CN103318870A - Preparation method of novel functionalized magnetic carbon nanotube composite material of ferrocenyl derivative - Google Patents

Preparation method of novel functionalized magnetic carbon nanotube composite material of ferrocenyl derivative Download PDF

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CN103318870A
CN103318870A CN201310273987XA CN201310273987A CN103318870A CN 103318870 A CN103318870 A CN 103318870A CN 201310273987X A CN201310273987X A CN 201310273987XA CN 201310273987 A CN201310273987 A CN 201310273987A CN 103318870 A CN103318870 A CN 103318870A
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mwnts
magnetic
carbon nanotube
composite material
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CN103318870B (en
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刘秀辉
裘宇
南志汉
郑李纯
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Northwest Normal University
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Abstract

The invention discloses a preparation method of a novel functionalized magnetic carbon nanotube composite material of ferrocenyl derivative. Magnetic Fe3O4 nano particles are combined with a carbon nanotube by adopting a 'hydrothermal method', also coated by polyethylene imide, and finally condensed into 6-aminocaproic acid ferrocene. An electrode decorated by the nano composite material has a good electric catalytic effect on cytochrome C.

Description

A kind of preparation method of novel ferrocene deriv functional magnetic carbon nano tube compound material
Technical field
The invention belongs to new material technology field, relate to a kind of preparation method of ferrocene deriv functional magnetic carbon nanotube.
Background technology
Carbon nanotube has favorable mechanical performance and physical properties, and this is relevant with strong carbon-to-carbon covalent linkage with its unique atomic structure.Carbon nanotube comprises aspects such as biosensor, medicament transport, gene transmission because its unique electric property and physical property are widely used at biological field.Strong Van der Waals force makes them reunite together usually rather than Individual existence between the carbon nanotube, makes carbon nanotube be insoluble to most of organic solvents; Meanwhile, because living things system is an aqueous environment, this has also caused serious obstruction to carbon nanotube in the application of biological field.Therefore, in order to increase the dispersive ability of carbon nanotube in medium, be necessary that the method for utilizing chemistry or physics connects some molecules at the smooth sidewall of carbon nanotube, functional group makes it have better solvability.
Magnetic ferric oxide nano particles is commonly referred to as the superparamagnetism ferriferrous oxide nano-particle.In more than ten years in the past, the superparamagnetism ferriferrous oxide nano-particle is widely used in numerous areas such as heavy metal separation in the blood, drug release, nucleus magnetic resonance (MRI) contrast medium and biosensor.More than these application not only require the ferric oxide nano particles particle diameter to be less than 100nm, and its size distribution is wanted evenly.In some special fields, even require ferric oxide nano particles that good biocompatibility is arranged, to organism have no side effect and monodispersity good.Have only magnetic ferric oxide nano particles is carried out certain functionalization, could use in above-mentioned field, therefore, preparation and functional magnetic ferric oxide nano particles are the magnetic nano-particle key in application.
Cytochrome c is a kind of protoheme class redox protein matter that contains, and is present in interior ground of the organism tenuigenin, to the research of cytochrome c, can disclose the inside and outside charge transfer mechanism of biological activity cytolemma.
Summary of the invention
Based on above-mentioned, the object of the present invention is to provide a kind of novel ferrocene deriv functional magnetic preparation method of carbon nano-tube.
The object of the present invention is achieved like this:
1. the preparation method of a novel ferrocene deriv functional magnetic carbon nano tube compound material the steps include:
A. 1～10mg multi-walled carbon nano-tubes ultra-sonic dispersion of purifying being crossed adds 1.0～5.0g sodium acetate, anhydrous, 0.2～0.8g FeCl in 20ml ethylene glycol 36H 2O and 2.0～6.0g 1, the 6-hexanediamine, violent stirring to solid dissolves fully, more above-mentioned solution is changed in the polytetrafluoroethyllining lining reactor, keeps 5h down at 150～300 ℃, and the gained black solid is washed three times with secondary water washing, magnetic resolution, vacuum-drying obtains Fe 3O 4-MWNTs solid;
B. get a certain amount of Fe of gained in a step 3O 4-MWNTs nanoparticle is dispersed in 0.5～2.0g10ml -1Polyetherimide (PEI) aqueous solution in, violent stirring is spent the night after ultrasonic 0.5～3.0 hour, black solid is washed 3 times with secondary water washing, magnetic resolution, vacuum-drying obtains NH 2-Fe 3O 4-MWNTs;
C. the b step is obtained the NH of amino functional 2Fe 3O 4-MWNTs 5～15mg is dispersed in the 10ml aqueous solution, add 1mg N-hydroxy-succinamide (NHS), stir 1h, then add 2～3mg 6-aminocaprolc acid ferrocene and 1mg phosphinylidyne diimine hydrochloric acid (EDC), solution stirring is spent the night, magnetic resolution product, black solid wash with water 2～3 times, and vacuum-drying obtains Fc-Fe 3O 4-MWNTs nano composite material.
Advantage of the present invention is:
1, the present invention adopts one step of hydrothermal method to prepare magnetic carbon nano-tube, and preparation process is simple, utilizes Fe in synthesizing 3O 4Magnetic to magnetic carbon nano-tube separate, purifying, method is simple, weak point consuming time;
2, the present invention utilizes the polyethylene imide coated magnetic carbon-nano tube, increases its solvability in water, can change the magnetic carbon nano-tube surface properties, make itself and ferrocene deriv synthetic simple, be easy to get;
3, the present invention utilizes ferrocene deriv functional magnetic carbon nanotube, and this material has good electrocatalysis effect to cytochrome c.
Description of drawings
The ultraviolet of Fig. 1 magnetic carbon nano-tube characterizes (1) carbon nanotube (2) Fe 3O 4(3) magnetic carbon nano-tube
Fig. 2 magnetic carbon nano-tube XRD characterizes
The thermogravimetric of Fig. 3 polyethylene imide coated magnetic carbon-nano tube characterizes
The cyclic voltammetry of Fig. 4 ferrocene deriv functional magnetic carbon nanotube characterizes
Differential pulse curve (1) the cyt c/Au of Fig. 5 cytochrome c, (2) Fc-Fe 3O 4-MWNTs/Au, (3) cyt c-Fc-Fe 3O 4/ Au, (4) cyt c-Fc-Fe 3O 4-MWNTs/Au.
Embodiment
In order to be illustrated more clearly in content of the present invention, below in conjunction with accompanying drawing and specific embodiment the present invention is further described again:
(1) the employed instrument of present embodiment and reagent
Thermogravimetric analyzer (TGA/DSC-1, Switzerland Mettler Toledo); Ultraviolet spectrophotometer (1102); X-ray diffractometer (XD-3A, day island proper Tianjin); Miniature hydrothermal synthesis reaction still (25ml, Taikan, Xi'an biotechnology); Electrochemical analyser (CHI660, Shanghai occasion China) is used for cyclic voltammetry experiment; Magnetic gold electrode (Tianjin English section); Saturated calomel reference electrode (Shanghai Ri Dao).
Multi-walled carbon nano-tubes (diameter 10 – 20 nm, length 1 – 2 μM, purity 〉=95%, nanometer port, Shenzhen company limited); Iron(ic) chloride (FeCl 36H 2O), iron protochloride (FeCl 24H 2O), sodium borohydride (NaBH 4), sodium acetate, anhydrous (NaAc), ethylene glycol (HOCH 2CH 2OH), hexanediamine (NH 2(CH 2) 4NH 2), toluene (C 6H 11CH 3) all available from Shanghai reagent company limited; Sodium hydroxide (NaOH), phosphoric acid (H 3PO 4), SODIUM PHOSPHATE, MONOBASIC (NaH 2PO 4) and Sodium phosphate dibasic (Na 2HPO 4) purchase in Beijing chemical reagents corporation; 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimine hydrochloric acid (EDCHCl), N-hydroxy-succinamide (NHS), polyethylene imide (PEI), formaldehyde ferrocene (Fc-CHO) is available from Aladdin reagent company; All reagent are analytical pure.
(2) preparation of ferrocene deriv functional magnetic carbon nano tube compound material the steps include:
A. multi-walled carbon nano-tubes 1～10mg ultra-sonic dispersion of purifying being crossed adds 1.0～5.0g sodium acetate, anhydrous, 0.2～0.8g FeCl in 20ml ethylene glycol 36H 2O, 2.0～6.0g 1, the 6-hexanediamine, violent stirring to solid dissolves fully.Change above-mentioned solution over to the polytetrafluoroethyllining lining reactor, keep 5h down at 150～300 ℃.The gained black solid is washed three times with secondary water washing, magnetic resolution, and vacuum-drying obtains Fe 3O 4-MWNTs solid.With ultraviolet spectrophotometer its structure is characterized, as Fig. 1.Curve 1, MWNTs have the absorption peak of a maximum, curve 2, Fe at 256 nm places 3O 4At 376 nm places a maximum absorption band is arranged.Curve 3 is Fe 3O 4The ultraviolet-visible spectrum of-MWNTs has absorption peak at 271 nm and 415 nm places respectively, can prove Fe 3O 4Combine with MWNTs.Characterize with the crystal formation of x-ray diffractometer to magnetic nano-particle, as Fig. 2.Among Fig. 2,2 θ=30.0 °, 35.4 °, 43.0 °, 53.4 °, 57.0 °, 62.5 ° diffraction peak is corresponding Fe respectively 3O 4(220), (311), (400), (422), (511), (440) crystal face, 24.4 ° diffraction peak is the characteristic peak of MWNTs, the magnetic nano-particle in thus can testimonial material is Fe 3O 4
B. get a certain amount of Fe 3O 4-MWNTs nanoparticle is dispersed in 0.5～2.0g10ml -1The PEI aqueous solution in, violent stirring is spent the night after ultrasonic 0.5～3.0 hour.Black solid is washed 3 times with secondary water washing, magnetic resolution, and vacuum-drying obtains NH 2-Fe 3O 4-MWNTs.With thermogravimetric analyzer it is characterized, as Fig. 3.Among Fig. 3, curve has obvious loss of weight at 169.0～349.8 ℃, the loss of the loss of weight in this stage be the non covalent bond key and small molecules group such as NH 2Weight loss; At 388.5～650.3 ℃ obvious loss of weight, be the decomposition weight loss that is wrapped in the polyethylene imide in the MWNTs outside.Can prove that by thermogravimetric analysis polyethylene acyl Asia successfully has been wrapped in the outside of magnetic carbon nano-tube.
C. with the Fe of amino functional 3O 4-MWNTs 5～15mg is dispersed in the 10ml aqueous solution, adds 1mg N-hydroxy-succinamide (NHS) and stirs 1h, then adds 2～3mg 6-aminocaprolc acid ferrocene and 1mg EDC, and solution stirring is spent the night.Magnetic resolution product, black solid wash with water 2～3 times, and vacuum-drying obtains Fc-Fe 3O 4-MWNTs nano composite material; With 2.0 mg Fc-Fe 3O 4-MWNTs adds in the 1.0 ml redistilled waters, ultra-sonic dispersion 1 h; Get 3.0 μ L dispersant liquid drops then and be coated in gold electrode surfaces, dry naturally.In 0～0.6V potential window scope, with 50 mVs -1Sweep velocity is carried out cyclic voltammetry scan, as Fig. 4.As can be seen from the figure Fc-Fe 3O 4-MWNTs modified gold electrode is measured a pair of redox peak near 0.3V, redox peak potential difference △ E p=95 mV, this is the redox peak of ferrocene deriv to the peak.Can prove that thus ferrocene deriv successfully has been grafted on NH 2-Fe 3O 4On-MWNTs the composite nano materials.

Claims (1)

1. the preparation method of a novel ferrocene deriv functional magnetic carbon nano tube compound material the steps include:
A. 1～10mg multi-walled carbon nano-tubes ultra-sonic dispersion of purifying being crossed adds 1.0～5.0g sodium acetate, anhydrous, 0.2～0.8g FeCl in 20ml ethylene glycol 36H 2O and 2.0～6.0g 1, the 6-hexanediamine, violent stirring to solid dissolves fully, more above-mentioned solution is changed in the polytetrafluoroethyllining lining reactor, keeps 5h down at 150～300 ℃, and the gained black solid is washed three times with secondary water washing, magnetic resolution, vacuum-drying obtains Fe 3O 4-MWNTs solid;
B. get a certain amount of Fe of gained in a step 3O 4-MWNTs nanoparticle is dispersed in 0.5～2.0g10ml -1The polyetherimide amine aqueous solution in, violent stirring is spent the night after ultrasonic 0.5～3.0 hour, black solid is washed 3 times with secondary water washing, magnetic resolution, vacuum-drying obtains NH 2-Fe 3O 4-MWNTs;
C. the b step is obtained the NH of amino functional 2Fe 3O 4-MWNTs 5～15mg is dispersed in the 10ml aqueous solution, add the 1mg N-hydroxy-succinamide, stir 1h, then add 2～3mg 6-aminocaprolc acid ferrocene and 1mg phosphinylidyne diimine hydrochloric acid, solution stirring is spent the night, magnetic resolution product, black solid wash with water 2～3 times, and vacuum-drying obtains Fc-Fe 3O 4-MWNTs nano composite material.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108912396A (en) * 2018-05-31 2018-11-30 西北师范大学 A kind of preparation method of ferrocene-multi-wall carbon nano-tube composite material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101618867A (en) * 2008-07-02 2010-01-06 中国科学院金属研究所 Method for preparing magnetic metal particle modified carbon nanotube

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Publication number Priority date Publication date Assignee Title
CN101618867A (en) * 2008-07-02 2010-01-06 中国科学院金属研究所 Method for preparing magnetic metal particle modified carbon nanotube

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Title
WENWEN LI ET AL.: "Multiamino-functionalized carbon nanotubes and their applications in loading quantum dots and magnetic nanoparticles", 《J. MATER. CHEM.》, vol. 16, 31 March 2006 (2006-03-31), pages 1852 - 1859 *

Cited By (1)

* Cited by examiner, † Cited by third party
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CN108912396A (en) * 2018-05-31 2018-11-30 西北师范大学 A kind of preparation method of ferrocene-multi-wall carbon nano-tube composite material

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