CN104607246A - Biomimetic catalytic carbon fiber and preparation method thereof - Google Patents
Biomimetic catalytic carbon fiber and preparation method thereof Download PDFInfo
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- CN104607246A CN104607246A CN201510002884.9A CN201510002884A CN104607246A CN 104607246 A CN104607246 A CN 104607246A CN 201510002884 A CN201510002884 A CN 201510002884A CN 104607246 A CN104607246 A CN 104607246A
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Abstract
The invention relates to a biomimetic catalytic carbon fiber and a preparation method thereof. The biomimetic catalytic carbon fiber is formed by combining a modified carbon fiber containing a pyridine group and metal phthalocyanine in a coordination bond way. The preparation method of the biomimetic catalytic carbon fiber comprises the following steps: dispersing a carbon fiber into a solvent under the condition that the reaction temperature is 60-100 DEG C, adding 4-aminopyridine and a condensing agent fully dissolved in the solvent, stirring and reacting for 2-48 hours, taking out the modified carbon fiber containing the pyridine group after the completion of reaction, respectively washing with a reaction solvent, N,N-dimethyl formamide, water and ethanol and drying at a temperature of 80-100 DEG C to obtain the modified carbon fiber; successively dispersing the modified carbon fiber in the solvent at a reaction temperature of 40-80 DEG C, adding metal phthalocyanine fully dissolved in the solvent, stirring and reacting for 2-48 hours, taking out the carbon fiber loaded with the metal phthalocyanine after the completion of reaction, washing with the reaction solvent, the N,N-dimethyl formamide, the water and the ethanol and drying at a temperature of 80-100 DEG C to obtain the biomimetic catalytic carbon fiber.
Description
Technical field
The present invention relates to a kind of carbon fiber and preparation method thereof, especially a kind of bionic catalysis carbon fiber and preparation method thereof, 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 bionic catalysis carbon fiber of operating and preparation method thereof.The application proposes pyridine groups 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 bionic catalysis carbon fiber, it is characterized in that: the modified carbon fiber containing pyridine groups is be combined by coordinate bond mode between metal phthalocyanine, the metal phthalocyanine feature used has formula 1 structure, wherein: M can be 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 preparation method of bionic catalysis carbon fiber described above, the method is under reaction temperature is the condition of 60-100 DEG C, carbon fiber is scattered in solvent, the 4-aminopyridine 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 80-100 DEG C; Then be under the condition of 40-80 DEG C in reaction temperature, modified carbon fiber is scattered in solvent, the metal phthalocyanine fully dissolved in a solvent is 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 to obtain bionic catalysis carbon fiber for 80-100 DEG C.
The condensing agent that the present invention adopts is isoamyl nitrite.
The described solvent that the present invention adopts is: DMF, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE or DMA.
The invention has the beneficial effects as follows: the gathering that the first, effectively can prevent metal phthalocyanine, make it maintain higher catalytic activity, its catalytic activity improves decades of times than the catalytic activity of Direct Bonding phthalocyanine on above-mentioned 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 of bionic catalysis carbon fiber production method of the present invention.
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.
Bionic catalysis carbon fiber of the present invention, it will be combined by coordinate bond mode between metal phthalocyanine containing the modified carbon fiber of pyridine groups, the metal phthalocyanine feature used has formula 1 structure, wherein: M can be 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,
Carbon fiber diameter of the present invention 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 of bionic catalysis carbon fiber described above, the method is under reaction temperature is the condition of 60-100 DEG C, carbon fiber is scattered in solvent, the 4-aminopyridine 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, DMF, water, ethanol to wash respectively, dry to obtain modified carbon fiber for 80-100 DEG C; Then be under the condition of 40-80 DEG C in reaction temperature, modified carbon fiber is scattered in solvent, the metal phthalocyanine fully dissolved in a solvent is 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 to obtain bionic catalysis carbon fiber for 80-100 DEG C.
The condensing agent that the present invention adopts is isoamyl nitrite.The described solvent that the present invention adopts is: DMF, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE or DMA.
Embodiment 1
A preparation method for bionic catalysis carbon fiber, its concrete steps are:
Take 0.5g4-aminopyridine to be fully dissolved in dimethyl sulfoxide (DMSO), join in the dimethyl sulphoxide solution containing 1.0g carbon fiber after ultrasonic dissolution, vigorous stirring in 60 DEG C of oil baths, 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 pyridine groups, with DMF, water, ethanol cyclic washing, dry the obtained modified carbon fiber containing pyridine groups for 80 DEG C; Then be under the condition of 40 DEG C in reaction temperature, respectively modified carbon fiber, 0.01g are scattered in oxolane without replacement cobalt phthalocyanine, abundant mixing, stirring reaction 48 hours, react the carbon fiber that rear taking-up load has cobalt phthalocyanine, use oxolane, DMF, water, ethanol to wash respectively, dry to obtain bionic catalysis carbon fiber for 80 DEG C.Use the bionic catalysis carbon 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 61.3 times.
Embodiment 2
A preparation method for bionic catalysis carbon fiber, its concrete steps are:
Take 4.5g4-aminopyridine and be fully dissolved in N, in dinethylformamide, join in the DMF containing 2.4g carbon fiber after ultrasonic dissolution, vigorous stirring in 60 DEG C of oil baths, 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 modified carbon fiber containing pyridine groups, with DMF, water, ethanol cyclic washing, dry obtained modified carbon fiber for 90 DEG C; Then be under the condition of 80 DEG C in reaction temperature, respectively modified carbon fiber, 0.45g tetranitro nickel phthalocyanine are scattered in 1-METHYLPYRROLIDONE, abundant mixing, stirring reaction 24 hours, react the carbon fiber that rear taking-up load has nickel phthalocyanine, use 1-METHYLPYRROLIDONE, DMF, water, ethanol to wash respectively, dry to obtain bionic catalysis carbon fiber for 80 DEG C.Use the bionic catalysis carbon 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 11.6 times.
Embodiment 3
A preparation method for bionic catalysis carbon fiber, its concrete steps are:
Take 5.0g4-aminopyridine 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 85 DEG C of oil baths, after temperature is raised to 85 DEG C, dropwise add condensing agent isoamyl nitrite, 85 DEG C are reacted 24 hours, are finally removed by reaction solution, take out the modified carbon fiber containing pyridine groups, with DMF, water, ethanol cyclic washing, dry obtained modified carbon fiber for 100 DEG C; Then be under the condition of 65 DEG C in reaction temperature, respectively modified carbon fiber, 5.0g are scattered in oxolane without replacement iron-phthalocyanine, abundant mixing, stirring and refluxing reacts 15 hours, react the carbon fiber that rear taking-up load has iron-phthalocyanine, use oxolane, DMF, water, ethanol to wash respectively, dry to obtain bionic catalysis carbon fiber for 90 DEG C.Use the bionic catalysis carbon 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 46.9 times.
Embodiment 4
A preparation method for bionic catalysis carbon fiber, its concrete steps are:
Take 5.0g4-aminopyridine and be fully dissolved in N, in dinethylformamide, the N containing 10.0g activated carbon fiber is joined after ultrasonic dissolution, in dinethylformamide solution, vigorous stirring in 100 DEG C of oil baths, condensing agent isoamyl nitrite is dropwise added after temperature is raised to 100 DEG C, 100 DEG C are reacted 8 hours, finally reaction solution is removed, take out the modified activated carbon fiber containing pyridine groups, with DMF, water, ethanol cyclic washing, dry obtained modified activated carbon fiber for 80 DEG C; Then be under the condition of 80 DEG C in reaction temperature, respectively modified activated carbon fiber, 4.0g are scattered in N without replacement copper phthalocyanine, in dinethylformamide, abundant mixing, stirring and refluxing reacts 8 hours, has reacted the activated carbon fiber that rear taking-up load has copper phthalocyanine, has used 1-METHYLPYRROLIDONE, N respectively, dinethylformamide, water, ethanol wash, and dry to obtain bionic catalysis activated carbon fiber for 80 DEG C.Use the bionic catalysis carbon 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 13.9 times.
Embodiment 5
A preparation method for bionic catalysis carbon fiber, its concrete steps are:
Take 10.0g4-aminopyridine 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 60 DEG C of oil baths, after temperature is raised to 60 DEG C, dropwise add condensing agent isoamyl nitrite, 60 DEG C are reacted 4 hours, are finally removed by reaction solution, take out the modified carbon fiber containing pyridine groups, with DMF, water, ethanol cyclic washing, dry obtained modified carbon fiber for 100 DEG C; Then be under the condition of 70 DEG C in reaction temperature, respectively modified carbon fiber, 2.5g tetra amino nickel phthalocyanine are scattered in N, in dinethylformamide, abundant mixing, stirring and refluxing reacts 8 hours, has reacted the carbon fiber that rear taking-up load has nickel phthalocyanine, has used N respectively, dinethylformamide, water, ethanol wash, and dry to obtain bionic catalysis carbon fiber for 90 DEG C.Use the bionic catalysis carbon 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 28.8 times.
Embodiment 6
A preparation method for bionic catalysis carbon fiber, its concrete steps are:
Take 0.5g4-aminopyridine to be fully dissolved in 1-METHYLPYRROLIDONE, join in the 1-METHYLPYRROLIDONE solution containing 8.0g carbon fiber after ultrasonic dissolution, vigorous stirring in 70 DEG C of oil baths, condensing agent isoamyl nitrite is dropwise added after temperature is raised to 70 DEG C, 70 DEG C are reacted 24 hours, are finally removed by reaction solution, take out the modified carbon fiber containing pyridine groups, with 1-METHYLPYRROLIDONE, water, ethanol cyclic washing, dry obtained modified carbon fiber for 90 DEG C; Then be under the condition of 80 DEG C in reaction temperature, respectively modified carbon fiber, 1.6g are scattered in N without replacement cobalt phthalocyanine, in dinethylformamide, abundant mixing, stirring reaction 12 hours, has reacted the carbon fiber that rear taking-up load has cobalt phthalocyanine, has used N respectively, dinethylformamide, water, ethanol wash, and dry to obtain bionic catalysis carbon fiber for 90 DEG C.Use the bionic catalysis carbon 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 36.2 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 (6)
1. a bionic catalysis carbon fiber, is characterized in that: the modified carbon fiber containing pyridine groups is combined by coordinate bond mode between metal phthalocyanine, and the metal phthalocyanine feature of use 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. bionic catalysis carbon fiber 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. bionic catalysis carbon fiber 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. the preparation method of a bionic catalysis carbon fiber as described in claim 1 or 2 or 3, it is characterized in that under reaction temperature is the condition of 60-100 DEG C, carbon fiber is scattered in solvent, the 4-aminopyridine 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 80-100 DEG C; Then be under the condition of 40-80 DEG C in reaction temperature, modified carbon fiber is scattered in solvent, the metal phthalocyanine fully dissolved in a solvent is 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 to obtain bionic catalysis carbon fiber for 80-100 DEG C.
5. the preparation method of bionic catalysis carbon fiber according to claim 4, is characterized in that described condensing agent is isoamyl nitrite.
6. the preparation method of bionic catalysis carbon fiber according to claim 4, is characterized in that described solvent is: DMF, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, DMA or oxolane.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106140300A (en) * | 2016-07-12 | 2016-11-23 | 河海大学 | Preparation method of one kind fenton catalyst and products thereof and application |
| 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 |
| CN115245752A (en) * | 2021-12-21 | 2022-10-28 | 浙江理工大学 | Preparation method of super-hydrophobic ceramic membrane |
| US11517889B2 (en) | 2020-12-21 | 2022-12-06 | Merichem Company | Catalytic carbon fiber contactor |
| US11524283B2 (en) | 2020-12-21 | 2022-12-13 | Merichem Company | Catalytic carbon fiber preparation methods |
| US11826736B2 (en) | 2021-11-29 | 2023-11-28 | Merichem Company | Catalytic carbon fiber preparation methods |
-
2015
- 2015-01-03 CN CN201510002884.9A patent/CN104607246A/en active Pending
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| RUIGUO CAO, ET AL: "promotion of oxygen reduction by a bio-inspired tethered iron phthalocyanine carbon nanotube-based catalyst", 《NATTURE COMMUNICATIONS》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106140300A (en) * | 2016-07-12 | 2016-11-23 | 河海大学 | Preparation method of one kind fenton catalyst and products thereof and application |
| 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 |
| US11517889B2 (en) | 2020-12-21 | 2022-12-06 | Merichem Company | Catalytic carbon fiber contactor |
| US11524283B2 (en) | 2020-12-21 | 2022-12-13 | Merichem Company | Catalytic carbon fiber preparation methods |
| US11826741B2 (en) | 2020-12-21 | 2023-11-28 | Merichem Company | Catalytic carbon fiber preparation methods |
| US11826736B2 (en) | 2021-11-29 | 2023-11-28 | Merichem Company | Catalytic carbon fiber preparation methods |
| CN115245752A (en) * | 2021-12-21 | 2022-10-28 | 浙江理工大学 | Preparation method of super-hydrophobic ceramic membrane |
| CN115245752B (en) * | 2021-12-21 | 2024-01-30 | 浙江理工大学 | Preparation method of super-hydrophobic ceramic membrane |
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Application publication date: 20150513 |