CN102527333B - Modified graphene oxide, preparation method and application thereof - Google Patents
Modified graphene oxide, preparation method and application thereof Download PDFInfo
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- CN102527333B CN102527333B CN201110427356XA CN201110427356A CN102527333B CN 102527333 B CN102527333 B CN 102527333B CN 201110427356X A CN201110427356X A CN 201110427356XA CN 201110427356 A CN201110427356 A CN 201110427356A CN 102527333 B CN102527333 B CN 102527333B
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Abstract
The invention discloses a modified graphene oxide and belongs to the technical field of water purification and graphene synthesis. The modified graphene oxide is prepared according to a preparation method which comprises the following steps: taking organic silicon compound; dissolving the organic silicon compound in a DMF (Dimethyl Formamide) solvent and then mixing with graphite oxide; ultrasonically treating the solution for 40 minutes, and then volatilizing the solvent while magnetically stirring; drying for 3 hours in an oven at 100-150 DEG C; drying for 2 hours in vacuum, thereby obtaining the modified graphite oxide; taking the modified graphite oxide, adding water, and then ultrasonically treating for 10-30 minutes, thereby obtaining an aqueous solution of the modified graphene oxide, wherein the aqueous solution is a uniformly dispersed brown solution; and after drying the aqueous solution, obtaining the modified graphene oxide. The modified graphene oxide provided by the invention is capable of adsorbing lead ions in water; the adsorbing efficiency is high; the usage of the adsorbent is less; the modified graphene oxide is environment-friendly; the operation is quick and convenient; and the problem of lead pollution in water is solved.
Description
Technical field
The present invention relates to a kind of modified graphene oxide and preparation method thereof, and the application of adsorbing heavy metal in water lead ion, purification of water quality and Graphene synthesis technical field belonged to.
Background technology
Lead is the toxic heavy metal that can put aside in human body and animal tissue.Lead contamination is mainly derived from battery, cosmetics, fire coal, fuel oil, paint, running water pipe etc. in daily life.And lead source mainly contains in the water body: the rock forming mineral stripping; The waste water of leaded mine, plumbous smelting enterprise; Produce the plant chimney stalk of lead compound.Lead is mainly with Pb in the natural water
2+Form exists, and the problem of lead contamination needs to be resolved hurrily in the water.
Method plumbous in the degradation water has a lot, for the plumbous waste water of high concentration, chemical deposition method (hydroxide, sulfide) is both economical method, because a lot of impurity are arranged in the waste water, can remove in the lump, can make concentration plumbous in the water reach lower level simultaneously.For the leaded aqueous solution of low concentration, the biodegrading process that can adopt has ion-exchange, hyperfiltration, absorption method etc.Although ion-exchange and counter-infiltration can be degraded to lower level to metal ion, its maintenance cost is higher.Absorption method is the method for relatively commonly using, and the adsorbent of employing has active carbon, zeolite, dust, metal oxide, shitosan, agricultural by-products.
Graphene was produced out since 2004, inquired into Graphene becomes each research field gradually at mechanical performance, light, electricity, heat and the excellent properties such as dispersion in polymeric matrix forward position focus.To be carbonaceous material mainly occur in (carboxylic group and lactonic acid group) on the acidic functionality to the absorption of lead ion to its possible adsorption mechanism, a large amount of hydroxyls, carboxyl and oxygen-containing functional group are contained in the graphene oxide surface, therefore can be used for adsorpting lead ion, but its adsorption efficiency is lower, is badly in need of the more excellent modified graphene oxide adsorbent of a kind of performance.
Summary of the invention
For above-mentioned prior art, the invention provides a kind of modified graphene oxide and preparation method thereof and application, lead ion in the adsorbable water of modified graphene oxide of the present invention, adsorption efficiency is very high, and the adsorbent consumption is few, relatively environmental protection operates fast and conveniently, can solve the problem of lead contamination in the water.
The present invention is achieved by the following technical solutions:
A kind of preparation method of modified graphene oxide: get organo-silicon compound, be dissolved in the DMF solvent, then mix with graphite oxide, solution is through ultrasonic (after power 70～150W) processes 40min, solvent flashing under magnetic agitation, in baking oven, 100～150 ℃ of baking 3h, vacuum baking 2h gets modified graphite oxide; Then, get modified graphite oxide, add water, it is ultrasonic that (power 70～150W) is processed 10min～30min, gets the modified graphene oxide aqueous solution, and solution is finely dispersed brown solution, the visible Fig. 2 of result that uses AFM to observe after the drying, namely gets modified graphene oxide.
The modifying process of described graphite oxide is:
The reaction of described modified graphite oxide hydrolysis is:
The structural formula of described organo-silicon compound is:
As raw material take 3-aminopropyl trimethoxysilane (APMS) (can buy from the market) and methyl acrylate (mol ratio was as 1: 2), take methyl alcohol as solvent, under 40～60 ℃, reaction 24～36h gained (Michael addition, chemical synthesis process for routine, as long as can obtain the used organo-silicon compound of the present invention according to the method, do not repeat them here), reaction equation is as follows:
Described graphite oxide obtains by following preparation method: adopt the Hummers oxidizing process, raw material is the natural flake graphite powder; At first with 1g graphite powder, 1gNaNO
3, 3g KMnO
4Stir in ice-water bath with the concentrated sulfuric acid of 23mL 98%, the reaction time is 2h; Then change 35 ℃ of stirred in water bath reaction 1h over to, form sticking paste; Then add the 150mL deionized water, continue stirring reaction 15min, slowly add again the 5mL mass fraction and be 30% H
2O
2, solution is by the black yellowing; Filter while hot, with a large amount of water washing products, after the products therefrom oven dry, be graphite oxide.Take by weighing graphite oxide, add water, ultrasonic (power 70～150W) is processed 10min～30min, gets the graphite oxide aqueous solution, and solution is finely dispersed yellow solution, the visible Fig. 1 of result that uses AFM to observe.
The mass ratio of described organo-silicon compound and DMF solvent is 1: (60～100), preferred 1: 80.
The mass ratio of described organo-silicon compound and graphite oxide is 1: (10～100), preferred 1: 20.
Described when adding water, every 1mg modified graphite oxide adds water 8～12mL, preferred 10mL.
Described DMF refers to DMF.
A kind of modified graphene oxide is take graphite oxide as raw material, prepares through above-mentioned preparation method.
Modified graphene oxide of the present invention, lead ion in the adsorbable water, adsorption efficiency are very high, and the adsorbent consumption is few, and relatively environmental protection operates fast and conveniently, can solve the problem of lead contamination in the water.
Description of drawings
Fig. 1 is the AFM figure after graphite oxide is peeled off in water.
Fig. 2 is the AFM figure after modified graphite oxide is peeled off in water.
The specific embodiment
The present invention is further illustrated below in conjunction with example.
Embodiment 1 (1) preparation graphite oxide: adopt the Hummers oxidizing process, raw material is the natural flake graphite powder; At first with 1g graphite powder, 1gNaNO
3, 3g KMnO
4Stir in ice-water bath with the concentrated sulfuric acid of 23mL 98%, the reaction time is 2h; Then change 35 ℃ of stirred in water bath reaction 1h over to, form sticking paste; Then add the 150mL deionized water, continue stirring reaction 15min, slowly add again the 5mL mass fraction and be 30% H
2O
2, solution is by the black yellowing; Filter while hot, with a large amount of water washing products, after the products therefrom oven dry, be graphite oxide.
(2) described organo-silicon compound prepare by the following method: take 3-aminopropyl trimethoxysilane (APMS) and methyl acrylate (mol ratio was as 1: 2) as raw material, take methyl alcohol as solvent, under 50 ℃, reaction 30h, and get final product, reaction equation (Michael addition) is as follows:
(3) get organo-silicon compound 1mg, be dissolved in the 80mg DMF solvent, then mix with the 20mg graphite oxide, solution is after ultrasonic (power 120W) processes 40min, and solvent flashing under magnetic agitation is in baking oven, 120 ℃ of baking 3h, vacuum baking 2h gets modified graphite oxide.
The graphite oxide 1mg that weighing step (1) is synthetic is dissolved in the 10mL deionized water, and ultrasonic (power 120W) processes 20min and obtain the graphite oxide aqueous solution.Pb (the NO that adds 4.8 μ L 0.01mol/L with microsyringe
3)
2The aqueous solution (Pb wherein
2+Content is 1mg/L), mixing shakes up.Can see the phenomenon that graphene oxide is reunited.Then clarified supernatant is collected in 3000rpm centrifugation, surveys residual volume plumbous in the water.Get with Atomic Absorption Spectrometry that lead amount is 0.23mg/L in the supernatant.Parallel determination twice again, records plumbous residual volume and be respectively 0.24mg/L and 0.20mg/L.Calculating graphene oxide is about 80% to the highest adsorption efficiency of lead.
The above-mentioned synthetic modified graphite oxide 1mg of weighing is dissolved in the 10mL deionized water, and ultrasonic (power 120W) processes 20min and obtain the modified graphene oxide aqueous solution.Pb (the NO that adds 48 μ L 0.01mol/L with microsyringe
3)
2(Pb wherein
2+Content is 1mg/L) aqueous solution, mixing shakes up.Can see the agglomeration of modified graphene oxide.Then clarified supernatant is collected in 3000rpm centrifugation, surveys residual volume plumbous in the water.Get with Atomic Absorption Spectrometry that lead amount is 5.2 μ g/L in the supernatant.Parallel determination twice again, records plumbous residual volume and be respectively 10 μ g/L and 11 μ g/L.Calculate modified graphene oxide to the maximum adsorption efficiency of lead greater than 99%.
Claims (7)
1. the preparation method of a modified graphene oxide, it is characterized in that: get organo-silicon compound, be dissolved in the DMF solvent, then mix with graphite oxide, solution behind ultrasonic processing 40min, solvent flashing under magnetic agitation, in baking oven, 100～150 ℃ of baking 3h, vacuum baking 2h gets modified graphite oxide; Then, get modified graphite oxide, add water, ultrasonic processing 10min～30min gets the modified graphene oxide aqueous solution, after the drying, namely gets modified graphene oxide; Described organo-silicon compound are take 3-aminopropyl trimethoxysilane and methyl acrylate as raw material, take methyl alcohol as solvent, and under 40～60 ℃, reaction 24～36h gained.
2. the preparation method of modified graphene oxide according to claim 1, it is characterized in that: described graphite oxide obtains by following preparation method: adopt the Hummers oxidizing process, at first with 1g graphite powder, 1g NaNO
3, 3g KMnO
4Stir in ice-water bath with the concentrated sulfuric acid of 23mL98%, the reaction time is 2h; Then change 35 ℃ of stirred in water bath reaction 1h over to, form sticking paste; Then add the 150mL deionized water, continue stirring reaction 15min, slowly add again the 5mL mass fraction and be 30% H
2O
2, solution is by the black yellowing; Filter while hot, wash product with water, after the products therefrom oven dry, be graphite oxide.
3. the preparation method of modified graphene oxide according to claim 1, it is characterized in that: the mass ratio of described organo-silicon compound and DMF solvent is 1:(60～100).
4. the preparation method of modified graphene oxide according to claim 1, it is characterized in that: the mass ratio of described organo-silicon compound and graphite oxide is 1:(10～100).
5. the preparation method of modified graphene oxide according to claim 1, it is characterized in that: the power of described ultrasonic processing is 70～150W.
6. the preparation method of modified graphene oxide according to claim 1 is characterized in that: described when adding water, every 1g modified graphite oxide adds water 8～12mL.
7. modified graphene oxide is characterized in that: be take graphene oxide as raw material, prepare through the preparation method of claim 1.
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| 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 |
| CN103553028B (en) * | 2013-10-24 | 2015-09-30 | 深圳市沃特新材料股份有限公司 | Graphene, the composite engineering plastics of compound can be stablized with engineering plastics |
| CN104525126B (en) * | 2014-12-18 | 2017-12-05 | 湖北中烟工业有限责任公司 | Biopolyamines modified graphite alkenes sorbing material and its preparation method and application |
| CN105983380B (en) * | 2015-02-09 | 2018-06-12 | 南京理工大学 | A kind of super-hydrophobic MTMS/ graphite oxides composite aerogel and preparation method thereof |
| CN105958044B (en) * | 2016-07-26 | 2019-01-22 | 江苏天煌照明集团有限公司 | A kind of cobalt acid lithium electrode material and preparation method thereof of modified graphene doping |
| CN106732383A (en) * | 2016-11-30 | 2017-05-31 | 无锡龙盈环保科技有限公司 | Modified heavy metal in water compound adsorbent of a kind of Graphene and preparation method thereof |
| CN106902748A (en) * | 2017-03-29 | 2017-06-30 | 青岛辰达生物科技有限公司 | The preparation method and sewage-treating agent of a kind of adsorbent for heavy metal |
| CN107090001B (en) * | 2017-06-02 | 2018-10-26 | 扬州大学 | A kind of preparation method of modified graphene oxide |
| RU2659285C1 (en) * | 2017-10-25 | 2018-06-29 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Тамбовский государственный технический университет" (ФГБОУ ВО "ТГТУ") | Sorbent based on modified graphene oxide and method of its production |
| CN109589916A (en) * | 2018-11-29 | 2019-04-09 | 浙江正洁环境科技有限公司 | A kind of heavy metal absorbent and preparation method thereof |
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| CN101935030A (en) * | 2010-08-31 | 2011-01-05 | 南京理工大学 | Functional graphene oxide for adjusting and controlling dispersibility of solvent by using organic chain segment as well as preparation method thereof |
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