CN102140145A - Method for grafting carbon nanotubes by using cyclodextrin - Google Patents
Method for grafting carbon nanotubes by using cyclodextrin Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 64
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 64
- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 48
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 12
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 12
- 229960004853 betadex Drugs 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000010907 mechanical stirring Methods 0.000 claims description 14
- 238000004176 ammonification Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229920002301 cellulose acetate Polymers 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000005374 membrane filtration Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 abstract description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 abstract 4
- 102100036475 Alanine aminotransferase 1 Human genes 0.000 abstract 2
- 108010082126 Alanine transaminase Proteins 0.000 abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 2
- 238000002156 mixing Methods 0.000 abstract 2
- 230000021523 carboxylation Effects 0.000 abstract 1
- 238000006473 carboxylation reaction Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000003795 desorption Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 208000016261 weight loss Diseases 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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Abstract
The invention discloses a method for grafting carbon nanotubes by using cyclodextrin and relates to a method for grafting carbon nanotubes, which solves the problems of poor dispersibility, poor solubility, poor electric conductivity and difficulty in operating of the conventional carbon nanotube. The method comprises the following steps of: 1, purifying MWNTs (Multi-Wall Nanotubes) at high temperature and performing carboxylation in mixed acid to obtain MWNTs-COOH; 2, mixing the MWNTs-COOH, HMD (Hexamethylene Diamine) and DMF (Dimethyl Formamide), introducing nitrogen, stirring and adding a THF (Tetrahydrofuran) solvent in which DCC (Dicyclohexylcarbodiimide) is dissolved for reacting; 3, filtering, washing and drying to obtain MWNTs-NH2; 4, preparing a CDP (Cyclodextrin Polymer); and 5, mixing the MWNTs-NH2 with CH2Cl2, stirring, adding GPTM (Glutamic Pyruvic Transaminase), adjusting the pH value, adding the CDP, washing and drying. After a carbon nanotube is functionally modified by using the special structure of beta-cyclodextrin, a carbon nanotube with a unique pore diameter characteristic can be obtained. Moreover, the method has the characteristics of easiness for operation, low cost and the like.
Description
Technical field
The present invention relates to a kind of method of grafting carbon nanotube.
Background technology
Carbon nanotube is a kind of unique nanostructure with remarkable characteristic electron and mechanical characteristics, the axial dimension of carbon nanotube is the micron number magnitude, and radial dimension is a nanometer scale, belongs to a newcomer in the carbon isomer family, is ideal One-dimensional Quantum material.
Because the low solubility and the low dispersity of carbon nanotube, and not easy to operate in any solvent, the process operation difficulty is so limited the application of CNT (carbon nano-tube).Thereby need improve its solvability and dispersiveness by surface modification.In addition, the method by chemistry or physics can also be compound to other functional groups or material the multi-functional material of surface preparation of carbon pipe.Therefore, the functional modification of carbon nanotube is a very important research field.
Summary of the invention
The invention provides a kind of method of utilizing the cyclodextrin grafting carbon nanotube, purpose is for the bad dispersibility that solves existing carbon CNT (carbon nano-tube), poorly soluble, poorly conductive and not easy-operating problem.
Utilize the method for cyclodextrin grafting carbon nanotube to carry out according to the following steps: one, MWNTs (multi-walled carbon nano-tubes) to be put into crucible, at 300～500 ℃ of calcination 5～12h, take out the cooling back, the carbon nanotube that gets purifying is designated as p-MWNTs, place mixed acid solution supersound process 3～12h then, after filtration, after the drying carboxylated carbon nanotube be designated as MWNTs-COOH; Two, with the MWNTs-COOH of 0.4g, 2.45 the DMF (N of the HMD of～9.79g (hexanediamine) and 40～163mL, dinethylformamide) mixes the back and feed nitrogen, mechanical stirring 30min then, add 13～50mL again and be dissolved with THF (tetrahydrofuran (THF)) solvent of 2.45～9.79g DCC (dicyclohexyl carbodiimide), react 1～4d under the room temperature; Three, after reaction finishes, with the aperture is the cellulose acetate membrane filtration of 0.45 μ m, uses THF and distilled water flush away unnecessary HMD and DCC then successively, will wash after product and take out, dry 24h in 80 ℃ of vacuum drying ovens again, the carbon nanotube of ammonification is designated as MWNTs-NH
2Four, with the beta-cyclodextrin of 2.5g (β-CD) be dissolved in the NaOH solution that 5mL concentration is 1mol/L, mechanical stirring 24h under the room temperature dropwise adds the 3.5mL epoxy chloropropane again, reaction 3h, after washing and drying, must CDP (cyclodextrin linear polymer); Five, with the MWNTs-NH of 0.2g
2CH with 50g
2Cl
2Place Erlenmeyer flask and stir 24h, drip the silane coupling agent GPTM of 2.5mL and stir 3h, regulate pH to 3～5 with HCl solution then, the CDP that adds 0.3g again, reaction 3h after washing and drying, promptly finishes and utilizes the cyclodextrin grafting carbon nanotube to be designated as MWNTs-CDP;
Wherein mixed acid solution is to be that 98% the vitriol oil and volumetric concentration are that 65% concentrated nitric acid mixes gained by volume at 1～3: 1 with volumetric concentration in the step 1; The power of supersound process is 100W in the step 1.
Beta-cyclodextrin is slightly tapered drum shape molecule among the present invention, have hydrophobic inner chamber and hydrophilic appearance, the special cavity of this " interior hydrophobic; outer hydrophilic ", can interact with hydrophobic molecule, form reversible host-guest inclusion compound, improve the solubleness of hydrophobicity guest molecule in water, reaction can be carried out in environment amenable water; Simultaneously, this cavity is rich electrical, can influence the electrical environment of guest molecule, makes to be reflected under the gentle condition and just can carry out effectively; Hydroxyl on the beta-cyclodextrin awl tube also can make reaction carry out towards favourable direction by the hydrogen bond action between the Subjective and Objective; Therefore, the special structure of beta-cyclodextrin has obtained a kind of carbon nanotube with unique aperture characteristics to the functionalization modification, has played the dispersiveness of improving carbon nanotube, solvability, the effect of electroconductibility and ease for operation.
The present invention utilizes silane coupling agent GPTM, and cyclodextrin is grafted on amidized carbon nanotube, makes its functional method, and technological operation is simple, and cost is lower, saves time; This is to propose to utilize the method for cyclodextrin to functionalization, the cyclodextrin grafting carbon nanotube that makes to have better thermostability and unique aperture at present first.The special aperture characteristics of cyclodextrin grafting carbon nanotube make it have very big potentiality to be applied to adsorb organic pollutant or heavy metal contaminants in the environment.
Description of drawings
Fig. 1 is the infrared spectrogram of the carbon nanotube grafted cyclodextrin polymkeric substance front and back of ammonification in the embodiment ten; Fig. 2 is the x-ray photoelectron spectroscopy figure of the carbon nanotube grafted cyclodextrin polymkeric substance front and back of ammonification in the embodiment ten; Fig. 3 is the heat decomposition curve figure of the carbon nanotube grafted cyclodextrin polymkeric substance front and back of ammonification in the embodiment ten; Fig. 4 is the BET absorption/desorption graphic representation of the carbon nanotube of purifying in the embodiment ten, and wherein ■ represents absorption, ▲ expression desorption; Fig. 5 is the BET absorption/desorption graphic representation of beta-cyclodextrin in the embodiment ten, and wherein ■ represents absorption, ▲ expression desorption; Fig. 6 is the BET absorption/desorption graphic representation of cyclodextrin grafted carbon nanotube in the embodiment ten, and wherein ■ represents absorption, ▲ expression desorption.
Embodiment
Embodiment one: present embodiment utilizes the method for cyclodextrin grafting carbon nanotube to carry out according to the following steps: one, MWNTs (multi-walled carbon nano-tubes) is put into crucible, at 300～500 ℃ of calcination 5～12h, take out the cooling back, the carbon nanotube that gets purifying is designated as p-MWNTs, place mixed acid solution supersound process 3～12h then, after filtration, after the drying carboxylated carbon nanotube be designated as MWNTs-COOH; Two, with the MWNTs-COOH of 0.4g, 2.45 the DMF (N of the HMD of～9.79g (hexanediamine) and 40～163mL, dinethylformamide) mixes the back and feed nitrogen, mechanical stirring 30min then, add 13～50mL again and be dissolved with THF (tetrahydrofuran (THF)) solvent of 2.45～9.79g DCC (dicyclohexyl carbodiimide), react 1～4d under the room temperature; Three, after reaction finishes, with the aperture is the cellulose acetate membrane filtration of 0.45 μ m, uses THF and distilled water flush away unnecessary HMD and DCC then successively, will wash after product and take out, dry 24h in 80 ℃ of vacuum drying ovens again, the carbon nanotube of ammonification is designated as MWNTs-NH
2Four, with the beta-cyclodextrin of 2.5g (β-CD) be dissolved in the NaOH solution that 5mL concentration is 1mol/L, mechanical stirring 24h under the room temperature dropwise adds the 3.5mL epoxy chloropropane again, reaction 3h, after washing and drying, must CDP (cyclodextrin linear polymer); Five, with the MWNTs-NH of 0.2g
2CH with 50g
2Cl
2Place Erlenmeyer flask and stir 24h, drip the silane coupling agent GPTM of 2.5mL and stir 3h, regulate pH to 3～5 with HCl solution then, the CDP that adds 0.3g again, reaction 3h after washing and drying, promptly finishes and utilizes the cyclodextrin grafting carbon nanotube to be designated as MWNTs-CDP;
Wherein mixed acid solution is to be that 98% the vitriol oil and volumetric concentration are that 65% concentrated nitric acid mixes gained by volume at 1～3: 1 with volumetric concentration in the step 1; The power of supersound process is 100W in the step 1.
Gained MWNTs-COOH is behind acid base titration in the present embodiment step 1, and carboxyl-content is 1～4mmol/g.
Embodiment two: what present embodiment and embodiment one were different is in the step 1 MWNTs to be put into crucible, at 300 ℃ of calcination 12h.Other step and parameter are identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is in the step 1 MWNTs to be put into crucible, at 500 ℃ of calcination 5h.Other step and parameter are identical with embodiment one.
Embodiment four: what present embodiment and embodiment one were different is in the step 1 MWNTs to be put into crucible, at 350～450 ℃ of calcination 7～10h.Other step and parameter are identical with embodiment one.
Embodiment five: what present embodiment and embodiment one were different is in the step 1 MWNTs to be put into crucible, at 400 ℃ of calcination 8h.Other step and parameter are identical with embodiment one.
Embodiment six: present embodiment is different with one of embodiment one to five is with the MWNTs-COOH of 0.4g in the step 2,2.45g HMD and the DMF of 40mL mix the back and feed nitrogen, mechanical stirring 30min then, add 13mL again and be dissolved with the THF solvent of 2.45g DCC, react 1d under the room temperature.Other step and parameter are identical with one of embodiment one to five.
Embodiment seven: present embodiment is different with one of embodiment one to five is with the MWNTs-COOH of 0.4g in the step 2,9.79g HMD and the DMF of 163mL mix the back and feed nitrogen, mechanical stirring 30min then, add 50mL again and be dissolved with the THF solvent of 9.79g DCC, react 4d under the room temperature.Other step and parameter are identical with one of embodiment one to five.
Embodiment eight: present embodiment is different with one of embodiment one to five is with the MWNTs-COOH of 0.4g in the step 2, the HMD of 6～9g and the DMF of 80～150mL mix the back and feed nitrogen, mechanical stirring 30min then, add 20～45mL again and be dissolved with the THF solvent of 6～9g DCC, react 2～3.5d under the room temperature.Other step and parameter are identical with one of embodiment one to five.
Embodiment nine: present embodiment is different with one of embodiment one to five is with the MWNTs-COOH of 0.4g in the step 2, the HMD of 8g and the DMF of 130mL mix the back and feed nitrogen, mechanical stirring 30min then, add 40mL again and be dissolved with the THF solvent of 8g DCC, react 3d under the room temperature.Other step and parameter are identical with one of embodiment one to five.
Embodiment ten: present embodiment utilizes the method for cyclodextrin grafting carbon nanotube to carry out according to the following steps: one, MWNTs is put into crucible, at 350 ℃ of calcination 6h, take out the cooling back, the carbon nanotube that gets purifying is designated as p-MWNTs, place mixed acid solution supersound process 6h then, after filtration, after the drying carboxylated carbon nanotube be designated as MWNTs-COOH; Two, with the MWNTs-COOH of 0.4g, the HMD of 8g and the DMF of 130mL mix the back and feed nitrogen, and mechanical stirring 30min adds the THF solvent that 40mL is dissolved with 8g DCC more then, reacts 3d under the room temperature; Three, after reaction finishes, with the aperture is the cellulose acetate membrane filtration of 0.45 μ m, uses THF and distilled water flush away unnecessary HMD and DCC then successively, will wash after product and take out, dry 24h in 80 ℃ of vacuum drying ovens again, the carbon nanotube of ammonification is designated as MWNTs-NH
2Four, the beta-cyclodextrin with 2.5g is dissolved in the NaOH solution that 5mL concentration is 1mol/L, and mechanical stirring 24h under the room temperature dropwise adds the 3.5mL epoxy chloropropane again, and reaction 3h after washing and drying, gets CDP; Five, with the MWNTs-NH of 0.2g
2CH with 50g
2Cl
2Place Erlenmeyer flask and stir 24h, drip the silane coupling agent GPTM of 2.5mL and stir 3h, regulate pH to 4 with HCl solution then, the CDP that adds 0.3g again, reaction 3h after washing and drying, promptly finishes and utilizes the cyclodextrin grafting carbon nanotube to be designated as MWNTs-CDP;
Wherein mixed acid solution is to be that 98% the vitriol oil and volumetric concentration are that 65% concentrated nitric acid mixed gained in 3: 1 by volume with volumetric concentration in the step 1; The power of supersound process is 100W in the step 1.
Gained MWNTs-NH in the step 3 in the present embodiment
2(carbon nanotube of ammonification) utilizes infrared spectra and x-ray photoelectron power spectrum to assess, and the result is shown in Fig. 1 (infrared spectrogram before and after the carbon nanotube grafted cyclodextrin polymkeric substance of ammonification), at 2891cm
-1Near individual broad is arranged and diffusing peak is methylene radical-CH
2-charateristic avsorption band has only methylene radical is just arranged on silane coupling agent and the cyclodextrin molecular, thereby proof has been introduced novel substance on aminating carbon nanotube; At 1045cm
-1Near stronger Si-O-stretching vibration peak is arranged, but coincide with the C-N absorption peak, so absorption intensity is very big, proves and on carbon nanotube, introduced new element; 3300 to 3500cm
-1Near-the NH absorption peak is MWNTs-NH
2, MWNTs-CDP is common, but obviously strengthen on the MWNTs-CDP spectrogram, that is because introduced in carbon nano tube surface and to be rich in-cyclodextrin molecular of OH, makes peak area increase.
Shown in Fig. 2 (the x-ray photoelectron energy spectrogram before and after the carbon nanotube grafted cyclodextrin polymkeric substance of ammonification), on the MWNTs-CDP spectrogram, except the Cls peak occurring at 284eV electron binding energy place, the Ols peak appears in 532eV electron binding energy place, 399eV electron binding energy place occurs outside the Nls peak, also 102.7, Si2p, Si2s peak also appearred in the 154.0eV place, this explanation Siliciumatom has been introduced in the surface of carbon nanotube.
MWNTs-NH in the present embodiment
2As shown in table 1 with the MWNTs-CDP constituent content, after carbon nanotube after the ammonification and the silane coupling agent reaction, Si content is 0.26%, and the Si/N ratio is 0.086, illustrates that about 10 N upward just can connect a coupling agent molecule, and percentage of grafting is still than higher; Owing to contain a large amount of hydroxyls among the CDP, the MWNTs that connects silane coupling agent again with the CDP graft reaction after, its oxygen level obviously increases, O/C is than obviously raising simultaneously.
Table 1
Shown in Fig. 3 (the thermogravimetric curve figure before and after the carbon nanotube grafted cyclodextrin polymkeric substance of ammonification), its decomposition temperature of the MWNTs after the CDP modification has increase slightly, and the cyclodextrin decomposition temperature just is exactly 300 ℃, so to begin most be that cyclodextrin is decomposing to MWNTs-CDP; MWNTs-NH
2Since 100 ℃ of thermal weight losses, may be the weightlessness that has some solvents such as DMF, THF, moisture etc. after the MWNTs modification; Second step is that small molecules chain such as amino is disconnected weightless and get; By MWNTs-NH
2, the MWNTs stability of the MWNTs after the modification after than ammonification is good as can be seen for the MWNTs-CDP weight-loss curve; But the rate of weight loss of MWNTs-CDP reaches 37% much larger than the former, illustrates that the CDP content in the grafting is higher.
Shown in Fig. 4,5 and 6 (the BET absorption/desorption graphic representation of the carbon nanotube of purifying, beta-cyclodextrin and cyclodextrin grafted carbon nanotube), in p/po＞0.8 o'clock, MWNTs and MWNTs-CDP have tangible hysteresis loop, and eurypyloue existence is described; In the beta-cyclodextrin curve, as can be seen, do not have tangible hysteresis curve, illustrate that its hole is a mesopore; The adsorptive capacity of the nitrogen of three kinds of materials is followed, MWNTs＞＞MWNTs-CDP＞β-CD, illustrate that the MWNTs-CDP performance is between carbon nanotube and beta-cyclodextrin; In the MWNTs-CDP curve, can also find, when p/po between 0.2-0.8, absorption or desorption curve have the epirelief phenomenon, may be with the fracture of hydrogen bond with form again relevant.
Table 2 is MWNTs-CDP, β-CD and p-MWNTs pore structure parameter: the BET specific surface area follow MWNTs＞＞β-CD＞MWNTs-CDP, and the BJH pore volume follow MWNTs＞＞MWNTs-CDP＞β-CD, mean pore size follow MWNTs＞＞MWNTs-CDP＞β-CD; The former is because the intermolecular reunion of MWNTs-CDP causes specific surface area to descend, and then both orders are consistent with the ordering of nitrogen adsorption amount, illustrates that MWNTs-CDP is with the two performance of β-CD and p-MWNTs; And the characteristics in the hole of this uniqueness of MWNTs-CDP will determine it can be applied to adsorb organic pollutant or heavy metal element in the environment.
Table 2
Claims (5)
1. method of utilizing the cyclodextrin grafting carbon nanotube, it is characterized in that utilizing the method for cyclodextrin grafting carbon nanotube to carry out according to the following steps: one, MWNTs to be put into crucible, at 300～500 ℃ of calcination 5～12h, take out the cooling back, the carbon nanotube that gets purifying is designated as p-MWNTs, place mixed acid solution supersound process 3～12h then, after filtration, after the drying carboxylated carbon nanotube be designated as MWNTs-COOH; Two, with the MWNTs-COOH of 0.4g, the HMD of 2.45～9.79g and the DMF of 40～163mL mix the back and feed nitrogen, and mechanical stirring 30min adds the THF solvent that 13～50mL is dissolved with 2.45～9.79g DCC more then, reacts 1～4d under the room temperature; Three, after reaction finishes, with the aperture is the cellulose acetate membrane filtration of 0.45 μ m, uses THF and distilled water flush away unnecessary HMD and DCC then successively, will wash after product and take out, dry 24h in 80 ℃ of vacuum drying ovens again, the carbon nanotube of ammonification is designated as MWNTs-NH
2Four, the beta-cyclodextrin with 2.5g is dissolved in the NaOH solution that 5mL concentration is 1mol/L, and mechanical stirring 24h under the room temperature dropwise adds the 3.5mL epoxy chloropropane again, and reaction 3h after washing and drying, gets CDP; Five, with the MWNTs-NH of 0.2g
2CH with 50g
2C1
2Place Erlenmeyer flask and stir 24h, drip the silane coupling agent GPTM of 2.5mL and stir 3h, regulate pH to 3～5 with HCl solution then, the CDP that adds 0.3g again, reaction 3h after washing and drying, promptly finishes and utilizes the cyclodextrin grafting carbon nanotube to be designated as MWNTs-CDP;
Wherein mixed acid solution is to be that 98% the vitriol oil and volumetric concentration are that 65% concentrated nitric acid mixes gained by volume at 1～3: 1 with volumetric concentration in the step 1; The power of supersound process is 100W in the step 1.
2. a kind of method of utilizing the cyclodextrin grafting carbon nanotube according to claim 1 is characterized in that in the step 1 MWNTs being put into crucible, at 350～450 ℃ of calcination 7～10h.
3. a kind of method of utilizing the cyclodextrin grafting carbon nanotube according to claim 1 is characterized in that in the step 1 MWNTs being put into crucible, at 400 ℃ of calcination 8h.
4. according to claim 1,2 or 3 described a kind of methods of utilizing the cyclodextrin grafting carbon nanotube, it is characterized in that in the step 2 MWNTs-COOH with 0.4g, the HMD of 6～9g and the DMF of 80～150mL mix the back and feed nitrogen, mechanical stirring 30min then, add 20～45mL again and be dissolved with the THF solvent of 6～9g DCC, react 2～3.5d under the room temperature.
5. a kind of method of utilizing the cyclodextrin grafting carbon nanotube according to claim 4, it is characterized in that in the step 2 MWNTs-COOH with 0.4g, the HMD of 8g and the DMF of 130mL mix the back and feed nitrogen, mechanical stirring 30min then, add 40mL again and be dissolved with the THF solvent of 8g DCC, react 3d under the room temperature.
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