CN102974308B - Cellulose semipermeable membrane-coated nanometer Fe3O4 solid-phase extractant and its preparation method and use - Google Patents

Cellulose semipermeable membrane-coated nanometer Fe3O4 solid-phase extractant and its preparation method and use Download PDF

Info

Publication number
CN102974308B
CN102974308B CN201210468247.7A CN201210468247A CN102974308B CN 102974308 B CN102974308 B CN 102974308B CN 201210468247 A CN201210468247 A CN 201210468247A CN 102974308 B CN102974308 B CN 102974308B
Authority
CN
China
Prior art keywords
cellulose
surfactant
coated
fe3o4
solid
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.)
Active
Application number
CN201210468247.7A
Other languages
Chinese (zh)
Other versions
CN102974308A (en
Inventor
赵晓丽
吴丰昌
汤智
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chinese Research Academy of Environmental Sciences
Original Assignee
Chinese Research Academy of Environmental Sciences
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chinese Research Academy of Environmental Sciences filed Critical Chinese Research Academy of Environmental Sciences
Priority to CN201210468247.7A priority Critical patent/CN102974308B/en
Publication of CN102974308A publication Critical patent/CN102974308A/en
Application granted granted Critical
Publication of CN102974308B publication Critical patent/CN102974308B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses a cellulose semipermeable membrane-coated nanometer Fe3O4 solid-phase extractant and its preparation method and use. Surfaces of magnetic nanometer Fe3O4 particles are modified by a surfactant and then are coated with a cellulose semipermeable membrane so that the cellulose semipermeable membrane-coated nanometer Fe3O4 solid-phase extractant is obtained. The preparation method comprises the following steps of 1, preparing Fe3O4 magnetic nanometer particles by a coprecipitation method, 2, adding the surfactant in an aqueous solution of the Fe3O4 magnetic nanometer particles, wherein the surfactant is absorbed on the surfaces of the Fe3O4 magnetic nanometer particles by a self-assembling method, and 3, coating the cellulose semipermeable membrane on the surfaces of the Fe3O4 magnetic nanometer particles. The cellulose semipermeable membrane-coated nanometer Fe3O4 solid-phase extractant has the advantages of large adsorption capacity, fast extraction speed, simple preparation processes, good environmental benefits, strong anti-interference capability and high yield. In an applied magnetic field, the cellulose semipermeable membrane-coated nanometer Fe3O4 solid-phase extractant can be separated from a base solution conveniently.

Description

Cellulose pellicle clad nano iron oxide solid extracting agent and method for making and application
Technical field
The present invention relates to a kind of cellulose coated-surfactant modified-nano-sized iron oxide solid extracting agent.
Another object of the present invention is to provide a kind of method preparing above-mentioned solid phase extractant.
The invention still further relates to the application of above-mentioned solid phase extractant in separation and concentration natural water body in organic pollution.
Background technology
The background of the art and current situation are roughly as follows: quick and precisely effectively analyzing and measuring organic micro-pollutant in complex environment water sample is the difficult point of Environmental Analytical Chemistry.Because the composition of ambient water sample is extremely complicated, and the content of pollutant is usually extremely low, and therefore, the pre-treatment of ambient water sample just becomes requisite link in a complete analysis method.Solid phase extraction techniques is the pre-treating method of the ambient water sample be most widely used at present, and common solid-phase extraction column has C18 bonded silica gel, ketjenblack EC, Oasis HLB etc.All the time, loading capacity finite sum is vulnerable to the problem of natural organic matter interference is the bottleneck that restriction solid-phase extraction column is applied in the pre-treatment of natural surroundings water body example.Natural organic matter is extensively present in all surface ecosystems, dissolving natural organic matter in natural water body is heterogeneous mixture of a class formation complexity, molecular weight from hundreds of to millions of not etc., this kind of macromolecular substances is often adsorbed onto the surface of extractant, cause the blocking of filler aperture, post effect reduces, adsorption capacity declines, the extraction column lost of life, finally cause the severe jamming [1,2] that small molecule analysis is measured.Therefore, exploitation one is applicable to complex environment water body, and the solid extracting agent of the lake that particularly natural organic matter comparision contents is high, municipal sewage, hole organic pollutants separation and concentration is extremely urgent.
In recent years, the application of magnetic Nano material in SPE receives the concern of people, has a small amount of bibliographical information to be applied to the separation and concentration of organic pollution in large volume ambient water sample.Magnetic Nano Fe 3o 4both there is the high specific area of nano material and remarkable absorption property, its distinctive superparamagnetism can be deposited in case at externally-applied magnetic field simultaneously, be easy to realize water sample with bulk mass product Separation of Solid and Liquid, have the great potential [3,4] as a kind of excellent solid extracting agent application.Cellulose is natural polymer the abundantest on the earth, has unique character, as nontoxic, safety, biodegradability, biocompatibility, hydrophily, chemical stability and cheap.Cellulose pellicle can be used for isolating the large molecule such as protein, nucleic acid, humic acid in sample and some suspended particulate substances, and small molecule contaminants then freely can be extracted agent absorption [5,6] by pellicle.Softex kw (CTAB) plasma type surfactant is passed through the method for self assembly to magnetic Nano Fe 3o 4carry out finishing, the novel extraction technology set up based on this kind of self-assembly system is verified has stronger extracting power to Some Organic Pollutants in environment.On this basis, to the magnetic Nano Fe that ionic surfactant is modified 3o 4carry out coated, form hydrophilic pellicle, not only can keep the extracting power that it is strong to organic pollution, the macromolecule contaminant such as humic acid can also to be eliminated in complex environment water sample to the interference of extracting and enriching by pellicle.
The document of relevant background technology part can be see:
[1].H.C.H. W.H.J.Vaes，A.P.Freidig，B.H. J.L.M.Hermens，Influence of pH and other modifying factors on the distributionbehavior of 4-Quinolones to solid phases and humic acids studied by“negligible-depletion”SPME-HPLC.Environ.Sci.Technol.2000，34，4989-4994.
[2].J.F.Peng，J.F.Liu，X.L.Hu，G.B.Jiang，Direct determination ofchlorophenols in environmental water samples by hollow fiber supported ionicliquid membrane extraction coupled with high-performance liquidchromatography.J.ChromatogrA.2007，1139，165-170.
[3].X.L.Zhao，Y.L.Shi，T.Wang，Y.Q.Cai，G.B.Jiang，Preparation ofsilica-magnetite nanoparticle mixed hemimicelle sorbents for extraction ofseveral typical phenolic compounds from environmental water samples.J.ChromatogrA，2008，1188，140-147.
[4].X.L.Zhao，Y.L.Shi，Y.Q.Cai，S.F.Mou.Cetyltrimethylammoniumbromide-coated magnetic nanoparticles for the pre-concentration of phenoliccompounds from environmental water samples.Environ.Sci.Technol.2008，42：1201-1206.
[5].B.Fugetsu，S.Satoh，T.Shiba，T.Mizutani，Y.B.Lin，N.Terui，Y.Nodasaka，K.Sasa，K.Shimizu，T. Akasaka，M.Shmdoh，K.Shibata，A.Yokoyama，Multiwalled carbon nanotubes as the adsorbents for affinity-basedelimination of ionic dyes.Environ.Sci.Technol.，2004，38，6890-6896.
[6].X.L.Zhang，H.Y.Niu，Y.Y.Pan，Y.L.Shi，Y.Q.Cai，Chitosan-coated octadecyl-functionalized magnetite nanoparticles：Preparationand application in extraction of trace pollutants from environmental watersamples.Anal.Chem.，2010，82(6)，2363-2371
Summary of the invention
The object of the present invention is to provide a kind of cellulose pellicle clad nano iron oxide solid extracting agent.
Another object of the present invention is the preparation method providing above-mentioned solid phase extractant.
For achieving the above object, cellulose pellicle clad nano iron oxide solid extracting agent provided by the invention is at magnetic Nano Fe 3o 4carry out the coated of cellulose membrane again after the finishing upper surface activating agent of particle, obtained by following method:
1) coprecipitation generates Fe 3o 4magnetic nanoparticle;
2) at Fe 3o 4add surfactant in the aqueous solution of magnetic nanoparticle, surfactant is adsorbed onto magnetic Nano Fe by the method for self assembly 3o 4the surface of magnetic nanoparticle;
3) at Fe 3o 4surface coating one deck cellulose pellicle of magnetic nanoparticle.
Described cellulose pellicle clad nano iron oxide solid extracting agent, wherein, magnetic Nano Fe 3o 4the particle diameter of particle is 10nm.
The preparation method of described cellulose pellicle clad nano iron oxide solid extracting agent, its key step is: 1) coprecipitation generates Fe 3o 4magnetic nanoparticle; 2) at Fe 3o 4add surfactant in the aqueous solution of magnetic nanoparticle, surfactant is adsorbed onto magnetic Nano Fe by the method for self assembly 3o 4the surface of magnetic nanoparticle; 3) at Fe 3o 4surface coating one deck cellulose pellicle of magnetic nanoparticle.
Described preparation method, wherein, utilizes externally-applied magnetic field that coprecipitation is generated Fe 3o 4magnetic nanoparticle is separated from reaction medium.
Described preparation method, wherein, surfactant is one or more of cationic surfactant cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC) and chlorination dococylpyridinium (DPC).
Described preparation method, wherein, coated cellulose pellicle is carboxymethyl cellulose, hydroxypropyl methylcellulose, hydroxyethylcellulose or methylcellulose.
Cellulose pellicle clad nano iron oxide solid extracting agent provided by the invention is applicable to the high complex environment Organic Pollutants In Water separation and concentration of humic acid content.
Compared with the known solid extracting agent for organic pollution in environment water, the coated magnetic nano solid extracting agent of cellulose pellicle provided by the invention has the following advantages:
1, antijamming capability is strong, the rate of recovery is high: cellulose pellicle can the large molecule such as humic acid, protein in isolation environment water sample and some suspended particulate substances, overcome the problem that solid extracting agent ubiquitous extraction yield when complex environment water samples such as pre-treatment sewage, lake water, pore waters is low, the rate of recovery declines.
2, adsorption capacity is high, and rate of extraction is fast: the solid extracting agent particle diameter generally used at present is generally micron order, and specific area is little, adsorption capacity is lower.Because the particle diameter of this new material is about 10nm, specific area is large, and consumption is few, and adsorption capacity is large; Because nano material particle diameter is little, absorption path is short, therefore the speed of liquid-solid equilibria is fast; Simultaneously because this material has good superparamagnetism, therefore only use the high-intensity magnetic field that additional, just can realize solid extracting agent easily and be separated with sample is quick and complete.
3, prepare simple, environmental friendliness: do not need complicated course of reaction in preparation process, special installation and harsh reaction condition, operation is simple, favorable reproducibility, and extractant can repeatedly use, and stability is high; Overcome the shortcoming that common solid phase extraction needs to consume a large amount of organic solvents, only use the surfactant of seldom amount, cellulose pellicle nontoxic, environmental friendliness.
4, with low cost, applied widely: the primary raw material used in preparation process is carboxymethyl cellulose, FeCl 36H 2o, FeCl 24H 2o and surfactant, cheap, it is convenient to buy; The kind of ionic surfactant is more, can according to the feature of analyte, by regulating kind and the concentration of solution ph and surfactant, controls its self assembly behavior at oxide surface easily.
Accompanying drawing explanation
Fig. 1 is the coated magnetic nano solid extracting agent structural representation of cellulose pellicle of the present invention.
Detailed description of the invention
Solid extracting agent of the present invention gets both that magnetic Nano material specific area is large, loading capacity is large and magnetic material is easy to the advantage of Magnetic Isolation, the interference performance of the macromolecular substances such as the anti-natural organic matter of the coated rear raising material of cellulose pellicle.
Referring to Fig. 1, is the coated magnetic nano solid extracting agent structural representation of employing carboxymethyl cellulose film of the present invention.1. Fe in figure 3o 4magnetic nanoparticle, 2. cellulose pellicle, 3. surfactant modified, 4. natural organic matter; 5. analyte.As can be seen from the figure, micromolecular analyte 1 can pass cellulose pellicle, is adsorbed onto the Fe of magnetic Nano extractant 3o 4magnetic nanoparticle surface, humic acid, high molecular weight protein 2 etc. then cannot pass cellulose pellicle, can not produce interference to solid extracting agent.
Preparation process of the present invention is:
The magnetic Nano Fe first adopting the method for co-precipitation to prepare particle diameter to be about 10nm 3o 4, cationic surface active agent (CTAB, CPC, DPC) is adsorbed onto magnetic Nano Fe by the method for self assembly 3o 4surface, stronger adsorption capacity is possessed to the hydrophobic organic pollutant in water body, again by method cellulose pellicle on material surface is coated of polymerization, by the thickness regulating cellulose polymeric reaction condition to regulate pellicle, micromolecular organic pollution is enable to pass rapidly through cellulose pellicle, be adsorbed onto the surface of extractant, reach adsorption equilibrium, and humic acid, the large molecule such as protein can not pass cellulose pellicle, thus avoid the aperture blocking that macromolecular material causes in complex environment water body, the problems such as adsorption capacity reduction and shortening in service life.
A concrete example is:
1) Fe 3o 4the preparation of Magnetic nano iron core: by 2.0g FeCl 3.6H 2o and 5.2g FeCl 2.4H 2o and 0.85mL concentrated hydrochloric acid is dissolved in 25mL in advance through N 2in degassed deionized water solution, warming-in-water to 80 DEG C; Under mechanical stirring, above dropwise is joined in the 250mL1.5mol/L NaOH aqueous solution, along with the carrying out of reaction, black precipitate is engendered in reactant liquor, after reaction terminates, utilize externally-applied magnetic field all precipitations to be separated from reaction medium, after repeatedly cleaning by deionized water, be kept in alkaline aqueous solution.
2) SURFACTANT ADSORPTION is self-assembled modified: get 0.5g Fe 3o 4magnetic nanoparticle, add in 100mL deionized water, regulate solution ph to 9.0, add 250mg cationicsurfactants (cetrimonium bromide), ultrasonic 5min, after leaving standstill 20min, surfactant forms hydrophobic micella by the method for self assembly at particle surface.
3) cellulose pellicle is coated: by the surfactant modified magnetic Nano Fe obtained 3o 4it is in the deionized water solution of 0.6mg/L that particle joins 250mL carboxymethyl cellulose concentration, solution ph is regulated to be 6.0 with HCl, add 2.0mL polyvinyl alcohol and 5mL glycerine, react 60min at water-bath 60 DEG C, can obtain particle diameter is coated, the surfactant modified Fe of about 10nm, cellulose pellicle 3o 4solid extracting agent, this extractant can be used for the separation and concentration of the complex environment Organic Pollutants In Water of high natural organic matter content.
What needs further illustrated is, under above-mentioned example the same terms, cationic surfactant in above-mentioned example can be replaced with cetylpyridinium chloride (CPC), chlorination dococylpyridinium (DPC) etc., coated cellulose pellicle replaces with hydroxypropyl methylcellulose, hydroxyethylcellulose, methylcellulose etc., all can obtain identical effect.
Test case
The property indices of the magnetic nano solid extracting agent that cellulose of the present invention is coated, through repeatedly testing, has good stability.
Have selected the representative that bisphenol-A (BPA), nonyl phenol (4-OP), octyl phenol (4-NP) etc. are hydrophobic contaminant, using perfluorochemicals such as perfluoro-heptanoic acid (PFHeA), perfluoro caprylic acid (PFOA), PFOS (PFOS), perfluoro-pelargonic acid (PFNA) and perfluoro decanoates (PFDeA) as the representative of amphiphilic pollutant simultaneously.Investigate the extracting power of extractant to two class organic pollutions above-mentioned in Taihu Lake lake water sample, Qinghe, Beijing water sample and deposit interstitial water sample.For the solid extracting agent only using 50mg in the water sample of 500mL, the extraction yield for this several organic pollution all can reach more than 90%, and the scope of recovery of standard addition is reappearance RSD≤7% of 83%-105%, analysis result.The pH value condition that SPE is suitable for is neutral, humic acid is little for the impact of extractant extraction yield and the rate of recovery, when the concentration of humic acid reaches 100mg/L (in usual natural water body, the content of humic acid is 0-50mg/L), extraction yield declines and is no more than 5%.Under the effect of externally-applied magnetic field, extractant can realize being separated completely with ambient water sample in 5min.

Claims (4)

1. a cellulose pellicle clad nano iron oxide solid extracting agent is at magnetic Nano Fe 3o 4carry out the coated of cellulose pellicle again after the finishing upper surface activating agent of particle, obtained by following method:
1) Fe 3o 4the preparation of Magnetic nano iron core: by 2.0g FeCl 36H 2o and 5.2g FeCl 24H 2o and 0.85mL concentrated hydrochloric acid is dissolved in 25mL in advance through N 2in degassed deionized water solution, warming-in-water to 80 DEG C; Under mechanical stirring, above dropwise is joined in the 250mL 1.5mol/L NaOH aqueous solution, along with the carrying out of reaction, black precipitate is engendered in reactant liquor, after reaction terminates, utilize externally-applied magnetic field all precipitations to be separated from reaction medium, after repeatedly cleaning by deionized water, be kept in alkaline aqueous solution;
2) SURFACTANT ADSORPTION is self-assembled modified: get 0.5g Fe 3o 4magnetic nanoparticle, adds in 100mL deionized water, and regulate solution pH value to 9.0, add 250mg cationic surfactant, ultrasonic 5min, after leaving standstill 20min, surfactant forms hydrophobic micella by the method for self assembly at particle surface; Described cationic surfactant is the one in cetyltrimethylammonium base amine, cetylpyridinium chloride, chlorination dococylpyridinium;
3) cellulose pellicle is coated: by the surfactant modified magnetic Nano Fe obtained 3o 4it is in the deionized water solution of 0.6mg/L that particle joins 250mL cellulose concentration, solution pH value is regulated to be 6.0 with HCl, add 2.0mL polyvinyl alcohol and 5mL glycerine, react 60min at water-bath 60 DEG C, obtaining particle diameter is coated, the surfactant modified Fe of 10nm, cellulose pellicle 3o 4solid extracting agent; Described cellulose is the one in carboxymethyl cellulose, hydroxypropyl methylcellulose, hydroxyethylcellulose, methylcellulose.
2. the preparation method of cellulose pellicle clad nano iron oxide solid extracting agent described in claim 1, its key step is:
1) Fe 3o 4the preparation of Magnetic nano iron core: by 2.0g FeCl 36H 2o and 5.2g FeCl 24H 2o and 0.85mL concentrated hydrochloric acid is dissolved in 25mL in advance through N 2in degassed deionized water solution, warming-in-water to 80 DEG C; Under mechanical stirring, above dropwise is joined in the 250mL1.5mol/L NaOH aqueous solution, along with the carrying out of reaction, black precipitate is engendered in reactant liquor, after reaction terminates, utilize externally-applied magnetic field all precipitations to be separated from reaction medium, after repeatedly cleaning by deionized water, be kept in alkaline aqueous solution;
2) SURFACTANT ADSORPTION is self-assembled modified: get 0.5g Fe 3o 4magnetic nanoparticle, adds in 100mL deionized water, and regulate solution pH value to 9.0, add 250mg cationic surfactant, ultrasonic 5min, after leaving standstill 20min, surfactant forms hydrophobic micella by the method for self assembly at particle surface; Described cationic surfactant is the one in cetyltrimethylammonium base amine, cetylpyridinium chloride, chlorination dococylpyridinium;
3) cellulose pellicle is coated: by the surfactant modified magnetic Nano Fe obtained 3o 4it is in the deionized water solution of 0.6mg/L that particle joins 250mL cellulose concentration, solution pH value is regulated to be 6.0 with HCl, add 2.0mL polyvinyl alcohol and 5mL glycerine, react 60min at water-bath 60 DEG C, obtaining particle diameter is coated, the surfactant modified Fe of 10nm, cellulose pellicle 3o 4solid extracting agent; Described cellulose is the one in carboxymethyl cellulose, hydroxypropyl methylcellulose, hydroxyethylcellulose, methylcellulose.
3. the application of cellulose pellicle clad nano iron oxide solid extracting agent organic pollution in separation and concentration natural water body described in claim 1.
4. application according to claim 3, wherein, realizes the Separation of Solid and Liquid in water body under the effect of externally-applied magnetic field.
CN201210468247.7A 2012-11-19 2012-11-19 Cellulose semipermeable membrane-coated nanometer Fe3O4 solid-phase extractant and its preparation method and use Active CN102974308B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210468247.7A CN102974308B (en) 2012-11-19 2012-11-19 Cellulose semipermeable membrane-coated nanometer Fe3O4 solid-phase extractant and its preparation method and use

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210468247.7A CN102974308B (en) 2012-11-19 2012-11-19 Cellulose semipermeable membrane-coated nanometer Fe3O4 solid-phase extractant and its preparation method and use

Publications (2)

Publication Number Publication Date
CN102974308A CN102974308A (en) 2013-03-20
CN102974308B true CN102974308B (en) 2015-02-11

Family

ID=47848825

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210468247.7A Active CN102974308B (en) 2012-11-19 2012-11-19 Cellulose semipermeable membrane-coated nanometer Fe3O4 solid-phase extractant and its preparation method and use

Country Status (1)

Country Link
CN (1) CN102974308B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103289445B (en) * 2013-05-23 2014-11-19 铜陵瑞莱科技有限公司 Method for preparing high-temperature-resistant iron oxide black granules
CN103674618B (en) * 2013-12-13 2016-06-01 中国环境科学研究院 Surfactant modified nano-TiO2Semi-permeable membranes water sample pre-treating process
CN104587986A (en) * 2014-12-17 2015-05-06 华南理工大学 Magnetic nano mixed semi micelle and preparation method thereof as well as application of magnetic nano mixed semi micelle in adsorbing and separating cationic dye from environmental water sample
CN105032380B (en) * 2015-08-03 2017-05-24 中国环境科学研究院 Preparation and application of endohedral triolein multi-vesicle magnetic nanoparticles

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101130157A (en) * 2007-07-19 2008-02-27 中国科学院生态环境研究中心 Preparation of mixed glue nucleus solitarius shell-type fe3o4 nano solid phase extractive agent and application of the same
CN101485973B (en) * 2009-01-07 2011-05-18 中国科学院生态环境研究中心 Preparation and application of alginic acid polymer coated Fe3O4@C18 magnetic nano solid phase extractive agent
CN101574645B (en) * 2009-06-05 2011-08-31 中国科学院生态环境研究中心 Magnetic nano-material extractant and preparation method thereof

Also Published As

Publication number Publication date
CN102974308A (en) 2013-03-20

Similar Documents

Publication Publication Date Title
Xie et al. Novel magnetic multi-templates molecularly imprinted polymer for selective and rapid removal and detection of alkylphenols in water
Huang et al. Application of molecularly imprinted polymers in wastewater treatment: a review
Ren et al. Magnetic covalent triazine-based frameworks as magnetic solid-phase extraction adsorbents for sensitive determination of perfluorinated compounds in environmental water samples
Liu et al. Nanomaterials for analysis and monitoring of emerging chemical pollutants
Yang et al. Magnetic solid phase extraction of brominated flame retardants and pentachlorophenol from environmental waters with carbon doped Fe3O4 nanoparticles
Lu et al. Flow injection chemiluminescence sensor based on core–shell magnetic molecularly imprinted nanoparticles for determination of chrysoidine in food samples
Huang et al. Study and comparison of polydopamine and its derived carbon decorated nanoparticles in the magnetic solid-phase extraction of estrogens
CN102974308B (en) Cellulose semipermeable membrane-coated nanometer Fe3O4 solid-phase extractant and its preparation method and use
Zhou et al. Magnetic solid phase extraction of bisphenol A, phenol and hydroquinone from water samples by magnetic and thermo dual-responsive core-shell nanomaterial
Nekouei et al. Mixed cloud point/solid phase extraction of lead (II) and cadmium (II) in water samples using modified-ZnO nanopowders
Zhang et al. Synthesis and properties of magnetic molecularly imprinted polymers based on multiwalled carbon nanotubes for magnetic extraction of bisphenol A from water
Ahmad et al. Separation and preconcentration of Pb (II) and Cd (II) from aqueous samples using hyperbranched polyethyleneimine-functionalized graphene oxide-immobilized polystyrene spherical adsorbents
Jakavula et al. A critical review on the synthesis and application of ion-imprinted polymers for selective preconcentration, speciation, removal and determination of trace and essential metals from different matrices
Liao et al. Low pressure operated ultrafiltration membrane with integration of hollow mesoporous carbon nanospheres for effective removal of micropollutants
Bhogal et al. Dual-template magnetic molecularly imprinted polymer-based sorbent for simultaneous and selective detection of phenolic endocrine disrupting compounds in foodstuffs
CN107632077B (en) Method for quantifying micro-plastic in landfill leachate
Yin et al. Graphene oxide functionalized magnetic nanoparticles as adsorbents for removal of phthalate esters
Kakhki Application of magnetic nanoparticles modified with cyclodextrins as efficient adsorbents in separation systems
Xue et al. Rapid detection of orange II dyes in water with SERS imprinted sensor based on PDA-modified MOFs@ Ag
Ge et al. Polypropylene membrane coated with carbon nanotubes functionalized with chitosan: Application in the microextraction of polychlorinated biphenyls and polybrominated diphenyl ethers from environmental water samples
Djerahov et al. Self-standing chitosan film loaded with silver nanoparticles as a tool for selective determination of Cr (VI) by ICP-MS
Beryani et al. Exploring the potential of graphene oxide nanosheets for porous media decontamination from cationic dyes
Lu et al. Highly fluorinated magnetic covalent organic framework for efficient adsorption and sensitive detection of microcystin toxin in aqueous samples
Huang et al. Ionic liquid assisted in situ growth of nano-confined ionic liquids/metal-organic frameworks nanocomposites for monolithic capillary microextraction of microcystins in environmental waters
Gong et al. Simultaneous removal of atrazine and heavy metal ions using sulfonated polymeric microspheres through an adsorptive filtration process: Insights into the synergistic and competitive adsorption

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CB03 Change of inventor or designer information

Inventor after: Zhao Xiaoli

Inventor after: Wu Fengchang

Inventor after: Tang Zhi

Inventor after: Dang Zhi

Inventor after: Hu Qing

Inventor before: Zhao Xiaoli

Inventor before: Wu Fengchang

Inventor before: Tang Zhi

CB03 Change of inventor or designer information