CN115805076B - Catalyst and preparation method thereof, array carbon nanotube and preparation method thereof - Google Patents
Catalyst and preparation method thereof, array carbon nanotube and preparation method thereof Download PDFInfo
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Abstract
The application relates to the technical field of carbon material preparation, and discloses a catalyst and a preparation method thereof, an array carbon nanotube and a preparation method thereof. A catalyst is prepared by calcining a catalyst precursor solution, wherein the catalyst precursor solution is prepared by dissolving a soluble active component containing active metal elements, a soluble carrier component containing carrier elements and a soluble complexing agent in water, the concentration of the active metal elements is 0.5-3mol/L, the concentration of the carrier elements is 0.5-5.0mol/L, and the concentration of the complexing agent is 3.0-7.0mol/L. The catalyst provided by the application is beneficial to preparing the array carbon nanotubes with low specific surface area and short array length, so that the high-dispersity array carbon nanotubes can be prepared, and the application dispersibility of the array carbon nanotubes can be improved.
Description
Technical Field
The application relates to the technical field of carbon material preparation, in particular to a catalyst and a preparation method thereof, an array carbon nano tube and a preparation method thereof.
Background
The carbon nano tube is a one-dimensional quantum material with a unique nano hollow structure, has excellent conductivity, and can be dispersed in a solvent to form conductive slurry to be applied to a lithium ion battery.
According to the aggregation state, the carbon nanotubes are divided into array carbon nanotubes and aggregated carbon nanotubes. The array carbon nanotubes have orderly arrangement and good orientation, so that the conductivity and the dispersibility of the array carbon nanotubes are generally better than those of the agglomerated carbon nanotubes. However, the array length of the array carbon nanotubes sold in the market at present is longer, certain entanglement is still provided among the single carbon nanotubes in the tube bundle, and the specific surface area of the long array carbon nanotubes is relatively higher, so that the dispersibility is lower than that of the short array carbon nanotubes with low specific surface area.
Based on this, the inventors believe that in order to improve the dispersibility of the array carbon nanotubes, it is necessary to provide a short array carbon nanotube having a low specific surface area, which is generally prepared by catalyzing a carbon source gas with a catalyst, so that the catalyst can significantly affect the physicochemical properties of the array carbon nanotube. At present, a catalyst for preparing the array carbon nano tube is obtained by adsorbing and impregnating active metal and a solid carrier, evaporating water and calcining, and the dispersion of the array carbon nano tube prepared by the catalyst is still poor, so that a catalyst favorable for preparing the array carbon nano tube with good dispersion is necessary to be developed.
Disclosure of Invention
In order to prepare an array carbon nano tube with high dispersibility, the application provides a catalyst and a preparation method thereof, and an array carbon nano tube and a preparation method thereof.
In a first aspect, the present application provides a catalyst, which adopts the following technical scheme:
a catalyst is prepared by calcining a catalyst precursor solution, wherein the catalyst precursor solution is prepared by dissolving a soluble active component containing active metal elements, a soluble carrier component containing carrier elements and a soluble complexing agent in water, the concentration of the active metal elements is 0.5-3mol/L, the concentration of the carrier elements is 0.5-5.0mol/L, and the concentration of the complexing agent is 3.0-7.0mol/L.
The active component, the carrier component and the complexing agent are dissolved in water together, the complexing agent is used as an organic ligand, the complexing agent can be simultaneously complexed with the active metal element and the carrier element to form a metal organic framework compound, under the calcining action, the metal organic framework compound expands, then is cracked and combusted, simultaneously, moisture and nonmetallic ions in the catalyst precursor solution are also evaporated and decomposed and removed, and then the rest metal element and oxygen in the air are self-assembled to form the metal oxide catalyst with a lamellar structure. By calcining the catalyst precursor solution, active metal elements can be uniformly distributed in carrier elements, and the catalyst activity is higher; and the catalyst with lamellar structure is easier to grow into the high-dispersivity array carbon nano tube with low specific surface area and short array, thereby being beneficial to preparing the conductive paste with high solid content and further reducing the cost of enterprises.
Further, the soluble active component is one or more of soluble manganese salt, ferric salt, cobalt salt, nickel salt and molybdate.
Still further, the soluble active component includes nitrate, chloride, sulfate, organic acid salt, and the like; the soluble manganese salt comprises manganese nitrate, manganese chloride, manganese sulfate, manganese acetate and the like; the soluble ferric salt comprises ferric nitrate, ferric chloride, ferric sulfate and the like; the soluble cobalt salt comprises cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate and the like; the soluble nickel salt comprises nickel nitrate, nickel chloride, nickel sulfate, nickel acetate and the like; the soluble molybdate includes ammonium heptamolybdate.
Further, the soluble carrier component is one or more combinations of soluble magnesium salts, aluminum salts, calcium salts, and aluminosilicates.
Still further, the soluble carrier component comprises nitrate, chloride, sulfate, organic acid salt, etc., and the soluble magnesium salt comprises magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium acetate, etc.; the soluble aluminum salt comprises aluminum nitrate, aluminum chloride, aluminum sulfate and the like; the soluble calcium salt comprises calcium chloride, calcium acetate, calcium nitrate and the like.
Further, the molar ratio of the active metal element to the carrier element is 1: (0.6-3).
Further, the molar ratio of the complexing agent to the sum of the active metal element and the carrier element is 1 (0.5-1.25).
The activity and morphology of the catalyst can be controlled by adjusting the mole ratio among the active metal element, the carrier element and the complexing agent, so that the morphology, the specific surface area, the resistivity and the like of the carbon nano tube prepared by the catalyst are controlled, and finally the array carbon nano tube with high dispersibility is obtained.
Preferably, the complexing agent comprises one or more of citric acid, tartaric acid, sorbic acid, ethylenediamine tetraacetic acid, ethylene glycol, polyethylene glycol, and glycerol.
In a second aspect, the application provides a preparation method of a catalyst, which adopts the following technical scheme:
a method for preparing a catalyst comprising the steps of:
step S1, dissolving an active component containing active metal elements, a carrier component containing carrier elements and a complexing agent in water, and uniformly mixing to obtain a catalyst precursor solution;
and S2, calcining the catalyst precursor solution at a high temperature of 500-900 ℃ for 10min-4h to obtain the catalyst.
In the catalyst precursor solution, the complexing agent is used for complexing the active metal element and the carrier element to form a metal organic framework compound, and the metal organic framework compound is calcined at a high temperature of 500-900 ℃ for 10min-4h, so that the catalyst is fully expanded, cracked and combusted, and finally the catalyst with a lamellar structure is obtained. The preparation process of the catalyst provided by the application is simple and easy to implement, has wide raw material sources, is favorable for shortening the production period of the carbon nano tube, and is suitable for industrialized mass production.
In a third aspect, the present application provides an array carbon nanotube, which adopts the following technical scheme:
an array carbon nanotube prepared by the catalyst, wherein the array length of the short array carbon nanotube with low specific surface area is 10-50 μm, and the specific surface area is 100-180m 2 And/g, wherein the powder resistivity is 10-25mΩ & cm.
Most of the commercially available array carbon nanotubes have an array length of 50 μm or more and a specific surface area of 200m or more 2 Above/g, thus commercially available arrays of arrayed carbon nanotubesThe length is longer, the specific surface area is also relatively higher, and the dispersion of the array carbon nanotube powder is poorer.
The array carbon nanotube powder prepared by the application not only has better conductive performance, but also has the array length of 10-50um and the specific surface area of 100-180m 2 And/g, which is obviously lower than the array length and specific surface area of the array carbon nanotubes sold in the market, thereby effectively improving the dispersibility of the carbon nanotubes.
In a fourth aspect, the present application provides a method for preparing an array carbon nanotube, which adopts the following technical scheme:
the preparation method of the array carbon nano tube comprises the following steps: the catalyst is reduced for 0-60min at 650-720 ℃ by introducing hydrogen, and then is subjected to catalytic reaction for 10-90min at 650-720 ℃ by introducing carbon source gas, so as to obtain the array carbon nanotube powder.
The carbon source gas is typically a hydrocarbon, and as the carbon source gas is continuously cracked at a high temperature of 650-720C, the c—h bonds are broken, thereby gradually forming carbon and hydrogen. Therefore, under the condition that no hydrogen is introduced, the hydrogen generated by the pyrolysis of the carbon source gas can reduce the active metal oxide on the surface of the catalyst into an active metal simple substance. The active metal simple substance has better catalytic effect on the carbon source deposited on the surface of the catalyst at 650-720 ℃, and the carbon source gas is controlled to catalytically react for 10-90min at 650-720 ℃ so as to crack and grow on the surface of the catalyst prepared by the application, thereby obtaining the array carbon nano tube powder with low specific surface area and short array length.
Further, the carbon source gas is any one of methane, ethane, propane, ethylene, and propylene.
Preferably, before hydrogen is introduced into the catalyst, nitrogen or inert gas is introduced into the catalyst, the temperature is raised to 680-700 ℃, and after the temperature is stable, hydrogen is introduced into the catalyst; further, after the introduction of the carbon source gas is finished, nitrogen or inert gas is introduced, and the mixture is naturally cooled to 20-30 ℃ to obtain the array carbon nanotube powder.
Preferably, the catalyst is added in an amount of 0.2-2g, and the flow rate of the carbon source gas is 1-3L/min.
In summary, the application has the following beneficial effects:
1. the active component, the carrier component and the complexing agent are matched in a specific concentration to form a catalyst precursor solution, and then the catalyst precursor solution is calcined, so that a lamellar catalyst is formed, and the lamellar catalyst is favorable for catalyzing carbon source gas to obtain the array carbon nano tube with low specific surface area and short array length.
2. The molar ratio of the active metal element to the carrier element is adjusted, and the molar ratio of the sum of the active metal element and the carrier element to the complexing agent is further adjusted, so that the activity and microscopic morphology of the catalyst are further regulated and controlled, the catalyst is facilitated to better catalyze carbon source gas, and the array carbon nano tube with low specific surface area and short array length is obtained.
3. The array carbon nano tube prepared by the application has the powder resistivity of 10-25mΩ cm, better conductive performance, the array length of 10-50 μm and the specific surface area of 100-180m 2 And/g, the array length is shorter, and the specific surface area is lower, so that compared with the array carbon nano tube in the prior art, the array carbon nano tube prepared by the application has obviously improved dispersibility, and the dispersibility is improved on the basis of keeping better conductivity.
Drawings
FIG. 1 is a scanning electron microscope image (upper image) of the catalyst prepared in preparation example 1 of the present application and a scanning electron microscope image (lower image) of the catalyst prepared in preparation comparative example 1.
Fig. 2 is a 500-fold scanning electron microscope (upper) and 5000-fold scanning electron microscope (lower) of the array carbon nanotubes prepared in example 1 of the present application.
Fig. 3 is a 500-fold scanning electron microscope (upper) and 5000-fold scanning electron microscope (lower) of the array carbon nanotubes prepared in example 3 of the present application.
FIG. 4 shows a Raman spectrum of an array carbon nanotube prepared in example 3 of the present application.
Fig. 5 is a 500 x scanning electron microscope (upper panel) and a 5000 x scanning electron microscope (lower panel) of comparative sample 1 according to the present application.
FIG. 6 is a 500-fold scanning electron microscope (upper panel) and a 5000-fold scanning electron microscope (lower panel) of comparative sample 2 according to the present application.
Detailed Description
Preparation example 1
A catalyst prepared by the method comprising:
step S1, stirring cobalt nitrate, aluminum nitrate and citric acid in 30mL of water until the cobalt nitrate, aluminum nitrate and citric acid are dissolved uniformly to obtain a catalyst precursor solution; wherein cobalt nitrate is an active component, and the concentration of cobalt element is 0.85mol/L; aluminum nitrate is used as a carrier component, and the concentration of aluminum element is 1.6mol/L; citric acid is used as a complexing agent, and the concentration of the citric acid is 4.9mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 into a crucible, and then placing the crucible in a muffle furnace for high-temperature calcination at 500 ℃ for 2 hours to obtain the catalyst (the structural morphology is specifically shown in the upper graph of FIG. 1).
Preparation example 2
A catalyst prepared by the method comprising: step S1, stirring nickel acetate, ammonium heptamolybdate, magnesium acetate and tartaric acid in 30mL of water until the nickel acetate, the ammonium heptamolybdate, the magnesium acetate and the tartaric acid are dissolved uniformly to obtain a catalyst precursor solution; nickel acetate and ammonium heptamolybdate are used as active components, the concentration of nickel element is 3.0mol/L, the concentration of molybdenum element is 0.51mol/L, magnesium acetate is used as a carrier component, the concentration of magnesium element is 4.98mol/L, tartaric acid is used as a complexing agent, and the concentration of tartaric acid is 6.79mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 to one third of a crucible, and then placing the crucible in a muffle furnace for high-temperature calcination at 500 ℃ for 4 hours to obtain the catalyst.
Preparation example 3
A catalyst prepared by the method comprising: step S1, stirring cobalt nitrate, manganese nitrate, aluminum nitrate and citric acid in 30mL of water until the cobalt nitrate, the manganese nitrate, the aluminum nitrate and the citric acid are uniformly dissolved to obtain a catalyst precursor solution, wherein the cobalt nitrate and the manganese nitrate are used as active components, the concentration of cobalt element is 0.73mol/L, the concentration of manganese element is 0.5mol/L, the aluminum nitrate is used as a carrier component, the concentration of aluminum element is 2.9mol/L, the citric acid is used as a complexing agent, and the concentration of citric acid is 7.0mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 into a crucible, and then placing the crucible in a muffle furnace for high-temperature calcination at 650 ℃ for 30min to obtain the catalyst.
Preparation example 4
A catalyst prepared by the method comprising: step S1, stirring ferric nitrate, ammonium heptamolybdate, aluminum nitrate, calcium nitrate and ethylenediamine tetraacetic acid in 30mL of water until the ferric nitrate, the ammonium heptamolybdate and the ethylenediamine tetraacetic acid are dissolved uniformly to obtain a catalyst precursor solution, wherein the ferric nitrate and the ammonium heptamolybdate are active components, the concentration of iron element is 2.45mol/L, the concentration of molybdenum element is 1.0mol/L, the calcium nitrate and the aluminum nitrate are carrier components, the concentration of calcium element is 0.5mol/L, the concentration of aluminum element is 1.57mol/L, the ethylenediamine tetraacetic acid is a complexing agent, and the concentration of ethylenediamine tetraacetic acid is 4.83mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 into a crucible, and then placing the crucible in a muffle furnace for high-temperature calcination at 900 ℃ for 10min to obtain the catalyst.
Preparation example 5
A catalyst prepared by the method comprising: step S1, stirring ferric nitrate, nickel nitrate, aluminum nitrate, magnesium nitrate and citric acid in 30mL of water until the ferric nitrate, the nickel nitrate and the magnesium nitrate are uniformly dissolved to obtain a catalyst precursor solution, wherein the concentration of iron element is 1.56mol/L, the concentration of nickel element is 0.5mol/L, the concentration of aluminum element and the magnesium nitrate are carrier components, the concentration of aluminum element is 1mol/L, the concentration of magnesium element is 4.58mol/L, citric acid is a complexing agent, and the concentration of citric acid is 6.11mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 into a crucible, and then placing the crucible in a muffle furnace to calcine at a high temperature of 500 ℃ for 1h to obtain the catalyst.
Preparation example 6
A catalyst prepared by the method comprising: step S1, stirring cobalt acetate, manganese nitrate, aluminum nitrate, magnesium acetate and ethylene glycol in 30mL of water until the cobalt acetate, the manganese nitrate, the aluminum nitrate and the magnesium acetate are dissolved uniformly to obtain a catalyst precursor solution, wherein the cobalt acetate and the manganese nitrate are used as active components, the concentration of cobalt element is 0.73mol/L, the concentration of manganese element is 0.93mol/L, the aluminum nitrate and the magnesium acetate are used as carrier components, the concentration of aluminum element is 3.32mol/L, the concentration of magnesium element is 1.66mol/L, the ethylene glycol is a complexing agent, and the concentration of ethylene glycol is 6.3mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 into a crucible, and then placing the crucible in a muffle furnace for high-temperature calcination at 750 ℃ for 30min to obtain the catalyst.
Preparation of comparative example 1
A comparative sample 1 was prepared by the following method: the difference from the preparation example 1 is that: and (3) performing spray drying on the catalyst precursor solution prepared in the step (S1) to obtain catalyst precursor powder. The catalyst precursor powder was then placed in a muffle furnace at 500 ℃ for calcination for 2h to yield the preparation comparative sample 1 (see the lower graph of fig. 1 for specific structural morphology).
Preparation of comparative example 2
A comparative sample 2 was prepared by the following method: the difference from preparation example 3 is that: in the step S1, cobalt nitrate, manganese nitrate and aluminum nitrate are stirred in 30mL of water until the cobalt nitrate, the manganese nitrate and the aluminum nitrate are uniformly dissolved, and a catalyst precursor solution is obtained, wherein the cobalt nitrate and the manganese nitrate are used as active components, the concentration of cobalt element is 0.73mol/L, the concentration of manganese element is 0.5mol/L, the aluminum nitrate is used as a carrier component, and the concentration of aluminum element is 2.9mol/L.
Preparation of comparative example 3
A comparative sample 3 was prepared by the following method: the difference from preparation example 3 is that: in the step S1, the concentration of cobalt element was 0.33mol/L, and the concentration of manganese element was 0.37mol/L.
Preparation of comparative example 4
A comparative sample 4 was prepared by the following method: the difference from preparation example 3 is that: in the step S1, cobalt nitrate, manganese nitrate and diaspore are uniformly stirred in 30mL of water to obtain a catalyst precursor suspension, wherein the concentration of cobalt element is 0.73mol/L, the concentration of manganese element is 0.5mol/L, and the concentration of aluminum element is 2.9mol/L.
In each of the above examples and the preparation comparative examples, the specific components of the active component, the carrier component and the complexing agent, and the molar ratio x of the active metal element and the carrier element and the molar ratio y of the complexing agent to the sum of the active metal element and the carrier element are shown in Table 1.
The calculation method of the molar ratio x of the active metal element to the carrier element is as follows:
the molar ratio y of complexing agent to the sum of active metal element and carrier element is calculated as follows:
TABLE 1
Example 1
An array carbon nanotube is prepared by the following method: placing 0.2g of the catalyst prepared in preparation example 1 into a vertical fluidized bed reactor, introducing 2L/min of nitrogen protection gas, starting a heating furnace to heat to 700 ℃, introducing 1L/min of hydrogen to reduce for 30min after the temperature is stable, introducing 1L/min of propylene to react for 30min after the reduction is finished, and continuously cooling to room temperature under the protection of 2L/min of nitrogen after the reaction is finished to obtain the array carbon nanotube powder (specific structural morphology is shown in figure 2).
Example 2
An array carbon nanotube is prepared by the following method: and 2g of the catalyst prepared in the preparation example 2 is placed in a vertical fluidized bed reactor, 3L/min of nitrogen protection gas is introduced, a heating furnace is started to heat to 700 ℃, after the temperature is stable, 2L/min of propylene is directly introduced to react for 10min, and after the reaction is finished, the catalyst is continuously cooled to room temperature under the protection of 3L/min of nitrogen, so as to obtain the array carbon nanotube powder.
Example 3
An array carbon nanotube is prepared by the following method: placing 0.5g of the catalyst prepared in preparation example 3 into a vertical fluidized bed reactor, introducing 1L/min of nitrogen protection gas, starting a heating furnace to heat to 680 ℃, introducing 1L/min of hydrogen to reduce for 10min after the temperature is stable, introducing 1L/min of propylene to react for 60min after the reduction is finished, and continuously cooling to room temperature under the protection of 1L/min of nitrogen after the reaction is finished to obtain low-array carbon nanotube powder (specific structural morphology is shown in figure 3).
Example 4
An array carbon nanotube is prepared by the following method: placing 2g of the catalyst prepared in preparation example 4 into a vertical fluidized bed reactor, introducing argon with the flow rate of 2L/min as a shielding gas, starting a heating furnace to heat to 700 ℃, introducing hydrogen with the flow rate of 1L/min to reduce for 60min after the temperature is stable, introducing propylene with the flow rate of 3L/min to react for 90min after the reduction is finished, and continuously cooling to room temperature under the protection of nitrogen with the flow rate of 2L/min after the reaction is finished to obtain the array carbon nanotube powder.
Example 5
An array carbon nanotube is prepared by the following method: placing 1.0g of the catalyst prepared in preparation example 5 into a horizontal fixed bed reactor, introducing 1L/min of nitrogen protection gas, starting a heating furnace to heat to 700 ℃, introducing 1.0L/min of hydrogen to reduce for 30min after the temperature is stable, introducing 1.0L/min of propylene to react for 60min after the reduction is finished, and continuously cooling to room temperature under the protection of 1L/min of nitrogen after the reaction is finished to obtain the array carbon nanotube powder.
Example 6
An array carbon nanotube is prepared by the following method: placing 1.0g of the catalyst prepared in preparation example 6 into a horizontal fixed bed reactor, introducing 1.0L/min of nitrogen protection gas, starting a heating furnace to heat to 680 ℃, introducing 1.0L/min of hydrogen to reduce for 30min after the temperature is stable, introducing 1.0L/min of propylene to react for 60min after the reduction is finished, and continuously cooling to room temperature under the protection of 1L/min of nitrogen after the reaction is finished to obtain the array carbon nanotube powder.
Comparative example 1
An example 1 was prepared by the following method: the difference from example 1 is that: the catalyst of example 1 was replaced equally with the preparation of comparative sample 1 (see fig. 5 for specific structural morphology).
Comparative example 2
An example 2 was prepared by the following method: the difference from example 3 is that: the catalyst of example 3 was replaced equally with the preparation of comparative sample 2 (see fig. 6 for specific structural morphology).
Comparative example 3
An example 3 was prepared by the following method: the difference from example 3 is that: comparative sample 3 was prepared by replacing the catalyst in example 3 by an equal amount.
Comparative example 4
An example 4 was prepared by the following method: the difference from example 3 is that: comparative sample 4 was prepared to replace the catalyst in example 3 by an equal amount.
The specific surface area, magnification and powder resistivity data of the low specific surface area short array carbon nanotubes prepared in each example and each comparative sample are shown in Table 2.
The calculation formula of the multiplying power is as follows:
multiplying power = (weight of carbon nanotube powder-weight of catalyst)/weight of catalyst
TABLE 2
The graphitization degree of the array carbon nanotube powder prepared in example 3 was measured by raman spectroscopy, and the raman spectrum in fig. 4 proves that the graphitization degree of the array carbon nanotube powder prepared in example 3 is high and the defects of the array carbon nanotube powder are small.
As can be seen from the data of examples 1 to 6 in Table 2, the magnifications of the array carbon nanotubes prepared in examples 1 to 6 are between 14 and 31, which proves that the preparation method of the array carbon nanotubes of the present application has a better yield. The resistivity of the array carbon nanotubes prepared in examples 1-6 was between 12.32 and 24.96, illustrating the preparation of examples 1-6The prepared array carbon nano tube has better conductivity. The specific surface area of the array carbon nano tube prepared by the application is 103-179m 2 The specific surface area of the commercial array carbon nano tube is mostly 200m 2 And/g, the specific surface area of the array carbon nano tube prepared by the application is obviously lower than that of the array carbon nano tube sold in the market. In view of the foregoing, the preparation method of the array carbon nanotubes according to the present application not only obtains carbon nanotubes with better conductivity in a higher magnification manner, but also has the characteristics of low specific surface area and short array length, thereby being favorable for dispersing and pulping and obtaining conductive paste with high solid content, or having better dispersibility in plastics, thereby improving the dispersing effect of the array carbon nanotubes in application.
As can be seen from the data of example 1 and comparative example 1 in table 2 by combining the data of fig. 1, fig. 2 and fig. 5, in the catalyst preparation process of example 1, the catalyst precursor solution was calcined to obtain a catalyst having a lamellar structure (see fig. 1, upper diagram), and the catalyst was able to obtain array carbon nanotubes having a distinct array morphology and a low specific surface area and a short array length (see fig. 2), in the catalyst preparation process of comparative example 1, the catalyst precursor solution was dried to powder and then calcined to obtain a powdery catalyst (see fig. 1, lower diagram), and therefore, the catalyst of comparative example 1 could not be self-assembled to form a catalyst having a lamellar structure as shown in the upper diagram of fig. 1, and by using this catalyst, comparative sample 1 (see fig. 5) having a high specific surface area and a non-distinct array morphology was obtained, and it was demonstrated that the catalyst precursor solution was directly calcined without drying to facilitate the preparation of high-dispersibility array carbon nanotubes.
As can be seen by comparing the data of example 3 and comparative example 2 in table 2 with those of fig. 3 and 6, the complexing agent is added during the preparation of the catalyst, which is favorable for obtaining the catalyst with better morphology and activity, so as to prepare the array carbon nanotube with low specific surface area, obvious array morphology and short array length (refer to fig. 3), thereby being favorable for obtaining the array carbon nanotube with high dispersibility, and obtaining the non-array carbon nanotube with insignificant array morphology (refer to fig. 6) without adding the complexing agent.
As can be seen from the comparison of the data of example 3 and comparative example 3 in table 2, the catalyst precursor solution is formed by the coordination of the active metal element, the carrier element and the complexing agent in a certain concentration, so that the catalyst precursor solution forms a catalyst with a lamellar structure and better activity after calcination, thereby obtaining the short array carbon nanotube capable of catalyzing the carbon source gas to generate a low specific surface area, high yield and obvious array morphology.
As can be seen from the comparison of the data of example 3 and comparative example 4 in table 2, the catalyst of comparative example 4 was carried out by substituting insoluble boehmite for soluble aluminum nitrate as a support component, and since boehmite was dispersed in water in a suspended state, boehmite as a support component and an active component could not be combined by self-assembly, so that there was a significant difference in morphology between the catalyst used in comparative example 4 and the catalyst used in example 3 of the present application, and thus the catalyst of comparative example 4 could not be used to prepare carbon nanotubes having an array morphology by preparing the catalyst of comparative example 4.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (7)
1. A catalyst, characterized in that: the catalyst is prepared by calcining a catalyst precursor solution, wherein the catalyst precursor solution is prepared by dissolving a soluble active component containing active metal elements, a soluble carrier component containing carrier elements and a soluble complexing agent in water, the concentration of the active metal elements is 0.5-3mol/L, the concentration of the carrier elements is 0.5-5.0mol/L, and the concentration of the complexing agent is 3.0-7.0mol/L; the molar ratio of the active metal element to the carrier element is 1: (0.6-3); the mole ratio of the complexing agent to the sum of the active metal element and the carrier element is 1 (0.5-1.25); the soluble active component is one or a combination of more of soluble manganese salt, ferric salt, cobalt salt, nickel salt and molybdate; the soluble carrier component is one or more of soluble magnesium salt, aluminum salt, calcium salt and aluminosilicate; the complexing agent comprises one or more of citric acid, tartaric acid, sorbic acid, ethylenediamine tetraacetic acid, ethylene glycol, polyethylene glycol and glycerol.
2. A method of preparing the catalyst of claim 1, wherein: the method comprises the following steps:
step S1, dissolving an active component containing active metal elements, a carrier component containing carrier elements and a complexing agent in water, and uniformly mixing to obtain a catalyst precursor solution;
and S2, calcining the catalyst precursor solution at a high temperature of 500-900 ℃ for 10min-4h to obtain the catalyst.
3. An array carbon nanotube, characterized in that: prepared by the catalyst of claim 1, the array length of the array carbon nano tube is 10-50 μm, and the specific surface area is 100-180m 2 And/g, wherein the powder resistivity is 10-25mΩ & cm.
4. A method for preparing the arrayed carbon nanotube of claim 3, wherein: introducing hydrogen, reducing the catalyst at 650-720 ℃ for 0-60min, and then introducing carbon source gas for catalytic reaction at 650-720 ℃ for 10-90min to obtain the array carbon nanotube powder.
5. The method for preparing the array carbon nanotube according to claim 4, wherein: the carbon source gas is any one of methane, ethane, propane, ethylene and propylene.
6. The method for preparing the array carbon nanotube according to claim 4, wherein: before introducing hydrogen, introducing nitrogen or inert gas into the catalyst, heating to 650-720 ℃, and after the temperature is stable, introducing hydrogen.
7. The method for preparing the array carbon nanotube according to claim 4, wherein: the input amount of the catalyst is 0.2-2g, and the flow rate of the carbon source gas is 1-3L/min.
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