CN104607244A - Carbon fiber material with catalytic function and preparation method thereof - Google Patents
Carbon fiber material with catalytic function and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carbon fiber material with catalytic function and a preparation method thereof. The carbon fiber material is formed by combining thiophenol group-containing modified carbon fibers with metal phthalocyanine in a way of coordination bond; the preparation method comprises the following steps: dispersing carbon fibers in a solvent, adding diamino diphenyl disulfide and a condensing agent, stirring for reaction, taking out the carbon fibers, respectively washing with a reaction solvent, N, N-dimethylformamide, water and ethanol, and drying at 60 DEG C to obtain modified carbon fibers; dispersing diphenyl disulfide group-containing modified carbon fibers in the solvent, adding triphenylphosphine that is fully dissolved in the solvent, stirring for reaction, taking out the carbon fibers, respectively washing with the reaction solvent, N, N-dimethylformamide, water and ethanol, and drying at 60 DEG C to obtain thiophenol group-containing modified carbon fibers; then dispersing the thiophenol group-containing modified carbon fibers in the solvent, adding metal phthalocyanine and organic bases, stirring for reaction, taking out the carbon fibers, respectively washing with the reaction solvent, N, N-dimethylformamide, water and ethanol, and drying to obtain the finished products.
Description
Technical field
The present invention relates to a kind of carbon fibre material and preparation method thereof, especially a kind of carbon fibre material and preparation method with catalysis, belongs to material, chemistry and chemical technology field.
Background technology
Metal phthalocyanine connects by imines bridged bond the pi-electron Conjugate macrocycle compound that four symmetrical iso-indoles unit form, central metallic ions can be the Determination of multiple metal elements in the periodic table of elements, the phenyl ring of Phthalocyanine periphery can introduce multiple substituting group, and metal phthalocyanine can also be aggregating formation monometallic or many metals poly phthalocyanine by sharing one or more phenyl ring.Its structure has following characteristics: (1) aromatic series pi-electron is conjugation on whole phthalocyanine ring, and LARGE CONJUGATE MOLECULES presents the flatness of height, and catalytic reaction can occur at the axial location of this plane; (2) aromatic rings had both had the characteristic of electron donor, had again the characteristic of electron acceptor; (3) chemical property is highly stable, its acidproof, alkaline-resisting, resistance to water logging, heat-resisting, fast light and resistance to various organic solvent.Above-mentioned feature, make them meet requirement to the intimate harshness of catalyst in catalytic process, can be used as catalyst for polytype reactions such as catalytic oxidation, reduction reaction, carbonylation, decomposition reaction, dehalogenation reaction, decarboxylic reaction, polymerisation and Friedel-Crafts reactions.Kind, the poly phthalocyanine of central metallic ions and peripheral substituent group cause the change etc. of conjugacy can affect the catalytic performance of metal phthalocyanine.In addition, in reaction medium, the degree of association of Phthalocyanine is also larger on the impact of its catalytic performance, structure due to metal phthalocyanine makes it have the dimer even trend of polymer that form non-activity in the solution, the formation of dimer will reduce the active site of axial coordination, thus causes catalytic efficiency significantly to reduce.That effectively can improve metal phthalocyanine by the method for load recycles performance.But current most of load-type metal phthalocyanine syntheti c route is still comparatively complicated, and its solvent resistant and resistant to elevated temperatures stability need to be improved further.In addition, the carrying method of general covalence graft is unfavorable for the transmission of electronics, have impact on the catalytic performance of catalyst.Therefore, a kind of simple and easy, gentle preparation method of exploitation is needed to synthesize the wider load-type metal phthalocyanine catalyst of the scope of application.
Chinese patent application, publication number 103721747A, patent name is " a kind of catalyzed carbon fiber and preparation method thereof ", adopt carbon fibre material as carrier, by containing the metal phthalocyanine of at least one amino by the condensation reaction of deaminizating, directly metal phthalocyanine is bonded directly on carbon fiber, wherein phthalocyanine ring be directly and carbon fibre material form covalent bond, though compared with the metal phthalocyanine of non-load, this catalyzed carbon fiber has higher catalytic activity.But in order to improve the catalytic activity of carbon fibre material supported metal phthalocyanine further, also need to improve the program.
Summary of the invention
The technical problem to be solved in the present invention is the deficiency overcoming above-mentioned background technology, and object is to provide that a kind of equipment is simple, simple process, be easy to a kind of carbon fibre material with catalysis of operating and preparation method thereof.The application proposes benzenethiol group in Direct Bonding on carbon fibre material, then by metal phthalocyanine on the mode bonding of coordinate bond, prepare the bionic catalysis carbon fiber that a class is novel, its catalytic activity improves decades of times than the catalytic activity of Direct Bonding phthalocyanine on above-mentioned carbon fiber.
For achieving the above object, the technical solution used in the present invention is:
A kind of carbon fibre material with catalysis, it is characterized in that: the modified carbon fiber containing benzenethiol group is combined by coordinate bond mode between metal phthalocyanine, the metal phthalocyanine feature used has formula 1 structure, wherein: M is manganese, iron, cobalt, nickel, copper transition metal ions; R
1, R
2, R
3, R
4be respectively-H ,-NH
2,-COOH ,-NO
2,-NHCOCH
3,-NHSO
3h ,-SO
3any one in H.
Described carbon fiber diameter is between 0.2-20 μm, and carbon fiber shape is carbon fiber or the activated carbon fiber of long filament shape, short fiber shape and chopped strand shape; Carbon fiber is oxidization fiber, carbonization silk, finished silk.
The metal phthalocyanine mass percent of described load is 0.08-8%, and the mass fraction of the pyridine groups of load is 0.2-15%.
A kind of above-mentioned preparation method with the carbon fibre material of catalysis, it is characterized in that: be under the condition of 50-100 DEG C in reaction temperature, carbon fiber is scattered in solvent, the diaminourea diphenyl disulfide fully dissolved in a solvent and condensing agent are added wherein, stirring reaction 2-48 hour, has reacted the modified carbon fiber of rear taking-up containing pyridine groups, has used reaction dissolvent, N respectively, dinethylformamide, water, ethanol wash, and dry to obtain modified carbon fiber for 60-100 DEG C; Then be under the condition of 20-60 DEG C in reaction temperature, to be scattered in solvent containing the group modified carbon fiber of diphenyl disulfide, the triphenylphosphine fully dissolved in a solvent is added wherein, stirring reaction 2-12 hour, react the carbon fiber that rear taking-up load has metal phthalocyanine, use reaction dissolvent, DMF, water, ethanol to wash respectively, dry containing the modified carbon fiber of benzenethiol group for 60-100 DEG C; Then be under the condition of 40-80 DEG C in reaction temperature, modified carbon fiber containing benzenethiol group is scattered in solvent, the metal phthalocyanine fully dissolved in a solvent and organic base are added wherein, stirring reaction 2-48 hour, react the carbon fiber that rear taking-up load has metal phthalocyanine, use reaction dissolvent, DMF, water, ethanol to wash respectively, dry the carbon fibre material with catalysis obtaining coordination bonding metal phthalocyanine for 20-100 DEG C.
Described condensing agent is isoamyl nitrite.
Described organic base is monoethanolamine, diethanol amine or triethylamine.
Described solvent is: DMF, dimethyl sulfoxide (DMSO), acetonitrile, absolute ethyl alcohol, 1-METHYLPYRROLIDONE, DMA or oxolane.
The invention has the beneficial effects as follows: the gathering that the first, effectively can prevent metal phthalocyanine, make it maintain higher catalytic activity, use the fiber that the method is obtained, its catalytic activity improves decades of times than the catalytic activity of Direct Bonding phthalocyanine on carbon fiber; ; The second, the impact overcoming some unfavorable factors in homogeneous reaction process is conducive to; Three, by metal phthalocyanine loaded on carbon fiber, decrease the secondary pollution brought because of catalyst loss; 4th, by the mode of axial coordination by metal phthalocyanine loaded on carbon fiber, be conducive to the transmission of electronics, improve its catalytic activity.
The present invention selects carbon fiber or activated carbon fiber to be carrier, and chemical stability is good, and the catalyzed carbon fiber made has higher catalytic activity, is easily separated from solution.In preparation process, combine with coordinate bond, there is technique simple, the advantages such as simple equipments.
The catalyzed carbon fiber that the present invention obtains can be applicable to multiple field, as: the catalytic oxidation of organic pollution, include the catalytic oxidation of organic dye, benzene ring type compounds, naphthalene nucleus compounds and poisonous aromatic compounds, and sulfur-containing compound remove reaction, what comprise sulfur alcohol compound, sulfide, sulfur-containing organic compound etc. removes reaction.In addition, can also remove pernicious gas in air, realize the purification to air.Therefore, the catalyzed carbon fiber that prepared by the present invention has a good application prospect.
Accompanying drawing explanation
Fig. 1 is the process schematic that the present invention has the carbon fibre material preparation method of catalysis.
Detailed description of the invention
For making the object of the embodiment of the present invention, technical scheme and advantage clearly, below in conjunction with the embodiment of the present invention and accompanying drawing, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention, should not be construed as the restriction to the application.
The carbon fibre material with catalysis of the present invention, it is combined by coordinate bond mode between metal phthalocyanine by the modified carbon fiber containing benzenethiol group, the metal phthalocyanine feature used has formula 1 structure, wherein: M is manganese, iron, cobalt, nickel, copper transition metal ions; R
1, R
2, R
3, R
4be respectively-H ,-NH
2,-COOH ,-NO
2,-NHCOCH
3,-NHSO
3h ,-SO
3any one in H.
Described carbon fiber diameter is between 0.2-20 μm, and carbon fiber shape is carbon fiber or the activated carbon fiber of long filament shape, short fiber shape and chopped strand shape; Carbon fiber is oxidization fiber, carbonization silk, finished silk.The metal phthalocyanine mass percent of described load is 0.08-8%, and the mass fraction of the pyridine groups of load is 0.2-15%.
As shown in Figure 1, a kind of preparation method as mentioned above with the carbon fibre material of catalysis, the method is: be under the condition of 50-100 DEG C in reaction temperature, carbon fiber is scattered in solvent, the diaminourea diphenyl disulfide fully dissolved in a solvent and condensing agent is added wherein, stirring reaction 2-48 hour, react the modified carbon fiber of rear taking-up containing pyridine groups, use reaction dissolvent, DMF, water, ethanol to wash respectively, dry to obtain modified carbon fiber for 60-100 DEG C; Then be under the condition of 20-60 DEG C in reaction temperature, to be scattered in solvent containing the group modified carbon fiber of diphenyl disulfide, the triphenylphosphine fully dissolved in a solvent is added wherein, stirring reaction 2-12 hour, react the carbon fiber that rear taking-up load has metal phthalocyanine, use reaction dissolvent, DMF, water, ethanol to wash respectively, dry containing the modified carbon fiber of benzenethiol group for 60-100 DEG C; Then be under the condition of 40-80 DEG C in reaction temperature, modified carbon fiber containing benzenethiol group is scattered in solvent, the metal phthalocyanine fully dissolved in a solvent and organic base are added wherein, stirring reaction 2-48 hour, react the carbon fiber that rear taking-up load has metal phthalocyanine, use reaction dissolvent, DMF, water, ethanol to wash respectively, dry the carbon fibre material with catalysis obtaining coordination bonding metal phthalocyanine for 20-100 DEG C.
Condensing agent of the present invention is isoamyl nitrite.Described organic base is monoethanolamine, diethanol amine or triethylamine.Described solvent is: DMF, dimethyl sulfoxide (DMSO), acetonitrile, absolute ethyl alcohol, 1-METHYLPYRROLIDONE, DMA or oxolane.
Embodiment 1
Have a preparation method for the carbon fibre material of catalysis, its concrete steps are as follows:
Take 0.5g diaminourea diphenyl disulfide to be fully dissolved in dimethyl sulfoxide (DMSO), join in the dimethyl sulphoxide solution containing 1.0g carbon fiber after ultrasonic dissolution, stir in oil bath, after temperature is raised to 60 DEG C, dropwise add condensing agent isoamyl nitrite, 60 DEG C are reacted 48 hours, are finally removed by reaction solution, take out the carbon fiber that load has diphenyl disulfide, with DMF, water, ethanol, acetone cyclic washing, dry obtained carbon fiber loaded diaminourea diphenyl disulfide for 60 DEG C; Then be under the condition of 30 DEG C in reaction temperature, load there is is the carbon fiber of diphenyl disulfide respectively, 0.5g triphenylphosphine is scattered in acetonitrile, abundant mixing, stir 12 hours, react the carbon fiber that rear taking-up load has benzenethiol, use acetonitrile, DMF, water, ethanol, acetone to wash respectively, 60 DEG C of vacuum dryings obtain the modified carbon fiber containing benzenethiol group; Then be under the condition of 80 DEG C in reaction temperature, to be scattered in oxolane without replacement cobalt phthalocyanine, triethylamine containing the modified carbon fiber of benzenethiol group, 0.01g respectively, abundant mixing, stirring reaction 24 hours, react the carbon fiber that rear taking-up load has cobalt phthalocyanine, use oxolane, DMF, water, ethanol, acetone to wash respectively, dry to obtain catalyzed carbon fiber for 60 DEG C.Use the fiber that the method is obtained, its catalytic activation H
2o
2the catalytic activity of specific activity Direct Bonding cobalt phthalocyanine on carbon fiber improve 23.5 times.
Embodiment 2
Have a preparation method for the carbon fibre material of catalysis, its concrete steps are as follows:
Take 4.5g diaminourea diphenyl disulfide and be fully dissolved in N, in dinethylformamide, the N containing 2.4g carbon fiber is joined after ultrasonic dissolution, in dinethylformamide, vigorous stirring in oil bath, condensing agent isoamyl nitrite is dropwise added after temperature is raised to 80 DEG C, 80 DEG C are reacted 24 hours, finally reaction solution is removed, take out the carbon fiber that load has diphenyl disulfide, with DMF, water, ethanol, acetone cyclic washing, dry obtained carbon fiber loaded diphenyl disulfide for 80 DEG C; Then be under the condition of 50 DEG C in reaction temperature, load there is is the carbon fiber of diphenyl disulfide respectively, 2.4g triphenylphosphine is scattered in dimethyl sulfoxide (DMSO), abundant mixing, stir 6 hours, react the carbon fiber that rear taking-up load has benzenethiol, use dimethyl sulfoxide (DMSO), DMF, water, ethanol, acetone to wash respectively, dry the obtained modified carbon fiber containing benzenethiol group for 70 DEG C; Then be under the condition of 90 DEG C in reaction temperature, to be scattered in 1-METHYLPYRROLIDONE containing the modified carbon fiber of benzenethiol group, 0.45g tetranitro nickel phthalocyanine, diethanol amine respectively, abundant mixing, stirring reaction 24 hours, react the carbon fiber that rear taking-up load has nickel phthalocyanine, use 1-METHYLPYRROLIDONE, DMF, water, ethanol, acetone to wash respectively, dry to obtain catalyzed carbon fiber for 80 DEG C.Use the fiber that the method is obtained, its catalytic activation H
2o
2the catalytic activity of specific activity Direct Bonding nickel phthalocyanine on carbon fiber improve 18.6 times.
Embodiment 3
Have a preparation method for the carbon fibre material of catalysis, its concrete steps are as follows:
Take 2.0g diaminourea diphenyl disulfide to be fully dissolved in dimethyl sulfoxide (DMSO), join in the dimethyl sulphoxide solution containing 5.0g carbon fiber after ultrasonic dissolution, vigorous stirring in oil bath, condensing agent isoamyl nitrite is dropwise added after temperature is raised to 80 DEG C, 80 DEG C are reacted 12 hours, finally reaction solution is removed, take out the carbon fiber that load has diphenyl disulfide, with dimethyl sulfoxide (DMSO), N, dinethylformamide, water, ethanol, acetone cyclic washing, dry the carbon fiber that obtained load has diphenyl disulfide for 40 DEG C; Then be under the condition of 30 DEG C in reaction temperature, load there is is the carbon fiber of diphenyl disulfide respectively, 2.0g triphenylphosphine is scattered in oxolane, abundant mixing, stir 2 hours, react the carbon fiber that rear taking-up load has benzenethiol group, use oxolane, DMF, water, ethanol, acetone to wash respectively, dry containing the carbon fiber of benzenethiol group for 30 DEG C; Then be under the condition of 65 DEG C in reaction temperature, to be scattered in oxolane without replacement iron-phthalocyanine, triethylamine containing the carbon fiber of benzenethiol group, 1.0g respectively, abundant mixing, stirring and refluxing reacts 20 hours, react the carbon fiber that rear taking-up load has iron-phthalocyanine, use oxolane, ethanol, acetone, water washing respectively, dry to obtain catalyzed carbon fiber for 30 DEG C.Use the fiber that the method is obtained, its catalytic activation H
2o
2the catalytic activity of specific activity Direct Bonding iron-phthalocyanine on carbon fiber improve 48.9 times.
Embodiment 4
Have a preparation method for the carbon fibre material of catalysis, its concrete steps are as follows:
Take 5.0g diaminourea diphenyl disulfide and be fully dissolved in N, in dinethylformamide, the N containing 10.0g activated carbon fiber is joined after ultrasonic dissolution, in dinethylformamide solution, stir in oil bath, condensing agent isoamyl nitrite is dropwise added after temperature is raised to 85 DEG C, 85 DEG C are reacted 8 hours, finally reaction solution is removed, take out the activated carbon fiber that load has diphenyl disulfide, with DMF, water, ethanol, acetone cyclic washing, dry the activated carbon fiber that obtained load has diphenyl disulfide for 80 DEG C; Then be under the condition of 60 DEG C in reaction temperature, load there is is the activated carbon fiber of diphenyl disulfide respectively, 4.0g triphenylphosphine is scattered in N, in dinethylformamide, abundant mixing, stir 2 hours, reacted the activated carbon fiber that rear taking-up load has benzenethiol, used N respectively, dinethylformamide, oxolane, water, ethanol, acetone wash, and dry containing the activated carbon fiber of benzenethiol group for 80 DEG C; Then be under the condition of 80 DEG C in reaction temperature, respectively activated carbon fiber loaded benzenethiol, 4.0g tetramino copper phthalocyanine, diethanol amine are scattered in oxolane, abundant mixing, stirring and refluxing reacts 8 hours, react the activated carbon fiber that rear taking-up load has copper phthalocyanine, use 1-METHYLPYRROLIDONE, DMF, water, ethanol, acetone to wash respectively, dry to obtain catalytic activity carbon fiber for 80 DEG C.Use the fiber that the method is obtained, its catalytic activation H
2o
2the catalytic activity of specific activity Direct Bonding copper phthalocyanine on carbon fiber improve 21.5 times.
Embodiment 5
Have a preparation method for the carbon fibre material of catalysis, its concrete steps are as follows:
Take 10.0g diaminourea diphenyl disulfide to be fully dissolved in dimethyl sulfoxide (DMSO), join in the dimethyl sulphoxide solution containing 5.0g carbon fiber after ultrasonic dissolution, stir in oil bath, after temperature is raised to 80 DEG C, dropwise add condensing agent isoamyl nitrite, 80 DEG C are reacted 4 hours, are finally removed by reaction solution, take out the carbon fiber that load has diphenyl disulfide, with DMF, water, ethanol, acetone cyclic washing, dry the carbon fiber that obtained load has diphenyl disulfide for 90 DEG C; Then be under the condition of 60 DEG C in reaction temperature, load there is is the carbon fiber of diphenyl disulfide respectively, 2.5g triphenylphosphine is scattered in N, in dinethylformamide, abundant mixing, stir 4 hours, reacted the carbon fiber that rear taking-up load has benzenethiol, used N respectively, dinethylformamide, oxolane, water, ethanol, acetone wash, and dry containing the modified carbon fiber of benzenethiol group for 50 DEG C; Then be under the condition of 70 DEG C in reaction temperature, N is scattered in respectively by containing the modified carbon fiber of benzenethiol group, 2.5g tetranitro iron-phthalocyanine, monoethanolamine, in dinethylformamide, abundant mixing, stirring and refluxing reacts 8 hours, has reacted the carbon fiber that rear taking-up load has iron-phthalocyanine, has used N respectively, dinethylformamide, water, ethanol, acetone wash, and dry to obtain catalyzed carbon fiber for 80 DEG C.Use the fiber that the method is obtained, its catalytic activation H
2o
2the catalytic activity of specific activity Direct Bonding iron-phthalocyanine on carbon fiber improve 26.8 times.
Embodiment 6
Have a preparation method for the carbon fibre material of catalysis, its concrete steps are as follows:
Take 0.5g diaminourea diphenyl disulfide to be fully dissolved in 1-METHYLPYRROLIDONE, join in the 1-METHYLPYRROLIDONE solution containing 8.0g carbon fiber after ultrasonic dissolution, stir in oil bath, condensing agent isoamyl nitrite is dropwise added after temperature is raised to 70 DEG C, 70 DEG C are reacted 24 hours, finally reaction solution is removed, take out the carbon fiber that load has diphenyl disulfide, with 1-METHYLPYRROLIDONE, water, ethanol, acetone cyclic washing, dry the carbon fiber that obtained load has diphenyl disulfide for 90 DEG C; Then be under the condition of 60 DEG C in reaction temperature, load there is is the carbon fiber of diphenyl disulfide respectively, 1.0g triphenylphosphine is scattered in 1-METHYLPYRROLIDONE, abundant mixing, stir 12 hours, react the carbon fiber that rear taking-up load has benzenethiol, use 1-METHYLPYRROLIDONE, oxolane, water, ethanol, acetone to wash respectively, dry containing the modified carbon fiber of benzenethiol group for 70 DEG C; Then be under the condition of 75 DEG C in reaction temperature, to be scattered in oxolane containing the modified carbon fiber of benzenethiol group, 1.6g tetranitro cobalt phthalocyanine, diethanol amine respectively, abundant mixing, stirring reaction 12 hours, react the carbon fiber that rear taking-up load has iron-phthalocyanine, use DMF, water, ethanol, acetone to wash respectively, dry to obtain catalyzed carbon fiber for 90 DEG C.Use the fiber that the method is obtained, its catalytic activation H
2o
2the catalytic activity of specific activity Direct Bonding cobalt phthalocyanine on carbon fiber improve 56.2 times.
Finally should be noted that: above embodiment only in order to technical scheme of the present invention to be described, is not intended to limit; Although with reference to previous embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (7)
1. one kind has the carbon fibre material of catalysis, it is characterized in that: the modified carbon fiber containing benzenethiol group is combined by coordinate bond mode between metal phthalocyanine, the metal phthalocyanine feature used has formula 1 structure, wherein: M is manganese, iron, cobalt, nickel, copper transition metal ions; R
1, R
2, R
3, R
4be respectively-H ,-NH
2,-COOH ,-NO
2,-NHCOCH
3,-NHSO
3h ,-SO
3any one in H,
2. the carbon fibre material with catalysis according to claim 1, is characterized in that described carbon fiber diameter is between 0.2-20 μm, and carbon fiber shape is carbon fiber or the activated carbon fiber of long filament shape, short fiber shape and chopped strand shape; Carbon fiber is oxidization fiber, carbonization silk, finished silk.
3. the carbon fibre material with catalysis according to claim 1 and 2, is characterized in that the metal phthalocyanine mass percent of load is 0.08-8%, and the mass fraction of the pyridine groups of load is 0.2-15%.
4. one kind has the preparation method of the carbon fibre material of catalysis as described in claim 1 or 2 or 3, it is characterized in that under reaction temperature is the condition of 50-100 DEG C, carbon fiber is scattered in solvent, the diaminourea diphenyl disulfide fully dissolved in a solvent and condensing agent are added wherein, stirring reaction 2-48 hour, react the modified carbon fiber of rear taking-up containing pyridine groups, use reaction dissolvent, N respectively, dinethylformamide, water, ethanol wash, and dry to obtain modified carbon fiber for 60-100 DEG C; Then be under the condition of 20-60 DEG C in reaction temperature, to be scattered in solvent containing the group modified carbon fiber of diphenyl disulfide, the triphenylphosphine fully dissolved in a solvent is added wherein, stirring reaction 2-12 hour, react the carbon fiber that rear taking-up load has metal phthalocyanine, use reaction dissolvent, DMF, water, ethanol to wash respectively, dry containing the modified carbon fiber of benzenethiol group for 60-100 DEG C; Then be under the condition of 40-80 DEG C in reaction temperature, modified carbon fiber containing benzenethiol group is scattered in solvent, the metal phthalocyanine fully dissolved in a solvent and organic base are added wherein, stirring reaction 2-48 hour, react the carbon fiber that rear taking-up load has metal phthalocyanine, use reaction dissolvent, DMF, water, ethanol to wash respectively, dry the carbon fibre material with catalysis obtaining coordination bonding metal phthalocyanine for 20-100 DEG C.
5. there is the preparation method of the carbon fibre material of catalysis according to claim 4, it is characterized in that described condensing agent is isoamyl nitrite.
6. there is the preparation method of the carbon fibre material of catalysis according to claim 4, it is characterized in that described organic base is monoethanolamine, diethanol amine or triethylamine.
7. the preparation method of bionic catalysis carbon fiber according to claim 4, is characterized in that described solvent is: DMF, dimethyl sulfoxide (DMSO), acetonitrile, absolute ethyl alcohol, 1-METHYLPYRROLIDONE, DMA or oxolane.
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| CN108246124A (en) * | 2017-12-17 | 2018-07-06 | 浙江理工大学 | A kind of preparation method with the pvdf membrane for being catalyzed self-cleaning function |
| CN116286779A (en) * | 2023-02-07 | 2023-06-23 | 浙江省舟山市水产研究所 | Method for purifying water environment of greenhouse prawn culture by microorganisms |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108246124A (en) * | 2017-12-17 | 2018-07-06 | 浙江理工大学 | A kind of preparation method with the pvdf membrane for being catalyzed self-cleaning function |
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| CN116286779A (en) * | 2023-02-07 | 2023-06-23 | 浙江省舟山市水产研究所 | Method for purifying water environment of greenhouse prawn culture by microorganisms |
| CN116286779B (en) * | 2023-02-07 | 2024-01-05 | 浙江省舟山市水产研究所 | Method for purifying water environment of greenhouse prawn culture by microorganisms |
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Application publication date: 20150513 Assignee: Zhejiang Sci-Tech University Shangyu Industrial Technology Research Institute Co., Ltd. Assignor: Zhejiang University of Technology Contract record no.: X2019330000038 Denomination of invention: Carbon fiber material with catalytic function and preparation method thereof Granted publication date: 20170616 License type: Common License Record date: 20191108 |