CN102500318B - Surface modification method of carbon nanotube, carbon nanotube and application thereof - Google Patents
Surface modification method of carbon nanotube, carbon nanotube and application thereof Download PDFInfo
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- CN102500318B CN102500318B CN 201110299121 CN201110299121A CN102500318B CN 102500318 B CN102500318 B CN 102500318B CN 201110299121 CN201110299121 CN 201110299121 CN 201110299121 A CN201110299121 A CN 201110299121A CN 102500318 B CN102500318 B CN 102500318B
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Abstract
The invention relates to a surface modification method of carbon nanotube and application of the surface modified carbon nanotube. The surface modification method comprises the following steps: (1) adding carbon nanotubes into concentrated nitric acid, heating and refluxing under stirring, cooling, centrifuging to obtain a solid matter, washing the solid matter with deionized water to pH 7, vacuum drying to obtain acidified carbon nanotubes, adding the acidified carbon nanotubes and thionyl chloride into an organic solvent, ultrasonic dispersing, stirring for reaction, distilling under reduced pressure to obtain a solid product, filtering the solid product with a nylon filter membrane, cleaning, vacuum drying to obtain carbon nanotube acyl chloride, adding carbon nanotube acyl chloride and sodium p-aminobenzenesulfonate into an organic solvent, ultrasonic dispersing, stirring for reaction, cooling the reaction solution to room temperature, suction-filtering with a nylon membrane, washing, and vacuum drying to obtain multi-wall carbon nanotubes modified by sodium p-aminobenzenesulfonate. The surface modified carbon nanotube prepared by the invention has significantly enhanced metal ion adsorption property and high recycle rate, and is easy to be separated.
Description
Technical field
The present invention relates to a kind of functionalized carbon nano-tube and application thereof, specifically carbon nano-tube modified with sodium sulfanilate and be used for absorbing heavy metal ions in water.
Background technology
Absorption method is the important method for treating water of a class, and its principle is to utilize the skin effect of adsorbent to remove water pollutant, reaches the purpose of purification.The adsorbent that is usually used at present water treatment comprises active carbon, metal oxide, natural minerals etc.Wherein active carbon is effective to Adsorption of Organic, but counterweight metal removal effect is bad.And metal oxide, natural minerals etc. are not good to the low concentration pollutant removal effect.CNT is because its huge skin effect and good chemical stability etc., has potential using value (Li Y H as a kind of novel absorption material, Wang S G, Zhang X F, et a1. Adsorption of fluoride from water by aligned carbon nanotubes. Material Research Bulletin, 2003,38 (38): 469-476; Wang H J, Zhou A L, Peng F, et a1. Adsorption characteristic of acidified carbon nanotubes for heavy metal Pb (II) in aqueous solution. Materials Science and Engineering A, 2007,466 (1-2): 201-206).But because CNT is easy to tangle, reunite in water, be difficult to disperse, so its adsorption can not be given full play to.To CNT carry out acid oxidase process can make its absorption property improve to some extent (Ceng Wu, Gong Xuemin, Peng Xianjia, etc.Carbon nanotube sol is to micro-Cd in the water
2+With Cu
2+The research of absorption, Chemical Engineering, 2009,37(6): 8-11).But because its surface lacks functional groups, a little less than metal ion interphase interaction, so absorption property can not effectively be improved, and is particularly poor to the adsorption effect of trace meter particle in the water.Therefore, must inquiring into more effectively, the functionalization method belongs to the particularly adsorption effect of trace metal ion of ion to improve it to underwater gold.At present develop some and CNT has been carried out the method for chemical modification with organic matter or polymer.As utilize nitration mixture processing CNT to make its Surface Creation carboxyl isoreactivity group, then ethylenediamine or sulfanilic acid are grafted to carbon nano tube surface (Li Juan, Fang Zhengping, Wang Jianguo, Deng. the variation of CNT micro-structural in grafting diamine process. Acta PhySico-Chimica Sinica, 2005,21 (11): 1244-1248; Yang Jiayi, Shi Tiejun, Jin Weiya, etc. sulfanilic acid two-step method modifying multiwall carbon nano-tube [J]. chemical journal, 2008,66(5): 552-556); Perhaps utilize SSS that the polymer graft modification of multi-walled carbon nano-tubes has also been obtained water-soluble multi-wall carbon nanotube (Du F P, Wu K B, Yang Y K, et al. Synthesis and electrochemical probing of water-soluble poly (sodium 4-styrenesulfonate-co-acrylic acid) grafted multiwalled carbon nanotubes. Nanotechnology, 2008,19 (8): 85716-085725).
Summary of the invention
Technical problem to be solved by this invention is to have proposed a kind of surface modification method of the CNT for the adsorbed water metal ion and the CNT that obtains thereof for above-mentioned prior art, namely use amino this sodium sulfonate grafting carbon nanotube and be used for the Adsorption underwater gold to belong to ion, the method can obtain the material of in water Uniform Dispersion and absorption property excellence.
The present invention solves the problems of the technologies described above the technical scheme that adopts: a kind of method of modifying of CNT includes following steps:
1) CNT is added in the red fuming nitric acid (RFNA), the mass ratio of CNT and red fuming nitric acid (RFNA) is 1:100 ~ 200, under 80 ~ 100 ℃ and the condition that stirs, added hot reflux 12 ~ 24 hours, after being cooled to room temperature, high speed centrifugation separates, the gained solid is washed till 7,50 ℃ ~ 70 ℃ vacuum drying of pH value 6 ~ 12 hours with deionized water, obtains the acidifying CNT;
2) the acidifying CNT that step 1) is obtained, thionyl chloride add in the organic solvent and ultrasonic dispersion 10 ~ 30 minutes, the mass ratio of acidifying CNT and thionyl chloride, organic solvent is respectively 1:200 ~ 500:50 ~ 200, then stirring reaction 20 ~ 30 hours under 70 ℃ ~ 100 ℃ temperature, thionyl chloride is removed in decompression distillation, the gained solid product filters, washs with nylon leaching film, 50 ℃ ~ 70 ℃ vacuum drying 12 ~ 24 hours obtain the chloride CNT;
3) chloride CNT, sodium sulfanilate were added organic solvent for ultrasonic dispersion 10 ~ 20 minutes; the mass ratio of chloride CNT and sodium sulfanilate and solvent is respectively 1:1 ~ 2:50 ~ 150; under 60 ℃ ~ 80 ℃, nitrogen protection; stirring reaction 18 ~ 36 hours; after question response liquid is cooled to room temperature; nylon leaching film suction filtration, washing, 50 ℃ ~ 70 ℃ vacuum drying 12 ~ 24 hours get the multi-walled carbon nano-tubes that sodium sulfanilate is modified.
Press such scheme, described CNT is SWCN or multi-walled carbon nano-tubes.
Press such scheme, described organic solvent is dimethyl formamide or oxolane.
The CNT that is obtained by the method for modifying of such scheme.
The carbon nanotubes application method of gained of the present invention, it is characterized in that comprising that the CNT adding that claim 4 is obtained contains in the aqueous solution of metal ion, concentration of metal ions is 5 ~ 50mg/L, the CNT consumption is 1 ~ 5g/L, ultrasonic 10 ~ 30min, constant temperature adsorbed after 1 ~ 2 hour, the nylon leaching film suction filtration.
Press such scheme, described metal ion is Cr
2+, Fe
2+Or Cu
2+
The invention provides a kind of method of modifying of the CNT for removing the water heavy metal particles, adopt strong acid to go out carboxyl in the carbon nano tube surface oxidation, then carboxyl is converted into acyl chlorides, utilize the higher reactivity of acyl chlorides, with sodium sulfanilate reaction, thus in the carbon nano tube surface grafting to amino this sodium sulfonate.
Superiority of the present invention is to have water-soluble and the functional group of ion exchange is arranged by introducing in carbon nano tube surface, has realized the water-soluble modified and functionalization of CNT.
Beneficial effect of the present invention is: after adopting this method that CNT is modified, the functional group that introduce on the surface promotes Uniform Dispersion among the carbon Guan Zaishui, simultaneously metallic there are again certain ion exchange and complexing, therefore the metallic absorption property is obviously strengthened, and be easy to separate, recycling rate of waterused is high, this method of modifying both can be used for carbon nano-tube modified, also can be used for modifying other material with carbon elements such as carbon dust, Graphene, carbon fiber, be expected to be applied in fields such as wastewater treatments.
Description of drawings
Fig. 1 is the thermogravimetic analysis (TGA) (TGA) of carbon nano tube modified front and back among the embodiment 1;
Fig. 2 is the transmission electron microscope picture (TEM) of carbon nano tube modified front and back among the embodiment 1, wherein Fig. 2 (a) CNT; Fig. 2 (b) sodium sulfanilate is carbon nano-tube modified;
Fig. 3 is the dispersed photo of carbon nano tube modified front and back in water among the embodiment 1, Fig. 3 (A) CNT, and Fig. 3 (B) acidifying CNT and Fig. 3 (C) sodium sulfanilate are carbon nano-tube modified.
The specific embodiment
The present invention will be further described in detail below in conjunction with drawings and Examples, but can not be construed as limiting the invention.
Embodiment 1
1.0 g multi-walled carbon nano-tubes are added in the red fuming nitric acid (RFNA) of 100 g, under 100 ℃ and the condition that stirs, added hot reflux 24 hours.After being cooled to room temperature, high speed centrifugation separates, and solid is washed till pH value 7 with deionized water.50 ℃ of vacuum drying 12 hours obtain the multi-walled carbon nano-tubes of acidifying.
200mg acidifying CNT, 40 g dimethyl formamides and 100 g thionyl chlorides are mixed ultrasonic dispersion 10 minutes.Then stirring reaction 20 hours under 70 ℃ temperature.Excessive thionyl chloride adopts the method for decompression distillation to remove.Solid product with nylon leaching film filter, the oxolane washing, 50 ℃ of vacuum drying 24 hours are the chloride CNT.
100mg chloride CNT, 100 mg sodium sulfanilates are added in the 5 g dimethyl formamides ultrasonic dispersion 10 minutes.Under 80 ℃, nitrogen protection, stirring reaction 18 hours.After question response liquid is cooled to room temperature, wash for several times to remove residue with nylon leaching film suction filtration, oxolane.50 ℃ of vacuum drying 12 hours, it is carbon nano-tube modified namely to get sodium sulfanilate.TGA result shows that the percentage composition of carbon nano-tube modified middle sodium sulfanilate is that 29.9%(sees Fig. 1).CNT dispersed and stable significantly strengthen (seeing Fig. 2 and Fig. 3) in water after modifying.
With 200mg to the carbon nano-tube modified adding of amino this sodium sulfonate 40g 50mg.L
-1Copper sulfate solution in, ultrasonic 30min.Constant temperature absorption was used the nylon leaching film suction filtration after 1 hour.Analytical test shows that the removal efficiency to copper ion reaches 90%.
Embodiment 2
1.0 g SWCNs are added in the red fuming nitric acid (RFNA) of 200 g, under 80 ℃ and the condition that stirs, added hot reflux 12 hours.After being cooled to room temperature, high speed centrifugation separates, and solid is washed till pH value 7 with deionized water.70 ℃ of vacuum drying 10 hours obtain the multi-walled carbon nano-tubes of acidifying.
200mg acidifying CNT, 10 g dimethyl formamides and 40 g thionyl chlorides are mixed ultrasonic dispersion 30 minutes.Then stirring reaction 30 hours under 100 ℃ temperature.Excessive thionyl chloride adopts the method for decompression distillation to remove.Solid product with nylon leaching film filter, the oxolane washing, 60 ℃ of vacuum drying 18 hours are the chloride CNT.
100mg chloride CNT, 200mg sodium sulfanilate are added in the 10 g dimethyl formamides ultrasonic dispersion 20 minutes.Under 60 ℃, nitrogen protection, stirring reaction 36 hours.After question response liquid is cooled to room temperature, wash for several times to remove residue with nylon leaching film suction filtration, oxolane.70 ℃ of vacuum drying 12 hours, it is carbon nano-tube modified namely to get sodium sulfanilate.
With 200mg to the carbon nano-tube modified adding of amino this sodium sulfonate 200g 5mg.L
-1The lead sulfate aqueous solution in, ultrasonic 30min, constant temperature absorption was used the nylon leaching film suction filtration after 2 hours.Analytical test shows that the removal efficiency to copper ion reaches 76%.
Embodiment 3
1.0 g SWCNs are added in the red fuming nitric acid (RFNA) of 150 g, under 90 ℃ and the condition that stirs, added hot reflux 18 hours.After being cooled to room temperature, high speed centrifugation separates, and solid is washed till 7,70 ℃ of vacuum drying of pH value 6 hours with deionized water, obtains the multi-walled carbon nano-tubes of acidifying.
200mg acidifying CNT, 30 dimethyl formamides and 60 g thionyl chlorides are mixed ultrasonic dispersion 30 minutes.Then stirring reaction 25 hours under 90 ℃ temperature.Excessive thionyl chloride adopts the method for decompression distillation to remove.Solid product with nylon leaching film filter, the oxolane washing, 70 ℃ of vacuum drying 12 hours are the chloride CNT.
100mg chloride CNT, 150mg sodium sulfanilate are added in the 15 g dimethyl formamides ultrasonic dispersion 20 minutes.Under 70 ℃, nitrogen protection, stirring reaction 24 hours.After question response liquid is cooled to room temperature, wash for several times to remove residue with nylon leaching film suction filtration, oxolane.60 ℃ of vacuum drying 12 hours, it is carbon nano-tube modified namely to get sodium sulfanilate.
With 200mg to the carbon nano-tube modified adding of amino this sodium sulfonate 100g 20mg.L
-1The lead sulfate aqueous solution in, ultrasonic 30min, constant temperature absorption was used the nylon leaching film suction filtration after 2 hours.Analytical test shows that the removal efficiency to copper ion reaches 80%.
Embodiment 4
1.0 g multi-walled carbon nano-tubes are added in the red fuming nitric acid (RFNA) of 100 g, under 100 ℃ and the condition that stirs, added hot reflux 24 hours.After being cooled to room temperature, high speed centrifugation separates, and solid is washed till pH value 7 with deionized water.50 ℃ of vacuum drying 12 hours obtain the multi-walled carbon nano-tubes of acidifying.
200mg acidifying CNT, 40 g dimethyl formamides and 100 g thionyl chlorides are mixed ultrasonic dispersion 10 minutes.Then stirring reaction 20 hours under 70 ℃ temperature.Excessive thionyl chloride adopts the method for decompression distillation to remove.Solid product with nylon leaching film filter, the oxolane washing, 50 ℃ of vacuum drying 24 hours are the chloride CNT.
100mg chloride CNT, 100 mg sodium sulfanilates are added in the 5 g dimethyl formamides ultrasonic dispersion 10 minutes.Under 80 ℃, nitrogen protection, stirring reaction 18 hours.After question response liquid is cooled to room temperature, wash for several times to remove residue with nylon leaching film suction filtration, oxolane.50 ℃ of vacuum drying 12 hours, it is carbon nano-tube modified namely to get sodium sulfanilate.
With 200mg to the carbon nano-tube modified adding of amino this sodium sulfonate 40g 200mg.L
-1Copper sulfate solution in, ultrasonic 30min.Constant temperature absorption was used the nylon leaching film suction filtration after 2 hours.Analytical test shows that the removal efficiency to copper ion reaches 90%.
Claims (3)
1. method of modifying that is used for the CNT of adsorbed water metal ion includes following steps:
1) CNT is added in the red fuming nitric acid (RFNA), the mass ratio of CNT and red fuming nitric acid (RFNA) is 1:100 ~ 200, under 80 ~ 100 ℃ and the condition that stirs, added hot reflux 12 ~ 24 hours, after being cooled to room temperature, high speed centrifugation separates, the gained solid is washed till 7,50 ℃ ~ 70 ℃ vacuum drying of pH value 6 ~ 12 hours with deionized water, obtains the acidifying CNT;
2) the acidifying CNT that step 1) is obtained, thionyl chloride add in the organic solvent and ultrasonic dispersion 10 ~ 30 minutes, the mass ratio of acidifying CNT and thionyl chloride, organic solvent is respectively 1:200 ~ 500:50 ~ 200, then stirring reaction 20 ~ 30 hours under 70 ℃ ~ 100 ℃ temperature, thionyl chloride is removed in decompression distillation, the gained solid product filters, washs with nylon leaching film, 50 ℃ ~ 70 ℃ vacuum drying 12 ~ 24 hours obtain the chloride CNT;
3) chloride CNT, sodium sulfanilate were added organic solvent for ultrasonic dispersion 10 ~ 20 minutes; the mass ratio of chloride CNT and sodium sulfanilate and organic solvent is respectively 1:1 ~ 2:50 ~ 150; under 60 ℃ ~ 80 ℃, nitrogen protection; stirring reaction 18 ~ 36 hours; after question response liquid is cooled to room temperature; nylon leaching film suction filtration, washing, 50 ℃ ~ 70 ℃ vacuum drying 12 ~ 24 hours obtain the CNT that sodium sulfanilate is modified.
2. according to the method for modifying of CNT claimed in claim 1, it is characterized in that described CNT is SWCN or multi-walled carbon nano-tubes.
3. according to the method for modifying of CNT claimed in claim 1, it is characterized in that described organic solvent is dimethyl formamide or oxolane.
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