CN105833851B - The preparation method of modified with functional group alginate graphene dual network nano-composite gel ball - Google Patents

The preparation method of modified with functional group alginate graphene dual network nano-composite gel ball Download PDF

Info

Publication number
CN105833851B
CN105833851B CN201610332640.1A CN201610332640A CN105833851B CN 105833851 B CN105833851 B CN 105833851B CN 201610332640 A CN201610332640 A CN 201610332640A CN 105833851 B CN105833851 B CN 105833851B
Authority
CN
China
Prior art keywords
gel ball
dual network
solution
composite gel
graphene
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
CN201610332640.1A
Other languages
Chinese (zh)
Other versions
CN105833851A (en
Inventor
马杰
庄媛
陈君红
陈晓燕
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.)
Tongji University
Original Assignee
Tongji 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 Tongji University filed Critical Tongji University
Priority to CN201610332640.1A priority Critical patent/CN105833851B/en
Publication of CN105833851A publication Critical patent/CN105833851A/en
Application granted granted Critical
Publication of CN105833851B publication Critical patent/CN105833851B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0262—Compounds of O, S, Se, Te
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4843—Algae, aquatic plants or sea vegetals, e.g. seeweeds, eelgrass
    • 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
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Medicinal Preparation (AREA)
  • Colloid Chemistry (AREA)

Abstract

The invention discloses a kind of preparation method of modified with functional group alginate graphene dual network nano-composite gel ball.Including：In acid, alkalescence or neutral aqueous solution, graphene oxide, sodium alginate and polyvinyl alcohol are added, by ultrasound and stirring until forming homogeneous solution.By the mixed solution instill divalence salt ion solution in, obtain hydroxylating list network gel ball, by gel ball in the aqueous solution containing reducing agent heating water bath, obtain hydroxylating dual network nano-composite gel ball.Dual network gel prepared by the present invention all has more preferable Salt-resistant alkali-resistant and absorption property than pure sodium alginate gel, single network gel.The hydroxylating dual network obtained is soaked in FeCl3In solution, H is added dropwise under ultraviolet lighting, magnetic agitation2O2Solution, obtains carboxylated dual network.Obtained hydroxylating, carboxylated dual network nano-composite gel ball are than the unmodified preceding absorption property with higher.

Description

The preparation of modified with functional group alginate-graphene dual network nano-composite gel ball Method
Technical field
It is contemplated that invent a kind of preparation of modified with functional group alginate-graphene dual network nano-composite gel ball Method.
Background technology
As natural polymer, sodium alginate is passed through into CaCl2Gel micro-ball prepared by solution crosslinking is widely used in water Middle dyestuff and heavy metal, on sodium alginate micro ball loading functional material and applied to absorption become research hot spot, especially It is nano material and magnetic material.Nano material is the active material of absorbent fields, and carbon nano science is nano science Study one of mostly important, the most active research field.After fullerene and carbon nanotubes, carbon nanomaterial field has gone out Existing nanometer angle, graphite alkene in human being's production and life until a series of new materials such as graphene and have shown that irreplaceable Critical role, the carbon nanomaterial using graphene as representative also highlight superiority in absorption.
The early 21st century, in order to improve the regularity of hydrogel network structure and the cross-linked structure free degree and play macromolecule , to improve the mechanical performance of gel, there is topological gel, nano-composite gel and dual network gel in the pliability of chain.Double nets Network gel is made of two gel rubber systems, and two network structures are mutually through presence independently of each other again.Application No. 201510129911.9 patent of invention propose, alginate-graphene composite double network nano-composite gel ball has excellent Absorption property.But it is less for the study on the modification of dual network gel at present, since sodium alginate contains with graphene oxide Hydroxyl and carboxyl, thus be expected to further improve absorption property by further increasing hydroxyl in material and carboxyl-content.
The content of the invention
It is contemplated that invent a kind of preparation of modified with functional group alginate-graphene dual network nano-composite gel ball Method.By the modified with functional group of the method for the present invention, the addition for first passing through polyvinyl alcohol increases hydroxy radical content in material, again Carboxyl-content is increased by photochemical catalytic oxidation, further improves the absorption property of existing dual network nano-composite gel ball.
In order to achieve the above object, the technical solution adopted in the present invention is：
(1) in acid, alkalescence or neutral aqueous solution, graphene oxide, sodium alginate and polyvinyl alcohol is added, is passed through Ultrasound and stirring increase hydroxy radical content until formation homogeneous solution by the addition of polyvinyl alcohol；
(2) mixed solution is instilled in divalence salt ion solution, temperature is 0 DEG C~100 DEG C so that sodium alginate is handed over Connection forms alginate, obtains hydroxylating list network gel ball；
(3) by gel ball, heating water bath, temperature are 50 DEG C~100 DEG C in the aqueous solution containing reducing agent, time 5h More than so that graphene oxide is self-assembled into as three-dimensional grapheme gel, acquisition hydroxylating dual network nano-composite gel ball；
(4) in order to which hydroxylating dual network gel is carried out photochemical catalytic oxidation modification, the hydroxylating dual network obtained is coagulated Glue is soaked in FeCl3In solution, a certain concentration H is configured2O2Solution, will soak the FeCl of dual network3Solution is positioned over ultraviolet Magnetic agitation under illumination, using peristaltic pump by H2O2Solution instills dropwise to have soaked the FeCl of dual network3Solution, is urged by light Changing oxidation makes part oxygen-containing functional group be converted into carboxyl, obtains carboxylated dual network.
It is characterized in that：The concentration of the graphene oxide is 0.1~20mg/mL, and sodium alginate concentration is 1~20mg/ ML, polyvinyl alcohol concentration are 0.1~20mg/mL, and hydroxy radical content increases and increases with polyvinyl alcohol content in material.
It is characterized in that：The divalence salt ion can be except Mg2+All divalent salts in addition.
It is characterized in that：Reducing agent can be hydrazine hydrate, sodium borohydride, sodium acid carbonate, lithium aluminium hydride reduction, formaldehyde, carbohydrate Compound, ascorbic acid, glutathione or amino acid.
It is characterized in that：The ratio of graphene and reducing agent is not less than 1:1.
It is characterized in that：Be 50 DEG C~100 DEG C by the temperature that the mixed solution carries out heating water bath, the time for 5~ 48h。
, it is characterised in that：FeCl3Solution concentration is 0.1~1%, H2O2Solution concentration is 0.1~20%, both volume ratios For 1:1, carboxyl-content increases and increases with photochemical catalytic oxidation degree in sample.
It is characterized in that：Obtained dual network nano-composite gel ball is than pure sodium alginate gel ball, single network gel ball All there is more preferable Salt-resistant alkali-resistant and absorption property.
The beneficial effects of the present invention are：
Present invention process is simple, easy to spread, and the content of the hydroxyl of gel ball and carboxyl functional group increases after modification, so that Enhance the adsorption capacity of material.
Brief description of the drawings
Fig. 1 is the dual network gel infrared spectrogram of the different polyvinyl alcohol contents of embodiment 1 and different degree of oxidation.
Fig. 2 is the dual network gel of the different polyvinyl alcohol contents of embodiment 1 to Ciprofloxacin and Cu2+Absorption.
Fig. 3 is the difference of embodiment 1 H2O2The dual network gel of content oxidation is to Ciprofloxacin and Cu2+Absorption.
Embodiment
The following examples are the further explanations to the present invention, rather than are limited the scope of the invention.
Embodiment 1
Step 1, three beakers are taken, add 40mg graphene oxides, 20mg sodium alginates and 20mL distilled water, respectively to Add 5,10 and 20mg polyvinyl alcohol in three beakers, ultrasonic 6h to, mechanical agitation 1h is to forming homogeneous solution.Separately take three burnings Cup, configures the CaCl of 20mL 10mg/mL2Solution, is dripped graphene oxide/sodium alginate/poly-vinyl alcohol solution with peristaltic pump Enter CaCl2Solution, obtains hydroxylating list network gel ball.
Step 2, three beakers are separately taken, are weighed and graphene oxide mass ratio 1:1 ascorbic acid and it is molten after, by hydroxylating Single network gel ball, which is put into ascorbic acid solution, heats 8h, obtains hydroxylating dual network nano-composite gel ball.It will be obtained Hydroxylating dual network be soaked in the FeCl of 100mL 1%3In solution, certain density 100mL H are configured2O2(quality is dense for solution Degree 1,2 and 5%), will soak the FeCl of dual network3Solution is positioned over the magnetic agitation under ultraviolet lighting, will using peristaltic pump H2O2Solution instills dropwise to have soaked the FeCl of dual network3Solution, after reaction, by gel ball with distilled water immersion 24h with Surface impurity is removed, obtains carboxylated dual network.
By the hydroxylating dual network nano-composite gel ball of the different polyvinyl alcohol contents of preparation and different degree of oxidation It is as shown in Figure 1 that carboxylated dual network nano-composite gel ball carries out IR Characterization, it is seen that hydroxy radical content is with polyvinyl alcohol on gel Content increases and increases, carboxyl-content increases and increases with degree of oxidation.
The dual network gel of different polyvinyl alcohol contents is to Ciprofloxacin and Cu2+Absorption it is as shown in Figure 2, it is seen that gel pair The adsorption effect of two kinds of pollutants increases with the increase of polyvinyl alcohol content.(content 0 is as unmodified in figure)
Different H2O2The dual network gel of content oxidation is to Ciprofloxacin and Cu2+Absorption it is as shown in Figure 3, it is seen that gel pair Cu2+Adsorption effect is significantly increased with carboxyl-content increase, and the absorption to Ciprofloxacin decreases, and thus speculates for heavy metal It is more preferable to adsorb carboxylated effect, it is more preferable for antibiotic absorption hydroxylating effect.
Embodiment 2
Three beakers are taken, add 80mg graphene oxides, 20mg sodium alginates and 20mL distilled water, are burnt respectively to three Add 5,10 and 20mg polyvinyl alcohol in cup, ultrasonic 6h to, mechanical agitation 1h is to forming homogeneous solution.Three beakers separately are taken, Configure the BaCl of 20mL 10mg/mL2Solution, is instilled graphene oxide/sodium alginate/poly-vinyl alcohol solution with peristaltic pump CaCl2Solution, obtains hydroxylating list network gel ball.Three beakers separately are taken, are weighed and graphene oxide mass ratio 1:1 it is anti-bad Hematic acid and it is molten after, hydroxylating list network gel ball is put into ascorbic acid solution and heats 8h, obtain hydroxylating dual network nanometer Plural gel ball.The hydroxylating dual network obtained is soaked in the FeCl of 100mL 1%3In solution, configuration is certain density 100mL H2O2Solution (mass concentration 1,2 and 5%), will soak the FeCl of dual network3Solution is positioned over the magnetic under ultraviolet lighting Power stirs, using peristaltic pump by H2O2Solution instills dropwise to have soaked the FeCl of dual network3Solution, after reaction, by gel Ball distilled water immersion 24h obtains carboxylated dual network to remove surface impurity.
Embodiment 3
Three beakers are taken, add 40mg graphene oxides, 20mg sodium alginates and 20mL distilled water, are burnt respectively to three Add 5,10 and 20mg polyvinyl alcohol in cup, ultrasonic 6h to, mechanical agitation 1h is to forming homogeneous solution.Three beakers separately are taken, Configure the BaCl of 20mL 10mg/mL2Solution, is instilled graphene oxide/sodium alginate/poly-vinyl alcohol solution with peristaltic pump CaCl2Solution, obtains hydroxylating list network gel ball.Three beakers separately are taken, are weighed and graphene oxide mass ratio 1:1 boron hydrogen Change sodium and it is molten after, hydroxylating list network gel ball is put into sodium borohydride solution and heats 8h, obtain hydroxylating dual network nanometer Plural gel ball.The hydroxylating dual network obtained is soaked in the FeCl of 100mL 1%3In solution, configuration is certain density 100mL H2O2Solution (mass concentration 1,2 and 5%), will soak the FeCl of dual network3Solution is positioned over the magnetic under ultraviolet lighting Power stirs, using peristaltic pump by H2O2Solution instills dropwise to have soaked the FeCl of dual network3Solution, after reaction, by gel Ball distilled water immersion 24h obtains carboxylated dual network to remove surface impurity.

Claims (8)

  1. A kind of 1. preparation method of modified with functional group alginate-graphene dual network nano-composite gel ball, it is characterised in that Comprise the following steps that：
    (1) in acid, alkalescence or neutral aqueous solution, graphene oxide, sodium alginate and polyvinyl alcohol is added, passes through ultrasound With stirring until forming homogeneous solution；
    (2) homogeneous solution is instilled in divalence salt ion solution, temperature is 0 DEG C ~ 100 DEG C so that sodium alginate cross-linking shape Into alginate, hydroxylating list network gel ball is obtained；
    (3) by gel ball, heating water bath, temperature are 50 DEG C ~ 100 DEG C in the aqueous solution containing reducing agent, and the time is more than 5h, So that graphene oxide is self-assembled into as three-dimensional grapheme gel, acquisition hydroxylating dual network nano-composite gel ball；
    (4) the hydroxylating dual network nano-composite gel ball obtained is soaked in FeCl3In solution, a certain concentration H is configured2O2 Solution, will soak the FeCl of hydroxylating dual network nano-composite gel ball3Solution is positioned over the magnetic agitation under ultraviolet lighting, Using peristaltic pump by H2O2Solution instills dropwise to have soaked the FeCl of hydroxylating dual network nano-composite gel ball3Solution, obtains Carboxylated dual network nano-composite gel ball.
  2. 2. a kind of modified with functional group alginate according to claim 1-graphene dual network nano-composite gel ball Preparation method, it is characterised in that：The concentration of the graphene oxide is 0.1 ~ 20 mg/mL, and sodium alginate concentration is 1 ~ 20 mg/ ML, polyvinyl alcohol concentration are 0.1 ~ 20 mg/mL.
  3. 3. a kind of modified with functional group alginate according to claim 1-graphene dual network nano-composite gel ball Preparation method, it is characterised in that：The divalence salt ion is except Mg2+All divalent salts in addition.
  4. 4. a kind of modified with functional group alginate according to claim 1-graphene dual network nano-composite gel ball Preparation method, it is characterised in that：Reducing agent is hydrazine hydrate, sodium borohydride, sodium acid carbonate, formaldehyde, saccharide compound, Vitamin C Acid, glutathione or amino acid.
  5. 5. a kind of modified with functional group alginate according to claim 1-graphene dual network nano-composite gel ball Preparation method, it is characterised in that：The mass ratio of graphene oxide and reducing agent is not less than 1:1.
  6. 6. a kind of modified with functional group alginate according to claim 1-graphene dual network nano-composite gel ball Preparation method, it is characterised in that：Step（3）The temperature of heating water bath is 50 DEG C ~ 100 DEG C, and the time is 5 ~ 48h.
  7. 7. a kind of modified with functional group alginate according to claim 1-graphene dual network nano-composite gel ball Preparation method, it is characterised in that：FeCl3Solution concentration is 0.1 ~ 1%, H2O2Solution concentration is 0.1 ~ 20 %, both are at volume ratio 1:1。
  8. 8. a kind of modified with functional group alginate according to claim 1-graphene dual network nano-composite gel ball Preparation method, it is characterised in that：Obtained modified with functional group alginate-graphene dual network nano-composite gel ball is than pure sea Sodium alginate gel ball, single network gel ball all have more preferable Salt-resistant alkali-resistant and absorption property.
CN201610332640.1A 2016-05-18 2016-05-18 The preparation method of modified with functional group alginate graphene dual network nano-composite gel ball Expired - Fee Related CN105833851B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610332640.1A CN105833851B (en) 2016-05-18 2016-05-18 The preparation method of modified with functional group alginate graphene dual network nano-composite gel ball

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610332640.1A CN105833851B (en) 2016-05-18 2016-05-18 The preparation method of modified with functional group alginate graphene dual network nano-composite gel ball

Publications (2)

Publication Number Publication Date
CN105833851A CN105833851A (en) 2016-08-10
CN105833851B true CN105833851B (en) 2018-04-17

Family

ID=56592761

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610332640.1A Expired - Fee Related CN105833851B (en) 2016-05-18 2016-05-18 The preparation method of modified with functional group alginate graphene dual network nano-composite gel ball

Country Status (1)

Country Link
CN (1) CN105833851B (en)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106311185B (en) * 2016-08-31 2019-01-18 武汉大学 A kind of polyvinyl alcohol/Aminosilylation graphene oxide macropore composite balls and its preparation method and application
CN106179277B (en) * 2016-08-31 2019-01-18 武汉大学 Sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent and its preparation method and application
CN106633108B (en) * 2016-11-23 2019-03-29 辽宁石油化工大学 A kind of preparation method of amination graphene-sodium alginate plural gel ball
CN107115850B (en) * 2017-06-14 2019-08-27 山东省科学院新材料研究所 The sodium alginate gel ball of graphene oxide-polyaniline compound synthesis removes the adsorptivity of lead in water body and cadmium heavy metal ion
CN107759808B (en) * 2017-09-18 2020-08-14 同济大学 Preparation method of sodium alginate/L-cysteine/reduced graphene oxide magnetic water/aerogel
CN107552020A (en) * 2017-09-18 2018-01-09 同济大学 The method of the polyvinyl alcohol of synthesizing blender carbon nanomaterial/sodium alginate gel ball adsorbent
CN108102956A (en) * 2017-12-18 2018-06-01 曲阜师范大学 A kind of preparation method and applications of graphene-based composite material immobilization denitrifying bacteria
CN109529888B (en) * 2018-11-26 2020-10-20 中国科学院生态环境研究中心 Three-dimensional graphene-based heterogeneous Fenton catalyst, and preparation method and application thereof
CN109870495A (en) * 2019-01-30 2019-06-11 同济大学 A kind of graphene-based field effect transistor nitrate sensor
CN109759026A (en) * 2019-01-30 2019-05-17 同济大学 Amido modified alginate-graphene dual network gel ball and its preparation method and application
CN109865504B (en) * 2019-04-03 2022-05-03 陕西省膜分离技术研究院有限公司 Rubidium ion adsorption microsphere and application thereof
CN109908877B (en) * 2019-04-03 2022-05-03 陕西省膜分离技术研究院有限公司 Preparation method of rubidium ion adsorption microspheres
CN111239221B (en) * 2020-03-19 2022-11-01 河海大学常州校区 Electrochemical detection method and system for trace heavy metal ions in water body
CN114288990B (en) * 2021-12-29 2023-02-24 北京科技大学 Preparation method of hydroxylated magnetic graphene oxide adsorbent
CN115198527B (en) * 2022-07-04 2023-09-26 同济大学 Layer-by-layer self-assembled flame-retardant fabric based on full biomass flame-retardant system and preparation method thereof
CN116272941A (en) * 2023-03-23 2023-06-23 东南大学 Graphene-based hydrogel sphere catalytic material and preparation method and application thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104760950A (en) * 2015-03-13 2015-07-08 同济大学 Preparation method of graphene hydrogel and application of the graphene hydrogel
CN104785177B (en) * 2015-03-23 2017-06-13 同济大学 A kind of preparation method of alginate Graphene composite double network gel ball
CN105237816B (en) * 2015-10-09 2017-10-13 青岛大学 A kind of preparation method and application of graphene oxide/sodium alginate liquid crystal composite solution

Also Published As

Publication number Publication date
CN105833851A (en) 2016-08-10

Similar Documents

Publication Publication Date Title
CN105833851B (en) The preparation method of modified with functional group alginate graphene dual network nano-composite gel ball
CN104785177B (en) A kind of preparation method of alginate Graphene composite double network gel ball
He et al. Stir bar sorptive extraction and its application
Cheng et al. Multifaceted applications of cellulosic porous materials in environment, energy, and health
Zhang et al. Corn stover–derived biochar for efficient adsorption of oxytetracycline from wastewater
Liu et al. Review on carbon-based composite materials for capacitive deionization
Fang et al. Synthesis, decoration and properties of three-dimensional graphene-based macrostructures: a review
Chen et al. Controllable preparation of porous hollow carbon sphere@ ZIF-8: Novel core-shell nanomaterial for Pb2+ adsorption
Li et al. Boosting adsorption and catalysis of polysulfides by multifunctional separator for lithium–sulfur batteries
CN105964522B (en) A kind of preparation method of graphene heat conducting film
CN110102260A (en) A kind of iron and manganese oxides-charcoal composite material and preparation method and application
CN105129927B (en) The preparation method of graphene/carbon nano-tube aeroge composite capacitance-type desalting electrode
CN104107681A (en) Preparation method of three-dimensional graphene-protein composite aerogel
CN104174388A (en) Metal organic frame composite material and preparation method thereof
CN102059082A (en) Method for preparing nano manganese dioxide/carbon composite microsphere
CN104941584B (en) Heavy metal ion SiO in a kind of adsorbed water body2/ C composite and its application
Sun et al. Preparation of CTS/PAMAM/SA/Ca2+ hydrogel and its adsorption performance for heavy metal ions
Dai et al. Scalable preparation of hierarchical porous carbon from lignin for highly efficient adsorptive removal of sulfamethazine antibiotic
Lu et al. Preparation of sulfonated porous carbon nanotubes/activated carbon composite beads and their adsorption of low density lipoprotein
CN110918051A (en) Strong adsorption type graphene-based composite material for sewage treatment
CN107759808A (en) The preparation method of sodium alginate/L cysteines/redox graphene magnetic water/aeroge
CN111437778A (en) Amino modified microcrystalline cellulose/graphene oxide aerogel and preparation method and application thereof
Li et al. Preparation of templated materials and their application to typical pollutants in wastewater: a review
Valencia et al. On the mineralization of nanocellulose to produce functional hybrid materials
CN113861600A (en) Bio-based porous material and preparation method and application thereof

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

Granted publication date: 20180417

Termination date: 20210518