CN101254916B - Method for in-situ synthesis of metal phthalocyanine/carbon nano-tube compound - Google Patents
Method for in-situ synthesis of metal phthalocyanine/carbon nano-tube compound Download PDFInfo
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- CN101254916B CN101254916B CN2008101038068A CN200810103806A CN101254916B CN 101254916 B CN101254916 B CN 101254916B CN 2008101038068 A CN2008101038068 A CN 2008101038068A CN 200810103806 A CN200810103806 A CN 200810103806A CN 101254916 B CN101254916 B CN 101254916B
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Abstract
The invention relates to an in situ synthetic method of metalphthalein/carbon nanotube composite, which belongs to the field of the inorganic/organic nanometer composite material research. The invention solves the problems of metalphthalein/carbon nanotube composite prepared by physical blend method, including weak combination between phthalocyanine molecule and carbon nanotubes, and non-uniform distribution of the phthalocyanine molecule on the surface of the carbon nanotubes. The synthetic method includes adding the carbon nanotubes to the organic solvent, and ultrasonic dispersing for 10-40min to obtain the suspension; and mixing the precursor with metal-salt at a molar ratio of 3-8:1, adding to the suspension at a weight ratio of mixture to the carbon nanotubes of 3-11:1, stirring and reacting at 160-240 DEG C in the nitrogen protecting atmosphere for 1-6h, filtering the resultant, rinsing with he absolute ethanol until the filtrate is colorless, and vacuum drying at 50-100 DEG C for 5-30h to obtain the objective product. The phthalocyanine molecule and the carbon nanotubes are combined tightly, and the phthalocyanine molecule can uniformly grow on the external wall of the carbon nanotubes to form microcrystals.
Description
Technical field
The invention belongs to inorganic/organic nanocomposite research field, be specifically related to a kind of method based on in-situ synthesis of metal phthalocyanine/carbon nano-tube compound.
Background technology
Carbon nanotube (CNT) is a kind of by the coaxial pipe of carbon atom with the hexagonal array single or multiple lift, radial dimension is a nanometer scale, axial dimension is the accurate One-dimensional Quantum material of micron dimension, thereby have very unique electricity and a mechanical property, became the research focus of basic science such as physics, chemistry, material even biology in recent years rapidly, the candidate material that has potentiality as the preparation nano-scale device has wide application scape in many high-tech areas.
At present, the carbon nanotube of various specified propertys causes people's interest gradually, carbon nano tube surface is modified the physics, the chemical property that make carbon nanotube with organic and inorganic or biomolecules and significantly change is taken place and give its how new performance, wherein, prepare the various functional organic molecule/carbon mano-tube composites that have, and it is carried out applied research is an extremely important research direction.Up to the present the carbon nanotube organic chemistry is modified and is realized by two kinds of approach that mainly a kind of is carbon nanotube end group or the chemically modified of carbon pipe sidewall covalent linkage; Another kind is that non covalent bond is modified, as physics coating, surfactant functionalization, polymers functionization, inner chamber functionalization etc.
Phthalocyanine-like compound has high conjugated structure and chemical stability, it is a class organic functions dyestuff, because of it has good light, heat and chemical stability, excellent light, electrical property, and the adjustable sex change of molecular structure makes it have broad application prospects at high-technology fields such as photoconduction, optical storage, photoelectrocatalysis, chemical sensor, photovoltaic cell, nonlinear optics, electrochromism demonstrations.
Existing bibliographical information adopts the physical blending legal system to be equipped with metal phthalocyanine/carbon nano-tube compound, though this method is fairly simple, combine between phthalocyanine molecule and the carbon nanotube and closely comes off easily, and the difficult uniform distribution of controlling molecule in carbon nano tube surface.
Summary of the invention
The objective of the invention is to utilize original position synthetic method that metal phthalocyanine class macrocyclic complex is coated on carbon nano tube surface, form stable metal phthalocyanine/carbon nano-tube compound with microlitic structure.
The method of in-situ synthesis of metal phthalocyanine/carbon nano-tube provided by the present invention, by in suitable organic solvent, with carbon nanotube and the required corresponding presoma of synthetic metal phthalocyanine complex, metal-salt is mixed, precursor molecule is that template generates the corresponding metal phthalocyanine complex in the cyclization of carbon nanotube outer wall surface with the metal ion, finally forms the stable metal phthalocyanine/carbon nano-tube compound with microlitic structure.
Concrete steps are as follows:
1) carbon nanotube is joined in the organic solvent, add-on is 2～20mg carbon nanotube/ml organic solvent, and ultrasonic oscillation disperses 10～40min, obtains carbon nanotube suspension;
2) with presoma and metal-salt in molar ratio after 3～8: 1 ground and mixed; join in the carbon nanotube suspension in the step 1); the mass ratio of presoma and metal salt mixture and carbon nanotube is 3～11: 1; under nitrogen protection; in 160～240 ℃ of stirring reaction 1～6h, product after filtration, dehydrated alcohol drip washing to filtrate be colourless after, again in 50～100 ℃ of vacuum-drying 5～30h; obtain black powder shape product, i.e. metal phthalocyanine/carbon nano-tube compound.
Wherein, described carbon nanotube is a multi-walled carbon nano-tubes, and diameter is 50～200nm, and length is 2～20 μ m; Organic solvent described in the step 1) is selected from a kind of in quinoline, oil of mirbane, chloronaphthalene or the trichlorobenzene; Step 2) presoma described in is adjacent dinitrile benzene or adjacent dinitrile benzene and 1,2,4, and 5-benzene tetramethyl nitrile is 3～6: 1 mixture in molar ratio; Step 2) metal-salt described in is FeCl
24H
2O, CoCl
26H
2O, CuCl
22H
2O, ZnCl
22H
2O, NiCl
26H
2O or MnCl
24H
2A kind of among the O.
Compared with prior art, the present invention has the following advantages:
1) the present invention is made be equipped with combine between the phthalocyanine molecule and carbon nanotube in the metal phthalocyanine/carbon nano-tube compound firm; And the phthalocyanine molecule can be at the carbon pipe outer wall formation crystallite of evenly growing.
2) the prepared metal phthalocyanine/carbon nano-tube compound of the present invention can be used for fields such as hydrogen storage, photoelectrocatalysis, chemical sensor.
Description of drawings
The electronic absorption spectroscopy of metal phthalocyanine/carbon nano-tube compound in dimethyl sulfoxide (DMSO) (DMSO) of Fig. 1, embodiment 1 preparation.
The metal phthalocyanine/carbon nano-tube compound transmission electron microscope photo of Fig. 2, embodiment 2 preparations.
The metal phthalocyanine/carbon nano-tube compound transmission electron microscope photo of Fig. 3, embodiment 3 preparations.
The metal phthalocyanine/carbon nano-tube compound electron diffraction photo of Fig. 4, embodiment 4 preparations.
Below in conjunction with the drawings and the specific embodiments the present invention is further described.
Embodiment
Embodiment 1
1) get the 0.10g multi-walled carbon nano-tubes, diameter is 50～70nm, and length is 20 μ m, adds in the 40ml oil of mirbane, and concussion disperses 20min under ultrasonic wave, obtains carbon nanotube suspension;
2) with the adjacent dinitrile benzene of 0.76g, 0.18g l, 2,4,5-benzene tetramethyl nitrile and 0.22g FeCl
24H
2After the O ground and mixed; add in the carbon nanotube suspension in the step 1); under nitrogen protection; in 200 ℃ of stirring reaction 4h; product filters after dehydrated alcohol drip washing to filtrate is colourless; product is obtained binuclear phthalocyanine iron/carbon mano-tube composite at 80 ℃ of vacuum-drying 24h, and accompanying drawing 1 is the electronic absorption spectroscopy of binuclear phthalocyanine iron/carbon mano-tube composite in DMSO, binuclear phthalocyanine iron Q band maximum absorption band occurs and appears at the 684nm place.
Embodiment 2
1) get the 0.20g multi-walled carbon nano-tubes, diameter is 50～70nm, and length is 20 μ m, adds 40ml oil of mirbane, and concussion disperses 20min under ultrasonic wave, obtains carbon nanotube suspension;
2) with the adjacent dinitrile benzene of 0.64g, 0.18g l, 2,4,5-benzene tetramethyl nitrile and 0.22g FeCl
24H
2After the O ground and mixed; add in the carbon nanotube suspension in the step 1); under nitrogen protection; at 200 ℃ of stirring reaction 4h; product filters after dehydrated alcohol drip washing to filtrate is colourless; product is obtained binuclear phthalocyanine iron/carbon mano-tube composite at 80 ℃ of vacuum-drying 24h, show that from accompanying drawing 2 binuclear phthalocyanines iron/carbon mano-tube composite transmission electron microscope photo binuclear phthalocyanine iron evenly is coated on the surface of carbon nanotube.
Embodiment 3
1) get the 0.10g multi-walled carbon nano-tubes, diameter is 50～70nm, and length is 20 μ m, adds 40ml oil of mirbane, and concussion disperses 40min under ultrasonic wave, obtains carbon nanotube suspension;
2) with the adjacent dinitrile benzene of 0.50g, 0.18g l, 2,4,5-benzene tetramethyl nitrile, 0.22g FeCl
24H
2After the O ground and mixed; add in the carbon nanotube suspension in the step 1); under nitrogen protection; at 200 ℃ of stirring reaction 4h; product filters after dehydrated alcohol drip washing to filtrate is colourless, and product is obtained binuclear phthalocyanine iron/carbon mano-tube composite at 80 ℃ of vacuum-drying 24h, and accompanying drawing 3 is binuclear phthalocyanine iron/carbon mano-tube composite high-resolution-ration transmission electric-lens photo; occur tangible lattice fringe in the photo, show that binuclear phthalocyanine iron forms orderly microlitic structure in carbon nano tube surface.
Embodiment 4
1) get the 0.10g multi-walled carbon nano-tubes, diameter is 50～70nm, and length is 20 μ m, adds 40ml oil of mirbane, and concussion disperses 30min under ultrasonic wave, obtains carbon nanotube suspension;
2) with the adjacent dinitrile benzene of 0.38g, 0.18g l, 2,4,5-benzene tetramethyl nitrile, 0.22g FeCl
24H
2After the O ground and mixed; add in the suspension liquid of the carbon nanotube in the step 1), under nitrogen protection, at 200 ℃ of stirring reaction 4h; product filters after dehydrated alcohol drip washing to filtrate is colourless, and product is obtained binuclear phthalocyanine iron/carbon mano-tube composite at 100 ℃ of vacuum-drying 5h.Accompanying drawing 4 is binuclear phthalocyanine iron/carbon mano-tube composite electron diffraction photo.
Embodiment 5
1) get the 0.80g multi-walled carbon nano-tubes, diameter is 70～100nm, and length is 2～5 μ m, adds 40ml oil of mirbane, and concussion disperses 30min under ultrasonic wave, obtains carbon nanotube suspension;
2) with the adjacent dinitrile benzene of 1.5g, 0.50g CoCl
26H
2After the O ground and mixed; add in the suspension liquid of the carbon nanotube in the step 1), under nitrogen protection, at 160 ℃ of stirring reaction 6h; product filters after dehydrated alcohol drip washing to filtrate is colourless, and product is obtained phthalocyanine cobalt/carbon mano-tube composite at 80 ℃ of vacuum-drying 24h.
Embodiment 6
1) get the 0.10g multi-walled carbon nano-tubes, diameter is 50～70nm, and length is 2～5 μ m, adds the 40ml trichlorobenzene, and concussion disperses 30min under ultrasonic wave, obtains carbon nanotube suspension;
2) with the adjacent dinitrile benzene of 0.50g, 0.20g CuCl
22H
2After the O ground and mixed; add in the suspension liquid of the carbon nanotube in the step 1), under nitrogen protection, at 180 ℃ of stirring reaction 2h; product filters after dehydrated alcohol drip washing to filtrate is colourless, and product is obtained CuPc/carbon mano-tube composite at 50 ℃ of vacuum-drying 30h.
Embodiment 7
1) get the 0.50g multi-walled carbon nano-tubes, diameter is 150～200nm, and length is 20 μ m, adds the 100ml chloronaphthalene, and concussion disperses 40min under ultrasonic wave, obtains carbon nanotube suspension;
2) with the adjacent dinitrile benzene of 1.0g, 0.17g ZnCl
22H
2After the O ground and mixed; add in the suspension liquid of the carbon nanotube in the step 1), under nitrogen protection, at 240 ℃ of stirring reaction 1h; product filters after dehydrated alcohol drip washing to filtrate is colourless, and product is obtained Phthalocyanine Zinc/carbon mano-tube composite at 80 ℃ of vacuum-drying 24h.
Embodiment 8
1) get the 0.10g multi-walled carbon nano-tubes, diameter is 50～70nm, and length is 2～5 μ m, adds the 50ml trichlorobenzene, and concussion disperses 30min under ultrasonic wave, obtains carbon nanotube suspension;
2) with the adjacent dinitrile benzene of 0.17g, 0.10g NiCl
26H
2After the O ground and mixed; add in the suspension liquid of the carbon nanotube in the step 1), under nitrogen protection, at 180 ℃ of stirring reaction 3h; product filters after dehydrated alcohol drip washing to filtrate is colourless, and product is obtained phthalocyanine nickel/carbon mano-tube composite at 80 ℃ of vacuum-drying 24h.
Embodiment 9
1) get the 0.10g multi-walled carbon nano-tubes, diameter is 50～70nm, and length is 2～5 μ m, adds the 40ml quinoline, and concussion disperses 10min under ultrasonic wave, obtains carbon nanotube suspension;
2) with the adjacent dinitrile benzene of 0.50g 0.20g MnCl
24H
2After the O ground and mixed; add in the suspension liquid of the carbon nanotube in the step 1), under nitrogen protection, at 180 ℃ of stirring reaction 4h; product filters after dehydrated alcohol drip washing to filtrate is colourless, and product is obtained manganese phthalocyanine/carbon mano-tube composite at 70 ℃ of vacuum-drying 30h.
Claims (2)
1. the method for an in-situ synthesis of metal phthalocyanine/carbon nano-tube compound is characterized in that, may further comprise the steps:
1) carbon nanotube is joined in the organic solvent, add-on is 2～20mg carbon nanotube/ml organic solvent, and ultrasonic oscillation disperses 10～40min, obtains carbon nanotube suspension;
2) with presoma and metal-salt in molar ratio after 3～8: 1 ground and mixed, join in the carbon nanotube suspension in the step 1), the mass ratio of presoma and metal salt mixture and carbon nanotube is 3～11: 1, under nitrogen protection, in 160～240 ℃ of stirring reaction 1～6h, product after filtration, dehydrated alcohol drip washing to filtrate be colourless after, again in 50～100 ℃ of vacuum-drying 5～30h, obtain black powder shape product, i.e. metal phthalocyanine/carbon nano-tube compound;
Organic solvent described in the step 1) is selected from a kind of in quinoline, oil of mirbane, chloronaphthalene or the trichlorobenzene; Step 2) presoma described in is adjacent dinitrile benzene or adjacent dinitrile benzene and 1,2,4, and 5-benzene tetramethyl nitrile is 3～6: 1 mixture in molar ratio; Step 2) metal-salt described in is FeCl
24H
2O, CoCl
26H
2O, CuCl
22H
2O, ZnCl
22H
2O, NiCl
26H
2O or MnCl
24H
2A kind of among the O.
2. according to the described method of claim 1, it is characterized in that described carbon nanotube is a multi-walled carbon nano-tubes, diameter is 50～200nm, and length is 2～20 μ m.
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| CN102181179B (en) * | 2011-03-15 | 2013-06-26 | 同济大学 | Method for preparing soluble substituted phthalocyanine-carbon nano tube composite photosensitive material by click chemical method |
| CN102323318B (en) * | 2011-05-26 | 2014-02-19 | 首都师范大学 | Enzyme electrode for detecting hydrogen peroxide and preparation method of enzyme electrode |
| CN102336759A (en) * | 2011-07-21 | 2012-02-01 | 首都师范大学 | Preparation method of planar binuclear metal phthalocyanine coordination compound |
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| CN103992327B (en) * | 2014-04-08 | 2016-06-01 | 许昌学院 | Solvent thermal reaction one step prepares the method for manganese phthalocyanine crystal |
| CN104176726B (en) * | 2014-09-05 | 2016-02-03 | 黑龙江大学 | The preparation method of N, N-dialkyl group substituted metal phthalocyanine/carbon nano tube compound material |
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| CN109232906A (en) * | 2018-09-20 | 2019-01-18 | 福建师范大学 | Polyfluoroalkyl axial substituted silicon (IV) phthalocyanine-carbon nanotube supramolecular system and the preparation method and application thereof |
| CN114904531B (en) * | 2022-05-23 | 2024-01-19 | 天津大学 | Supported non-noble metal monoatomic catalyst for oxidative dehydrogenation coupling reaction, and preparation method and application thereof |
| CN116024601A (en) * | 2022-12-28 | 2023-04-28 | 大连理工大学 | Carbon nano tube-based porous hollow fiber electrode for electrocatalytic reduction reaction and application |
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| US6808746B1 (en) * | 1999-04-16 | 2004-10-26 | Commonwealth Scientific and Industrial Research Organisation Campell | Multilayer carbon nanotube films and method of making the same |
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