CN105833851A - Method for preparing functional group modified alginate-graphene dual-network nano-composite gel beads - Google Patents

Method for preparing functional group modified alginate-graphene dual-network nano-composite gel beads Download PDF

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CN105833851A
CN105833851A CN201610332640.1A CN201610332640A CN105833851A CN 105833851 A CN105833851 A CN 105833851A CN 201610332640 A CN201610332640 A CN 201610332640A CN 105833851 A CN105833851 A CN 105833851A
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graphene
gel ball
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马杰
庄媛
陈君红
陈晓燕
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Tongji University
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Abstract

The invention discloses a method for preparing functional group modified alginate-graphene dual-network nano-composite gel beads. The method comprises the following steps: adding graphene oxide, sodium alginate and polyving alcohol into an acid, alkali or neutral solution, and stirring with ultrasonic waves till a uniform solution is obtained; dripping the mixed solution into a divalent saline ion solution so as to obtain hydroxylation single-network gel beads, and performing water bath heating on the gel beads in a solution with a reducing agent, so as to obtain the hydroxylation dual-network nano-composite gel beads. Compared with pure sodium alginate gel and single-network gel, the dual-network gel prepared by using the method is relatively good in salt and alkali resistance and adsorption property. Carboxylation dual-network can be prepared by soaking the prepared hydroxylation dual-network in a FeCl3 solution and dripping an H2O2 solution drip by drip under ultraviolet radiation and magnetic stirring. Compared with unmodified gel beads, the hydroxylation and carboxylation dual-network nano-composite gel beads are relatively good in adsorption property.

Description

The preparation method of modified with functional group alginate-Graphene dual network nano-composite gel ball
Technical field
It is contemplated that invent a kind of modified with functional group alginate-Graphene dual network nano-composite gel ball Preparation method.
Background technology
As natural polymer, sodium alginate is passed through CaCl2Gel micro-ball prepared by solution crosslinking is extensively used Dyestuff and heavy metal in water, loading functional formed material be applied to adsorb become and grind on sodium alginate micro ball The focus studied carefully, especially nano material and magnetic material.Nano material is the active material of absorbent fields, and Carbon nano science is one of nano science research research field mostly important, that enliven the most.Continue fullerene and carbon After nanotube, has there is nanometer angle, graphite alkene until a series of new material such as Graphene in carbon nanomaterial field And have shown that irreplaceable critical role in human being's production and life, the carbon nanometer with Graphene as representative Material also highlights superiority in absorption.
The early 21st century, in order to improve the regularity of hydrogel network structure and cross-linked structure degree of freedom and play The pliability of macromolecular chain, to improve the mechanical performance of gel, occur in that topology gel, nano-composite gel and Dual network gel.Dual network gel is made up of two gel rubber systems, and two network structures mutually run through and mutual It is individually present.The patent of invention of Application No. 201510129911.9 proposes, alginate-Graphene Composite Double Network nano-composite gel ball has the absorption property of excellence.But the current study on the modification for dual network gel is relatively Few, owing to sodium alginate and graphene oxide all contain hydroxyl and carboxyl, thus it is expected to by increasing material further Hydroxyl and carboxyl-content in material improve absorption property further.
Summary of the invention
It is contemplated that invent a kind of modified with functional group alginate-Graphene dual network nano-composite gel ball Preparation method.Through the modified with functional group of the inventive method, the interpolation first passing through polyvinyl alcohol increases in material Hydroxy radical content, increase carboxyl-content further through photochemical catalytic oxidation, improve existing dual network nanometer further The absorption property of pluralgel ball.
For realizing object above, the technical solution adopted in the present invention is:
(1) in acid, alkalescence or neutral aqueous solution, graphene oxide, sodium alginate and polyethylene are added Alcohol, by ultrasonic and stirring until forming homogeneous solution, increases hydroxy radical content by the interpolation of polyvinyl alcohol；
(2) being instilled in divalent salts solion by described mixed solution, temperature is 0 DEG C～100 DEG C so that Sargassum Acid sodium is cross-linked to form alginate, it is thus achieved that hydroxylating list network gel ball；
(3) by gel ball heating in water bath in the aqueous solution containing reducing agent, temperature is 50 DEG C～100 DEG C, the time For more than 5h so that graphene oxide is self-assembled into as three-dimensional grapheme gel, it is thus achieved that hydroxylating dual network is received Rice pluralgel ball；
(4) the double net of hydroxylating that is modified in order to hydroxylating dual network gel being carried out photochemical catalytic oxidation, that will be obtained Network soak is in FeCl3In solution, configure finite concentration H2O2Solution, will soak the FeCl of dual network3 Solution is positioned over magnetic agitation under ultraviolet lighting, uses peristaltic pump by H2O2Solution dropwise instills having soaked double The FeCl of network3Solution, makes part oxygen-containing functional group be converted into carboxyl by photochemical catalytic oxidation, it is thus achieved that carboxylated Dual network.
It is characterized in that: the concentration of described graphene oxide is 0.1～20mg/mL, sodium alginate concentration is 1～20 Mg/mL, polyvinyl alcohol concentration is 0.1～20mg/mL, and in material, hydroxy radical content increases with polyvinyl alcohol content And increase.
It is characterized in that: described divalent salts ion can be in addition to Mg2+All divalent salts in addition.
It is characterized in that: reducing agent can be hydrazine hydrate, sodium borohydride, sodium bicarbonate, lithium aluminium hydride reduction, formaldehyde, Saccharide compound, ascorbic acid, glutathion or aminoacid.
It is characterized in that: Graphene is not less than 1:1 with the ratio of reducing agent.
It is characterized in that: the temperature that described mixed solution carries out heating in water bath is 50 DEG C～100 DEG C, the time is 5～48h.
, it is characterised in that: FeCl3Solution concentration is 0.1～1%, H2O2Solution concentration is 0.1～20%, two Person's volume ratio is 1:1, and in sample, carboxyl-content increases with photochemical catalytic oxidation degree and increases.
It is characterized in that: the dual network nano-composite gel ball prepared coagulates than pure sodium alginate gel ball, single network Glueballs all has more preferable Salt-resistant alkali-resistant and absorption property.
The beneficial effects of the present invention is:
Present invention process is simple, easy to spread, and after modification, the hydroxyl of gel ball and the content of carboxyl functional group increase, Thus enhance the absorbability of material.
Accompanying drawing explanation
Fig. 1 is the different polyvinyl alcohol content of embodiment 1 and the dual network gel infrared spectrogram of different degree of oxidation.
Fig. 2 is that the dual network gel of the different polyvinyl alcohol content of embodiment 1 is to ciprofloxacin and Cu2+Absorption.
Fig. 3 is the different H of embodiment 12O2The dual network gel of content oxidation is to ciprofloxacin and Cu2+Absorption.
Detailed description of the invention
The following examples are to further illustrate the present invention rather than limit the scope of the present invention.
Embodiment 1
Step 1, takes three beakers, all adds 40mg graphene oxide, 20mg sodium alginate and 20mL Distilled water, adds 5,10 and 20mg polyvinyl alcohol respectively in three beakers, and ultrasonic 6h to, machinery stirs Mix 1h to forming homogeneous solution.Separately take three beakers, all configure the CaCl of 20mL 10mg/mL2Solution, With peristaltic pump, graphene oxide/sodium alginate/poly-vinyl alcohol solution is instilled CaCl2Solution, it is thus achieved that hydroxylating list Network gel ball.
Step 2, separately takes three beakers, weigh with the ascorbic acid of graphene oxide mass ratio 1:1 and molten after, Hydroxylating list network gel ball is put into heating 8h in ascorbic acid solution, it is thus achieved that hydroxylating dual network nanometer is multiple Close gel ball.The hydroxylating dual network obtained is soaked in the FeCl of 100mL 1%3In solution, configure one Determine the 100mL H of concentration2O2Solution (mass concentration 1,2 and 5%), will soak the FeCl of dual network3Molten Liquid is positioned over magnetic agitation under ultraviolet lighting, uses peristaltic pump by H2O2Solution dropwise instills having soaked double The FeCl of network3Solution, after reaction terminates, by gel ball with distilled water immersion 24h to remove surface impurity, Obtain carboxylated dual network.
By hydroxylating dual network nano-composite gel ball and the different oxidation journey of the different polyvinyl alcohol contents of preparation The carboxylated dual network nano-composite gel ball of degree carries out Infrared Characterization as shown in Figure 1, it is seen that on gel, hydroxyl contains Amount increases with polyvinyl alcohol content increase, carboxyl-content increases with degree of oxidation and increases.
The dual network gel of different polyvinyl alcohol contents is to ciprofloxacin and Cu2+Absorption as in figure 2 it is shown, can See that the adsorption effect of two kinds of pollutant is all increased by gel along with the increase of polyvinyl alcohol content.(content 0 in figure It is unmodified)
Different H2O2The dual network gel of content oxidation is to ciprofloxacin and Cu2+Absorption as it is shown on figure 3, can See that gel is to Cu2+Adsorption effect significantly increases with carboxyl-content increase, and the absorption to ciprofloxacin decreases, Thus speculate that effect carboxylated for heavy metal adsorption is more preferable, more preferable for antibiotic absorption hydroxylating effect.
Embodiment 2
Take three beakers, all add 80mg graphene oxide, 20mg sodium alginate and 20mL distilled water, Adding 5,10 and 20mg polyvinyl alcohol respectively in three beakers, ultrasonic 6h to, mechanical agitation 1h is extremely Form homogeneous solution.Separately take three beakers, all configure the BaCl of 20mL 10mg/mL2Solution, with wriggling Graphene oxide/sodium alginate/poly-vinyl alcohol solution is instilled CaCl by pump2Solution, it is thus achieved that hydroxylating list network coagulates Glueballs.Separately take three beakers, weigh with the ascorbic acid of graphene oxide mass ratio 1:1 and molten after, by hydroxyl Change single network gel ball and put into heating 8h in ascorbic acid solution, it is thus achieved that hydroxylating dual network nano-composite gel Ball.The hydroxylating dual network obtained is soaked in the FeCl of 100mL 1%3In solution, configure finite concentration 100mL H2O2Solution (mass concentration 1,2 and 5%), will soak the FeCl of dual network3Solution is placed Magnetic agitation under at ultraviolet lighting, uses peristaltic pump by H2O2Solution dropwise instills and will soak dual network FeCl3Solution, after reaction terminates, by gel ball with distilled water immersion 24h to remove surface impurity, it is thus achieved that carboxylic Base dual network.
Embodiment 3
Take three beakers, all add 40mg graphene oxide, 20mg sodium alginate and 20mL distilled water, Adding 5,10 and 20mg polyvinyl alcohol respectively in three beakers, ultrasonic 6h to, mechanical agitation 1h is extremely Form homogeneous solution.Separately take three beakers, all configure the BaCl of 20mL 10mg/mL2Solution, uses peristaltic pump Graphene oxide/sodium alginate/poly-vinyl alcohol solution is instilled CaCl2Solution, it is thus achieved that hydroxylating list network gel Ball.Separately take three beakers, weigh with the sodium borohydride of graphene oxide mass ratio 1:1 and molten after, by hydroxylating Heating 8h in sodium borohydride solution put into by single network gel ball, it is thus achieved that hydroxylating dual network nano-composite gel ball. The hydroxylating dual network obtained is soaked in the FeCl of 100mL 1%3In solution, configure certain density 100mL H2O2Solution (mass concentration 1,2 and 5%), will soak the FeCl of dual network3Solution is positioned over Magnetic agitation under ultraviolet lighting, uses peristaltic pump by H2O2Solution dropwise instills and will soak the FeCl of dual network3 Solution, after reaction terminates, by gel ball with distilled water immersion 24h to remove surface impurity, it is thus achieved that carboxylated double Network.

Claims (8)

1. the preparation method of modified with functional group alginate-Graphene dual network nano-composite gel ball, it is characterised in that tool Body step is as follows:
(1) in acid, alkalescence or neutral aqueous solution, graphene oxide, sodium alginate and polyvinyl alcohol are added, by ultrasonic With stirring until forming homogeneous solution；
(2) being instilled in divalent salts solion by described mixed solution, temperature is 0 DEG C～100 DEG C so that sodium alginate cross-linking is formed Alginate, it is thus achieved that hydroxylating list network gel ball；
(3) by gel ball heating in water bath in the aqueous solution containing reducing agent, temperature is 50 DEG C～100 DEG C, and the time is more than 5h, Graphene oxide is made to be self-assembled into as three-dimensional grapheme gel, it is thus achieved that hydroxylating dual network nano-composite gel ball；
(4) by the hydroxylating dual network soak that obtained in FeCl3In solution, configure finite concentration H2O2Solution, will soak The FeCl of dual network3Solution is positioned over magnetic agitation under ultraviolet lighting, uses peristaltic pump by H2O2Solution dropwise instills and will soak The FeCl of dual network3Solution, it is thus achieved that carboxylated dual network.
The system of a kind of modified with functional group alginate the most according to claim 1-Graphene dual network nano-composite gel ball Preparation Method, it is characterised in that: the concentration of described graphene oxide is 0.1～20mg/mL, and sodium alginate concentration is 1～20mg/mL, Polyvinyl alcohol concentration is 0.1～20mg/mL.
The system of a kind of modified with functional group alginate the most according to claim 1-Graphene dual network nano-composite gel ball Preparation Method, it is characterised in that: described divalent salts ion can be in addition to Mg2+All divalent salts in addition.
The system of a kind of modified with functional group alginate the most according to claim 1-Graphene dual network nano-composite gel ball Preparation Method, it is characterised in that: reducing agent can be hydrazine hydrate, sodium borohydride, sodium bicarbonate, lithium aluminium hydride reduction, formaldehyde, saccharide Compound, ascorbic acid, glutathion or aminoacid.
The system of a kind of modified with functional group alginate the most according to claim 1-Graphene dual network nano-composite gel ball Preparation Method, it is characterised in that: Graphene is not less than 1:1 with the ratio of reducing agent.
The system of a kind of modified with functional group alginate the most according to claim 1-Graphene dual network nano-composite gel ball Preparation Method, it is characterised in that: the temperature that described mixed solution carries out heating in water bath is 50 DEG C～100 DEG C, and the time is 5～48h.
The system of a kind of modified with functional group alginate the most 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%, and both volume ratios are 1:1。
The system of a kind of modified with functional group alginate the most according to claim 1-Graphene dual network nano-composite gel ball Preparation Method, it is characterised in that: the dual network nano-composite gel ball prepared is than pure sodium alginate gel ball, single network gel ball all There is 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)

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CN106179277A (en) * 2016-08-31 2016-12-07 武汉大学 Sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent and its preparation method and application
CN106311185A (en) * 2016-08-31 2017-01-11 武汉大学 Polyvinyl alcohol/amino silanized graphene oxide macroporous compound spheres as well as preparation method and application of compound spheres
CN106633108A (en) * 2016-11-23 2017-05-10 辽宁石油化工大学 Preparation method of aminated graphene-sodium alginate composite gel ball
CN107115850A (en) * 2017-06-14 2017-09-01 山东省科学院新材料研究所 The sodium alginate gel ball of graphene oxide Polyaniline synthesis is removed to the adsorptivity of lead in water body and cadmium heavy metal ion
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
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CN109865504A (en) * 2019-04-03 2019-06-11 陕西省膜分离技术研究院有限公司 Rubidium ion adsorption microspheres and its application
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CN109908877A (en) * 2019-04-03 2019-06-21 陕西省膜分离技术研究院有限公司 The preparation method of rubidium ion adsorption microspheres
CN111239221A (en) * 2020-03-19 2020-06-05 河海大学常州校区 Electrochemical detection method and system for trace heavy metal ions in water body
CN114288990A (en) * 2021-12-29 2022-04-08 北京科技大学 Preparation method of hydroxylated magnetic graphene oxide adsorbent
CN115198527A (en) * 2022-07-04 2022-10-18 同济大学 Layer-by-layer self-assembly 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

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