 ~ 1.85g：2.83~4.24g：50mg.
Wherein, step（2）Described in stir at room temperature 1h formation aqueous phase composition.
Wherein, step（2）Described in oil phase composition in methyl methacrylate and RAFT auxiliary agents mol ratio be 20：0.04
~0.24。
Wherein, the RAFT auxiliary agents are S, S '-two (α, α '-dimethyl-α ' '-acetic acid) trithiocarbonate.
Wherein, step（2）Described in oil phase add aqueous phase in, 2h is stirred after dripping off at room temperature.
Wherein, step（2）Middle azodiisobutyronitrile and RAFT auxiliary agent mol ratio is 1:1~6.
The corresponding non-imprinted polymer of the present invention（NIP）As blank control, the similar synthetic method of its preparation method as above,
But it is not added with Cd (NO3)2·4H2O。
The present invention is simultaneously tested prepared material by adsorption test and choice experiment：
（1）Adsorption experiment：
By the Cd of 25mL concentration knowns () solution is added in colorimetric cylinder, is placed in water bath with thermostatic control and is stood, and investigates absorption molten
The adsorption capacity of liquid.After absorption, test fluid clear liquid at the middle and upper levels is obtained by centrifuging collection, unadsorbed Cd () concentration use
Atomic absorption spectrophotometer (FAAS) and plasma emission spectrometer（ICP）Determine, and absorption is calculated according to result and hold
Amount（Q e, mg/g）.
WhereinC 0(mg/L) andC e(mg/L) respectively be absorption before and after Cd () concentration,W (g) it is adsorbent amount,V
(L) it is test fluid volume.
（2）Choice tests
Selection Cd ()、Ni()、Co()、Cu()、Hg()、Zn() it is binary competitive Adsorption ion, it is respectively configured
Four kinds of ions of the above and Cd () mixed solution, the concentration of every kind of ion is all 5mg/L.The solution for taking 25mL to configure is added
Into colorimetric cylinder, 20mg Cd (II)-IIP and NIP are separately added into, test fluid is placed in 35 DEG C of water-bath and stands 12h respectively.
After the completion of time of repose, supernatant is centrifugally separating to obtain, the concentration of unadsorbed various competitive Adsorption substrates is sent out with plasma
Penetrate spectrometer（ICP）Determine.
The technological merit of the present invention：
The present invention is first in microemulsion system, and the method being polymerize using RAFT has synthesized a kind of graphite oxide alkenyl cadmium
Ion imprinted polymer, the adsorbent, which has, has adsorption capacity big Cd (II), and selectivity is high, and separating effect significantly, is repeated
The advantages of access times are more.This provides a class newly side for the heavy metal element Cd (II) in selective separation enrichment environmental sample
Method.The advantage of the present invention is in particular in following three points：
（1）Appropriate matrix is selected effectively to improve adsorption capacity in the preparation process of surface imprinted polymer, so
Present invention selection using its higher surface area and high activity functional group, increases number of active sites, can had using GO as base material
Effect improves the adsorption capacity of the ion imprinted polymer adsorbent prepared.
（2）The RAFT polymerizations mentioned in aforementioned background art prepare ion imprinted polymer with its advantage, but exist simultaneously
There is inactivation, molecular weight and particle diameter distribution, present invention selection in the RAFT polymerizations in the system such as emulsion and trickle emulsion
RAFT polymerizations are carried out in microemulsion, using the stability and the consumption of regulation RAFT auxiliary agents of microemulsion, make polymerization process stable
It is controllable, it is simple to operate.It can be seen that the imprinted polymer Microsphere Size size of preparation is close from the SEM figures of accompanying drawing 1, illustrate synthesis
Imprinted polymer molecular weight and particle size distribution are narrow, embody the special advantage of the RAFT polymerizations in microemulsion system.
（3）The ion imprinted polymer for preparing graphite oxide alkenyl using RAFT polymerizations in microemulsion system at present does not have
Report, graphite oxide alkenyl cadmium ion imprinted polymer prepared by the present invention, Cd can be drawn by the selectivity factor figure of accompanying drawing 2
(II)-IIP shows the selectivity of good recognition performance and height to Cd (II).
Brief description of the drawings
Fig. 1 is the collection of illustrative plates of ESEM：Wherein（a）Base material GO SEM figures,（b）,（c）With（d）Respectively example 1,2,3
Middle synthesis imprinted polymer Cd ()-IIP SEM figure.
Fig. 2 be example 2 in Cd (II) relative to competitive Adsorption ion Ni ()、Co()、Cu()、Hg()、Zn()
Selective absorption coefficient results, wherein K,What is represented is Cd (II) relative to competitive Adsorption ion Ni (II), Co (II), Cu
(II), Hg (II), Zn (II) selectivity factor.
Embodiment
With reference to specific implementation example, the present invention will be further described.
Embodiment 1：
（1）The preparation of graphene oxide
In 250mL beaker, 23mL 98% concentrated sulfuric acid is added, ice-water bath is placed in.Then, under conditions of stirring, plus
Enter 1g aquadags powder and 0.5g sodium nitrate.Again under strong stirring, keeping temperature in 3g potassium permanganate, reaction is slowly added to
Less than 20 DEG C；Then ice-water bath is removed, temperature is increased to 35 DEG C, sustained response 30min.Under agitation, it is slowly added to
46mL deionized waters, and it is warming up to 98 DEG C, solution presentation brown, reaction 15min；Then about 140mL 60 DEG C of heat is added
30% hydrogen peroxide of deionized water and 4.5mL, until it is in brown color that reaction, which terminates solution,.Finally by centrifugation, first with 5% salt
Pickling is to sulfate radical-free, then is washed with deionized water to neutrality, finally by ultrasonically treated, dried at 50 DEG C and can be prepared by oxidation
Graphene.
（2）The preparation of graphite oxide alkenyl cadmium ion imprinted polymer
In tri- mouthfuls of beakers of 100mL, 30mL deionized waters, the nitric hydrate cadmiums of 1.23g tetra-, 2.83g cetyls three are added
Methyl bromide ammonium, 50mg graphene oxides, ultrasound makes it be uniformly dispersed, and 1h formation aqueous phase compositions are stirred at room temperature；In small beaker
In, add 20mmoL methyl methacrylates and 0.08mmoL RAFT auxiliary agents S, S '-two (α, α '-dimethyl-α ' '-acetic acid) three
Sulfocarbonate（BDAT）, it is uniformly dispersed to form oil phase composition.Oil phase is added in aqueous phase dropwise by dropping funel, after dripping off
2h is stirred at room temperature；Then logical nitrogen, and be warming up to 75 DEG C, addition 0.04mmoL AIBN, sealing, reaction 3.5h.Reaction terminates
Afterwards, washed for several times, be dried in vacuo at 50 DEG C with water, methanol successively, you can be able to the cadmium ion trace that graphene oxide is base material
Polymer composites adsorbent, remembers Cd (II)-IIP.Non- imprinted polymer（NIP）The similar synthetic method of preparation method such as
On, but it is not added with Cd (NO3)2·4H2O。
（3）Adsorption test
Cd (II) solution for taking 25mL initial concentrations to be respectively 300mg/L is added in 25mL colorimetric cylinders, with watery hydrochloric acid or
Weak aqua ammonia regulation pH value is 6,10mg traces and non-trace adsorbent is separately added into, in the water-bath for test fluid being individually placed to 35 DEG C
Stand after 12h, be centrifugally separating to obtain Cd (II) concentration not to be adsorbed in supernatant liquor, supernatant liquor and surveyed with atomic absorption spectrum
It is fixed, and adsorption capacity is calculated according to result.As a result it is 80.77mg/ to show saturated extent of adsorption of Cd (the II)-IIP at 35 DEG C
G, far above the 36.75mg/g of non-trace adsorbent.
（4）Selectivity experiment
Cd() and Ni ()、Co()、Cu()、Hg()、Zn() mixing binary system competitive Adsorption, take 25
The concentration that mL has been configured be 5mg/L Cd ()/M() mixed solution is added in colorimetric cylinder, adjusted with watery hydrochloric acid or weak aqua ammonia
PH value is 6, is separately added into 20mg Cd (II)-IIP and NIP.Test fluid is placed in 35 DEG C of water-bath and stands 12h.Time of repose
After the completion of, be centrifugally separating to obtain Cd (II) not to be adsorbed in supernatant liquor, supernatant liquor and other competitive Adsorption ion M ()
Concentration determined with ICP, adsorption capacity is calculated according to result.As a result show that Cd (II)-IIP are shown to Cd (II) good
Recognition performance, wherein Cd (II) relative to competitive Adsorption ion Ni ()、Co()、Cu()、Hg()、Zn() selectivity
Coefficient is respectively 14.11,11.22,20.01,2.12 and 8.24, rather than trace adsorbent NIP Cd (II) is shown it is very poor
Adsorptive selectivity.
Embodiment 2：
（1）The preparation of graphene oxide
In 250mL beaker, 23mL 98% concentrated sulfuric acid is added, ice-water bath is placed in.Then, under conditions of stirring, plus
Enter 1g aquadags powder and 0.5g sodium nitrate.Again under strong stirring, keeping temperature in 3g potassium permanganate, reaction is slowly added to
Less than 20 DEG C；Then ice-water bath is removed, temperature is increased to 35 DEG C, sustained response 30min.Under agitation, it is slowly added to
46mL deionized waters, and it is warming up to 98 DEG C, solution presentation brown, reaction 15min；Then about 140mL 60 DEG C of heat is added
30% hydrogen peroxide of deionized water and 4.5mL, until it is in brown color that reaction, which terminates solution,.Finally by centrifugation, first with 5% salt
Pickling is to sulfate radical-free, then is washed with deionized water to neutrality, finally by ultrasonically treated, dried at 50 DEG C and can be prepared by oxidation
Graphene.
（2）The preparation of cadmium ion imprinted polymer composite material adsorbent by base material of graphene oxide
In 100mL three-necked flasks, 30mL deionized waters, the nitric hydrate cadmiums of 1.54g tetra-, 3.53g cetyls three are added
Methyl bromide ammonium, 50mg graphene oxides, ultrasound makes it be uniformly dispersed, and 1h formation aqueous phase compositions are stirred at room temperature；In small beaker
In, add 20mmoL methyl methacrylates and 0.12mmoL RAFT auxiliary agents S, S '-two (α, α '-dimethyl-α ' '-acetic acid) three
Sulfocarbonate（BDAT）, it is uniformly dispersed to form oil phase composition.Oil phase is added in aqueous phase dropwise by dropping funel, after dripping off
2h is stirred at room temperature；Then logical nitrogen, and be warming up to 70 DEG C, addition 0.04mmoL AIBN, sealing, reaction 3.5h.Reaction terminates
Afterwards, washed for several times, be dried in vacuo at 50 DEG C with water, methanol successively, you can be able to the cadmium ion trace that graphene oxide is base material
Polymer composites adsorbent, remembers Cd (II)-IIP.Non- imprinted polymer（NIP）The similar synthetic method of preparation method such as
On, but it is not added with Cd (NO3)2·4H2O。
（3）Adsorption test
Cd (II) solution for taking 25mL initial concentrations to be 300mg/L is added in 25mL colorimetric cylinders, with watery hydrochloric acid or dilute ammonia
Water regulation pH value is 6, is separately added into 10mg traces and non-trace adsorbent, test fluid is placed in 35 DEG C of water-bath and stands 12h
Afterwards, Cd (II) concentration Atomic Absorption Spectrometry not to be adsorbed in supernatant liquor, supernatant liquor, and root are centrifugally separating to obtain
Adsorption capacity is calculated according to result.As a result it is 83.46mg/g to show saturated extent of adsorption of Cd (the II)-IIP at 35 DEG C, is far above
The 36.42mg/g of non-trace adsorbent.
（4）Selectivity experiment
Cd() and Ni ()、Co()、Cu()、Hg()、Zn() mixing binary system competitive Adsorption, take 25
The concentration that mL has been configured be 5mg/L Cd ()/M() mixed solution is added in colorimetric cylinder, adjusted with watery hydrochloric acid or weak aqua ammonia
PH value is 6, is separately added into 20mg Cd (II)-IIP and NIP.Test fluid is placed in 35 DEG C of water-bath and stands 12h.Stand and complete
Afterwards, be centrifugally separating to obtain in supernatant liquor, supernatant liquor not by unadsorbed Cd (II) and other competitive Adsorption ion M ()
Concentration is determined with ICP, and adsorption capacity is calculated according to result.As a result show that Cd (II)-IIP show good knowledge to Cd (II)
Other performance, wherein Cd (II) relative to competitive Adsorption ion Ni ()、Co()、Cu()、Hg()、Zn() selectivity system
Number is respectively 14.86,11.00,20.12,2.23 and 8.06, rather than trace adsorbent NIP shows very poor suction to Cd (II)
Attached selectivity.
Fig. 2 be example 2 in Cd (II) relative to competitive Adsorption ion Ni ()、Co()、Cu()、Hg()、Zn()
Selectivity factor figure, as a result shows that Cd (II)-IIP show the selectivity of good recognition performance and height to Cd (II).
Embodiment 3：
（1）The preparation of graphene oxide
In 250mL beaker, 23mL 98% concentrated sulfuric acid is added, ice-water bath is placed in.Then, under conditions of stirring, plus
Enter 1g aquadags powder and 0.5g sodium nitrate.Again under strong stirring, keeping temperature in 3g potassium permanganate, reaction is slowly added to
Less than 20 DEG C；Then ice-water bath is removed, temperature is increased to 35 DEG C, sustained response 30min.Under agitation, it is slowly added to
46mL deionized waters, and it is warming up to 98 DEG C, solution presentation brown, reaction 15min；Then about 140mL 60 DEG C of heat is added
30% hydrogen peroxide of deionized water and 4.5mL, until it is in brown color that reaction, which terminates solution,.Finally by centrifugation, first with 5% salt
Pickling is to sulfate radical-free, then is washed with deionized water to neutrality, finally by ultrasonically treated, dried at 50 DEG C and can be prepared by oxidation
Graphene.
（2）The preparation of graphite oxide alkenyl cadmium ion imprinted polymer
In tri- mouthfuls of beakers of 100mL, 30mL deionized waters, the nitric hydrate cadmiums of 1.85g tetra-, 4.24g cetyls three are added
Methyl bromide ammonium, 50mg graphene oxides, ultrasound makes it be uniformly dispersed, and 1h formation aqueous phase compositions are stirred at room temperature；In small beaker
In, add 20mmoL methyl methacrylates and 0.24mmoL RAFT auxiliary agents S, S '-two (α, α '-dimethyl-α ' '-acetic acid) three
Sulfocarbonate（BDAT）, it is uniformly dispersed to form oil phase composition.Oil phase is added in aqueous phase dropwise by dropping funel, after dripping off
2h is stirred at room temperature；Then logical nitrogen, and be warming up to 75 DEG C, addition 0.04mmoL AIBN, sealing, reaction 3.5h.Reaction terminates
Afterwards, washed for several times, be dried in vacuo at 50 DEG C with water, methanol successively, you can be able to the cadmium ion trace that graphene oxide is base material
Polymer composites adsorbent, remembers Cd (II)-IIP.Non- imprinted polymer（NIP）The similar synthetic method of preparation method such as
On, but it is not added with Cd (NO3)2·4H2O。
（3）Adsorption test
Cd (II) solution for taking 25mL initial concentrations to be respectively 300mg/L is added in 25mL colorimetric cylinders, with watery hydrochloric acid or
Weak aqua ammonia regulation pH value is 6,10mg traces and non-trace adsorbent is separately added into, in the water-bath for test fluid being individually placed to 35 DEG C
Stand after 12h, be centrifugally separating to obtain Cd (II) concentration not to be adsorbed in supernatant liquor, supernatant liquor and surveyed with atomic absorption spectrum
It is fixed, and adsorption capacity is calculated according to result.As a result it is 81.22mg/ to show saturated extent of adsorption of Cd (the II)-IIP at 35 DEG C
G, far above the 37.15mg/g of non-trace adsorbent.
（4）Selectivity experiment
Cd() and Ni ()、Co()、Cu()、Hg()、Zn() mixing binary system competitive Adsorption, take 25mL
The concentration configured be 5mg/L Cd ()/M() mixed solution is added in colorimetric cylinder, and pH is adjusted with watery hydrochloric acid or weak aqua ammonia
It is worth for 6, is separately added into 20mg Cd (II)-IIP and NIP.Test fluid is placed in 35 DEG C of water-bath and stands 12h.Time of repose is complete
Cheng Hou, be centrifugally separating to obtain Cd (II) not to be adsorbed in supernatant liquor, supernatant liquor and other competitive Adsorption ion M ()
Concentration is determined with ICP, and adsorption capacity is calculated according to result.As a result show that Cd (II)-IIP show good knowledge to Cd (II)
Other performance, wherein Cd (II) relative to competitive Adsorption ion Ni ()、Co()、Cu()、Hg()、Zn() selectivity system
Number is respectively 14.17,11.02,20.08,2.07 and 8.11, rather than trace adsorbent NIP shows very poor suction to Cd (II)
Attached selectivity.
Fig. 1 is the collection of illustrative plates of ESEM：Wherein（a）Base material GO SEM figures,（b）,（c）With（d）Respectively example 1,2,3
Middle synthesis imprinted polymer Cd ()-IIP SEM figure.
It can be seen that base material GO surface comparison rules and flat-satin, and imprinted polymer Cd ()-IIP surfaces
Become coarse, uneven, formed by the microballoon accumulation of many adjoining dimensions, because RAFT polymerization processes are stably and controllable
Process, when RAFT assistant concentrations are higher, polymerization process controllability is good, and the polymer molecular weight and particle diameter distribution of synthesis are narrow, gather
Compound Microsphere Size is close, template ion Cd () after elution, leave many imprinted cavities, rough surface.Printing process makes system
The surface of the cadmium ion imprinted polymer using GO as base material obtained becomes coarse, not only increases adsorption surface area, and make knot
Closing site distribution number also increases, beneficial to its adsorption capacity of raising.
Claims (5)
1. a kind of preparation method of graphite oxide alkenyl cadmium ion imprinted polymer, it is characterised in that carry out according to the following steps：
（1）The preparation of graphene oxide：
In 250mL beaker, 98% concentrated sulfuric acid is added, ice-water bath is placed in；Then, under conditions of stirring, aquadag is added
Powder and sodium nitrate；Again under strong stirring, it is slowly added to keeping temperature in potassium permanganate, reaction and is less than 20 DEG C；Then remove
Ice-water bath, 35 DEG C, sustained response 30min are increased to by temperature；Under agitation, deionized water is slowly added to, and is warming up to
98 DEG C, brown is presented in solution, reacts 15min；Then 60 DEG C of hot deionized water and 30% hydrogen peroxide are added, until reacting knot
Beam solution is in brown color；Finally by centrifugation, sulfate radical-free is first washed till with 5% hydrochloric acid, then be washed with deionized water to neutrality, most
Afterwards by ultrasonically treated, dry and can be prepared by graphene oxide；
（2）The preparation of graphite oxide alkenyl cadmium ion imprinted polymer：
In 100mL three-necked flasks, deionized water, four nitric hydrate cadmiums, cetyl trimethylammonium bromide, graphite oxide are added
Alkene, ultrasound makes it be uniformly dispersed, and stirring at room temperature forms aqueous phase composition；In small beaker, add methyl methacrylate and
RAFT auxiliary agents, are uniformly dispersed to form oil phase composition；Oil phase is added in aqueous phase dropwise by dropping funel, stirred at room temperature after dripping off
Mix；Then lead to nitrogen and heat up, add azodiisobutyronitrile, sealing reaction；After reaction terminates, number is washed with water, methanol successively
It is secondary, vacuum drying, you can obtain graphite oxide alkenyl cadmium ion imprinted polymer；
Step（2）Described in aqueous phase composition in four nitric hydrate cadmiums, cetyl trimethylammonium bromide and graphene oxide ratio
Example is 1.23 ~ 1.85g：2.83~4.24g：50mg；Step（2）Described in oil phase composition methyl methacrylate and RAFT help
The mol ratio of agent is 20：0.04~0.24；The RAFT auxiliary agents are S, S '-two (α, α '-dimethyl-α ' '-acetic acid) three thio carbon
Acid esters.
2. a kind of preparation method of graphite oxide alkenyl cadmium ion imprinted polymer according to claim 1, its feature exists
In step（2）Described in stir at room temperature 1h formation aqueous phase composition.
3. a kind of preparation method of graphite oxide alkenyl cadmium ion imprinted polymer according to claim 1, its feature exists
In step（2）Described in oil phase add aqueous phase in, 2h is stirred after dripping off at room temperature.
4. a kind of preparation method of graphite oxide alkenyl cadmium ion imprinted polymer according to claim 1, its feature exists
In step（2）Middle azodiisobutyronitrile and RAFT auxiliary agent mol ratio is 1:1~6.
5. graphite oxide alkenyl cadmium ion imprinted polymer prepared by method as claimed in claim 1 is used for single-minded Selective recognition
With absorption Cd2+。
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| CN108043371A (en) * | 2018-01-13 | 2018-05-18 | 常州大学 | A kind of double-template is oriented to the preparation method and applications of trace composite membrane |
| CN109574120A (en) * | 2018-12-16 | 2019-04-05 | 陈绪涛 | A kind of graphene doping textile dyestuff Wastewater purification material and preparation method thereof |
| CN110201646A (en) * | 2019-05-14 | 2019-09-06 | 桂林理工大学 | A kind of diatom base cadmium ion trace adsorbent and its preparation method and application |
| CN112611785B (en) * | 2020-11-26 | 2022-11-08 | 北京信息科技大学 | Field-effect tube micro sensor and preparation method and application thereof |
| CN114878660B (en) * | 2022-04-29 | 2024-02-06 | 上海市刑事科学技术研究院 | Graphene oxide surface molecular imprinting composite material, preparation method and application |
| CN115382515A (en) * | 2022-08-22 | 2022-11-25 | 太原理工大学 | Graphene-based surface ion imprinting material for selectively adsorbing gallium ions and preparation method and application thereof |
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