CN100590071C - Preparation of water-soluble carbon nano-tube and nano-precious metal particle load method - Google Patents
Preparation of water-soluble carbon nano-tube and nano-precious metal particle load method Download PDFInfo
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- CN100590071C CN100590071C CN200810062829A CN200810062829A CN100590071C CN 100590071 C CN100590071 C CN 100590071C CN 200810062829 A CN200810062829 A CN 200810062829A CN 200810062829 A CN200810062829 A CN 200810062829A CN 100590071 C CN100590071 C CN 100590071C
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 59
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000002245 particle Substances 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000010970 precious metal Substances 0.000 title claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002923 metal particle Substances 0.000 claims abstract description 10
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims abstract description 3
- 239000000600 sorbitol Substances 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 12
- 239000002048 multi walled nanotube Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical compound [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 230000033444 hydroxylation Effects 0.000 claims description 2
- 238000005805 hydroxylation reaction Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 9
- 239000000376 reactant Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000012643 polycondensation polymerization Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 abstract 1
- 235000015165 citric acid Nutrition 0.000 description 12
- 238000000227 grinding Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 101710134784 Agnoprotein Proteins 0.000 description 4
- 238000005374 membrane filtration Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000729 poly(L-lysine) polymer Polymers 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- -1 carbon nano tube compound Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- TZNXEWGKCWPLQI-UHFFFAOYSA-N pyren-1-ylmethanamine Chemical compound C1=C2C(CN)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 TZNXEWGKCWPLQI-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
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Abstract
The invention relates to a method for preparing a water-solubility carbon nanotube and a method for loading nanometer noble metal particles. The invention is based on the solvent-free modification ofthe carbon nanotube and the in-situ load of the nanometer noble metal particles on the carbon nanotube. In the method, a condensation polymerization of sorbitol and citric acid is carried out on the surface of the carbon nanotube to introduce polycarboxyl and polyhydroxy in order to improve the dispersion stability of the carbon nanotube in water and consequently improves the water-solubility of the carbon nanotube. The method has the advantages that: (1) as no solvent is used when the water-solubility of the carbon nanotube is modified, the method is an environment-friendly method for modifying the carbon nanotube; (2) the dispersion performance of the modified carbon nanotube in the water can be adjusted through a molar ratio of added reactants; (3) functional groups such as carboxyls and hydroxyls on the modified carbon nanotube are utilized to realize further functionalized modification to the carbon nanotube so as to prepare a carbon nanotube-based functional composite material. The load of the noble metal particles carries out in-situ load by utilizing the polycarboxyl and polyhydroxy on the modified carbon nanotube.
Description
Technical field
The present invention relates to a kind of preparation of water-soluble carbon nanometer tube and the carrying method of nano noble metal particles, particularly sorbyl alcohol and citric acid at the solvent-free condensation polymerization of carbon nano tube surface and the original position carrying method of nano silver particles.
Background technology
Water-soluble carbon nanometer tube on biology potential application and the potential application aspect the carbon nanotube-based circumstance friendly composite material caused great concern.Water-soluble one of its scale operation and key in application factor of becoming gradually of carbon nanotube, people have proposed the preparation method of several water-soluble carbon nanometer tubes, wherein a kind of method is exactly by various chemical covalent modification methods the sidewall of carbon nanotube or the port behind the open pipe to be carried out covalency to derive, realize that its dissolving disperses or effectively peels off, and perhaps adopts violent treatment process such as long-time acidifying oxidation, microwave-assisted oxidation to obtain water-soluble carbon nanometer tube.Though yet this method solubleness is good, the charge stripping efficiency height, thus the perfect structure of meeting destroying carbon nanometer tube itself influences its various premium propertiess, and complex disposal process is difficult to control; Another kind of is carbon nanotube to be wrapped up by small molecules tensio-active agent or amphipathic nature polyalcohol with various non-covalent modification methods realizing that its dissolving disperses and peels off, these class methods are little to the damage of carbon nanotube, it is gone up and keeps its original performance, but often have that solubleness is little, poor stability and charge stripping efficiency be low, the more high shortcoming of employed tensio-active agent or polymer concentration, and it is single that these methods are often introduced group, is unfavorable for that the further modification and the function of carbon nanotube is compound.
Nanotube/nano composition causes numerous investigators' interest gradually owing to have the potential application at aspects such as nanoelectronic, sensing and catalysis.And in this nanotube/nano composition, receive much concern owing to carbon nanotube has good electric property, mechanical property, heat conductivility and optical property.The investigator is consistent think the method that is necessary to develop the mild conditions modified carbon nano-tube in case when the preparation carbon nano tube compound material superior electrical, the mechanical property of protection carbon nanotube.(AdvancedMaterials 2007,19 (20), 3167-3170) earlier with poly-L-lysine (PLL) modification MWNTs for people such as Bale.Then with the MWNT-PLL mixture under dark state with AgNO
3Solution effects 24 hours.At last, wash with water except that unnecessary AgNO
3, add NaBH
4Reduction silver has obtained the carbon nanotube of nano silver particles load.People such as Ou (Journal of Physical Chemistry B 2006,110 (5), 2031-2036) adopt 1-pyrene methylamine to prepare the MWNTs of high-density golden nanometer particle load as connecting base, the oxidation aspect that this MWNT-Au nano composition is expected at carbon monoxide has potential application.
Because strong acid treatment causes brokenly ring to carbon nanotube easily; The introducing of simple function group has certain limitation to the carbon nanotube function is compound; Adopt strong reductant with nano metal particles wayward to size of particles when the carbon nano tube surface load, produce and easily produce a large amount of particles in solution.Therefore, be necessary to adopt gentle condition that carbon nanotube is handled, water-soluble to improve it; Carbon nanotube is introduced multi-functional group, especially week reduction group to realize the original position load of nano noble metal particles in carbon nano tube surface.
Summary of the invention
The present invention overcomes these problems that exist in the prior art, and a kind of preparation of water miscible carbon nanotube and the carrying method of nano noble metal particles are provided.
The preparation method of water-soluble carbon nanometer tube grinds the citric acid of 1 weight part carbon nanotube and 10～100 weight parts and sorbitol mixture evenly, the mol ratio of citric acid and sorbyl alcohol consumption is 4: 1～8: 1,100～170 ℃ of heating 1～6 hour, add the water ultra-sonic dispersion, filter 1～8 time, cross filter solid and add water ultra-sonic dispersion, centrifugation, inclining supernatant liquid, promptly gets water-soluble carbon nanometer tube.
Described carbon nanotube is the carbon nanotube that hydroxyl and carboxyl are contained in original carbon nanotube, hydroxylation carbon nanotube, carboxylic carbon nano-tube or surface.
Described carbon nanotube is for adopting single wall, double-walled or the multi-walled carbon nano-tubes of catalyse pyrolysis, arc-over, template or the preparation of laser evaporation method.
Water-soluble carbon nanometer tube nano surface precious metal particle load method is that water-soluble carbon nanometer tube is mixed with 0.00001～1M precious metal ion solution, at stirring at room 8～48h, and centrifugation, the gained solid promptly gets the carbon nanotube of nano noble metal particles load.
Described precious metal is silver, gold, platinum or palladium.
The present invention has following advantage: (1) does not use solvent when carbon nanotube is water-soluble modified, is a kind of carbon nano-tube modification method of environmental protection; (2) dispersing property of modified carbon nanotube in water can be regulated by the mol ratio of the reactant that adds; (3) utilize functional group on the modified carbon nano-tube, can realize that as carboxyl and hydroxyl further functional modification to carbon nanotube is to realize the carbon nanotube base functional composite material.The load of the noble metal among the present invention utilizes many carboxyls, the poly-hydroxy on the modified carbon nanotube to carry out the original position load.
Description of drawings
Fig. 1 (a) is the multi-walled carbon nano-tubes of contrast embodiment 1 prescription modification;
Fig. 1 (b) is the water-soluble multi-wall carbon nanotube of embodiment 1 prescription modification;
Fig. 1 (c) is the carbon nano-tube aqueous solutions after the embodiment 4 prescription load silver particles;
Fig. 2 (a) is the carbon nanotube transmission electron microscope picture after the embodiment 4 prescription load silver particles;
Fig. 2 (b) is the carbon nanotube transmission electron microscope picture after the embodiment 5 prescription load silver particles;
Fig. 3 is the carbon nanotube sem photograph after the embodiment 4 prescription load silver particles.
Embodiment
Embodiment 1
It is even that 50mg multi-walled carbon nano-tubes, 5 mmole citric acids and 1 mmole sorbyl alcohol are carried out mixed grinding, 150 ℃ of heating 3 hours, add water ultra-sonic dispersion, 0.22 μ m membrane filtration 4 times, cross filter solid and add the water ultra-sonic dispersion, 7000rpm separated in centrifugal 15 minutes, inclining supernatant liquid, promptly gets water-soluble carbon nanometer tube.
Embodiment 2
It is even that 50mg Single Walled Carbon Nanotube, 5 mmole citric acids and 1 mmole sorbyl alcohol are carried out mixed grinding, 150 ℃ of heating 3 hours, add water ultra-sonic dispersion, 0.22 μ m membrane filtration 4 times, cross filter solid and add the water ultra-sonic dispersion, 7000rpm separated in centrifugal 15 minutes, inclining supernatant liquid, promptly gets water-soluble carbon nanometer tube.
Embodiment 3
It is even that the carboxylated multi-walled carbon nano-tubes of 50mg, 4 mmole citric acids and 0.8 mmole sorbyl alcohol are carried out mixed grinding, 150 ℃ of heating 2 hours, add water ultra-sonic dispersion, 0.22 μ m membrane filtration 3 times, cross filter solid and add the water ultra-sonic dispersion, 7000rpm separated in centrifugal 15 minutes, inclining supernatant liquid, promptly gets water-soluble carbon nanometer tube.
Embodiment 4
It is even that the carboxylated Single Walled Carbon Nanotube of 50mg, 4 mmole citric acids and 0.8 mmole sorbyl alcohol are carried out mixed grinding, 150 ℃ of heating 2 hours, add water ultra-sonic dispersion, 0.22 μ m membrane filtration 4 times, cross filter solid and add the water ultra-sonic dispersion, 7000rpm separated in centrifugal 15 minutes, inclining supernatant liquid, promptly gets water-soluble carbon nanometer tube.
Embodiment 5
Get the water-soluble carbon nanometer tube and the 1mL 0.001MAgNO of 1m1 embodiment 1 preparation
3Solution mixes, at stirring at room 24h, and centrifugation, the gained solid is the carbon nanotube of nano silver particles load.
Embodiment 6
Get the water-soluble carbon nanometer tube and the 1mL 0.001M AgNO of 1ml embodiment 1 preparation
3Solution mixes, at stirring at room 48h, and centrifugation, the gained solid is the carbon nanotube of nano silver particles load.
Embodiment 7
Get the water-soluble carbon nanometer tube and the 1mL 0.005M HAuCl of 1ml embodiment 1 preparation
4Solution mixes, at stirring at room 24h, and centrifugation, the gained solid is the carbon nanotube of nano Au particle load.
Embodiment 8
Get the water-soluble carbon nanometer tube and the 4mL 0.005M H of 1ml embodiment 1 preparation
2PtCl
6Solution mixes, at stirring at room 24h, and centrifugation, institute and solid are the carbon nanotube of nanometer platinum particles load.
The comparative example 1
It is even that 50mg multi-walled carbon nano-tubes, 3 mmole citric acids and 1 mmole sorbyl alcohol are carried out mixed grinding, and 150 ℃ of heating 3 hours, it was ultrasonic to add water, finds that reactant is difficult to be dispersed in the water, can not get water-soluble carbon nanometer tube.
The comparative example 2
It is even that 50mg Single Walled Carbon Nanotube, 3 mmole citric acids and 1 mmole sorbyl alcohol are carried out mixed grinding, and 150 ℃ of heating 3 hours, it was ultrasonic to add water, finds that reactant is difficult to be dispersed in the water, can not get water-soluble carbon nanometer tube.
The comparative example 3
It is even that the carboxylated multi-walled carbon nano-tubes of 50mg, 2 mmole citric acids and 1 mmole sorbyl alcohol are carried out mixed grinding, and 150 ℃ of heating 3 hours, it was ultrasonic to add water, finds that reactant is difficult to be dispersed in the water, can not get water miscible carbon nanotube.
Below in conjunction with accompanying drawing 1, Fig. 2 and Fig. 3 the water-dispersion stability of water-soluble carbon nanometer tube provided by the present invention and the shape characteristic after the loaded metal silver particles are described.Fig. 1 is the multi-walled carbon nano-tubes of contrast embodiment 1 prescription modification, the water-soluble multi-wall carbon nanotube of embodiment 1 prescription modification and the carbon nano-tube aqueous solutions photo after the embodiment 4 prescription load silver.As can be seen when the proportioning of citric acid and sorbyl alcohol not at that time, institute's modified carbon nanotube difficulty is scattered in the water, shown in Fig. 1 (a).When citric acid and sorbyl alcohol proportioning can obtain stable water-soluble carbon nanometer tube, shown in Fig. 1 (b).Water-soluble carbon nanometer tube is carried out after the metallics load, and its water-soluble decreasing is shown in Fig. 1 (c).
When gained water-soluble carbon nanometer tube of the present invention is carried out the metallic silver corpuscle load, different AgNO
3Concentration will influence the load density of particle in carbon nano tube surface, as Fig. 2 (b) sample because concentration is big thereby particle load density is bigger than Fig. 2 (a).Fig. 3 is the sem photograph of Fig. 2 (a) sample correspondence.
Claims (4)
1. the preparation method of a water-soluble carbon nanometer tube, it is characterized in that the citric acid and the sorbitol mixture of 1 weight part carbon nanotube and 10～100 weight parts are ground evenly, the mol ratio of citric acid and sorbyl alcohol consumption is 4: 1～8: 1,100～170 ℃ of heating 1～6 hour, add the water ultra-sonic dispersion, filter 1～8 time, cross filter solid and add water ultra-sonic dispersion, centrifugation, inclining supernatant liquid, promptly gets water-soluble carbon nanometer tube.
2. a kind of water-soluble carbon nanometer tube preparation method according to claim 1 is characterized in that described carbon nanotube is the carbon nanotube that hydroxyl and carboxyl are contained in original carbon nanotube, hydroxylation carbon nanotube, carboxylic carbon nano-tube or surface.
3. a kind of water-soluble carbon nanometer tube preparation method according to claim 1 is characterized in that described carbon nanotube is for adopting single wall, double-walled or the multi-walled carbon nano-tubes of catalyse pyrolysis, arc-over, template or the preparation of laser evaporation method.
4. water-soluble carbon nanometer tube nano surface precious metal particle load method of method preparation according to claim 1, it is characterized in that the solution of water-soluble carbon nanometer tube with 0.00001～1M precious metal ion is mixed, at stirring at room 8～48h, centrifugation, the gained solid promptly gets the carbon nanotube of nano noble metal particles load; Described precious metal is silver, gold, platinum or palladium.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104192792B (en) | 2008-11-14 | 2016-06-29 | 清华大学 | The preparation method of nanostructured |
| TWI393669B (en) * | 2009-04-10 | 2013-04-21 | Hon Hai Prec Ind Co Ltd | Carbon nanotube composite and method for making the same |
| CN102064311B (en) * | 2010-12-08 | 2013-08-21 | 清华大学 | Preparation method of carbon nanometer tube metal particle composite |
| CN102145255B (en) * | 2011-01-05 | 2013-06-19 | 中国科学院高能物理研究所 | Method for separately preparing water-soluble nano particles with same isoelectric points |
| CN103521750B (en) * | 2012-07-05 | 2016-04-13 | 清华大学 | Carbon nanometer tube metal particle composite and comprise the catalyst material of this compound |
| CN103071805B (en) * | 2013-02-05 | 2015-04-01 | 南京工业大学 | Preparing method of supported type gold-platinum alloy nanocluster material |
| CN104672730B (en) * | 2015-03-16 | 2017-05-17 | 深圳市金百纳纳米科技有限公司 | Water-soluble carbon nanotube material and preparation method thereof |
| CN105214653B (en) * | 2015-08-28 | 2018-09-21 | 北京化工大学 | A kind of preparation method of carbon nanotube loaded nanoparticle catalyst |
| CN109490394A (en) * | 2018-10-24 | 2019-03-19 | 东莞理工学院 | A kind of preparation method of nanogold-carbon nano tube compound material and its application in electro-catalysis |
| CN115055672B (en) * | 2022-06-15 | 2023-10-24 | 安徽理工大学 | Method for preparing coral-shaped gold nano/carbon nano tube composite material |
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