CN102336759A - Preparation method of planar binuclear metal phthalocyanine coordination compound - Google Patents

Preparation method of planar binuclear metal phthalocyanine coordination compound Download PDF

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CN102336759A
CN102336759A CN2011102056648A CN201110205664A CN102336759A CN 102336759 A CN102336759 A CN 102336759A CN 2011102056648 A CN2011102056648 A CN 2011102056648A CN 201110205664 A CN201110205664 A CN 201110205664A CN 102336759 A CN102336759 A CN 102336759A
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binuclear
phthalocyanine
organic solvent
carbon
metal phthalocyanine
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左霞
杨士锋
李腾飞
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Capital Normal University
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Abstract

The invention relates to a preparation method of a planar binuclear metal phthalocyanine coordination compound, and belongs to the technical field of a phthalocyanine coordination compound. The preparation method comprises the following steps: adding o-dicyanobenzene or derivatives of o-dicyanobenzene, 1,2,4,5-benzenetetranitrile and bivalent metal salt according to a molar ratio of (2-6):1:1 to an organic solvent suspension containing carbon nanotubes, and ultrasonically oscillating to form a homogenous mixed liquid; stirring and reacting for 1-8 hours at the temperature of 160-240 DEG C under nitrogen protection, filtering the product, leaching with absolute ethanol, and drying in vacuum at the temperature of 50-100 DEG C for 10-30 hours to obtain binuclear metal phthalocyanine/carbon nanotube complex; and dissolving binuclear metal phthalocyanine complex on the surface of the carbon nanotubes in the binuclear metal phthalocyanine/carbon nanotube complex with an organic solvent, filtering and evaporating the obtained solution to remove the organic solvent. The preparation method has the advantage that a large amount of single binuclear metal phthalocyanine coordination compound can be obtained at relatively lower temperature within a short time.

Description

The preparation method of a kind of plane binuclear metallo phthalocyanine title complex
Technical field
The present invention relates to the preparation method of plane binuclear metallo phthalocyanine title complex, belong to the phthalocyanine complex technical field.
Background technology
The phthalocyanines title complex is the macrocylc compound with four azepines, four benzoporphyrin structures, has plane big π key conjugated system.The phthalocyanines title complex has half stronger electric conductivity because of it, photoconductivity, and photochemical activity, light compositing is active, and characteristics such as luminous and fluorescence make it in medical science, catalysis, organic semiconductor, fields such as optical conductor have broad application prospects.
Two phthalocyanine molecules can form plane binuclear metallo phthalocyanine title complex through the mode key of shared phenyl ring with linking together.Big π key conjugated system is bigger in the structure of plane binuclear metallo phthalocyanine complex molecule, and stability and catalytic activity are superior to the monokaryon phthalocyanine.
The general compound method of plane binuclear metallo phthalocyanine title complex is scorification and solvent method.Scorification is with Tetra hydro Phthalic anhydride, 1,2,4, and 5-pyromellitic acid dianhydride, metal-salt, urea and ammonium molybdate high-temperature fusion prepare the method for binuclear metallo phthalocyanine compound; Solvent method is 1; 3-diimino isoindoline is at N; Refluxing in N-dimethylaminoethanol (DMAE) solvent prepares no metal binuclear phthalocyanine compound, and this no metal binuclear phthalocyanine compound can further react in DMAE with the anhydrous metal muriate make plane binuclear metallo phthalocyanine compound.One Chinese patent application number is 85108932, open day on November 11st, 1992, the patented claim of " compound method of binuclear phthalocyanine cobalt ammonium sulphonate desulfurization catalyst "; Utilize scorification to synthesize the binuclear phthalocyanine cobalt ammonium sulphonate; Though this method is simple, the generation of monokaryon metal phthalocyanine compound is followed in reaction, because binuclear metallo phthalocyanine and monokaryon metal phthalocyanine compound structural similitude; Separation difficulty is difficult to obtain single binuclear metallo phthalocyanine title complex.
Summary of the invention
The objective of the invention is for overcome long reaction time in the prior synthesizing method, product is difficult for problems such as purifying, providing a kind of is template with the carbon nanotube simply, efficiently, induces the method that generates plane binuclear metallo phthalocyanine title complex.
The invention provides a kind of is the method that template prepares plane binuclear metallo phthalocyanine title complex with the carbon nanotube.Through 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 corresponding binuclear metallo phthalocyanine title complex in the cyclization of carbon nanotube outer wall surface with the metals ion, with the binuclear metallo phthalocyanine title complex dissolving of organic solvent with carbon nano tube surface, obtains purified plane binuclear metallo phthalocyanine title complex then.
The preparation method of a kind of plane of the present invention binuclear metallo phthalocyanine title complex is characterized in that, comprises the steps:
1) according to mol ratio 2～6: 1: 1 with adjacent dicyanobenzenes or adjacent dicyanobenzenes verivate, 1,2,4; 5-benzene tetramethyl nitrile and divalent metal salt join in the organic solvent suspension liquid of carbon nanotubes, and ultrasonic concussion forms uniform mixing liquid, wherein; Adjacent dicyanobenzenes or adjacent dicyanobenzenes verivate, 1; 2,4, the mixture of 5-benzene tetramethyl nitrile and metal-salt and the mass ratio of carbon nanotube are 2～11: 1.
2) above-mentioned mixed solution is under nitrogen protection; In 160～240 ℃ of stirring reaction 1～8h, product is after filtration, absolute ethyl alcohol drip washing to filtrating are colourless, again in 50～100 ℃ of vacuum-drying 10～30h; Obtain black powder shape product, i.e. binuclear metallo phthalocyanine/carbon mano-tube composite.
3) with the binuclear metallo phthalocyanine title complex dissolving of organic solvent with carbon nano tube surface in binuclear metallo phthalocyanine/carbon mano-tube composite, filter, the gained solution evaporation is removed organic solvent, obtains Powdered plane binuclear metallo phthalocyanine title complex.
Wherein, the organic solvent described in the step 1) is selected from a kind of in quinoline, oil of mirbane, chloronaphthalene or the trichlorobenzene; Carbon nanotube described in the step 1) is a multi-walled carbon nano-tubes, and diameter is 50～200nm, and length is 2～20 μ m; Metal-salt described in the step 1) 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; The structural formula of adjacent dicyanobenzenes or adjacent dicyanobenzenes verivate is following:
Figure BDA0000077511310000031
X=H, R, OR, F, Cl, Br, I, wherein R=-CH in the formula 3,-C 2H 5,-C 3H 7
Organic solvent described in the step 3) is selected from N, a kind of in dinethylformamide, toluene, chloroform, the methylene dichloride.
Gained of the present invention plane binuclear metallo phthalocyanine complex structure formula is following:
Figure BDA0000077511310000032
M=Fe, Co, Cu, Zn, Ni, Mn in the structural formula; X=H, R, OR, F, Cl, Br, I, wherein R=-CH 3,-C 2H 5,-C 3H 7
The constitutional features of The compounds of this invention and pattern are through ultraviolet-visible spectrum (UV-Vis), and transmission electron microscope (TEM) characterizes.
The similar of carbon nanotube is in the laminate structure of graphite; The P electronics of carbon atom forms large-scale delocalized pi-bond on the carbon nanotube; π-πGong Ezuoyong can take place in the compound with having a planar conjugate structure, therefore also can with phthalocyanines title complex generation π-πGong Ezuoyong.The π of discovery carbon nanotube and binuclear metallo phthalocyanine title complex-π interacts and obviously is better than the monokaryon metal phthalocyanine complex in our research, so carbon nanotube has the selective adsorption characteristic to the binuclear metallo phthalocyanine title complex.
Advantage of the present invention:
1) in this method since between carbon nanotube and the binuclear metallo phthalocyanine title complex very strong π-π interact, the binuclear metallo phthalocyanine title complex induces time under relatively lower temp at carbon nanotube, in a short period of time just can bulk deposition in carbon nano tube surface.
2) carbon nanotube has selectivity to the inducing action of phthalocyanine metal complex; In the method binuclear metallo phthalocyanine title complex can bulk deposition in carbon nano tube surface; The monokaryon metal phthalocyanine is difficult in its surface growth, therefore adopts this method to help obtaining single binuclear metallo phthalocyanine title complex.
Description of drawings
The ultraviolet-visible light spectrogram of plane binuclear metallo phthalocyanine title complex in DMSO 99.8MIN. (DMSO) of Fig. 1, embodiment 1 preparation;
The transmission electron microscope picture of the plane binuclear metallo phthalocyanine title complex/carbon mano-tube composite of Fig. 2, embodiment 2 preparations.
Embodiment
Embodiment 1
With the adjacent dicyanobenzenes of 0.50g, 0.31g 1,2,4,5-benzene tetramethyl nitrile and 0.35g FeCl 24H 2After the O ground and mixed, add and contain in the quinoline suspension liquid of 0.15g carbon nanotube, ultrasonic concussion formed uniform mixed solution in 5 minutes; Under nitrogen protection, in 160 ℃ of stirring reaction 8h, product filters after absolute ethyl alcohol drip washing to filtrating is colourless; Product is obtained binuclear phthalocyanine iron/carbon mano-tube composite at 80 ℃ of vacuum-drying 24h; Use N, dinethylformamide adopts the Rotary Evaporators evaporation to remove N the binuclear phthalocyanine iron complex dissolving of carbon nano tube surface in binuclear phthalocyanine iron/carbon mano-tube composite; Dinethylformamide obtains Powdered plane binuclear phthalocyanine iron.
Embodiment 2
With the adjacent dicyanobenzenes of 0.60g4-methyl, 0.31g 1,2,4,5-benzene tetramethyl nitrile and 0.35g FeCl 24H 2After the O ground and mixed, add and contain in the quinoline suspension liquid of 0.15g carbon nanotube, ultrasonic concussion formed uniform mixed solution in 5 minutes; Under nitrogen protection, in 160 ℃ of stirring reaction 8h, product filters after absolute ethyl alcohol drip washing to filtrating is colourless; Product is obtained methyl substituted binuclear phthalocyanine iron/carbon mano-tube composite at 80 ℃ of vacuum-drying 24h; Use N, dinethylformamide adopts the Rotary Evaporators evaporation to remove N the methyl substituted binuclear phthalocyanine iron complex dissolving of carbon nano tube surface in methyl substituted binuclear phthalocyanine iron/carbon mano-tube composite; Dinethylformamide obtains Powdered plane methyl substituted binuclear phthalocyanine iron.
Embodiment 3
With the adjacent dicyanobenzenes of 0.60g4-ethyl, 0.31g 1,2,4,5-benzene tetramethyl nitrile and 0.41g CoCl 26H 2After the O ground and mixed; Add and contain in the oil of mirbane suspension liquid of 0.15g carbon nanotube, ultrasonic concussion formed uniform mixed solution in 5 minutes, under nitrogen protection; In 180 ℃ of stirring reaction 4h; Product filters after absolute ethyl alcohol drip washing to filtrating for colourless, obtains ethyl substituted binuclear phthalocyanine cobalt/carbon mano-tube composite with product at 80 ℃ of vacuum-drying 24h, with the ethyl substituted binuclear phthalocyanine cobalt complex dissolving of toluene with carbon nano tube surface in ethyl substituted binuclear phthalocyanine cobalt/carbon mano-tube composite; Adopt the Rotary Evaporators evaporation to remove toluene, obtain Powdered plane ethyl substituted binuclear phthalocyanine cobalt.
Embodiment 4
With the adjacent dicyanobenzenes of 0.80g4-propyl group, 0.31g 1,2,4,5-benzene tetramethyl nitrile and 0.35g FeCl 24H 2After the O ground and mixed; Add and contain in the chloronaphthalene suspension liquid of 0.15g carbon nanotube, ultrasonic concussion formed uniform mixed solution in 5 minutes, under nitrogen protection; In 200 ℃ of stirring reaction 6h; Product filters after absolute ethyl alcohol drip washing to filtrating for colourless, obtains propyl group substituted binuclear FePC/carbon mano-tube composite with product at 80 ℃ of vacuum-drying 24h, with the propyl group substituted binuclear FePC title complex dissolving of chloroform with carbon nano tube surface in propyl group substituted binuclear FePC/carbon mano-tube composite; Adopt the Rotary Evaporators evaporation to remove chloroform, obtain Powdered plane propyl group substituted binuclear FePC.
Embodiment 5
With the adjacent dicyanobenzenes of 0.30g4-methoxyl group, 0.08g 1,2,4,5-benzene tetramethyl nitrile and 0.11g CoCl 26H 2After the O ground and mixed; Add and contain in the trichlorobenzene suspension liquid of 0.10g carbon nanotube, ultrasonic concussion formed uniform mixed solution in 5 minutes, under nitrogen protection; In 180 ℃ of stirring reaction 6h; Product filters after absolute ethyl alcohol drip washing to filtrating for colourless, obtains methoxyl group substituted binuclear phthalocyanine cobalt/carbon mano-tube composite with product at 80 ℃ of vacuum-drying 24h, with the methoxyl group substituted binuclear phthalocyanine cobalt complex dissolving of methylene dichloride with carbon nano tube surface in methoxyl group substituted binuclear phthalocyanine cobalt/carbon mano-tube composite; Adopt the Rotary Evaporators evaporation to remove methylene dichloride, obtain Powdered plane methoxyl group substituted binuclear phthalocyanine cobalt.
Embodiment 6
With the adjacent dicyanobenzenes of 0.30g4-oxyethyl group, 0.08g 1,2,4,5-benzene tetramethyl nitrile and 0.11g CoCl 26H 2After the O ground and mixed; Add and contain in the quinoline suspension liquid of 0.10g carbon nanotube, ultrasonic concussion formed uniform mixed solution in 5 minutes, under nitrogen protection; In 200 ℃ of stirring reaction 4h; Product filters after absolute ethyl alcohol drip washing to filtrating for colourless, obtains oxyethyl group substituted binuclear phthalocyanine cobalt/carbon mano-tube composite with product at 80 ℃ of vacuum-drying 24h, with the oxyethyl group substituted binuclear phthalocyanine cobalt complex dissolving of methylene dichloride with carbon nano tube surface in oxyethyl group substituted binuclear phthalocyanine cobalt/carbon mano-tube composite; Adopt the Rotary Evaporators evaporation to remove methylene dichloride, obtain Powdered plane oxyethyl group substituted binuclear phthalocyanine cobalt.
Embodiment 7
With the adjacent dicyanobenzenes of 0.30g4-propoxy-, 0.08g 1,2,4,5-benzene tetramethyl nitrile and 0.09g FeCl 24H 2After the O ground and mixed, add and contain in the trichlorobenzene suspension liquid of 0.10g carbon nanotube, ultrasonic concussion formed uniform mixed solution in 5 minutes; Under nitrogen protection, in 230 ℃ of stirring reaction 2h, product filters after absolute ethyl alcohol drip washing to filtrating is colourless; Product is obtained propoxy-substituted binuclear FePC/carbon mano-tube composite at 80 ℃ of vacuum-drying 24h; Use N, dinethylformamide adopts the Rotary Evaporators evaporation to remove N the propoxy-substituted binuclear FePC title complex dissolving of carbon nano tube surface in propoxy-substituted binuclear FePC/carbon mano-tube composite; Dinethylformamide obtains Powdered plane propoxy-substituted binuclear FePC.
Embodiment 8
With the adjacent dicyanobenzenes of 0.80g4-chlorine, 0.31g 1,2,4,5-benzene tetramethyl nitrile and 0.30g CuCl 22H 2After the O ground and mixed, add and contain in the quinoline suspension liquid of 0.15g carbon nanotube, ultrasonic concussion formed uniform mixed solution in 5 minutes; Under nitrogen protection, in 160 ℃ of stirring reaction 8h, product filters after absolute ethyl alcohol drip washing to filtrating is colourless; Product is obtained chloro binuclear phthalocyanine copper/carbon mano-tube composite at 80 ℃ of vacuum-drying 24h; Use N, dinethylformamide adopts the Rotary Evaporators evaporation to remove N the chloro binuclear phthalocyanine copper complex dissolving of carbon nano tube surface in chloro binuclear phthalocyanine copper/carbon mano-tube composite; Dinethylformamide obtains Powdered plane chloro binuclear phthalocyanine copper.
Embodiment 9
With the adjacent dicyanobenzenes of 0.80g4-bromine, 0.31g 1,2,4,5-benzene tetramethyl nitrile and 0.30g ZnCl 22H 2After the O ground and mixed; Add and contain in the oil of mirbane suspension liquid of 0.15g carbon nanotube, ultrasonic concussion formed uniform mixed solution in 5 minutes, under nitrogen protection; In 180 ℃ of stirring reaction 6h; Product filters after absolute ethyl alcohol drip washing to filtrating for colourless, obtains bromo binuclear phthalocyanine zinc/carbon mano-tube composite with product at 80 ℃ of vacuum-drying 24h, with the bromo binuclear phthalocyanine Zn complex dissolving of toluene with carbon nano tube surface in bromo binuclear phthalocyanine zinc/carbon mano-tube composite; Adopt the Rotary Evaporators evaporation to remove toluene, obtain Powdered plane bromo binuclear phthalocyanine zinc.
Embodiment 10
With the adjacent dicyanobenzenes of 0.90g4-fluorine, 0.31g 1,2,4,5-benzene tetramethyl nitrile and 0.41g NiCl 26H 2After the O ground and mixed; Add and contain in the chloronaphthalene suspension liquid of 0.20g carbon nanotube, ultrasonic concussion formed uniform mixed solution in 5 minutes, under nitrogen protection; In 200 ℃ of stirring reaction 4h; Product filters after absolute ethyl alcohol drip washing to filtrating for colourless, obtains fluoro binuclear phthalocyanine nickel/carbon mano-tube composite with product at 80 ℃ of vacuum-drying 24h, with the fluoro binuclear phthalocyanine nickel complex dissolving of chloroform with carbon nano tube surface in fluoro binuclear phthalocyanine nickel/carbon mano-tube composite; Adopt the Rotary Evaporators evaporation to remove chloroform, obtain Powdered plane fluoro binuclear phthalocyanine nickel.
Embodiment 11
With the adjacent dicyanobenzenes of 1.0g4-iodine, 0.31g 1,2,4,5-benzene tetramethyl nitrile and 0.34g MnCl 24H 2After the O ground and mixed; Add and contain in the trichlorobenzene suspension liquid of 0.20g carbon nanotube, ultrasonic concussion formed uniform mixed solution in 5 minutes, under nitrogen protection; In 240 ℃ of stirring reaction 2h; Product filters after absolute ethyl alcohol drip washing to filtrating for colourless, obtains iodo binuclear phthalocyanine manganese/carbon mano-tube composite with product at 80 ℃ of vacuum-drying 24h, with the iodo binuclear phthalocyanine manganese complex dissolving of methylene dichloride with carbon nano tube surface in iodo binuclear phthalocyanine manganese/carbon mano-tube composite; Adopt the Rotary Evaporators evaporation to remove methylene dichloride, obtain Powdered plane iodo binuclear phthalocyanine manganese.

Claims (5)

1. the preparation method of a plane binuclear metallo phthalocyanine title complex is characterized in that, may further comprise the steps:
1) according to mol ratio 2～6: 1: 1 with adjacent dicyanobenzenes or adjacent dicyanobenzenes verivate, 1,2,4; 5-benzene tetramethyl nitrile and divalent metal salt join in the organic solvent suspension liquid of carbon nanotubes, and ultrasonic concussion forms uniform mixing liquid, wherein; Adjacent dicyanobenzenes or adjacent dicyanobenzenes verivate, 1; 2,4, the mixture of 5-benzene tetramethyl nitrile and metal-salt and the mass ratio of carbon nanotube are 2～11: 1;
2) above-mentioned mixed solution is under nitrogen protection; In 160～240 ℃ of stirring reaction 1～8h, product is after filtration, absolute ethyl alcohol drip washing to filtrating are colourless, again in 50～100 ℃ of vacuum-drying 10～30h; Obtain black powder shape product, i.e. binuclear metallo phthalocyanine/carbon mano-tube composite;
3) with the binuclear metallo phthalocyanine title complex dissolving of organic solvent with carbon nano tube surface in binuclear metallo phthalocyanine/carbon mano-tube composite, filter, the gained solution evaporation is removed organic solvent, obtains Powdered plane binuclear metallo phthalocyanine title complex;
The structural formula of adjacent dinitrile benzene or adjacent dinitrile benzene derivative is following:
Figure FDA0000077511300000011
X=H, R, OR, F, Cl, Br, I, wherein R=-CH in the formula 3,-C 2H 5,-C 3H 7
2. according to the method for claim 1, it is characterized in that the organic solvent described in the step 1) is selected from a kind of in quinoline, oil of mirbane, chloronaphthalene or the trichlorobenzene.
3. according to the method for claim 1, it is characterized in that the carbon nanotube described in the step 1) is a multi-walled carbon nano-tubes, diameter is 50～200nm, and length is 2～20 μ m.
4. according to the method for claim 1, it is characterized in that the metal-salt described in the step 1) 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.
5. according to the method for claim 1, it is characterized in that the organic solvent described in the step 3) is selected from N, a kind of in dinethylformamide, toluene, chloroform, the methylene dichloride.
CN2011102056648A 2011-07-21 2011-07-21 Preparation method of planar binuclear metal phthalocyanine coordination compound Pending CN102336759A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103787302A (en) * 2014-01-23 2014-05-14 黑龙江大学 Preparation method of tetrafluoropropoxy-substituted metal phthalocyanine/carbon nanotube composite material
CN106268956A (en) * 2016-08-08 2017-01-04 常州大学 A kind of double-core carboxyl cobalt phthalocyanine/attapulgite composite photo-catalyst and preparation method thereof
CN111362952A (en) * 2020-02-13 2020-07-03 中南大学 Preparation and application of mono-substituted metal phthalocyanine derivative

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101254916A (en) * 2008-04-11 2008-09-03 北京工业大学 Method for in-situ synthesis of metal phthalocyanine/carbon nano-tube compound
WO2010051102A2 (en) * 2008-09-09 2010-05-06 Sun Chemical Corporation Carbon nanotube dispersions
WO2010063888A1 (en) * 2008-12-02 2010-06-10 Valtion Teknillinen Tutkimuskeskus A catalyst layer for electrochemical applications
CN101985352A (en) * 2010-12-07 2011-03-16 电子科技大学 Method for preparing multi-walled carbon nanotubes from phthalocyanine iron polymer by high temperature solid-phase cracking

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101254916A (en) * 2008-04-11 2008-09-03 北京工业大学 Method for in-situ synthesis of metal phthalocyanine/carbon nano-tube compound
WO2010051102A2 (en) * 2008-09-09 2010-05-06 Sun Chemical Corporation Carbon nanotube dispersions
WO2010063888A1 (en) * 2008-12-02 2010-06-10 Valtion Teknillinen Tutkimuskeskus A catalyst layer for electrochemical applications
CN101985352A (en) * 2010-12-07 2011-03-16 电子科技大学 Method for preparing multi-walled carbon nanotubes from phthalocyanine iron polymer by high temperature solid-phase cracking

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103787302A (en) * 2014-01-23 2014-05-14 黑龙江大学 Preparation method of tetrafluoropropoxy-substituted metal phthalocyanine/carbon nanotube composite material
CN103787302B (en) * 2014-01-23 2015-06-10 黑龙江大学 Preparation method of tetrafluoropropoxy-substituted metal phthalocyanine/carbon nanotube composite material
CN106268956A (en) * 2016-08-08 2017-01-04 常州大学 A kind of double-core carboxyl cobalt phthalocyanine/attapulgite composite photo-catalyst and preparation method thereof
CN106268956B (en) * 2016-08-08 2019-05-14 常州大学 A kind of double-core carboxyl cobalt phthalocyanine/attapulgite composite photo-catalyst and preparation method thereof
CN111362952A (en) * 2020-02-13 2020-07-03 中南大学 Preparation and application of mono-substituted metal phthalocyanine derivative

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Application publication date: 20120201