CN109206554A - A kind of ion imprinted polymer material of photo-reduction Cr VI and its preparation and application - Google Patents
A kind of ion imprinted polymer material of photo-reduction Cr VI and its preparation and application Download PDFInfo
- Publication number
- CN109206554A CN109206554A CN201710534799.6A CN201710534799A CN109206554A CN 109206554 A CN109206554 A CN 109206554A CN 201710534799 A CN201710534799 A CN 201710534799A CN 109206554 A CN109206554 A CN 109206554A
- Authority
- CN
- China
- Prior art keywords
- imprinted polymer
- polymer material
- reduction
- added
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/044—Elimination of an inorganic solid phase
- C08J2201/0444—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2335/02—Characterised by the use of homopolymers or copolymers of esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Analytical Chemistry (AREA)
- Toxicology (AREA)
- Materials Engineering (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a kind of preparation methods of the ion imprinted polymer material of photo-reduction Cr VI, belong to field of new materials.This method is using potassium bichromate as template, 2- vinylpyridine is function monomer, trimethylol-propane trimethacrylate and ethylene glycol dimethacrylate are crosslinking agent, toluene is pore-foaming agent, graphene oxide is solid surfactant, prepares hexavalent chromium imprinted polymer material using pickering emulsion technology.Under illumination condition, primary electron is gone back in graphene oxide offer, reduction of hexavalent chromium is converted by valence state of the electron mediator (ferric ion) between trivalent and divalent, the functional group that reduzate trivalent chromium is then oxidized graphene surface is adsorbed by charge effect.This method combines ionic imprinting technique with photocatalysis technology, realizes hexavalent chromium absorbing and reducing in the conception of one, and can hexavalent chromium in selective cleaning water, and do not need to carry out secondary treatment to the trivalent chromic ion of generation.
Description
Technical field
The present invention relates to field of new materials, relate to ion imprinted polymer material and its preparation method and application, and in particular to
Chromium ion imprinted polymer material and its preparation method and application.
Background technique
With China's rapid industrial development, heavy metal pollution event emerges one after another, and causes a series of environmental problems.Study carefully it
Reason mostlys come from the random discharge and leakage of heavy metal.Chromium pollutant is mainly derived from mining, metal spray painting, and timber is prevented
Corruption, dyestuff, (Dhal B, Thatoi HN, the Das NN et al.Chemical and such as leather and stainless steel production
microbial remediation of hexavalent chromium from contaminated soil and
mining/metallurgical solid waste:a review[J].J Hazard Mater,2013,250-251:272-
291.).Chromium in environment mainly exists in the form of trivalent chromium and Cr VI, wherein trivalent chromium participant and the intracorporal sugar of animal
With the metabolism of fat, but long-term exposure trivalent chromium may cause the cumulative toxicity of chromium.And Cr VI is that the mankind determine carcinogenic substance, poison
Property is 10~100 times of trivalent chromium, and human body can be entered by skin, alimentary canal and respiratory tract, causes anaemia, dermatitis, nose
The diseases such as inflammation, ephritis, neuritis, Long Term Contact can also cause respiratory inflammation and induce lung cancer, and serious sexavalence chromium poisoning is also
It can causing death (KanmaniP, Aravind J, PrestonD.Remediationof chromiumcontaminants
usingbacteria[J].International Journal of Environmental Science and
Technology,2011,9(1):183-193；The harm of Zhang Hanchi, Zhang Jijun, Liu Feng chromium and prevention and treatment [J], Inner Mongol petroleum
Chemical industry, 2003,30:72-73.).Trivalent chromium in water body can result in the inhibition of the certain metal enzyme systems of inside plants, thus
Inhibit plant growth, toxic effect (Shanker A K, Cervantes C, Loza-Tavera H, et are generated to plant
al.Chromium toxicity in plants[J].Environment International,2005,31(5):739-
753.) the Cr VI stability, and in water body is strong and has bio-toxicity, under field conditions (factors) by hexavalent chromium polluted water body
It is difficult to repair, and there are long-term toxic exposure (Dinda D, Gupta A, Saha S K.Removal of with plant to biology
toxic Cr(VI)by UV-active functionalized graphene oxide for water purification
[J].Journal of Materials Chemistry A,2013,1(37):11221-11228.).Therefore, also by Cr VI
Originally it is trivalent chromium, while trivalent chromium being removed, for the pollution of chromium in processing environment, the chromium toxicity in reduction environment, has important
Meaning.
The processing method of hexavalent chromium wastewater mainly has physico-chemical process and bioanalysis at present, and main mechanism is to utilize reducing substances
It is trivalent chromium by hexavalent chrome reduction.There are operating costs and the cost of raw material in physico-chemical process treatment process excessively high, poor selectivity, production
Primary sludge amount is big, easily causes secondary pollution problems, and that there is reducing powers is low, the processing time is long and raw for bioanalysis
Object security problems (Romanenko VI,Koren'kov VN.Pure culture of bacteria using
chromates and bichromates as hydrogen acceptors during development under
anaerobic conditions[J].Mikrobiologiia,1977,46(3):414-417；Tang Jie, Zhu Kairan, Lv Xiaoshu,
Cr (VI) minimizing technology summary [J] .2011. chinese scientific papers is online in equal water).Ionic imprinting technique and photocatalysis technology
It is widely used to the Adsorption of heavy metal ion, ion imprinted polymer material and photocatalysis for Cr VI design
Material also emerges in multitude (Ren Z, Kong D, Wang K, et al.Preparation and adsorption
characteristics of an imprinted polymer for selective removal of Cr(VI)ions
from aqueous solutions[J].Journal of Materials Chemistry A,2014,2(42):17952-
17961；Waldmann N.S.,Paz Y.Photocatalytic reduction of Cr(VI)by titanium
dioxide coupled to functionalized CNTs:An example of counterproductive charge
separation[J].The Journal of Physical Chemistry C,2010,114(44):18946-18952.)。
However these material intermediate ion imprinted polymers are just in the specific adsorption of Cr VI, Cr VI is only shifted and
Its toxicity is not reduced；Catalysis material just for metal ion reduction, and it is not selective to hexavalent chrome reduction, secondly
Reduzate trivalent chromium is not handled.Therefore, develop one kind can selective light reduction of hexavalent chromium, and can locate in time
The new material of reason reduzate trivalent chromium is of great significance.
Summary of the invention
Material for existing processing Cr VI is specific adsorption Cr VI without reducing its toxicity also or only
Metal ion is restored and does not have specific adsorption to Cr VI and reduzate trivalent chromium handle etc. asking
Topic, the task of the present invention is ion imprinted polymer material for providing a kind of photo-reduction Cr VI and its preparation method and application,
Make it have can specific adsorption and photo-reduction Cr VI, and can simultaneously absorbing and reducing product trivalent chromium the features such as, with
Overcome the deficiencies in the prior art.
Realizing concrete scheme of the invention is:
The ion imprinted polymer material of photo-reduction Cr VI provided by the invention, for spherical or spherical structure, the ball
The internal layer of shape or spherical structure is hexavalent chromium trace hole, and the entire outer surface of spherical shape or spherical structure is to aoxidize
Graphene coated, referred to as graphene layer, it is multiple for crosslinking between graphene layer and the internal layer being made of hexavalent chromium trace hole
Zoarium, referred to as crosslinking composite layer.
The ion imprinted polymer material of photo-reduction Cr VI provided by the invention is the 2- using potassium bichromate as template molecule
Vinylpyridine is function monomer, and trimethylol-propane trimethacrylate and ethylene glycol dimethacrylate are crosslinking
Agent, toluene are pore-foaming agent, and graphene oxide is solid surfactant, utilize pik woods (Pickering) emulsion method
(Chevalier Y,Bolzinger M A.Emulsions stabilized with solid nanoparticles:
Pickering emulsions[J].Colloids and Surfaces A:Physicochemical and
Engineering Aspects, 2013,439:23-34.) emulsion oil-in-water microballoon is formed, two isobutyl of initiator azo is added
Ion imprinted polymer material precursor object is prepared in nitrile initiated polymerization, which is first cleaned with tetrahydrofuran, then is used
Sodium hydroxide-acetonitrile mixed solution washes away template molecule potassium bichromate, is then washed with deionized water to neutrality, true through 40~60 DEG C
The ion imprinted polymer material for the photo-reduction Cr VI that sky is dried to obtain.
The preparation method of the ion imprinted polymer material of photo-reduction Cr VI provided by the invention, comprising the following steps:
Step 1: excessive template molecule potassium bichromate is placed in centrifuge tube, adds function monomer 2- vinylpyridine
Pyridine, crosslinking agent trimethylol-propane trimethacrylate and ethylene glycol dimethacrylate and pore-foaming agent toluene, concussion are mixed
It is even, graphene oxide water solution is then added, adds deionized water, solution concussion is uniformly mixed so as to obtain micro- containing emulsion oil-in-water
Pik woods (Pickering) emulsion system of ball；Wherein template molecule reaches saturation in water phase and enters organic phase, into having
The template molecule of machine phase is coordinated with function monomer；2- vinylpyridine, trimethylol-propane trimethacrylate, diformazan
The molar ratio of base acrylic acid glycol ester, toluene and deionized water is 1:0.2~0.5:4~8:3~7:10~20；Concentration is 8
~20mg mL-1Graphene oxide water solution volume and deionized water to be added volume ratio is added be 1:3~6；
Step 2: two isobutyl of initiator azo is added into pik woods (Pickering) emulsion system made from step 1
Nitrile, and logical nitrogen deoxygenation, wherein 2- vinylpyridine and azodiisobutyronitrile molar ratio are 1:0.5~2, and solution concussion mixes,
It is placed in 8~15h of reaction under 65~75 DEG C of water bath conditions, obtains ion imprinted polymer material precursor object, which first uses dense
Degree is 12mol L-1Tetrahydrofuran cleaning, then wash away template point with sodium hydroxide-acetonitrile mixture that volume ratio is 1~5:1
Sub- potassium bichromate, wherein naoh concentration is 0.05~0.2mol L-1, acetonitrile concentration is 19mol L-1, then use deionization
It is washed to neutrality, 40~60 DEG C of vacuum drying are to get the ion imprinted polymer material for arriving photo-reduction Cr VI.
Graphene oxide water solution concentration described in above-mentioned preparation method is 8~20mg mL-1, graphene oxide is water-soluble
Liquid can be prepared with Hu Mo (Hummers) method, and the method using Hu Mo (Hummers) method preparation graphene oxide water solution is:
Reaction vessel such as conical flask are placed in ice-water bath, graphite powder and potassium nitrate are sequentially added, is then slowly added into sulfuric acid, and stir
It mixes, is slow added into potassium permanganate, continue to stir；Ice-water bath is removed, reaction vessel is placed in oil bath, is warming up to 30~40
DEG C, 1~2h is stirred, warm distilled water is then added, is warming up to 95~100 DEG C again, stirs 1~1.5h, temperature is then added again
Distilled water and 30% hydrogen peroxide, continue 10~15min of stirring and terminate reaction；Obtained reaction product is first used into hydrochloric acid solution
Cleaning, then wash with distilled water, and it is centrifuged removal supernatant, cleaning to solution pH value can stop cleaning to get oxygen is arrived when being greater than 5
Graphite aqueous solution.[method of Hu Mo (Hummers) method preparation graphene oxide water solution can refer to following document:
Preparation of graphitic oxide.Journal of the American Chemical Society,80
(6),1339-1339.]。
The ion imprinted polymer material of photo-reduction Cr VI provided by the invention is to the adsorption capacity of Cr VI
0.613mg g-1, imprinting factor reaches 1.5 times, can be in reduction of hexavalent chromium under illumination condition and absorbing and reducing product trivalent chromium, it can
The chromium toxicity in environment is reduced for the pollution of chromium in processing environment.
The present invention also provides the process approach of the ion imprinted polymer material photo-reduction Cr VI, and specific steps are such as
Under:
Take the ion imprinted polymer prepared in right amount and be scattered in the acidic aqueous solution containing Cr VI, in the solution plus
Enter appropriate ferric ion, wherein ion imprinted polymer concentration is 1~5mg mL-1, hexavalent chromium concentration is 1~12mg L-1,
Acid solution pH value is 1~5,3~10mg of ferric ion concentration L-1.Mixed solution stirring and adsorbing reacts 30~60min, into
Row illumination, the variation of Cr VI in real-time monitoring supernatant solution, wherein 90000~110000lux of intensity of illumination, incident wavelength are low
In 500nm.
A kind of ion imprinted polymer material of photo-reduction Cr VI carries out photo-reduction to Cr VI in an acidic solution, molten
The rate of descent of Cr VI is up to 60~90% in liquid.During the photo-reduction, graphene oxide provides reduction as electron donor
Electronics, ferric ion will go back primary electron as electron mediator with the valence state conversion between its trivalent and divalent and quickly pass to
Cr VI, the functional group that reduzate trivalent chromium is then oxidized graphene surface are adsorbed by charge effect.
Compared with traditional pik woods (Pickering) emulsion method, preparation process of the present invention, which demonstrates metal ion, can also make
Corresponding imprinted polymer material is synthesized for template application pik woods (Pickering) emulsion method.Secondly, preparation process of the present invention
The theory that template will polymerize in soluble phase in conventional method is broken, so that template is existed using the method that excess template is added
Soluble phase utilizes a small amount of template completion printing process for entering indissoluble phase after reaching saturation.With traditional hexavalent chromium trace
Polymer material is compared, and the present invention is prepared for can specific adsorption Cr VI and the trace to Cr VI progress photo-reduction
Polymer material.
Compared with traditional Cr VI catalysis material, material of the present invention is without containing light such as traditional titanium dioxide, zinc oxide
Catalyst, but be capable of specificity for Cr VI carry out photo-reduction, and can simultaneously adsorption treatment reduzate trivalent chromium.
The present invention chooses that nature is abundant during photo-reduction and the ferric ion of nonhazardous is as electron mediator, and three
Valence iron ion makes electronics be easier to pass to Cr VI by the valence state conversion between trivalent and divalent.Material of the present invention realizes
Cr VI of the Cr VI absorbing and reducing in the conception of one, thorough purified water that can be selective, and do not need to generation
Trivalent chromium carry out secondary treatment.Graphene oxide is both stable pik woods (Pickering) lotion in material of the present invention
Solid surfactant, and be electron donor during photo-reduction or electron mediator ferric ion and reduzate three
The adsorbent of valence chromium.
Detailed description of the invention
Fig. 1 is a kind of synthesis schematic diagram (1) of the ion imprinted polymer material of photo-reduction Cr VI of the present invention, Yi Jiguang
Reduction of hexavalent chromium process (2) and mechanism schematic diagram (3).
Fig. 2 is the electron microscope of ion imprinted polymer (a) He nonionic imprinted polymer (blank control) (b), wherein inserting
Figure is the graphene oxide of polymer surfaces.
Fig. 3 is the isothermal suction to hexavalent chromium of ion imprinted polymer and nonionic imprinted polymer (blank control)
Attached curve.
Fig. 4 is the absorption power of ion imprinted polymer and nonionic imprinted polymer (blank control) to hexavalent chromium
Learn feature.
Fig. 5 be under illumination condition ion imprinted polymer and nonionic imprinted polymer (blank control) to hexavalent chromium
Selective reduction performance.
Fig. 6 is ion imprinted polymer and nonionic imprinted polymer (blank control) selective light reduction of hexavalent chromium process
The distribution of Cr VI and total chromium in middle solution.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
A kind of embodiment 1: preparation (pik woods (Pickering) of the ion imprinted polymer material of photo-reduction Cr VI
Emulsion method)
Concentration 16.5mg mL is prepared using Hu Mo (Hummers) method-1Graphene oxide water solution.By 0.45g dichromic acid
Potassium, the commercially available 2- vinylpyridine of 0.15mL, the commercially available trimethylol-propane trimethacrylate of 0.15mL, the commercially available diformazan of 1.5mL
Base acrylic acid glycol ester and the commercially available toluene of 0.8mL are placed in 15mL centrifuge tube, and concussion mixes.1.0mL preparation is added simultaneously
Graphene oxide water solution (16.5mg mL-1) and 4.0mL deionized water, solution concussion mixing.20mg azo is added to mixture
Mixture is firmly shaken into uniform lotion, is placed under 70 DEG C of water bath conditions and reacts 10h by bis-isobutyronitrile, and logical nitrogen 5min；It will
Obtained polymer first washes away unreacted organic reagent with commercially available tetrahydrofuran, then with 0.1mol L-1Sodium hydroxide-acetonitrile
(1:1, v/v) mixed liquor washes away template, is finally washed with water to neutrality, and 50 DEG C of vacuum drying obtain pik woods (Pickering) cream
The ion imprinted polymer of liquid method preparation.Pik woods (Pickering) emulsion method prepares nonionic imprinted polymer (blank pair
According to) process it is same as above, template potassium bichromate is only added without in preparation process.
By polymer material obtained by the above method, it is spherical shape or spherical that electron microscope, which can see polymer material,
Graphene oxide is coated on surface of polymer material (see Fig. 2).Ion imprinted polymer material reaches the adsorption capacity of Cr VI
To 0.613mgg-1, the adsorption capacity of nonionic imprinted polymer material is only 0.396mgg-1, show specific recognition Cr VI
Imprinted sites prepared (see Fig. 3).Due to remaining the presence of imprinted sites after removal template ion, imprinted polymer exists
It can reach adsorption equilibrium in 30min, show preferable adsorption efficiency (see Fig. 4).
Embodiment 2: ion imprinted polymer material photo-reduction Cr VI application examples
Prepare 50mL PH4 aqueous solution (wherein hexavalent chromium concentration 3mg L-1, ferric iron concentration 5mg L-1) it is placed in crystallising dish
In (diameter 90mm), takes the 50mg ion imprinted polymer of preparation and nonionic imprinted polymer to be added separately in solution, stir
After mixing absorption 30min, carry out illumination (intensity of illumination 90000lux, incident wavelength 440nm), and in illumination 30,60,90,120,
Supernatant is taken when 180min, using the content of Cr VI in national standard method measurement supernatant, monitors sexavalence in supernatant solution
The variation of chromium.
Since there are print identification sites in ion imprinted polymer, relative to non-imprinted polymer, ion blotting
Polymer can adsorb more Cr VIs, so that Cr VI be made to be easier to obtain electronics and be reduced (see Fig. 5).In photo-reduction sexavalence
Cr VI and total chromium concn content basic one during chromium, in ion imprinted polymer and nonionic imprinted polymer solution
It causes, therefore can determine that reduzate trivalent chromic ion is not free in solution, but be adsorbed in polymer surfaces (see Fig. 6).
Embodiment 3: influence of the pore-foaming agent volume to ion imprinted polymer material absorption property
Ion imprinted polymer material is prepared according to 1 method of embodiment, the difference is that utilization different volumes (0.4,0.6,
0.8,1.0,1.2mL) toluene investigates pore-foaming agent volume to the shadow of ion imprinted polymer material absorption property as pore-foaming agent
It rings.By the investigation to ion imprinted polymer material to hexavalent chromium absorption property, structure shows pore-foaming agent volume of toluene
Absorption property highest for the ion imprinted polymer material prepared when 0.8mL.
Embodiment 4: graphene oxide water solution is prepared using Hu Mo (Hummers) method
250mL conical flask is placed in ice-water bath, 0.5g graphite powder and 0.5g potassium nitrate is added, is then slowly added into
23mL 18.4mol L-1Sulfuric acid, stir 5min, be slow added into 3g potassium permanganate, stir 10min；Ice-water bath is removed, by three
Angle flask is placed in oil bath, is warming up to 35 DEG C, stirs 1.5h, and 40mL45 DEG C of distilled water is then added, is warming up to 98 DEG C again, stirs
1h is mixed, the hydrogen peroxide of 50mL 45 DEG C of distilled water and 15mL 30% is then added, continues to stir 10min；Obtained reaction is produced
Object is first cleaned with the hydrochloric acid solution that volume fraction is 5%, then wash with distilled water, and is centrifuged removal supernatant, usually cleaning to PH
Value, which is greater than 5, can stop cleaning, and this method, which is washed till when pH value is 5, stops cleaning to get the graphene oxide for being 180mL to volume
Aqueous solution, concentration are 16.25mg mL-1.The present embodiment preparation method refers to following document: Graphene oxide-iron
complex:synthesis,characterization and visible-light-driven
photocatalysis.Journal of Materials Chemistry A,1(3),644-650.。
Claims (8)
1. a kind of ion imprinted polymer material of photo-reduction Cr VI, for spherical or spherical structure, the spherical shape or spherical
The internal layer of structure is hexavalent chromium trace hole, and the entire outer surface of spherical shape or spherical structure is graphene oxide packet
It covers, referred to as graphene layer, is crosslinking complex between graphene layer and the internal layer being made of hexavalent chromium trace hole.
2. the ion imprinted polymer material of photo-reduction Cr VI according to claim 1, which is characterized in that it is with weight
Potassium chromate is template molecule, and 2- vinylpyridine is function monomer, trimethylol-propane trimethacrylate and dimethyl propylene
Olefin(e) acid glycol ester is crosslinking agent, and toluene is pore-foaming agent, and graphene oxide is solid surfactant, utilizes pik woods
(Pickering) emulsion method forms emulsion oil-in-water microballoon,
Initiator azodiisobutyronitrile initiated polymerization is added, ion imprinted polymer material precursor object, the precursor is prepared
Object is first cleaned with tetrahydrofuran, then washes away template molecule potassium bichromate with sodium hydroxide-acetonitrile mixed solution, then uses deionization
It is washed to neutrality, the ion imprinted polymer material of obtained photo-reduction Cr VI is dried in vacuo through 40~60 DEG C.
3. chromium of the ion imprinted polymer material of photo-reduction Cr VI of any of claims 1 or 2 in processing environment is dirty
Dye reduces the chromium toxicity in environment.
4. the ion imprinted polymer material of photo-reduction Cr VI of any of claims 1 or 2 restores sexavalence under illumination condition
The application of chromium and absorbing and reducing product trivalent chromium.
5. the preparation method of ion imprinted polymer material of any of claims 1 or 2, comprising the following steps:
Step 1: excessive template molecule potassium bichromate is placed in centrifuge tube, is added function monomer 2- vinylpyridine, is handed over
Join agent trimethylol-propane trimethacrylate and ethylene glycol dimethacrylate and pore-foaming agent toluene, concussion mixes, so
After graphene oxide water solution is added, add deionized water, solution concussion is uniformly mixed so as to obtain containing emulsion oil-in-water microballoon
Pik woods (Pickering) emulsion system；Wherein template molecule reaches saturation in water phase and enters organic phase, into organic phase
Template molecule be coordinated with function monomer；2- vinylpyridine, trimethylol-propane trimethacrylate, dimethyl propylene
The molar ratio of olefin(e) acid glycol ester, toluene and deionized water is 1:0.2~0.5:4~8:3~7:10~20；Concentration be 8~
20mg mL-1Graphene oxide water solution volume and deionized water to be added volume ratio is added be 1:3~6；
Step 2: being added initiator azodiisobutyronitrile into pik woods (Pickering) emulsion system made from step 1, and
Logical nitrogen deoxygenation, wherein 2- vinylpyridine and azodiisobutyronitrile molar ratio are 1:0.5~2, and solution concussion mixes, and are placed in 65
8~15h is reacted under~75 DEG C of water bath conditions, obtains ion imprinted polymer material precursor object, which is first with concentration
12mol L-1Tetrahydrofuran cleaning, then with volume ratio be 1~5:1 sodium hydroxide-acetonitrile mixture wash away template molecule weight
Potassium chromate, wherein naoh concentration is 0.05~0.2mol L-1, acetonitrile concentration is 19mol L-1, then it is washed with deionized water
To neutrality, 40~60 DEG C of vacuum drying are to get the ion imprinted polymer material for arriving photo-reduction Cr VI.
6. preparation method according to claim 5, which is characterized in that the graphene oxide water solution concentration be 8~
20mg mL-1。
7. preparation method according to claim 5 or 6, which is characterized in that the graphene oxide water solution is application
The preparation of Hu Mo (Hummers) method.
8. preparation method according to claim 7, which is characterized in that prepare graphite oxide using Hu Mo (Hummers) method
The specific method of aqueous solution is: reaction vessel such as conical flask is placed in ice-water bath, graphite powder and potassium nitrate are sequentially added,
It is then slowly added into sulfuric acid, and is stirred, potassium permanganate is slow added into, continues to stir；Ice-water bath is removed, reaction vessel is placed in
In oil bath, it is warming up to 30~40 DEG C, stirs 1~2h, warm distilled water is then added, is warming up to 95~100 DEG C again, stirring 1~
Then the hydrogen peroxide of warm distilled water and 30% is added again, continues 10~15min of stirring and terminates reaction by 1.5h；By what is obtained
Reaction product is first cleaned with hydrochloric acid solution, then wash with distilled water, and is centrifuged removal supernatant, when cleaning to solution pH value is greater than 5
It can stop cleaning to get graphene oxide water solution is arrived.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710534799.6A CN109206554B (en) | 2017-07-03 | 2017-07-03 | Ion imprinted polymer material for photo-reduction of hexavalent chromium and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710534799.6A CN109206554B (en) | 2017-07-03 | 2017-07-03 | Ion imprinted polymer material for photo-reduction of hexavalent chromium and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109206554A true CN109206554A (en) | 2019-01-15 |
| CN109206554B CN109206554B (en) | 2020-10-16 |
Family
ID=64992426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710534799.6A Expired - Fee Related CN109206554B (en) | 2017-07-03 | 2017-07-03 | Ion imprinted polymer material for photo-reduction of hexavalent chromium and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109206554B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111992193A (en) * | 2020-07-31 | 2020-11-27 | 湖北省烟草科学研究院 | Graphene oxide-based lead ion imprinted composite material and preparation method and application thereof |
| CN112569911A (en) * | 2020-11-20 | 2021-03-30 | 南昌航空大学 | Method for synthesizing VTA-Cr (VI) -IIPs adsorbent by taking quaternary ammonium salt as monomer |
| CN113912317A (en) * | 2021-11-12 | 2022-01-11 | 湖南先锋防水科技有限公司 | Cement production method by adding naphthalene sulfonate water reducing agent |
| CN114956215A (en) * | 2022-06-06 | 2022-08-30 | 清华大学 | Perchloric acid system containing pentavalent neptunium ions and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945580A (en) * | 2015-07-16 | 2015-09-30 | 江苏大学 | Manufacturing method and application of Cr(VI) anion imprinted material |
| CN106432606A (en) * | 2016-11-11 | 2017-02-22 | 中国科学院青海盐湖研究所 | Magnetic Cr(VI) ionic imprinting polymer and preparation method and application thereof |
-
2017
- 2017-07-03 CN CN201710534799.6A patent/CN109206554B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945580A (en) * | 2015-07-16 | 2015-09-30 | 江苏大学 | Manufacturing method and application of Cr(VI) anion imprinted material |
| CN106432606A (en) * | 2016-11-11 | 2017-02-22 | 中国科学院青海盐湖研究所 | Magnetic Cr(VI) ionic imprinting polymer and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| 周庆芳 等: "二氧化钛/氧化石墨烯纳米复合材料光催化还原六价铬", 《陕西科技大学学报》 * |
| 李积升等: "C(rⅥ)-离子印迹聚合物的合成研究", 《化学工程师》 * |
| 王宗来 等: "分子印迹聚合物微球的制备研究进展", 《现代化工》 * |
| 黄丹丹等: "铬(Ⅵ)离子印迹聚合物的研究进展", 《天津化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111992193A (en) * | 2020-07-31 | 2020-11-27 | 湖北省烟草科学研究院 | Graphene oxide-based lead ion imprinted composite material and preparation method and application thereof |
| CN112569911A (en) * | 2020-11-20 | 2021-03-30 | 南昌航空大学 | Method for synthesizing VTA-Cr (VI) -IIPs adsorbent by taking quaternary ammonium salt as monomer |
| CN112569911B (en) * | 2020-11-20 | 2022-07-05 | 南昌航空大学 | Method for synthesizing VTA-Cr (VI) -IIPs adsorbent by taking quaternary ammonium salt as monomer |
| CN113912317A (en) * | 2021-11-12 | 2022-01-11 | 湖南先锋防水科技有限公司 | Cement production method by adding naphthalene sulfonate water reducing agent |
| CN114956215A (en) * | 2022-06-06 | 2022-08-30 | 清华大学 | Perchloric acid system containing pentavalent neptunium ions and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109206554B (en) | 2020-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3885039A1 (en) | Graphite-like carbon nitride doped modified microsphere catalyst, and preparation method therefor and application thereof | |
| CN109206554A (en) | A kind of ion imprinted polymer material of photo-reduction Cr VI and its preparation and application | |
| Pavithra et al. | Removal of toxic Cr (VI) ions from tannery industrial wastewater using a newly designed three-phase three-dimensional electrode reactor | |
| Alvarado et al. | Integration of ion exchange and electrodeionization as a new approach for the continuous treatment of hexavalent chromium wastewater | |
| CN108911101B (en) | Method for efficiently removing heavy metal ions based on ball milling oxalic acid zero-valent iron | |
| Cai et al. | Influence of TiO2 hollow sphere size on its photo-reduction activity for toxic Cr (VI) removal | |
| CN104828902B (en) | A kind of method of petal-shaped magnetic iron oxide molybdenum sulfide complex catalysts reduction treatment chromate waste water | |
| CN103934034A (en) | Preparation method of loading iron based metal organic skeleton out phase Fenton catalyst and application thereof | |
| CN105566400B (en) | Heterogeneous cobalt metal-organic framework and preparation and the application in field of waste water treatment | |
| CN105854900A (en) | Catalytic wet oxidation catalyst applied to harmless treatment of ammonia-nitrogen wastewater and preparation method thereof | |
| CN106423272A (en) | Supported titanium dioxide/graphene oxide pellets and preparation method and application thereof | |
| CN108996655A (en) | A kind of microwave-assisted Fe/Fe3The method of C@C quick catalysis degradation of organic waste water | |
| CN114832784A (en) | Phosphoric acid modified silicon dioxide microsphere and preparation method and application thereof | |
| CN110215921A (en) | A kind of preparation method and application of core-shell structure magnetic nano-composite catalyst | |
| CN106542581A (en) | A kind of preparation method of hollow Hemicentrotus seu Strongylocentrotuss shape manganese dioxide | |
| CN104549385A (en) | Graphene oxide composite FePO4 heterogeneous visible light Fenton catalyst and preparation method thereof | |
| CN110465293A (en) | The preparation method and application of magnetic visible light heterogeneous Fenton catalyst | |
| Zhou et al. | Removal of chromium from electroplating sludge by roasting-acid leaching and catalytic degradation of antibiotics by its residue | |
| CN103495398A (en) | Preparing method and application of carbon-supported magnetic fiber material with one-dimensional core-shell structure | |
| CN108940349A (en) | The method of carbonitride Z-type photochemical catalyst removal dyestuff contaminant is mixed using siliver chromate/sulphur | |
| CN108554458A (en) | Core/membranous type composite bismuth vanadium photocatalyst and preparation method thereof | |
| CN104998607A (en) | Chromium adsorbent and application thereof | |
| Liu et al. | Preparation and catalytic properties of Cu2O–CoO/Al2O3 composite coating prepared on aluminum plate by microarc oxidation | |
| CN107456993B (en) | A kind of preparation method of water process ozone catalyst and products thereof and application | |
| CN113816470B (en) | Cu/amorphous Al 2 O 3 Catalyst, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201016 Termination date: 20210703 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |