CN105645392B - A kind of preparation method and application of amination graphene - Google Patents

A kind of preparation method and application of amination graphene Download PDF

Info

Publication number
CN105645392B
CN105645392B CN201610012813.1A CN201610012813A CN105645392B CN 105645392 B CN105645392 B CN 105645392B CN 201610012813 A CN201610012813 A CN 201610012813A CN 105645392 B CN105645392 B CN 105645392B
Authority
CN
China
Prior art keywords
graphene
amination
preparation
amination graphene
dicyclohexylcarbodiimide
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.)
Expired - Fee Related
Application number
CN201610012813.1A
Other languages
Chinese (zh)
Other versions
CN105645392A (en
Inventor
王方
卢妙杰
王中良
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.)
Tianjin Normal University
Original Assignee
Tianjin Normal University
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 Tianjin Normal University filed Critical Tianjin Normal University
Priority to CN201610012813.1A priority Critical patent/CN105645392B/en
Publication of CN105645392A publication Critical patent/CN105645392A/en
Application granted granted Critical
Publication of CN105645392B publication Critical patent/CN105645392B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/02—Single layer graphene
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Sorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a kind of preparation method of amination graphene, belong to environment functional material field, and in particular to a kind of preparation method and application of amination graphene.Graphene oxide powder is dissolved in dimethyl formamide solution, is separately added into ethylenediamine and N, the tetrahydrofuran solution of N ' dicyclohexylcarbodiimides, reaction obtains the ammonia amination graphene of monatomic lamellar structure.Preparation method of the present invention is simple；It is gentle to prepare reaction, it is safe；The amination graphene being prepared is monatomic lamellar structure, and amination degree is high, and nitrogen content is higher than other preparation methods in product, is conducive to the absorption of heavy metal ions in wastewater, has good application prospect in terms of heavy metal wastewater thereby is handled.

Description

A kind of preparation method and application of amination graphene
The application obtains Tianjin institution of higher education " innovation team's training plan "（TD12-5037）Won with Tianjin Normal University Scholar's fund（52XB1403）Subsidy.
Technical field
The invention belongs to environment functional material field, and in particular to a kind of preparation method of amination graphene and its handle Application in heavy metal containing sewage.
Background technology
Graphene has received significant attention since 2004 are found because of the electricity and mechanical property of its protrusion.Due to Graphene has unique monatomic lamellar structure, its specific surface area is huge, therefore has to the pollutant in water environment very strong Adsorption capacity.However, graphene is easily reunited in aqueous, it is unfavorable for absorption of the pollutant on its surface, and work( Can graphite alkene（Such as graphene oxide, amination graphene etc.）Surface there is the functional group such as carboxyl, hydroxyl, amino, make Its surface hydrophilicity strengthens, and substantially increases its dispersiveness in aqueous, can effectively adsorb the pollutant in water environment. It is stronger with the interaction of heavy metal ion since with heavy metal ion complexing can occur for amino, therefore compared to other Functionalization graphene, amination graphene are stronger to the absorption property of Heavy Metals in Water Environment ion.The amino of synthesized high-performance Graphite alkene is of great significance for the heavy metal pollution in processing water environment.
In existing research, the method for modified acquisition amination graphene is various.If patent 201410339486 is by third Dicyan is directly grafted on surface of graphene oxide, and amination graphene is obtained by reduction.Patent 201210569837 is using electricity Solution, amination graphene is prepared using graphene oxide and ammonium hydroxide as raw material.Patent 201410124106 by graphene oxide, Dimethylformamide, organic amine and Dicyclohexylcarbodiimide prepare a kind of amino modified oxidation stone after mixing is ultrasonically treated The black compound forward osmosis membrane of alkene.However, the most process of these methods is complicated at present, to the operation requirement in preparation process and environment bar Part is more demanding, and products therefrom cannot ensure as monatomic lamellar structure.For this reason, the present invention proposes that one kind prepares monatomic The method of Rotating fields amination graphene.This method is easy to operate, and reaction is gentle, and low to temperature requirement, environmental pollution is small, solves High requests of the other methods to operating environment and equipment, and ensure that the monatomic lamellar structure and high nitrogen content of product. Amination graphene prepared by this method goes heavy metal ion efficiency in water removal to significantly improve.
The content of the invention
It is an object of the invention to provide a kind of amination graphene preparation method and be applied in waste water a huge sum of money Belong to the removal of ion.
The most process of existing amination graphene preparation method is complicated at present, to the operation requirement in preparation process and ring Border condition is more demanding, and products therefrom cannot ensure as monatomic lamellar structure.For this reason, the present invention proposes that one kind prepares single original The method of sub-pieces Rotating fields amination graphene, its feature comprise the following steps：
（1）It is 1 to take mass ratio:15~1:300 graphene oxide powder and dimethylformamide, being uniformly mixed makes its shape Into stable suspension；
（2）By tetrahydrofuran and N, N '-dicyclohexylcarbodiimide is with mass ratio 5:1~10:1 mixing, stirs evenly；
（3）In step（1）In the suspension of preparation, add and N, N '-dicyclohexylcarbodiimide equal mass second two Amine and step 2）The tetrahydrofuran solution of the N of preparation, N '-dicyclohexylcarbodiimide, stirs 3 ~ 5 d, filters, that is, completes oxidation The amination of graphene；
（4）By step（3）The amination graphene of gained is respectively washed repeatedly with methanol and distilled water, to go division operation mistake Residual organic matter in journey；
（5）In step（4）Appropriate ultra-pure water is added in the amination graphene of middle acquisition, water bath sonicator is allowed to scattered equal It is even；
（6）By step（5）Middle gained amination graphene colloidal solution freeze-drying, up to the ammonia of monatomic lamellar structure Base graphite alkene.Step（1）With（2）In, the uniformly mixed method is the method using water bath sonicator, and the time is 15~20 min.In step（3）In, the ethylenediamine, N, the mass ratio of N '-dicyclohexylcarbodiimide and graphene oxide is 10:10:1 ~40:40:1.In step（3）In, the stirring means are magnetic stirrer, are carried out at room temperature；During the suction filtration Use the organic phase filter membrane that filter membrane is 0.22 μm.In step（4）In, the cleaning method is according to distilled water after first methanol Order is cleaned, and is at least cleaned 4 times with every kind of solvent, it is ensured that residual organic matter all cleans up；Step（5）In, water bath sonicator For temperature no more than 50 oC, the time is the h of 2 h~4.
The preparation method of amination graphene of the present invention, graphene oxide powder used are mono-layer graphite oxide Alkene.
The present invention further discloses application of the amination graphene in terms of heavy metal ions in wastewater is adsorbed of preparation； The heavy metal ion refers to Cu2+、Cd2+、Pb2+、Zn2+Deng.The results show：Amino graphite prepared by the present invention Alkene has significant effect in terms of heavy metal ions in wastewater is adsorbed, particularly amination graphene Adsorption of Cu2+Ability on compare Regular oxidation graphene improves about 2 times.
More detailed description of the present invention is as follows：
（1）It is 1 to take mass ratio:15、1:50、1:100、1:300 graphene oxide powder and dimethylformamide, mixing Uniformly form it into stable suspension；
（2）By tetrahydrofuran and N, N '-dicyclohexylcarbodiimide is with mass ratio 5:1、7:1、8:1、10:1 mixing, stirring Uniformly；
（3）In step（1）In the suspension of preparation, add and N, N '-dicyclohexylcarbodiimide equal mass second two Amine and step 2）The tetrahydrofuran solution of the N of preparation, N '-dicyclohexylcarbodiimide, stirs 3 d, filters, that is, completes oxidation stone The amination of black alkene；
（4）By step（3）The amination graphene of gained is respectively washed repeatedly with methanol and distilled water, to go division operation mistake Residual organic matter in journey；
（5）In step（4）Appropriate ultra-pure water is added in the amination graphene of middle acquisition, water bath sonicator is allowed to scattered equal It is even；
（6）By step（5）Middle gained amination graphene colloidal solution freeze-drying, up to the ammonia of monatomic lamellar structure Base graphite alkene.
In a preferred embodiment of the present invention, it is characterised in that step（1）With（2）In, it is described uniformly mixed Method is that the time is 20 min using the method for ultrasound.
In a preferred embodiment of the present invention, it is characterised in that step（3）In, the ethylenediamine, N, the rings of N '-two The mass ratio of hexyl carbodiimide and graphene oxide is 20:20:1；The stirring is magnetic stirrer, and room temperature carries out； It is described to filter using organic filter membrane that filter membrane is 0.22 μm.
In a preferred embodiment of the present invention, it is characterised in that step（4）In, the method for the cleaning be according to The order cleaning of distilled water, is at least cleaned 4 times with every kind of solvent after first methanol.Purpose is the residual removed during previous action Organic matter.
In a preferred embodiment of the present invention, it is characterised in that step（5）In, the temperature of the water-bath is no more than 50 oC, time are 2 h.
In a preferred embodiment of the present invention, it is characterised in that step（6）In, the freeze-drying time is 3 d.
In a preferred embodiment of the present invention, it is characterised in that graphene oxide powder used is selected mono-layer oxidized Graphene.
Compared with prior art, the present invention has the following advantages：
（1）Operating procedure of the present invention is simple, and reaction is gentle, can complete to react under room temperature, it is not necessary to which higher is anti- Temperature is answered, safe and environmental pollution is small；
（2）Pass through x-ray photoelectron（XPS）Profiling results know that the nitrogen content of amination graphene greatly improves, and add The form of nitrogen is more to be existed with amino state.
（3）Pass through high power transmission electron microscope（TEM）Collection of illustrative plates understands that the product of acquisition is monatomic laminated structure, tool There is more preferable dispersiveness, be conducive to the absorption of Pollutants in Wastewater.
（4）For the copper ion in waste water, amination graphene is greatly improved than the adsorption capacity of native oxide graphene, Removal available for heavy metal ions in wastewater.
Brief description of the drawings
Fig. 1 is the x-ray photoelectron of amination graphene and graphene oxide（XPS）Collection of illustrative plates；
Fig. 2 is the infrared of amination graphene and graphene oxide（FTIR）Collection of illustrative plates；
Fig. 3 is the transmission electron microscope of amination graphene and graphene oxide（TEM）Collection of illustrative plates；
Fig. 4 is adsorption isotherm of the copper ion in amination graphene and graphene oxide.
Specific embodiment
With reference to specific embodiment, the present invention is further explained.It is to be understood that these embodiments are merely to illustrate the present invention Rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art Member can make the present invention various changes or modification, and such equivalent forms equally fall within the application the appended claims and limited Scope.The chemical reagent such as wherein used graphene oxide powder, dimethylformamide, ethylenediamine are commercially available.
Embodiment 1
（1）0.1 g graphene oxide powders are dissolved in 1.6 mL dimethylformamides, stirs evenly and forms it into stabilization Suspension；
（2）By 11 mL tetrahydrofurans and the N of 1.6 mL, N '-dicyclohexylcarbodiimide mixing, stirs evenly；
（3）In step 1）In the suspension of preparation, 2.2 mL ethylenediamines and step 2 are added）The N of preparation, N '-dicyclohexyl The tetrahydrofuran solution of carbodiimide, stirs 3 d, filters, up to amination graphene；
（4）By step（3）The amination graphene of gained is respectively washed several times with methanol and distilled water, to go division operation During residual organic matter；
（5）To step（4）Appropriate ultra-pure water, 20 min of water bath sonicator are added in the amination graphene of middle acquisition；
（6）By step（5）Middle gained amination graphene freeze-drying, obtains the amino graphite of monatomic lamellar structure Alkene.
Embodiment 2
（1）0.1 g graphene oxide powders are dissolved in 5.2 mL dimethylformamides, stirs evenly and forms it into stabilization Suspension；
（2）By 15.7 mL tetrahydrofurans and the N of 1.6 mL, N '-dicyclohexylcarbodiimide mixing, stirs evenly；
（3）In step 1）In the suspension of preparation, 2.2 mL ethylenediamines and step 2 are added）The N of preparation, N '-dicyclohexyl The tetrahydrofuran solution of carbodiimide, stirs 3 d, filters, up to amination graphene；
（4）By step（3）The amination graphene of gained is respectively washed several times with methanol and distilled water, to go division operation During residual organic matter；
（5）To step（4）Appropriate ultra-pure water, 20 min of water bath sonicator are added in the amination graphene of middle acquisition；
（6）By step（5）Middle gained amination graphene freeze-drying, obtains the amino graphite of monatomic lamellar structure Alkene.
Embodiment 3
（1）0.1 g graphene oxide powders are dissolved in 10 mL dimethylformamides, stirs evenly and forms it into stabilization Suspension；
（2）By 18 mL tetrahydrofurans and the N of 1.5 mL, N '-dicyclohexylcarbodiimide mixing, stirs evenly；
（3）In step 1）In the suspension of preparation, 2.2 mL ethylenediamines and step 2 are added）The N of preparation, N '-dicyclohexyl The tetrahydrofuran solution of carbodiimide, stirs 3 d, filters, up to amination graphene；
（4）By step（3）The amination graphene of gained is respectively washed several times with methanol and distilled water, to go division operation During residual organic matter；
（5）To step（4）Appropriate ultra-pure water, 20 min of water bath sonicator are added in the amination graphene of middle acquisition；
（6）By step（5）Middle gained amination graphene freeze-drying, obtains the amino graphite of monatomic lamellar structure Alkene.
Embodiment 4
（1）0.1 g graphene oxide powders are dissolved in 32 mL dimethylformamides, stirs evenly and forms it into stabilization Suspension；
（2）By 22.5 mL tetrahydrofurans and the N of 1.7 mL, N '-dicyclohexylcarbodiimide mixing, stirs evenly；
（3）In step 1）In the suspension of preparation, 2.2 mL ethylenediamines and step 2 are added）The N of preparation, N '-dicyclohexyl The tetrahydrofuran solution of carbodiimide, stirs 3 d, filters, up to amination graphene；
（4）By step（3）The amination graphene of gained is respectively washed several times with methanol and distilled water, to go division operation During residual organic matter；
（5）To step（4）Appropriate ultra-pure water, 20 min of water bath sonicator are added in the amination graphene of middle acquisition；
（6）By step（5）Middle gained amination graphene freeze-drying, obtains the amino graphite of monatomic lamellar structure Alkene.
Embodiment 5
Application Example
Amination graphene greatly improves the adsorption capacity of heavy metal ion than native oxide graphene, available for waste water The removal of middle bivalent cupric ion.
It is 20 ml to take volume, and the copper ion of 4,8,12,22,50 mg/L of initial concentration, adds HCl/NaOH to adjust pH value For 5.4, each sample adds 10 mg of amination graphene/graphene oxide prepared by embodiment 3.By reaction bulb as rotation Amination graphene/graphene oxide is separated with aqueous solution after being reacted 3 days in mixer, is completed to Cu in aqueous solution2+Suction Attached processing.Residue Cu in solution2+Concentration use inductively coupled plasma atomic emission spectrometry instrument（ICP-OES）It is measured, The adsorption isotherm being calculated is shown in Fig. 4.
Conclusion：
（1）Cu2+In low concentration（4 mg/L）When, the adsorption isothermequation in amination grapheneK dFor 15000, and in oxygen Adsorption isothermequation on graphite alkeneK dFor 32000.
（2）Cu2+In high concentration（50 mg/L）When, the adsorption isothermequation in amination grapheneK dFor 6600, and in oxygen Adsorption isothermequation on graphite alkeneK dFor 3500.
（3）Adsorption of Cu in amination graphene2+Ability improve about 2 times than graphene oxide.
The above is only the preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-described embodiment, With various process programs of the present inventive concept without substantial differences in protection scope of the present invention.

Claims (2)

  1. A kind of 1. application of amination graphene in terms of heavy metal ions in wastewater is adsorbed；The heavy metal ion refers to Cu2+、Cd2+、Pb2+、Zn2+；The preparation method of the amination graphene is：
    （1）It is 1 to take mass ratio:15 ~ 300 graphene oxide powder and dimethylformamide, is uniformly mixed and forms it into stabilization Suspension；
    （2）By tetrahydrofuran and N, N '-dicyclohexylcarbodiimide is with mass ratio 5:1~10:1 mixing, stirs evenly；
    （3）In step（1）In the suspension of preparation, add and N, N '-dicyclohexylcarbodiimide equal mass ethylenediamine and Step（2）The tetrahydrofuran solution of the N of preparation, N '-dicyclohexylcarbodiimide, stirs 3 ~ 5 d, filters, that is, completes oxidation stone The amination of black alkene；
    （4）By step（3）The amination graphene of gained is respectively washed repeatedly with methanol and distilled water, to remove in operating process Residual organic matter；
    （5）In step（4）Appropriate ultra-pure water is added in the amination graphene of middle acquisition, water bath sonicator is allowed to be uniformly dispersed；
    （6）By step（5）Middle gained amination graphene colloidal solution freeze-drying, up to the amination of monatomic lamellar structure Graphene；It is characterized in that in step（1）With（2）In, the uniformly mixed method is using the method for water bath sonicator, time For 15~20 min；Step（3）In, the ethylenediamine, N, the mass ratio of N '-dicyclohexylcarbodiimide and graphene oxide is 10:10:1 or 20:20:1 or 40:40:1；Step（3）In, the stirring means are magnetic stirrer, are carried out at room temperature； The organic phase filter membrane that filter membrane is 0.22 μm is used during the suction filtration；Graphene oxide powder used is mono-layer graphite oxide Alkene.
  2. 2. application according to claim 1, it is characterised in that in step（4）In, the cleaning method is according to first methanol The order cleaning of distilled water afterwards, is at least cleaned 4 times, it is ensured that residual organic matter is all cleaned up with every kind of solvent；Step（5）In, For the temperature of water bath sonicator no more than 50 oC, the time is the h of 2 h~4.
CN201610012813.1A 2016-01-11 2016-01-11 A kind of preparation method and application of amination graphene Expired - Fee Related CN105645392B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610012813.1A CN105645392B (en) 2016-01-11 2016-01-11 A kind of preparation method and application of amination graphene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610012813.1A CN105645392B (en) 2016-01-11 2016-01-11 A kind of preparation method and application of amination graphene

Publications (2)

Publication Number Publication Date
CN105645392A CN105645392A (en) 2016-06-08
CN105645392B true CN105645392B (en) 2018-04-13

Family

ID=56486956

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610012813.1A Expired - Fee Related CN105645392B (en) 2016-01-11 2016-01-11 A kind of preparation method and application of amination graphene

Country Status (1)

Country Link
CN (1) CN105645392B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106215722A (en) * 2016-08-08 2016-12-14 贵阳时代沃顿科技有限公司 A kind of high temperature resistant composite nanometer filtering film of grafted graphene oxide coating and preparation method thereof
CN108417403A (en) * 2018-03-09 2018-08-17 西安交通大学 A kind of preparation method of the porous nitrogen-doped graphene membrane electrodes of 3D
CN108505049B (en) * 2018-05-28 2019-12-10 中国科学院理化技术研究所 Graphite oxide corrosion inhibitor and preparation and application thereof
CN109942868A (en) * 2019-02-25 2019-06-28 王雪峰 A kind of preparation method of waterproof tensile fiber type element packaging film
CN110538672A (en) * 2019-07-25 2019-12-06 广东工业大学 Composite visible light response photocatalyst material and preparation method and application thereof
CN113244890B (en) * 2021-05-25 2023-07-14 成都师范学院 Preparation method and application of halloysite nanotube/graphene oxide composite material

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103861565B (en) * 2012-12-14 2016-01-27 吉首大学 The preparation of the graphene oxide sorbing material that the linear amino molecule of one class is modified
GB201408221D0 (en) * 2014-05-09 2014-06-25 Univ Manchester Functionalised graphene
CN104923156A (en) * 2015-05-20 2015-09-23 东华大学 Carbon-base loaded adsorbent for removing heavy metal in wastewater and preparation and use thereof

Also Published As

Publication number Publication date
CN105645392A (en) 2016-06-08

Similar Documents

Publication Publication Date Title
CN105645392B (en) A kind of preparation method and application of amination graphene
US10822259B2 (en) Method for removing hexavalent chromium from water bodies by sodium oxalate-modified zero-valent iron
CN104971697B (en) Preparation and application methods for magnetic biochar material used for removing arsenic pollution in water body
CN1751783A (en) Composite absorption material for removing arsenic from water and its prepn. method
Li et al. Enhanced removal of Cr (VI) by nitrogen-doped hydrochar prepared from bamboo and ammonium chloride
CN103934034A (en) Preparation method of loading iron based metal organic skeleton out phase Fenton catalyst and application thereof
Rahim et al. Self-assembly of a metal–phenolic sorbent for broad-spectrum metal sequestration
CN102417214B (en) Method for adsorbing heavy metals by using three-dimensional compound consisting of graphene sheet and magnetotactic bacteria
CN107983295B (en) Core-shell structure iron-copper bi-metal material and its preparation method and application
CN104043396B (en) The preparation method of a kind of magnetic amination graphene oxide and application
CN105498707A (en) Preparation method and application of modified graphene oxide/chitosan composite material
CN114832784B (en) Phosphoric acid modified silicon dioxide microsphere and preparation method and application thereof
Kong et al. Selective removal of heavy metal ions from aqueous solutions with surface functionalized silica nanoparticles by different functional groups
CN104587956A (en) Preparation method of coated nano zero-valent iron taking multilayer activated-carbon-coated graphene oxide composite powder as carrier
CN106179202A (en) A kind of composite modified biological carbon materials of iron-based amino and preparation and application
CN109012565A (en) A kind of method of the magnetic carbon material Adsorption heavy metal ions in wastewater of nitrating
Liu et al. Arsenic detoxification by iron-manganese nodules under electrochemically controlled redox: Mechanism and application
CN107008230A (en) Magnetic composite adsorbent and preparation method thereof
Ma et al. Synthesis of magnetic biochar derived from cotton stalks for the removal of Cr (VI) from aqueous solution
CN108579683A (en) A kind of sulfonates metal organic framework UIO-66@mSi-SO3The preparation method of H
CN106512952A (en) Method for treating antibiotic and heavy metal combined pollution water by using modified graphene oxide
Yang et al. Insight into photo-fenton catalytic degradation of tetracycline by environmental friendly nanocomposite 1T-2H hybrid phases MoS2/Fe3O4/g-C3N4
CN104475040A (en) Modified magnetic nano adsorption material as well as preparation method and application thereof
Shih et al. Online coupling of ultraviolet titanium dioxide film reactor with poly (methyl methacrylate) solid phase extraction–inductively coupled plasma mass spectrometry for speciation of trace heavy metals in freshwater
CN101811032B (en) Preparation and application methods of Cd (II) imprinted magnetic material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into 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: 20180413

Termination date: 20190111

CF01 Termination of patent right due to non-payment of annual fee