Catalyst for preparing small-caliber single-walled carbon nanotube and preparation method and application thereof
Technical Field
The invention relates to the technical field of single-walled carbon nanotube preparation, in particular to a catalyst for preparing a small-caliber single-walled carbon nanotube, a preparation method and application thereof.
Background
As a novel carbon material, carbon nanotubes have many excellent properties such as mechanical properties, electrical conductivity, and thermal conductivity due to their specific structure. Carbon nanotubes can be roughly classified into single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, and the like according to the number of the wall layers, the single-walled carbon nanotubes have a one-dimensional carbon nanotube hollow tubular structure composed of carbon atoms and can be regarded as seamless carbon tubes formed by winding single-layer graphene, and carbon nanotube tubular structures similar to the structure thereof include double-walled carbon nanotubes and multi-walled carbon nanotubes and are regarded as concentric tubular structures formed by winding double-layer graphene and multi-layer graphene, respectively.
Among them, single-walled carbon nanotubes (SWNTs) are typical one-dimensional nanomaterials, and their special tubular structures determine the excellent physical, chemical, electrical and mechanical properties of carbon nanotubes, so that they have very important application values in many fields, and especially have gradually gained prominence in the aspects of energy storage, environmental protection, electronic and electrical fields, composite materials, medical fields, etc. At present, methods for growing single-walled carbon nanotubes mainly include an arc discharge method, a laser evaporation catalytic precipitation technology, a Chemical Vapor Deposition (CVD) method and the like, the first two methods are very complicated in operation, and a solid carbon source needs to be evaporated into carbon atoms at a high temperature of more than 3000 ℃, which severely limits the number of carbon nanotubes that can be synthesized, and in addition, the carbon nanotubes grown by evaporating the carbon atoms are highly entangled in shape and are mutually mixed with other carbon impurities and metal catalysts, so that the application range of the carbon nanotubes is severely limited. The chemical vapor deposition process for preparing single-wall carbon nanotube has the advantages of convenient control, high yield, less impurity content in the product, etc. and is the main process for preparing single-wall carbon nanotube.
Due to the thinning of the tube diameter of the SWNTs, the lower the conductive threshold value when the SWNTs are used for conductive fillers is, the lower the conductive threshold value can be as low as one ten thousandth, which cannot be reached by the conventional materials, and how to keep the preparation of the carbon nano tube with the thin tube diameter is an important difficulty in the preparation field. In recent years, many researchers have also worked on the diameter-controllable growth of single-walled carbon nanotubes, for example, the patent CN201010234322.4 of shanghai university of transportation discloses a method for preparing single-walled carbon nanotubes with controllable diameter, which adopts a high-temperature arc ablation method to fill carbon powder and metal catalyst into carbon electrodes, and prepares carbon nanotubes by direct arc ablation, but the method mainly aims at the arc catalysis method, and the method is high in cost and not easy for mass production.
Therefore, how to prepare the single-walled carbon nanotube with small caliber is still the problem to be solved at present.
Disclosure of Invention
In order to solve the problems, the invention provides a catalyst for preparing a small-caliber single-walled carbon nanotube and a preparation method and application thereof, wherein a very small amount of noble metal Pt is doped into a Fe-Mo-based catalyst to form a Fe-Mo-Pt-based trimetal catalyst, and CH of Pt4Has strong decomposition capability, can decompose and obtain a large amount of carbon species, and improves the carbon yield. In addition, the infiltration of Pt can effectively reduce the tube diameter of SWNTs and significantly improve the overall quality of SWNTs.
The invention provides a catalyst for preparing a small-caliber single-walled carbon nanotube, which comprises an active component and a carrier, wherein the active component comprises a main active component and an auxiliary active component, the main active component is iron and platinum, and the auxiliary active component is molybdenum.
Further, the content of iron in the catalyst is 1-10 wt%.
Further, the content of platinum in the catalyst is 0.03-0.5 wt%.
Further, the molar ratio of the iron atoms to the molybdenum atoms in the catalyst is (25-60):1, preferably 30: 1.
Further, the carrier is selected from at least one of silica, alumina and magnesia, and is preferably magnesia.
Further, the particle diameter of the active component of the catalyst is 8-15 nm.
The invention provides a preparation method of a catalyst for preparing a small-caliber single-walled carbon nanotube, which comprises the following steps:
s1: weighing soluble molybdenum salt and an auxiliary agent, mixing and dissolving in water, adding nitric acid, and uniformly stirring to obtain a solution A;
s2: weighing soluble ferric salt, soluble platinum salt and an initiator, adding into ethanol, heating and stirring to obtain a solution B;
s3: mixing the solution A and the solution B, then adding the carrier under vigorous stirring, stirring uniformly, continuing stirring, heating and evaporating to dryness to obtain a solid C;
s4: and drying the solid C, then grinding, and finally roasting to obtain the catalyst for preparing the single-walled carbon nanotube with small tube diameter.
The molar ratio of the iron atoms in the soluble iron salt to the molybdenum atoms in the soluble molybdenum salt is (25-60): 1.
Further, the carrier is weighed according to the iron content of 1-10 wt% in the catalyst.
Further, weighing the soluble platinum salt according to the platinum content of 0.03-0.5 wt% in the catalyst.
Further, the soluble ferric salt is selected from at least one of ferric chloride, ferric nitrate and ferric sulfate.
Further, the soluble molybdenum salt is selected from at least one of ammonium molybdate and sodium molybdate.
Further, the soluble platinum salt is selected from at least one of chloroplatinic acid and sodium chloroplatinate.
Further, the initiator is selected from urea.
Further, the auxiliary agent is at least one selected from citric acid and sodium citrate.
Further, the carrier is selected from at least one of silica, alumina and magnesia, and is preferably magnesia.
Furthermore, the evaporation temperature is 120-180 ℃, and the evaporation time is 2-6 h.
Further, the drying temperature is 60-100 ℃, and the drying time is 6-48 h.
Further, the roasting temperature is 300-400 ℃, and the roasting time is 2-6 h.
In a third aspect, the present invention provides a method for preparing single-walled carbon nanotubes, comprising the steps of:
s1: placing the catalyst provided by the invention or the catalyst prepared by the preparation method provided by the invention in a reaction device, and heating to a reaction temperature;
s2: introducing methane containing water vapor and inert gas for reaction;
s3: and purifying the product obtained in the step S2 to obtain the single-wall carbon nanotube.
Further, the reaction temperature is 600-900 ℃, preferably 700-800 ℃.
Further, the concentration of the water vapor is 100-1000 ppm.
Further, the inert gas is one of helium and argon.
Further, the concentration of the methane is 20-50%.
Compared with the prior art, the invention at least has the following technical effects:
(1) the invention adopts low-temperature roasting, trace Mo and Fe form a special iron molybdate structure, the carbon yield and the SWNTs purity are effectively improved, and H is utilized2O is used as an etchant, the microstructure of FeMo is not damaged, the catalyst has better sintering resistance, the service life of the catalyst is prolonged, and trace H is added2O can regulate and control the quality and the property of SWNTs, and effectively improves the quality of products.
(2) The invention dopes a very small amount of noble metal Pt into the Fe-Mo-based catalyst to form the Fe-Mo-Pt-based trimetal catalyst, wherein CH of Pt4The decomposition capability is strong, a large number of carbon species can be decomposed and obtained, the carbon yield is obviously improved, and in addition, the Pt infiltration can effectively reduce the tube diameter of the SWNTs and obviously improve the overall quality of the SWNTs.
(3) The growth of the SWNTs follows a tangential growth mode, the grain diameters of the Fe-Mo-Pt-based catalyst prepared by the method are all concentrated in 8-15nm, and the grain diameters are close to the average pipe diameter of the SWNTs prepared by the catalyst.
(4) The preparation method has the advantages of simple preparation process, low cost, low energy consumption, small tube diameter of the prepared SWNTs, high quality and suitability for large-batch industrial production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a graph showing the particle size distribution of catalysts Cat-1 to Cat-4 prepared in examples 1 to 4;
FIG. 2 shows carbon yields and I of SWNTs for examples 1 to 4G/ID;
FIG. 3 is an SEM photograph of catalysts Cat-1 to Cat-4 prepared in examples 1 to 4;
FIG. 4 is an XRD pattern of catalysts Cat-1 to Cat-4 prepared in examples 1 to 4;
FIG. 5 is an SEM photograph of SWNTs-1 to SWNTs-4 prepared in examples 1 to 4;
FIG. 6 is a tube diameter distribution diagram of SWNTs-1 to SWNTs-4 prepared in examples 1 to 4;
FIG. 7 is a TEM image and a tube diameter distribution chart of SWNTs-5 prepared in comparative example 1;
FIG. 8 is a tube diameter distribution diagram of SWNTs-6 prepared in comparative example 2.
Detailed Description
The invention provides a preparation method of a catalyst for preparing a small-caliber single-walled carbon nanotube, which comprises the following steps:
s1: weighing soluble molybdenum salt and an auxiliary agent, mixing and dissolving in water, adding nitric acid, and uniformly stirring to obtain a solution A; according to the embodiment of the invention, the soluble molybdenum salt is selected from at least one of ammonium molybdate and sodium molybdate, and the auxiliary agent is selected from at least one of citric acid and sodium citrate.
S2: weighing soluble ferric salt, soluble platinum salt and an initiator, adding into ethanol, heating and stirring to obtain a solution B; according to the embodiment of the invention, the soluble ferric salt is selected from at least one of ferric chloride, ferric nitrate and ferric sulfate, the soluble platinum salt is selected from at least one of chloroplatinic acid and sodium chloroplatinate, and the initiator is selected from urea.
S3: mixing the solution A and the solution B, then adding the carrier under vigorous stirring, stirring uniformly, continuing stirring, heating and evaporating to dryness to obtain a solid C; according to the embodiment of the invention, the evaporation temperature is 120-.
S4: drying the solid C, then grinding, and finally roasting to obtain the Fe-Mo-Pt-based catalyst; according to the embodiment of the invention, the drying temperature is 60-100 ℃, the drying time is 6-48h, the roasting temperature is 300-400 ℃, and the roasting time is 2-6 h.
The molar ratio of the iron atoms in the soluble iron salt to the molybdenum atoms in the soluble molybdenum salt is (25-60): 1.
According to the embodiment of the invention, the carrier is weighed according to the iron content of the catalyst of 1-10 wt%.
According to the embodiment of the invention, the soluble platinum salt is weighed according to the platinum content of 0.03-0.5 wt% in the catalyst.
The invention also provides a preparation method of the single-walled carbon nanotube, which comprises the following steps:
s1: placing the catalyst prepared by the preparation method or the catalyst provided by the invention in a reaction device, and heating to a reaction temperature; the reaction temperature according to the embodiment of the invention is 600-900 ℃, and preferably 700-800 ℃.
S2: introducing methane containing water vapor and inert gas for reaction
S3: and purifying the product obtained in the step S2 to obtain the single-walled carbon nanotubes SWNTs.
The detailed preparation process and conditions of the preparation method provided by the present invention are illustrated by the following examples.
Example 1
(1) Preparation of the catalyst: 0.131g ammonium molybdate and 2g citric acid were weighed and mixed and dissolved in 20mL deionized water, 5mL 10% HNO was added3Stirring uniformly to obtainTo solution A; weighing 5.47g of ferric nitrate, 4.461g of chloroplatinic acid and 1g of urea, adding into 50mL of ethanol, heating to 80 ℃, and uniformly stirring to obtain a solution B; adding the solution A into the solution B, further adding 54g of light MgO (commercially available) under vigorous stirring, stirring uniformly, then continuing stirring, raising the temperature to 150 ℃, and continuously stirring for 160min to obtain a solid C; putting the solid C into a 120 ℃ oven for drying overnight, grinding the solid C into powder after complete drying, heating the powder to 400 ℃ at the speed of 2 ℃/min, and roasting the powder for 180min to obtain the catalyst Fe30Mo10.01Pt/MgO, denoted Cat-1, with Fe content of about 2 wt% and Pt content of about 0.03 wt%.
(2) Preparation of SWNTs: placing 0.3g of Cat-1 catalyst in a quartz reaction tube with the inner diameter of 12mm, introducing 100sccm argon, and heating to the reaction temperature of 800 ℃ for 45 min; introducing a mixed gas of 500sccm methane, water vapor and argon, wherein the concentration of the methane is 30 percent, and the concentration of the water vapor is 200ppm, and starting the SWNTs growth reaction; closing the reaction gas after 60min, stopping heating, keeping 100sccm Ar, and cooling to room temperature; the product was removed and then purified to yield single-walled carbon nanotubes, designated SWNTs-1.
Example 2
The procedure for preparing the catalyst and the selection of the materials were the same as in example 1, except that the amount of chloroplatinic acid used in this example was 7.435g, and the procedure for preparing the catalyst and the selection of the materials were the same as in example 1. The catalyst prepared in this example was designated Cat-2.
Preparation of SWNTs: the procedure and materials for preparing SWNTs in this example were the same as those in example 1, except that Cat-2 was used as the catalyst in this example, and the procedure and materials for preparing SWNTs were the same as those in example 1. The SWNTs prepared in this example were referred to as SWNTs-2.
Example 3
The procedure for preparing the catalyst and the selection of the materials were the same as in example 1, except that the amount of chloroplatinic acid used in this example was 14.87g, and the procedure for preparing the catalyst and the selection of the materials were the same as in example 1. The catalyst prepared in this example was designated Cat-3.
Preparation of SWNTs: the procedure and materials for preparing SWNTs in this example were the same as those used in example 1, except that Cat-3 was used as the catalyst in this example, and the remaining procedure and materials for preparing SWNTs were the same as those used in example 1. SWNTs prepared in this example were designated as SWNTs-3.
Example 4
The procedure for preparing the catalyst and the selection of the materials were the same as in example 1, except that the amount of chloroplatinic acid used in this example was 74.35g, and the procedure for preparing the catalyst and the selection of the materials were the same as in example 1. The catalyst prepared in this example was designated Cat-4.
Preparation of SWNTs: the procedure and materials for preparing SWNTs in this example were the same as those used in example 1, except that Cat-4 was used as the catalyst in this example, and the remaining procedure and materials for preparing SWNTs were the same as those used in example 1. SWNTs prepared in this example were designated as SWNTs-4.
The catalysts prepared in examples 1 to 4 and the corresponding SWNTs were subjected to performance tests, and the specific results are shown in table 1:
TABLE 1 carbon yield and SWNTs I for catalysts obtained in examples 1-4G/IDValue of
Sample (I)
|
Catalyst and process for preparing same
|
Content of Pt
|
Carbon yield (%)
|
IG/ID |
Example 1
|
Cat-1
|
0.03
|
22.40
|
21.2
|
Example 2
|
Cat-2
|
0.05
|
26.20
|
21.3
|
Example 3
|
Cat-3
|
0.1
|
28.62
|
23.0
|
Example 4
|
Cat-4
|
0.5
|
35.12
|
21.9 |
As can be seen from the above table, the carbon yield of catalyst Cat-4 reached 35.12% when the Pt loading was increased to 0.5 wt%, which resulted from Pt having a stronger CH4Cracking ability so as to significantly increase the carbon yield of the catalyst.
According to the calculation of the Scherrer formula, a particle size distribution diagram of the Fe-Mo-Pt-based catalyst is obtained, and the result is shown in figure 1, and as can be seen from figure 1, the particle sizes of the Fe-Mo-Pt-based catalyst are all concentrated in 8-15nm, which is close to the value of the average tube diameter of the corresponding SWNTs, and it can be seen that the growth of the SWNTs in the system provided by the invention follows a 'tangential growth' mode, and the influence of Pt loading quantity on the particle sizes of the catalyst and the tube diameters of the SWNTs is small.
FIG. 2 shows the carbon yield and SWNTs I of the Fe-Mo-Pt based catalyst prepared according to the present inventionG/IDAs can be seen from FIG. 2, as the Pt loading increases, the Fe-Mo-Pt based catalyst carbonThe yield increased gradually while the IG/ID of the SWNTs remained high. I of SWNTs grown on Fe-Mo-Pt-based series catalysts after addition of PtG/IDThe difference is small, mainly concentrated between 20.0 and 23.0, and the Pt is seen to be effectively added to improve the overall quality of the SWNTs.
As shown in FIGS. 3 to 6, FIGS. 3(a) to (d) are SEM images of the catalysts Cat-1 to Cat-4 prepared in examples 1 to 4, respectively, and it can be seen from FIG. 3 that the incorporation of Pt did not change the "porous foam-like" morphology of the catalyst and the sizes of the pores of the catalyst were substantially the same. It can be seen that the appearance of the catalyst is less affected by the incorporation of a small amount of Pt.
FIG. 4(a) is an XRD pattern of catalysts Cat-1 to Cat-4 prepared in examples 1 to 4, and it can be seen from FIG. 4(a) that a diffraction peak of MgO as a carrier is dominant and a diffraction peak of other metals or oxides thereof is substantially covered by a diffraction peak of MgO. Further selecting the catalyst Cat-4 for detailed analysis, the result is shown in FIG. 4(b), and the comparative analysis with FIG. 4(a) shows that the catalyst Cat-4 still presents a very regular MgO peak after being calcined, and does not form Fe-Mo-Pt alloy.
FIGS. 5(a) to (d) are SEM images of SWNTs-1 to SWNTs-4 prepared in examples 1 to 4, respectively, and it can be seen from FIG. 5 that the tube diameters of the SWNTs prepared by the Fe-Mo-Pt-based catalyst provided by the present invention are fine and uniform. Further, the tube diameters were counted, and as a result, the average tube diameter of the SWNTs was mainly concentrated around 13.6nm as shown in fig. 6.
Comparative example 1
(1) Preparation of the catalyst: 0.131g ammonium molybdate and 2g citric acid were weighed and mixed and dissolved in 20mL deionized water, 5mL 10% HNO was added3Stirring uniformly to obtain a solution A; weighing 5.47g of ferric nitrate and 1g of urea, adding into 50mL of ethanol, heating to 80 ℃, and uniformly stirring to obtain a solution B; adding the solution A into the solution B, further adding 54g of light MgO (commercially available) under vigorous stirring, stirring uniformly, then continuing stirring, raising the temperature to 150 ℃, and continuously stirring for 160min to obtain a solid C; putting the solid C into a 120 ℃ oven for drying overnight, grinding the solid C into powder after complete drying, heating the powder to 400 ℃ at the speed of 2 ℃/min, and roasting the powder for 180min to obtain the catalyst Fe30Mo1/MgO, denoted Cat-5, with a Fe content of about 2 wt%.
(2) Preparation of SWNTs: comparative example 1 the procedure for the preparation of SWNTs and the selection of materials were the same as in example 1, except that Cat-5 was used as the catalyst in comparative example 1 and the remaining procedures and materials for the preparation of SWNTs were the same as in example 1. The SWNTs prepared in comparative example 1 were designated as SWNTs-5.
Further performance testing of Cat-5 revealed a carbon yield of 20.5%, although the carbon yield of the FeMo catalyst was not significantly reduced compared to Cat-1, the tube diameter of the SWNTs obtained therefrom was increased, as shown in fig. 7, and fig. 7 is a TEM image and a tube diameter distribution diagram of the SWNTs prepared in comparative example 1, and it can be seen that when the FeMo catalyst was not doped with Pt, the average particle size of the catalyst was significantly increased to 19.9nm, and at the same time, no Pt addition resulted in more MWNTs (black arrows in fig. 7 are short MWNTs).
Comparative example 2
(1) Preparation of the catalyst: 0.131g ammonium molybdate and 2g citric acid were weighed and mixed and dissolved in 20mL deionized water, 5mL 10% HNO was added3Stirring uniformly to obtain a solution A; weighing 5.47g of ferric nitrate, 148.7g of chloroplatinic acid and 1g of urea, adding into 50mL of ethanol, heating to 80 ℃, and uniformly stirring to obtain a solution B; adding the solution A into the solution B, further adding 54g of light MgO (commercially available) under vigorous stirring, stirring uniformly, then continuing stirring, raising the temperature to 150 ℃, and continuously stirring for 160min to obtain a solid C; and (3) putting the solid C into a 120 ℃ oven for drying overnight, completely drying, grinding into powder, heating to 400 ℃ at the speed of 2 ℃/min, and roasting for 180min to obtain the catalyst named Cat-6, wherein the content of Fe is about 2 wt%, and the content of Pt is about 1 wt%.
(2) Preparation of SWNTs: comparative example 2 the procedure for preparing SWNTs and the selection of materials were the same as in example 1, except that Cat-6 was used as the catalyst in comparative example 2 and the remaining procedure for preparing SWNTs and the selection of materials were the same as in example 1. The SWNTs prepared in comparative example 2 were designated as SWNTs-6.
The carbon yield is 38.2% and still improved when the loading amount of Pt reaches 1 wt% through calculation, but as shown in FIG. 8, the average tube diameter of the prepared carbon nanotube is 22.5nm, and although most SWNTs have smaller tube diameters, the tube diameters of the prepared SWNTs are not uniformly distributed on the whole, because a large amount of carbon species are generated by Pt with too high concentration, so that more SWNTs with large tube diameters are formed, and the quality of the SWNTs is reduced.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify the above-described embodiments without departing from the spirit and scope of the present invention. Therefore, the scope of the invention should be determined from the following claims.