CN111943722A - Controllable method for synthesizing carbon nano tube on surface of foamed ceramic and application thereof - Google Patents

Controllable method for synthesizing carbon nano tube on surface of foamed ceramic and application thereof Download PDF

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CN111943722A
CN111943722A CN202010688406.9A CN202010688406A CN111943722A CN 111943722 A CN111943722 A CN 111943722A CN 202010688406 A CN202010688406 A CN 202010688406A CN 111943722 A CN111943722 A CN 111943722A
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foamed ceramic
carbon nanotubes
ceramic
controllable method
synthesizing carbon
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梁波
郭劲
陈瑜
杨文欢
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Guangdong University of Technology
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Abstract

The invention belongs to the technical field of advanced carbon material preparation, and discloses a controllable method for synthesizing carbon nanotubes on the surface of foamed ceramic and application thereof, wherein in the method, the foamed ceramic and a mixed solution are subjected to hydrothermal reaction at 100-180 ℃, the obtained hydrothermally modified foamed ceramic is heated to 400-700 ℃ for calcination and oxidation, then hydrogen is introduced, and the obtained foamed ceramic is heated to 500-700 ℃ for reduction reaction to obtain ferronickel bimetal modified foamed ceramic; introducing protective atmosphere, heating to 500-800 ℃, introducing alkane hydrocarbon and dry air to perform partial oxidation reforming reaction, and thus obtaining the carbon nano tube on the surface of the foamed ceramic. The method is simple, low in cost and suitable for batch production, the carbon nano tube with controllable diameter, length and shape can be prepared on the surface of the foamed ceramic, and the composite material has the advantages of stable structure, excellent mechanical property, good heat transfer conductivity and wide application market.

Description

Controllable method for synthesizing carbon nano tube on surface of foamed ceramic and application thereof
Technical Field
The invention belongs to the technical field of advanced carbon material preparation, and particularly relates to a controllable method for synthesizing carbon nanotubes on the surface of foamed ceramic and application thereof.
Background
Carbon nanotubes are a novel one-dimensional carbon nanomaterial, which was discovered by doctor of electronic corporation of japan (NEC) in 1991. The carbon nano tube has excellent mechanical property, electric conduction and heat conduction performance and adsorption performance. Due to their excellent properties, carbon nanotubes are expected to play an important role in the fields of nanoelectronics, material science, biology, chemistry, and the like. At present, the method is mainly applied to optical sensors, heat sensors, catalysts, filters and the like. The development of new methods for controllable synthesis of carbon nanotubes is of great significance to the development of carbon nanotubes.
At present, methods for preparing carbon nanotubes include arc discharge methods, catalytic cracking methods, laser ablation methods, polymer reaction synthesis, and the like. The arc discharge method is to utilize the arc effect between two graphite rod electrodes to consume the anode graphite rod and deposit carbon nanotube containing product on the cathode. The method has the advantages of violent arc discharge, difficult control of process and products and more impurities in the composition. The laser ablation method is a method for preparing the single-walled carbon nanotube with the diameter distribution range of 0.81-1.51 nm by evaporating the carbon target containing Fe/Ni by using double-pulse laser in argon gas flow, and the carbon nanotube prepared by the method has high purity, but has complex equipment, large energy consumption and high investment cost.
In the patent (CN106517148B), an ester organic compound is used as a carbon source, and is self-heated and reformed with water and oxygen under the action of a catalyst to synthesize the carbon nano-tube, and according to the difference of the types of the catalysts, the length of the prepared carbon nano-tube is 100-500 nm, and the diameter of the prepared carbon nano-tube is 7-30 nm. In the patent (CN101559939B), acetylene, ethylene and the like are used as carbon sources, and carbon nanotubes with the diameter of 5-20 nm are prepared on a polished copper substrate. When the carbon nanotube is applied to a catalyst, a filter, etc., since the catalyst material requires a large specific surface area, excellent heat transfer efficiency; filters also require large specific surface area, excellent adsorption and resistance to acid and alkali corrosion, and porous ceramic foams are the best substrate material for these applications.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, a method for controllably synthesizing carbon nanotubes on the surface of foamed ceramic is provided.
The invention also aims to provide the carbon nano tube/foamed ceramic composite material prepared by the method.
The invention also aims to provide application of the carbon nano tube/foamed ceramic composite material.
The purpose of the invention is realized by the following technical scheme:
a controllable method for synthesizing carbon nanotubes on the surface of foamed ceramic comprises the following specific steps:
s1, dissolving nickel nitrate hexahydrate, ferric nitrate nonahydrate, ammonium fluoride and urea in deionized water, and stirring to obtain a mixed solution;
s2, mixing the foamed ceramic with the mixed solution, carrying out hydrothermal reaction at 100-180 ℃, and then washing and drying to obtain the hydrothermal modified foamed ceramic;
s3, introducing dry air, heating the hydrothermally modified foamed ceramic to 400-700 ℃, calcining and oxidizing, introducing protective atmosphere for purging, introducing hydrogen, heating to 500-700 ℃, and carrying out reduction reaction to obtain the ferronickel bimetal modified foamed ceramic;
and S4, heating to 500-800 ℃ in a protective atmosphere, introducing alkane hydrocarbon and dry air to perform partial oxidation reforming reaction, and cooling to room temperature to synthesize the carbon nano tube on the surface of the foamed ceramic.
Preferably, the molar ratio of the nickel nitrate hexahydrate, the ferric nitrate nonahydrate, the ammonium fluoride and the urea in the step S1 is (1-3): (1-2): (10-15): (20-30).
Preferably, the molar ratio of the total amount of the nickel nitrate hexahydrate, the iron nitrate nonahydrate, the ammonium fluoride and the urea in the step S1 to the deionized water is (3-6): (300-400).
Preferably, in the step S2, the length of the foamed ceramic is 15-18 mm, the width of the foamed ceramic is 6-10 mm, and the height of the foamed ceramic is 6-10 mm.
Preferably, the hydrothermal reaction time in the step S2 is 12-20 h.
Preferably, the calcining and oxidizing time in the step S3 is 2-4 h; the time of the reduction reaction is 2-4 h; the time of the reforming reaction in the step S4 is 1-2 h; the protective atmosphere in steps S3 and S4 is nitrogen or inert gas.
Preferably, the alkane hydrocarbon in step S4 is propane or methane; the flow rate of the alkane hydrocarbon is 40-50 sccm, and the flow rate of the air is 200-400 sccm.
Preferably, the diameter of the carbon nanotube synthesized on the surface of the foamed ceramic in the step S3 is 10-90 nm, and the length is 100-900 nm.
A carbon nano tube/foamed ceramic composite material is prepared by the method.
The carbon nano tube/foamed ceramic composite material is applied to the fields of catalyst carriers and sewage treatment.
The principle of the invention for preparing the carbon nano tube is as follows: the overall reaction of the propane partial oxidation reforming process is shown in equation (R1), but according to different experimental parameters (catalytic system, operating conditions, etc.), a more complex network of reactions actually occurs simultaneously.
Figure BDA0002588452290000031
The reaction of formula (R1) is exothermic and can be reflected by a given reaction enthalpy. This exothermic nature most likely causes a local temperature increase that will promote deposition of the carbon nanotubes on the catalyst. Therefore, it is difficult to eliminate carbon deposition caused by side reactions such as decomposition of propane (R2), reduction of carbon monoxide (R3), and reduction of carbon dioxide (R4).
Figure BDA0002588452290000032
Figure BDA0002588452290000033
Figure BDA0002588452290000034
Therefore, after the foamed ceramic is modified by the catalyst, the controllable carbon nano tube can be synthesized by controlling a catalytic system, reforming parameters and the like in the process of partial oxidation and reforming of propane.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention synthesizes carbon nano tubes on the foamed ceramics by partial oxidation reforming of hydrocarbon such as alkane, and the like, the alkane hydrocarbon is taken as a carbon source, proper amount of dry air is introduced, partial oxidation reforming is carried out under the action of the foamed ceramics modified by the catalyst, and the carbon nano tubes are formed on the surface of the foamed ceramics.
2. The method can prepare the carbon nano tube with controllable diameter and length on the surface of the foamed ceramic under the normal pressure condition, has simple preparation process and low cost, is suitable for mass production, and has high quality of the prepared carbon nano tube and the composite material thereof, wide application and wide market prospect.
3. The carbon nano tube/foamed ceramic composite material prepared by the invention has the advantages of stable structure, excellent mechanical property, good heat transfer and electric conductivity and wide application market.
Drawings
FIG. 1 is a schematic diagram of the modified ceramic foam prepared in example 1 and a schematic diagram of the carbon nanotube/ceramic foam composite prepared in example 2, and a partial micro-topography diagram thereof.
FIG. 2 is a schematic diagram of an apparatus for carrying out the present invention.
FIG. 3 is an SEM photograph of carbon nanotubes prepared in examples 2-4 and a size analysis thereof.
FIG. 4 is a TEM photograph of the carbon nanotubes prepared in examples 2-4.
FIG. 5 is a thermogravimetric analysis chart of the carbon nanotubes prepared in examples 2-4.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. Dissolving 3.49mmol of nickel nitrate hexahydrate, 0.388mmol of ferric nitrate nonahydrate, 18mmol of ammonium fluoride and 46mmol of urea in 62mL of deionized water, and stirring at the rotation speed of 400r/min at 25 ℃ for 10min to obtain a mixed solution;
2. mixing the blocky foamed ceramic with the mixed solution, carrying out hydrothermal reaction for 16h at 120 ℃, then washing, and drying for 6h at 60 ℃ to obtain the hydrothermal modified foamed ceramic;
3. the modified foamed ceramic is calcined at 600 ℃ for 2h for oxidation, and then is reduced at 600 ℃ for 2h under the protection of hydrogen to obtain the ferronickel bimetal modified foamed ceramic.
FIG. 1 is a schematic representation and a partial micro-topography of a modified ceramic foam prepared in example 1 and carbon nanotube/ceramic foam composites prepared in examples 2-4. Wherein (a) is the hydrothermally modified ceramic foam of example 1, which is blue-green in color; (b) the nickel-iron bimetal modified foamed ceramic in the embodiment 1 is reddish brown; (c) is the carbon nanotube/ceramic foam composite of example 2, which is black. (d) The microstructure of the ferronickel bimetallic modified foamed ceramic in the example 1, (e) is a transmission electron microscope topography of the carbon nanotube/foamed ceramic composite material in the example 2. As can be seen from fig. 1, the formation of the nickel-iron nanosheets and the carbon nanotubes can be observed in (d) and (e), respectively, which illustrates that the nickel-iron bimetal modified foamed ceramic prepared through hydrothermal treatment, calcination, oxidation and reduction has a large amount of nickel-iron nanosheets loaded on the surface thereof, and the nickel-iron nanosheets provide an environment for the synthetic growth of the carbon nanotubes, thereby preparing the carbon nanotube/foamed ceramic composite material.
Example 2
A piece of the nickel-iron bimetal modified foamed ceramic prepared in example 1 was weighed and charged into a reactor, and the apparatus for the specific process is shown in FIG. 2. FIG. 2 is a schematic diagram of an apparatus for carrying out the present invention. As can be seen from FIG. 2, the inlet of the tube furnace is communicated with four pipelines, namely inert gas nitrogen, propane and dry air for reforming and hydrogen for reduction; the modified foamed ceramic is placed in the middle position of a tube furnace and is heated and electrically heatedAnd controlling the temperature occasionally, thereby completing the preparation of the carbon nano tube/foamed ceramic composite material. N was introduced at a rate of 300sccm2Purging, and heating the reactor to 600 ℃ after 10 min; after the temperature stabilized, propane was fed in at a rate of 40sccm, followed by dry air at a rate of 285 sccm; propane and dry air are mixed and then enter a reactor, partial oxidation reforming reaction is carried out for 60min on the mixture and the ferronickel bimetal modified foamed ceramic prepared in the embodiment 1, the carbon nano tube synthesis is started, after the reaction is finished, the introduction of the dry air is stopped, the introduction of the propane is stopped, and finally the protective gas N is introduced2And cooling the reactor to room temperature to obtain the carbon nano tube growing on the surface of the foamed ceramic.
Example 3
A piece of the nickel-iron bimetal modified foamed ceramic prepared in example 1 was weighed and charged into a reactor, and the apparatus for the specific process is shown in FIG. 2. N was introduced at a rate of 300sccm2Purging, and heating the reactor to 600 ℃ after 10 min; after the temperature had stabilized, propane was fed at 40sccm followed by dry air at 329 sccm; propane and dry air are mixed and then enter a reactor, partial oxidation reforming reaction is carried out for 60min on the mixture and the ferronickel bimetal modified foamed ceramic prepared in the embodiment 1, the carbon nano tube synthesis is started, after the reaction is finished, the introduction of the dry air is stopped, the introduction of the propane is stopped, and finally the protective gas N is introduced2And cooling the reactor to room temperature to obtain the carbon nano tube growing on the surface of the foamed ceramic.
Example 4
A piece of the nickel-iron bimetal modified foamed ceramic prepared in example 1 was weighed and charged into a reactor, and the apparatus for the specific process is shown in FIG. 2. N was introduced at a rate of 300sccm2Purging, and heating the reactor to 600 ℃ after 10 min; after the temperature stabilized, propane was fed in at a rate of 40sccm, followed by dry air at a rate of 380 sccm; propane and dry air are mixed and then enter a reactor, partial oxidation reforming reaction is carried out for 60min on the mixture and the ferronickel bimetal modified foamed ceramic prepared in the embodiment 1, the carbon nano tube synthesis is started, after the reaction is finished, the introduction of the dry air is stopped, the introduction of the propane is stopped, and finally, the introduction of the dry air is stoppedProtective gas N2And cooling the reactor to room temperature to obtain the carbon nano tube growing on the surface of the foamed ceramic.
A small part of each sample of the carbon nanotubes of examples 2 to 4 was fixed on a sample table by a conductive adhesive, and a layer of conductive metal (platinum or gold) was sprayed on the surface of the sample, and then a scanning electron microscope and a transmission electron microscope were performed to observe the distribution of the carbon nanotubes. FIG. 3 is an SEM photograph of carbon nanotubes prepared in examples 2-4 and a size analysis thereof. As can be seen from fig. 3, a plurality of carbon nanotubes are synthesized and distributed on the surface of the ceramic foam, are cylindrical, are intertwined with each other and are hollow, and form a three-dimensional network structure. FIG. 4 is a TEM photograph of the carbon nanotube materials obtained in examples 2-4. Wherein, (a) is a transmission electron micrograph with a ruler of 100 nm; (b) transmission electron micrographs with 10nm scale are presented. As can be seen from FIG. 4, the diameters of the carbon nanotubes in examples 2-4 are mostly distributed around 35nm, whereas the diameter size distribution of the carbon nanotubes in example 3 is (10-90 nm), and the average diameter range is slightly reduced in examples 2 (10-80 nm) and 4 (20-90 nm).
In order to know the structure and yield of the carbon nanotubes, a small part of the carbon nanotubes obtained in examples 2 to 4 was scraped off and placed on a sample stage, and then heated from 400 ℃ to 800 ℃ at a rate of 10 ℃/min in air for thermogravimetric analysis, and fig. 5 is a thermogravimetric analysis graph of the carbon nanotube material obtained in examples 2 to 4. As can be seen from FIG. 5, the carbon nanotubes in examples 2-4 all showed similar oxidation behavior and two-step degradation occurred at 400-700 ℃. The results indicate that different types of carbonaceous structures are present in the reaction product. At the same time, these two mass losses are due to the gasification of carbon into CO and CO2(COX). In addition, example 3 shows a higher yield (4 wt%) of carbon nanotubes compared to examples 2 and 4.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A controllable method for synthesizing carbon nanotubes on the surface of foamed ceramic is characterized by comprising the following specific steps:
s1, dissolving nickel nitrate hexahydrate, ferric nitrate nonahydrate, ammonium fluoride and urea in deionized water, and stirring to obtain a mixed solution;
s2, mixing the foamed ceramic with the mixed solution, carrying out hydrothermal reaction at 100-180 ℃, and then washing and drying to obtain the hydrothermal modified foamed ceramic;
s3, introducing dry air, heating the hydrothermally modified foamed ceramic to 400-700 ℃, calcining and oxidizing, introducing protective atmosphere for purging, introducing hydrogen, heating to 500-700 ℃, and carrying out reduction reaction to obtain the ferronickel bimetal modified foamed ceramic;
and S4, heating to 500-800 ℃ in a protective atmosphere, introducing alkane hydrocarbon and dry air to perform partial oxidation reforming reaction, and cooling to room temperature to synthesize the carbon nano tube on the surface of the foamed ceramic.
2. The controllable method for synthesizing carbon nanotubes on the surface of foamed ceramic according to claim 1, wherein the molar ratio of nickel nitrate hexahydrate, iron nitrate nonahydrate, ammonium fluoride and urea in step S1 is (1-3): (1-2): (10-15): (20-30).
3. The controllable method for synthesizing carbon nanotubes on the surface of foamed ceramic according to claim 1, wherein the molar ratio of the total amount of nickel nitrate hexahydrate, iron nitrate nonahydrate, ammonium fluoride and urea to deionized water in step S1 is (3-6): (300-400).
4. The controllable method for synthesizing carbon nanotubes on the surface of a ceramic foam according to claim 1, wherein the length of the ceramic foam in step S2 is 15-18 mm, the width of the ceramic foam is 6-10 mm, and the height of the ceramic foam is 6-10 mm.
5. The controllable method for synthesizing carbon nanotubes on the surface of foamed ceramic according to claim 1, wherein the hydrothermal reaction time in step S2 is 12-20 h.
6. The controllable method for synthesizing carbon nanotubes on the surface of foamed ceramic according to claim 1, wherein the time of calcination and oxidation in step S3 is 2-4 h; the time of the reduction reaction is 2-4 h; the time of the reforming reaction in the step S4 is 1-2 h; the protective atmosphere in steps S3 and S4 is nitrogen or inert gas.
7. The controllable method for synthesizing carbon nanotubes on the surface of ceramic foam according to claim 1, wherein said alkane hydrocarbon is propane or methane in step S4.
8. The controllable method for synthesizing carbon nanotubes on the surface of a ceramic foam according to claim 1, wherein the carbon nanotubes synthesized on the surface of a ceramic foam in step S3 have a diameter of 10-90 nm and a length of 100-900 nm.
9. A carbon nanotube/ceramic foam composite produced by the method of any one of claims 1 to 8.
10. Use of the carbon nanotube/ceramic foam composite of claim 9 in catalyst supports, sewage treatment applications.
CN202010688406.9A 2020-07-16 2020-07-16 Controllable method for synthesizing carbon nano tube on surface of foamed ceramic and application thereof Pending CN111943722A (en)

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